KR100899012B1 - Preparation method of magnesium, calcium and potassium mineral water from deep ocean water - Google Patents

Abstract

The present invention relates to an apparatus for producing mineral water or mineral salts from deep sea water, and more particularly, by electrodialysis applying a combination of monovalent and divalent cation selective exchange membranes and monovalent and divalent anion selective exchange membranes sequentially. Desalination treatment method, desalination treatment method by treatment of pressure higher than osmotic pressure of seawater through reverse osmosis membrane, desalination treatment method by removing part of water by evaporation, and desalination treatment method, using silver, gold or platinum electrode It is characterized by using a desalination treatment method by electrolysis. According to the present invention, by selectively separating specific minerals such as magnesium, calcium and potassium or salt from the deep ocean water that is rich in mineral content and free from contamination by chemicals or bacteria, mineral water and mineral salts whose content is adjusted for each mineral is controlled. It can manufacture.

Deep sea water, mineral water, electrodialysis, cation selective exchange membrane, anion selective exchange membrane, electrolysis, reverse osmosis

Description

Preparation method of magnesium, calcium and potassium mineral water from deep ocean water}

The present invention relates to a device for producing mineral water or mineral salts from deep sea water, and more particularly, to a particular mineral such as magnesium, calcium or salt from deep sea water rich in minerals and free from contamination by chemicals or bacteria. It relates to a method of producing mineral water or mineral salt that can be selectively separated to control the content of each mineral.

Deep sea water refers to sea water 200 meters or less from the surface of the sea and is called deep sea water separately from surface water. There is no phytoplankton that consumes nutrients in the deep sea where sunlight does not reach, so deep ocean water is rich in nutrients decomposed by bacteria and contains eutrophic (mineral) minerals such as calcium and magnesium. . Less than 200 meters from surface seawater, low concentrations of organic matter, no contamination by Escherichia coli or common bacteria, less likelihood of contamination by chemicals from land or air, less change at low temperatures throughout the year, and formed over thousands of years. Its water is stable. In addition, it is known that the essential trace elements or various mineral components are contained in a balanced manner and have excellent properties such as excellent scavenging action against active oxygen due to the action of dissolved metal ions.

Due to the useful effects of deep sea water, various attempts have been made to use salts and beverages having high mineral content from deep sea water. Deep sea water itself has a strong salty taste, so it is difficult to drink as it is, in order to use it, it is necessary to separate the excess salt. However, there is a problem that calcium and magnesium, which are useful hardness and minerals, are also removed in the process of separating salts, and various attempts have been made to compensate for this. Salt produced from deep sea water does not contain any environmental pollutants, and it has a low concentration of harmful metals and contains various minerals useful for human body compared to salt produced in surface seawater. There is a characteristic. However, it is possible to maximize the benefits of deep seawater by not only obtaining salt from deep seawater with low pollution, but also by preparing mineral salts with controlled mineral content.

Patents 663084, 688636, 667968, 686979, and the like describe a method for producing mineral salt or mineral water from deep sea water using electrolysis, electrodialysis or reverse osmosis membrane. However, this is simply a method of preparing a beverage or salt from which excess salt (NaCl) has been removed in order to alleviate the inexpensive taste of deep sea water, or a process of separating monovalent and divalent ions. Therefore, the above technique has a technical limitation in producing a mineral water or a mineral salt containing a large amount of the specific mineral by selectively separating specific minerals, that is, magnesium, calcium or potassium, not sodium.

Minerals that are in an ionized state are called active minerals that can be used by the human body, and mineral mineral supplements have recently been reported to have low human utilization because they are not ionized. In addition, the lack of minerals in the body is different depending on the physical characteristics, genetics and lifestyle of the person, so that the minerals can be selectively separated to provide the minerals for each person's characteristics. For example, antagonistic interactions between minerals, for example, Na and K play a major role in maintaining the body's blood pressure and water content while maintaining a balance in the body. Mg and Ca also play an important role in maintaining mutual mineral content. When this balance is broken, adult diseases such as diabetes and metabolic syndrome are caused. Therefore, if each mineral component can be selectively separated from the deep sea water containing a variety of active minerals, it will be easy to supply appropriate minerals easily absorbed by each individual.

The present invention is to solve the problems of the prior art as described above, to produce a mineral water or mineral salt selectively containing each mineral by crystallization by electrodialysis, electrolysis, reverse osmosis and solubility difference from the deep sea For the purpose of

Therefore, the present invention, (A) taking the deep sea water and passing through the filter; (B) electrodialysis through the monovalent cation selective exchange membrane and the monovalent anion selective exchange membrane; And (C) electrodialyzing the electrolyzed mineral water in step (B) through a monovalent cation selective exchange membrane and a divalent anion selective exchange membrane or a divalent cation selective exchange membrane and a monovalent anion selective exchange membrane. Magnesium Provides a method for the simultaneous production of mineral water and calcium mineral water.

In addition, the present invention, (A) taking the deep sea water and passing the filter; (B) electrodialysis of the filtered deep sea water through the monovalent cation selective exchange membrane and the monovalent anion selective exchange membrane; And (C) potassium salt comprising the step of filtering and removing the precipitated sodium salt by evaporating the mineral salt obtained by electrodialysis in step (B) in an evaporator. It provides a method for producing mineral water.

According to the present invention, mineral water or mineral salts selectively containing each mineral can be prepared by crystallization by electrodialysis, electrolysis, reverse osmosis, and solubility from the deep ocean.

The present invention for achieving the above object is a desalination treatment method by electrodialysis applying a combination of monovalent and divalent cation selective exchange membrane and monovalent and divalent anion selective exchange membrane, pressure higher than osmotic pressure of seawater through reverse osmosis membrane It is characterized by using a desalination treatment method by the treatment of desalination, a desalination treatment method by removing a portion of the water after evaporation, and a desalination treatment method by electrolysis using silver, gold or platinum electrodes. .

The electrodialysis membrane is used depending on the ions to be separated, i.e., -1 and +1 membranes to separate -1 and +1 ions, and -1 to separate -1 and +2 ions. And +2 use the membrane. On the contrary, when the -divalent and + 1-valent membranes are used, -2-valent and + 1-valent ions can be separated. That is, in the electrodialysis process, the monovalent cation selective exchange membrane selectively permeates only the monovalent cations, and the monovalent anion selective exchange membrane selectively permeates only the monovalent anions. Therefore, when electrodialysis is performed by the combination of the monovalent cation selective exchange membrane and the monovalent anion selective exchange membrane, only monovalent cations such as Na ⁺ , K ⁺ and Cl ⁻ and monovalent anions can be selectively removed. On the other hand, when the monovalent cation selective membrane and the divalent anion selective membrane are combined, only monovalent cations and divalent anions such as Na ⁺ , K ⁺ and SO ₄ ^{2 -} can be selectively removed. 2 can remove the Ca ²⁺ and Mg ²⁺ using the difference of speed that can Ca ^{+ 2,} Mg ^{+ 2,} so only capable of transmitting separate them from selected cationic membranes deep sea water, in particular transmission.

In the desalination treatment using reverse osmosis, seawater is filtered and desalted by applying a pressure of 50 ~ 70kg / cm higher than the osmotic pressure of seawater with a semipermeable membrane in between. As said semipermeable membrane, a cellulose or a polyamide membrane can be used. As can be seen in the embodiment of the present invention, desalination treatment using reverse osmosis can concentrate the ions and obtain desalted water.

The method of desalination after removing a part of water by evaporation uses a difference in solubility, and is particularly effective for separating sodium and potassium salts and separating magnesium and calcium salts.

Electrolysis is preferably electrolyzed using gold, silver or platinum electrodes. As can be seen from the examples, the removal of Cl ⁻ and SO ₄ ^{2 −} was not efficient by the carbon electrode, and alkali mineral water could not be obtained. However, when silver, gold, or platinum electrodes were used, Cl ⁻ and SO ₄ ^{2 −} could be removed, and alkaline mineral water with high pH could be prepared. Among them, the use of platinum electrodes was the most efficient and additionally. Na ions can also be removed. The following is a reaction formula for removing chlorine from a platinum electrode and a gold electrode and preparing an alkaline water.

Pt + 2NaCl + 2Cl ₂ → (Na) ₂ PtCl ₆ (Precipitation)

2Au + 4NaCl + 1 / 2O ₂ + H ₂ O → 2NaAuCl ₂ (precipitate) + 2NaOH

1 is a general process showing the manufacturing process of the mineral water or mineral salt according to the present invention by selectively applying the necessary processes in the process diagram it is possible to produce a high mineral water or mineral salt content of each mineral. Abbreviations used in FIG. 1 are as follows; R / O, reverse osmosis; ED, electrodialysis; E / V, evaporation; M / T, mixing tank; C / F, centrifugation; E / L, electrolysis.

More specifically, the present invention in one aspect (A) taking the deep sea water and passing through the filter; (B) electrodialysis through the monovalent cation selective exchange membrane and the monovalent anion selective exchange membrane; And (C) electrodialyzing the mineral water electrodialyzed in step (B) through a monovalent cation selective exchange membrane and a divalent anion selective exchange membrane or a divalent cation selective exchange membrane and a monovalent anion selective exchange membrane. Featured Magnesium The present invention relates to a method for simultaneously producing mineral water and calcium mineral water.

In step (B), since only NaCl and KCl can pass through the ion selective exchange membrane, NaCl and KCl are removed through the electrodialyzed dialysis water. (C) phase, remaining in the concentrated ^{Mg 2 +, Ca 2 +,} SO 4 2 , which in an electrodialysis process, ^- at the same time to eliminate the use of the difference of the moving speed of the Mg ²⁺ and Ca ^{2 + -} SO ₄ ² of It is possible to manufacture magnesium mineral water and calcium mineral water separately.

In this case, the deep sea water may be subjected to electrodialysis after only filtration, but the deep sea water may be concentrated by reverse osmosis, followed by electrodialysis.

In order to remove the calcium mineral and magnesium mineral of Mg ^{2 +} and Ca ^{2 +} than effectively removing the calcium salt (CaSO ₄ and CaCO ₃₎ The evaporation to precipitate in the evaporator sea water just prior to the step (B) It is more preferable to include it further.

In addition, the calcium mineral water (A) taking deep sea water and passing through the filter; (B) evaporating the filtered deep sea water in an evaporator to obtain a precipitated calcium salt by filtration; (C) dissolving the calcium salt obtained in step (B) in the permeated water filtered through the reverse osmosis membrane of the deep sea water; And (D) electrodialysis of the reverse osmosis membrane permeated water in which the calcium salt is dissolved through the monovalent cation selective exchange membrane and the divalent anion selective exchange membrane.

In this case, the deep sea water may be subjected to electrodialysis after only filtration, but the deep sea water may be concentrated by reverse osmosis, followed by electrodialysis.

Another aspect of the present invention relates to a method for producing potassium mineral water, comprising the steps of: (A) taking deep ocean water and passing the filter through; (B) electrodialysis of the filtered deep sea water through the monovalent cation selective exchange membrane and the monovalent anion selective exchange membrane; And (C) evaporating the mineral brine obtained by electrodialysis in the step (B) in an evaporator to remove the precipitated sodium salt by filtration.

In this case, the deep sea water may be subjected to electrodialysis after only filtration, but the deep sea water may be concentrated by reverse osmosis, followed by electrodialysis.

In addition, in order to more effectively remove calcium contained in the potassium mineral water, the step of evaporating the seawater in an evaporator immediately before the step (B) and further comprising the step of removing the precipitated calcium salts (CaSO ₄ and CaCO ₃ ). desirable.

The number of mineral calcium prepared by the above process, the addition of magnesium can be mineral and potassium mineral is, when each of the electrolysis using a gold or platinum electrode of mineral Cl ^- can be added to the removal, SO ₄ ^-2, Alkaline calcium mineral water, alkaline magnesium mineral water and alkaline potassium mineral water can be prepared by adjusting the pH of the mineral water to alkalinity.

Carbonated water may be prepared by dissolving calcium salt ((CaSO ₄ and CaCO ₃ ) obtained in the process of preparing mineral water of the present invention in water and injecting carbon dioxide gas.

Another aspect of the present invention relates to a method for preparing a mineral salt having a low sodium content. More specifically, (A) taking the deep sea water and passing the filter; (B) electrodialysis of the filtered deep sea water through the monovalent cation selective exchange membrane and the monovalent anion selective exchange membrane; C) mixing potassium mineral water according to claim 6 in a volume ratio of 1: 0.5 to 1.5 with mineral brine obtained by electrodialysis in step (B); And (D) evaporating the mixed mineral water of step (C) in an evaporator.

The present invention will be described in detail through the following examples. However, these examples are for illustrative purposes only and the present invention is not limited thereto.

Example

In the following examples, cations were analyzed using ICP (inductively coupled plasma) and ppb units were used for ICP-MS. In the case of anions, they were quantified using IC (ion chromatography).

Example  1: electrodialysis (ED)

Fill the sample tank with 9L of reverse osmosis concentrated water, 4L of 5% sodium nitrate solution in the electrolytic chamber, 4L of demineralized water in the concentration tank, operate the electrodialysis apparatus and check the change of electrical conductivity after 1 ~ 50mS / cm. Electrodialysis was performed until electrical conductivity appeared. At this time, the electrodialysis membrane was used a cationic monovalent anion divalent membrane (AC-120-4G40), the electrodialysis apparatus was used ACILYZER-2 of ASTOM.

Table 1 below shows the amount of metal ions according to electrical conductivity during dialysis of deep sea water using electrodialysis.

EC (ms / cm) Metal ion content (ppm) 50 mS / cm 40 mS / cm 20 mS / cm 10 mS / cm 8 mS / cm 3mS / cm Na 11000 6200 ~ 7100 2000 ~ 2400 75-150 35-55 1-5 K 400 250-300 40-60 2 ~ 8 4 ~ 5 0 Mg 1270 1240-1250 1150-1240 450-650 25-55 4-10 Ca 430 400-420 360-400 40-70 8 ~ 10 2 ~ 5 Cl 19000 9100-11000 6400-6800 400-550 115-130 5-12 SO4 2700 2000-2600 1600-1900 250-350 30-35 3 ~ 6 Hardness 6400 6200 ~ 6300 5700-6200 2000 ~ 2900 120-200 20-50

Example  2: Electrolysis (E / L)

After taking 1 L of the sample, the power supply was fixed at 0.5 A, and a current was flown for 1 to 5 hours, and then the mineral content in the sample was measured.

Tables 2 to 5 show the results of analyzing the sample (ppm) of the sample taken according to the electrolysis time using the carbon electrode, silver electrode, gold electrode and platinum electrode, respectively.

    Mineral Hour (hr) Mg Ca K Na Cl SO ₄ Hardness pH Early 200 50.3 51.6 71.9 876.4 146.0 965.7 6.8 One 204.3 50.1 51.5 72.3 863.1 145.2 963.3 6.9 3 210.1 51.2 50.3 73.1 861.5 144.1 989.9 6.2 5 212.7 51.9 52.0 74.0 858.2 143.0 1001.9 5.9

    Mineral Hour (hr) Mg Ca K Na Cl SO ₄ Hardness pH Early 200 50.3 51.6 71.9 876.4 146.0 965.7 6.8 One 224.2 65.1 60.5 76.5 463.1 117.5 1104 8.7 3 253.6 73.6 72.1 81.1 371.4 101.3 1219.7 9.2 5 261.5 75.4 76.0 84.0 288.6 96.1 1286 10.1

    Mineral Hour (hr) Mg Ca K Na Cl SO ₄ Hardness pH Early 200 50.3 51.6 71.9 876.4 146.0 965.7 6.8 One 220.1 64.5 61.8 70.4 475.5 126.1 1059.8 8.4 3 243.4 71.6 68.6 68.1 401.2 112.3 1172.6 9.0 5 251.6 72.5 72.0 66.3 367.1 100.4 1209 9.8

    Mineral Hour (hr) Mg Ca K Na Cl SO ₄ Hardness pH Early 200 50.3 51.6 71.9 876.4 146.0 965.7 6.8 One 225.2 67.1 66.3 60.4 326.2 95.3 1086.8 9.7 3 255.6 76.4 75.3 53.2 234.7 76.3 1234 10.4 5 268.1 78.2 77.5 42.0 189.1 66.5 1290.3 11.5

Example  3: reverse osmosis ( RO )

After opening the deep sea water supply valve, the reverse osmosis membrane was operated. As a reverse osmosis membrane, fouling resistance (FRM) reverse osmosis membrane (Saehan) was used as a 7 x RE8040SR elements / vessel (Commercial plant). At this time, while operating the osmotic pressure regulator while observing the pressure gauge to 50 ~ 70 kg / cm to produce filtered water and concentrated water.

After reverse osmosis treatment, the ion content in reverse osmosis filtered water and concentrated water is shown in Table 3.

Treated water ions Metal ion content (ppm) Deep ocean water Reverse Osmosis Filtrate Reverse Osmosis Concentrated Water Na 11110.1 60.0-75.0 14500-15000 K 394.1 4.0-5.5 501.6 Mg 1211.5 0.04-0.06 2450 ~ 2800 Ca 455.2 0.005 ~ 0.012 660.0-670.0 Cl 19357.3 150.0-155.0 25432.1 SO ₄ 2645.4 4.5-6.0 3800-4500 PO ₄ 34.5 0 35-45 Li 20.1 0 20-30 NO ₃ 41 (43.2) 0 50-65 (50-55)

Production Example

Preparation Example 1 Mg ^{2 +} Mineral Water

Seawater or primary or secondary RO Brine -1, +1 film after the first ED, NaCl and KCl are removed, -1, +2 film or -2, +1 film Ca ^{2 +} Separated to prepare Mg ⁺⁺ mineral water.

Preparation Example 2: Mg ^{+ 2-containing} minerals

After the water or RO Brine was passed through a filter to remove Ca ^{2 +} ions directed to the first evaporator in accordance with <Production Example 1> to produce a number of mineral-containing Mg ^{+ 2.}

Preparation Example 3: Ca ^{+ 2-containing} minerals

After seawater intake, pass the filter, CaSO ₄ and CaCO ₃ obtained by sending RO Brine or seawater to the evaporator, mixed with the permeated water from the 1st and 2nd RO, melted again, -2 is sent to +1 film ED and SO ₄ ^{2 -} and CO ₃ ^2- is prepared by removing a number of minerals containing Ca ^{+ 2.}

Preparation Example 4 Ca ^{2 +} Mineral Water

Is -1, the sea water or RO Brine, after the +1 Gamak ED to remove the NaCl and KCl, and +1, -1 or -2 Gamak is, the difference between the moving speed of the Ca ^{2 +} ion in the +2 Gamak ED To prepare Ca ²⁺ mineral water.

Preparation Example 5 K ⁺ Mineral Water

Brine from seawater or RO is sent to -1 and +1 membrane ED to separate KCl and NaCl, and then sent to an evaporator to separate NaCl into crystals to prepare K ⁺ mineral water.

Preparation Example 6 K ⁺ Mineral Water

Send water or RO Brine was passed through the filter to the evaporator is to remove the Ca ^{2 +} ion first, and then the filtrate back to -1, +1 Gamak sent to the ED to remove the KCl and NaCl, after removing the NaCl as in Preparation Example 5-1 K ⁺ mineral water is prepared from +1 film ED.

Preparation Example 7 Alkaline Mineral Water

Alkaline mineral water between pH 7.8 and 11 is prepared while removing Cl ₂ and SO ₄ ^{2 −} from the mineral water prepared in Preparation Examples 1 to 6 using an electrolysis device.

Preparation Example ^{8: Mg 2 +, Ca 2} +, K + number of mineral

Brine or sea water RO -1 a, +1 Gamak in ED B, SO ₄ ^{2 -} and CO ₃ ^{2 -} 2, etc., each preparation after removing the anion 1-6 of Mg ^{2 +,} Ca ^{2 +,} a K ⁺ Prepare mineral water.

Preparation Example 9 Mineral Carbonated Water

Mineral carbonated water is prepared by injecting CO ₂ into CaSO ₄ and CaCO ₃ obtained through the evaporator in Preparation Example 2 and Preparation Example 6.

Preparation Example 10 K / Ca / Mg-Containing Mineral Salts

In the preparation example 5, K / Ca / Mg-containing mineral salt was prepared by using an evaporator with K ⁺ -containing filtrate removed NaCl and -1, Mg ^{2 +} and Ca ²⁺ -containing mineral water passed through +1 membrane ED.

Table 7 below shows the ion content (ppm) of mineral water according to each preparation example.

Preparation Example One 2 3 4 5 6 8 10 Na 10-50 1-5 0.5 ~ 1 10-50 50-100 10-50 - 100-300 K 0 0 0 0 400-590 500-590 - 400-500 Mg 1000-1300 1000-1500 0 30-70 25-50 0 - 1000-1200 Ca 100-150 1-5 450-590 300-460 50-100 10-20 - 450-500 Cl 10-50 10-50 1-5 10-50 80-120 1-5 - 1000-2000 SO ₄ ^{2 -} 100-300 100-300 100-300 30-60 25-50 10-20 1-5 1500-1800 CO ₃ ^{2 -} 50-70 55-80 50-70 20-30 10-30 5-10 1-5 500-1000 B 5 ~ 6.5 5 ~ 6.5 1 ~ 2 1 ~ 2 1-1.5 0.5 ~ 1 0.1-0.2 6 ~ 6.5

Figure 1 is an overall process showing the manufacturing process of mineral water or mineral salt according to the present invention.

Claims (4)

(A) withdrawing deep sea water and passing the filter; (B) electrodialysis of the filtered deep sea water through the monovalent cation selective exchange membrane and the monovalent anion selective exchange membrane; (C) The electrolysed mineral water in step (B) is electrodialyzed through a monovalent cation selective exchange membrane and a divalent anion selective exchange membrane or a divalent cation selective exchange membrane and a monovalent anion selective exchange membrane to obtain magnesium mineral water and calcium mineral water. Obtaining separately; And (D) evaporating the mineral brine obtained by electrodialysis in step (B) in an evaporator to filter and remove the precipitated sodium salt to obtain potassium mineral water; Method for producing magnesium mineral water, calcium mineral water and potassium mineral water, characterized in that comprises a. The method for preparing magnesium mineral water, calcium mineral water and potassium mineral water according to claim 1, further comprising the step of concentrating by reverse osmosis between steps (A) and (B). delete delete

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