JPS5973561A - Preparation of natural taurine - Google Patents

Abstract

PURPOSE:To obtain high-purity taurine relatively inexpensively, by subjecting a water-soluble division of a taurine-containing aquatic animal, wherein highly cencentrated salt coexists, to electrophoresis so that it is desalted, passing it through an anion exchange resin so that taurine is adsorbed on it. CONSTITUTION:A water-soluble division of taurine-containing aquatic animal (e.g., octopus, cuttlefish, oyster, scallop, etc.), wherein highly concentrated salt exists, is subjected to electrophoresis in order to remve chlorine ion mainly, so that it is desalted, it is then passed through an anion exchange resin of OH type, hydrogencarbonate type, or F type, so that taurine is adsorbed on the resin. Adsorbed taurine is washed with water, eluted with an alkali solution, acidic solution, or a neutral salt solution, and cooled. A water-soluble organic solvent is added to the eluted solution, to give the desired substance. USE:Promoting secretion of bile, improving absorption of fats, having perspiration suppressing action, anticonvulsive action, antihypertensive action, etc. Being added to various kinds of drinks and foods and used.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention primarily relates to a method for producing high purity taurine from the water-soluble fraction of aquatic animals.

Taurine is a type of aminosulfonic acid, and like amino acids, it exhibits properties as an amphoteric electrolyte, and its physiologically active properties include promoting bile secretion and improving fat absorption. Furthermore, taurine is known to exhibit antiperspirant, antispasmodic, antihypertensive, cholesterol-lowering, and liver function-improving effects.

In recent years, with the spread of health foods, it has been expected to add and utilize taurine, which has many physiological activities as described above, to food and drink products. however.

The currently produced taurine is a chemically synthesized product for pharmaceutical use, and its addition to food and drinks is not permitted.

Incidentally, the current use of taurine in foods is limited to health foods containing oyster extract as a natural taurine-containing substance.

However, such oyster extract has a taurine content of about 3.
It is a small amount of about 5%, and oysters are added.

Since it is an extract obtained by boiling, it contains a large amount of impurities and is relatively expensive.

The present invention was made in view of the current situation as described above, and allows highly purified taurine to be collected at a relatively low cost from the water-soluble fraction of aquatic animals containing taurine. The purpose of the present invention is to provide a method for producing natural taurine.

The present inventor has arrived at the present invention based on the knowledge that the above object can be advantageously achieved by applying adsorption means using an ion exchange resin to the water-soluble section of the aquatic animal. The present invention will be explained in detail below.

The present invention involves passing a water-soluble fraction of an aquatic animal containing taurine through an anion exchange resin, adsorbing taurine onto the resin, and then eluting the adsorbed taurine with an alkali, acid, or neutral salt solution. The method is characterized in that taurine is crystallized by cooling the obtained eluate or adding a water-soluble organic solvent to the eluate.

Octopus is an aquatic animal that contains taurine.

Oysters, squid, scallops, pearl oysters, abalone, and cod.

Examples include sole.

In the present invention, a water-soluble fraction such as a broth or extract obtained by boiling these aquatic animals or extracting with hot water is cooled to room temperature and then subjected to a filter treatment as necessary. , OH type, hydrogen carbonate type, or F type anion exchange resin, and the taurine in the water-soluble fraction is adsorbed onto the resin.

By passing liquid through the anion exchange resin in the water-soluble section, the pigments and carbohydrates contained in the water-soluble section.

Water-soluble proteins, amino acids, odor components, etc. pass through the resin without being adsorbed, and only taurine is selectively adsorbed.

Among the anion exchange resins used here, OH type ones are particularly preferred, and industrially, those having a particle size of 10 mesh to 100 mesh are advantageous in terms of work efficiency. That is,
Below 10 meshes, the adsorption amount of taurine per unit amount of resin decreases, while above 100 meshes, the flow rate of liquid passing decreases.

This OH type anion exchange resin is obtained by passing an aqueous solution of IJum or ammonium hydroxide (4 to 8% hydroxide) through a commercially available C type anion exchange resin and washing it with water until it becomes neutral. ) can be prepared. By the way.

C-type anion exchange resin cannot adsorb taurine.

In addition, if the water-soluble fraction of the aquatic animal contains a high concentration of salt, it will significantly inhibit the adsorption of taurine to the anion exchange resin, so when passing the solution through the resin, remove it by, for example, electrodialysis. Treat with salt.

In the present invention, the taurine adsorbed by passing the water-soluble fraction of the aquatic animal through the anion exchange resin as described above is washed with water and then eluted with an alkaline solution, an acid solution, or a neutral salt solution. The alkaline solution used here can be exemplified by aqueous ammonia with a concentration of 1 to 30%, preferably 2% to 10%,
It was. The acid solution is 0.1N to 6N, preferably IN to 2N.
An example is an aqueous solution of hydrochloric acid or aqueous acetic acid, and the neutral salt solution is 0.1 to 30%, preferably 196 to 5%.
An example is a saline solution.

When the liquid eluted as described above is cooled to a temperature of around 05C using a condenser, cooling tower, etc., taurine crystallizes out, and the taurine crystals are filtered.

Separate and collect using methods such as centrifugation.

In addition, 2.5 to 50% (1 (volume t)), preferably 50% to 50% of the eluate, is added directly to the eluate or by cooling to a concentration that does not lead to crystallization of taurine. 150 inches of ethanol.

It is also possible to add a water-soluble organic solvent such as methanol or acetone to lower the solubility of taurine in the solution to cause crystallization, and to separate and collect the formed crystals.

Note that after the taurine crystallized in this way is separated, some taurine remains in the eluate without crystallizing, so if necessary, the solution is passed through an activated carbon column to remove the amount of taurine in the solution. After removing pigments, odor components, etc., taurine in the multi-liquid is crystallized by concentrating it with an evaporator and cooling it again, or by adding a water-soluble organic solvent, or by repeating this operation. It is also possible to separate and collect one.

In addition, since the eluate in which taurine remains is a solution containing alkali, acid, or neutral salt, the solution is passed through an activated carbon column to remove pigments and odor components, and then the taurine adsorbed on the resin is eluted. When used in circulation, the taurine concentration in the eluate of adsorbed taurine obtained thereby increases, and the eluate can be cooled to crystallize taurine without concentrating it, which is particularly advantageous for industrial scale production. It is.

The crystalline taurine collected in this way can be added to various foods and drinks as natural taurine and used as it is, but if some acid, alkali or neutral salt remains on the surface of the taurine crystal, the taurine crystals should be washed with hot water. (For example, around 50C)
After dissolving in taurine, it is cooled and crystallized, or a water-soluble organic solvent is added to precipitate taurine, and the precipitated taurine is separated and collected by p-filtration, centrifugation, etc. to increase its purity. be able to.

Further, in order to remove the above acid, alkali and neutral salt, the taurine crystals may be washed directly with cold water containing the above water-soluble organic solvent.

As mentioned above, the taurine crystal obtained by the present invention is
Although it can be used as it is, since it contains water, it is convenient for practical use in fires if it is dried by a conventional method and used in powder form. Incidentally, the taurine obtained according to the present invention is 99
．． Since it exhibits a purity of 51 or higher, it can be added to various foods and drinks as natural taurine.

As mentioned above, according to the present invention, high-purity products can be produced using broth obtained when processing various aquatic animals (many of such broths are often discarded) or hot water extract as a starting material. Since taurine can be obtained by a relatively simple method, it can be said that it will greatly contribute to the utilization of natural taurine.

EXAMPLES The present invention will be explained in more detail with reference to Examples below.

Example 1 Octopus broth containing 0.3% by weight of taurine (less than 1.0 weight of water-soluble protein, less than 0.5 weight of fat).

Carbohydrate 0.5% by weight or less, salt content 2.2% by weight) 6
The solid content in the broth was separated and removed by passing through 0.01 for 1 hour, and then desalinated using an electrodialysis membrane (salt content of the broth after desalting was 0.012 cm). The solution was passed through a 21-volume column of anion exchange resin (Dowex, manufactured by Dow Chemical Company), and taurine in the broth was adsorbed onto the resin.

Next, 101 distilled water was passed through the resin column to wash the resin, and then 1.5N hydrochloric acid aqueous solution 21 was passed through the column to elute the taurine adsorbed on the resin. The average taurine content in the eluate is 8g/1001m? Met.

The entire amount of this eluate was cooled to 5C in a condenser to crystallize taurine, and the precipitated taurine crystals were separated and separated using a fender.

The amount of taurine obtained was 95 g.

Taurine thus obtained was added to 5 (l of warm water 600
1.21 of ethanol was further added to precipitate the taurine in the solution, and this precipitate was separated and collected using a glass filter. The obtained precipitate was dried in a vacuum dryer for 90 minutes.
Dry for 3 hours at
%) was obtained. The purity of this taurine powder was determined to be 99.5% using an automatic amino acid analyzer.

Example 2 10 kg of pearl oyster containing 8% by weight of taurine io was added with 10 At of warm water (50C), mixed with a homomixer, and then centrifuged to separate 15 A' of pearl oyster extract.

The obtained extract (taurine content 0.5% by weight) was
OH-type strongly basic anion exchange resin with mesh to 50 mesh particle size (AmberA'its I RA 410
Japan Organo Shokai fR) 1! The resin was passed through a column to adsorb taurine in the extract onto the resin.

Next, the resin column was washed with 51 parts of distilled water, and 1.5N acetic acid aqueous solution 11 was passed through the kneading column to elute taurine adsorbed on the resin. The taurine content in the eluate was on average 7 g/10 CJal.

The eluate thus obtained was cooled to 5C using a condenser to crystallize taurine, and the precipitated taurine was separated and collected using a filter.

On the other hand, in order to recover the taurine (concentration approximately 3%) remaining in the eluate, the eluate was concentrated in an evaporator to a taurine concentration of 20 g or more, and then ethanol was added to the volume of 50 g. It was cooled to crystallize taurine.

The total amount of taurine obtained as described above was 70 Ij
Met.

procedure? 111 official book 1981 10 J] I t.

Kazuo Wakasugi, Commissioner of the Japan Patent Office3, Relationship with the person making the amendment Patent applicant name (669) Snow Brand Milk Products Co., Ltd.4, agent address 2-7-7 Higashi-Shinbashi, Minato-ku, Tokyo! ;3 New Draft Kokusai Hino 1 No. 5, Date of amendment order Voluntary 6, Number of inventions increased by amendment 7, Contents of amendment Description 8, Subject of amendment The entire description is amended as shown in the attached sheet.

Full text corrected specification 1, title of the invention, method for producing natural taurine 2, claims ρ fire cultivation method. Taurine is adsorbed onto the resin, and then, after washing with water, the adsorbed taurine is eluted with an alkaline solution, an acid solution, or a neutral salt/8 solution, and the resulting eluate is cooled, or a water-soluble organic solvent is added to the eluate. A method for producing natural taurine, which comprises adding and crystallizing taurine.

The manufacturing method according to claim 1, wherein the main alkaline solution, acid solution, or neutral salt solution is a taurine-containing solution obtained after separating and collecting taurine from the eluate.

3. The production method according to claim 1, wherein the taurine-containing solution is a solution with a high taurine content obtained by repeated use for elution of taurine adsorbed on a resin.

The present invention relates to a method for producing highly purified taurine from the water-soluble fraction of taurine-containing aquatic animals in the presence of high concentrations of common salt.

Taurine is a type of aminosulfonic acid, and like amino acids, it exhibits properties as an amphoteric electrolyte, and its physiologically active properties include promoting bile secretion and improving fat absorption. Furthermore, taurine is known to exhibit antiperspirant, antispasmodic, antihypertensive, cholesterol-lowering, and liver function-improving effects.

In recent years, with the spread of health foods, it has been expected to add and utilize taurine, which has many physiological activities as described above, to foods and drinks. However, the currently produced taurine is a chemically synthesized product for pharmaceutical use, and its addition to food and drinks is not permitted.

By the way, recently, taurine-containing aquatic animal extracts such as aquatic molluscs have been decationized using a cation exchange resin.
Next, the obtained permeate is passed through an activated strongly basic anion exchange resin to adsorb the phosphorus in the extract, and then the adsorbed taurine is eluted using a weak acid solution. A method for producing taurine has been proposed.

However, this proposed method is not practically suitable for producing taurine from the broth produced when taurine-containing aquatic animals are used as raw materials for processed foods. In other words, taurine-containing aquatic animals (e.g., octopuses, oysters, etc.) are generally used as raw materials for processed seafood foods by boiling them in a saline solution containing about 0.2% to 3% and then serving them as is or after further processing. The broth (water-soluble category) that is produced at this time contains taurine (in the past, much of this broth was discarded without being used).
.

When producing taurine from such a broth as a raw material, it is extremely difficult to efficiently obtain taurine even if the broth is used as an extract in the proposed method. In other words, since the broth contains at least 0.2% salt as well as taurine, even if the broth is passed through a cation exchange resin, sodium ions (Na
``)L is not adsorbed, and all chlorine ions (cp''-) coexist with taurine in the passing liquid. Therefore, when this permeate is then passed through a strongly basic anion exchange resin, both taurine and chloride ions are adsorbed to the resin, and taurine is an amphoteric electrolyte and acts as an anion in the alkaline region from its isoelectric point. ), even if the solution is continued to flow, the adsorbed taurine will be eluted since chlorine ions have a stronger adsorption power than taurine, making it virtually impossible to obtain taurine.

The present invention has been made in view of the above-mentioned current situation, and the present invention has been made in view of the above-mentioned current situation, and is directed to water-soluble classification of the above-mentioned aquatic animals in which a high concentration of common salt coexists, such as the above-mentioned broth obtained during the processing of taurine-containing aquatic animals. It is an object of the present invention to provide a method for producing natural taurine, which allows highly purified taurine to be collected from natural taurine at a relatively low cost.

The main purpose of the present inventor is to remove chloride ions from the water-soluble fraction of taurine-containing aquatic animals when producing taurine using the water-soluble fraction of the taurine-containing aquatic animal as a raw material, in which a high concentration of salt as described above coexists. The present invention was realized based on the finding that when taurine is desalted by electrodialysis and then passed through an anion exchange resin, substantially only taurine is adsorbed to the resin. The present invention will be explained in detail below.

In the production of natural taurine, the present invention applies electrodialysis to desalinate the water-soluble fraction of taurine-containing aquatic animals in which a high concentration of common salt coexists, and then desalinates the OH-type, bicarbonate-type, or F-type. The taurine in the water-soluble category is adsorbed onto the resin by passing the solution through the anion exchange resin prepared above, and then, after washing with water, the adsorbed taurine is eluted with an acid solution or an acid solution or a neutral salt /8/&. The taurine-containing aquatic animals used in the present invention include octopus, squid, and oysters. , scallops, pearl oysters, abalone cod, and sole. As mentioned above, these aquatic animals are all 0.2%
After being boiled in about 3% saline solution, they can be eaten as is or after further processing, and the resulting broth is mainly used as a water-soluble fraction of these aquatic animals.

That is, in the present invention, at least 0.2
The OH type is obtained by cooling the water-soluble fraction in which % or more of common salt coexists to room temperature, filtering it if necessary, and desalting it by electrodialysis.

The taurine in the water-soluble fraction is adsorbed onto the resin by applying the solution to an anion exchange resin in the hydrogen carbonate type or F type.

The reason why the broth is desalted by electrodialysis as described above in the present invention is as follows.

Taurine and at least 0.2% of salt coexist in the broth, but salt dissociates into sodium ions and chloride ions in the broth, while taurine is an ampholyte, so taurine Even if the broth in which chloride and chlorine ions coexist is passed through an anion exchange resin, as mentioned above, the adsorption power of chlorine ions to the resin is stronger than that of taurine, so the adsorption power of taurine is hindered and the actual can't get taurine.

Therefore, in the present invention, at least 0.
As a pretreatment for passing the water-soluble fraction in which 2% or more common salt coexists with taurine to an anion exchange resin, the main purpose is to remove chlorine ions (sulfur and lithium ions are also removed at the same time). ) processing.

Desalination treatment by electrodialysis reduces the salt concentration in the water-soluble category to 0.
．． This is done so that the amount is less than 2%, preferably 0.05% or less.

By passing the desalted water-soluble fraction through the anion exchange resin, pigments, tJJI substances, water-soluble proteins, amino acids, odor components, etc. contained in the water-soluble fraction are transferred to the resin. It passes through without being adsorbed, and only taurine is selectively adsorbed.

Among the anion exchange resins used here, OT-1 type is particularly preferable, and industrially 10 mesh to 100 mesh
Mesh particle size is advantageous in terms of work efficiency. That is, below 10 meshes, the adsorption amount of taurine per unit amount of resin decreases, while above 100 meshes, the flow rate of liquid passing decreases.

This OH type anion exchange resin is commercially available CI! It can be prepared by passing a 4 to 8% aqueous solution of thorium hydroxide or ammonium hydroxide through an anion exchange resin and washing with water until it becomes neutral. Incidentally, C1 type anion exchange resin cannot adsorb taurine.

In the present invention, the taurine adsorbed on the anion exchange resin as described above is then washed with water and then eluted with an alkaline solution, an acid solution, or a neutral salt solution. The alkaline solution used here can be exemplified by ammonia water with a concentration of 1 to 30%, preferably 2% to 10%, and the acid solution can be 0.1%
Examples include N to 6N, preferably IN to 2N hydrochloric acid aqueous solution or acetic acid aqueous solution, and examples of neutral salt solutions include 0.1% to
A 30%, preferably 1% to 5%, saline solution may be exemplified.

When the solution eluted as described above is cooled to around 5° C. using a cooler, cooling tower, etc., taurine crystallizes out, and the taurine crystals are separated and collected by methods such as filtration and centrifugation.

In addition, 2.5% to 500% (volume) of the eluate, preferably 5% to 500% (volume) of the eluate, is added directly to the eluate or by cooling to a concentration that does not lead to crystallization of taurine.
0% to 15,0% ethanol.

It is also possible to add a water-soluble organic solvent such as methanol or acetone to lower the solubility of taurine in the solution to cause crystallization, and to separate and collect the formed crystals.

After separating the crystallized taurine in this way, some taurine remains in the eluate without crystallizing, so the concentrated solution may be passed through an activated carbon column as necessary to remove the concentration of taurine in the solution. 1 & from which pigments, odor components, etc. have been removed, taurine in the liquid is crystallized and separated by concentrating it with an evaporator, etc. and cooling it again, or by adding a water-soluble leading solvent, or by repeating this operation. It can also be collected.

In addition, since the eluate in which taurine remains is a solution containing alkali, acid, or neutral salt, the solution is passed through an activated carbon column to remove pigments and odor components, and then the taurine adsorbed on the resin is eluted. When used in circulation, the taurine concentration in the resulting eluate increases, and taurine can be crystallized by cooling the eluate without concentrating it, which is particularly advantageous for industrial scale production.

The crystalline taurine collected in this way can be added to various foods and drinks as natural taurine and used as it is, but if some acid, alkali or neutral salt remains on the surface of the taurine crystal, the taurine crystals should be washed with hot water. (For example, around 50℃)
Purity can be increased by melting the taurine, cooling it and crystallizing it, or adding a water-soluble organic solvent to precipitate taurine, and separating and collecting the precipitated taurine by filtration, centrifugation, etc. .

Further, in order to remove the above acid, alkali and neutral salt, the taurine crystals may be washed directly with cold water containing the above water-soluble organic solvent.

Next, when separating and collecting taurine from the broth of taurine-containing aquatic animals as described above, we will examine the content of salt coexisting in the broth passed through the anion exchange resin and the recovery of taurine from the broth. Table 1 shows the results of investigating the relationship between the amount and recovery rate. In addition, the broth used had a taurine content of 0.2% and a salt content of 3%, and the broth was subjected to electrodialysis to desalinate to various salt contents. 20 (1,4001,6007!, 80
The liquid was passed through at a flow rate of 0x and 1000z. .

As shown in Table 1, the amount and recovery rate of taurine from kneaded broth obtained by subjecting broth as a raw material to electrodialysis and desalting to reduce the salt content in the broth increases.

As mentioned above, the taurine crystal obtained by the present invention is
Although it can be used as it is, since it contains water, it is convenient for practical use in fires if it is dried by a conventional method and used in powder form. Note that the taurine obtained by the present invention is 99
．． Since it exhibits a purity of 5% or more, it can be added to various foods and drinks as natural taurine.

As mentioned above, according to the present invention, relatively high-purity taurine is produced using water-soluble fractions containing high concentrations of salt, such as broth obtained when processing various aquatic animals, as a starting material. Since it can be obtained by a simple method, it can be said to make a large contribution to the utilization of natural taurine.

EXAMPLES The present invention will be explained in more detail with reference to Examples below.

Example Octopus broth containing 0.3% by weight of taurine (less than 1.0% by weight of water-soluble protein, 0.5% fat, 11% or more, 0 carbohydrates)
．． 5% by weight or less, salt content 2.2%) (after passing ioff for 71 y to separate and remove the fixed content in the broth, electrodialysis device (I!2i area In(, current density 2Δ/(I n
() -(: Desalted by circulation for about 4 hours (
Salt content of desalinated 1-rich broth 0.012%), particle size 20-5
0 mesh OH type strongly basic anion exchange resin (Ilo
wex.

The solution was passed through a 2β volume column (manufactured by Dow Chemical Company) to adsorb taurine in the broth onto the resin.

Next, distilled water of ION was passed through the resin column described in "1" to wash the resin, and then L 5 N aqueous hydrochloric acid solution 2e was passed therethrough to elute taurine adsorbed on the resin.

The average content of taurine-containing I in the eluate was 8 g/100 m#.

The entire amount of this eluate was cooled to 5°C using a condenser to crystallize taurine, and the crushed taurine crystals were separated by filtration using a filter.

3 The amount of taurine obtained was 95 g.

The taurine thus obtained was added to 60°C of hot water at 50°C.
0m7! Dissolve and add 1.2 ethanol! was added to precipitate taurine in the solution, and this precipitate was separated and collected using a glass filter. The obtained precipitate was dried in a vacuum dryer at 90°C for 3 hours, and 85g of taurine powder (moisture 0)
．． 25%). The purity of this taurine powder was determined to be 99.5% using an automatic amino acid analyzer.

Applicant: Snow Brand Milk Products Co., Ltd. Agent Miya 1) Hirotoyo 4

Claims (4)

[Claims] (1) The water-soluble category of the aquatic animal containing taurine is OH type, hydrogen carbonate type, or F type, and the water is passed through an anion exchange resin to adsorb taurine in the water-soluble category to the resin, Next, after washing with water, the adsorbed taurine is eluted with an alkaline solution, an acid solution, or a neutral salt solution, and the resulting eluate is cooled, or a water-soluble organic solvent is added to the eluate to crystallize taurine. A method for producing natural taurine, characterized by: (2) The manufacturing method according to claim 1, wherein the water-soluble fraction is desalinated. (3) The alkaline solution, acid solution or neutral salt solution is
The manufacturing method according to claim 1, which is a taurine-containing solution obtained after separating and collecting taurine from the eluate. (4) The production method according to claim 3, wherein the taurine-containing solution is a solution with a high taurine content obtained by repeated use for elution of taurine adsorbed on a resin.