JPS6045228B2 - How to make natural colorants - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing natural colorants by concentrating carotene contained in fats and oils.

Carotene, which is contained in fats and oils as a type of unsaponifiable substance, has useful uses as a food coloring agent or a vitamin A precursor.

The most common method for obtaining carotene concentrates from fats and oils is to rinse the fats and oils with alcohol to decompose the main component, glyceride, into glycerin and fatty acid esters, and then to contain unsaponifiables such as carotene. By separating the fatty acid ester phase from the glycerin phase and then distilling it,
This method is to recover it as a distillation residue.

However, in this method, the fatty acid ester phase must be distilled under conditions in which carotene is not thermally decomposed, so the fatty acid ester cannot be sufficiently distilled off. Although it is a carotene concentrate, it still contains relatively large amounts of fatty acid esters. When it is desired to further concentrate a carotene concentrate such as the above-mentioned distillation residue, the distillation residue is fed and then dried to form a powder, as taught in U.S. Pat. No. 2,440,029. Alternatively, as taught in French patent no. A method is available for recovering caroticum by applying solvent extraction to the material.

However, neither of these methods can sufficiently extract carotene, and the latter method in particular has the disadvantage that metal soaps are mixed into the extract. In the present invention, not only when the above-mentioned distillation residue is used as a starting material, but also when oil or fat containing carotene itself is used as a starting material, substantially all of the carotene contained in these starting materials is concentrated to a high concentration. A method of producing natural colorants is provided. That is, the method for producing a natural coloring agent according to the present invention involves (a) converting a carotene-containing oil or a mixture of an unsaponifiable substance and a saponifiable substance obtained by separating most of the glycerides from the oil into a lower grade Saponification is carried out in the presence of alcohol and potassium hydroxide in an amount equal to or more than the saponification equivalent, and (b) the obtained saponification reaction mixture is diluted with water or water and a lower alcohol until the water concentration in the liquid is 20 to 40 Wt. %, a saponification reaction mixture solution having a lower alcohol concentration of 45 to (1)% is prepared, and (C) a chain hydrocarbon of ClO or less, benzene, toluene, and xylene is added to the saponification reaction mixture solution. One or more selected extraction solvents are mixed in an amount 0.5 to 5 times the amount (volume) of the saponification reaction mixture solution to obtain relatively highly polar unsaponifiable substances other than carotene and saponification products. (d) after separating this extract phase from said aqueous phase; , removing the extraction solvent from the extract phase at a temperature of 120° C. or less to recover the carotene concentrate. Proceeding to explain the present invention in more detail in the order of steps, according to the present invention, a mixture of an unsaponifiable substance and a saponifiable substance obtained by separating most of the glycerides from a carotene-containing oil or fat is: It is then subjected to saponification treatment.

here,. The mixture of unsaponifiables and saponifiables obtained by separating most of the glycerides from carotene-containing fats and oils refers to the residue obtained by removing the three main components, 3 glycerides, from carotene-containing fats and oils by appropriate means. , carotene, sterine, and hydrocarbons, and saponifiable substances such as glycerides, fatty acids, and fatty acid esters. A typical example of the above-mentioned mixture is to decompose glyceride into 4-glycerin and fatty acid ester by alcoholysis of carotene-containing fat and oil, then separate the fatty acid ester phase containing unsaponifiables such as carotene from the glycerin phase, and then decompose the fatty acid ester into 4-glycerin and fatty acid ester. Although it is a distillation residue obtained by subjecting the ester phase to distillation, the mixture referred to in the present invention is not limited to this. Generally speaking, the saponification treatment target of the present invention contains carotene of 0.1 VII. % or more, and the total amount of unsaponifiables is preferably 15% or less. The saponification treatment of the present invention is carried out in the presence of a lower alcohol and a saponification equivalent or more of potassium hydroxide.

As the lower alcohol in this case, any monovalent aliphatic saturated alcohol having 1 to 4 carbon atoms can be used. The amount of lower alcohol to be used can be arbitrarily selected within a range that allows saponification to be carried out smoothly, but generally it can be about 0.5 to 4 times (volume) the amount of the object to be saponified. In the saponification treatment step of the present invention, ideally all saponifiable substances contained in the object to be treated are saponified.
It is essential that the amount of potassium hydroxide used be at least the saponification equivalent of the object to be saponified, and generally 2 of the saponification equivalent.
It is preferable to have an excess of about 0%. In actual operations, potassium hydroxide is usually used after being dissolved in a lower alcohol. The saponification temperature and saponification time are selected within the range of 60 to 120° C. and 3 hr depending on the properties of the object to be treated and the amounts of lower alcohol and potassium hydroxide used. Note that during the saponification treatment, it is preferable to blow nitrogen. By the saponification treatment as described above, substantially all of the saponifiable substances contained in the object to be treated are saponified, glycerides are converted to glycerin and soap, fatty acid esters are converted to soap and alcohol, and free fatty acids are converted to soap.
Each transforms.

Since the saponification reaction mixture thus obtained contains a relatively large amount of soap (particularly noticeable when fats and oils themselves are the saponification target), they may solidify when cooled to room temperature. Therefore, in the present invention, by diluting the saponification reaction mixture with water or water and a lower alcohol, solidification at room temperature is prevented and a solution optimal for the subsequent solvent extraction is prepared.
In the dilution step of the present invention, water or water and a lower alcohol are used as diluents, and by adding these diluents to the saponification reaction mixture, the water concentration in the liquid can be increased from 20 to 20.
40W't%, lower alcohol concentration 45-60Wt%
A solution is prepared. This solution is a red, opaque liquid that does not solidify even at room temperature. When using a lower alcohol as a diluent, a monohydric aliphatic saturated alcohol having 1 to 4 carbon atoms is used, which alcohol is combined with the lower alcohol used in the saponification step;
They do not necessarily have to be of the same species. The saponification reaction mixture solution prepared in the dilution step is then subjected to solvent 1 extraction treatment. In the solvent extraction step of the present invention, the saponification reaction mixture solution obtained in the previous dilution step (hereinafter referred to as the liquid to be extracted) and the extraction solvent are first intimately mixed.

In this case, the extraction solvent is pentane, hexane,
One or more extraction solvents selected from the group consisting of chain saturated hydrocarbons below ClO exemplified by petroleum ether, benzene, toluene, and xylene are used.
The exact amount of extraction solvent used differs depending on the individual extraction solvent, but in general it is 0.5 to 5 times the amount (volume) of the liquid to be extracted.
Allowable range. By mixing the liquid to be extracted and the extraction solvent, among the unsaponifiable substances contained in the liquid to be extracted, only unsaponifiable substances with relatively low polarity such as carotene are selectively removed.
Because it is extracted into an extraction solvent, the final result is an aqueous phase containing soap, glycerin, lower alcohols, and relatively highly polar unsaponifiable substances, and an extraction solvent phase (extract phase) containing carotene, etc. It is formed.

The extract phase obtained in the solvent extraction step is then separated from the aqueous phase by suitable means, after which the extraction solvent is removed from the extract phase.

In this case, water, soap, methanol, etc. are distributed in the above extract phase, although to some extent,
Prior to removing the extraction solvent, it is preferable, although not essential, to wash the extract phase with water and then dry it to remove water, soap, and methanol in advance. The extraction solvent was removed at a temperature of 120°C to avoid thermal decomposition of carotene.
°C or less, typically under reduced pressure using a rotary evaporator.

By removing the extraction solvent, it is possible to obtain a carotene concentrate, which is the object of the present invention.
It contains 0% at a high concentration of 2-20%. The carotene concentrate obtained by the method of the present invention has a red color and is usually in the form of a soft solid, which can be used as it is as a food coloring agent. As detailed above, the carotene concentration method of the present invention uses carotene-containing fats and oils or a mixture of unsaponifiables and saponifiables obtained by separating most of the glycerides from the fats and oils as a starting material. Substantially all of the saponifiable substances contained in the raw materials are solubilized in water and lower alcohols by saponification, and then relatively less polar unsaponifiable substances such as carotene are extracted with the above-mentioned extraction solvent. Since only the substance is extracted, there is almost no loss of carotene during the concentration process.

Therefore, according to the present invention, carotene can be concentrated from the above-mentioned starting materials at a high recovery rate and at a high concentration. EXAMPLES Next, the structure and effects of the present invention will be explained in more detail with reference to Examples, but these Examples are not intended to limit the present invention.

Example 1 After alcoholyzing carotene-containing oil (palm oil) to decompose its main component, glyceride, into glycerin and fatty acid ester, the fatty acid ester phase is separated from the glycerin phase, and then the fatty acid ester is separated from the fatty acid ester phase. The distillation residue obtained by distilling off was used as the starting material in this example.

The carotene concentration of this distillation residue was 0.44%, and its saponification equivalent (S■) was 179.1. A solution of 22.4 parts of potassium hydroxide dissolved in 158 parts of methanol was added to 1 (1) part (by weight, the same hereinafter) of the above distillation residue, and this was added while blowing nitrogen and refluxing the methanol. The mixture was maintained at a temperature of 80'C in a water bath for 2 hours to complete the saponification reaction. Immediately after the saponification reaction was completed, 121.5 parts of methanol and 126.5 parts of water were added to the saponification reaction mixture to prepare a liquid to be extracted having a water content of 25%, a methanol content of 55%, and a soap content of 20%. Next, this liquid to be extracted was transferred to separation load 5, and hexane, 157.17
The mixture was mixed and shaken thoroughly. After stopping the shaking, leave the separated liquid load for about 2 minutes to separate the aqueous phase (lower layer) and extract phase (
An upper layer) was formed and the two were separated. The aqueous phase obtained here was mixed with hexane again to form an aqueous phase and an extract phase, and this aqueous phase was further extracted with hexane. This operation was repeated three times in total. The total amount of hexane used at this time was 628
．． It was part 6. The extract phases obtained from the three extraction operations performed on the aqueous phase and the first extraction operation were mixed, washed with water and dried, and then hexane was distilled off under reduced pressure using a rotary evaporator to achieve a carotene concentration of 17.
2.3 volumes of 1% carotene concentrate were obtained. The carotene recovery rate in this case was 93.0%. Comparative Example 1 100 parts of the distillation residue used as the starting material in Example 1 was saponified under the same conditions as in Example 1, and 36 parts of methanol and 105 parts of water were added to the resulting saponification reaction mixture to reduce the water content to 32.7 parts. %, a methanol content of 36.1%, and a soap content of 31.2%.

Next, this liquid to be extracted was transferred to a separation load, and when a portion of hexane (marked 1) was added and shaken, the liquid to be extracted was emulsified, and it was completely impossible to separate the extract phase and the aqueous phase. Comparative Example 2 100 parts of the distillation residue used as the starting material in Example 1 was added to Example 1.
7 (2) to the saponification reaction mixture obtained.
) and ♀ part of water were added to prepare a liquid to be extracted having a water content of 16.1%, a methanol content of 52.8%, and a soap content of 31.1%.

However, since this liquid to be extracted solidifies at room temperature, it was impossible to carry out the extraction operation. Example 2 Distillation residue obtained from palm oil with the same formulation as described in Example 1 (carotene concentration 0.28%, SV18O.3)
) was used as the starting material.

A solution of 22.5 parts of potassium hydroxide dissolved in 160 parts of methanol was added to 100 parts of this distillation residue, and the mixture was heated to 80°C in a water bath while blowing nitrogen and refluxing the methanol. It was held for 2 hours. After saponification is complete. Immediately add 1 part of methanol and 127 parts of water to the saponification reaction mixture, with a water content of 25% and a methanol content of 55%.
A liquid to be extracted containing 20% soap was prepared. Thereafter, this extracted liquid was extracted with 63 cm of petroleum ether, and the obtained extract phase (petroleum ether phase) was washed with water and dried, and the petroleum ether was distilled off to concentrate the carotene concentration to 9.7%. 2.65 parts of the product were obtained. The carotene recovery rate was 91.8%. Example 3 A 4-distillation residue (carotene concentration 0.30%, SV18O.7) obtained from palm oil using the same recipe as in Example 1 was used as a starting material.

To 1 part of this distillation residue, a solution of 22.6 parts of potassium hydroxide dissolved in 1 (1) part of ethanol was added, and the mixture was heated in a water bath while blowing nitrogen and refluxing the ethanol. The temperature was maintained at 90°C for 2 hours. Immediately after saponification, add the ethanol in 9(2) to the saponification reaction mixture to obtain a water content of 30%, an ethanol content of 50%, and a soap content of 2.
A 0% extraction liquid was prepared. Next, this extracted liquid was extracted with 8 parts of hexane, and the obtained extract phase was washed with water and dried, and the hexane was distilled off to reduce the carotene concentration to 10.
．． 2.71 parts of 1% concentrate were obtained. Carotene recovery rate is 9
It was 1.2%. Example 4 Distillation residue No. 7 (carotene concentration 0.34%, S 179.0) obtained from palm oil using the same recipe as in Example 1 was used as a starting material.

To 1 (4) parts of this distillation residue, a solution of 22.4 parts of potassium hydroxide dissolved in 1 (4) parts of methanol was added,
While blowing nitrogen gas and refluxing methanol,
The mixture was kept at a temperature of 80°C in a water bath for 2 hours. Thereafter, 300 parts of methanol and 450 parts of water were added to the saponification reaction mixture to obtain a solution of 45% water and 45% methanol.
%, and a liquid to be extracted with a soap content of 10% was prepared. Next, this extracted liquid was heated to 109? After extraction with benzene, the obtained extract phase was washed with water and dried, and the benzene was distilled off to obtain 2.85 parts of a concentrate having a carotene concentration of 10.9%. The carotene recovery rate was 91.5%. Example 5 In this example, palm oil (carotene concentration 0%, S 201.
2) The product itself was used as a starting material.

Claims (1)

[Claims] 1(a) Saponification of a mixture of an unsaponifiable substance and a saponifiable substance obtained by separating a fat or oil containing carotene or most of the glycerides from the fat or oil in the presence of a lower alcohol and potassium hydroxide in an amount equal to or more than the saponification equivalent. (b) Diluting the obtained saponification reaction mixture with water or water and a lower alcohol to prepare a saponification reaction mixture solution having a water concentration of 20 to 40 wt% and a lower alcohol concentration of 45 to 60 wt%. death,
(c) One or more extraction solvents selected from the group consisting of chain hydrocarbons having C_1_0 or less, benzene, toluene, and xylene are added to this saponification reaction mixture solution in an amount of 0.5 to The aqueous phase containing relatively highly polar unsaponifiables other than carotene, saponification products, and lower alcohols and the relatively less polar unsaponifiables including carotene are mixed in 5 times the volume (volume). (d) separating the extract phase from the aqueous phase and removing the extraction solvent from the extract phase at a temperature below 120° C. to recover the carotene concentrate; A method for producing natural colorants consisting of: