WO2023163369A1 - Method for preparing nano calcium citrate - Google Patents

Abstract

The present invention relates to a method for preparing nano calcium citrate and, specifically, to a method for preparing nano calcium citrate, comprising the steps of: dissolving citric acid in a solvent of ethanol and water (step 1); and mixing calcium carbonate with the solution formed in step 1 and irradiating ultrasonic waves so as to prepare nano calcium citrate (step 2).

Description

Manufacturing method of nano calcium citrate

The present invention relates to a method for preparing nano calcium citrate.

Calcium is one of the essential minerals for the composition and activities of various organisms. In the case of animals, it is not only a component necessary for the composition and production of bones and blood, but also plays a role in transmitting information to the heart or brain. In plants, calcium is an important element for meristem growth and root development. Calcium is an element that plays an important role in maintaining the life activity of animals and plants, and is used for various purposes such as health functional foods and food additives. In particular, active research and application of calcium ions as raw materials for various food additives and health functional foods are currently being conducted.

In order to be suitably used for various purposes, the dissolution rate of calcium must be fast and its ionization degree must be high. Currently, various types of calcium compounds are used, such as calcium carbonate, calcium citrate, calcium gluconate, calcium lactate, calcium phosphate, calcium hydroxide, and calcium sulfate. Among them, calcium citrate is commonly known as tricalcium citrate (TCC), and has a calcium content of 21% or more and is widely used in food additives and health functional foods at an affordable price, so the manufacturing method is of great interest. there is. In addition, tricalcium citrate (TCC) has a solubility as low as 0.85 g/L at 20° C., which limits its use. Research is being actively conducted to supplement the problem of low solubility.

In this regard, Korean Patent Registration No. 10-2063807 discloses a method for producing high ionized calcium using an ultrasonic synthesis method, specifically mixing at least one selected from the group consisting of calcium carbonate and calcium oxide in a solvent and irradiating with ultrasonic waves. pre-processing; forming a mixture by mixing an organic acid with the solution of the above step; A method for increasing the solubility of an organic acid calcium salt has been disclosed as a method for preparing an organic acid calcium salt comprising: and irradiating ultrasonic waves to a mixture formed by mixing the organic acid.

In order to prepare calcium citrate having a higher solubility, the present inventors prepared calcium citrate through calcium carbonate and citric acid using ultrasonic waves, adding calcium carbonate to a solution in which citric acid was dissolved and simultaneously irradiating ultrasonic waves to obtain significantly higher solubility. And it was confirmed that nano-sized calcium citrate having a degree of dispersion could be prepared, and the present invention was completed.

The purpose of one aspect is

It is to provide a method for producing nano calcium citrate.

In order to achieve the above purpose,

On one side,

dissolving citric acid in solvents of ethanol and water (step 1); and

A method for producing nano-calcium citrate is provided, comprising: mixing calcium carbonate with the solution formed in step 1 and irradiating ultrasonic waves to prepare nano-calcium citrate (step 2).

Step 2 is preferably performed by irradiating ultrasonic waves while mixing calcium carbonate with the solution formed in step 1.

In addition, in the step 2, the ultrasound may be irradiated with an intensity of 2 kHz to 200 kHz.

In addition, in step 2, the ultrasound may be irradiated for 5 to 20 minutes.

In addition, the solvent includes 0.1 to 3 times the weight of ethanol as water, nano calcium citrate manufacturing method.

In addition, the mixing in step 2 may be mixing citric acid in a molar ratio of 0.8 to 5 with respect to calcium carbonate.

In addition, step 1 may be a step of dissolving citric acid by mixing it with a solvent of ethanol and water and irradiating ultrasonic waves.

At this time, in step 1, the ultrasonic wave may be irradiated with an intensity of preferably 1 kHz to 100 kHz.

In addition, in step 1, ultrasonic waves may be irradiated for 1 to 10 minutes.

The method for preparing nano calcium citrate prepares nano calcium citrate having an average particle size of 50 mn to 500 nm.

The nano calcium citrate manufacturing method

It may further include a step of washing and drying the nano calcium citrate prepared in step 2 (step 3).

At this time, the washing may be performed by centrifugation or filtration.

In addition, the drying may be performed at a temperature of 30 ℃ to 150 ℃.

The calcium carbonate may be shell-derived calcium carbonate.

Also, the citric acid may be hydrous citric acid or anhydrous citric acid.

In addition, the method for producing nano-calcium citrate produces tricalcium citrate (Ca ₃ (C ₆ H ₅ O ₇ ) ₂ ).

The method for preparing nano-calcium citrate according to one aspect has an effect of easily preparing nano-calcium citrate having high solubility and dispersibility at low cost and within a short time.

1 is a schematic diagram of a manufacturing process for a method for manufacturing nano-calcium citrate according to an aspect;

Figure 2 is a graph showing the particle size distribution of calcium citrate prepared according to a comparative example,

Figure 3 is a graph showing the particle size distribution of calcium citrate prepared according to the embodiment,

Figure 4 is a photograph comparing the solubility of calcium citrate prepared according to one embodiment and a comparative example.

Hereinafter, preferred embodiments of the present invention will be described with reference to the accompanying drawings. However, embodiments of the present invention may be modified in various forms, and the scope of the present invention is not limited to the embodiments described below.

On one side,

dissolving citric acid in solvents of ethanol and water (step 1); and

A method for producing nano-calcium citrate is provided, comprising: mixing calcium carbonate with the solution formed in step 1 and irradiating ultrasonic waves to prepare nano-calcium citrate (step 2).

One aspect relates to a method for producing nano calcium citrate having high solubility and dispersibility.

Hereinafter, a method for manufacturing nano calcium citrate according to an embodiment will be described in detail for each step with reference to the drawings.

1 is a schematic diagram of a manufacturing process for a method for manufacturing nano-calcium citrate according to an aspect.

The method for preparing nano calcium citrate according to an embodiment includes dissolving citric acid in a solvent of ethanol and water (step 1).

Step 1 is a step of dissolving citric acid in solvents of ethanol and water.

In the method for preparing nano calcium citrate according to an embodiment, in preparing nano calcium citrate having high solubility and dispersibility by using water and ethanol as solvents, it is possible to prevent the growth of particles by interfering with the growth of nuclei of calcium citrate. .

At this time, it is preferable that the solvent includes ethanol in an amount of 0.1 to 3 times the weight of water, and it may be more preferable to include 0.3 to 1 times the weight of water.

If ethanol is included in an amount less than 0.1 times that of water, the nucleation of calcium citrate is delayed in the subsequent step of preparing calcium citrate, so it takes a long time for calcium citrate to precipitate, and also the aggregation between calcium citrate particles causes particles The size increases, and ultimately, calcium citrate with low solubility can be obtained. In addition, when ethanol is included in an amount three times or more that of water, calcium carbonate is dissolved in the subsequent mixing step with calcium carbonate, and nucleation in which calcium citrate is formed by reaction with citric acid in a calcium ion state is too fast, and this is also citric acid. It can cause aggregation between calcium particles. Accordingly, in this case, the particle size of the calcium citrate produced also increases, ultimately obtaining calcium citrate with low solubility, and there may be a problem in economics due to the use of excessive ethanol.

In addition, the citric acid may be mixed with the solvent in a ratio of at least 0.8 moles or more, preferably 0.8 to 5 moles, based on 1 mole of calcium carbonate.

If the citric acid is added in an amount of less than 0.8 mol relative to 1 mol of calcium carbonate, the amount of citric acid dissolved in the mixed solution is low, causing a problem in that all calcium carbonate is not dissolved or calcium citrate with low solubility is generated. When the amount of citric acid exceeds 5 moles relative to 1 mole of calcium carbonate, citric acid that does not participate in the reaction is excessively used, which may cause a problem of lowering economic feasibility.

In addition, step 1 may be performed by mixing citric acid with solvents of ethanol and water and dissolving by irradiating ultrasonic waves.

At this time, in the step 1, the ultrasound may be irradiated with an intensity of 1 kHz to 100 kHz, preferably for 1 minute to 10 minutes.

In the method for preparing nano calcium citrate according to an embodiment, dissolution of citric acid can be achieved more quickly by irradiating ultrasonic waves in step 1.

Next, the method for producing nano calcium citrate according to an embodiment is

and mixing calcium carbonate with the solution formed in step 1 and irradiating ultrasonic waves to prepare nano calcium citrate (step 2).

Step 2 is a step for preparing nano calcium citrate by mixing calcium carbonate with a solution in which citric acid is dissolved.

At this time, it is preferable to mix the mixture so that the citric acid is mixed in a ratio of at least 0.8 moles or more, preferably 0.8 to 5 moles, relative to 1 mole of calcium carbonate.

In the method for preparing nano-calcium citrate according to an embodiment, ultrasonic waves may be irradiated while mixing calcium carbonate with the solution formed in step 1. Accordingly, ultrasonic waves may be irradiated at the same time as mixing with calcium carbonate, and ultrasonic waves may be further irradiated to the mixture formed by the mixing.

In the method for producing nano-calcium citrate according to an embodiment, the particle size of the calcium citrate prepared by adding calcium carbonate to a solution in which citric acid is dissolved and simultaneously irradiating ultrasonic waves can be reduced to a nano-size. Accordingly, nano calcium citrate having high solubility and dispersibility can be prepared.

At this time, in step 2, the ultrasound may be irradiated with an intensity of 2 kHz to 200 kHz, and may be irradiated for 5 minutes to 20 minutes.

Accordingly, the ultrasound may be irradiated at an intensity of 2 kHz to 200 kHz within a time range of 5 minutes to 12 hours, preferably at an intensity of 15 kHz to 25 kHz within a time range of 5 minutes to 1 hour, and more preferably It may be irradiated within a time range of 5 minutes to 15 minutes at an intensity of 15 kHz to 25 kHz.

If, in step 2, when ultrasonic waves are irradiated at an intensity of less than 2 kHz, there is a problem in that nano calcium citrate having an average particle size of 50 mn to 500 nm is not produced because the ultrasonic irradiation is not sufficiently performed, and at an intensity of more than 200 kHz When irradiated, since calcium citrate aggregates due to the heat caused by ultrasonic irradiation to form an aggregate, this may also cause a problem in that nano calcium citrate having an average particle size of 50 mn to 500 nm is not produced.

On the other hand, the method for producing nano calcium citrate according to an embodiment is

It may further include a step (step 3) of obtaining nano calcium citrate powder by washing and drying the nano calcium citrate prepared in step 2.

The step 3 is a step of washing and drying the nano calcium citrate present in the reaction solution after performing the step 2.

Specifically, the washing may be performed by centrifuging or filtering the nano-calcium citrate present in the reaction solution, washing with ethanol, and centrifuging or filtering three or more times.

In addition, the temperature for the drying is not particularly limited, but may be carried out at 30 ° C to 150 ° C, preferably 50 ° C to 120 ° C, 50 ° C to 100 ° C, and the most Preferably it can be carried out at a temperature of 80 ℃.

In addition, the time for the drying is not particularly limited, but may be performed for 1 hour to 20 hours, preferably 3 hours to 18 hours, and more preferably 4 hours to 10 hours. And, most preferably, it can be performed for 5 hours.

Calcium carbonate used in the nanocalcium citrate manufacturing method according to an embodiment may be shell-derived calcium carbonate, and the shell-derived calcium carbonate means powdered shells such as oysters, cockles, and clams after removing foreign substances.

Citric acid used in the method for preparing nano-calcium citrate according to an embodiment may be hydrous citric acid or anhydrous citric acid, but preferably may be anhydrous citric acid.

The method for producing nano-calcium citrate according to an embodiment is a method for producing nano-calcium citrate, specifically, tricalcium citrate (Ca ₃ (C ₆ H ₅ O ₇ ) ₂ ).

In the method for producing nano calcium citrate according to one aspect, calcium citrate is produced more quickly by dissolving citric acid in water and ethanol and mixing with calcium carbonate, and at the same time, ethanol is formed on the surface of calcium citrate crystals by hydrogen bonding between COO ^- and OH ^- By being adsorbed on the calcium citrate, it is possible to prevent the growth of calcium citrate particles, thereby suppressing the growth of the particles.

In addition, nano calcium citrate of 50 nm to 500 nm having remarkably high solubility and dispersibility can be prepared by irradiating ultrasonic waves simultaneously with mixing with calcium carbonate.

Since the nano-calcium citrate prepared according to one aspect increases the ionization concentration of calcium and dissolves well in water, absorption of calcium can be further improved.

The present invention will be described in more detail through examples and experimental examples below. However, the following examples and experimental examples are only examples for explanation of the present invention, and the scope of the present invention is not limited thereto.

<Example 1> Preparation of nano calcium citrate

Step 1: Dissolve 1.17 mol of citric acid in a container containing 400 mL of distilled water and 200 mL of ethanol.

Step 2: While adding 1 mol of calcium carbonate to the container, ultrasonic wave at 20 kHz (50%) intensity was irradiated for 10 minutes.

As the ultrasound was irradiated, it was observed that the cloudy solution changed to transparent, and then immediately turned cloudy again. it means. In addition, it can be seen that nano calcium citrate is formed by pulverization by irradiated ultrasonic waves.

The mixed solution prepared with the nano-calcium citrate was centrifuged or filtered to separate the nano-calcium citrate and the solution, wash the separated nano-calcium citrate three or more times, and wash the nano-calcium citrate at 80° C. for 5 hours. It was dried to obtain nano calcium citrate powder.

<Comparative Example 1> Preparation of calcium citrate

Step 1: Dissolve calcium carbonate in a container containing 400 mL distilled water and 200 mL ethanol.

Step 2: 1.17 mol of citric acid was added to the container, and ultrasonic waves at an intensity of 20 kHz (50%) were irradiated to the mixed solution.

According to the stirring, it was observed that the cloudy solution turned slightly transparent and then immediately turned cloudy again, which means that citric acid was dissolved and then reacted with calcium carbonate to generate nucleation with calcium citrate.

The calcium citrate-prepared mixed solution is centrifuged or filtered to separate the calcium citrate and the solution, wash the separated calcium citrate three or more times, and dry the washed calcium citrate at 80° C. for 5 hours to obtain calcium citrate powder was obtained.

<Experimental Example 1> Elemental analysis of nano calcium citrate

For structural analysis of the nano calcium citrate prepared in Example 1, elemental analysis was performed using an elemental analyzer, and the results are shown in Table 1 below.

	Ca	C	H
Theoretical content of Formula 1 structure	24.12	28.92	2.02
Example 1	24.5	30.2	2.9

<Formula 1>

Formula 1 shows the structure of tricalcium citrate (Ca ₃ (C ₆ H ₅ O ₇ ) ₂ ).

As shown in Table 1, the nano-calcium citrate prepared in Example 1, Formula 1 corresponds to the Ca, C, and H content of the structure of tricalcium citrate (Ca ₃ (C ₆ H ₅ O ₇ ) ₂ ) can confirm.

From the above results, it can be seen that the nano-calcium citrate prepared in Example 1 is tricalcium citrate (Ca ₃ (C ₆ H ₅ O ₇ ) ₂ ).

<Experimental Example 2> Analysis of particle size of calcium citrate

In order to analyze the particle size of the calcium citrate prepared according to the methods of Examples and Comparative Examples, the particle size was analyzed using Horiba's LA-960 model, and the results are shown in FIGS. 2 and 3.

As shown in Figure 2, in the case of calcium citrate prepared by Comparative Example 1, the particle size distribution is generally wide and shows a wide particle size distribution from 100 nm to 10 μm on average. On the other hand, as shown in FIG. 3, in the case of the nano-calcium citrate prepared in Example 1, it can be confirmed that nano-sized calcium citrate having an average distribution of 140 nm was prepared.

Through the above results, the method of Example 1, in which ultrasonic waves were irradiated while adding calcium carbonate to a solution in which citric acid was dissolved, was more pulverized in the process of preparing calcium citrate, resulting in calcium citrate having a uniform nano-size of 50 nm to 500 nm. It can be confirmed that this was produced.

<Experimental Example 3> Solubility test of nano calcium citrate

In order to compare the solubility of the nano calcium citrate prepared in Example 1 and the calcium citrate of Comparative Example 1, 8.5 mg, 20 mg, and 50 mg of the nano calcium citrate of Example 1 and the calcium citrate of Comparative Example 1 were dissolved in 10 ml of distilled water, respectively. and the results are shown in Figure 4.

As shown in Figure 4, in the case of the nano-calcium citrate prepared in Example 1, 50 mg was all dissolved in 10 ml of distilled water and the transparent state was maintained, whereas 8.5 mg of calcium citrate in Comparative Example 1 was all dissolved in 10 ml of distilled water. It was not, so it showed a hazy dispersed state.

Through the above results, the calcium citrate of Comparative Example 1 has a solubility of 0.85 g/L or less under the same conditions, whereas the method for preparing nano-calcium citrate according to one aspect has a solubility of 5 g/L or more, which is 5 times greater than that of the calcium citrate of Comparative Example 1. It can be confirmed that the above nano-calcium citrate having a remarkably high solubility can be prepared in a very short time of about 10 minutes.

Claims (16)

1. dissolving citric acid in solvents of ethanol and water (step 1); and

   A method for producing nano-calcium citrate, comprising: mixing calcium carbonate with the solution formed in step 1 and irradiating ultrasonic waves to prepare nano-calcium citrate (step 2).
2. According to claim 1,

   Step 2 above

   A method for producing nano-calcium citrate, which is performed by irradiating ultrasonic waves while mixing calcium carbonate with the solution formed in step 1.
3. According to claim 1,

   In step 2, the ultrasound is irradiated at an intensity of 2kHz to 200kHz, a method for producing nano calcium citrate.
4. According to claim 1,

   In step 2, the ultrasound is irradiated for 5 to 20 minutes, a method for producing nano calcium citrate.
5. According to claim 1,

   The solvent comprises 0.1 to 3 times the weight of ethanol as water, nano calcium citrate manufacturing method.
6. According to claim 1,

   Step 1 above

   A method for producing nano-calcium citrate, which is a step of mixing citric acid with a solvent of ethanol and water and dissolving it by irradiating ultrasonic waves.
7. According to claim 6,

   In step 1, ultrasonic waves are irradiated at an intensity of 1 kHz to 100 kHz, nano calcium citrate manufacturing method.
8. According to claim 6,

   In step 1, ultrasonic waves are irradiated for 1 to 10 minutes, a method for producing nano calcium citrate.
9. According to claim 1,

   The mixing in step 2 is to mix citric acid at a molar ratio of 0.8 to 5 with respect to 1 mole of calcium carbonate, nano calcium citrate manufacturing method.
10. According to claim 1,

    The method for producing nano-calcium citrate is a method for producing nano-calcium citrate, which produces nano-calcium citrate having an average particle size of 50 nm to 500 nm.
11. According to claim 1,

    The nano calcium citrate manufacturing method

    Washing and drying the nano-calcium citrate prepared in step 2 to obtain nano-calcium citrate powder (step 3); further comprising, nano-calcium citrate production method.
12. According to claim 11,

    The ceruk is carried out by centrifugation or filtration method, nano calcium citrate production method.
13. According to claim 11,

    The drying is carried out at a temperature of 30 ℃ to 150 ℃, nano calcium citrate manufacturing method.
14. According to claim 1,

    The calcium carbonate is shell-derived calcium carbonate, nano calcium citrate manufacturing method.
15. According to claim 1,

    The citric acid is hydrous citric acid or anhydrous citric acid, nano calcium citrate manufacturing method.
16. According to claim 1,

    The method for producing nano-calcium citrate is a method for preparing tricalcium citrate (Ca ₃ (C ₆ H ₅ O ₇ ) ₂ ), nano-calcium citrate.

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