Mineral-containing composition and method for producing the same

Abstract

To provide a composition obtained by concentrating mineral components in hot spring water or mineral spring water.SOLUTION: A method for producing a mineral-containing composition, comprising the following steps (1) to (4), wherein warm water and / or mineral water springing out from the ground and having (A) pH3. 5 to pH10. 5 and (B) iron ions in an amount of 20mg / L or less is used as a starting material liquid: (1) The starting solution is mixed with acetic acid in an amount of 0.25 to 0. 1kg per 75kg of the starting solution. (2) Heating is performed before and / or after the mixing of acetic acid to set the temperature of the mixed solution to 50 to 85 °C. (3) Calcium carbonate calcined at 140 °C to 210 °C is mixed with 1. to 2. 5kg per 1kg acetate mixed in (1), and the mixture is allowed to stand at 40 °C or less for 12 hours or more to generate crystals and precipitates. (4) Solutions containing crystals and precipitates 0.05 to 0. 1kg of nitrates per 2kg are mixed, and crystals are collected. According to the present production method, a large amount of crystals can be generated quickly, and a composition in which minerals in hot spring water or mineral spring water are concentrated can be provided.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a mineral-containing composition made from hot spring water or mineral spring water, and a method for producing the same. [Background technology]

[0002] Concentrating and utilizing the useful components contained in hot springs has been a common practice since ancient times. For example, in many hot spring resorts, hot spring deposits are used to produce yunohana (sparkling mineral deposits) and used as bath additives. Apart from traditional methods, other methods are known, such as using reverse osmosis membranes to concentrate the ions dissolved in hot springs in a balanced manner (see

[0007] in Patent Document 1) and concentrating useful components using an evaporator (see

[0005] in Patent Document 2). These concentrates are thought to contain many hot spring minerals. Note that "minerals" is a general term for elements other than the four elements that constitute living organisms (oxygen, carbon, hydrogen, and nitrogen), such as sodium, potassium, calcium, magnesium, and phosphorus.

[0003] Meanwhile, minerals contained in seawater are also used as raw materials for cosmetics and bath additives, and methods for concentrating minerals from seawater after removing salt are known. For example, a method is known in which acetic acid is added to concentrated seawater to remove sodium chloride and mercury, and then the minerals are concentrated (Patent Document 3

[0016] ), and a method is known in which acetic acid and calcium carbonate are added, the resulting precipitate is removed, the clear aqueous solution is heated and concentrated, and then crystallized at room temperature to obtain the minerals in seawater (Patent Document 4

[0019] ). However, these methods are merely methods for concentrating minerals in seawater, and it was unclear whether they could be applied to hot spring water and mineral spring water, which contain different components and their amounts, such as sodium chloride. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 5-92188 [Patent Document 2] Patent Publication No. 2002-273412 [Patent Document 3] JP 10-120578 [Patent Document 4] Patent Publication No. 2016-96726 Summary of the Invention [Problem to be solved by the invention]

[0005] An object of the present invention is to provide a composition in which the mineral components in hot spring water or mineral spring water are concentrated, and further to provide a method for producing the same. [Means for solving the problem]

[0006] In order to achieve the above object, the inventors of the present invention have conducted extensive research and have come up with the following method: use hot spring water or mineral spring water as a raw material liquid, mix acetic acid and calcium carbonate, leave the mixture for a certain period of time to form crystals, and then devise a method for rapidly forming the crystals in large quantities.

[0007] 1. The raw material liquid is hot water and / or mineral water that springs from the ground and has (A) a pH of 3.5 to 10.5 and (B) an iron ion content of 20 mg / L or less, The method for producing a mineral-containing composition from the raw material liquid includes the following steps (1) to (4): (1) Mix 0.25 to 0.75 kg of acetic acid per 1 kg of raw material liquid. (2) Heat the mixture before and / or after mixing with acetic acid to bring the temperature of the mixture to 50-85°C. (3) Calcium carbonate calcined at 140°C to 210°C is mixed in an amount of 0.25 to 2.5 kg per 1 kg of acetic acid mixed in (1), and left at 40°C or lower for 12 hours or more to cause crystallization and precipitation. (4) Mix 0.05 to 0.2 kg of nitrate per 1 kg of solution containing crystals and precipitates, then collect the crystals. 2. The raw material liquid is hot water and / or mineral water that springs from the ground and has a pH of (A) 3.5 to 10.5 and (B) an iron ion content of less than 20 mg / L, A method for producing a mineral-containing composition from the raw material liquid, comprising the following steps (1) to (4), and also comprising steps (5) to (7) one to three times: (1) Mix 0.25 to 0.75 kg of acetic acid per 1 kg of raw material liquid. (2) Heat the mixture before and / or after mixing with acetic acid to bring the temperature of the mixture to 50-85°C. (3) Calcium carbonate calcined at 140°C to 210°C is mixed in an amount of 0.25 to 2.5 kg per 1 kg of acetic acid mixed in (1), and left at 40°C or lower for 12 hours or more to cause crystallization and precipitation. (4) Mix 0.05 to 0.2 kg of nitrate per 1 kg of solution containing crystals and precipitates, then collect the crystals. (5) The recovered crystals are dissolved in a raw material solution of 1 / 4 to 4 / 4 (by weight) of the raw material solution of (1). (6) Remove the insoluble components to obtain a solution. (7) Step (2) should be read as "Adjust the temperature of the solution in (6) to 50-85°C" and steps (2) to (4) should be carried out. 3. The method for producing a mineral-containing composition according to 2 above, wherein the raw material liquid further satisfies the following conditions: (C) Sulfate ions 9.808g / L or less (D) Iodine is 12.69 g / L or less (E) Carbon dioxide is less than 1 mL / L 4. A mineral-containing composition produced by any one of the production methods 1 to 3 above. 5. A bath additive composition, which is the composition of 4 above. [Effects of the Invention]

[0008] According to the present invention, acetic acid and calcium carbonate are mixed into hot spring water or mineral spring water, and crystals are formed quickly and in large quantities. By collecting the crystals, a mineral-containing composition can be provided in which the minerals in the hot spring water or mineral spring water are concentrated. [Brief explanation of the drawings]

[0009] [Figure 1]This shows the appearance of the composition of the present invention. The crystallized component is the composition of the present invention. A and B include components that have not crystallized. A shows the appearance from the side, and B shows the appearance from above. C shows the appearance of crystals scooped out of the solution. DETAILED DESCRIPTION OF THE INVENTION

[0010] In the present invention, hot water or mineral water that springs from the ground is used as a raw material liquid, and acetic acid and calcium carbonate are mixed with this, heated, and gradually cooled to precipitate frost-like needle-like crystals, which are then collected to produce a mineral-containing composition. The present invention will be described in detail below.

[0011] 1. About the raw material liquid In the present invention, the raw material liquid is "hot water and / or mineral water that springs from the ground." Hot water and mineral water that springs from the ground refer to so-called hot spring water and mineral spring water (hereinafter sometimes referred to as hot spring water, etc.). More precisely, it corresponds to hot water and mineral water as defined by the Hot Springs Act at the time of filing. Hot spring water and the like are known to contain higher concentrations of minerals than tap water. Minerals are a general term for anything other than the four elements that make up living organisms (oxygen, carbon, hydrogen, and nitrogen), including sodium, potassium, calcium, magnesium, and phosphorus. Electrical conductivity (hereinafter sometimes referred to as the EC value), which is highly correlated with the amount of dissolved substances in hot spring water and the like, is used as an indicator of the amount of minerals contained, and the EC value of hot spring water and the like is approximately 0.06 to 0.27 S / m. Because the raw material liquid is hot spring water and the like, the EC value can also be specified as approximately 0.06 to 0.27 S / m, allowing it to be distinguished from tap water and other waters with a low mineral content.

[0012] 2. Mixing with acetic acid Acetic acid is mixed into the raw material liquid. The amount of acetic acid mixed is preferably 0.25 to 0.75 kg, more preferably 0.3 to 0.6 kg, per 1 kg of the raw material liquid. In the present invention, acetic acid is mixed into the raw material solution to stabilize the water-solubilization of alkali metal salts, alkaline earth metal salts, particularly calcium salts, contained in hot spring water, etc. Specifically, calcium chloride, calcium carbonate, and calcium sulfate, which are calcium salts contained in hot spring water, are converted into calcium acetate by mixing a large amount of acetic acid, and the water-solubilization is stabilized. Furthermore, since iron ions inhibit the reaction that produces calcium acetate, it is preferable not to use water from iron-containing springs, etc., where iron ions are present in large amounts, and the iron ion concentration should preferably be 20 mg / L or less.Furthermore, it is even more preferable that sulfate ions, iodine, and carbon dioxide, which may also inhibit the reaction, be 9.808 g / L or less, 12.69 g / L or less, and 1 mL / L or less, respectively. The pH of the raw material solution is preferably 3.5 to 10.5. If the pH is too low or too high, the reaction to produce calcium acetate is inhibited. Furthermore, the pH after mixing with acetic acid is more preferably 3.5 to 7, and even more preferably 5.0 to 7.0.

[0013] 3. Temperature after mixing with acetic acid The temperature after mixing acetic acid with the raw material liquid should be 50 to 85°C. Heating can be done before or after mixing with acetic acid, or both, as long as the temperature is reached. Through trial and error, we found that by using this temperature range, calcium acetate crystals, which are produced in a later step, are produced in a shorter time and in larger quantities. In particular, if the temperature is too low, crystals may not form or may be produced in small quantities.

[0014] 4. Mixing calcium carbonate It is preferable to mix 0.25 to 2.5 kg of calcium carbonate per 1 kg of acetic acid, and it is more preferable that the amount of calcium carbonate mixed for the first time is 1.2 to 2.2 kg, and it is more preferable that the amount mixed for the second time or later is 0.3 to 1.8 kg. Calcium acetate crystals are formed by mixing calcium carbonate and leaving it at room temperature. Room temperature is around 25°C, but it is thought that crystals will form even at slightly higher or lower temperatures, so it is more preferable to leave it at 10°C to 40°C, and even more preferably at 10°C to 30°C, which is closer to room temperature. It is thought that not only calcium acetate but also salts derived from hot spring ingredients are crystallized. In fact, when the crystallized salt is dissolved and analyzed, it is found that in addition to calcium ions, it also contains relatively high concentrations of sodium ions that were not added from outside (Table 1, Table 2). Calcined calcium carbonate is used. The calcination temperature is preferably 140 to 210°C. Through trial and error, it was discovered that using calcium carbonate calcined in this temperature range allows more crystals to form in a shorter time. The crystals form as needle-shaped crystals in a frost-like pattern. Crystals form when left for 12 hours or more. Although a direct comparison is not possible, a method in which calcium carbonate and acetic acid are reacted and added to a seawater concentrate containing minerals allows crystallization to occur at room temperature for 40 to 50 days (Patent Document 4

[0019] ), indicating that the method of the present invention can produce crystals in a short period of time. Furthermore, although there is no upper limit to the time allowed to stand, in consideration of production efficiency, a time of 12 to 48 hours is more preferable, and 12 to 24 hours is even more preferable.

[0015] 5. Nitrate Mixtures Nitrate is mixed into the solution containing the frost-like needle crystals. Examples of nitrate include sodium nitrate, magnesium nitrate, potassium nitrate, calcium nitrate, and ammonium nitrate. The amount of nitrate to be mixed is preferably 0.05 to 0.2 kg, more preferably 0.08 to 0.16 kg, per 1 kg of solution containing the crystals and precipitates. Surprisingly, the addition of nitrate improves the recovery rate of the crystal components. After mixing the nitrate, scoop out and collect only the resulting crystals, without collecting the precipitate. Discard the supernatant and precipitate. By collecting only the crystals, it is thought that any harmful substances such as mud or mercury that may be present can be removed. The recovered crystals are the composition of the present invention.

[0016] 6. Mixing hot spring water etc. into the crystals again These crystals can then be dissolved again in hot spring water or other raw material liquid, and steps 3 to 5 above can be repeated. However, when repeating, acetic acid should not be added. This allows the minerals in the hot spring water to be more concentrated. However, if the process is repeated too many times, the amount of calcium carbonate added from outside will increase and will not dissolve, resulting in an increase in precipitates and a decrease in yield. Therefore, the process should be repeated one, two, or three times. More specifically, the resulting crystals are mixed with hot spring water or the like in an amount (weight ratio) of 1 / 4 to 4 / 4, more preferably 1 / 4 to 3 / 4, of the amount (weight ratio) of the hot spring water or the like used as the raw material solution to dissolve the crystals. Insoluble components are removed by filtration or the like. This solution is then heated to 50 to 85°C, following the procedures 3 to 5 above, and calcined calcium carbonate is mixed in. The solution is then left to stand, preferably at 10 to 40°C, even more preferably at 10 to 30°C, to obtain new crystals. This process is repeated 1 to 3 times.

[0017] 7.Other Processing The recovered crystals, i.e., the composition of the present invention, may be dissolved in a solution such as hot spring water and used. Magnesium chloride and potassium carbonate may be added to further enhance the mineral content. It is also preferable to add activated carbon to the solution to remove color and impurities. Heat sterilization is also preferable.

[0018] 8. Mineral-containing composition derived from hot spring water The mineral-enriched hot spring water-derived mineral-containing composition produced by the above-mentioned production method contained abundant mineral components such as sodium ions, potassium ions, magnesium ions, and calcium ions. The concentration of sodium ions, which were not added from outside, was also significantly increased (see Tables 1 and 2). It is more preferable that the solution has a pH of 5 to 6.5, a specific gravity of 1.15 or more, and an EC value of 7500 or more. The mineral-containing composition of the present invention has a moisturizing effect when used as a bath additive. The comparative example, which uses seawater as the raw material liquid, also contains the same minerals, but the effect is greater than that of this composition. Therefore, it is possible that the balance of mineral components and trace amounts of mineral components contribute to the moisturizing effect. If trace amounts of mineral components are effective, it would be impossible or impractical to identify all of them.

[0019] 9. Use as a bath additive The composition of the present invention can be used as a bath additive. When used as a bath additive, it exhibits a moisturizing effect and may also be effective against atopic dermatitis. [Example]

[0020] 1. Example 1 [Production of the mineral-containing composition of the present invention] The mineral-containing composition of the present invention was produced using hot spring water as a raw material. (1) 150 mL of hot spring water from Yunohara Hot Spring (source: 2-4-57 Yunohara, Yuzawa City, Akita Prefecture, Table 1) was used as the raw material solution. 50 g of acetic acid (Azuma Corporation, "99% Pure Acetic Acid") was added to this, and then the solution was heated to 80°C. (2) On the other hand, calcium carbonate (Mamacalso, manufactured by Nitto Funka Kogyo Co., Ltd.) was calcined at 160°C. 100 g of this calcined calcium carbonate was added to the solution in (1). The solution was added in small portions slowly while stirring to prevent the solution from overflowing from the container due to the reaction. The solution was then left to stand at room temperature for 19 hours. (3) The solution separated into a supernatant, frosty needle-like crystals, and a precipitate. 25.5 g of calcium nitrate was added to the solution. Then, the needle-like crystals were scooped out with a large ladle and the crystals alone were collected. (4) The crystals were dissolved again in 55 mL of hot spring water from Yunohara Onsen. The solution was filtered through filter paper (Advantec No. 1), and the filtrate was collected. (5) This filtrate was heated to 60°C in the same manner as in (1). 50 g of calcium carbonate calcined in the same manner as in (2) was gradually added to the filtrate while stirring. The mixture was then left at room temperature for 19 hours. (6) As in (3), calcium nitrate was added and the resulting crystals were scooped out. (7) (4) to (5) were repeated two more times with 25 g of calcium carbonate added, and the resulting crystals were scooped up to obtain the mineral-containing composition of the present invention using hot spring water as the raw material liquid (hereinafter, sometimes referred to as the hot spring water-derived mineral-containing composition) (FIGS. 1A, 1B, and 1C (Experimental Example 1-2)). (8) Furthermore, 55 mL of hot spring water from Yunohara Onsen was added to the crystals, and 9.2 g of magnesium chloride (white bittern, manufactured by Naikai Salt Co., Ltd.) and 7.14 g of potassium carbonate (food additive potassium carbonate, manufactured by Matsuba Pharmaceutical Co., Ltd.) were added to enhance the mineral content, and the mixture was then heated to 80°C to dissolve the crystals. (9) Activated carbon (granular activated carbon manufactured by Taihei Chemical Industry Co., Ltd.) was added to the solution of (8) and stirred. This was left at room temperature for 19 hours to allow the insoluble components to settle, and the supernatant was collected. This supernatant was then filtered through filter paper. (10) The filtrate was sterilized by heating at 80°C for 36 seconds.

[0021] 2. Example 2 [Analysis of mineral content] The minerals contained in the mineral-containing composition derived from hot spring water and enriched with mineral components of the present invention were analyzed, and the results are shown in Table 2. When compared with the analysis of the hot spring water components at the time of gushing (Table 1), there was a significant increase in sodium ions that were not added externally, suggesting that the mineral components derived from the hot spring water were concentrated. In addition, the pH, specific gravity, and EC values ​​were measured, and the results were pH 5.4, specific gravity 1.16, and EC 15600. The measuring equipment used was as follows. pH meter: MMK SCIENTIFIC pH meter Hydrometer: Standard hydrometer manufactured by Nippon Keiryoki Kogyo Co., Ltd. EC meter: MMK SCIENTIFIC TDS & EC meter

[0022] [Table 1]

[0023] [Table 2]

[0024] 3. Example 3 [Study on improving crystal recovery amount using nitrate] Calcium nitrate was used in Example 1 (Experimental Example 1-2), but when Example 1 was performed, sodium nitrate was added instead of calcium nitrate (Experimental Example 1-1) and no nitrate was added (Comparative Experimental Example 1-1). It was found that the weight of the crystals was larger in both the method in which nitrate was added to the solution containing the crystals (Experimental Examples 1-1 and 1-2) and the method in which nitrate was not added (Comparative Experimental Example 1-1), and that more crystals could be recovered (Table 3, Figures 1A, B, and C). Furthermore, the liquid level and crystal length values ​​were also larger, which is thought to be why larger crystals were obtained.

[0025] [Table 3]

[0026] 4. Comparative Example 1 <Production of mineral-containing composition using seawater as raw material> (1) Seawater was used as the raw material liquid, and the production was carried out in accordance with Example 1. The following mainly describes the differences. The numbers in parentheses correspond to those in Example 1. (A) (1) (2) → Calcium carbonate and acetic acid were reacted with seawater, which was heated to 100°C, and then added to the seawater. The calcium carbonate used was calcined at a temperature of 220°C or higher. (B)(3) → The solution had a low mineral concentration, so no crystals formed. After leaving it at room temperature for 12 hours or more, the precipitate was removed by filtration, and after heating and concentrating it, it was left to crystallize, and the crystals were collected. (C) (4) to (7) → Hot spring water was replaced with seawater and treated in the same manner as (A) and (B) above. (D) Mineral enrichment, activated carbon addition, and sterilization were carried out in the same manner as in (8) and (9).

[0027] 5. Example 4 <Effects when used as a bath additive> The mineral-containing composition derived from hot spring water and enriched with mineral components of the present invention and the mineral-containing composition derived from seawater and enriched with mineral components of Comparative Example 1 were used as bath additives to compare their effects. (1) Experimental Example 4-1 (I) Materials and methods Ten milliliters of the mineral-containing composition derived from hot spring water and enriched with mineral components of the present invention was dissolved in approximately 250 liters of bathwater, and eight female subjects in their 20s to 50s bathed once a day for eight consecutive months. The subjects were then asked to complete a questionnaire after use. For each symptom, such as atopic dermatitis, they were asked to score "improved" (2 points), "slightly improved" (1 point), or "unchanged" (0 points), and the average score was calculated. Note that some subjects did not originally have symptoms, and in those cases, the field was left blank; therefore, not all items were answered by eight subjects. (II) Results All symptoms, including "atopic dermatitis" and "dryness and wrinkles on the palms and backs of the hands," were improved (Table 4, Experimental Example 4-1). (2) Comparative Experiment Example 4-1 (I) Materials and methods The test was carried out in the same manner as in Experimental Example 4-1, except that the dissolving composition was the mineral-enriched seawater-derived mineral-containing composition of Comparative Example 1 and the test period was six years. (II) Results The results were a mixture of evaluations of "improved," "slightly improved," and "no change" (Table 4, Comparative Experimental Example 4-1). (3) Summary of results In Experimental Example 4-1, improvement was observed for all symptoms, but in Comparative Experimental Example 4-1, responses of "improved," "slightly improved," and "unchanged" were mixed. The average score was also higher in Experimental Example 4-1, demonstrating that the mineral-containing composition derived from hot spring water with enriched mineral components in Experimental Example 4-1 is more effective as a bath additive.

[0028] [Table 4]

[0029] 6.Reference example 1 <Effects on atopic dermatitis> (I) Materials and methods 10 mL of the mineral-containing composition derived from hot spring water and enriched with mineral components produced in Example 1 was dissolved in 250 L of bath water, and one subject with atopic dermatitis bathed in the bath once a day for eight months. (II) Results The area of ​​the red area on the affected area of ​​the back decreased, and the symptoms of atopic dermatitis were greatly improved. Photographs of the subjects before and after use have been omitted at their request. [Industrial Applicability]

[0030] According to the present invention, a mineral-containing composition obtained by concentrating minerals in hot spring water or mineral spring water can be provided, which can be used as a bath additive and is useful in the hot spring industry that produces such compositions and in other industries that produce bath additives.The composition may also be useful in the cosmetics industry from the viewpoint of its moisturizing effect.

Claims

1. (A) a pH of 3.5 to 10.5, and (B) hot water and / or mineral water that springs from the ground and has an iron ion content of 20 mg / L or less, The method for producing a mineral-containing composition from the raw material liquid includes the following steps (1) to (4). (1) Mix 0.25 to 0.75 kg of acetic acid per 1 kg of the raw material liquid. (2) Heat the mixture before and / or after mixing with acetic acid until the temperature of the mixture reaches 50 to 85°C. (3) Calcium carbonate calcined at 140°C to 210°C is mixed in an amount of 0.25 to 2.5 kg per 1 kg of the acetic acid mixed in (1), and left to stand at 40°C or lower for 12 hours or more to cause crystallization and precipitation. (4) Mix 0.05 to 0.2 kg of nitrate per 1 kg of solution containing crystals and precipitates, then collect the crystals.

2. (A) pH 3.5 to pH 10.5, and (B) hot water and / or mineral water that springs from the ground and has an iron ion content of less than 20 mg / L, The method for producing a mineral-containing composition from the raw material liquid includes the following steps (1) to (4), and also includes steps (5) to (7) one to three times: (1) Mix 0.25 to 0.75 kg of acetic acid per 1 kg of the raw material liquid. (2) Heat the mixture before and / or after mixing with acetic acid until the temperature of the mixture reaches 50 to 85°C. (3) Calcium carbonate calcined at 140°C to 210°C is mixed in an amount of 0.25 to 2.5 kg per 1 kg of the acetic acid mixed in (1), and left to stand at 40°C or lower for 12 hours or more to cause crystallization and precipitation. (4) Mix 0.05 to 0.2 kg of nitrate per 1 kg of solution containing crystals and precipitates, then collect the crystals. (5) The recovered crystals are dissolved in a raw material solution in an amount (weight ratio) of 1 / 4 to 4 / 4 of the raw material solution of (1). (6) Remove insoluble components to obtain a solution (7) Step (2) is read as "The temperature of the solution in (6) is adjusted to 50 to 85°C," and steps (2) to (4) are carried out.

3. 3. The method for producing a mineral-containing composition according to claim 2, wherein the raw material liquid further satisfies the following conditions: (C) Sulfate ions: 9.808 g / L or less (D) Iodine is 12.69 g / L or less (E) Carbon dioxide is 1 mL / L or less

4. A mineral-containing composition produced by the method according to any one of claims 1 to 3.

5. A bath additive composition, which is the composition of claim 4.

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