Method for producing calcium carbonate

Abstract

The present invention addresses the problem of providing a method for producing calcium carbonate in which an extraction rate of calcium from a calcium-containing solid is improved. The present invention relates to a method for producing calcium carbonate, the method comprising: (a) a step for charging a solid containing calcium and two or more calcium extraction agents into water and filtering the obtained mixture; and (b) a step for introducing carbon dioxide into a filtrate having a pH of 7 or higher and precipitating calcium carbonate, wherein the calcium extraction agents contain at least one selected from the group consisting of basic organic substances and at least one selected from the group consisting of acidic organic compounds and neutral organic compounds.

Description

Method for producing calcium carbonate

[0001] This invention relates to a method for producing calcium carbonate.

[0002] There are several methods for producing calcium carbonate. For example, Patent Document 1 reports a method for producing calcium carbonate in which a solid containing calcium is added to an aqueous solution containing a neutral amino acid such as DL-alanine to dissolve calcium ions, carbon dioxide is introduced to precipitate calcium carbonate, and then a magnesium salt is added to aggregate the calcium carbonate. Patent Document 2 reports a method for regenerating a solid residue from which calcium ions have been dissolved, comprising an elution step of adding a solid containing calcium to an aqueous solution containing a neutral amino acid to dissolve calcium ions into the aqueous solution, and a control step of controlling the basicity, which is the molar ratio of calcium oxide to silicon dioxide contained in the solid residue from which the calcium ions have been dissolved in the elution step. Patent Document 3 reports a method for extracting alkali metals and / or alkaline earth metals from a solid containing alkali metals and / or alkaline earth metals, the method comprising an elution step of adding the solid to an aqueous solution containing a neutral amino acid to dissolve the alkali metals and / or alkaline earth metals into the aqueous solution containing a neutral amino acid. Patent document 4 reports that using acidic amino acids results in a high extraction rate. However, to efficiently precipitate calcium carbonate, the pH of the solution should preferably be 7 or higher, which may necessitate a pH adjustment step after extraction. However, if NaOH, a common pH adjuster, is used to adjust the pH, the inclusion of Na may reduce the precipitation efficiency of calcium carbonate in the calcium carbonate precipitation step. In addition, when the extractant solution is reused repeatedly, Na accumulates in the solution, which may also be a problem. Furthermore, if ammonia is used as a pH adjuster, ammonia may volatilize as ammonia gas in solutions with a pH of 7 or higher. This not only lowers the pH of the solution but may also necessitate equipment to treat the ammonia gas volatilized during the process.

[0003] Japanese Patent Application Laid-Open No. 2020-83681, Japanese Patent Application Laid-Open No. 2020-81936, International Publication No. 2014 / 007332, Patent No. 6020565

[0004] There is still room for further improvement in the extraction rate of calcium in existing methods. Therefore, an object of the present invention is to provide a method for producing calcium carbonate with an improved extraction rate of calcium from solids containing calcium.

[0005] As a result of diligent research by the present inventors to solve the above problems, they found that the calcium extraction rate can be improved by including at least two types of calcium extractants, and thus completed the present invention. That is, the present invention provides a method for producing calcium carbonate having the following features: 1. A method for producing calcium carbonate comprising the steps of (a) adding a calcium-containing solid and two or more types of calcium extractants to water and filtering the resulting mixture, and (b) introducing carbon dioxide into a filtrate with a pH of 7 or higher to precipitate calcium carbonate, wherein the calcium extractant contains at least one selected from the group consisting of basic organic substances and at least one selected from the group consisting of acidic organic compounds and neutral organic compounds. 2. The method according to 1 above, wherein the basic organic substance is selected from the group consisting of basic amino acids, basic polyamino acids, amines, and polyamines, the acidic organic compound is selected from the group consisting of acidic amino acids, dicarboxylic acids, and hydroxy acids, and the neutral organic compound is selected from the group consisting of neutral amino acids. 3. 1. The method according to 1 or 2, wherein the basic organic compound is selected from the group consisting of lysine, arginine, cadaverine, and ε-poly-Lys. 4. The method according to 1 or 2, wherein the acidic organic compound is selected from the group consisting of glutamic acid, citric acid, tartaric acid, malic acid, or glutaric acid. 5. The method according to 1 or 2, wherein the neutral organic compound is selected from the group consisting of methionine, alanine, or phenylalanine. 6. The method according to 1 or 2, wherein the calcium extractant is a combination of a basic organic compound which is lysine, arginine, cadaverine, or ε-poly-Lys and an acidic organic compound which is glutamic acid, citric acid, tartaric acid, malic acid, or glutaric acid. 7. The method according to 1 or 2, wherein the calcium extractant is a combination of a basic organic compound which is lysine, arginine, cadaverine, or ε-poly-Lys and a neutral organic compound which is methionine, alanine, or phenylalanine. 8. The method according to 1 above, wherein the calcium extractant is one of the following combinations. 9. The method according to any one of claims 1 to 8, wherein the concentration of the calcium extractant is 0.001 to 4 M. 10. The method according to any one of claims 1 to 9, wherein the molar ratio of one selected from the group consisting of basic organic compounds to one selected from the group consisting of acidic or neutral organic compounds is 9:1 to 1:9. 11. The manufacturing method according to any one of claims 1 to 10, wherein the pH of the filtrate after the introduction of carbon dioxide is 7 to 12. 12. The manufacturing method according to any one of claims 1 to 11, wherein the pH of the aqueous suspension is 7 to 12.

[0006] According to the present invention, it is possible to dramatically improve the extraction rate of calcium, thereby obtaining calcium carbonate in high yield and high quantity.

[0007] Figure 1A shows the results of comparing the transmittance data of an amino acid aqueous solution (L-Glu / L-Lys=0.25M / 0.25M) in Reference Example 2 for Aureobasidium pullulans NBRC6353 with and without ε-poly-Lys addition over time. Figure 1B shows the results of comparing the transmittance data of an amino acid aqueous solution (L-Glu / L-Lys=0.25M / 0.25M) in Reference Example 2 for Bacillus thuringiensis NBRC3951 with and without ε-poly-Lys addition over time. Figure 1C shows the results of comparing the transmittance data of an amino acid aqueous solution (L-Glu / L-Lys=0.5M / 0.5M) in Reference Example 2 for Bacillus subtilis NBRC 101239 with and without ε-poly-Lys addition over time. Figure 1D shows the results of comparing the transmittance data of an amino acid aqueous solution (L-Ala=1.0M) in Reference Example 2 for Aureobasidium pullulans NBRC6353 with and without the addition of ε-poly-Lys over time. Figure 1E shows the results of comparing the transmittance data of an amino acid aqueous solution (L-Ala=1.0M) in Reference Example 2 for Emericella nidulans NBRC31837 with and without the addition of ε-poly-Lys over time. Figure 1F shows the results of comparing the transmittance data of an amino acid aqueous solution (L-Ala=1.0M) in Reference Example 2 for Rhodotorula glutinis ATCC2527 with and without the addition of ε-poly-Lys over time. Figure 2 shows the results of comparing the transmittance data of an amino acid aqueous solution (L-Glu / L-Lys = 0.5M / 0.5M) in Reference Example 3 for Bacillus subtilis NBRC 101239, with and without the addition of ε-poly-Lys, over time.

[0008] The present invention provides a method for producing calcium carbonate, comprising: (a) adding a calcium-containing solid and two or more calcium extractants to water and filtering the resulting mixture; and (b) introducing carbon dioxide into a filtrate with a pH of 7 or higher to precipitate calcium carbonate.

[0009] Step (a) In step (a), a calcium-containing solid and two or more calcium extractants are added to water, and the resulting mixture is filtered. The calcium extractants contain at least one selected from the group consisting of basic organic substances and at least one selected from the group consisting of acidic organic compounds and neutral organic compounds. The order in which the calcium-containing solid and the calcium extractants are added to water does not matter, but it is preferable to add the calcium extractants to the water first to dissolve them into a solution, and then add the calcium-containing solid so that a uniform extractant solution can come into contact with the solid. After adding both, it is preferable to stir for 15 minutes or more until the calcium extraction rate plateaus, so that sufficient calcium extraction is completed. The time until the calcium extraction rate plateaus can be appropriately set by those skilled in the art. More preferably, it is preferable to stir for 30 to 60 minutes. The fineness of the filter paper used when filtering the mixture of the calcium-containing solid, the calcium extractant, and water can be appropriately determined according to the size of the calcium-containing solid. The type of water used is not specified, but when calculating the calcium extraction rate, it is necessary to exclude the calcium derived from the water itself. There are no particular restrictions on the water temperature.

[0010] The pH of the filtrate obtained in step (a) must be 7 or higher (at 25°C). pH adjustment can be made more basic by increasing the proportion of cement if the calcium-containing solid is concrete or mortar containing cement. pH adjustment can also be made by appropriately adding basic amino acids or polylysine. It has been found that when the pH is adjusted using an alkali metal (e.g., NaOH), alkali metal carbonates (e.g., Na2CO3) are preferentially formed in step (b), making it difficult for calcium carbonate to precipitate. In addition, NH3 salts (e.g., ammonium chloride) have also been reported as calcium extractants (Patent No. 3954009), but since they volatilize when the pH becomes basic, it is necessary to add an additional calcium extractant, and the equipment must be prepared to withstand the volatilization of NH3 gas. Therefore, it is preferable to select the calcium extractant used in the present invention from the substances listed below, and its concentration should be adjusted so that the pH of the filtrate does not become acidic. As described later, steps (a) and (b) can be repeated, but if the pH decreases due to repeated use, the pH can be adjusted to 7 or higher by adding a basic organic substance, such as a basic amino acid or polylysine.

[0011] (Calcium-containing solids) Examples of calcium-containing solids include cement, concrete or mortar made by mixing cement with water and gravel and hardening it, building materials or waste materials containing concrete and / or mortar, and steelmaking slag generated in the steel manufacturing process. It is said that the general pH of cement is 12 to 13 because the minerals contained in cement react with water to produce Ca(OH)2. When using building materials or waste materials or steelmaking slag as calcium-containing solids, it is preferable to crush them to an appropriate size (for example, a particle size of about 2 to 200 μm as measured using a dry particle size analyzer under atmospheric conditions). This increases the contact area with the calcium extractant, thereby improving the extraction rate. The concentration of the calcium-containing solid can be appropriately set so that the slurry can be stirred. For example, 0.1 to 200 g / L is preferred, and 10 to 100 g / L is more preferred. This range is preferable because it particularly improves the calcium extraction rate and, as a result, increases the yield of calcium carbonate.

[0012] (Calcium Extractants) In the present invention, at least two types of calcium extractants are used. The calcium extractants are at least one selected from the group consisting of basic organic compounds and at least one selected from the group consisting of acidic organic compounds and neutral organic compounds. It is particularly preferable that the calcium extractant contains at least one selected from the group consisting of basic organic compounds and at least one selected from the group consisting of acidic organic compounds. It is also particularly preferable that the calcium extractant contains at least one selected from the group consisting of basic organic compounds and at least one selected from the group consisting of neutral organic compounds. It is especially preferable that the calcium extractant contains at least one selected from the group consisting of basic organic compounds and at least one selected from the group consisting of acidic organic compounds.

[0013] Examples of basic organic compounds include basic amino acids, basic polyamino acids, amines, and polyamines. Examples of basic amino acids include lysine (Lys), arginine (Arg), and histidine (His). Lysine or arginine is preferred, and lysine is more preferred. Examples of basic polyamino acids include polylysine, for example, ε-poly-Lys (specifically ε-Lys-Lys or ε-Lys-Lys-Lys), and polyarginine. Polylysine is preferred, and ε-Lys-Lys is more preferred. Examples of amines include ethylenediamine, cadaverine, and agmatine. Cadaverine is preferred. Among the basic organic compounds used in the present invention, lysine, arginine, and ε-poly-Lys are particularly preferred, and lysine and ε-Lys-Lys are especially preferred. Since polylysine is a polycation, it has excellent antibacterial properties and is also used as a food preservative. By using polylysine, spoilage of other calcium extractants during recycling can be prevented, and the number of times the calcium extractant can be recycled can be increased. Furthermore, as shown in Table 15, polylysine can suppress the change in calcium extractant concentration over time, so that the calcium extractant can maintain its extraction performance for a long period of time in the presence of polylysine. As a result, stable operation of the calcium extraction and carbonation processes can be achieved. The polylysine content may be on the order of ppm, for example, 100 to 130,000 ppm, preferably 300 to 70,000 ppm. For example, when polylysine consists of 30 lysine residues, the molar mass of polylysine is 4,700 g / mol, and the polylysine content expressed as a molar concentration is preferably 2.1 μM to 27.7 mM, more preferably 6.4 μM to 14.9 mM. Compared to the case without polylysine, the Ca extraction rate may be improved by more than double with the addition of polylysine.

[0014] Examples of acidic organic compounds include acidic amino acids, dicarboxylic acids, and hydroxy acids. Examples of acidic amino acids include aspartic acid (Asp) and glutamic acid (Glu). Glutamic acid is preferred. Examples of dicarboxylic acids include malonic acid, succinic acid, glutaric acid, fumaric acid, maleic acid, and tartaric acid. Glutaric acid is preferred. Examples of hydroxy acids include malic acid, tartaric acid, and citric acid. Citric acid is preferred. Examples of polyamino acids include polyglutamic acid. Among the acidic organic compounds used in this invention, glutamic acid and glutaric acid are particularly preferred, and glutaric acid is especially preferred.

[0015] Examples of neutral organic compounds include neutral amino acids. Methionine, alanine, and phenylalanine are preferred neutral organic compounds used in this invention. When the calcium extractant used in this invention is a compound having an asymmetric carbon, it may be the L-form, D-form, or DL-form. At the same concentration, the DL-form is preferred because it yields a higher extraction rate. While not bound by any particular theory, it is thought that a DL-DL mixture may increase the number of complexes that can be formed compared to L or D alone, thus potentially increasing the amount of complex that can be eluted. In this specification, unless otherwise specified, the L-form is used.

[0016] The following combinations are particularly preferred for the calcium extractant of the present invention. Using the above combination of calcium extractants is preferable because it allows for the extraction of calcium with an extraction rate of 20% or more.

[0017] The following combinations are particularly preferred for the calcium extractant of the present invention. Using the above combination of calcium extractants is preferable because it allows for the extraction of calcium with an extraction rate of 60% or more.

[0018] It is also preferable that the calcium extractant be one of the following combinations: [Combination 1A] A calcium extractant containing at least one selected from the group consisting of basic organic compounds and at least one selected from the group consisting of acidic organic compounds. [Combination 2A] A calcium extractant containing one selected from the group consisting of basic organic compounds and one selected from the group consisting of acidic organic compounds. [Combination 3A] A calcium extractant containing at least one basic organic compound selected from the group consisting of basic amino acids, basic polyamino acids, amines, and polyamines, and at least one acidic organic compound selected from the group consisting of acidic amino acids, dicarboxylic acids, and hydroxy acids. [Combination 4A] A calcium extractant containing at least one basic organic compound selected from the group consisting of basic amino acids and basic polyamino acids, and at least one acidic organic compound selected from the group consisting of acidic amino acids. [Combination 5A] A calcium extractant containing at least one basic organic compound selected from the group consisting of lysine and polylysine, and an acidic organic compound that is glutamic acid. [Combination 6A] A calcium extractant containing at least one basic organic compound selected from the group consisting of basic amino acids and an acidic organic compound which is at least one dicarboxylic acid selected from the group consisting of malonic acid, succinic acid, glutaric acid, fumaric acid, and maleic acid. [Combination 7A] A calcium extractant containing at least one basic organic compound selected from the group consisting of lysine and polylysine and an acidic organic compound which is at least one dicarboxylic acid selected from the group consisting of malonic acid, succinic acid, glutaric acid, fumaric acid, and maleic acid, or citric acid. [Combination 8A] A calcium extractant containing at least one basic organic compound selected from the group consisting of amines and polyamines and an acidic organic compound which is at least one selected from the group consisting of acidic amino acids. [Combination 9A] A calcium extractant containing at least one basic organic compound which is an amine selected from the group consisting of ethylenediamine, cadaverine, and agmatine and an acidic organic compound which is glutamic acid.[Combination 10A] A calcium extractant containing a basic organic compound which is at least one amine selected from the group consisting of ethylenediamine, cadaverine, and agmatine, and an acidic organic compound which is at least one dicarboxylic acid selected from the group consisting of malonic acid, succinic acid, glutaric acid, fumaric acid, and maleic acid. [Combination 11A] A calcium extractant containing a basic organic compound which is cadaverine, and an acidic organic compound which is at least one dicarboxylic acid selected from the group consisting of malonic acid, succinic acid, glutaric acid, fumaric acid, and maleic acid. [Combination 12A] A calcium extractant containing a basic organic compound which is at least one amine selected from the group consisting of ethylenediamine and cadaverine, and an acidic organic compound which is glutaric acid. [Combination 13A] A calcium extractant containing a basic organic compound which is ethylenediamine, and an acidic organic compound which is at least one dicarboxylic acid selected from the group consisting of malonic acid and succinic acid.

[0019] As mentioned above, the concentration of polylysine is as described above, but the concentration of the calcium extractant can be set arbitrarily, as long as a solution viscosity that would be difficult to handle in downstream processes such as the calcium carbonate filtration process is avoided. For example, 0.001 to 4 mol / L is preferred, and 0.2 to 2.5 mol / L is more preferred. This range is preferable because it particularly improves the calcium extraction rate and, as a result, increases the yield of calcium carbonate. When using a basic organic compound and an acidic organic compound, it is preferable to have a molar concentration ratio of basic organic compound:acidic organic compound = 9:1 to 1:9, more preferably 8:2 to 4:6, as this improves the extraction rate and results in a post-extraction solution pH of 7 or higher.

[0020] Step (b) In step (b), carbon dioxide is introduced into a filtrate with a pH of 7 or higher to precipitate calcium carbonate. The carbon dioxide used in step (b) can be in any state. For example, any gas containing carbon dioxide is acceptable, not limited to pure carbon dioxide gas, but also including exhaust gas produced when fossil fuels such as liquefied natural gas, liquefied petroleum gas, or coal are burned. Solid dry ice is also acceptable. Calcium carbonate is formed by the reaction of carbon dioxide with calcium in the filtrate. The method of bringing the introduced carbon dioxide into contact with the filtrate is not particularly limited and can be done, for example, by blowing carbon dioxide gas into the filtrate (preferably by blowing while stirring). Carbon dioxide is more soluble in water at lower temperatures and higher pressures. The temperature of the filtrate when introducing carbon dioxide is preferably 5 to 50°C. The pressure of the filtrate when introducing carbon dioxide does not need to be specially adjusted and is preferably within the normal range. The amount of carbon dioxide introduced can be appropriately determined according to the amount of calcium extracted. The pH of the filtrate can be measured using a glass electrode at 25°C. Continuing to stir for 10 to 20 minutes after introducing carbon dioxide is preferable because it improves the recovery rate of calcium carbonate.

[0021] The calcium carbonate precipitated in step (b) can be recovered by filtration or other means. The recovered calcium carbonate can be used in known applications, such as wastewater neutralization, flue gas desulfurization, livestock feed, building materials, concrete, fillers, fertilizers, paints, cosmetics, etc. Furthermore, if carbon dioxide contained in the exhaust gas of power plants or factories is used as a raw material, the amount of carbon dioxide released into the atmosphere can be reduced, and it can also be used as a material as described above, thus contributing to a reduction in environmental impact. After recovering the calcium carbonate, a new calcium-containing solid may be added to the filtrate and steps (a) and (b) may be repeated. At this time, the calcium extractant that has been reduced by performing steps (a) and (b) may be added back in.

[0022] Table 1 shows the reagents used in the examples.

[0023]

[0024] Table 2 shows the analytical method and conditions for calcium concentration.

[0025]

[0026] [Method for Calcium Carbonate Production and Calculation of Calcium Extraction Rate] The amount of Ca in the cement used for extraction was calculated from the Ca concentration of 46.5 wt% in the research cement. Meanwhile, the Ca concentration in the filtrate after extraction under each condition was quantified by ion chromatography. The volume of the filtrate was calculated from the volume of extractant solution (mL) and its specific gravity (g / mL), and the amount of Ca in the filtrate was calculated from the volume of the filtrate and the Ca concentration in the filtrate. The extraction rate was calculated by dividing the amount of Ca in the filtrate by the amount of Ca in the cement used and multiplying by 100. Each extractant and ultrapure water were used to prepare a solution at the concentrations shown in the table below. 45 mL of this solution was placed in an Erlenmeyer flask, and the amount of cement shown in the table below was added. The mixture was then stirred with a magnetic stirrer for 60 minutes. The resulting mixture was filtered using a 0.45 μm filter, and the pH of the resulting filtrate was measured. After confirming that the pH of the filtrate was 7 or higher, carbon dioxide gas was introduced to obtain calcium carbonate. The amount of calcium (Ca) in the filtrate was quantified by ion chromatography analysis. The Ca extraction rate was then calculated from the obtained quantitative values. Since the amount of Ca in ultrapure water is on the order of ppb, it was determined that it does not affect the amount of Ca in the filtrate, and therefore was not considered in the calculation of the Ca extraction rate. The pH of the filtrate was determined at 25°C using a glass electrode.

[0027] Reference example 1 The pH of the filtrate after calcium extraction was 9.5. Using data number 40 as the control condition, it was found that increasing the extractant concentration improved the extraction rate. Furthermore, DL-Ala showed an extraction rate approximately 4% higher than L-Ala at the same concentration. Data number 2 was performed with a liquid volume of 513 mL.

[0028] Example 1

[0029] The pH of the filtrate after calcium extraction was 8.9–9.4. In data number 5, combining L-Glu and L-Lys resulted in an extraction rate equal to or better than the control conditions in data number 40. Furthermore, increasing the extractant concentration increased the extraction rate, and optimizing the amount of cement added further improved the extraction rate.

[0030] Example 2

[0031] The pH of the filtrate after calcium extraction was 8.5–9.0. Combining Glu and ε-poly-Lys resulted in a dramatic improvement in extraction rate. In particular, the extraction rate was more than double that of data number 5, which used only monomers, indicating the importance of the combination of the polymer ε-poly-Lys and L-Glu. Furthermore, the extraction rate improved with increasing extractant concentration. By optimizing the cement content, a combination achieving an overwhelmingly high Ca extraction rate of over 70% was also discovered.

[0032] Example 3

[0033] The pH of the filtrate after calcium extraction was 9.3. Combining L-Glu and L-Arg resulted in a higher extraction rate compared to data number 40. From data number 5 and this example, it was found that combining acidic amino acids with basic amino acids yields a higher extraction rate than combining neutral amino acids.

[0034] Example 4

[0035] When examining combinations of organic acids and ε-poly-Lys, extraction rates were low with tartaric acid and malic acid, while with citric acid, the extraction rate was equal to or higher than that of the control (data number 40). Furthermore, with glutaric acid, a very high extraction rate of over 70% was obtained, similar to the combination of L-Glu and ε-poly-Lys.

[0036] Example 5

[0037] The pH of the filtrate after calcium extraction was 10.4. As a combination of organic acids and amines other than amino acids, in the combination of glutaric acid and cadaverine, an extraction rate 39% higher than that of data number 40 under control conditions was obtained. On the other hand, when ε-poly-Lys was added, the extraction rate tended to decrease.

[0038] Example 9

[0039] The pH of the filtrate after calcium extraction was 9.3 - 9.4. When a trace amount of ε-poly-Lys was added to the combination of L-Glu and L-Lys, the extraction rate tended to increase according to the added amount. Under the condition that the added amount of ε-poly-Lys was 6400 ppm, the extraction rate increased by about 10% compared with no addition.

[0040] Example 10

[0041] The pH of the filtrate after calcium extraction was 10.3. Similar to Example 5 (data number 48), when ε-poly-Lys was added to glutaric acid and cadaverine, the extraction rate decreased.

[0042] Example 11

[0043] The pH of the filtrate after calcium extraction was 9.4. When L-Met was used as an extractant, it was found that adding 1600 ppm of ε-poly-Lys increased the extraction rate by 10%.

[0044] Example 12

[0045] The pH of the filtrate after calcium extraction was 9.6. As a result of adding ε-poly-Lys to L-Ala and DL-Ala, in the case of L-Ala, the extraction rate tended to increase according to the added amount, and under the condition of adding 1600 ppm, the extraction rate improved by about 7% compared with the non-addition condition. On the other hand, for DL-Ala, no addition effect of ε-poly-Lys was observed, and the extraction rate decreased below the non-addition level.

[0046] Example 13 <0​The pH of the filtrate after calcium extraction was 9.9. When ε-poly-Lys was added to β-Ala, a tendency for the extraction rate to increase in proportion to the amount added was observed.

[0048] Example 14

[0049] The pH of the filtrate after calcium extraction was 9.0. L-Phe was prepared as a slurry of suspended L-Phe crystals, not as a solution, and adjusted to the concentrations shown in the table above. Adding ε-poly-Lys tended to increase the extraction rate. Furthermore, at 1600 ppm addition, the extraction rate was more than double that of the controlless solution.

[0050] The procedure for each data number is described below. For data number 2, a 1.0 M amino acid solution was prepared using L-Ala and ultrapure water. 513 mL of this amino acid solution was placed in an Erlenmeyer flask, 21.5 g of research cement was added, and the mixture was stirred with a magnetic stirrer for 60 minutes. After stirring, the solution was filtered using a 0.45 μm filter, and the resulting filtrate was analyzed by ion chromatography to quantify the amount of Ca contained in the filtrate. As a result, the Ca concentration was 0.51 wt%, and the extraction rate was 26.3%.

[0051] Data No. 5: Using L-Glu and L-Lys and ultrapure water, an amino acid solution was prepared with each component at a concentration of 0.5 M, for a total of 1.0 M. 45 mL of this amino acid solution was placed in an Erlenmeyer flask, 1.94 g of research cement was added, and the mixture was stirred with a magnetic stirrer for 60 minutes. After stirring, the solution was filtered through a 0.45 μm filter, and the resulting filtrate was analyzed by ion chromatography to quantify the amount of Ca contained in the filtrate. The results showed a Ca concentration of 0.57 wt% and an extraction rate of 29.9%.

[0052] Data No. 6: Using L-Glu and L-Lys and ultrapure water, an amino acid solution was prepared with each component at a concentration of 1.0 M, for a total of 2.0 M. 45 mL of this amino acid solution was placed in an Erlenmeyer flask, 1.94 g of research cement was added, and the mixture was stirred with a magnetic stirrer for 60 minutes. After stirring, the solution was filtered through a 0.45 μm filter, and the resulting filtrate was analyzed by ion chromatography to quantify the amount of Ca contained in the filtrate. The results showed a Ca concentration of 0.66 wt% and an extraction rate of 35.7%.

[0053] Data No. 7: Using L-Glu and L-Lys and ultrapure water, an amino acid solution was prepared with each component at a concentration of 1.0 M, for a total of 2.0 M. 45 mL of this amino acid solution was placed in an Erlenmeyer flask, 2.72 g of research cement was added, and the mixture was stirred with a magnetic stirrer for 60 minutes. After stirring, the solution was filtered through a 0.45 μm filter, and the resulting filtrate was analyzed by ion chromatography to quantify the amount of Ca contained in the filtrate. The results showed a Ca concentration of 1.00 wt% and an extraction rate of 39.0%.

[0054] Data No. 8: Using L-Glu and L-Lys and ultrapure water, an amino acid solution was prepared with each component at a concentration of 1.0 M, for a total of 2.0 M. 45 mL of this amino acid solution was placed in an Erlenmeyer flask, 3.88 g of research cement was added, and the mixture was stirred with a magnetic stirrer for 60 minutes. After stirring, the solution was filtered through a 0.45 μm filter, and the resulting filtrate was analyzed by ion chromatography to quantify the amount of Ca contained in the filtrate. The results showed a Ca concentration of 1.24 wt% and an extraction rate of 33.6%.

[0055] Data No. 9: Using L-Glu and L-Lys and ultrapure water, an amino acid solution was prepared with each component at a concentration of 1.0 M, for a total of 2.0 M. 45 mL of this amino acid solution was placed in an Erlenmeyer flask, 4.66 g of research cement was added, and the mixture was stirred with a magnetic stirrer for 60 minutes. After stirring, the solution was filtered using a 0.45 μm filter, and the resulting filtrate was analyzed by ion chromatography to quantify the amount of Ca contained in the filtrate. The results showed a Ca concentration of 1.34 wt% and an extraction rate of 30.3%.

[0056] Data No. 10: Using L-Glu and L-Lys and ultrapure water, an amino acid solution was prepared with each component at a concentration of 1.25 M, for a total of 2.5 M. 45 mL of this amino acid solution was placed in an Erlenmeyer flask, 1.94 g of research cement was added, and the mixture was stirred with a magnetic stirrer for 60 minutes. After stirring, the solution was filtered through a 0.45 μm filter, and the resulting filtrate was analyzed by ion chromatography to quantify the amount of Ca contained in the filtrate. The results showed a Ca concentration of 0.69 wt% and an extraction rate of 38.4%.

[0057] Data No. 13: Solutions were prepared using L-Glu and ε-poly-Lys (50% powder) with ultrapure water, each at a concentration of 0.5 M, for a total of 1.0 M. 45 mL of the solution was placed in an Erlenmeyer flask, 1.94 g of research cement was added, and the mixture was stirred with a magnetic stirrer for 60 minutes. After stirring, the solution was filtered through a 0.45 μm filter, and the resulting filtrate was analyzed by ion chromatography to quantify the amount of Ca contained in the filtrate. The results showed a Ca concentration of 1.21 wt% and an extraction rate of 63.1%.

[0058] For data number 14, solutions were prepared using L-Glu and ε-poly-Lys (50% powder) with ultrapure water at concentrations of 0.3 M and 0.7 M respectively, for a total of 1.0 M. 45 mL of each solution was placed in an Erlenmeyer flask, 1.94 g of research cement was added, and the mixture was stirred with a magnetic stirrer for 60 minutes. After stirring, the solution was filtered through a 0.45 μm filter, and the resulting filtrate was analyzed by ion chromatography to quantify the amount of Ca contained in the filtrate. The results showed a Ca concentration of 0.75 wt% and an extraction rate of 38.9%.

[0059] A 1.0 M solution was prepared using ε-poly-Lys (50% powder) and ultrapure water. 45 mL of the solution was placed in an Erlenmeyer flask, 1.94 g of research cement was added, and the mixture was stirred with a magnetic stirrer for 60 minutes. After stirring, the solution was filtered using a 0.45 μm filter, and the resulting filtrate was analyzed by ion chromatography to quantify the amount of Ca contained in the filtrate. The results showed a Ca concentration of 0.18 wt% and an extraction rate of 9.3%.

[0060] Data No. 16: Solutions of L-Glu and ε-poly-Lys (25% solution) and ultrapure water were prepared at concentrations of 0.5 M each, for a total of 1.0 M. 45 mL of the solution was placed in an Erlenmeyer flask, 1.94 g of research cement was added, and the mixture was stirred with a magnetic stirrer for 60 minutes. After stirring, the solution was filtered through a 0.45 μm filter, and the resulting filtrate was analyzed by ion chromatography to quantify the amount of Ca contained in the filtrate. The results showed a Ca concentration of 1.16 wt% and an extraction rate of 60.1%.

[0061] For data number 17, a solution was prepared using L-Glu and ε-poly-Lys (25% solution) and ultrapure water, with each solution at a concentration of 0.75 M and a total concentration of 1.5 M. 45 mL of the solution was placed in an Erlenmeyer flask, 1.94 g of research cement was added, and the mixture was stirred with a magnetic stirrer for 60 minutes. After stirring, the solution was filtered using a 0.45 μm filter, and the resulting filtrate was analyzed by ion chromatography to quantify the amount of Ca contained in the filtrate. The results showed a Ca concentration of 1.34 wt% and an extraction rate of 71.4%.

[0062] Data No. 18: Solutions of 1.0 M each of L-Glu and ε-poly-Lys (25% solution) and ultrapure water were prepared, totaling 2.0 M. 45 mL of the solution was placed in an Erlenmeyer flask, 1.94 g of research cement was added, and the mixture was stirred with a magnetic stirrer for 60 minutes. After stirring, the solution was filtered through a 0.45 μm filter, and the resulting filtrate was analyzed by ion chromatography to quantify the amount of Ca contained in the filtrate. The results showed a Ca concentration of 1.24 wt% and an extraction rate of 67.4%.

[0063] Data No. 19: A solution was prepared using L-Glu and ε-poly-Lys (25% solution) and ultrapure water, with each solution at a concentration of 1.0 M, for a total of 2.0 M. 45 mL of the solution was placed in an Erlenmeyer flask, 2.72 g of research cement was added, and the mixture was stirred with a magnetic stirrer for 60 minutes. After stirring, the solution was filtered through a 0.45 μm filter, and the resulting filtrate was analyzed by ion chromatography to quantify the amount of Ca contained in the filtrate. The results showed a Ca concentration of 1.74 wt% and an extraction rate of 67.3%.

[0064] Data No. 20: A solution of 1.0 M each of L-Glu and ε-poly-Lys (25% solution) and ultrapure water was prepared, totaling 2.0 M. 45 mL of the solution was placed in an Erlenmeyer flask, 3.88 g of research cement was added, and the mixture was stirred with a magnetic stirrer for 60 minutes. After stirring, the solution was filtered through a 0.45 μm filter, and the resulting filtrate was analyzed by ion chromatography to quantify the amount of Ca contained in the filtrate. The results showed a Ca concentration of 2.26 wt% and an extraction rate of 61.5%.

[0065] Data No. 21: Solutions were prepared using L-Glu and L-Arg with ultrapure water, each at a concentration of 0.5 M, for a total of 1.0 M. 45 mL of the solution was placed in an Erlenmeyer flask, 1.94 g of research cement was added, and the mixture was stirred with a magnetic stirrer for 60 minutes. After stirring, the solution was filtered through a 0.45 μm filter, and the resulting filtrate was analyzed by ion chromatography to quantify the amount of Ca contained in the filtrate. The results showed a Ca concentration of 0.68 wt% and an extraction rate of 35.4%.

[0066] Data No. 26: A solution was prepared using citric acid and ε-poly-Lys (25% solution) with ultrapure water, each at a concentration of 0.5 M, for a total of 1.0 M. 45 mL of the solution was placed in an Erlenmeyer flask, 1.94 g of research cement was added, and the mixture was stirred with a magnetic stirrer for 60 minutes. After stirring, the solution was filtered through a 0.45 μm filter, and the resulting filtrate was analyzed by ion chromatography to quantify the amount of Ca contained in the filtrate. The results showed a Ca concentration of 0.57 wt% and an extraction rate of 30.2%.

[0067] Data No. 27: Solutions were prepared using tartaric acid and ε-poly-Lys (25% solution) with ultrapure water, each at a concentration of 0.5 M, for a total of 1.0 M. 45 mL of the solution was placed in an Erlenmeyer flask, 1.94 g of research cement was added, and the mixture was stirred with a magnetic stirrer for 60 minutes. After stirring, the solution was filtered using a 0.45 μm filter, and the resulting filtrate was analyzed by ion chromatography to quantify the amount of Ca contained in the filtrate. The results showed a Ca concentration of 0.09 wt% and an extraction rate of 4.9%.

[0068] Data No. 28: A solution was prepared using malic acid and ε-poly-Lys (25% solution) with ultrapure water, each at a concentration of 0.5 M, for a total of 1.0 M. 45 mL of the solution was placed in an Erlenmeyer flask, 1.94 g of research cement was added, and the mixture was stirred with a magnetic stirrer for 60 minutes. After stirring, the solution was filtered using a 0.45 μm filter, and the resulting filtrate was analyzed by ion chromatography to quantify the amount of Ca contained in the filtrate. The results showed a Ca concentration of 0.11 wt% and an extraction rate of 5.9%.

[0069] Data No. 34: Solutions were prepared using glutaric acid and cadaverine with ultrapure water at concentrations of 0.5 M each, for a total of 1.0 M. 45 mL of the solution was placed in an Erlenmeyer flask, 1.94 g of research cement was added, and the mixture was stirred with a magnetic stirrer for 60 minutes. After stirring, the solution was filtered through a 0.45 μm filter, and the resulting filtrate was analyzed by ion chromatography to quantify the amount of Ca contained in the filtrate. The results showed a Ca concentration of 0.77 wt% and an extraction rate of 39.2%.

[0070] A 1.5 M solution was prepared using L-Ala and ultrapure water (data number 35). 45 mL of the solution was placed in an Erlenmeyer flask, 1.94 g of research cement was added, and the mixture was stirred with a magnetic stirrer for 60 minutes. After stirring, the solution was filtered through a 0.45 μm filter, and the resulting filtrate was analyzed by ion chromatography to quantify the amount of Ca contained in the filtrate. The results showed a Ca concentration of 0.63 wt% and an extraction rate of 32.9%.

[0071] Data No. 36: Solutions were prepared using L-Glu and L-Lys with ultrapure water, each at a concentration of 0.75 M, for a total of 1.5 M. 45 mL of the solution was placed in an Erlenmeyer flask, 1.94 g of research cement was added, and the mixture was stirred with a magnetic stirrer for 60 minutes. After stirring, the solution was filtered through a 0.45 μm filter, and the resulting filtrate was analyzed by ion chromatography to quantify the amount of Ca contained in the filtrate. The results showed a Ca concentration of 0.71 wt% and an extraction rate of 38.1%.

[0072] Data No. 38: A 1.0 M solution was prepared using DL-Ala and ultrapure water. 45 mL of the solution was placed in an Erlenmeyer flask, 1.94 g of research cement was added, and the mixture was stirred with a magnetic stirrer for 60 minutes. After stirring, the solution was filtered using a 0.45 μm filter, and the resulting filtrate was analyzed by ion chromatography to quantify the amount of Ca contained in the filtrate. The results showed a Ca concentration of 0.60 wt% and an extraction rate of 30.9%.

[0073] Data No. 40: A 1.0 M solution was prepared using L-Ala and ultrapure water. 45 mL of the solution was placed in an Erlenmeyer flask, 1.94 g of research cement was added, and the mixture was stirred with a magnetic stirrer for 60 minutes. After stirring, the solution was filtered using a 0.45 μm filter, and the resulting filtrate was analyzed by ion chromatography to quantify the amount of Ca contained in the filtrate. The results showed a Ca concentration of 0.54 wt% and an extraction rate of 27.8%.

[0074] Data No. 43: A 1.0 M solution was prepared using DL-Ala and ultrapure water, and then ε-poly-Lys (25% solution) was added to a concentration of 1600 ppm. 45 mL of the solution was placed in an Erlenmeyer flask, 1.94 g of research cement was added, and the mixture was stirred with a magnetic stirrer for 60 minutes. After stirring, the solution was filtered using a 0.45 μm filter, and the resulting filtrate was analyzed by ion chromatography to quantify the amount of Ca contained in the filtrate. The results showed a Ca concentration of 0.60 wt% and an extraction rate of 30.8%.

[0075] Data No. 45: A 1.0 M solution was prepared using L-Ala and ultrapure water, and then ε-poly-Lys (25% solution) was added to a concentration of 1600 ppm. 45 mL of the solution was placed in an Erlenmeyer flask, 1.94 g of research cement was added, and the mixture was stirred with a magnetic stirrer for 60 minutes. After stirring, the solution was filtered using a 0.45 μm filter, and the resulting filtrate was analyzed by ion chromatography to quantify the amount of Ca contained in the filtrate. The results showed a Ca concentration of 0.69 wt% and an extraction rate of 35.2%.

[0076] Data No. 47: Solutions were prepared using glutaric acid and ε-poly-Lys (25% solution) with ultrapure water, each at a concentration of 0.5 M, for a total of 1.0 M. 45 mL of the solution was placed in an Erlenmeyer flask, 1.94 g of research cement was added, and the mixture was stirred with a magnetic stirrer for 60 minutes. After stirring, the solution was filtered through a 0.45 μm filter, and the resulting filtrate was analyzed by ion chromatography to quantify the amount of Ca contained in the filtrate. The results showed a Ca concentration of 1.37 wt% and an extraction rate of 70.5%.

[0077] Data No. 48: Solutions of glutaric acid and cadaverine with ultrapure water were prepared at concentrations of 0.5 M each, totaling 1.0 M. ε-poly-Lys (25% solution) was then added to a total concentration of 1600 ppm. 45 mL of the solution was placed in an Erlenmeyer flask, 1.94 g of research cement was added, and the mixture was stirred with a magnetic stirrer for 60 minutes. After stirring, the solution was filtered through a 0.45 μm filter, and the resulting filtrate was analyzed by ion chromatography to quantify the amount of Ca contained in the filtrate. The results showed a Ca concentration of 0.68 wt% and an extraction rate of 35.0%.

[0078] Data No. 49: Solutions were prepared using L-Glu and L-Lys with ultrapure water, each at a concentration of 0.5 M, for a total of 1.0 M. Then, ε-poly-Lys (25% solution) was added to a total concentration of 160 ppm. 45 mL of the solution was placed in an Erlenmeyer flask, 1.94 g of research cement was added, and the mixture was stirred with a magnetic stirrer for 60 minutes. After stirring, the solution was filtered through a 0.45 μm filter, and the resulting filtrate was analyzed by ion chromatography to quantify the amount of Ca contained in the filtrate. The results showed a Ca concentration of 0.65 wt% and an extraction rate of 34.1%.

[0079] Data No. 50: Solutions were prepared using L-Glu and L-Lys with ultrapure water, each at a concentration of 0.5 M, for a total of 1.0 M. Then, ε-poly-Lys (25% solution) was added to a total concentration of 320 ppm. 45 mL of the solution was placed in an Erlenmeyer flask, 1.94 g of research cement was added, and the mixture was stirred with a magnetic stirrer for 60 minutes. After stirring, the solution was filtered through a 0.45 μm filter, and the resulting filtrate was analyzed by ion chromatography to quantify the amount of Ca contained in the filtrate. The results showed a Ca concentration of 0.74 wt% and an extraction rate of 38.6%.

[0080] Data No. 51: Solutions of L-Glu and L-Lys with ultrapure water were prepared at concentrations of 0.5 M each, totaling 1.0 M. Then, ε-poly-Lys (25% solution) was added to a total concentration of 960 ppm. 45 mL of the solution was placed in an Erlenmeyer flask, 1.94 g of research cement was added, and the mixture was stirred with a magnetic stirrer for 60 minutes. After stirring, the solution was filtered through a 0.45 μm filter, and the resulting filtrate was analyzed by ion chromatography to quantify the amount of Ca contained in the filtrate. The results showed a Ca concentration of 0.73 wt% and an extraction rate of 38.0%.

[0081] Data No. 52: Solutions were prepared using L-Glu and L-Lys with ultrapure water, each at a concentration of 0.5 M, for a total of 1.0 M. Then, ε-poly-Lys (25% solution) was added to a total concentration of 1600 ppm. 45 mL of the solution was placed in an Erlenmeyer flask, 1.94 g of research cement was added, and the mixture was stirred with a magnetic stirrer for 60 minutes. After stirring, the solution was filtered through a 0.45 μm filter, and the resulting filtrate was analyzed by ion chromatography to quantify the amount of Ca contained in the filtrate. The results showed a Ca concentration of 0.71 wt% and an extraction rate of 37.2%.

[0082] Data No. 53: Solutions of glutaric acid and cadaverine with ultrapure water were prepared at concentrations of 1.0 M each, for a total of 2.0 M. Then, ε-poly-Lys (25% solution) was added to a total concentration of 1600 ppm. 45 mL of the solution was placed in an Erlenmeyer flask, 1.94 g of research cement was added, and the mixture was stirred with a magnetic stirrer for 60 minutes. After stirring, the solution was filtered through a 0.45 μm filter, and the resulting filtrate was analyzed by ion chromatography to quantify the amount of Ca contained in the filtrate. The results showed a Ca concentration of 0.99 wt% and an extraction rate of 52.1%.

[0083] Data No. 54: Solutions were prepared using L-Glu and L-Lys with ultrapure water at concentrations of 0.5 M each, for a total of 1.0 M. Then, ε-poly-Lys (25% solution) was added to a total concentration of 6400 ppm. 45 mL of the solution was placed in an Erlenmeyer flask, 1.94 g of research cement was added, and the mixture was stirred with a magnetic stirrer for 60 minutes. After stirring, the solution was filtered through a 0.45 μm filter, and the resulting filtrate was analyzed by ion chromatography to quantify the amount of Ca contained in the filtrate. The results showed a Ca concentration of 0.76 wt% and an extraction rate of 39.7%.

[0084] Data No. 55: A 1.0 M solution was prepared using DL-Ala and ultrapure water, and then ε-poly-Lys (25% solution) was added to a concentration of 160 ppm. 45 mL of the solution was placed in an Erlenmeyer flask, 1.94 g of research cement was added, and the mixture was stirred with a magnetic stirrer for 60 minutes. After stirring, the solution was filtered through a 0.45 μm filter, and the resulting filtrate was analyzed by ion chromatography to quantify the amount of Ca contained in the filtrate. The results showed a Ca concentration of 0.51 wt% and an extraction rate of 25.9%.

[0085] Data No. 56: A 1.0 M solution was prepared using DL-Ala and ultrapure water, and then ε-poly-Lys (25% solution) was added to a concentration of 320 ppm. 45 mL of the solution was placed in an Erlenmeyer flask, 1.94 g of research cement was added, and the mixture was stirred with a magnetic stirrer for 60 minutes. After stirring, the mixture was filtered using a 0.45 μm filter, and the resulting filtrate was analyzed by ion chromatography to quantify the amount of Ca contained in the filtrate. The results showed a Ca concentration of 0.56 wt% and an extraction rate of 28.5%.

[0086] Data No. 57: A 1.0 M solution was prepared using L-Ala and ultrapure water, and then ε-poly-Lys (25% solution) was added to a concentration of 160 ppm. 45 mL of the solution was placed in an Erlenmeyer flask, 1.94 g of research cement was added, and the mixture was stirred with a magnetic stirrer for 60 minutes. After stirring, the solution was filtered using a 0.45 μm filter, and the resulting filtrate was analyzed by ion chromatography to quantify the amount of Ca contained in the filtrate. The results showed a Ca concentration of 0.59 wt% and an extraction rate of 30.0%.

[0087] Data No. 58: A 1.0 M solution was prepared using L-Ala and ultrapure water, and then ε-poly-Lys (25% solution) was added to a concentration of 320 ppm. 45 mL of the solution was placed in an Erlenmeyer flask, 1.94 g of research cement was added, and the mixture was stirred with a magnetic stirrer for 60 minutes. After stirring, the solution was filtered using a 0.45 μm filter, and the resulting filtrate was analyzed by ion chromatography to quantify the amount of Ca contained in the filtrate. The results showed a Ca concentration of 0.57 wt% and an extraction rate of 29.2%.

[0088] Data No. 67: A 0.2 M solution was prepared using L-Met and ultrapure water. 45 mL of the solution was placed in an Erlenmeyer flask, 0.39 g of research cement was added, and the mixture was stirred with a magnetic stirrer for 60 minutes. After stirring, the solution was filtered using a 0.45 μm filter, and the resulting filtrate was analyzed by ion chromatography to quantify the amount of Ca contained in the filtrate. The results showed a Ca concentration of 0.17 wt% and an extraction rate of 42.5%.

[0089] Data No. 68: A 0.2 M solution was prepared using L-Met and ultrapure water, and then ε-poly-Lys (25% solution) was added to a concentration of 160 ppm. 45 mL of the solution was placed in an Erlenmeyer flask, 0.39 g of research cement was added, and the mixture was stirred with a magnetic stirrer for 60 minutes. After stirring, the solution was filtered using a 0.45 μm filter, and the resulting filtrate was analyzed by ion chromatography to quantify the amount of Ca contained in the filtrate. The results showed a Ca concentration of 0.16 wt% and an extraction rate of 40.9%.

[0090] Data No. 69: A 0.2 M solution was prepared using L-Met and ultrapure water, and then ε-poly-Lys (25% solution) was added to a concentration of 320 ppm. 45 mL of the solution was placed in an Erlenmeyer flask, 0.39 g of research cement was added, and the mixture was stirred with a magnetic stirrer for 60 minutes. After stirring, the mixture was filtered using a 0.45 μm filter, and the resulting filtrate was analyzed by ion chromatography to quantify the amount of Ca contained in the filtrate. The results showed a Ca concentration of 0.17 wt% and an extraction rate of 41.8%.

[0091] Data No. 70: A 0.2 M solution was prepared using L-Met and ultrapure water, and then ε-poly-Lys (25% solution) was added to a concentration of 1600 ppm. 45 mL of the solution was placed in an Erlenmeyer flask, 0.39 g of research cement was added, and the mixture was stirred with a magnetic stirrer for 60 minutes. After stirring, the solution was filtered using a 0.45 μm filter, and the resulting filtrate was analyzed by ion chromatography to quantify the amount of Ca contained in the filtrate. The results showed a Ca concentration of 0.20 wt% and an extraction rate of 50.5%.

[0092] Data No. 79: A 0.2 M slurry solution was prepared using L-Phe and ultrapure water. 45 mL of the slurry solution was placed in an Erlenmeyer flask, 0.39 g of research cement was added, and the mixture was stirred with a magnetic stirrer for 60 minutes. After stirring, the solution was filtered using a 0.45 μm filter, and the resulting filtrate was analyzed by ion chromatography to quantify the amount of Ca contained in the filtrate. The results showed a Ca concentration of 0.03 wt% and an extraction rate of 8.6%.

[0093] Data No. 80: A 0.2 M slurry solution was prepared using L-Phe and ultrapure water, and then ε-poly-Lys (25% solution) was added to a concentration of 160 ppm. 45 mL of the slurry solution was placed in an Erlenmeyer flask, 0.39 g of research cement was added, and the mixture was stirred with a magnetic stirrer for 60 minutes. After stirring, the mixture was filtered using a 0.45 μm filter, and the resulting filtrate was analyzed by ion chromatography to quantify the amount of Ca contained in the filtrate. The results showed a Ca concentration of 0.05 wt% and an extraction rate of 12.0%.

[0094] Data No. 81: A 0.2 M slurry solution was prepared using L-Phe and ultrapure water, and then ε-poly-Lys (25% solution) was added to a concentration of 320 ppm. 45 mL of the slurry solution was placed in an Erlenmeyer flask, 0.39 g of research cement was added, and the mixture was stirred with a magnetic stirrer for 60 minutes. After stirring, the mixture was filtered using a 0.45 μm filter, and the resulting filtrate was analyzed by ion chromatography to quantify the amount of Ca contained in the filtrate. The results showed a Ca concentration of 0.06 wt% and an extraction rate of 13.8%.

[0095] Data No. 82: A 0.2 M slurry solution was prepared using L-Phe and ultrapure water, and then ε-poly-Lys (25% solution) was added to a concentration of 1600 ppm. 45 mL of the slurry solution was placed in an Erlenmeyer flask, 0.39 g of research cement was added, and the mixture was stirred with a magnetic stirrer for 60 minutes. After stirring, the mixture was filtered using a 0.45 μm filter, and the resulting filtrate was analyzed by ion chromatography to quantify the amount of Ca contained in the filtrate. The results showed a Ca concentration of 0.08 wt% and an extraction rate of 19.7%.

[0096] Data No. 83: A 1.0 M solution was prepared using β-Ala and ultrapure water. 45 mL of the solution was placed in an Erlenmeyer flask, 1.94 g of research cement was added, and the mixture was stirred with a magnetic stirrer for 60 minutes. After stirring, the solution was filtered using a 0.45 μm filter, and the resulting filtrate was analyzed by ion chromatography to quantify the amount of Ca contained in the filtrate. The results showed a Ca concentration of 0.30 wt% and an extraction rate of 15.5%.

[0097] Data No. 84: A 1.0 M solution was prepared using β-Ala and ultrapure water, and then ε-poly-Lys (25% solution) was added to a concentration of 160 ppm. 45 mL of the solution was placed in an Erlenmeyer flask, 1.94 g of research cement was added, and the mixture was stirred with a magnetic stirrer for 60 minutes. After stirring, the solution was filtered using a 0.45 μm filter, and the resulting filtrate was analyzed by ion chromatography to quantify the amount of Ca contained in the filtrate. The results showed a Ca concentration of 0.43 wt% and an extraction rate of 22.1%.

[0098] Data No. 85: A 1.0 M solution was prepared using β-Ala and ultrapure water, and then ε-poly-Lys (25% solution) was added to a concentration of 320 ppm. 45 mL of the solution was placed in an Erlenmeyer flask, 1.94 g of research cement was added, and the mixture was stirred with a magnetic stirrer for 60 minutes. After stirring, the solution was filtered using a 0.45 μm filter, and the resulting filtrate was analyzed by ion chromatography to quantify the amount of Ca contained in the filtrate. The results showed a Ca concentration of 0.45 wt% and an extraction rate of 23.1%.

[0099] Data No. 86: A 1.0 M solution was prepared using β-Ala and ultrapure water, and then ε-poly-Lys (25% solution) was added to a concentration of 1600 ppm. 45 mL of the solution was placed in an Erlenmeyer flask, 1.94 g of research cement was added, and the mixture was stirred with a magnetic stirrer for 60 minutes. After stirring, the solution was filtered using a 0.45 μm filter, and the resulting filtrate was analyzed by ion chromatography to quantify the amount of Ca contained in the filtrate. The results showed a Ca concentration of 0.49 wt% and an extraction rate of 25.1%.

[0100] Example 15: Ca extraction and calcium carbonate acquisition using L-Glu / L-Lys mixed solution 36.8 g of L-Glu and 36.6 g of L-Lys were dissolved in 448.5 g of water to prepare a mixed solution of L-Glu 0.5 mol / L and L-Lys 0.5 mol / L. 450.3 g of this solution was placed in a beaker, and 19.4 g of Portland cement was added while stirring with a magnetic stirrer at room temperature. After stirring for 1 hour, the solution was filtered using a 0.45 μm filter to obtain 432.4 g of a clear filtrate with a pH of 9.3. The Ca concentration in this filtrate was analyzed by cation chromatography and found to be 0.76 wt%. 430.9 g of the aforementioned Ca-containing aqueous solution was placed in a beaker, and stirring was continued for 15 minutes while blowing CO2 gas at 300 mL / min at room temperature. Subsequently, the injection of CO2 gas was stopped, and stirring was continued at room temperature for 12 hours to obtain a slurry from which calcium carbonate had precipitated. The slurry was filtered through a 0.45 μm filter, and the resulting solid was dried under reduced pressure at 40°C to obtain solid calcium carbonate. At this time, the recovery rate of Ca contained in the solution was 81.4%.

[0101] Example 16: Ca extraction and calcium carbonate acquisition using L-Glu / ε-poly-Lys mixed solution 36.8 g of L-Glu and 128.9 g of ε-poly-Lys (25% aqueous solution) were dissolved in 357.4 g of water to prepare a mixed solution of L-Glu 0.5 mol / L and ε-poly-Lys 0.5 mol / L (as molar concentration when converted to monomer L-Lys). 450.4 g of this solution was placed in a beaker, and 19.4 g of Portland cement was added while stirring with a magnetic stirrer at room temperature. After stirring for 1 hour, the solution was filtered using a 0.45 μm filter to obtain 428.8 g of a clear filtrate with a pH of 8.9. The Ca concentration in this filtrate was analyzed by cation chromatography and found to be 1.10 wt%. 426.4 g of the aforementioned Ca-containing aqueous solution was placed in a beaker, and stirring was continued for 8 minutes at room temperature while blowing in CO2 gas at a rate of 300 mL / min. After that, the blowing of CO2 gas was stopped, and stirring was continued at 15°C for 20 hours to obtain a slurry in which calcium carbonate had precipitated. The slurry was filtered through a 0.45 μm filter, and the resulting solid was dried under reduced pressure at 40°C to obtain a solid calcium carbonate. At this time, the recovery rate of Ca contained in the solution was 66.4%.

[0102] Reference Example 2: Decomposition Inhibitory Effect of Extractant Solution by ε-poly-Lys Six types of amino acid aqueous solutions were prepared using L-Glu, L-Lys, and L-Ala. Culture solutions of strains of mold, yeast, and Bacillus subtilis were also prepared. 250 μL of the culture solution was added to 10 mL of the amino acid aqueous solution and shaken in a shaker at 25-27°C. 1-1: L-Glu 0.25 mol / L, L-Lys 0.25 mol / L 1-2: L-Glu 0.25 mol / L, L-Lys 0.25 mol / L, ε-poly-Lys 1,000 ppm 2-1: L-Glu 0.5 mol / L, L-Lys 0.5 mol / L 2-2: L-Glu 0.5 mol / L, L-Lys 0.5 mol / L, ε-poly-Lys 1,000 ppm 3-1: L-Ala 1.0 mol / L 3-2: L-Ala 1.0 mol / L, ε-poly-Lys 1,000 ppm The amino acid aqueous solutions with the aforementioned culture medium added were sampled over time, and the transmittance (550 nm) was measured using a spectrophotometer. Tables 14-1 to 14-6 show the combinations of bacterial strains and solution compositions used, along with their transmittance over time. Figures 1A to 1F compare the transmittance data for each bacterial strain with and without ε-poly-Lys addition. It was found that adding ε-poly-Lys reduced transmittance, i.e., inhibited bacterial growth, in various combinations of bacterial strains and amino acid solutions.

[0103]

[0104] Reference Example 3: Under the conditions shown in Table 15 below, the concentrations of L-Glu and L-Lys in aqueous solutions were measured over time. The results showed that the amino acid concentrations were maintained in the system with ε-poly-Lys added, while the amino acid concentrations decreased in the system without ε-poly-Lys.

[0105]

Claims

1. A method for producing calcium carbonate, comprising the steps of (a) adding a calcium-containing solid and two or more calcium extractants to water and filtering the resulting mixture, and (b) introducing carbon dioxide into a filtrate with a pH of 7 or higher to precipitate calcium carbonate, wherein the calcium extractant contains at least one selected from the group consisting of basic organic substances and at least one selected from the group consisting of acidic organic compounds and neutral organic compounds.

2. The method according to claim 1, wherein the basic organic substance is selected from the group consisting of basic amino acids, basic polyamino acids, amines, and polyamines; the acidic organic compound is selected from the group consisting of acidic amino acids, dicarboxylic acids, and hydroxy acids; and the neutral organic compound is selected from the group consisting of neutral amino acids.

3. The method according to claim 1, wherein the basic organic compound is selected from the group consisting of lysine, arginine, cadaverine, and ε-poly-Lys.

4. The method according to claim 1, wherein the acidic organic compound is selected from the group consisting of glutamic acid, citric acid, tartaric acid, malic acid, or glutaric acid.

5. The method according to claim 1, wherein the neutral organic compound is selected from the group consisting of methionine, alanine, or phenylalanine.

6. The method according to claim 1, wherein the calcium extractant is a combination of a basic organic compound which is lysine, arginine, cadaverine, or ε-poly-Lys, and an acidic organic compound which is glutamic acid, citric acid, tartaric acid, malic acid, or glutaric acid.

7. The method according to claim 1, wherein the calcium extractant is a combination of a basic organic compound which is lysine, arginine, cadaverine, or ε-poly-Lys, and a neutral organic compound which is methionine, alanine, or phenylalanine.

8. The method according to claim 1, wherein the calcium extractant is any combination of the following:

9. The method according to claim 1, wherein the concentration of the calcium extractant is 0.001 to 4 M.

10. The method according to claim 1, wherein the molar ratio of one selected from the group consisting of basic organic compounds to one selected from the group consisting of acidic or neutral organic compounds is 9:1 to 1:

9.

11. The manufacturing method according to claim 1, wherein the pH of the filtrate after the introduction of carbon dioxide is 7 to 12.

12. The manufacturing method according to claim 1, wherein the pH of the aqueous suspension is 7 to 12.

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