JPH01290659A - Production of natural carotene condensate - Google Patents

Abstract

PURPOSE:To obtain the title compound containing no harmful components, useful for preventing various kinds of geriatric diseases, by hydrolyzing a raw material containing natural carotene and fats and oils, extracting by using d-limonenen, etc., and removing d-limonone, etc., from the extracted solution under specific conditions. CONSTITUTION:A raw material (e.g. corn oil or peanut oil) containing natural carotene and fats and oils is hydrolyzed, natural carotene is extracted from the prepared mixture with d-limonene or orange oil, d-limonene or orange oil is removed from the extracted solution under conditions not decompose carotene to give a natural carotene condensate. Hydrolysis is carried out by using KOH in a hydrous lower alcohol. The hydrolyzate mixturer is extracted with <=10C paraffinic hydrocarbon (e.g. hexane or petroleum ether), the solvent is removed and then operation of adding d-limonene may be carried out.

Description

DETAILED DESCRIPTION OF THE INVENTION (a) Field of Industrial Application The present invention relates to a method for producing a natural carotene concentrate, which does not contain solvent components harmful to food or medicine, from natural carotene-containing raw materials.

(b) Conventional technology β-carotene is currently attracting worldwide attention for its role in preventing various adult diseases including cancer, anti-aging, and beauty, and is expected to grow into a major product next to vitamins C and E. is expected.

Natural carotene is mass-produced by culturing and extracting algae, but the β-carotene content is very low at 1.0 to 3.5%, so when used as a natural coloring agent, it must be concentrated and purified. It is necessary to increase the carotene content.

Conventionally, the purification method for natural carotene has been to obtain high-concentration natural carotene by hydrolysis followed by partition extraction between petroleum ether and 85-95% methanol-water (Natural Coloring Handbook, pages 163-165). Mitsushige)) is known.

There has also been reported a method in which natural fats and oils containing carotene are hydrolyzed and then carotene is extracted as a non-hydrolyzated product with a paraffinic hydrocarbon solvent such as hexane (Japanese Patent Publication No. 45228/1983). Furthermore, natural fats and oils containing carotene are alcoholized with lower alcohol to collect an oil layer containing carotene and mainly composed of fatty acid lower alkyl esters. A method has also been devised to precipitate carotene by mixing water and a hydrophilic organic solvent such as
No. 62, JP-A No. 63-5074).

In addition, natural fats and oils containing carotene are brought into contact with a styrene-divinylbenzene copolymer resin to adsorb carotene and oily substances on this resin, and then brought into contact with alcohol to elute and separate the oily substances. A method for eluting and separating carotene using a hydrophobic solvent has also been reported (Japanese Patent Application Laid-Open No. 61-12657).

(c) Problems to be solved by the invention However, the conventional methods require a step of removing the extraction solvent from the carotene-containing extract to obtain a carotene concentrate; Even if degassing is performed in a nitrogen stream at a temperature at which carotene does not decompose, carotene crystals precipitate during solvent recovery and the solvent used is encapsulated in these crystals, so the solvent is not completely recovered. According to experiments by the inventors of this invention, normally about 500
~80011) It was observed that the PI solvent remained. Therefore, when used as a food coloring, there are major safety issues.

As a method for concentrating carotene without using an extraction solvent, natural fats and oils containing β-carotene are subjected to alcoholysis to decompose its main component, glyceride, into glycerin and fatty acid ester, and then unsaponifiables such as carotene are contained. A method has been reported in which the fatty acid ester layer is separated from the glycerin layer and then distilled to recover it as a distillation residue. However, in this method, the fatty acid ester layer must be distilled under conditions that do not thermally decompose carotene. Although it is a carotene concentrate, it still contains a relatively large amount of fatty acid ester. When further concentrating this, the distillation residue is hydrolyzed, dried and powdered, and the resulting carotene is extracted with a solvent (US Pat. No. 2,440,029), or the hydrolysis product is extracted with a divalent metal salt. A method of recovering carotene by metathesis and solvent extraction (French Patent No. 991,477) is known.

However, these methods also involve problems in terms of safety, as the solvent remains in the carotene concentrate obtained.

(d) Means for Solving the Problems The present invention involves subjecting raw materials containing a mixture of natural carotene and fats and oils to hydrolysis treatment, extracting natural carotene from the resulting mixture with d-limonene or orange oil, and extracting the extracted liquid. A method for producing a natural carotene concentrate, which consists of obtaining a natural carotene concentrate by removing d-limonene or orange oil from a carotene under conditions that do not decompose the carotene, and a method for hydrolyzing a raw material containing a mixture of natural carotene and fats and oils. C, from the resulting mixture. Extract with the following paraffinic hydrocarbon and remove the solvent; Add d-limonene or orange oil to the carotene concentrate obtained in step 2 to dissolve the carotene, and then add d-limonene or orange oil under conditions that do not decompose carotene. Provided is a method for producing a natural carotene concentrate, the method comprising: removing a natural carotene concentrate to obtain a natural carotene concentrate.

The "raw materials containing a mixture of natural carotene and fats and oils" used as raw materials for this invention include naturally occurring fats and oils (e.g. corn oil, peanut oil, balm oil, etc.) and their concentrates, and natural carotene-containing raw materials. These include extracts obtained by extracting algae with oil or fat, and concentrates thereof, extracts obtained by extracting bacteria with β-carotene-producing ability, yeast or algae cultures with oil or fat, and the like. These raw materials contain fats and oils in addition to natural carotene, and are subjected to hydrolysis treatment to remove the fats and oils. The method of hydrolysis is not particularly limited,
Any conventional method can be used.

A typical hydrolysis method includes a method using potassium hydroxide in a water-containing lower alcohol.

As the hydrous alcohol, 90 to 80% methanol is preferable. Further, potassium hydroxide is used in an amount of at least equimolar excess, preferably about 20%, relative to the fat or oil. Note that the hydrolysis is preferably carried out in an inert gas (eg, M gas) in order to avoid decomposition of natural carotene.

Next, d-limonene or orange oil in an amount of 2 to 5 times (per volume) is added to the above hydrolyzed mixture to remove relatively highly polar unsaponifiable substances other than carotene, saponification products, lower alcohols, etc. an aqueous layer (lower layer) containing the water and an extraction layer (lower layer) containing relatively low polar unsaponifiables including carotene.
After separating this extracted layer from the aqueous layer, for example, after washing with a water-containing lower alcohol, d-limonene or orange oil is removed under conditions that do not decompose carotene to obtain a natural carotene concentrate. .

Specifically, the conditions that do not decompose carotene are usually 10
This means at a temperature below 0°C and in an inert gas stream. Also, d-limonene or orange oil is removed by reducing the pressure to, for example, 5 to 100 Hg at the above temperature.

Further, the above hydrolyzed mixture is extracted with a paraffinic hydrocarbon below CIO (eg, hexane, petroleum ether, etc.), and the solvent is removed by a conventional method. At this time, the solvent is 0.1 to 1
Approximately % remains. D-limonene or orange oil may be added to the concentrate to dissolve carotene, and d-limonene or orange oil may be removed under conditions that do not decompose carotene. This completely removes paraffinic hydrocarbons.

Note that d-limonene, a natural product, is a main component contained in orange oil, and its safety has been sufficiently proven.

(e) Examples Next, examples will be shown to explain the structure and effects of the present invention in more detail, but these examples are not intended to limit the present invention.

[Example 1] Natural carotene-containing oily substance (carotene concentration 1.4%) 1
00 parts, was added to a solution of 22.4 ffi of potassium hydroxide dissolved in 163 parts of methanol and 58 parts of water, and stirred at a temperature of 80° C. for 2 hours while blowing nitrogen gas to perform a hydrolysis reaction. After the hydrolysis reaction was completed, the liquid to be extracted was transferred to a branch funnel, 300 parts of d-limonene was mixed therein, and the mixture was sufficiently shaken. After stopping the shaking, let it stand and remove the aqueous layer (
The lower FJ) and extracted WJ (upper layer) were separated. After adding water to the lower layer obtained here so that the total water content was 40 to 45%, the operation of extraction with 300 wJ of d-limonene was repeated twice.

The extracted layers obtained from the two extraction operations performed on the lower layer and the first extraction operation were mixed, washed with 25% water-containing methanol, and heated to 80% using a rotary evaporator.
d- under reduced pressure (5-10o+m) Ig) at 0-100℃
Limonene was distilled off to obtain 2.41 parts of carotene agricultural product with a carotene concentration of 55%. In this case, the carotene recovery rate is 9
It was 4.7%.

[Example 2] Natural carotene-containing oily substance (carotene concentration 3.5%) 1
00 parts were subjected to a hydrolysis reaction in the same manner as in Example 1. After the hydrolysis reaction was completed, the process of extracting carotene with 400 parts of d-limonene, adding water to the lower layer (water content 41%), and further extracting with 400 parts of d-limonene was repeated twice. The obtained extraction layers were mixed, washed with 25% aqueous methanol, and then heated at a temperature of 100"C under reduced pressure (5 to lhdg).
d-limonene was distilled off to obtain 5.59 parts of carotene concentrate with a carotene concentration of 60%. The carotene recovery rate in this case was 95.8%.

[Comparative Example 1] Natural carotene-containing oily substance (carotene concentration 3.5%) 1
00 parts were subjected to hydrolysis in the same manner as in Example 1. After the hydrolysis reaction was completed, carotene was extracted with 400 parts of n-hexane, water was added to the lower layer, and extraction was performed twice with 400 parts of n-hexane. The extract layers were combined, washed with 25% aqueous methanol, and then n-hexane was distilled off under reduced pressure to obtain 6.3 parts of carotene concentrate with a carotene concentration of 50%. Carotene recovery rate was 90%. The residual hexane in this concentrate was analyzed by gas chromatography and found to be 800pp.
m of hexane remained. This carotene concentrate was heated at a temperature of 100°C under reduced pressure (5 mmHg) in a nitrogen stream for 4 hours.
After 8 hours of degassing, the hexane residual concentration was 500p.
The decrease was only below pm.

[Comparative Example 2] The carotene concentrate obtained in Comparative Example 1 (n-hexane residual concentration 500 ppm) was heated to 150°C under reduced pressure (5 om
Degassing was performed for 12 hours in a Hg), 'M bare air flow.

Residual hexane was 10 ppm. However, a significant decrease in purity was observed, with the carotene concentration ranging from 50% to 25%.

[Example 3] Comparative example! 6 g of the carotene concentrate obtained in step 1 (residual n-hexane concentration 800 ppm) is added to 15 g of d-limonene and completely dissolved at a temperature of 80°C. Then temperature 80-10
d- in a nitrogen stream at 0°C under reduced pressure (5+a+++Hg)
Limonene was distilled off to obtain a carotene concentrate. The residual hexane in this concentrate was Oppm. Further, the residual concentration of d-limonene was 520 ppm, the carotene concentration was 50%, and no decrease in purity was observed.

(f) Effects of the Invention According to the present invention, a natural carotene concentrate can be obtained without using any petroleum-based solvents, and therefore there is no need to worry about residual solvents. Furthermore, since d-limonene has a high solubility in carotene, processing capacity is improved, and a natural carotene concentrate with a high yield and high concentration can be obtained.

Furthermore, a natural carotene concentrate with no residual solvent can be obtained from a carotene concentrate with residual petroleum solvent obtained by a known method. Therefore, the natural carotene concentrate obtained in the present invention can be used as is as a food coloring agent.

Claims (1)

[Claims] 1. Hydrolyze a raw material containing a mixture of natural carotene and oil, extract natural carotene from the resulting mixture with d-limonene or orange oil, and extract d-limonene or orange oil from the extract. A method for producing a natural carotene concentrate, comprising removing oil under conditions that do not degrade the carotene to obtain a natural carotene concentrate. 2. Hydrolyze raw materials containing a mixture of natural carotene and fats and oils, extract from the resulting mixture with paraffinic hydrocarbons of C_1_0 or less, remove the solvent, and add d-limonene or orange to the carotene concentrate obtained. A method for producing a natural carotene concentrate, which comprises adding oil to dissolve the carotene and then removing d-limonene or orange oil under conditions that do not decompose the carotene to obtain a natural carotene concentrate.