JPS62273996A - Extraction and separation of steroid from fat or oil raw material - Google Patents

Abstract

PURPOSE:To efficiently obtain a high-purity steroid, by saponifying a fat or oil raw material with an alkali, extracting a steroid with a solvent, separating the solvent, extracting the extraction residue with supercritical gaseous carbon dioxide, adjusting the pressure and temperature to separate valuable components and extracting the steroid with an extracting solvent. CONSTITUTION:A fat or oil raw material is introduced into a saponification tank 2 and an alkali 3 is added from alkali storage tank 3 to saponify the fat or oil raw material 1. The resultant saponified material is then transferred to a solvent extraction tank 4 and brought into contact with a solvent fed from a solvent storage tank 5 to dissolve and extract a steroid in the solvent. The resultant extract is separated into the extracting solvent and an extraction residue containing the steroid in a centrif ugal separator 6. Supercritical gaseous carbon dioxide is then fed from a gaseous carbon dioxide feeder 7 into an extraction tank 11 and brought into contact with the extraction residue to extract the residual valuable components and solvent. The pressure and temperature of the supercritical gaseous carbon dioxide are adjusted in separation tanks 12, 13 and 14 to separate the valuable components and solvent. The valuable components are then brought into contact with a steroid extracting solvent to extract and separate the solvent and aimed steroid.

Description

Detailed Description of the Invention 3. Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a method for extracting and separating physiologically active substances using supercritical gas, and in particular to extracting and separating physiologically active substances using supercritical gas, and in particular for extracting and separating physiologically active substances that are present in trace amounts in fish oil raw materials. The present invention relates to a supercritical gas extraction and separation method suitable for efficiently extracting and separating cholesterol with high purity.

[Conventional technology]

In recent years, there has been an extraction separation method that uses a supercritical gas (a state where the pressure is above the critical pressure and the temperature is above the critical temperature in the pressure-temperature diagram) as a solvent. This extraction separation method is a technology that utilizes changes in the dissolving power of supercritical gas, and 1) the dissolving power can be easily controlled by adjusting pressure or temperature. 2) Compared to liquid solvent extraction method,
Supercritical gases have a lower viscosity than liquids and a larger diffusion coefficient, so they can be used for high-viscosity substances and high-boiling-point substances, allowing for faster extraction and phase separation. 3) Compared to distillation, it is easier to use an appropriate supercritical gas. This selection allows operation at relatively low temperatures, making it effective for heat-sensitive substances such as natural products. 4) Features include the use of inexpensive solvent gases and the ability to easily separate and recover extracted solutes by changing pressure or temperature.

Therefore, its application as extraction and separation is being considered in various fields.
1-33185° Japanese Patent Publication No. 53-18772. 55-6
9585. Examples of industrialization include decaffeination of coffee and hop extraction of beer as shown in Japanese Patent Application Laid-Open No. 57-26585 (References: New Separation Technology, Chapter 16 Supercritical Gas Extraction, Sanitary Technology Interest, S59.11). 1 Research is progressing as a new extraction technology in the food and pharmaceutical fields, and rapid development is being seen. Particularly in the food and pharmaceutical fields, research on supercritical carbon dioxide extraction methods using harmless carbon dioxide gas is active from the perspective of the toxicity of extraction solvents to the human body (References: 8th Technical Seminar, Supercritical Gas Extraction Current state of technology and future prospects.

(The Society of Chemical Engineers, Tokai Branch, 1985).

In general, distillation uses the difference in vapor pressure of substances, and extraction uses the difference in affinity between the solvent and solute amounts, but supercritical gas extraction uses the difference in vapor pressure and affinity in a fluid in a supercritical state. These are used at the same time and are well known. The higher the density of the supercritical gas fluid, the greater the dissolving power, and the main factors that determine the dissolving power of supercritical gas extraction are the density of the supercritical gas and the intermolecular interactions between the molecules of the gas used and the molecules of the solute to be extracted. When extracting chemically similar components, they are extracted in descending order of vapor pressure.For example, when carbon dioxide is used as a solvent gas, the density of supercritical carbon dioxide is such that it dissolves mutually with the target component. It is brought into contact with the raw material to be extracted under conditions of pressure and temperature that match, and then separated from the supercritical carbonized gas raw material, and by changing the pressure or temperature, supercritical carbon dioxide or the critical point of carbon dioxide gas (temperature 31. 1℃, pressure cuff 2.9
Extraction is carried out by lowering the temperature to a lower temperature and separating the extractable substances.

Animal and vegetable oils contain various valuable components.

For example, fish oil is mainly composed of glycerides and is fatty.

It contains carbohydrates, phospholipids, cholesterol, etc., but it is characterized by its high content of various unsaturated fatty acids.

Generally, when steroids 1 such as cholesterol are extracted and separated from oil and fat raw materials, the oil and fat are saponified, and unsaponifiable substances are washed and collected with ether or the like.

This can be obtained by cooling it with alcohol such as ethanol and recrystallizing it (References 2 Oil and Fat Chemical Handbook 9 Japan Oil Chemists Association,
Maruzen 559) However, the darning method requires a large amount of solvent if the amount of target oil or fat is large, and also requires a huge amount of energy, such as using a distillation method to recover solvents such as alcohol.

On the other hand, as shown in JP-A No. 60-115698, glycerides in fish oil are transesterified with alcohol using an alkali as a catalyst to form fatty acid esters.
This is brought into contact with supercritical carbon dioxide gas.

There is a device that extracts valuable components. The purpose of this extraction device is to esterify triglycerides, which are high-boiling components in fish oil, to convert most of them into fatty acid esters, and then extract specific valuable unsaturated fatty acids. In this regard, a method for highly concentrating cholesterol in the residue (
Patent application No. 60-59660) was proposed. However, there is the following problem.

1) Cholesterol cannot be extracted directly from fish oil.

That is, the step of transesterifying triglycerides in fish oil cannot be omitted.

2) High purity cholesterol cannot be extracted and separated.

This is what is called concentration.

An object of the present invention is to provide an extraction method capable of solving the above problems and extracting and separating cholesterol from fish oil raw materials with high purity.

[Problem that the invention seeks to solve]

Conventional technology involves saponifying fats and oils, washing and collecting cholesterol in the unsaponifiable matter with ether, and cooling and recrystallizing it with alcohol. Particularly in the case of alcohol, since it has good solubility in water and dissolves NaOH and soap, cholesterol purification requires repeated cooling and recrystallization operations. , purified by distillation. Furthermore, because the solvent's dissolving power is reduced by dissolving water.

Using more solvent than necessary. Furthermore, since these solvents are recovered by distillation, a considerable amount of energy is required.

An object of the present invention is to provide a cholesterol extraction and separation method that solves the above-mentioned problems, and allows extraction and separation of highly pure cholesterol and solvent recovery by supercritical gas extraction.

[Means for solving problems]

In order to achieve the above purpose, from saponified products obtained by saponifying oil and fat raw materials.

1) Soap is not dissolved, but extracted using an organic solvent that dissolves and contains unsaponifiable cholesterol.

2) Other valuable components from the extraction residue and extraction solvent extracted with the solvent using supercritical gas.

Extract and separate cholesterol and solvent.

In particular, cholesterol and solvent can be separated and recovered with high purity by supercritical gas extraction.

[Effect]

In order to achieve the above object, the present invention describes in detail a method for extracting and separating cholesterol from fish oil raw materials using supercritical carbon dioxide gas, which includes the following steps.

b) In the refining of fish oil, the first step uses the residual oil separated by deacidification treatment to remove impurities (mainly free fatty acids) from the fish oil as an extraction raw material.

10) The second step of adding alkali to the residual oil and saponifying it
Process.

c) A third step of adding an organic solvent to the saponified product to extract cholesterol into the solvent.

2) A fourth step of separating the extraction solvent and the extraction residue.

e) A fifth step of bringing the extraction residue into contact with supercritical carbon dioxide gas to extract valuable components and solvent remaining in the extraction residue.

f) A sixth step of changing the solubility of the supercritical carbon dioxide gas, separating valuable components, and then bringing them into contact with the extraction solvent of the fourth step to extract the solvent.

g) Seventh step of separating the solvent from supercritical carbon dioxide gas or liquefied or high-pressure carbon dioxide gas with changed solubility.

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

B) First step Fish oil contains various components. The main component is glyceride, and other components include free fatty acids, proteins, carbohydrates, phospholipids, cholesterol, pigments, sediment, and water.

To make refined fish oil, ingredients other than glycerides are used as impurities to achieve the purity required depending on the purpose of use. Here, purification mainly means removing harmful impurities such as free fatty acids, phospholipids, mucilage, and sand. In the present invention, the most commonly performed alkali purification will be described. Caustic soda is often used as alkali.

A deacidification process is performed to precipitate the free fatty acids in fish oil as soap, which is then removed as residual oil by centrifugation. The obtained fish oil undergoes processes such as decolorization and filtration to become purified fish oil. During the deacidification treatment, other impurities are also adsorbed by the soap in the residual oil that is removed, and the remaining oil contains more cholesterol as an impurity than the other impurities that are also separated. Therefore, residual oil is also used as a raw material.

2) Step The residual oil removed in the deacidification step mentioned above contains, in addition to soap and impurities, a type of unsaponified glyceride and fatty acids that cannot be sufficiently separated by centrifugation or the like. These are easily dissolved in the solvent used in the next process, so an alkali is added.
Furthermore, it is saponified and made into a 5-stone sapon. Apply appropriate heat and stirring to promote saponification. What is the saponification reaction of fats and oils?

This results in most of the soap, unsaponifiables, and glycerin. Cholesterol is an unsaponifiable substance.

C) Third step Cholesterol, which is an unsaponifiable substance, is adsorbed on soap, and in order to efficiently extract it with a solvent.

A third solvent that dissolves cholesterol but does not dissolve soap, and is preferably a solvent that does not dissolve with other glycerin or water.
The figure shows the extraction results using various organic solvents1.For example, benzene has no solubility in soap and glycerin, and water1
It has a solubility of less than 0.05 g in 0.00 g, and by adding an appropriate amount, cholesterol can be selectively extracted. acetone.

Methyl ethyl ketone is soluble in water and dissolves soap produced by saponification to extract water and fatty acids. Therefore, the purity of cholesterol is improved, and in the present invention,
An example using benzene will be described.

2) Fourth step In the mixed slurry of the saponified product and benzene, the extraction residue settles and is separated from benzene, but it is preferable to quickly separate it by centrifugation or the like.

e) The extraction residue separated in the previous step of the fifth step contains not only benzene but also higher fatty acids and other valuable components. In order to recover these, the extraction residue is brought into contact with supercritical carbon dioxide gas and extracted into supercritical carbon dioxide gas. Although soap is not extracted by supercritical carbon dioxide, the following reaction occurs when it comes into contact with carbon dioxide under supercritical conditions.

■COz + Hx O→Hx COs, a reversible exchange reaction of saponification occurs, and high-quality fatty acids are produced, which are extracted with benzene into supercritical carbon dioxide gas. Here, the remaining benzene acts as a third substance (entrainer) that promotes fatty acid extraction by supercritical carbon dioxide gas, and can be efficiently extracted.

f) Step 6 The solubility of a substance in the supercritical state can be decreased by decreasing the pressure or increasing the temperature.

The valuable components and benzene extracted into the supercritical carbon dioxide gas can be easily separated, for example, by reducing the pressure. First, the pressure is lowered to separate valuable components (for example, fatty acids) from the supercritical carbon dioxide gas under solubility conditions that allow the separation of valuable components (eg, fatty acids). here.

Depending on the type of solvent, supercritical carbon dioxide may be in the state of liquefaction below the critical point or high-pressure carbon dioxide under conditions that allow extraction of the solvent. Furthermore, the supercritical carbon dioxide gas or liquefied or high-pressure carbon dioxide gas from which valuable components have been separated is brought into contact with the extraction solvent (benzene) separated in the fourth step to extract benzene. Thereby, the cholesterol in the solvent is separated.

e) 7th Step - Benzene can be easily separated from the supercritical carbon dioxide gas or carbon dioxide gas from which benzene was extracted in the above step by further reducing the pressure.

In this way, by changing the pressure or temperature of supercritical carbon dioxide gas and extracting or separating under conditions that match the solubility of the substance, extract residues, high-quality fatty acids, or cholesterol are produced, respectively.

Each can be extracted and separated with benzene, and in particular, cholesterol, which is the target component of the present invention, can be extracted with high purity. Furthermore, since the used solvent can be efficiently recovered with high purity, it can be reused.

On the other hand, when the fish oil raw materials and saponified products in the first to fifth steps are at room temperature (around 20°C) or lower, the oil and fat components and soap solidify, resulting in a marked decrease in fluidity and difficulty in handling. Become. for example.

The saponified product becomes fluidized at a temperature of 35°C or higher. Therefore, it can be handled as a slurry by processing at a temperature of 35° C. or above and below the boiling point of the solvent used.

〔Example〕

The present invention will be explained below using the drawings.

FIG. 1 shows the process flow of the present invention for extracting and separating cholesterol from fish oil using supercritical carbon dioxide gas, step by step.
The first step is to use the residual oil that is removed by the commonly performed deacidification treatment from the fish oil raw material, the second step is to saponify it by adding an alkali, and then add benzene to the saponified product to remove cholesterol. The third step is to extract benzene into benzene, the fourth step is to separate the extracted benzene and the extraction residue, and the fifth step is to bring the extracted residue into contact with supercritical carbon dioxide gas to separate valuable components.
The process consists of a sixth step in which extracted benzene and supercritical carbon dioxide are melted and cholesterol is separated, and a seventh step in which benzene is separated.

Hereinafter, an embodiment of the second rR according to the present invention will be explained in detail using a schematic ws diagram. Although the first step is not shown, 1 indicates the raw material residual oil, 2 indicates the saponification tank, 3 indicates the alkali storage tank, 2' indicates the steam piping for heating the saponification tank, 4 in a solvent extraction tank.

5 is a solvent storage tank, 4' is a steam pipe for heating the extraction tank to an appropriate temperature, 2a and 4a are stirring devices for stirring the respective tanks, and 6 is a centrifugal separator.

On the other hand, 7 indicates a carbon dioxide gas supply device, 8 is a liquefier that liquefies carbon dioxide gas, 9 is a high-pressure pump that pumps and pressurizes liquefied carbon dioxide gas, and 10 is a pressurized liquefied carbon dioxide gas that is brought to a supercritical state. 11 is an extraction tank that brings the extraction residue into contact with supercritical carbon dioxide, 12 is a first stage separation tank that separates the extracted valuables, and 13 is a heat exchanger that brings the extraction solvent and supercritical carbon dioxide into contact with each other. The second-stage separation tank in which the cholesterol is left in contact and the third-stage separation tank 14 in which the extracted solvent is separated is not shown.

11 a r 12 a + 13 a + 14 a
A heater capable of controlling the temperature of each tank for extraction and separation, 11b
13b and 14b indicate pressure holding valves for controlling the pressure of each tank.

Next, a predetermined amount of residual oil removed by deoxidation treatment is supplied from supply pipe 1 to saponification treatment tank 2, an appropriate amount of alkali is added from alkali storage tank 3, and steam 4 pipe 2
' and a stirrer 2a to perform saponification treatment while applying appropriate heating and stirring to obtain a saponified product.Next, the saponified product is introduced into an extraction tank 4, and an appropriate amount of benzene is added from a solvent storage tank 5. Similarly to the saponification process, unsaponifiable cholesterol is dissolved in benzene and extracted while applying appropriate heating and stirring. Here, in the case of solvent extraction, it is necessary to heat appropriately so that the temperature is below the boiling point of the solvent (in the case of benzene, the temperature is 80° C.).

In addition, saponified cypress 2. Extracted cypress 4 is processed sequentially in one tank,
Continuous treatment is possible by providing multiple tanks and switching between them. The mixed slurry of the extraction solvent and extraction residue obtained in this way is separated by a mixed core separator, the extraction residue is transferred to the extraction tank 11 of the supercritical carbon dioxide extraction device, and the extraction solvent is transferred to the second stage separation 13. 1. The present invention describes a batch type supercritical carbon dioxide extraction apparatus, but continuous processing is possible by continuously supplying each with a high-pressure pump.

In the supercritical carbon dioxide extraction device, carbon dioxide gas supplied from a carbon dioxide gas supply device 7 is liquefied in a liquefier 8, and the liquid is sent by a high-pressure pump 9 to be pressurized to a critical pressure or higher. This pressurized liquefied carbon dioxide gas is heated to a supercritical state by the heat exchanger 10 and becomes a supercritical extraction solvent. Supercritical carbon dioxide is
Extraction residue already supplied to the extraction tank and extraction tank 11
The residual solvent and valuable components (for example, high-quality fatty acids) produced by contact with supercritical carbon dioxide gas are extracted. The extraction tank 11 is set to a predetermined supercritical pressure of 9 m degrees by a pressure holding valve 11b and a heater 11a. The extracted supercritical carbon dioxide gas is introduced into the first stage separation 12 from the extraction tank. Sodium carbonate, water, glycerin, etc. remain in the extraction tank and are discharged from the bottom of the extraction tank. 1st stage separation tank 1
The supercritical carbon dioxide gas introduced in step 2 separates fatty acids and other valuable components, and under solubility conditions that dissolve benzene, the pressure and temperature are changed to separate only the valuable components. The pressure and temperature at this time are controlled by the pressure holding valve 13b and the heater 12a. The supercritical carbon dioxide gas, which has been changed to conditions that dissolve benzene, is transferred to the second stage separation tank 13,
Only benzene is extracted by contacting with the already supplied extracted benzene. The supercritical carbon dioxide gas from which benzene has been extracted is introduced into the third stage separation tank 14 via the pressure holding valve 13b.

Therefore, the cholesterol extracted by benzene remains in the second stage separation tank 13 and is recovered from the bottom of the tank.

The supercritical carbon dioxide gas introduced into the third stage separation tank is reduced to a predetermined pressure for separating benzene, and becomes carbon dioxide gas. In this example, the pressure is 20 kg/dQ. The pressure of the third stage separation tank is controlled by a pressure holding valve 14b, and the carbon dioxide gas from which benzene has been separated is circulated and reused via the pressure holding valve 14b. The benzene separated in the third stage separation tank is collected in the solvent storage tank 5 and reused.

In this way, after saponifying and solvent extraction of fish oil raw materials, multi-stage extraction with supercritical carbon dioxide gas produces high-quality fatty acids,
High purity cholesterol and benzene can be extracted and separated. Particularly effective is the ability to recover and reuse the solvent used in solvent extraction at a high yield.

According to the supercritical carbon dioxide gas extraction from extracted benzene and extraction residue according to the present invention, the extraction results shown in Table 1 are obtained.

Furthermore, Table 2 shows the differences in the purity of cholesterol depending on the type of solvent.

Table 2: Methyl ethyl ketone [Effects of the invention] According to the present invention, highly purified valuable components can be obtained in high yield, and the separation efficiency is also high.

[Brief explanation of drawings]

FIG. 1 is a processing flow diagram showing an embodiment of the present invention. FIG. 2 shows a schematic diagram of the device.

Claims (1)

[Claims] 1. A method for extracting and separating steroids from oil and fat raw materials, which includes the steps shown below. (a) A process of adding alkali to oil and fat raw materials and saponifying them. (b) A step of bringing the saponified product into contact with an organic solvent and dissolving and extracting steroids in the solvent. (c) A step of separating the solvent in which the steroids were extracted and dissolved and the extraction residue. (d) Bring supercritical carbon dioxide into contact with the extraction residue to extract residual valuable components and solvent, adjust the pressure and temperature of the supercritical carbon dioxide to separate valuable components and solvent, and then extract the steroid. A step of contacting with a solvent to extract and separate the solvent and the steroid. 2. Extracting and separating steroids from the oil and fat raw materials as set forth in claim 1, wherein steps (a) to (d) of item 1 are carried out at a temperature of 35°C or higher and lower than the boiling point of the solvent. Method. 3. A method for extracting and separating steroids from an oil or fat raw material according to claim 2, wherein the oil or fat raw material is fish oil and the steroid is cholesterol.