JPS61268762A - Concentration of naturally-occurring dyestuff - Google Patents

Abstract

PURPOSE:To obtain the titled dyestuff for food additive use free from offensive odor, by extraction of paprika orange with high-pressure carbon dioxide to eliminate the odoriferous component contained followed by extraction of the residual liquor with ultra-critical carbon dioxide to separate the red dyestuff- contg. residual liquor from extract containing both yellow dyestuff and fatty oil. CONSTITUTION:Extraction tank 1 is charged with a paprika orange obtained through solvent extraction technique, etc. followed by feeding liquefied high- pressure carbon dioxide pressurized by pump 5 from storage tank 7 to the extraction tank 1, where extraction treatment is carried out to transfer the odoriferous component contained to the high-pressure carbon dioxide phase, said component being then discharged out of the tank 1. The residual liquor is subjected to extraction treatment with ultra-critical carbon dioxide to separate the extract consisting mainly of yellow dyestuff and fatty oil in the second separator tank 3 to obtain, in the tank 1, a red dyestuff-rich residual liquor, thus accomplishing the objective separation and concentration of the naturally- occurring dyestuff.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application) The present invention removes malodorous components and residual solvents that impair the flavor from paprika oleoresin, produces a highly concentrated pigment in a tube, and at the same time produces paprika flavor. The present invention relates to a method for simultaneously recovering aroma components containing aroma components.

Conventional technology) Conventionally, viscous liquid products (oleoresins) obtained by extracting active ingredients such as flavor components and pigments from natural raw materials using organic solvents such as hexane have been imported from foreign countries. ing.

Especially paprika (scientific name: Capsicum annuu)
The oleoresin obtained from M L ) has a unique orange-red color tone and heat stability, and is widely used in many foods.

(Problems to be Solved by the Invention) However, since the method for producing oleoresin is generally carried out by solvent extraction, all substances soluble in the active ingredient are extracted, and unnecessary components other than the active ingredients are removed. In addition to not improving the purity of the product, it is inevitable that trace amounts of solvent will remain, which poses health concerns.

In the case of paprika oleoresin, in addition to pigment components, it also contains flavor components and various unnecessary components, resulting in a characteristic tar odor,
The food industry is eagerly awaiting the completion of an odorless paprika oleoresin, as its unpleasant, tarnished odor narrows its scope of use and limits its usage.

However, the technology for extracting only specific active ingredients from natural raw materials has not yet been perfected anywhere in the world, and the technology for separating only specific active ingredients from oleoresin is considered impossible using a one-man method.

The reason for this is that extracts such as oleoresin contain a wide variety of components, and each component has extremely similar physical properties.

With recent advances in chromatographic separation technology, there is hope for a method for mass-preparation of pure components, but dilution and solvent removal are required, making it difficult to obtain high-70% dyes in one step.

The purpose of the present invention is to remove odor components from paprika oleoresi and easily obtain a pigment concentrate containing no residual solvent, and at the same time to easily separate and collect the odor components into malodor components and paprika aroma components. The object of the present invention is to provide a method for concentrating natural pigments.

Means for Solving the Problems) That is, the present invention provides a method for concentrating natural pigments, which is characterized by comprising the following steps (a) and (b).

(a) A first step in which paprika oleoresin is extracted using high-pressure carbon dioxide to extract odor components.

(b) The raffinate from which odor components have been removed in the first step is extracted using supercritical carbon dioxide, resulting in an extract mainly containing yellow pigments and fats and oils and a raffinate rich in red pigments. The second step is separating it into liquids.

Hereinafter, the present invention will be explained in detail by steps.

(b) First step (deodorizing step) In the first step, paprika oleoresin is extracted with high pressure carbon dioxide to extract and remove odor components and organic solvent residual fraction to obtain a deodorized product and separate odor components. It is something to be taken.

Here, paprika oleoresin refers to paprika (a perennial leader of the Solanaceae family, scientific name; Capsicu + W annuu
+++ It is a viscous liquid product obtained by solvent extraction of the fruits of Paprika, and its main components are cabsanthin; α-carotene and violaxanthin; curbutoxanthin and cabsorbin; cryptocarbucin, etc., and has the characteristic aroma of paprika The ingredients are based on 2-methoxy-alkylpyrazine.

Further, the high-pressure carbon dioxide used for extraction refers to carbon dioxide at a temperature and pressure near the critical temperature (31.1° C.) and critical pressure (72.8 atm) of carbon dioxide.

For example, when extracting paprika oleoresin, the pressure is 50 to 150 atm, preferably 80 to 120 atm, and the temperature is 20 to 50°C, preferably 30 to 40°C.

Furthermore, when extracting (deodorizing) paprika oleoresin with high-pressure carbon dioxide, the weight ratio of the high-pressure carbon dioxide and the oleoresin is 40-100, preferably 50-80.

Conventional deodorizing methods include, for example, ■steam distillation, ■organic solvent extraction, ■enzymatic decomposition, ■acid or alkaline washing, and adsorption.
Neither method can completely deodorize, but only change odor or simply reduce odor.

However, when paprika oleoresin is brought into contact with high-pressure carbon dioxide under the above-mentioned conditions, unpleasant odor components such as tar odor and tar odor components that are perceived as bad odor are first extracted from the aroma components in cough oleoresin, and the raffinate liquid is It begins to exhibit its original paprika smell.

As the extraction continues, the original odor components of paprika are also extracted, and in the end, only a faint and beautiful scent remains.

In this way, this step is a step of deodorizing the odor components of paprika oleoresin, but preferably, for example, by keeping the pressure and temperature of high-pressure carbon dioxide constant and changing the treatment time, the odor components of paprika oleoresin are deodorized. can be separated into unpleasant odor components and original paprika odor components.

In this case, the processing time is 4. 0-7.
0 hours, preferably about 5.0 to 6.0 hours, and the paprika odor components are extracted for an additional 1.5 to 6.0 hours.
, 5 hours, preferably 4. It is about 0 to 5.0 hours.

The total treatment time of this deodorizing step is sufficient to be about 5.5 to 13.5 hours, preferably about 7.0 to 11.0 hours, and it is very easy to carry out and is a method that is significantly superior to conventional methods. be.

(b) Second step (pigment concentration step) The paprika oleoresin raffinate obtained in the first step is substantially free of malodorous components, but contains target red pigments such as cabsanthin, cryptoxanthin, and cabsorbin. It is an orange-red viscous liquid that contains other impurities such as yellow pigments such as carotene, violaxanthin, and rutenalin, oils, and waxes, but the color value is usually 100,000.
It is low, about 0.

In this step, impurity components other than red pigments (yellow pigments, oils and fats, wax, etc.) are extracted and removed from the odor-free raffinate obtained in the first step using supercritical carbon dioxide. , which concentrates red pigments.

Here, supercritical carbon dioxide refers to carbon dioxide at a temperature and pressure that exceeds the critical temperature (31.1°C) and critical pressure (72.8°C) of carbon dioxide. For extraction processing, pressure 150-30
0 atm, preferably 200-250 atm, temperature 31.1
-50°C, preferably 35-40°C.

In this case, the raffinate is extracted with supercritical carbon dioxide (
In the case of concentration treatment), the weight ratio of the carbon dioxide and the raffinate is appropriately determined depending on the desired color value of the 111 substance.

The red pigment concentrate (raffinate) obtained in this step is rich in red pigments, exhibits a bright color tone, and has a carbon dioxide/paprika ole orange (raffinate) weight ratio of 100 to 100.
150 (processing time 13.5 to 20 hours), the color value is around 200,000, and the color value is 180 to 200 (processing time 2
4 to 28 hours), a color value of about 300,000 can be easily obtained.

On the other hand, in addition to impurities such as fats and oils and waxes, yellow pigments with a color value of 20,000 or more can be recovered from the extract if the processing time is about 20 to 25 hours, and these pigments can also be used as plant pigments. Have quality available.

Hereinafter, the present invention will be explained in more detail using the drawings.

Figures 1 and 2 are flow sheets of a natural dye deodorizing/concentrating device, which is an embodiment of the present invention.

This deodorization/concentration device includes an extraction tank 1, a first separation tank 2, a second separation tank 3, a condenser 4, a liquid return pump 5, a superheater 6, a liquid return storage tank 7, a pressure reducing valve 8, a pipe 9, a valve 10, etc. It consists of

First, to explain Fig. 1, paprika oleoresin obtained by solvent extraction method etc. is filled into an extraction tank, and then the cough tank is sealed and heated to a predetermined temperature. The carbon is pressurized by the liquid return pump 5, and while passing through the superheater 6, it becomes high pressure carbon dioxide near the critical point and is transferred to the extraction tank 1.
sent to.

In the extraction tank 1, high-pressure carbon dioxide blown from the bottom comes into contact with paprika oleoresin, and odor components are extracted by the high-pressure carbon dioxide phase and exit the tank. The pressure of the carbon dioxide phase is reduced by a pressure reducing valve 8, and extracts such as odor components dissolved in the carbon dioxide phase are separated in the first separation tank 2.

Excess gaseous carbon dioxide is either discharged to the outside via pipe 9 or recycled into the system after liquefaction in condenser 4.

When the deodorizing operation (first step) is completed, the piping is switched using the valve IO, the first separation tank 2 is disconnected, the second separation tank 3 is installed in the line, and the dye concentration operation (second step) begins.

Such concentration operation may be performed by increasing the pressure to supercritical carbon dioxide conditions and performing circulation operation.

At this time, by setting the temperature and pressure conditions to selectively extract yellow pigments, oils, etc., the concentration of red pigments in extraction tank 1 gradually increases, and concentrated red pigments are obtained. At the same time, in the second separation tank 3, an extract with a low color value containing yellow pigments and fats and oils as main components and containing no odor components is obtained.

As described above, the apparatus shown in FIG. 1 is a process in which two separation tanks are arranged side by side, and the deodorizing process and the concentration process are switched depending on the processing time, and the extraction pressure is also changed.

On the other hand, in the apparatus shown in Fig. 2, by arranging the first separation tank 2, the second separation tank 3, and the pressure reducing valve in series, the extraction process is first performed using supercritical carbon dioxide in the extraction tank 1, and the raffinate is In addition to concentrating the red pigment in the liquid, odor components, yellow pigments, and impurities such as fats and oils are transferred to the carbon dioxide phase, and then extracted from the extraction tank 1 with high-pressure carbon dioxide that is depressurized in the first minute. The odor components were extracted from the extracted liquid, and the raffinate liquid mainly composed of yellow pigment and oil was extracted in the first minute, and the raffinate liquid mainly composed of yellow pigment and oil was extracted in the second minute MF? !
The odor component is separated as an extract liquid in 3.

In addition, in the apparatus shown in Figure 1, the process is performed using high pressure carbon dioxide/
In contrast to supercritical carbon dioxide extraction, the process using the apparatus of Figure 2 is supercritical carbon dioxide/high pressure carbon dioxide extraction. In the case of FIG. 2, the supercritical carbon dioxide extraction and the high-pressure carbon dioxide extraction that are performed first are the same as the second step and the first step, respectively, at the same temperature, pressure, and treatment time.

In addition, although the present invention has been described using paprika oleoresin, 11! Needless to say, the present invention is widely applicable to i-product oleoresins, and furthermore, the present invention can be applied to general purification of oleoresins to remove impurities such as odor components.

Effects of the Invention) As described above, according to the present invention, it is possible to easily produce highly concentrated natural pigments that do not contain malodorous components or residual solvents, and it is possible to expand the field of application of natural pigments, as well as to This opens the door to the use of domestically produced paprika, which was not used in the production of paprika oleoresin.

Example) Hereinafter, the present invention will be explained in more detail with reference to Examples.

EXAMPLE According to the flow sheet shown in FIG. 1, paprika oleoresin was deodorized and concentrated.

1st step (dephosphorization) Paprika oleoresin 1 as a raw material is placed in extraction tank 1 with an internal volume of 41
Kr was added, and high-pressure carbon dioxide was circulated at 7.4 kg/hr for extraction. At this time, the valve 10 shown in FIG. 1 was operated to allow carbon dioxide to flow only into the first separation tank 2. The operating conditions are as follows.

Pressure (atmospheric pressure) Temperature ('C) Extraction tank 1 120 40 First separation tank 2; 40 40 Sampling was carried out from the extraction tank and the first separation tank at regular intervals, and weight and color value measurements and sensory tests were conducted. The results are shown in Table 1.

The raw paprika oleoresin had a color value of 95.000° tar, an unpleasant odor mainly consisting of tar odor, and a bitter and astringent taste.

On the other hand, as is clear from Table 1, the extraction processing time is long (I see, the unpleasant odor of the residue (raffinate liquid) in extraction tank 1 disappears, and the product processed for 6 hours has virtually no unpleasant odor. It was paprika oleoresin.

Further, when the circulation operation was performed, the collected material in the first separation tank V had the original paprika odor.

Furthermore, almost no red pigment component was extracted, and the loss of the pigment component was also very small.

2nd step (concentration) The raw paprika oleoresin, which had been deodorized for 6 hours in the first step, was subsequently concentrated. In addition, operate valve 1° and
Carbon dioxide was allowed to flow only through separation tank 3. The operating conditions are as follows.

Pressure (atmospheric pressure) Temperature ('c) Extraction tank 1 200 40 Second separation tank 3; 40 40 Table 2 shows the results of operations with various treatment times.

As is clear from Table 2, by extracting for 25 hours, a paprika pigment with approximately three times the color value and no unpleasant odor or bitter or astringent taste was obtained as a residue (raffinate), and this pigment component was The yield was 96.7Z. In addition, the collected material (raffinate liquid) in the second separation tank 3 is an orange-yellow pigment 6 with no unpleasant odor.
23g was recovered.

In Tables 1 and 2, *1) Weight ratio of carbon dioxide and paprika oleoresin.

*2) Color value according to the color Baliney method, i.e. ■Sample preparation: Weigh 0.2g of the sample, dilute it with acetone and
0rrl. Take 1 ml of this and further dilute it with acetone to make 100 ml.

■ Measurement: Absorbance cell (10m x 10mm x 4
Put the diluted sample into Qw)i) and measure the absorbance at 460 nm.

■ Calculation; Color value - Absorbance x61. OOO/sample amount (
g) *3) Sensory test was conducted by 5 panelists.

×: unpleasant odor, Δ: odor, O: pleasant odor.

*4) Collected material for each treatment time 0 For example, the collected material in the 8-hour treatment in Table 1 is collected during the processing time of 8 to 10 hours.

*5) The value after 6 hours of deodorization treatment was defined as 0.

Book 6) Weight ratio of carbon dioxide to weight of raffinate after 6 hours of deodorization treatment.

*7) Value for 1 kg of raw material (paprika oleoresin).

[Brief explanation of drawings]

1 and 2 are flow sheets of a natural dye deodorizing/concentrating device, which is an embodiment of the present invention. In Figures 1 and 2, 1 is an extraction tower, 2 is a first separation tank, and 3
4 is a second separation tank, 4 is a condenser, 5 is a liquid return pump, 6 is a superheater, 7 is a liquid return storage tank, 8 is a pressure reducing valve, and 9 is a pipe. Patent applicant Mitsubishi Kakoki Co., Ltd. Amma Spice Co., Ltd.

Claims (1)

[Claims] (1) A method for concentrating natural plant pigments, comprising the following steps (a) and (b). (a) A first step in which paprika oleoresin is extracted using high-pressure carbon dioxide to extract odor components. (b) The raffinate from which odor components have been removed in the first step is extracted using supercritical carbon dioxide, resulting in an extract mainly containing yellow pigments and fats and oils and a raffinate rich in red pigments. The second step is separating it into liquids.