WO2008153274A1

WO2008153274A1 - Preparation method of mineral water and mineral salt from deep ocean water

Info

Publication number: WO2008153274A1
Application number: PCT/KR2008/002511
Authority: WO
Inventors: Moonsoo Kim
Original assignee: Yoo, Yung-Geun
Priority date: 2007-06-11
Filing date: 2008-05-02
Publication date: 2008-12-18
Also published as: KR100868493B1

Abstract

Disclosed herein is a method of producing mineral water or mineral salt from deep ocean water using desalination processes, the desalination processes including a desalination process using electrodialysis in which monovalent and bivalent cation exchange membranes and monovalent and bivalent anion exchange membranes are sequentially combined, a desalination process using pressure higher than the osmotic pressure of ocean water through a reverse osmosis membrane, a desalination process of removing some ocean water through evaporation to deposit salt therefrom and then removing the deposited salt, and a desalination process using electrolysis in which silver, gold or platinum electrodes are used. Provided a method of producing mineral water and mineral salt from deep ocean water, in which minerals, such as magnesium, calcium, salts thereof, etc., are selectively separated from deep ocean water which has a high mineral content and is not contaminated with chemicals or bacteria, thus adjusting the content of each mineral.

Description

PREPARATION METHOD OF MINERAL WATER AND MINERAL SALT FROM DEEP OCEAN WATER

Technical Field

[1] The present invention relates to a method of producing mineral water and mineral salt from deep ocean water, and, more particularly, to a method of producing mineral water and mineral salt from deep ocean water, in which minerals, such as magnesium, calcium, salts thereof, etc., are selectively separated from deep ocean water, which has a high mineral content and is not contaminated with chemicals or bacteria, thus adjusting the content of each mineral. Background Art

[2] The term "deep ocean water" refers to ocean water present at a place located 200 m or more from the surface of ocean water, and is different from surface ocean water. Since phytoplankton, which ingests nutrients, is not present in deep ocean water, at which solar light does not arrive, deep ocean water is rich in nutrients decomposed by bacteria and includes minerals, such as calcium, magnesium, and the like, in large quantities. That is, deep ocean water is eutrophied and mineralized. Deep ocean water, which is ocean water present at a place located 200 m or more from the surface of ocean water, has a low organic matter concentration, is not contaminated by coli bacteria or general bacteria, is almost impossible to contaminate by chemicals emitted from land or air, has a constant temperature throughout the year, and is stable because it has formed over several thousand years. Further, since deep ocean water includes essential microelements and various mineral components in balanced amounts, it is known to have an excellent function for efficiently removing active oxygen due to the action of metal ions dissolved therein.

[3] Due to the useful effects of deep ocean water, various attempts to produce salt and potable water having a high mineral content from the deep ocean water have been made. Since deep ocean water is very salty, it is not suitable for direct ingestion. Therefore, in order to use the deep ocean water, excess salt must be separated from the deep ocean water. However, in the process of separating salt from the deep ocean water, there is a problem in that calcium, magnesium, etc., which are useful mineral components, are removed therefrom along with the salt. Therefore, various attempts to solve the above problem have been made.

[4] Since the salt produced from deep ocean water does not include environmental pollutants, and includes various mineral components useful to the human body having lower concentrations of harmful metals than salt produced from surface ocean water, deep ocean water is characterized in that high-quality salt, which is good for health, can be produced therefrom. In this case, when mineral salt, including mineral components useful to the human body, is produced from deep ocean water, compared to when salt is simply obtained from non-contaminated deep ocean water, the advantages of deep ocean water can be maximized.

[5] Korean Patent Registration Nos. 663084, 688636, 667968 and 686979 disclose methods of producing mineral salt or mineral water from deep ocean water using electrolysis, electrodialysis, and reverse osmosis. However, these patent documents relate only to methods of producing potable water or salt by removing excess salt (NaCl) from deep ocean water or only to processes of separating monovalent ions or bivalent ions from deep ocean water. Therefore, the technologies disclosed in these patent documents have technical limitations in producing mineral water or mineral salt including specific minerals, such as magnesium, calcium and potassium, other than sodium, in large quantities by selectively separating the specific minerals from deep ocean water.

[6] Ionized minerals are active minerals which can be used by the human body.

Recently, it has been reported that, in the case of mineral supplementation systems, minerals are not ionized, thus decreasing mineral availability to the human body. Since bodily mineral deficiencies differ according to human's physical characteristics, genetic properties and living habits, minerals suitable for human's physical characteristics can be supplied to the human body only when minerals can be selectively separated from deep ocean water. As an example of antagonism between minerals, generally, sodium (Na) and potassium (K) serve an important role of maintaining blood pressure and water content in the body while remaining in balance in the body. Magnesium (Mg) and calcium (Ca) also maintain a balance of content therebetween. As such, when the balance in the body is broken, adult diseases, such as diabetes, metabolic syndromes, and the like, are caused. Therefore, when each mineral component can be selectively separated from deep ocean water including various active minerals, minerals suitable for human's physical characteristics can be easily supplied to the body in a state in which they can be easily absorbed in the body. Disclosure of Invention Technical Problem

[7] Accordingly, the present invention has been made keeping in mind the above problems occurring in the prior art, and an object of the present invention is to provide a method of producing mineral water or mineral salt, selectively including minerals, from deep ocean water using electrolysis, electrodialysis, reverse osmosis, and crystallization due to solubility differences therebetween. Technical Solution

[8] In order to accomplish the above object, the present invention provides a method of producing mineral water or mineral salt from deep ocean water using desalination processes, in which the desalination processes include a desalination process using electrodialysis, in which monovalent and bivalent cation exchange membranes and monovalent and bivalent anion exchange membranes are sequentially combined, a desalination process using pressure higher than the osmotic pressure of ocean water through reverse osmosis membrane, a desalination process of removing some of the ocean water through evaporation to deposit salt therefrom and then removing the deposited salt, and a desalination process using electrolysis, in which silver, gold or platinum electrodes are used.

[9] Various kinds of electrolysis membranes may be used according to the kind of ions to be separated. That is, when monovalent anions and monovalent cations are to be separated, a monovalent anion exchange membrane and a monovalent cation exchange membrane may be used, and, when monovalent anions and bivalent cations are to be separated, a monovalent anion exchange membrane and a bivalent cation exchange membrane may be used. Further, when bivalent anions and monovalent cations are to be separated, a bivalent anion exchange membrane and a monovalent cation exchange membrane may be used. That is, in electrodialysis, only monovalent cations selectively permeate a monovalent cation exchange membrane, and only monovalent anions selectively permeate a monovalent anion exchange membrane. Therefore, when electrodialysis is conducted by combining a monovalent cation exchange membrane with a monovalent anion exchange membrane, monovalent cations, such as Na⁺ and K⁺, and a monovalent anion, such as Cl^", can be selectively removed. In contrast, when electrodialysis is conducted by combining a monovalent cation exchange membrane with a bivalent anion exchange membrane, monovalent cations, such as Na⁺ and K⁺, and a monovalent anion, such as SO ^", can be selectively removed. Since a bivalent cation exchange membrane passes only Ca ⁺ and Mg ⁺ included in deep ocean water, the Ca ⁺ and Mg ⁺ can be separated from the deep ocean water through the bivalent cation exchange membrane. In particular, the Ca ⁺ and Mg ⁺ can be separated from each other using the difference in the permeation rate therebetween.

[10] Desalination treatment using reverse osmotic pressure is performed by applying a high pressure of 50 ~ 70 kg/cm, which is higher than the osmotic pressure of ocean water, to ocean water through a semipermeable membrane, thus filtering the ocean water. As the semipermeable membrane, a cellulose membrane or a polyamide membrane may be used. As found in the following Examples of the present invention, through the desalination treatment using reverse osmotic pressure, ocean water can be turned into fresh water, and in addition, ions are concentrated.

[11] After evaporating ocean water to remove some of the water from the ocean water, desalination treatment is performed using the difference in solubility, and, particularly, can be effectively used to separate sodium salt and potassium salt from each other and to separate magnesium salt and calcium salt from each other.

[12] It is preferred that electrolysis be performed using gold, silver or platinum electrodes.

As found in the following Examples of the present invention, when carbon electrodes are used in electrolysis, Cl and SO cannot be efficiently removed, and furthermore, alkaline mineral water cannot be obtained. However, when gold, silver or platinum electrodes are used in electrolysis, Cl and SO can be removed, and alkaline mineral water having a high pH can also be obtained. Among these electrodes, platinum electrodes can be most efficiently used, and, additionally, Na ions can be removed. The process of removing chlorine and producing alkaline water using platinum electrodes and gold electrodes is represented by the following Equation.

[13] Pt + 2NaCl + 2Cl₂ → (Na)₂PtCl₆ (precipitated)

[14] 2Au + 4NaCl + 1/20 + H O → 2NaAuCl (precipitated) + 2NaOH

[15] FIG. 1 is an entire process view showing the process of producing mineral water or mineral salt from deep ocean water according to the present invention. As shown in FIG. 1, mineral water or mineral salt, having a high mineral content, can be produced by selecting necessary processes in the process view. The abbreviations used in FIG. 1 are as follows: R/O (reverse osmosis), ED (electrodialysis), E/V (evaporation), M/T (mixed tank), C/F (centrifugal separation), and E/L (electrolysis).

[16] Specifically, an aspect of the present invention provides a method of simultaneously producing magnesium mineral water and calcium mineral water, comprising the steps of: (A) taking deep ocean water and then filtering the deep ocean water; (B) electro- dialyzing the filtered ocean water using a monovalent cation exchange membrane and a monovalent anion exchange membrane; and (C) electrodialyzing the electrodialyzed water using a monovalent cation exchange membrane and a bivalent anion exchange membrane or a bivalent cation exchange membrane and a monovalent anion exchange membrane.

[17] In step (B), since only NaCl and KCl can pass through the ion exchange membranes,

NaCl and KCl are removed from the deep ocean water through electrodialysis. In step (C), SO of Ca ⁺, Mg ⁺ and SO remaining in concentrated water during the elec-

4 4 trodialysis can be removed, and, simultaneously, magnesium mineral water and calcium mineral water can be separated from each other using the difference in the permeation rate between Mg ⁺ and Ca ⁺, thus simultaneously producing the magnesium mineral water and calcium mineral water. [18] In this case, the electrodialysis process may be performed after deep ocean water is merely filtered, but may also be performed after the filtered deep ocean water is concentrated by reverse osmotic pressure.

[19] In order to more efficiently separate Mg ⁺ and Ca ⁺ included in the calcium mineral water and magnesium mineral water, the method of simultaneously producing magnesium mineral water and calcium mineral water according to an aspect of the present invention may further include, immediately before the step (B): evaporating the filtered ocean water in an evaporator to deposit calcium salts (CaSO and CaCO ) and then removing the deposited calcium salts.

[20] Another aspect of the present invention provides a method of producing calcium mineral water, including the steps of: (A) taking deep ocean water and then filtering the deep ocean water; (B) evaporating the filtered ocean water in an evaporator to deposit calcium salt and then filtering the deposited calcium salt; (C) dissolving the filtered calcium salt in permeated water filtered through a reverse osmosis membrane; and (D) electrodialyzing the calcium salt-dissolved permeated water using a monovalent cation exchange membrane and a bivalent anion exchange membrane.

[21] In this case, the electrodialysis process may be performed after deep ocean water is merely filtered, but may also be performed after the filtered deep ocean water is concentrated by reverse osmotic pressure.

[22] A further aspect of the present invention provides a method of producing potassium mineral water, comprising the steps of: (A) taking deep ocean water and then filtering the deep ocean water; (B) electrodialyzing the filtered ocean water using a monovalent cation exchange membrane and a bivalent cation exchange membrane; and (C) evaporating the electrodialyzed water in an evaporator to deposit sodium salt and then removing the deposited calcium salt by filtering the electrodialyzed water.

[23] In this case, the electrodialysis process may be performed after deep ocean water is merely filtered, but may also be performed after the filtered deep ocean water is concentrated by reverse osmotic pressure.

[24] In order to more efficiently remove calcium included in the potassium mineral water, the method of producing potassium mineral water according to a further aspect of the present invention may further include, immediately before the step (B): evaporating the filtered ocean water in an evaporator to deposit calcium salts (CaSO and CaCO ) and

4 3 then removing the deposited calcium salts.

[25] When the calcium mineral water, magnesium mineral water and potassium mineral water, produced through the above processes, are additionally electrolyzed using silver, gold, or platinum electrodes, respectively, Cl and SO included in the respective mineral waters can be additionally removed, and alkaline mineral waters having high pH, such as alkaline calcium mineral water, alkaline magnesium mineral water and alkaline potassium mineral water, can also be obtained. [26] When the calcium salts (CaSO and CaCO ), obtained through the process of

4 3 producing mineral water according to the present invention, is dissolved in water and then carbon dioxide (CO ) gas is injected thereinto, carbonated water can also be produced.

[27] A still further aspect of the present invention provides a method of producing mineral salt, comprising the steps of: (A) taking deep ocean water and then filtering the deep ocean water; (B) electrodialyzing the filtered ocean water using a monovalent cation exchange membrane and a monovalent anion exchange membrane; (C) mixing the electrodialyzed water with the potassium mineral water of claim 6 at a volume ratio of 1:0.5-1.5; and (D) evaporating the mixed mineral water in an evaporator.

Advantageous Effects

[28] According to the present invention, mineral water or mineral salt, selectively including minerals, can be produced from deep ocean water through electrodialysis, electrolysis, reverse osmosis, or crystallization due to differences in solubility. Brief Description of the Drawings

[29] FIG. 1 is a schematic process view showing a process of producing mineral water or mineral salt from deep ocean water according to the present invention. Mode for the Invention

[30] Hereinafter, the present invention will be described in detail with reference to the following Examples.

[31] A better understanding of the present invention may be obtained through the following examples, which are set forth to illustrate, but are not to be construed as the limit of the present invention.

[32]

[33] Examples

[34] In the following examples, cations were analyzed using inductively-coupled plasma

(ICP), and parts per billion (ppb) thereof were measured using inductively-coupled plasma mass spectrometry (ICP-MS). Further, anions were quantitatively determined using ion chromatography.

[35]

[36] Example 1: Electrodialysis (ED)

[37] A sample tank was filled with 9L of reverse osmotic concentrated water, an electrolyte tank was filled with 5% of a sodium nitrate solution, and a concentration tank was filled with desalinated water, and then the electrodialyzer was operated. The electrodialysis was conducted until about 1 - 50 mS/cm of electric conductivity appeared while changes in electric conductivity were observed. In this case, a monovalent cation-bivalent anion membrane(AC-120-4G40) was used as an elec- trodialysis membrane, and ACILYZER-2, manufactured by ASTOM CORP., was used as the electrodialyzer.

[38] The following Table 1 shows the amount of metal ions according to electric conductivity at the time of electrodialyzing deep ocean water. [39] Table 1 [Table 1] [Table ]

[40] [41] Example 2: Electrolysis (E/L) [42] IL of a sample was taken, a power supply was set to 0.5 A, and current flowed into the sample for 1 - 5 hours, and then the amount of mineral in the sample was measured.

[43] The following Tables 2 to 5 show the results of analysis of the amount (ppm) of mineral in the sample according to the electrolysis time using carbon electrodes, silver electrodes, gold electrodes and platinum electrodes, respectively.

[44] Table 2 [Table 2] [Table ]

[45] Table 3 [Table 3] [Table ]

[46] Table 4 [Table 4] [Table ]

[47] Table 5 [Table 5] [Table ]

[48] [49] Example 3: Reverse osmosis (RO) [50] A deep ocean water supply valve was opened, and then a reverse osmosis membrane was operated. A fouling resistance membrane (FRM, manufactured by Saehan Corp.) was used as the reverse osmosis membrane, and 7 x RE8040SR elements/vessel (commercial plant) was used as a reverse osmosis apparatus. In this case, filter water and concentrated water were produced by controlling the osmotic pressure at a pressure of 50 -70 kg/cm using an osmotic pressure regulator.

[51] The amount of ions in the filter water and concentrated water after the reverse osmosis treatment are shown in Table 6. [52] Table 6 [Table 6] [Table ]

[53] [54] Preparation Examples [55] Preparation Example 1 : Mg ⁺ mineral water [56] Ocean water or primary or secondary RO brine was primarily electrodialyzed using a monovalent anion membrane and a monovalent cation membrane to remove NaCl and KCl therefrom. Subsequently, the resultant product was secondarily electrodialyzed using a monovalent anion membrane and a bivalent cation membrane or a bivalent anion membrane and a monovalent cation membrane to separate Ca ⁺ therefrom, thereby preparing Mg ⁺ mineral water.

[57] [58] Preparation Example 2: Mg ⁺-containing mineral water [59] Filtered ocean water or RO brine was sent into an evaporator, and Ca 2^z+⁺ i .ons were removed therefrom, and then Mg ⁺-containing mineral water was prepared using the same method as in Preparation Example 1.

[60] [61] Preparation Example 3: Ca ⁺-containing mineral water [62] Ocean water was taken and then filtered. Subsequently, CaSO and CaCO , obtained by evaporating RO brine or ocean water, was mixed with permeated water that had been passed through primary and secondary reverse osmosis (RO) processes, and was then dissolved therein. Subsequently, the resultant was electrodialyzed using a bivalent anion membrane and a monovalent cation membrane to remove SO and CO ,

4 3 thereby preparing Ca ⁺-containing mineral water.

[63]

[64] Preparation Example 4: Ca ⁺ mineral water

[65] Ocean water or RO brine was primarily electrodialyzed using a monovalent anion membrane and a monovalent cation membrane to remove NaCl and KCl therefrom. Subsequently, the resultant product was secondarily electrodialyzed using a monovalent cation membrane and a bivalent anion membrane or a monovalent anion membrane and a bivalent cation membrane, thereby preparing Ca ⁺ mineral water using the difference in the permeation rate of Ca ⁺.

[66]

[67] Preparation Example 5: K⁺ mineral water

[68] Ocean water or RO brine was electrodialyzed using a monovalent anion membrane and a monovalent cation membrane to separate NaCl and KCl therefrom. Subsequently, the resultant product was sent into an evaporator to separate NaCl in a crystallized state, thereby preparing K⁺ mineral water.

[69]

[70] Preparation Example 6: K⁺ mineral water

[71] Filtered ocean water or RO brine was sent into an evaporator, and Ca ⁺ ions were previously removed therefrom, and then the remainder was electrodialyzed using a monovalent anion membrane and a monovalent cation membrane to remove NaCl and KCl therefrom, as in Preparation Example 5. Subsequently, the resultant product was further electrodialyzed using a monovalent anion membrane and a monovalent cation membrane, thereby preparing K⁺ mineral water.

[72]

[73] Preparation Example 7: Alkaline mineral water

[74] Cl and SO were removed from the mineral water prepared in Preparation

Examples 1 to 6 using an electrolyzer, thereby preparing alkaline mineral water having a ph of 7.8 ~ 11.

[75]

[76] Preparation Example 8: Mg ⁺, Ca ⁺, K⁺ mineral water

[77] Ocean water or RO brine was electrodialyzed using a monovalent anion membrane and a monovalent cation membrane to remove bivalent anions, such as B, SO and CO , thereby preparing Mg ⁺, Ca ⁺, K⁺ mineral water of Preparation Examples 1 to 6, respectively.

[78] [79] Preparation Example 9: Mineral carbonated water [80] CO was injected into CaSO and CaCO , obtained by evaporating RO brine or ocean water in Preparation Examples 2 and 6, thereby preparing mineral carbonated water.

[81] [82] Preparation Example 10: K/Ca/Mg containing mineral salt [83] K⁺ mineral water including no NaCl, prepared in Preparation Example 5, and Mg ⁺ and Ca ⁺ containing mineral water, electrodialyzed using a monovalent anion membrane and a monovalent cation membrane, were evaporated using an evaporator, thereby preparing K/Ca/Mg containing mineral salt.

[84] [85] The amount of ion in mineral water of Preparation Examples is shown in Table 7. [86] Table 7 [Table 7] [Table ]

[87]

Industrial Applicability

[88] Although the preferred embodiments of the present invention have been disclosed for illustrative purposes, those skilled in the art will appreciate that various modifications, additions and substitutions are possible, without departing from the scope and spirit of the invention as disclosed in the accompanying claims.

Claims

[1] A method of simultaneously producing magnesium mineral water and calcium mineral water, comprising:

(A) taking deep ocean water and then filtering the deep ocean water;

(B) electrodialyzing the filtered ocean water using a monovalent cation exchange membrane and a monovalent anion exchange membrane; and

(C) electrodialyzing the electrodialyzed water using a monovalent cation exchange membrane and a bivalent anion exchange membrane or a bivalent cation exchange membrane and a monovalent anion exchange membrane.

[2] The method of simultaneously producing magnesium mineral water and calcium mineral water according to claim 1, further comprising, between (A) and (B): concentrating the filtered ocean water using reverse osmosis pressure.

[3] The method of simultaneously producing magnesium mineral water and calcium mineral water according to claim 1 or 2, further comprising, immediately before (B): evaporating the filtered ocean water in an evaporator to deposit calcium salt and then removing the deposited calcium salt.

[4] A method of producing calcium mineral water, comprising:

(A) taking deep ocean water and then filtering the deep ocean water;

(B) evaporating the filtered ocean water in an evaporator to deposit calcium salt and then filtering the deposited calcium salt;

(C) dissolving the filtered calcium salt in permeated water filtered through a reverse osmosis membrane; and

(D) electrodialyzing the calcium salt-dissolved permeated water using a monovalent cation exchange membrane and a bivalent anion exchange membrane.

[5] The method of producing calcium mineral water according to claim 4, further comprising, between (A) and (B): concentrating the filtered ocean water using reverse osmosis pressure.

[6] A method of producing potassium mineral water, comprising:

(A) taking deep ocean water and then filtering the deep ocean water;

(B) electrodialyzing the filtered ocean water using a monovalent cation exchange membrane and a bivalent cation exchange membrane; and

(C) evaporating the electrodialyzed water in an evaporator to deposit sodium salt and then removing the deposited calcium salt by filtering the electrodialyzed water.

[7] The method of producing potassium mineral water according to claim 6, further comprising, between (A) and (B): concentrating the filtered ocean water using reverse osmosis pressure. [8] The method of producing potassium mineral water according to claim 6 or 7, further comprising, immediately before (B): evaporating the filtered ocean water in an evaporator to deposit calcium salt and then removing the deposited calcium salt. [9] A method of producing mineral salt, comprising:

(A) taking deep ocean water and then filtering the deep ocean water;

(B) electrodialyzing the filtered ocean water using a monovalent cation exchange membrane and a monovalent anion exchange membrane;

(C) mixing the electrodialyzed water with the potassium mineral water of claim 6 at a volume ratio of 1:0.5-1.5; and

(D) evaporating the mixed mineral water in an evaporator.