CN1814721A - Method for preparing fatty acid - Google Patents
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- CN1814721A CN1814721A CN 200510054223 CN200510054223A CN1814721A CN 1814721 A CN1814721 A CN 1814721A CN 200510054223 CN200510054223 CN 200510054223 CN 200510054223 A CN200510054223 A CN 200510054223A CN 1814721 A CN1814721 A CN 1814721A
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Abstract
This invention relates to a method for preparing multiple unsaturated fatty acid conjugate isomers including: processing a first fatty acid mixture with saturated, single unsaturated and multi- unsaturated fatty acid with alcohol to form a solid part and a liquid part with a second fatty acid mixture, in which, compared with the first one, the mol ratio of the gross of the multi-unsaturated fatty acid and that of the saturated and single unsaturated is higher than the second mixture, separating the solid part and the liquid part and processing the second fatty acid mixture or its ramification or its reaction products by alkali with the help of a solvent to form conjugate isomers of some multi-unsaturated fatty acid.
Description
Technical field
The present invention relates to a kind ofly contain lipid acid, particularly contain the preparation method of the material of polyunsaturated fatty acid conjugated isomers, also relating to can be by the product of this method preparation and food, foodstuff additive or the medicine that contains this product.
Background technology
Known polyunsaturated fatty acid conjugated isomers helps healthy, and has been used in the food.Usually, these products contain linoleic acid isomers, wherein along 9, anti-11 and anti-10, normally have maximum isomer in these materials along 12 isomer, exist with 1: 1 weight ratio usually.
The conjugation polyunsaturated fatty acid is the compound that contains adjacent carbon-to-carbon double bond (for example one or more-the CH=CH-CH=CH-key).The conjugation polyunsaturated fatty acid can be by corresponding non-conjugated fatty acid preparation.For example, EP-A-0902082 has described preparation conjugation polyunsaturated fatty acid, as the method for conjugated linolic acid (CLA).This method comprises uses alkaline purification with non-conjugated polyunsaturated fatty acid in solvent, described solvent is the alcohol with at least 3 carbon atoms and at least two hydroxyls.
Usually contain the linolic acid of about 80wt%, the oleic acid of 12wt% and the unsaturated fatty acids of about 8wt% such as the typical polyunsaturated fatty acid source of Thistle oil.Adopt fractionation and distillation, only can remove saturated fatty acid, this means that linoleic acid content can not surpass 90wt%.Therefore, the amount of the conjugated linolic acid that can produce in aforesaid follow-up conjugation step also is restricted to maximum 90wt%.
The material that therefore need have high content conjugated polyunsaturated fatty acid.
US6395778 has described the method that a kind of preparation contains non-conjugated esters of polyunsaturated fatty acids enriched mixture.This method comprises that the transesterification of oil is to form fatty acid ester, urea to be added the first step that also cools off or concentrate the mixture that obtains in the fatty acid ester blends.Contain urea and polyunsaturated fatty acid ester in the throw out, liquid portion contains multiple esters of polyunsaturated fatty acids.Disclosed concrete fatty acid ester is unconjugated, and contains the two keys of at least five carbon-magnetic.Do not advise that this method can use free fatty acids to carry out.
EP-A-1211304 discloses a kind of method that contains the methyl alcohol of urea as the non-conjugated unsaturated fatty acids of choice of Solvent Crystallization Separation by employing.
The also follow-up conjugation of unexposed lipid acid in US6395778 or EP-A-1211304.
Summary of the invention
We have found that a kind of method for preparing the conjugation polyunsaturated fatty acid with surprising high yield.And when acting on the polyunsaturated fatty acid that contains two carbon-to-carbon double bonds, this method obtains with respect to suitable, and trans isomer lipid acid still less is anti-, trans isomer.Be surprised to find that the efficient height of this method depends on solvent used in this method.
Therefore, the invention provides the method that a kind of preparation contains the material of conjugation polyunsaturated fatty acid, it comprises:
In the presence of ethanol, handle first fatty acid mixt that contains saturated fatty acid, monounsaturated fatty acids and non-conjugated polyunsaturated fatty acid, to form (i) solid part and (ii) to contain the liquid portion of second fatty acid mixt, wherein second fatty acid mixt is than first fatty acid mixt, and polyunsaturated fatty acid total amount and mol ratio saturated and the monounsaturated fatty acids total amount are higher;
Separate this solid part and liquid portion; And
In the presence of solvent with alkaline purification this second fatty acid mixt or derivatives thereof or reaction product, to form the conjugated isomers of some polyunsaturated fatty acid at least.
Method of the present invention can prepare and contain in fatty acid total amount in the material, relatively the conjugation polyunsaturated fatty acid of more amount.Preferably, this material contains in fatty acid total amount, and 90wt%, more preferably 91wt%, more preferably 92wt%, 93wt% at least most preferably at least at least at least are as 94wt% or the conjugation polyunsaturated fatty acid of 95wt% at least at least.
Term lipid acid used herein, polyunsaturated fatty acid and relevant term refer to contain the straight-chain carboxylic acid of 12-24 carbon atom, preferred 14-18 carbon atom.Saturated fatty acid carbon-carbon double key not in alkyl chain, that can enumerate has tetradecanoic acid (being called C14:0), palmitinic acid (C16:0) and a stearic acid (C18:0).Monounsaturated fatty acids contains a carbon-to-carbon double bond in alkyl, that can enumerate has oleic acid (C18:1) and an elaidic acid (C18:1).Polyunsaturated fatty acid contains in alkyl chain two or more (preferred two) carbon-to-carbon double bond, that can enumerate has linolic acid (C18:2) and a linolenic acid (C18:3).
Have been found that method of the present invention is effective especially when saturated fat acid-proof, monounsaturated fatty acids and polyunsaturated fatty acid contain 18 carbon atoms.Conjugation polyunsaturated fatty acid by such lipid acid preparation is preferably conjugated linolic acid (CLA).The geometric position of depending on two carbon-to-carbon double bonds, CLA can exist with various isomeric forms, comprising: along 9, anti-11; Anti-10, suitable 12; Along 9, along 11; Along 10, along 12; Anti-9, anti-11; And anti-10, anti-12.Along 9, anti-11 and anti-10, maximum usually along 12 isomer.Method of the present invention can be used to prepare any or all isomer in the isomer, and obtains the form of isomer mixture usually, wherein along 9, anti-11 and anti-10, is main body CLA isomer along 12 isomer.
Method of the present invention comprises to be handled first fatty acid mixt that contains saturated fatty acid, monounsaturated fatty acids and polyunsaturated fatty acid in the presence of ethanol, to form (i) solid part and (ii) to contain the step of the liquid portion of second fatty acid mixt.This processing provides than first fatty acid mixt, total polyunsaturated fatty acid and total higher liquid portion of mol ratio saturated and monounsaturated fatty acids.Preferably, this processing comprises with urea to be handled, thereby solid part contains usually and at least a portion saturated fatty acid and/or monounsaturated fatty acids urea together.This processing obtains being rich in the mixture of polyunsaturated fatty acid for the first fatty acid mixt raw material thus.It has surprisingly been found that, use ethanol to replace the methyl alcohol of being instructed among the EP-A-1211304 in this stage of present method, through obtaining the productive rate of higher conjugated isomers after the follow-up conjugation step of the present invention, and, when polyunsaturated fatty acid contains two carbon-to-carbon double bonds, suitable if desired, trans isomer, then can help reducing anti-trans isomer.
In treatment step, the urea and first fatty acid mixt are usually with liquid mixing.Preferably, add in first fatty acid mixt by ethanolic soln or, this solution is mixed with this fatty acid mixt with opposite form with urea.This step is carried out under about 10 ℃-80 ℃ temperature usually, and if necessary, and it is the highest 80 ℃ so that temperature is increased to optionally and then to carry out heating steps.Preferably this reaction mixture is cooled to certain temperature then, for example 0 ℃-30 ℃, urea is crystallized out from mix.To contain the urea crystallization of fractional saturation lipid acid and/or monounsaturated fatty acids, for example, from mixture, separate by filtration or centrifugal.The liquid that obtains comprises second fatty acid mixt that is rich in polyunsaturated fatty acid.
The amount that is used for the urea of the preferred specific embodiments of present method preferably is enough to make urea: the alcoholic acid weight ratio was at least 1: 5, preferably was at least 1: 4, and more preferably weight ratio is in 1: 4 to 1: 2 scope.In first fatty acid mixt, the amount of urea preferably is enough to make urea: the weight ratio of first fatty acid mixt was at least 2: 1, preferably was at least 3: 1, and more preferably weight ratio is in 3: 1 to 5: 1 scope.
The solvent of present method comprises ethanol.Ethanol can contain one or more other solvents of maximum 20wt%, as water and/or methyl alcohol.Therefore, first fatty acid mixt is handled in the presence of the 80wt% alcoholic acid solvent containing at least usually.Preferably, for economic reasons, ethanol contains the water of 2wt%-10wt%.
Second fatty acid mixt that first fatty acid mixt obtains after treatment optionally can be further processed step (in the conjugation step with alkaline purification before) to form its derivative or reaction product.For example, further treatment step can comprise purifying, removes solvent from liquid, esterification to be to form the C of lipid acid
1-C
6The combination of alkyl ester and these steps.Usually, any derivatization or reaction should not have fatty acid distribution or the remarkable effect that changes fatty acid residue distribution in the mixture after deriving or reacting in the remarkable change mixture.Special do not wish to reduce in the mixture polyunsaturated fatty acid with respect to the amount of other lipid acid.
First fatty acid mixt can obtain by method as known in the art.First fatty acid mixt can be derived by the animal or plant source usually and be obtained.In fatty acid total amount, first fatty acid mixt preferably obtains by containing the oil that 50wt%-85wt% contains the polyunsaturated fatty acid of 18 carbon atoms.Suitable vegetables oil comprises Thistle oil, Trisun Oil R 80, rapeseed oil, Oleum Gossypii semen, soybean oil and linseed oil.
First fatty acid mixt is preferably by comprising that the alkali of for example using such as sodium hydroxide obtains the method that oil is hydrolyzed.This method can be carried out in the presence of such as the alcoholic acid solvent, and and then carries out acidifying usually to form free lipid acid.Free lipid acid can be extracted and optionally carry out purifying.
In the method for the invention, in the presence of solvent, use alkaline purification second fatty acid mixt or derivatives thereof or the reaction product, to form the conjugated isomers of some polyunsaturated fatty acid at least.Second fatty acid mixt preferably contains free fatty acids.Present method can be carried out according to the instruction of EP-A-0902082, and the content of the document is incorporated herein by reference.
The solvent that is used for this step of present method is preferably the alcohol with at least 3 carbon atoms and at least two hydroxyls.
Particularly suitable solvent is 1,3-dihydroxypropane or 1,2-dihydroxypropane (that is: propylene glycol).These solvents are food grade, and therefore the trace that remains in the product is harmless.This reaction is preferably carried out in the presence of the glycerine not having.
The alkali that is used for the conjugation step can be any alkali, but best as the result that alkali obtains with NaOH or KOH.Suitable alkali concn is greater than 0.25 moles per litre of solvent, preferred 0.25-3.5 mol, most preferably 1.25-2.75 mol.Use the alkali of a large amount more can cause forming to exist the product of multiple isomer (particularly C18:2 anti-/ anti--isomer).
This product is suitable (preferred: as pH1-3) to separate in by crude product mixture, so oil is separated, be washed with water to pH6-8 and dry from water until reaching acid pH by the acid of adding dilution in the soap lye that forms.The adding of acid causes forming the inorganic salt of the positively charged ion (as sodium ion or potassium ion) that contains alkali and sour negatively charged ion (as chlorion or sulfate radical).Thus, the salt of formation can be vitriolate of tartar for example.The existence that has been found that salt can hinder the follow-up extraction of product.Therefore, after preferred present method is included in acidification step, remove at least a portion by the step of alkali with the sour salt that forms.When salt crystallization or when precipitation in reaction mixture, salt that can be by separate solid form from reaction mixture is to remove salt.Preferably, to promote the crystallization or the precipitation of salt, the removal amount of salt is increased by reaction mixture.Usually,, salt is removed with water, then cools off water to remove precipitation or crystalline salt (for example, by filtering) thus by water phase separated from nonaqueous phase.
Thus, the present invention is preferably included in the step with second fatty acid mixt of acidifying after the alkaline purification.Optionally can this acidizing product of purifying.Also preferably remove the formed salt of at least a portion acidifying, the mixture that obtains is purified subsequently.Term " purifying " is meant any increase of the conjugated isomers amount of how unsaturated isomer in the mixture, is not to be meant 100% purity.Purifying can be undertaken by removing any residual water, optionally washes with water and drying, then carries out such as the further treatment step of distillatory.
The conjugation polyunsaturated fatty acid for preparing among the present invention can be further processed step, as forming monoglyceride, triglyceride or the triglyceride level of polyunsaturated fatty acid conjugated isomers.This step can adopt esterification techniques well known in the art to carry out.
Product of the present invention can be used as the raw material of particular procedure method, and in described processing, for other isomer, the amount of one or more isomer of conjugation polyunsaturated fatty acid (for example geometrical isomer) is horn of plenty more.The treatment process that is suitable for is described in WO97/18320 to some extent.Thus, the present invention attempts to provide a kind of method of using product of the present invention to make one or more isomer enrichments of conjugation polyunsaturated fatty acid as raw material.
In yet another aspect, the invention provides ethanol is used for by make polyunsaturated fatty acid from containing polyunsaturated fatty acid and purposes saturated and that mixture monounsaturated fatty acids is separated with the urea crystallization as solvent.Esterification treatment can make one or more isomer enrichments as described in the WO97/18320, and described document is incorporated herein by reference.
In yet another aspect, the present invention also provides a kind of product that obtains by method of the present invention.The previous fatty acid mixt that can not prepare the conjugated isomers that contains saturated fatty acid, monounsaturated fatty acids and polyunsaturated fatty acid, wherein in fatty acid total amount, the conjugated isomers of polyunsaturated fatty acid exists with the amount greater than 90wt%.
Preferably, product of the present invention contains at least 90wt% (more preferably 92wt% at least, as 93wt% or 94wt% at least at least, even more preferably 95wt% at least) conjugated linolic acid, at least the 43wt% conjugated linolic acid suitable-9, instead-11 isomer and the trans-10 of 43wt% conjugated linolic acid at least, suitable-12 isomer, perhaps all monoglycerides of these acid of same amount, triglyceride, and triglyceride level, wherein, suitable-9, anti--11 isomer and anti-10, the weight ratio of suitable-12 isomer is 1.1: 1-1: 1.1 (more preferably 1.05: 1-1: in the scope 1.05).All per-cent is all in the lipid acid gross weight.These products can contain the anti-of the conjugated linolic acid that is less than 1.5wt% (more preferably less than 1.0wt%, for example being less than 0.7wt%) or its glyceryl ester, trans isomer.This product can contain the saturated fatty acid of maximum 0.2wt% and/or the monounsaturated fatty acids of maximum 7.5wt%, or the glyceryl ester of these two kinds of lipid acid.
The present invention also provides a kind of food, foodstuff additive or medicine that contains product of the present invention.
Product of the present invention optionally can be used as the blend use with auxiliary fat.
This blend can contain 0.3-95wt%, preferred 2-80wt%, the most preferably product of the present invention of 5-40wt% and 99.7-5wt%, preferred 98-20wt%, the auxiliary fat that is selected from following material of 95-60wt% most preferably: esterification mixture between the composition of theobroma oil, theobroma oil Equivalent, plam oil or its cut, palm-kernel oil or its cut, described fat or its cut, perhaps liquid oil is selected from: Trisun Oil R 80, high oleic sunflower oil, soybean oil, rapeseed oil, Oleum Gossypii semen, fish oil, Thistle oil, high oleic safflower oil, Semen Maydis oil and MCT-oil.
Food of the present invention (this term comprises animal-feed) can contain fatty phase, and wherein fat contains product of the present invention mutually.Suitable food is selected from: the sauce of spread food (spreads), oleomargarine, cream, condiment, sweet oil, ice-creams, baked goods, infant food, chocolate, sweet food, sauce, tunicle, cheese and soup stock.
Foodstuff additive of the present invention or medicine can be to be applicable in the intestines or capsule form or other form of intestines external administration, and contain product of the present invention.
The example of the food that is suitable for comprises those that are selected from following material: the sauce of oleomargarine, fat stable state or water stable state or bistable state spread food, the sauce of degreasing spread food, such as confectionery, ice-creams, ice-creams tunicle, ice-creams content, seasonings, mayonnaise, cheese, missible oil substitute, dried soup, beverage, bar cake, the sauce of chocolate or chocolate tunicle or chocolate weighting material or baked goods weighting material, select axle, milk-product, clinical nutrition product and infant formulas system.
Medicine comprises composite medicine, as the form of tablet, pill, capsule, capsule sheet, the multiparticle that comprises particle, pearl, bead and microcapsule granule, powder, soup, syrup, suspension and solution.Pharmaceutical composition can contain medicine acceptable diluent or carrier.Pharmaceutical composition preferably adapts to intestines external administration (for example oral).Composition for oral administration can be solid or liquid form, and can adopt tablet, powder, suspension and syrupy form.Optionally, composition contains one or more seasonings and/or tinting material.
Be applicable to that the drug acceptable carrier in the said composition is known in the pharmacy industry field.Composition of the present invention can contain the conjugated fatty acids of 0.1-99wt%.Composition prepares with unit dosage form usually.The unitary dose of preferred conjugated fatty acids is 1mg-1000mg (100mg-750mg more preferably).The vehicle that is used to prepare these compositions is a vehicle as known in the art.
The example of foodstuff additive comprises that capsule material is selected from gelatin, starch, treated starch, starch derivative with the soft gel that contains capsule material or the product of form of hard gelatin capsules, as glucose, sucrose, lactose and fructose.Capsule material can optionally contain linking agent or polymerizing agent, stablizer, antioxidant, the light absorber that is used to protect photosensitive filler, sanitas etc.Preferably, the unitary dose of conjugated fatty acids is 1mg-1000mg (100mg-750mg more preferably) in the foodstuff additive.
Embodiment
Following non-limiting example is for example understood the present invention.Except as otherwise noted, in embodiment and whole specification sheets, all per-cent all is weight percents.
Embodiment
Embodiment 1
27.3 gram NaOH are dissolved in the ethanol of 200ml 95%.Add 100 gram Thistle oils and solution was refluxed 2 hours.The mixture sulphuric acid hydrolysis that obtains is used the 900ml hexane extraction 3 times then, merges hexane layer and be washed with distilled water to pH to be approximately 7, evaporates organic layer with rotatory evaporator then.Under 30 ℃, be dissolved in 270 gram ureas in the ethanol of 1500ml 95% and add lipid acid, then this mixture heating up to 60 ℃ was kept 1 hour, be cooled to 20 ℃ then and kept 3 hours.Filter this material to remove urea crystallization and evaporated filtrate subsequently.In flask, 16.8 gram KOH are dissolved in the 55ml propylene glycol, add then by the 50 gram fatty acid mixts (it contains the linolic acid greater than 90%) that obtain in the filtrate after the evaporation.Washed flask 15 hours with nitrogen down at 150 ℃.Behind the conjugation reaction, reaction mixture is placed 10% hot sulphuric acid soln, abandon lower floor,, dry in nitrogen at last with the hot wash upper strata to pH7.Analyze conjugated linolic acid with GC, HPLC, the results are shown in Table 1.
Embodiment 2 (Comparative Examples)
Except replace 95% ethanol to carry out adopting identical condition to repeat the process of embodiment 1 the reaction with urea with methyl alcohol.After the reaction, analyze conjugated linolic acid, the results are shown in Table 1.
Table 1 FAME (fatty acid methyl ester) analyzes
| Embodiment | 1 ethanol | 2 methyl alcohol |
| C14:0 | 0.0 | 0.0 |
| C16:0 | 0.1 | 0.3 |
| C16:1c | 0.1 | 0.1 |
| C18:0 | 0.0 | 0.0 |
| C18:1c | 6.9 | 8.6 |
| C18:2c，c | 0.4 | 0.4 |
| C18:3c，c，c | 0.1 | 0.2 |
| CLA-9，11 c，c | 1.0 | 1.1 |
| CLA-10，12 c，c | 1.1 | 1.1 |
| CLA-11，13 c，c | 1.3 | 1.0 |
| CLA-OX | 0.0 | 0.3 |
| C18:2 t，t | 1.1 | 1.3 |
| CLA-t，t | 1.2 | 2.0 |
| CLA-9，11 c，t | 43.0 | 41.6 |
| CLA-10，12 t，c | 43.3 | 42.1 |
| SAFA | 0.1 | 0.4 |
| Main CLA | 86.3 | 83.7 |
| Total CLA | 91.2 | 89.1 |
*Cx:y refers to contain the lipid acid of x carbon atom and y two keys
*C refers to suitable, and t refers to instead
*CLA is a conjugated linolic acid; CLA-OX refers to the CLA oxidation products
*At CLA-m, among the n, m and n are the position of two keys in the chain, for example, CLA-9,11 refer to 9, the 11-diolefinic acid
*SAFA refers to saturated lipid acid
The advantage that replaces the inventive method of methyl alcohol with ethanol has been shown in the table, that is: the amount of total CLA and main CLA isomer is higher, and anti-trans isomer is less.
Embodiment 3
The sauce of spread food that contains the triglyceride level of embodiment 1 product can be formulated as follows, the method that adopts WO97/18320 to describe.
| The fat phase | wt％ |
| Fats mixt *Hymono 7804 tinting materials (2% β-Hu Luobusu) total amount | 40 0.3 0.02 40.32 |
| Water (pH 5.1) | wt％ |
| Water skim-milk gelatin (270 Blang's nurse) potassium sorbate citric acid powder total amount | 56.44 1.5 1.5 0.15 0.07 59.66 |
*The blend of the glyceryl ester of hard stock/Trisun Oil R 80/embodiment 1 product (being 13/82/5 by weight)
Embodiment 4
The seasonings that contains the glyceryl ester of embodiment 1 product can be formulated as follows, the method that adopts WO97/18320 to describe.
| wt％ | |
| Liquid oil *Star Dri 5 dried yolk xanthan gum (Xanthum gum) edible vinegar water | 25.0 20.0 0.8 0.4 5.0 48.8 |
*The mixture of esterification between the composition of product and Trisun Oil R 80
Embodiment 5
Present embodiment relates to the conjugation of the enrichment Thistle oil of pilot plant scale.
(50wt% solution is KOH) with 115 kilograms of mixed with propylene glycol with 60 kg of hydrogen potassium oxides.With this mixture heating up to 70 ℃, use nitrogen bubbling in mixture simultaneously.Then, stop nitrogen bubble, add 95 kilograms of enrichment safflower lipid acid that adopt the urea preparation according to the present invention in the alkalitropism propylene glycol.
Temperature is increased to 110 ℃ then, mixture was stirred 2 hours under this temperature.Then, temperature is increased to 135 ℃, mixture is stirred under this temperature is lower than 1% until C18:2c content.Extract sample at interval and analyze FAME by GC and form this process of supervision with regular time.Total is carried out three batches, and average total reaction time is 82 hours.
The soap that from each batch, obtains with vitriol oil hydrolysis.Behind the conjugation reaction, mixture is cooled to 70 ℃ also with the dilution of 250L thermal softening water.Then, add 30 kilograms of vitriol oils with the hydrolysis soap.
Leave standstill the mixture that obtains, discharge bottom.
Merging is by three batches of oil phases that obtain, and with 80 ℃ of thermal softening water washings.The washing back forms emulsion layer for the first time, only can discharge the water that a part is added thus.In washing for the second time, keep emulsion, behind the water that a discharge part is added, make oil drying by applying vacuum.
Distill this exsiccant oil by short-path distillation.Output is 170 kilograms.Because emulsion, product yield are lost (about 40%).
The FAME of product analyzes and lists in the following table 2.
Table 2
| The terminal mixture | End product | |
| C14:0 C16:0 C16:1c C18:0 CLA t, t CLA c9, c11 CLA c10, c12 CLA 11,13 C18:1t C18:1c CLA-OX C18:2 t, t C18:2 c, c C20:0 C20:1c SAFA master CLA CLA c9, t11 CLA t10, the total CLA of c12 | 0 0.2 0.1 0 0.9 0.9 0.9 1 0 4.9 0.1 0.6 0.9 0 0 0.3 89.4 44 45.5 93.2 | 0 0.2 0.1 0 1.4 1 1 0.8 0 4.7 0.2 0.4 1.3 0 0 0.2 88.8 43.3 45.5 93.2 |
Embodiment 6
Under nitrogen protection, in stirred tank reactor, 7700 kilograms of enrichment safflower lipid acid are joined in 9780 kilograms of propylene glycol.To wherein add 5120 kg of hydrogen potassium oxides (50wt% solution, KOH) and under nitrogen, be heated to 110 ℃.After removing water, with temperature be increased to 139 ℃ and stirring under this temperature the suitable content of C18:2 is lower than 1% in FAME analyzes.Total reaction time is 42 hours.
After the conjugation, mixture at first is cooled to 100 ℃, with 25 tons of softening water dilutions, then is cooled to 55 ℃ then.Be somebody's turn to do the soap of dilution with 3090 kilograms of vitriol oils (98wt%) hydrolysis.Leave standstill the water layer of this fatty acid mixt and discharge bottom.In the process of discharging bottom, the vitriolate of tartar crystallization that forms in the hydrolytic process is removed fully with water.Remaining fatty acid is cooled to 55 ℃ mutually with all remaining vitriolate of tartar of crystallization.These vitriolate of tartar also are removed to prevent forming emulsion in subsequent step.
With lipid acid heat phase to 95 ℃, and use 10 tons and 5 tons of thermal softening water (95 ℃) to wash in two steps respectively.In washing step, find no emulsion.After the washing, oil is dried and is used for distillation.
Distill the lipid acid of washing to obtain 6200 kilograms of products by short-path distillation.Loss of yield reduces to 20%.
The FAME of product analyzes and is listed in the table below in 3.
Table 3
| Product analysis | |
| C14:0 C16:0 C16:1c C18:0 CLA t, t CLA c9, c11 CLA c10, c12 CLA 11,13 C18:1t C18:1c CLA-OX C18:2 t, t C18:2 c, c C20:0 C20:1c SAFA master CLA CLA c9, t11 CLA t10, the total CLA of c12 | 0.0 0.2 0.1 0.1 0.9 0.9 0.9 0.8 0.0 4.8 0.2 0.6 0.6 0.0 0.0 0.4 89.9 44.3 45.6 93.6 |
Claims (22)
1. preparation contains the method for the material of polyunsaturated fatty acid conjugated isomers, comprising:
In the presence of ethanol, handle first fatty acid mixt that contains saturated fatty acid, monounsaturated fatty acids and polyunsaturated fatty acid, to form (i) solid part and (ii) to contain the liquid portion of second fatty acid mixt, wherein second fatty acid mixt is than first fatty acid mixt, polyunsaturated fatty acid total amount and saturated and the mol ratio monounsaturated fatty acids total amount is higher;
Separate this solid part and liquid portion; And
In the presence of solvent with alkaline purification this second fatty acid mixt or derivatives thereof or reaction product, to form the conjugated isomers of some polyunsaturated fatty acid at least.
2. the method for claim 1, wherein said material contains the polyunsaturated fatty acid conjugated isomers of 90wt% at least.
3. method as claimed in claim 1 or 2, wherein polyunsaturated fatty acid contains 12-24 carbon atom.
4. the described method of one of claim as described above, wherein saturated fatty acid, monounsaturated fatty acids and polyunsaturated fatty acid contain 18 carbon atoms.
5. the described method of one of claim as described above, wherein conjugated isomers is linoleic conjugated isomers.
6. the described method of one of claim as described above wherein handle first fatty acid part with urea, and solid part contains urea.
7. the described method of one of claim is as described above wherein handled first fatty acid mixt in the presence of the 80wt% alcoholic acid solvent containing at least.
8. the described method of one of claim as described above wherein was further processed step to second fatty acid mixt, to form its derivative or reaction product before with alkaline purification.
9. method as claimed in claim 9, wherein further treatment step is selected from the removal, esterification of purifying, solvent to form the C of lipid acid
1-C
6The combination of alkyl ester and these steps.
10. the described method of one of claim as described above, wherein in fatty acid total amount, first fatty acid mixt obtains by containing the oil that 50wt%-85wt% contains the lipid acid of 18 carbon atoms.
11. the described method of one of claim as described above, wherein first fatty acid mixt exists down the method with the basic hydrolysis vegetables oil to obtain by being included in ethanol as solvent.
12. method as claimed in claim 11, wherein vegetables oil is selected from Thistle oil, Trisun Oil R 80, rapeseed oil, Oleum Gossypii semen, soybean oil and linseed oil.
13. the described method of one of claim as described above, wherein solvent contains the alcohol with at least 3 carbon atoms and at least two hydroxyls.
14. the described method of one of claim as described above, wherein solvent is a propylene glycol.
15. the described method of one of claim as described above, it is included in after the alkaline purification, makes the second fatty acid mixt acidifying.
16. method as claimed in claim 15 is wherein removed the formed salt of at least a portion acidifying, and this mixture that obtains of subsequent purificn.
17. the described method of one of claim further comprises the monoglyceride, triglyceride or the triglyceride level that form the polyunsaturated fatty acid conjugated isomers as described above.
18. ethanol is used for by make polyunsaturated fatty acid from containing polyunsaturated fatty acid and purposes saturated and that mixture monounsaturated fatty acids is separated with the urea crystallization as solvent.
19. the product that obtains by the method for one of claim 1-17.
20. product as claimed in claim 19, it contains the conjugated linolic acid of 90wt% at least, at least the 43wt% conjugated linolic acid suitable-9, instead-11 isomer and the trans-10 of 43wt% conjugated linolic acid at least, suitable-12 isomer, or its monoglyceride, triglyceride or triglyceride level, wherein, suitable-9, anti--11 isomer and trans-10s, the weight ratio of suitable-12 isomer is 1.1: 1-1: in 1.1 the scope.
21. product as claimed in claim 20, it contains the anti-of the conjugated linolic acid that is less than 1.5wt%, trans isomer.
22. contain food, foodstuff additive or medicine just like one of claim 19-21 described product.
Priority Applications (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100542237A CN100516188C (en) | 2005-02-04 | 2005-02-04 | Method for preparing fatty acid |
| US11/883,642 US7910757B2 (en) | 2005-02-04 | 2006-02-02 | Process for the preparation of fatty acids |
| AT06706675T ATE509085T1 (en) | 2005-02-04 | 2006-02-02 | METHOD FOR PRODUCING FATTY ACIDS |
| JP2007553554A JP5414180B2 (en) | 2005-02-04 | 2006-02-02 | Method for producing fatty acid |
| KR1020077018320A KR101282098B1 (en) | 2005-02-04 | 2006-02-02 | Process for the preparation of fatty acids |
| ES06706675T ES2395254T3 (en) | 2005-02-04 | 2006-02-02 | Procedure for the preparation of fatty acids |
| PCT/EP2006/001020 WO2006082093A1 (en) | 2005-02-04 | 2006-02-02 | Process for the preparation of fatty acids |
| EP06706675A EP1844131B1 (en) | 2005-02-04 | 2006-02-02 | Process for the preparation of fatty acids |
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| CNB2005100542237A CN100516188C (en) | 2005-02-04 | 2005-02-04 | Method for preparing fatty acid |
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| CN1814721A true CN1814721A (en) | 2006-08-09 |
| CN100516188C CN100516188C (en) | 2009-07-22 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102229527A (en) * | 2009-12-14 | 2011-11-02 | 脂质营养品有限公司 | Technological method |
| CN103826714A (en) * | 2011-07-06 | 2014-05-28 | 巴斯夫制药（卡兰尼什）公司 | SMB process for producing highly pure EPA from fish oil |
| US8901331B2 (en) | 2008-03-17 | 2014-12-02 | Stepan Specialty Products, Llc | Process for refining a triglyceride oil |
| CN109828047A (en) * | 2019-02-25 | 2019-05-31 | 中国农业科学院油料作物研究所 | The kit of the accurate Structural Identification of unsaturated fatty acid in a kind of grease |
-
2005
- 2005-02-04 CN CNB2005100542237A patent/CN100516188C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8901331B2 (en) | 2008-03-17 | 2014-12-02 | Stepan Specialty Products, Llc | Process for refining a triglyceride oil |
| CN102229527A (en) * | 2009-12-14 | 2011-11-02 | 脂质营养品有限公司 | Technological method |
| CN102229527B (en) * | 2009-12-14 | 2016-05-04 | 脂质营养品有限公司 | Process |
| CN103826714A (en) * | 2011-07-06 | 2014-05-28 | 巴斯夫制药（卡兰尼什）公司 | SMB process for producing highly pure EPA from fish oil |
| CN103826714B (en) * | 2011-07-06 | 2016-03-09 | 巴斯夫制药（卡兰尼什）公司 | For the SMB method of production high-purity EPA from fish oil |
| CN109828047A (en) * | 2019-02-25 | 2019-05-31 | 中国农业科学院油料作物研究所 | The kit of the accurate Structural Identification of unsaturated fatty acid in a kind of grease |
| CN109828047B (en) * | 2019-02-25 | 2021-08-31 | 中国农业科学院油料作物研究所 | Kit for identifying accurate structure of unsaturated fatty acid in grease |
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| Publication number | Publication date |
|---|---|
| CN100516188C (en) | 2009-07-22 |
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