JP3277196B2 - Composition for food material containing calcium and magnesium as main components and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a composition for a food material containing calcium and magnesium as main components and a method for producing the same.

[0002]

2. Description of the Related Art According to the National Nutrition Survey by the Ministry of Health and Welfare, calcium (Ca) is deficient in nutrients and vitamins and minerals.
~ 550 mg intake, 50-100 mg / person /
Days short. Ca is the main component of bone, and if it is deficient, it causes osteoporosis. Ca plays an important physiological action in the body. In order to make up for this Ca deficiency, many foods and Ca supplements to which Ca has been added have been marketed to help improve nutrition.

[0003] However, minerals have an antagonistic action with many other minerals, and if the balance is lost, adverse effects are caused. In the case of Ca, it is considered that the balance with magnesium (Mg) is particularly important. Mg has the function of activating a number of enzymes that control metabolic reactions in the body, but is lost by stress. Although the target intake of Mg is 300 mg / person / day, it is actually 20 mg / person / day.
50-100 mg / person / day deficient with an average intake of 0-250 mg.

When drinking hard water containing a large amount of Mg or Ca, it has been known that the intake ratio of Ca / Mg from food is related to health. Finland has a high Ca / Mg intake ratio, whereas mortality from ischemic heart disease is high.
There is a report that mortality is low in Japan where the Ca / Mg intake ratio is low.

In order to prevent these circulatory diseases, enhance immunity in the body, and counter stress, it is important to take not only Ca but also Mg at the same time.
It is appropriate to balance at a / Mg = 2/1.

[0006] Calcium carbonate, bovine bone calcium, fish bone powder calcium, eggshell, pearl calcium, scallops, crushed shells and the like are known and commercially available as inorganic food materials for the purpose of supplementing calcium. I have. However, they are all based on calcium and do not contain magnesium.

[0007] Magnesium chloride and magnesium sulfate are used as magnesium-containing inorganic food materials, but these magnesium salts have a drawback that they are difficult to handle because they are "garlic" and deliquescent when tasted.

Dolomite [Ca.Mg (CO ₃ ) ₂ ] simultaneously containing calcium and magnesium is tasteless and odorless.
Despite being ideal as a mineral supplement, the history of "people" eaten by people was not common in Japan.

A typical dolomite mineral in Japan is:
It is abundantly produced in the Kuzuu district, Tochigi prefecture, and belongs to the Chichibu Kuro Formation. The typical components are as follows.

[0010]

[Table 1]

The dolomite mineral does not contain any harmful metal elements, indicating that it is highly biosafe. But,
Dolomite mineral is a typical sedimentary rock and contains organic matter. This organic substance undergoes either dehydrogenation (coalification) or hydrogenation (petroleum hydrocarbon) through diagenesis and metamorphism, and ultimately graphite (free carbon) and methane. Exist as. Its abundance varies depending on the production area and mining layer,
It may contain organic substances such as amino acids and low molecular weight hydrocarbons. For this reason, the whiteness is low and gray or grayish white. The color of these rocks is roughly proportional to the free carbon content. 0 with black dolomite.
038%, 0.032% of gray and 0.020% of white contain free carbon. These impurities are presumed to coexist with the clay mineral at the grain boundaries of the dolomite crystal from the origin of the dolomite mineral. When such free carbon and organic substances are contained, problems occur in color, safety, and the like when dolomite is used as a food material.

In general, inorganic food materials derived from minerals have poor texture when the particle size is coarse and low absorbability (bioavailability) of the target mineral component, so that 325 mesh (44 μm) to 400 mesh (37 μm). At present, it is ground to a degree. The finer the powder, the better the bioabsorbability, but the contamination (contamination) resulting from the abrasion of the apparatus and equipment during the pulverization becomes severe, so that the adjustment to the above-mentioned level was the limit. Therefore, the free carbon which exists with the clay mineral in the crystal grain boundary,
It is difficult to remove impurities such as organic substances (proteins, amino acids, etc.) and low-molecular hydrocarbons. To obtain mineral powders for food materials free of these impurities, a method other than grinding and using high-purity minerals is used. Did not.

[0013]

DISCLOSURE OF THE INVENTION The present invention provides a composition for a food material containing calcium and magnesium as a main component, which contains few impurities, has improved whiteness, and has no problem in safety, and a method for producing the same. The purpose is to do.

[0014]

Means for Solving the Problems The composition of the present invention containing calcium and magnesium as a main component is composed of a naturally occurring dolomite [Ca.Mg (CO ₃ ) ₂ ] mineral. , Finely pulverized to an average particle diameter of 3.0 μm or less and a maximum particle diameter of 25 μm or less, or the above mineral is finely pulverized to an average particle diameter of 3.0 μm or less and a maximum particle diameter of 25 μm or less, and In the presence of an oxygen-containing gas
It is characterized by being heat-treated in a temperature range of up to 450 ° C.

Dolomite [Ca.Mg (CO ₃ ) ₂ ] has a molar ratio of calcium (Ca) to magnesium (Mg) of 1/1.
It is a carbonate in which Ca and Mg (at a weight conversion ratio of about 2/1) are uniformly mixed at the atomic level. The thermal decomposition of dolomite is a two-step reaction, in which a heat treatment is performed at 500 to 700 ° C. to perform a decarboxylation reaction of Mg such as Ca · Mg (CO ₃ ) ₂ → CaCO ₃ + MgO + CO ₂ ↑. If the heat treatment temperature is further increased, a decarboxylation reaction of Ca such as CaCO ₃ + MgO → CaO + MgO + CO ₂行 う is performed at 700 to 900 ° C. or higher. Each reaction temperature varies depending on the gas atmosphere, heat treatment time, mineral size, and the like. When the decarboxylation reaction of Mg at 500 to 700 ° C. occurs as in the above reaction, Ca and Mg that have been uniformly mixed at the atomic level in the dolomite crystal are separated.

[0016] The origin of the dolomite mineral has not been established yet, and it has been speculated from the geoscientific point of view that it may have been formed by alteration after carbonate sedimentation. Biological dolomite minerals are aggregates of fossils,
Various organic compounds contained therein undergo a diagenesis and a metamorphosis, a part of which undergoes a condensation reaction, is finally graphitized via a kerogen (oil base), and the other part is decomposed. After a simpler carbon compound, CH ₄
Etc. are low molecular hydrocarbons. These substances are estimated from the crystal formation process of carbonate, aluminum, iron,
It exists in the crystal grain boundaries together with a clay mineral composed of silicon or the like. Dolomite minerals vary depending on the place of production and mining layer, but have a coarse crystal grain size of 50-100 μm.
m, since it is 10-30 μm in a microcrystalline state, ore is finely pulverized to a crystal particle size or less, and contains methane by separating these impurities present at grain boundaries and crystal particles of carbonate minerals. Low molecular hydrocarbon gases, proteins, substances derived from organic substances such as amino acids, free carbon, and the like are easily removed.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION The average particle diameter of the pulverized particles is 3.0.
μm or less, a maximum particle diameter of 25 μm or less, preferably an average particle diameter of 2.0 μm or less, and a maximum particle diameter of 10 μm or less.
When the average particle diameter exceeds 3.0 μm and the maximum particle diameter exceeds 25 μm, the area where the grain boundaries are exposed on the surface of the pulverized particles decreases. As a result, the amount of volatilization of low-molecular hydrocarbons, free carbon and the like existing at the grain boundaries is reduced.

As the pulverizer, it is preferable to use a hard mill having less contamination, such as a hard mill (super hybrid mill) manufactured by Ishikawajima-Harima Heavy Industries and a CVX mill manufactured by Kurimoto Iron Works. Since these are mainly crushed by friction between dolomite minerals, a fine powder with little contamination derived from the crusher can be obtained. The finely ground dolomite having an average particle diameter of 3.0 μm or less and a maximum particle diameter of 25 μm or less is subjected to separation / rupture at the dolomite crystal particle interface at the time of the fine pulverization, and then the crystal particles themselves are pulverized. The low-molecular hydrocarbon gas such as methane existing in the grain boundaries is partially released and volatilized by the exposure of the grain boundaries. Further, the temperature in the pulverizer increases due to friction between the minerals during the pulverization process, so that the release of volatile organic substances is promoted. The smaller the particle size after grinding and the higher the product temperature, the more the amount of low-molecular hydrocarbons and volatile organic substances to be removed increases. Is also possible. When other pulverizers and pulverization methods are used, contamination due to abrasion of devices and equipment during fine pulverization, that is, contamination of metals and heavy metal elements that are harmful to living bodies, is not preferred.

In order to completely remove volatile organic substances and free carbon from the pulverized dolomite, a temperature range of 300 to 450 ° C., preferably 400 to 450 ° C., in the presence of an oxygen-containing gas such as air. It is better to heat treat within the range. Free carbon coexisting with the clay mineral at the dolomite grain boundaries is burned by oxygen and released as carbon dioxide. At 300 ° C. or lower, the oxidation reactivity is low. Also,
When the heat treatment is performed at 500 ° C. or more, the decomposition reaction of inorganic carbon is accelerated and can be removed in a short time, but it is not preferable because part of dolomite is decomposed and MgO is generated.
In addition, below 300 ° C where decomposition and removal of free carbon is impossible,
For example, thermal decomposition and removal of methane, proteins, amino acids and the like are possible even by heating at 100 to 300 ° C. If the raw ore is of good quality, just pulverize it or pulverize it with 100 ~
Heat treatment in the temperature range of 300 ° C, impurities in raw ore,
Especially when inorganic carbon is large, pulverization and 400-450
Different embodiments can be selected depending on the quality of the raw ore, such as performing the heat treatment in a temperature range of ° C.

Coarse pulverized product, for example, an average particle size of 50 μm
Even in the case of particles having a particle size of about the same, it is possible to decompose and remove inorganic carbon by heating at a high temperature of, for example, about 800 to 1000 ° C., but this is not preferable because a dolomite decomposition reaction occurs as described above.

Heat treatment makes it possible to sterilize pathogenic fungi such as various viable bacteria, coliforms, molds and yeasts at the same time.

Use of the obtained composition for food material is as follows:
It can be used as a food additive such as bread, biscuit, rice, buckwheat, flour, etc .;

Hereinafter, specific examples of the composition of the present invention and the effects thereof will be described with reference to Examples, but the present invention is not limited to the following Examples.

[0024]

Example 1 Dolomite of the components shown in Table 1 from Aizawa, Kuzuu-cho, Tochigi Prefecture, was subjected to a jaw crusher to obtain a particle diameter of 5 mm.
It was ground to the following. A portion of 1 mm or less of the pulverized dolomite is removed, impurities having a particle diameter of 5 to 1 mm are removed by washing with water, and fine powder is obtained using a hard mill SH-150 manufactured by Ishikawajima-Harima Heavy Industries. Dolomite was obtained. The obtained fine powder dolomite was subjected to vacuum drying in a desiccator for 2 days to completely remove attached moisture.

The particle size distribution (average particle size and maximum particle size) of the pulverized product is measured by a particle size distribution analyzer LA-9 manufactured by HORIBA.
The measurement was performed with ethanol as a dispersion medium using No. 20. Table 2 shows the results
As shown in the figure, the average particle diameter is 1.24 μm, and the maximum particle diameter is 1.
It was 5.6 μm. The analysis of the contamination component derived from the pulverizer of the finely pulverized dolomite was measured using an ICP emission spectrometer P-4000 manufactured by Hitachi. Table 3 shows the results
Shown in

[0026]

[Table 2]

[0027]

[Table 3]

Approximately 100 g of the finely ground dolomite of Example 1
The sample was collected, 3N hydrochloric acid was added to dissolve the carbonate, filtered through a glass filter, and washed with water. The obtained residue was dried under vacuum for 1 day to obtain a hydrochloric acid-insoluble residue. Table 4 shows the amount of the residue.

[0029]

[Table 4]

[0030]

[Table 5]

100 g of the pulverized dolomite of Example 1 was collected, and the temperature was set to 100 ° C., 200 ° C., 300 ° C. in an electric furnace.
400 ° C, 500 ° C, 600 ° C, 700 ° C and 1000
Heat treatment was performed at 2 ° C. for 2 hours in the presence of an oxygen-containing gas (air). The crystal phase of each heat-treated product was identified using a powder X-ray diffractometer MXP3 AHF manufactured by Mac Science. The results are shown in FIG.

The thermal weight loss after heat treatment at 100-1000 ° C. is shown in Table 5 and is also shown in FIG.
FIG. 5 shows an enlarged thermogravimetric loss at 0 to 400 ° C.

The whiteness of the finely ground dolomite and each heat-treated product was measured using a Kett Electric Laboratory (Kett Elect).
ric Laboratry ) and measured three times using a whiteness meter C-100, and the average value was determined. Table 6 shows the results.

[0034]

[Table 6]

[0035]

Example 2 An experiment was performed in the same manner as in Example 1 except that a CVX mill manufactured by Kurimoto Iron Works was used as a pulverizer. As shown in Table 2, the result of the particle size distribution measurement was an average particle diameter of 2.10 μm and a maximum particle diameter of 22.8 μm. Table 3 shows the analysis results of the contamination components derived from the pulverizer of the finely ground dolomite, Table 4 shows the amount of the hydrochloric acid-insoluble residue, and FIGS.
Table 5 shows the thermal weight loss after heat treatment at 00 to 1000 ° C.
4 and also shown in FIG.
FIG. Table 6 shows the whiteness measurement results of the finely ground dolomite and each heat-treated product.
Shown in

[0036]

[Comparative Example 1] Hosokawa Micron impact crusher
The experiment was performed in the same manner as in Example 1 except that the ACM pulverizer was used. The results of the particle size distribution measurement are shown in Table 2,
The average particle size was 9.01 μm, and the maximum particle size was 44.0 μm. Table 3 shows the analysis results of contamination components derived from the pulverizer of the finely pulverized dolomite, Table 4 shows the amount of hydrochloric acid-insoluble residue, and FIG. 3 shows the identification result of the crystal phase. Table 3 shows the thermogravimetric loss after heat treatment at 100 to 1000 ° C. 5, and also shown in FIG. 4, and the thermal weight loss at 100 to 400 ° C. is enlarged and shown in FIG. Table 6 shows the results of whiteness measurement of the finely ground dolomite and each heat-treated product.

As a result of analyzing the contamination components derived from the pulverizer of the finely pulverized dolomite, the impact pulverization was performed.
In the case of Comparative Example 1 using an impact crusher such as an ACM pulverizer , the content of Fe increased, but the increase of other components was negligible. In the case where the crusher mainly using the crushing by the friction between the minerals is used in Examples 1 and 2,
The increase in Fe content was small.

The hydrochloric acid-insoluble residue is considered to be the content of clay minerals and organic substances such as free carbon, amino acids and proteins. As can be seen from Table 4, the amount of the hydrochloric acid-insoluble residue decreases as the particle size of the pulverized particles decreases. This is because the grain boundaries are exposed by finely pulverizing the particles to a crystal grain size or less, and impurities such as low-volatile organic substances present there are decomposed and released by frictional heat between the minerals at the time of pulverization. It can be seen that impurities were also removed during the pulverization process.

From the results of the identification of the crystal phase in FIG.
In the pulverized dolomite, there is generation of MgO due to decomposition of dolomite at a heat treatment of 500 ° C., dolomite is completely decomposed at a heat treatment of 600 ° C., and generation of CaO by decomposition of CaCO ₃ is observed at 700 ° C. Also, from the results of identification of the crystal phases of the dolomite powders obtained in Example 2 and Comparative Example 1 in FIGS. 2 and 3, MgO was generated by decomposition of dolomite by heat treatment at 600 ° C., and complete dolomite was obtained at 700 ° C. It can be confirmed that it has been decomposed into. Decomposition of dolomite as milled particle size is small, it can be seen that proceeds easily. 10
In the heat treatment at 00 ° C., it can be confirmed that carbonate is decomposed and CaO and MgO are generated in both the example and the comparative example.

The thermogravimetric loss in Table 5, FIG. 4 and FIG.
It is thought to be due to the total amount of free carbon, amino acids, proteins, and low molecular hydrocarbons, and the release of carbon dioxide from the decarboxylation of carbonate. When the thermogravimetric loss at 100 ° C. is observed, the weight is reduced due to the release of low molecular weight hydrocarbons in both the examples and comparative examples. In Examples, weight loss due to the decomposition of free carbon and organic substances is observed in the heat treatment at 100 to 300 ° C.
In addition, a rapid weight loss due to the progress of decomposition of free carbon and organic substances is observed in the heat treatment at 300 to 400 ° C. Since the weight reduction rate increases as the pulverized particle size decreases, 100 to 40 as the particle size decreases.
At a relatively low temperature of 0 ° C., removal of impurities is easy.
On the other hand, in Comparative Example 1, it can be seen that the weight loss in this temperature range is small, and the decomposition of free carbon and organic substances is small. With the particle diameter of Comparative Example 1, it is difficult to decompose and remove impurities in a temperature range of about 100 to 400 ° C.

In Example 1, although a small amount of MgO was observed in the heat treatment at 500 ° C. for 2 hours, decomposition of organic substances and free carbon and release of carbon dioxide due to generation of MgO were accompanied. . In the second embodiment, 600
Generation of MgO was observed by heat treatment at 2 ° C. for 2 hours, and it was found that decomposition of organic substances and free carbon was accompanied by release of carbon dioxide due to generation of MgO. In Comparative Example 1,
As in Example 2, generation of MgO was observed by heat treatment at 600 ° C. for 2 hours, and it was found that the release of carbon dioxide was accompanied by the generation of MgO. It is considered that the decomposition of carbon has not progressed much. In the heat treatment at 1000 ° C., both Examples and Comparative Examples showed the same weight loss, and it is considered that decomposition of carbonate, decomposition of organic substances and free carbon was completely performed.

The whiteness depends on the free carbon content of the mineral as described above. Therefore, a decrease in the content of free carbon due to an increase in whiteness can be estimated. Table 6 shows the results of whiteness measurement of each of the pulverized product and the heat-treated product. In Example 1, the whiteness was gradually improved from 200 ° C., and the whiteness was significantly improved at 400 ° C. even though the carbonate was not decomposed. Also in Example 2, an increase in whiteness was observed in the heat-treated product at 400 ° C. or higher. This is thought to be due to the decomposition and removal of free carbon, and this result is in good agreement with the result of the thermogravimetric reduction. On the other hand, in Comparative Example 1, the degree of whiteness slightly increased in the heat-treated product at 500 ° C., and it was difficult to remove free carbon by heat treatment at a low temperature. The heat-treated product at 1000 ° C. converged to the same value in both the examples and comparative examples, and low-molecular carbonization containing methane contaminated together with clay minerals at the grain boundaries of carbonate minerals mainly composed of dolomite. The decarboxylation reaction between organic substances such as hydrogen gas, proteins, amino acids and the like, free carbon and carbonate minerals is all completed, and the thermogravimetric loss converges to almost the same value.

[0043]

EFFECT OF THE INVENTION A composition for a food material containing calcium and magnesium as a main component, containing few impurities, improving whiteness, and having no problem in safety while maintaining the original dolomite carbonate mineral composition. Is obtained.

[Brief description of the drawings]

1 is an X-ray diffraction pattern of a heat-treated product of the pulverized dolomite of Example 1. FIG.

FIG. 2 is an X-ray diffraction pattern of a heat-treated product of the pulverized dolomite of Example 2.

FIG. 3 is an X-ray diffraction pattern of a heat-treated product of finely ground dolomite of Comparative Example 1.

FIG. 4: Thermal weight loss of finely ground dolomite (100 to 10)
(00 ° C.).

FIG. 5: Thermal weight loss of finely ground dolomite (100 to 40)
0 ° C.).

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-62-100261 (JP, A) JP-A-5-155775 (JP, A) JP-A-11-89541 (JP, A) (58) Field (Int.Cl. ⁷ , DB name) A23L 1/304 C04B 2/00 JICST file (JOIS) JAFIC file (JOIS)

Claims (4)

(57) [Claims] [Claim 1] A dolomite [Ca.Mg (C
O _{3) 2]} a mineral consisting mainly average particle diameter 3.0μm or less, food material composition composed mainly of calcium and magnesium, characterized in that is obtained by finely pulverizing the maximum particle size of 25μm . 2. Dolomite produced in nature [Ca.Mg (C
O ₃ ) ₂ ] as a main component is finely pulverized to an average particle diameter of 3.0 μm or less and a maximum particle diameter of 25 μm or less, and the finely pulverized product is subjected to a temperature range of 100 to 450 ° C. in the presence of an oxygen-containing gas. A composition for food material containing calcium and magnesium as main components, which is heat-treated. 3. A dolomite [Ca.Mg (C
A method for producing a composition for a food material containing calcium and magnesium as a main component, comprising pulverizing a mineral mainly containing O ₃ ) ₂ ] to an average particle size of 3.0 μm or less and a maximum particle size of 25 μm or less. . 4. Dolomite [Ca.Mg (C
O ₃ ) ₂ ] as a main component is finely pulverized to an average particle diameter of 3.0 μm or less and a maximum particle diameter of 25 μm or less, and the finely pulverized product is subjected to a temperature range of 100 to 450 ° C. in the presence of an oxygen-containing gas. A method for producing a composition for a food material containing calcium and magnesium as main components, characterized by heat-treating the composition.