DE3521294A1 - METHOD FOR OBTAINING CAROTINE FROM NATURAL OILS AND FATS - Google Patents

Description

TER MEER · MÜLLER. STEINMEISTER ^Lion Corp. -

description

The invention relates to a method for treating oils and fats for the effective recovery of in therein Trace amounts of carotene contained.

It is known that carotene, which is a carotenoid hydrocarbon represents, can be used as provitamin A or as an edible color. You can have carotene by synthesis or by extracting the trace amounts contained in natural oils and fats. Following the traditional method of extracting carotene from natural oils and fats, the carotene containing natural oils and fats, whereupon the unsaponified carotene with a solvent is extracted, or you can alcoholysis with a low molecular weight carotene-containing natural oils and fats Subject alcohol to the formation of fatty acid lower alkyl esters, which then under reduced Pressure to be distilled off in order to accumulate the carotene in the distillation residues in this way.

The former method comprising solvent extraction shows poor carotene recovery efficiency, a large amount of solvent is required if the carotene is recovered in high yields shall be. This leads to high production costs. Furthermore, the oils and fats result after the extraction of the Carotene is a colored soap that cannot simply be put to useful further use. The latter method, in which distillation is carried out under reduced pressure, must be at low pressure Temperatures in a high vacuum are carried out to prevent the decomposition of the carotene. This brings high Device costs and operating costs with it and leads

ORIGINAL INSPECTED

TER MEER MÜLLER STEINMEISTER Lion Corp. - FAP-275

also at high production costs.

The object of the present invention is therefore to provide a method for treating natural oils and to indicate fats with which it is possible to reduce the carotene traces contained therein in high yields and in concentrated form at low cost.

It has now been found as a result of intensive studies of the process for the efficient production of carotene from natural oils and fats with high yields and in high concentrations shown that the above The object can be achieved by alcoholysis of the carotene-containing natural oils and fats Subjected with a low molecular weight monoalcohol, containing the carotene and essentially consisting of Fatty acid lower alkyl esters collects existing oil phase, the oil phase to separate the carotene with a hydrophilic Solvent and water mixed and the carotene separated in this way wins.

The invention therefore relates to the method according to the main claim. The subclaims particularly concern preferred embodiments of this subject matter of the invention.

According to the invention carotene-containing natural oils and Fats with a low molecular weight monoalcohol subjected to alcoholysis, during which an oil phase is formed, which contains carotene and consists essentially of fatty acid lower alkyl esters. This oil phase is with a added hydrophilic solvent and water. In this way the solubility of the hydrophobic carotene and the fatty acid lower alkyl ester in the hydrophilic solvent is reduced. This has the consequence that the Solution separates into two layers, namely one that Caro-

TER MEER · MÖLLER ■ SΓΕΙΝΜΕΙΒΤΈΝ ^ i _0n Corp. - FAP-2T5

tin and a small amount of the fatty acid lower alkyl ester, and a further layer which comprises the larger amount of the fatty acid lower alkyl ester / the hydrophilic solvent and water. The layer containing high concentrations of carotene is then recovered. If you win the carotene layer at 30 to 70 ⁰ C and then the remaining layer of the hydrophilic solvent at 10 to 3O ⁰ C cools, one can separate the fatty acid alkyl esters and win. In the same way, the hydrophilic solvent is recovered, which is then fed back into the process.

The collected carotene layer can preferably be brought into contact with a styrene-divinylbenzene copolymer, to attach carotene and the remaining esters present in the carotene layer to the copolymer resin. Afterward the copolymer resin is brought into contact with a low molecular weight monoalcohol such as methanol or ethanol, in order to dissolve the esters present on the resin in the low molecular weight monoalcohol, whereby the carotene remains adsorbed on the resin. After eluting the esters with the low molecular weight monoalcohol from the Resin the resin is brought into contact with a hydrophobic solvent in order to remove the carotene present on the resin to dissolve in the solvent and to elute from the resin with the solvent. That way it gets the eluted carotene in a highly concentrated form.

It is according to the invention using simple devices and procedures possible to obtain carotene in concentrated form and in high yields from natural oils and fats containing trace amounts of carotene. Furthermore, the method according to the invention results discolored fatty acid lower alkyl esters purified as a by-product.

TER SEA. MÖLLER. STEINMEISTER LionCorp. -

The invention is described in more detail below with reference explained on the accompanying drawing. the

The single figure shows the relationship between the column temperature by means of a graph in the elution of the esters with methanol and the carotene concentration in the event that a carotene-containing fatty acid lower alkyl ester in a column with a styrene-divinylbenzene copolymer resin is brought into contact to concentrate the carotene.

The inventive method begins with the carotene-containing natural oils and fats with a low molecular weight To subject monoalcohol to alcoholysis and then the carotene-containing and essentially off To win fatty acid lower alkyl esters existing oil phase. The carotene-containing natural oils are more precise and fats with a low molecular weight monoalcohol, such as methanol or ethanol, added, which in the natural Oils and fats present glycerides through alcoholysis in glycerol and lower alkyl esters higher Fatty acids are converted. The carotene present in the oils and fats remains with the unreacted ones Glycerides in the alkyl ester phase (oil phase). The oil phase is removed by standing or by centrifugation separated from the glycerin. The selection of the carotene-containing to be treated by the method according to the invention natural oils and fats is not particularly limited. However, palm oil is preferably used.

In the next step, the carotene-containing and consisting essentially of fatty acid lower alkyl esters Oil phase mixed with a hydrophilic solvent and water to promote excretion and separation of the Effect carotene. The carotene in high concentration

ORIGlNAL INSPECTED

TER MEER MÜLLER 8TEINM & STER Lion Corp. -

Nen-containing layer is made by standing and centrifuging severed.

Regarding the method and order of mixing there are no restrictions on the oil phase with the hydrophilic solvent and water. Preferably one solves the oil phase in the hydrophilic solvent and then gives the water to the solution formed to be in this Way to separate the carotene.

Also with regard to the type of hydrophilic solvent to be used there are no particular restrictions. Preferred examples of solvents of this kind are methanol, ethanol, isopropanol and acetone. These solvents can be used individually or in combination with one another insert. The hydrophilic solvent can be added with advantage in such a way that the concentration the fatty acid oxyalkyl ester is 5 to 20% by weight, based on the hydrophilic solvent. if if methanol or ethanol is used as the hydrophilic solvent, carotene separates in the lower layer while using isopropanol or acetone as a hydrophilic solvent, carotene is in the upper layer accumulates.

The amount of water can preferably be 1 to 20% by weight, based on the hydrophilic solvent. One may perform this step at temperatures of 10 to 70 ⁰ C. The carotene layer separated in this way contains carotene, a certain amount of fatty acid lower alkyl ester and the hydrophilic solvent. The solvent can advantageously be distilled off in the customary manner in order to obtain a carotene concentrate in this way. The layer of the hydrophilic solvent remaining after the carotene layer has been separated off essentially contains fatty acid lower alkyl esters and one

OFÜGINAl

TER MEER · MÜLLER. STEINMEISTKR Lion Corp. -

small amount of carotene. After the hydrophilic solvent has been separated off, the discolored fatty acid lower alkyl esters are recovered. With a simple cleaning treatment, they can be turned into a high quality raw material to be converted for higher fatty acids and surfactants.

As already mentioned above, the carotene-containing oil phase consisting essentially of fatty acid lower alkyl esters is mixed with a hydrophilic solvent and water to separate off the carotene. This step can be carried out preferably at 30 to 70 ⁰ C. After the layer containing carotene in high concentrations is collected, the remaining hydrophilic solvent layer is supplemented with the same hydrophilic solvent, if necessary. This step can preferably be ^{carried out at 10 to 30 °} C. in order to effect the separation of the fatty acid lower alkyl esters, which contain only small amounts of carotene, in an effective manner. In this way, the fatty acid lower alkyl esters and, at the same time, the hydrophilic solvent and water are obtained.

There should be a large temperature difference between the first stage, in which the layer containing carotene is collected in high concentrations, and the second stage, in which the fatty acid lower alkyl esters are collected. In practice, the preferred temperature difference is 20 to 4O ⁰ C. The hydrophilic solvent and the water, which has been gained in this way containing a small amount of fatty acid alkyl esters and carotene. The recovered solvent can be reused as a solvent for separating off the carotene without separating off the esters or carotene contained therein.

TER MEER MÜLLER STEINMEISTER Lion Corp. - FAP-275

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The layer enriched in carotene in the manner described above can also be used in either the present Form or after the removal of the water and hydrophilic solvent still present therein with a Styrene-divinylbenzene copolymer resin can be brought into contact, in this way, the carotene and the remaining To adsorb esters on the copolymer resin. Then the copolymer resin with a low molecular weight Mono alcohol contacted to dissolve the esters in the low molecular weight mono alcohol. Afterward bringing the copolymer resin into contact with a hydrophobic solvent to remove the carotene in the solvent to solve. In this way, the concentration of carotene is further increased.

When carotene and the fatty acid lower alkyl esters are brought into contact with the styrene-divinylbenzene copolymer resin are, carotene and the esters are easily adsorbed on the copolymer resin because it has a high adsorptive Has affinity for hydrophobic substances. Then the copolymer resin with a low molecular weight Mono-alcohol brought into contact, in that the carotene is only poorly soluble, with the result that only the esters are dissolved in the low molecular weight monoalcohol. After separation of the ester brings the copolymer resin is brought into contact with a hydrophobic solvent such as hexane, chloroform or petroleum ether, in which solvents carotene is readily soluble. In this way, only carotene is left in the solvent dissolved so that a solution containing carotene in high concentrations is obtained.

Regarding the form of the styrene-divinylbenzene copolymer resin there are no particular restrictions, although the resin is preferably in powder form or used in granular form.

TERMEER-MALLER-STElNMElBTKR: Lion Corp. - FAP-275

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There are also no particular restrictions on the method by which one can get high carotene Concentration containing layer with the styrene-divinylbenzene copolymer resin brings in contact. This can be done using a column or in batches. The column method is preferred in view of the efficient adsorption of the carotene. You can get those on carotene enriched layer in an amount of 0.2-0.5 g / ml of the resin introduced into the column with advantage lead the pillar. If the loading is more than 0.5 g / ml resin, the resin will quickly become saturated, resulting in The consequence is that the carotene can pass through unadsorbed.

The carotene-enriched layer can be brought into contact with the styrene-divinylbenzene copolymer resin in a more effective manner by previously diluting the layer with a low molecular weight monoalcohol which is used for the later-mentioned elution of the esters.
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Styrene-divinylbenzene copolymer resins adsorb hydrophobic substances better than hydrophilic substances. Because of Due to this characteristic, this resin adsorbs carotene, ester and alcohol in that order.

The copolymer resin to which the carotene-containing layer adsorbs is then with a low molecular weight monoalcohol, preferably a low molecular weight C1 -C4 monoalcohol, brought into contact, in the carotene is not soluble. In this way, those present in the carotene-enriched layer become alcohol-soluble Ester dissolved in the alcohol. The carotene remains in adsorbed form on the resin. Preferably the low molecular weight monoalcohols used are methanol or ethanol. The low molecular weight mono-

TER MEER MÜLLER STFINMEhSTgR _{Lion Corp #} _ pAP-275

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Use alcohols individually or in combination with one another. To elute the esters, one can use the low molecular weight Use monoalcohol in an amount that corresponds to 1 to 5 times the volume of the resin. 5

After the esters have been separated off, the copolymer resin is brought into contact with a hydrophobic solvent the carotene readily dissolves, with the result that the carotene is eluted with the solvent, whereupon the eluate is obtained.

Regarding the type of hydrophobic solvent in which the carotene is readily soluble, there are no particular restrictions. Preferred examples for Such solvents are hexane, chloroform and petroleum ether. You can use these solvents individually or in Use combination with each other. For safety reasons, especially if the carotene obtained to be used for food products, for example as food coloring, is hexane as Solvents particularly preferred.

To elute the carotene, the hydrophobic solvent can be used in an amount equal to the 0.5 to 2 times the resin volume. In this way it becomes possible to practically completely remove the adsorbed carotene to elute.

If one carries out the action mentioned above in a column can be the column temperature at 0 to 80 ⁰ C, preferably 0 to 20 ⁰ C, hold to the adsorption of the enriched carotene layer and the elution to favor the ester to the low molecular weight mono-alcohol . At these temperatures, the adsorption of the carotene increases and with it the concentration ratio. The column temperature during the elution of the carotene with the hydro-

TER MEER · MÖLLER. STEINMEISTER Lion Corp. -

Phobic solvent can be any temperature that is below the boiling point of the hydrophobic solvent lies. The resin from which the carotene has been separated can be used repeatedly if you look at that remaining hydrophobic solvents on the resin are replaced by the alcohol used to elute the esters.

The carotene separated and recovered from the resin in this way may vary depending on the purpose can be used in the resulting form without separating off the hydrophobic solvent. Preferably however, the solvent should be distilled off in the usual way.

The fatty acid lower alkyl esters eluted from the resin. can also be recycled.

As already mentioned above, there is the inventive Process in it, the carotene-containing natural oils and fats an alcoholysis with a low molecular weight To subjugate monoalcohol, the carotene-containing and consisting essentially of fatty acid lower alkyl esters win oil phase, the oil phase to separate the carotene with a hydrophilic solvent and To mix water and to win the carotene separated in this way. In this way it becomes possible in a simple way to concentrate the carotene present in natural oils and fats and to obtain which one practically completely decomposed and discarded when using conventional cleaning methods is not put to effective further use. The method according to the invention does not make high temperature treatments required and therefore gives the carotene in high yields without losses due to the decomposition of carotene. Furthermore, fatty acid lower alkyl esters arise as a by-product, of which the carotene

ORIGINAL INSPECTED

TER MEER · MÜLLER ■ STFINMEISTCR Lion Corp. -

is separated.

The carotene-containing and consisting of fatty acid lower substantially oil phase is mixed at 30 to 7O ⁰ C with a hydrophilen.Lösungsmittel and water to recover the enriched carotene layer in this manner. The remaining hydrophilic solvent layer is ^{cooled to 10 to 30 °} C. in order to cause the fatty acid lower alkyl esters to precipitate. The esters are recovered while at the same time the hydrophilic solvent is recovered and reused. The recovery of the hydrophilic solvent in this case only requires the application of a small amount of heat compared to the recovery of the hydrophilic solvent by distillation. The recovered solvent can be used repeatedly to elute the carotene after making up the solvent losses and adding water (about 1/10 the amount of the oil phase). In this way, the method according to the invention can be carried out very economically, in particular with regard to energy consumption.

The concentration of carotene can be increased to a great extent by adding the above-mentioned amount of carotene layer enriched with a styrene-divinylbenzene copolymer resin brings in contact, which adsorbs the carotene and the remaining esters. By eluting the Esters with a low molecular weight monoalcohol from the resin and then eluting the carotene with one hydrophobic solvent, the eluted carotene is recovered.

The following examples serve to further illustrate the invention.

ORIGINAL! HSFECTED

TER MEER MÜLLER STFINMEISTKR Lion Corp. -

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example 1

30 g of crude palm oil, which contains 620 ppm of carotene, are subjected to esterification by adding 10 g of methanol and 0.24 g of sodium hydroxide to form the methyl esters. The ester layer formed is collected, washed with 5 g of water and then dehydrated in the usual manner. Then, the Esterschicht is dissolved in 210 g of methanol, after which 8.5 g of water is added to the methanol solution and then allowed to stand for 1 hour at 20 ⁰ C. The lower layer, in which carotene has been excreted, is recovered and the remaining trace amounts of methanol and water are removed. In this way, 5.8 g of a concentrate are obtained which contains 2720 ppm of carotene (carotene concentration: 4.4 times, carotene recovery: 84.8%).

After the methanol and the water have been separated off from the upper layer, 23.3 g of a discolored ester are obtained. which contains 97 ppm carotene.

The concentrate obtained in the manner described above (5.8 g), which contains 2720 ppm of carotene, is mixed, with 40 g of methanol and 1.5 g of water, after which the mixture is allowed to stand. After the methanol has been separated off and the water from the lower layer gives 1.2 g of a concentrate containing 1.1% carotene.

Example 2

30 g of crude palm oil, which contains 583 ppm of carotene, are treated in the manner described in Example 1. The ester layer obtained is dissolved in 450 g of methanol, 45 g of water are added to the methanol solution and it is left to stand ^{at 60 ° C. for 1 hour.} The lower layer, in which the carotene was deposited, is recovered and the remaining trace amounts of methanol and water are removed. In this

ORIGINAL INSPECTED

TER MEER MÜLLER STEINMb'ISTHR Lion Corp. -

5.5 g of a concentrate containing 2500 ppm of carotene are obtained (carotene concentration: 4.3-fold, carotene recovery: 78.6%).

After the upper layer has cooled to 20 ^° C. and left to stand, 7 g of a discolored ester separate out which contains 150 ppm of carotene. After the discolored ester has been recovered, 447 g of methanol, 44 g of water and 14.7 g of fatty acid lower alkyl ester containing 73 ppm of carotene are recovered. The methanol solution obtained in this way can be used repeatedly to elute the carotene.

Example 3

30 g of crude palm oil containing 518 ppm of carotene are treated in the manner described in Example 1. The Esterschicht formed is dissolved in 200 g of ethanol, after which the solution is treated with 54 g of water and allowed to stand for 1 hour at 20 ⁰ C. The lower layer, in which carotene is excreted, is recovered and freed from trace amounts of ethanol and water. In this way, 8.0 g of a concentrate containing 1400 ppm of carotene are obtained (carotene concentration: 2.7-fold, carotene recovery: 72.1%).

After the water and the ethanol have been separated off from the upper layer, 21.0 g of a discolored ester containing 175 ppm of carotene are obtained.
30th

Example 4

30 g of crude palm oil, which contains 530 ppm of carotene, are treated in the manner described in Example 1. The ester layer formed is dissolved in 200 g of isopropanol and 147 g of water are added to the solution, after which one

ORIGINAL INSPECTED

TER MEER - MÜLLER STEINMfc-ISTE-IR Lion Corp. - FAP-

lets stand ^{at 2O 0} C for one hour. The upper layer, in which the carotene has been excreted, is recovered and freed from remaining trace amounts of isopropanol and water. In this way, 16.8 g of a concentrate containing 866 ppm of carotene are obtained (carotene concentration: 1.6-fold, carotene recovery: 90.9%).

Example 5

30 g of crude palm oil, which contains 600 ppm of carotene, are treated in the manner described in Example 1. Dissolve the Esterschicht formed in 200 g of acetone and the solution is mixed with 45 g of water, after allowed to stand for one hour at 20 ⁰ C. You win the top one

15 · Layer in which carotene has been excreted 'and removes trace amounts of acetone and water. In in this way, 14.8 g of a concentrate containing 990 ppm of carotene are obtained (carotene concentration: 1.7 times, Carotene recovery: 81.4%).

Exampleö

30 g of crude palm oil, which contains 670 ppm of carotene, are treated in the manner described in Example 1. The ester layer formed is mixed with 220 g of a methanol solution containing 4% by weight of water. After thorough mixing, the solution is centrifuged at 20 ^° C. The lower layer is recovered and dehydrated. After passing the solution through a filled with 20 ml of powdery styrene-divinylbenzene copolymer resin column at 20 ⁰ C., 100 ml of methanol leads with a space velocity of 3.5 h through the column to the .Ester to eluioren and detach. Subsequently, 30 ml of hexane are passed through the solution in order to elute and separate off carotene. After the hexane has been distilled off from the eluate, 0.12 g of a 13.2% carotene component is obtained

BAD ORK31NAL

TER MEER -MÜLLER ■ STEINMfI-STKH Lion Corp.

holding concentrate. (Carotene concentration: 197-fold, carotene recovery: 78.8%).

Comparative example
5

30 g of crude palm oil, which contains 620 ppm of carotene, are subjected to esterification with formation of the methyl ester by adding 10 g of methanol and 0.24 g of sodium hydroxide. The ester layer formed is recovered and washed with 5 g of water, after which the ester is dissolved in 100 ml of methanol. The solution of the ester is carried out in methanol by one with 100 ml powdery styrene-divinylbenzene copolymer resin column filled at 80 ⁰ C in such a manner that the carotene, the Palmölmethylester and the unreacted PaImöl be adsorbed. 200 ml of methanol are then passed through the column at a space velocity of 2 hours in order to elute and separate off the ester and the unreacted palm oil. 100 ml of η-hexane are then passed through the column to elute and separate off the carotene. After the hexane has been distilled off from the eluate, 0.35 g of a concentrate containing 3.9% carotene is obtained (carotene concentration: 63-fold, carotene recovery: 73%).

The procedure described above is used for different Column temperatures related to elution

the ester carried out with methanol. The results are summarized in the accompanying drawing, in which the concentration of carotene is plotted against the column temperature.
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LION CORPORATION EAP-275

Number:
Int. Cl. ⁴ :
Registration date:
Disclosure date:

C 07 C 175/00

June 13, 1985 January 9, 1986

(-fold) s ¹⁰ °

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10 20 30 40 50 60 70 80 90

COLUMN TEMPERATURE IN THE ELUTION OF ESTERS WITH METHANOL ( ⁰ C)

Claims (9)

Oils and fats Priority: June 27, 1984, Japan, No. 59-132476 (P) Nov. 09, 1984, Japan, No. 59-236013 (P) claims 10 1. Process for the production of carotene from natural oils and fats, characterized that one carotene-containing natural oils and fats alcoholysis with a low molecular weight Subjects to monoalcohol, the carotene-containing and consisting essentially of fatty acid lower alkyl esters Oil phase wins, the oil phase is mixed with a hydrophilic solvent and water to separate the carotene and the carotene layer separated in this way wins. TER MEER MÜLLER STEINMEISTER ^Lion Corp. - FAP-275 2. The method according to claim 1, characterized in that one is used as the hydrophilic solvent a single solvent or a mixture of solvents selected from methanol, ethanol, iso- propanol and acetone are used. 3. Process according to claims 1 or 2, characterized in that the oil phase containing carotene and consisting essentially of fatty acid lower alkyl esters ^{is mixed at 10 to 70 °} C. with the hydrophilic solvent and water. 4. The method according to any one of claims 1 to 3, characterized in that the 15 · Carotene-containing and essentially from fatty acid lower alkyl esters Existing oil phase for the separation of the carotene with a hydrophilic solvent and water mixed, then the separated carotene layer wins, the hydrophilic solvent and water removed from the remaining hydrophilic solvent layer and recovered the fatty acid lower alkyl ester. 5. The method according to claim 4, characterized in that one oil phase, the carotene-containing and consisting of Fettsaureniedrigalkylestern substantially for the deposition of carotene at 30 to 7O ⁰ C with the hydrophilic solvent and water are mixed, then the separated carotene layer wins, the remaining hydrophilic solvent layer to separate the fatty acid lower alkyl esters from the hydrophilic solvent and water is ^{cooled to a temperature of 10 to 30 °} C. and the esters separated off in this way are recovered. 6. The method according to any one of claims 1 to 5, characterized in that the TER MEER MÜLLER STEINMEISTER Lion Corp. - FAP-275 recovered carotene layer with a styrene-divinylbenzene copolymer resin brings the resin into contact to adsorb carotene and the residual esters on the resin Eluting the ester from the resin with a low molecular weight monoalcohol and then contacting the Resin to elute the carotene from the resin is brought into contact with a hydrophobic solvent in order to get into this Way to concentrate the carotene further. 7. The method according to claim 6, characterized in that one is as low molecular weight Monoalcohol a single alcohol or an alcohol mixture selected from low molecular weight C 1 -C 4 monoalcohols used. 8. The method according to claim 6, characterized that a single or a mixed solvent is used as the hydrophobic solvent, selected from hexane, chloroform and petroleum ether. 9. The method according to any one of claims 6 to 8, characterized in that one brings about the adsorption of carotene layer and the elution of the ester at a temperature of 0 to 8O ⁰ C.