KR102063807B1 - Preparation method of the high activated calcium by sonochemistry - Google Patents

Abstract

One object of the present invention is to provide a method for preparing an organic acid calcium salt (calcium citrate, calcium lactate) which has a high degree of ionization and is easily dissolved in water. Pre-treatment by mixing at least one selected from the group consisting of calcium carbonate and calcium oxide in a solvent to achieve the above object by ultrasonic irradiation; Mixing the organic acid with the solution of the step to form a mixture; And irradiating ultrasonic waves to the mixture formed by mixing the organic acid. It provides a method for producing an organic acid calcium salt comprising a. According to this, there exists an effect which can provide the organic acid calcium salt which has high ionization degree and can dissolve several times more than the solubility which each compound has. In addition, the manufacturing method of the organic acid calcium salt has an excellent effect that the process and equipment can be prepared in less than 10 minutes.

Description

Preparation method of high ionized calcium using ultrasonic synthesis {PREPARATION METHOD OF THE HIGH ACTIVATED CALCIUM BY SONOCHEMISTRY}

The present invention relates to a method for producing an organic acid calcium salt having a high degree of ionization, and more particularly, by increasing the ionization concentration of calcium through a pretreatment step to improve the reactivity by reducing the particle size of the calcium carbonate as a starting material to nano size The present invention relates to the preparation of organic acid calcium salts having a high degree of ionization which can be dissolved in water to better absorb calcium and significantly shorten manufacturing cost and time.

Calcium is one of the minerals essential for the composition and activity of life. Animals are not only necessary for the composition and production of bone and blood, but are also responsible for the communication of the heart and brain. Calcium is an important factor in plant growth and root development. Calcium is an element that plays an important role in maintaining the life and activity of animals and plants, and is used for various purposes such as health functional foods and food additives. In particular, applications and research as a variety of functional cosmetics using calcium ions are being actively made.

In order to be used for various applications, the dissolution rate of calcium must be fast and its ionization degree must be high. Currently, various forms of calcium compounds are used, such as calcium carbonate, calcium citrate, calcium gluconate, calcium lactate, calcium phosphate, calcium hydroxide, calcium sulfate, and the like. Among them, calcium citrate and calcium lactate have a high degree of ionization and have a great interest in the production method.

For example, Korean Patent No. 10-1683150 discloses a method for producing calcium citrate, specifically, citric acid and calcium carbonate are dissolved in water to make a mixture, and ethanol is added to mature for 48 hours to prepare calcium citrate. A method of doing this is disclosed. However, there is a problem that needs to be aged for a long time.

Accordingly, there is a demand for a simple process and a technique for manufacturing in a short time with high ionization.

Therefore, the inventors of the present invention are in the process of overcoming the problems of the conventional method for preparing the organic acid calcium salt, when preparing the organic acid calcium salt using ultrasonic waves by reducing the size of the starting material through the ultrasonic pretreatment to reduce the specific surface area As the reactivity becomes wider, the synthesis time was much faster than about 10 minutes compared to the conventional manufacturing method, and the organic acid calcium salt prepared from the ionization degree was found to show a much higher value than the conventional manufacturing method.

Republic of Korea Patent Publication No. 10-2014-0036736 Republic of Korea Patent No. 10-1683150

One object of the present invention is to provide a method for preparing an organic acid calcium salt having a high degree of ionization.

In order to achieve the above object,

One aspect of the present invention comprises the steps of mixing at least one selected from the group consisting of calcium carbonate and calcium oxide in a solvent and pre-treatment by ultrasonic irradiation; Mixing the organic acid with the solution formed in the step to form a mixture; And irradiating ultrasonic waves to the mixture formed by mixing the organic acid. It provides an organic acid calcium salt manufacturing method comprising a.

According to an aspect of the present invention, it is possible to provide an organic acid calcium salt having high ionization degree and very easily dissolved in water, compared to the organic acid calcium salt prepared by the conventional manufacturing method, wherein the manufacturing time is very fast time of about 10 minutes There is an effect that can be synthesized.

Figure 1 is a schematic diagram of the manufacturing process of the organic acid calcium salt prepared by the ultrasonic synthesis method,
2 is a result of distribution of particle size of calcium carbonate before and after ultrasonic pretreatment,
3 is an X-ray diffraction graph of calcium citrate and calcium lactate prepared according to an embodiment of the present invention,
Figure 4 shows the thermogravimetric analysis of calcium citrate and calcium lactate prepared according to an embodiment of the present invention.

A method for producing an organic acid calcium salt having a high degree of ionization. Hereinafter, the present invention will be described in detail.

One aspect of the present invention provides a method for producing calcium citrate or calcium lactate in a short time using ultrasonic waves in the preparation of organic acid calcium salt having a high degree of ionization. Specifically, the step of pre-treatment by mixing at least one selected from the group consisting of calcium carbonate and calcium oxide in a solvent by ultrasonic irradiation; Mixing the organic acid with the solution of the step to form a mixture; And irradiating ultrasonic waves to the mixture formed by mixing the organic acids. It provides a method for producing an organic acid calcium salt comprising a.

The organic acid may be citric acid or lactic acid.
The citric acid may be one or more selected from the group consisting of hydrous citric acid and anhydrous citric acid.
The lactic acid may be at least one selected from the group consisting of D-lactic acid and L-lactic acid.

delete

In the method for preparing calcium citrate according to an embodiment of the present invention, after the pretreatment of calcium carbonate as a starting material, the particle size is reduced, citric acid anhydride is mixed, a mixture is made, and ultrasonic irradiation is performed.

1 is a schematic diagram of a method for producing calcium citrate according to an embodiment of the present invention.

Mixing at least one selected from the group consisting of calcium carbonate and calcium oxide in a solvent, and performing pretreatment by irradiating with ultrasonic waves;

Preparing a mixed solution by dissolving anhydrous citric acid in the solution formed in the step; And

Calcium citrate can be prepared by the method comprising; irradiating ultrasonic waves to the mixed solution prepared by dissolving the anhydrous citric acid.

It is preferable to use water and ethanol as the solvent in the pretreatment step. When only water is used without ethanol, organic acid calcium salt cannot be precipitated as the reactant is dissolved, and water and ethanol must be mixed. Simultaneously with the reaction, calcium organic acid precipitates.

In addition, the ultrasonic wave of the pretreatment step is preferably irradiated with an intensity of 1 to 100kHz.

The ultrasonic intensity of the pretreatment step may be irradiated within a time range of 1 minute to 60 minutes at an intensity of 1 to 100 kHz, and specifically, may be irradiated within a time range of 1 minute to 10 minutes at an intensity of 20 kHz, and more. Specifically, it can be irradiated within a time range of 3 minutes-5 minutes at an intensity of 20 kHz.

If the ultrasonic wave is irradiated with an intensity of less than 1 kHz, the ultrasonic irradiation is not made enough, calcium carbonate of the desired size is not produced, when irradiated with an intensity of more than 100 kHz, calcium carbonate due to heat by ultrasonic irradiation This instantaneous dissolution only has the problem of forming calcium carbonate of the original size again at room temperature.

In addition, the ultrasonic wave of the step of irradiating the ultrasonic wave to the mixed solution prepared by dissolving the citric anhydride is preferably irradiated with 2 to 200kHz intensity.

Ultrasonic intensity of the step of irradiating the ultrasonic wave to the mixed solution prepared by dissolving the citric anhydride can be irradiated within the time range of 5 minutes-12 hours at 2 to 200 kHz intensity, specifically 5 minutes-at 20 kHz intensity- It may be irradiated within a time range of 1 hour, and more specifically, may be irradiated within a time range of 10 minutes to 20 minutes with an intensity of 20 kHz.

If the ultrasonic wave is irradiated with an intensity of less than 2 kHz, there is a problem that the ultrasonic irradiation is not made sufficiently and calcium citrate of the desired form is not produced, and when irradiated with an intensity of more than 200 kHz, calcium citrate due to heat by ultrasonic irradiation This may cause a problem that aggregates to form an aggregate.

Furthermore, after performing the step of irradiating the ultrasonic wave to the mixed solution prepared by dissolving the citric anhydride may be further performed to wash and dry the calcium citrate.

Hereinafter, the manufacturing method will be described in detail step by step.

The washing and drying step is a step of washing and drying the calcium citrate in the reaction solution after performing the step of irradiating the ultrasonic wave to the mixed solution prepared by dissolving the citric anhydride.

Specifically, after performing the step of irradiating the ultrasonic wave to the mixed solution prepared by dissolving the anhydrous citric acid, the calcium citrate in the reaction solution can be separated by centrifugation, washed and centrifuged three times using ethanol By performing the above, recovery of the powder is possible.

Drying temperature of the washing and drying step is not particularly limited, but may be carried out at a temperature of 30 to 150 ℃, specifically may be carried out at a temperature of 50 to 120 ℃, more specifically of 50 to 100 ℃ It may be carried out at a temperature, more specifically at a temperature of 70 ℃.

The drying time of the washing and drying step is not particularly limited, but may be performed for 1 to 20 hours, specifically for 3 to 18 hours, more specifically for 4 to 10 hours More specifically, it may be performed for 5 hours.

In addition, Figure 1 is a schematic diagram of a method for producing calcium lactate according to an embodiment of the present invention.

Ultrasonic pretreatment by mixing at least one selected from the group consisting of calcium carbonate and calcium oxide in a solvent;

Preparing a mixed solution by dissolving lactic acid in a solution of the pretreatment step; And

Calcium lactate may be prepared by the method comprising; irradiating ultrasonic waves to the mixed solution prepared by dissolving the lactic acid.

Detailed preparation methods are the same as those mentioned for the preparation of calcium citrate.

Hereinafter, the present invention will be described in more detail with reference to Examples and Experimental Examples. However, the following Examples and Experimental Examples are only examples for the description of the present invention, and the scope of the present invention is not limited to the following Examples and Experimental Examples.

<Example 1>

Of calcium citrate  Produce

5 mmol of calcium carbonate was placed in a container containing 5 mL distilled water and 10 mL ethanol, and pretreated by ultrasonic wave at 20 kHz (50%) intensity for 5 minutes using an ultrasonic irradiator. 23.4 mmol of citric acid was dissolved in the pretreated solution. Ultrasound of 20 kHz (50%) intensity was irradiated for 10 minutes.

As the ultrasonic irradiation in the pretreatment process, it was observed that the particle size of calcium carbonate, which was 10 μm, was reduced to a size of 100-200 nm, which means that the specific surface area of calcium carbonate becomes larger and the reactivity becomes very high.

In addition, as the lactic acid was dissolved in the pretreated calcium carbonate solution and irradiated with ultrasound, it was observed that the initially transparent solution became cloudy over time, indicating that calcium citrate was successfully synthesized.

An excess of ethanol was added to the mixed solution prepared with calcium citrate, the calcium citrate and the supernatant were separated by centrifugation, and the supernatant was removed at least three times. The precipitate was repeated at 70 ° C. for 5 hours. It dried and the calcium citrate powder was obtained.

<Example 2>

Calcium lactate  Produce

5 mmol of calcium carbonate was placed in a vessel containing 5 mL distilled water and 10 mL ethanol, and pretreated by ultrasonic wave at 20 kHz (50%) intensity for 5 minutes using an ultrasonic irradiator. Then, 10 mmol of lactic acid was added to the pretreated solution and stirred. While preparing a mixed solution, the ultrasonic wave was irradiated with ultrasonic waves of 20 kHz (50%) intensity for 10 minutes.

As the ultrasonic irradiation in the pretreatment process, it was observed that the particle size of calcium carbonate, which was 10 μm, was reduced to a size of 100-200 nm, which means that the specific surface area of calcium carbonate becomes larger and the reactivity becomes very high.

In addition, as the lactic acid was dissolved in the pretreated calcium carbonate solution and irradiated with ultrasonic waves, it was observed that the initially transparent solution became cloudy over time, indicating that calcium lactate was successfully synthesized.

The excess ethanol was added to the mixed solution prepared with calcium lactate, the calcium lactate and the supernatant were separated by centrifugation, and the supernatant was removed at least three times. The precipitate was repeated at 70 ° C. for 5 hours. It dried and the calcium lactate powder was obtained.

Comparative Example 1

In the method for preparing calcium lactate, except that the pretreatment step was omitted, the same procedure as in the preparation method of calcium lactate of Example 2 was carried out. Specifically, 5 mmol of calcium carbonate was diluted with 5 mL of distilled water and 10 mL. Into a container containing ethanol, 10 mmol of lactic acid was added to prepare a mixed solution while stirring, and then ultrasonic waves of 20 kHz (50%) intensity were irradiated for 10 minutes using an ultrasonic irradiator.

Experimental Example 1

Particle Size Analysis Before and After Ultrasonic Pretreatment of Calcium Carbonate

When the pretreatment to the starting material calcium carbonate in the above embodiment, Horiba LA-960 model was used to analyze the particle size before and after the pretreatment, the results are shown in FIG.

As shown in Fig. 2, when preparing the organic acid calcium salt of the example, calcium carbonate having a very small size is produced as compared with the case where the ultrasonic pretreatment is not performed.

Through this, it was confirmed that the ultrasonic pretreatment of the above example requires that the particle size of the calcium carbonate, which is the starting material of the organic acid calcium salt, becomes very small, thereby increasing the reactivity and decreasing the reaction time as the specific surface area increases.

Experimental Example 2

Of calcium citrate  X-ray diffraction analysis

X-ray diffraction analysis was performed to analyze the components of the calcium citrate prepared in Example. Rigaku's D / MAX2200V / PC model was used, and the results are shown in FIG. 3.

As shown in Fig. 3, an XRD pattern of calcium citrate significantly different from calcium carbonate which is the starting material of the example is observed.

Through this, it was confirmed that the calcium citrate prepared in the above example was produced crystalline.

Experimental Example 3

Calcium citrate Calcium lactate Heat weight  analysis

It was observed using a thermogravimetric analyzer to analyze the calcium citrate and calcium lactate prepared in the above examples. TA Instrument's TGA Q5000 model was used, and the results are shown in FIG. 4.

As shown in Figure 4, the pyrolysis of the calcium citrate prepared in Example occurs step by step, the desorption step of physically adsorbed water, the desorption step of chemically adsorbed water, calcium carbonate formation step by the decomposition of calcium citrate, and CO ₂ production Calcium oxide is formed.

The pyrolysis of calcium lactate is the same as the pyrolysis process mentioned above, in addition to the decomposition of calcium lactate.

Experimental Example 4

Calcium citrate Calcium lactate  Ion concentration analysis

The content was measured using an ion concentration meter to analyze calcium citrate and calcium lactate prepared in the above examples. Thermo Scientific's iCAP 6500 duo Inductively Coupled Plasma-Emission Spectrometer model was used and the results are shown in Table 1 below.

Ca content (wt%) Na content (wt%) Mg content (wt%) Commercial Pearl Calcium Lactate 13.2 0.0034 0.0166 Calcium citrate
(Example 1) 12.6 - - Calcium lactate
(Example 2) 16 - -

As shown in Table 1, the calcium citrate and calcium lactate prepared in Example showed a similar or more calcium content than commercially available calcium lactate, it was confirmed that the purity is high almost no impurities.

Experimental Example 5

Calcium citrate Calcium lactate  Solubility Analysis

In order to determine the solubility of calcium citrate and calcium lactate prepared in the above example, the characteristics were measured using an atomic absorption spectrophotometer. Metrohm's MIC-7 Advanced Ion Chromatograph model was used, and the results are shown in Table 2 below.

Ca ^{2 +} concentrations (mg / L) Commercially Soluble Calcium Carbonate 11.363 Commercial Calcium Lactate 90.719 Calcium lactate
(Comparative Example 1) 95.014 Calcium citrate
(Example 1) 111.330 Calcium lactate
(Example 2) 104.836

As shown in Table 2, in the case of calcium citrate and calcium lactate prepared in the embodiment of the present invention, the solubility of calcium compared to commercially available water-soluble calcium carbonate, commercial calcium lactate, and calcium lactate that was not pretreated (Comparative Example 1) It is much higher.

Claims (12)

Pretreatment by mixing at least one selected from the group consisting of calcium carbonate and calcium oxide with a solvent and performing ultrasonic irradiation;
Mixing the organic acid with the solution of the step to form a mixture; And
Irradiating ultrasonic waves to the mixture formed by mixing the organic acids;
Method for producing an organic acid calcium salt comprising a.
The method of claim 1,
The organic acid is a method for producing an organic acid calcium salt, characterized in that citric acid or lactic acid.
The method of claim 2,
The citric acid is a method for producing an organic acid calcium salt, characterized in that at least one selected from the group consisting of hydrous citric acid and anhydrous citric acid.
The method of claim 2,
The lactic acid is a method for producing an organic acid calcium salt, characterized in that at least one selected from the group consisting of D- lactic acid and L- lactic acid.
The method of claim 1,
Ultrasonic wave of the pretreatment step is a method for producing an organic acid calcium salt, characterized in that irradiated for 1 minute to 10 minutes at an intensity of 1 to 100 kHz.
The method of claim 1,
Ultrasonic waves irradiated to the mixture formed by mixing the organic acid is irradiated for 5 to 20 minutes at an intensity of 2 to 200 kHz.
The method of claim 1,
The organic acid calcium salt is a method for producing an organic acid calcium salt, characterized in that the calcium citrate or calcium lactate.
The method of claim 1,
After performing the step of irradiating the ultrasonic wave to the mixture formed by mixing the organic acid, the method for producing an organic acid calcium salt, characterized in that further performing the step of washing and drying the calcium compound.
The method of claim 8,
The washing step is to separate the calcium compound and the supernatant by centrifugation, and then the method of producing an organic acid calcium salt, characterized in that to remove the supernatant.
The method of claim 9, wherein the washing step is performed 3 to 10 times.
The method of claim 8,
The drying step is a method for producing an organic acid calcium salt that is carried out for 1 to 20 hours at a temperature of 30 to 150 ℃.
The method of claim 1,
The solvent is a method for producing an organic acid calcium salt, characterized in that water and ethanol.

Images