JPS635073A - Production of carotene-containing concentrated material - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

Detailed Description of the Invention The present invention involves recovering carotene from oily substances containing carotene, such as natural fats or fatty acid lower alkyl esters obtained by alcoholysis of natural fats and oils, and producing a carotene-containing concentrate. Relating to a method of manufacturing.

Brown rice carotene has a wide range of uses as a food coloring agent and as a substance with provitamin A action.

Carotene can be obtained by synthesis or by recovering carotene contained in natural oils and fats. Methods for recovering carotene from natural products include saponifying natural fats and oils containing carotene and then extracting the carotene as unsaponifiable matter with a solvent, and alcoholysis by adding lower alcohols to natural fats and oils containing carotene. Generates fatty acid lower alkyl esters.

A method is known in which carotene is concentrated in the distillation residue by distilling it under reduced pressure.

However, the former solvent extraction method has a poor recovery rate of carotene, and requires the use of a large amount of solvent to recover carotene in a high yield, resulting in high costs and the fact that all the fats and oils after carotene recovery are The problem is that the resulting soap is colored, making it difficult to use it effectively. Also.

The latter method, which involves distillation under reduced pressure, requires the distillation operation to be carried out at low temperature and high vacuum while preventing the decomposition of carotene, which increases equipment costs and operating costs, which also raises the problem of high costs.

In addition, an oily substance containing carotene is brought into contact with a styrene-divinylbenzene copolymer resin to be adsorbed, and then brought into contact with alcohol to elute and separate the oily substance, followed by contact with a hydrophobic solvent that is easily soluble in carotene. A method for separating carotene by eluating it has also been reported (Japanese Patent Application Laid-Open No. 1983-1999)
-12657).

The present invention involves adsorbing and absorbing oily substances containing carotene into resin.
An object of the present invention is to provide a method for producing a carotene-containing concentrate, which enables carotene to be recovered in high yield and in a highly concentrated state even from an oily substance containing a trace amount of carotene by elution.

Constitution of the Invention The method for producing a carotene-containing concentrate of the present invention is characterized by including the following steps.

(A) 2. A step in which an oily substance containing carotene is brought into contact with a polyacrylate resin or a polymethacrylate resin, and the carotene and oily substance are adsorbed onto the resin.

(B): A step of bringing alcohol into contact with the adsorption resin after step (A), and eluting and separating the oily substance into the alcohol.

(C): After step (B), a step of bringing the resin into contact with a hydrophobic solvent in which carotene is readily soluble, and eluting and separating carotene into the hydrophobic solvent.

Hereinafter, the present invention will be explained in more detail along each step.

In the present invention, first, if necessary, an oily substance containing carotene is liquefied by heating and brought into contact with a polyacrylic acid ester resin or a polymethacrylic acid ester resin, and the carotene and oily substance are adsorbed onto this resin.

Here, the type of carotene-containing oily substance is not particularly limited, but carotene-containing natural fats and oils such as palm oil can be preferably used. Furthermore, in the present invention, fatty acid lower alkyl esters obtained by reacting carotene-containing natural oils and fats with lower monoalcohols can also be suitably used as the oily substance. That is, by adding a lower monoalcohol to a carotene-containing natural oil or fat, glycerides in the natural oil or fat are alcoholysed and converted into glycerin and lower alkyl esters of higher fatty acids.
Carotene in fats and oils is contained in the alkylnistil phase (oil phase) together with unreacted glycerides. This oil phase is collected by separating it from glycerin by an appropriate means such as static separation or centrifugation, and then used.

Approximately three times as much carotene-containing am product can be obtained compared to when natural oils and fats are used directly as starting materials. Note that natural oils and fats generally contain a small amount of gum, but in any of the above cases, it is preferable to remove this gum in order to increase carotene recovery efficiency.

In the present invention, there are no restrictions on the shape of the polyacrylic ester resin or polymethacrylic ester resin, but granular resins are preferably used.

There are no restrictions on the method of bringing the above oily substance into contact with the polyacrylic ester resin or polymethacrylic ester resin, and any appropriate method such as a column method or batch method can be adopted, but the column method is the most efficient method for removing carotene. This is preferable because it can be adsorbed to. In this case, the amount of oily substance loaded against the resin capacity in the kamura is 0.2~o, sg/
It is preferable to set it as mQ-resin, and it is 0.5
g/mQ -resin, the resin may reach a saturated adsorption state and carotene may flow out from the column.

In addition, when bringing an oily substance into contact with polyacrylic ester resin or polymethacrylate ester resin, it is preferable to dilute the oily substance with alcohol used for eluting the oil component, which will be described later.This makes contact with the resin more efficient. You can make it happen.

Polyacrylic ester resins and polymethacrylic ester resins have the property that the more hydrophobic they are in polar solvents, the easier they are to adsorb. They are preferentially adsorbed in order. Furthermore, when the oil phase of a reaction solution obtained by reacting natural oils and fats with lower monoalcohols is used as the oily substance, carotene, unreacted glyceride, fatty acid ester, and alcohol are preferentially adsorbed in this order.

Next, in the method of the present invention, the polyacrylic ester resin or polymethacrylic ester resin that has adsorbed the carotene-containing oil substance is brought into contact with a carotene-non-eluting alcohol, preferably a lower monoalcohol having 1 to 4 carbon atoms,
Only alcohol-soluble oils present in oily substances are removed.
Elute and separate in alcohol.

As explained above, polyacrylic acid ester resins and polymethacrylic acid ester resins have the property that the more hydrophobic they are, the more easily they are adsorbed in polar solvents, so substances that are more hydrophobic than carotene are preferentially eluted and separated into alcohol. Ru. When natural fats and oils containing carotene are used as the oily substance, the fats and oils therein are preferentially eluted and separated. When used, fatty acid lower alkyl esters and unreacted glycerides therein are preferentially eluted and separated, and carotene remains adsorbed on the resin. When natural fats and oils are used, it is particularly preferable to use n-butanol, isopropanol, and n-propanol, and when fatty acid lower alkyl esters are used, methanol and ethanol are preferably used as elution solvents.

In the present invention, the polyacrylic acid ester resin or polymethacrylic acid ester resin after the oil content has been further separated is brought into contact with a hydrophobic solvent that easily dissolves carotene, and the carotene is eluted and separated into this hydrophobic solvent. Collect.

In this case, there is no restriction on the type of hydrophobic solvent in which carotene is easily soluble, but one or a mixed solvent of two or more of hexane, chloroform, petroleum ether, etc. is preferably used. When the recovered carotene is used for foods such as food coloring, it is particularly preferable to use hexane as the elution solvent from the viewpoint of safety.

The elution operation of carotene is preferably carried out using a hydrophobic solvent with an amount of 0.5 to 2 times the resin capacity, so that the carotene adsorbed on the resin can be almost completely eluted.

Note that when the production method of the present invention is carried out by a column method, the appropriate column temperature in the stages of oily substance adsorption and oily substance elution with alcohol is 0 to 80°C.
Especially when natural oils and fats are used as the oily substance, 50 to 6
The temperature is preferably about 0°C, and when a fatty acid lower alkyl ester is used, the temperature is preferably about ○ to 20°C. This increases carotene adsorption and improves the concentration ratio.

Further, the column temperature in the carotene elution step using the hydrophobic solvent can be any temperature below the boiling point of the hydrophobic solvent.

The resin in the column from which carotene has been removed can be used repeatedly by replacing the attached hydrophobic solvent with alcohol for eluting oily substances.

The carotene separated from the resin and collected by the above method may be used as it is without distilling off the solvent (FJ aqueous solvent) depending on the purpose, but it is preferably used after the solvent is distilled off. The solvent can be distilled off by a conventional method.

In addition, the oily substances eluted and separated from polyacrylic acid ester resins and polymethacrylic acid ester resins are obtained in a state in which carotene has been eliminated to a considerable extent, and the oily substances can be removed as they are or by simple purification. It can be used effectively. For example, when natural fats and oils are used, light-colored fats from which carotene has been removed can be recovered;
Refined fats and oils can be obtained by subjecting this to purification treatment such as clay treatment, if necessary. In addition, when fatty acid lower alkyl esters are used, higher fatty acid alkyl esters from which carotene has been removed can be recovered, and by subjecting them to simple purification treatment if necessary, high quality higher fatty acids and surfactant raw materials can be obtained. Can be done.

As explained above, the method for producing a carotene-containing acondensate of the present invention involves bringing an oily substance containing carotene into contact with a polyacrylic ester resin or a polymethacrylic ester resin to infuse the resin with carotene. adsorbs and oily substances,
Next, the resin is brought into contact with alcohol to elute and separate the oily substance into the alcohol, and then the resin is brought into contact with a hydrophobic solvent in which carotene is easily soluble, and the carotene is eluted and separated in the hydrophobic solvent. Conventionally, by
Carotene in natural fats and oils, which is almost completely resolved in the natural fats and oils refining process, and whose effective use has been a national challenge, can be concentrated and recovered reliably and at high concentrations with simple operations.

Moreover, since the method of the present invention does not require a high-temperature treatment step, carotene in natural fats and oils can be recovered in high yield with simple equipment and operations without loss due to decomposition. Furthermore, it is also possible to recover oil in a purified state at the same time.

Next, examples will be shown to specifically explain the present invention.

Example 1 30 g of crude balm oil containing 600 Pρm of carotene are dissolved in 100 ml of isopropyl alcohol.

Add this solution to polymethyl methacrylate resin powder 1'00
The liquid is passed through a column filled with 55° C. to adsorb carotene and palm oil onto the resin. After the liquid passage is completed, 100 ml of isopropyl alcohol is passed through the column at SV = 2 (Hr-1) to elute and separate the fats and oils (palm oil). Next, after bringing the column temperature to room temperature, 100 ml of n-hexane was passed through the column to elute and separate carotene. Hexane was distilled off from this hexane solution to obtain 2.5 g of carotene concentrate containing 5200 ppm of carotene.

Carotene concentration ratio: 8.7 times Carotene recovery rate: 72% In addition, isopropyl alcohol was distilled off from the above isopropyl alcohol effluent, and the degree of carotene disintegration was 250 ppm.
We obtained 27g of palm oil which has been decolorized to
．． After adding 3 g and treating at 100° C., the activated clay was removed to obtain refined palm oil decolorized to S1/40 Vibonto Color-2.

Example 2 50 g of crude palm oil containing 584 ppm carotene are dissolved in 50 ml of butanol. This solution is passed through a column filled with 100 ml of methyl sulfuric acid resin powder at a column temperature of 60° C., and carotene and palm oil are adsorbed onto the resin. After passing the liquid.

SV = 200n+1 n-butanol in the column
3 (Hr-") to elute and separate the oil and fat components. Next, after bringing the column temperature to room temperature, 50 ml of n-hexane is passed through the column to elute and separate carotene. From this hexane solution Hexane was distilled off to obtain 5.6 g of carotene concentrate containing 3000 ppm of carotene.

Carotene concentration ratio: approximately 5.1 times Carotene recovery rate: 58% Example 3 10 g of methanol and 0.24 g of caustic soda were added to 30 g of crude palm oil containing 620 ppm of carotene, and a methyl esterification reaction was performed to produce an ester. After the layer has been collected and washed with 5 g of water, it is dissolved in 100 ml of methanol. This ester methanol solution is passed through a column packed with 100 ml of polymethyl methacrylate resin powder at a column temperature of 20° C., and the methyl ester of carotene and palm oil and unreacted palm oil are adsorbed onto the resin. After passing through the column, add 100 methanol to the column.
ml is passed through at SV = 2 (Hr-') to elute and separate the ester and unreacted palm oil. Next, 100 ml of n-hexane was passed through the column to elute and separate carotene. Hexane was distilled off from this hexane solution to obtain a carotene concentrate containing 9,700 ppm of carotene.
I got g.

Carotene concentration ratio: approximately 15.6 times Carotene recovery rate: 62.6% Example 4 Methanol Log and 0.24 g of caustic soda were added to 30 g of crude palm oil containing 549 ppm of carotene, and a methyl esterification reaction was performed to produce The resulting ester layer was collected, washed with 5 g of water, and then dissolved in 100 ml of methanol. This solution was passed through a column filled with 100 ml of polymethyl acrylate resin powder at a column temperature of 10°C, and after 6 passes to adsorb carotene and palm oil methyl ester and unreacted palm oil to the resin, the column was filled with 100 ml of polymethyl acrylate resin powder. Add 100ml of ethanol to SV = 1
．． 5 (Hr-') to elute and separate the ester and unreacted palm oil. Next, after the column temperature was brought to room temperature, 60 ml of n-hexane was passed through the column to elute and separate carotene. Hexane was distilled off from this hexane solution to obtain 1.0 g of carotene concentrate containing 8200 ppm of carotene.

Carotene concentration ratio: approximately 14.9 times Carotene recovery rate: 49.8% Ethanol was distilled off from the ethanol effluent to obtain 28.5 g of palm oil methyl ester decolorized to a carotene concentration of 282 ppm.

J'-〉North

Claims (1)

[Claims] 1. Bring an oily substance containing carotene into contact with a polyacrylic ester resin or polymethacrylic ester resin so that the carotene and oily substance are adsorbed onto the resin, and then apply alcohol to the polyacrylic ester resin or polymethacrylic ester resin. After contacting the polyacrylic acid ester resin or polymethacrylic acid ester resin with a hydrophobic solvent in which carotene is readily soluble, the carotene is eluted into the hydrophobic solvent. 1. A method for producing a carotene-containing concentrate, the method comprising separating the carotene-containing concentrate.