JPH1059924A - Solid taurine and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prevent taurine from blocking and enable the intake of trace elements which tend to lack in vivo. SOLUTION: This solid taurine is prepared by allowing a metal salt to stick to the surface of taurine crystals. This sticking can be carried out, for example, by precipitating solid taurine from a slurry containing water as a dispersion medium, taurine crystals and the metal salt. The metal salt is selected from the group consisting of zinc sulfate, potassium sulfate, magnesium sulfate, calcium acetate, zinc acetate, potassium acetate and magnesium acetate.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to solid taurine and a method for producing the same.

[0002]

2. Description of the Related Art Taurine is said to have a cholesterol lowering effect, and its use in health foods such as drinks and pharmaceuticals is increasing. Taurine is usually synthesized by a reaction in an aqueous phase. Taurine precipitated from the reaction mixture obtained by the reaction is purified, dried, filled into a container and packed.

[0003]

The conventional taurine is inconvenient in its workability, for example, it is difficult to take out of the container because it is easily solidified during packing. This is considered to be because the sulfone group of the taurine molecule is hygroscopic, so that the water adsorbed from the air atmosphere mediates and the taurine crystal aggregates.

[0004] It is an object of the present invention to prevent the caulking of taurine and to ingest trace elements, which tend to be insufficient in the living body.

[0005]

According to the present invention, in order to solve the above-mentioned problems, a metal salt of an inorganic acid and / or an organic acid is attached to a taurine crystal surface. In this case, the metal salt is, for example, at least one compound selected from the group consisting of zinc sulfate, potassium sulfate, magnesium sulfate, calcium acetate, zinc acetate, potassium acetate, and magnesium acetate. Since this metal salt contains a trace element that is liable to be lacking in a living body, it may be taken together with taurine.

The method for producing solid taurine according to the present invention is to precipitate solid taurine from a slurry containing taurine crystals and a metal salt using water as a dispersion medium. In this case, the precipitation of solid taurine is performed, for example, by mixing the slurry with a water-soluble solvent having a solubility in taurine and a metal salt lower than that of water. The above-mentioned precipitation may be carried out during the taurine production process, after the purification of taurine, and before the drying of taurine.

[0007]

In the present invention, the attachment of a metal salt to the taurine crystal surface means, for example, that the metal salt particles are bonded to the taurine crystal surface, that the metal salt particles are wholly or partially. Embedded in the taurine crystal surface, that a metal salt layer is formed on the taurine crystal surface, that the metal salt and taurine form a solid solution (mixed crystal) on the taurine crystal surface, or that the metal salt In other words, it means that the metal salt is attached to the taurine crystal surface in a state in which the metal salt is not easily peeled off (fixed state), for example, the metal salt is adsorbed on the taurine crystal surface.

[0008] One preferred form of the adhered state in the present invention is that the metal salt provides a very small amount of anti-caking effect to taurine, and that the molecular structure of taurine (that is, taurine has a sulfone group and an amino group at both ends). Taking into account the fact that the amino group has a positive charge and the sulfone group has a negative charge in the molecule) and the results of measurement of the amount of metal salt dissolved by the sequential dissolution method described later. When the metal salt is attached to the surface, it is considered that taurine and the metal salt are in a form in which one molecule of the metal salt and two molecules of taurine form a complex. When the metal salt forms a complex with taurine on the taurine crystal surface, it can be estimated that the hygroscopic property inherent to the sulfone group of taurine disappears and an anti-caking effect appears. When the metal salt forms a complex with taurine on the taurine crystal surface, the solid taurine of the present invention can be referred to as a taurine metal complex.

Preferred metal salts include, for example, zinc sulfate, potassium sulfate, magnesium sulfate, calcium acetate, zinc acetate, potassium acetate, and magnesium acetate. Only one of them is used.
The above may be used together. At least one metal salt selected from the group consisting of zinc sulfate, potassium sulfate, magnesium sulfate, calcium acetate, zinc acetate, potassium acetate and magnesium acetate is particularly excellent in the effect of preventing the solidification of solid taurine, and is useful in vivo. Is preferable because it can be an effective trace element for preventing various adult diseases caused by deficiency in the above.

[0010] The greater the amount of metal salt deposited, the higher the anti-caking effect, but the lower the taurine purity in solid taurine. Considering that the effect of preventing solidification is obtained while maintaining the purity of the solid taurine at a certain level, the amount of the metal salt deposited is the ratio of the metal element to the taurine in the metal salt, for example, 0.1%. 1 to 10.0% by weight (atomic
%), Preferably 0.5 to 2.5% by weight (atomic%).

[0011] The solid taurine according to the present invention is produced by attaching a metal salt to the surface of a taurine crystal.
For example, a method of mixing metal salt particles and taurine crystal, a method of wetting a taurine crystal surface with an aqueous metal salt solution and drying, and a method of wetting a taurine crystal surface with a mixed aqueous solution of a metal salt and taurine and drying The method is carried out by, for example, a method in which solid taurine is precipitated from a slurry containing water as a dispersion medium and containing taurine crystals and a metal salt (the dispersion medium is water).

A method for wetting and drying a taurine crystal surface with a metal salt aqueous solution (or a mixed aqueous solution of a metal salt and taurine) is described, for example, by using a conventional fluidized bed dryer to remove the aqueous solution of a taurine crystal in a fluidized bed state. And drying. The precipitation of solid taurine from a slurry containing water as a dispersion medium and containing taurine crystals and a metal salt (hereinafter, referred to as “slurry A”) is, for example, as follows.
(1) mixing the slurry A with a water-soluble solvent having a lower solubility in taurine and a metal salt than water (hereinafter, simply referred to as “water-soluble solvent”), or (2) spray-drying the slurry A, And so on.

The slurry A is prepared, for example, by mixing a metal salt, a taurine crystal and water, adding a taurine crystal to an aqueous metal salt solution, or mixing a taurine pre-slurry having a taurine crystal suspended in water with a metal salt aqueous solution. Or by mixing the taurine pre-slurry with a metal salt. The slurry A may be the reaction mixture (slurry) itself obtained by the synthesis reaction of taurine. The weight ratio of taurine and water in the slurry A is, for example, the solubility of taurine and metal salt in water,
In consideration of the fluidity of the slurry and the amount of the water-soluble solvent to be mixed (purged), the ratio is preferably in the range of 1: 0.3 to 1:10.

The mixing of the slurry A and the water-soluble solvent in the precipitation method (1) is performed, for example, by adding a water-soluble solvent to the slurry A or adding the slurry A to the water-soluble solvent. Preferably, the slurry A is gradually added while stirring the water-soluble solvent. Compared to the solubility of taurine and metal salts in water, the solubility in a mixed solvent of a water-soluble solvent and water is extremely small,
The dissolved taurine and metal salt precipitate. In addition,
After the above mixing, aging is preferably performed. The aging condition is, for example, to stir for 30 minutes and then to stand overnight.

From the suspension containing the precipitated solid taurine,
Solid taurine is separated by a usual solid-liquid separation method (for example, filtration) and dried. The drying is preferably performed at a temperature of 70 ° C. to 120 ° C. in consideration of the fact that moisture is easily volatilized. The water-soluble solvent only needs to have a solubility in taurine and the metal salt lower than that of water, and can be appropriately selected and used according to the type of the metal salt used. The water-soluble solvent is, for example, a water-soluble organic solvent, and is preferably a single solvent or a mixed solvent of two or more selected from the group consisting of a water-soluble alcohol and a water-soluble ketone. The water-soluble alcohol is, for example, at least one selected from the group consisting of methanol and ethanol. The water-soluble ketone is, for example, acetone. Zinc sulfate, potassium sulfate, magnesium sulfate,
Calcium acetate, zinc acetate, potassium acetate and magnesium acetate are insoluble or poorly soluble in methanol, ethanol and acetone.

The weight ratio of the slurry A to the water-soluble solvent is
In consideration of filterability and economy, the ratio is in the range of 1: 1 to 1:10. Spray-drying (spray-drying) of the slurry A in the precipitation method (2) can be performed by a usual spray-drying apparatus. Taurine for obtaining taurine crystals may be prepared by any synthetic method, or may be separated from animal bile or mollusc meat extract.

The method of wetting and drying a taurine crystal surface with an aqueous solution of a metal salt (or an aqueous solution of a metal salt and taurine) as described above can be performed simultaneously in the conventional production process of taurine. For example, taurine is synthesized by reacting sodium sulfite and β-aminoethyl acid sulfate, and the resulting taurine crystal is purified and dried in a production process of purifying the taurine crystal at a stage after purifying the taurine crystal. The metal salt aqueous solution (or a mixed aqueous solution of metal salt and taurine) is sprayed onto the taurine crystal and dried.

The above-mentioned precipitation method can be performed simultaneously in the conventional production process of taurine. For example, in a production process of reacting sodium sulfite with β-aminoethyl acid sulfate to synthesize taurine, purifying the obtained taurine crystal, and drying the resultant, (ia)
At the stage where a slurry of taurine crystals is obtained, the metal salt is added, and the above-mentioned precipitation method (1) is performed. The metal salt and water were added to the purified taurine crystals to perform the above-mentioned precipitation method (1), and the solid taurine obtained by solid-liquid separation was dried. The salt is added and the spray-drying method (2) is performed. Or

In a conventional taurine production process of reacting sodium sulfite with β-aminoethyl acid sulfate to synthesize taurine, purifying the resulting taurine crystal, and drying it, potassium sulfite is used instead of sodium sulfite. When potassium is used, potassium sulfate is derived from potassium sulfite used as a raw material in the above synthesis reaction, so that if necessary, the reaction mixture is concentrated to precipitate taurine crystals and formed into a slurry. The material becomes slurry A as it is.

As described above, according to the present invention, the taurine manufacturing process can be simply performed without substantially changing the conventional manufacturing process.
Solid taurine having an anti-caking effect can be obtained only by partially changing the process (change by adding a solid taurine precipitation step) or by changing a part of the raw material used. The solid taurine of the present invention is used, for example, in pharmaceuticals or health foods for ingesting trace elements.

[0021]

EXAMPLES Examples of the present invention and comparative examples outside the scope of the present invention will be shown below, but the present invention is not limited to the following examples. Example 1 Taurine crystal 10 in 100.0 g of distilled water
0.0 g and anhydrous potassium sulfate (commercially available reagent first grade) 5.0
g was added thereto and mixed gently at 25 ° C. to obtain a slurry.
Next, the temperature of the slurry was increased to 70 ° C. while stirring the slurry, and the slurry was maintained at 70 ° C. for 10 minutes. Thereafter, the slurry was mixed with 450 g of ethanol to precipitate a solid. After mixing, the mixture was stirred and maintained at 25 ° C for 30 minutes, and allowed to stand at 25 ° C overnight. The next day, the liquid temperature was adjusted to 25 ° C, and solid-liquid separation was performed by filtration. The obtained cake was dried at 105 ° C overnight to obtain solid taurine.

Example 2 The procedure of Example 1 was repeated except that 8.9 g of zinc sulfate heptahydrate (a commercially available first-class reagent) was used instead of potassium sulfate. Example 3 The procedure of Example 1 was repeated, except that 22.2 g of magnesium sulfate heptahydrate (a commercially available first-class reagent) was used instead of potassium sulfate.

Example 4 The procedure of Example 1 was repeated except that 10.0 g of calcium acetate monohydrate (a commercially available first-class reagent) was used instead of potassium sulfate. Example 5 The procedure of Example 1 was repeated except that 6.7 g of zinc acetate dihydrate (a commercially available first-class reagent) was used instead of potassium sulfate.

Example 6 The procedure of Example 1 was repeated except that 5.0 g of anhydrous potassium acetate (a commercially available primary reagent) was used instead of potassium sulfate. (Example 7) The procedure of Example 1 was repeated except that 17.8 g of magnesium acetate tetrahydrate (a commercially available first-class reagent) was used instead of potassium sulfate.

<Consolidation Test> 50 to 70 g of the solid taurine obtained in Examples 1 to 7 and the taurine (Comparative Example 1) used as a raw material of Examples 1 to 7 were each put in a glass bottle, and a packing and a lid were placed. And leave it still. Seven days later, the bottle was slowly inverted with the lid kept on, and the falling state of the crystal sample was observed.

：: The entire sample dropped, and no consolidation of crystals was observed. Δ: Part of the sample dropped, but the rest remained in the bottle in a consolidated state. X: All the samples were solidified in the bottle and did not fall. The results are shown in Table 1.

[0027]

[Table 1]

The solid taurine of Examples 1 to 7 in which a metal salt is attached to a taurine crystal, regardless of the type of the metal salt,
Good results were obtained for the prevention of taurine caking. On the other hand, the taurine crystal itself to which the metal salt was not adhered (Comparative Example 1) did not show an anti-caking effect. The effect of preventing solidification in the examples is obtained by attaching metal salts to the taurine crystal surface. In one preferred embodiment, taurine and a metal salt are slurried and added to a water-soluble medium such as ethanol, and the adhesion is realized by precipitating crystals by a difference in solubility. It is presumed that the salt forms a partly complex salt-like loose bond to the sulfone group of the taurine molecule. That is, the taurine molecule has an amino group and a sulfone group at both ends, and the amino group is polarized toward the positive charge and the sulfone group is polarized toward the negative charge. Therefore,
The metal salt on the taurine crystal surface includes an anion of the metal salt on the amino group side of two molecules of taurine (a sulfonate ion in Examples 1 to 3 and an acetate ion in Examples 4 to 7).
It is presumed that the metal ion of the metal salt is bonded to the sulfone group side of the two molecules of taurine. It is considered that this complex salt-like bond weakens the hygroscopicity of the sulfone group in the taurine molecule, and gives good results in preventing taurine from solidifying.

For the solid taurine obtained in Examples 1 to 3, SO ₄ ^2- was quantified by the following method. 5 g of the solid taurine sample was precisely weighed and made up to 100 ml with distilled water. Dilute 2 ml to 100 ml and dilute 0.2 ml
, And 5 g of methanol was added.
l. The SO ₄ ^2- ion in the 10 ml solution was subjected to ion chromatography (Shim-pack IC-A).
3: Shimadzu Corporation). In the SO ₄ ^2-ion content in the solid taurine found this, and the added weight percentage to SO ₄ ^2-ion content in the metal salt (content) was determined and the weight percentage of solids taurine amount. Table 2 shows the results.

[0030]

[Table 2]

From Table 2, it can be seen that almost all of the SO ₄ ^2- ion in the added metal salt is contained in solid taurine. From this result, it is understood that not only metal ions such as K ⁺ and Zn ²⁺ are contained in solid taurine, but the salt of each metal ion and SO ₄ ^2- ion is contained in solid taurine. . The solid taurine obtained in Example 1 was sequentially dissolved (investigation of ion distribution from the crystal surface to the inside) by the following method. A suction filtration device as shown in FIG. 1 was assembled, and 1 g of sample 2 was precisely weighed on filter paper 1. The crystal surface was immersed in 2 ml of distilled water 3 and subjected to suction filtration, and this operation was repeated five times to obtain filtrates 1 to 5, respectively. The amount of K ions in the filtrate was measured with an atomic absorption spectrophotometer. The measured amount of K ions was converted to the amount of metal salt, and the weight percentage based on the precisely weighed value of the sample weight and the weight percentage based on the added metal salt amount were calculated. The results are shown in Table 3 and FIG.

[0032]

[Table 3]

As can be seen from the results in Table 3 and FIG.
70% of the solid taurine obtained in
The above K ₂ SO ₄ was eluted, and 1
The elution amount was 0% or less. In the solid taurine obtained in Example 1, it is considered that the metal salt and the taurine form a complex on the surface of the taurine crystal. That is, the metal salt is ion-adsorbed to the taurine crystal and easily eluted into water, and the elution amount in the first washing is much larger than the elution amount in the second and subsequent washings. It is thought that it became.

[0034]

The solid taurine of the present invention is obtained by adhering a metal salt to the surface of taurine crystal, so that it is difficult to solidify and is used for ingesting trace elements that are liable to be insufficient in the living body. be able to. According to the method for producing solid taurine of the present invention, the above-described solid taurine can be easily produced. The method of the present invention is convenient because it can be easily incorporated into a conventional method for producing taurine, or a taurine crystal obtained by a conventional method for producing taurine can be easily processed.

[Brief description of the drawings]

FIG. 1 is a schematic diagram of a suction filtration device used for a sequential dissolution method.

FIG. 2 is a correlation diagram showing the results of the sequential dissolution method, between the number of washings and the amount of elution.

Claims (5)

[Claims] 1. A solid taurine having a metal salt of an inorganic acid and / or an organic acid attached to the surface of a taurine crystal. 2. The solid taurine according to claim 1, wherein the metal salt is at least one compound selected from the group consisting of zinc sulfate, potassium sulfate, magnesium sulfate, calcium acetate, zinc acetate, potassium acetate and magnesium acetate. . 3. The method according to claim 1, wherein solid taurine is precipitated from a slurry containing taurine crystals and a metal salt using water as a dispersion medium.
Or the method for producing solid taurine according to 2. 4. The method for producing solid taurine according to claim 3, wherein the precipitation is carried out by mixing the slurry with a water-soluble solvent having a solubility in taurine and a metal salt lower than that of water. 5. The method for producing solid taurine according to claim 3, wherein the precipitation is carried out in a taurine production step, after purification of taurine, and before drying of taurine.