KR20130134078A - Method for separate manufacturing of mineral salts (calcium and magnesium salts) isolated from alkaline water by electrolysis of sea water and mineral water - Google Patents

Abstract

The present invention relates to a manufacturing method of natural mineral food materials and mineral addition materials of drinking dip sea water by adjusting pH of alkaline water produced by electrolysis of sea water, dip sea water or sea water concentrate to produce magnesium salt and calcium salt precipitate, concentrating and separating. More specifically, the present invention relates to a manufacturing method of high hardness mineral beverage and mineral beverage in which the magnesium:calcium mineral content is adjusted by a step of manufacturing concentrated water and penetrated water by pre-treating sea water or dip sea water, and firstly passing a reverse osmosis membrane (RO); a step of manufacturing acid water and alkaline water by electrolyzing the concentrated water; a step of producing alkaline water with 10-13 of the hydrogen ion concentration (pH) by adjusting the electric current amount in manufacturing the alkaline water; a step of producing calcium salts and magnesium salts upon pH in a precipitation bath from the alkaline water with 10-13 of the hydrogen ion concentration, and precipitating and separating; and a step of mixing the separated calcium salts and magnesium salts, and dissolving in desalinated water. [Reference numerals] (AA) Sea water (deep sea water) source;(BB) Pre-processing membrane (MF membrane, Sand filter);(CC) Reverse osmosis membrane or electrodialysis membrane;(DD) Concentrate;(EE) Electrolysis;(FF) Produced water;(GG) Acidic water;(HH) Alkaline water;(II) Using sterilization antiseptic agent;(JJ) Adjusting the quantity of electric charge;(K1,K2,K3,K4) Precipitation bath;(LL) Separation/Drying;(M1) Calcium salt (Mg:Ca=1:2);(M2) Calcium/Magnesium salt (Mg:Ca=2:1);(M3) Magnesium salt (Mg:Ca=4:1);(M4) Magnesium salt (Mg:Ca=5:1);(NN) Mixing;(OO) Adjusting mineral water quality (Mg/Ca ratio adjusting);(PP) Manufacturing mineral adjusted water and beverage

Description

(Method for separate manufacturing of mineral salts (calcium and magnesium salts) isolated from alkaline water by electrolysis of sea water and mineral water }

The present invention adjusts the hydrogen ion concentration of alkaline water produced by electrolysis of seawater or deep seawater and concentrated seawater to form calcium salt and magnesium salt precipitates for each hydrogen ion concentration and low energy of seawater or deep sea water and concentrated water in the sedimentation tank. The present invention relates to a method for separating and extracting calcium salts and magnesium salts, and a method for preparing mineral salts and mineral drinks using the same.

For 1.0 kg of normal seawater, on average 965 g (96.5%) is water, 18.98 g (1.9%) for chlorine ions, 10.556 g (Na ⁺ , 1.1%) for sodium ions, 2.649 g (SO42-, 0.3%) for sulfate ), Magnesium ion is 1.272 g (Mg2 +, 0.1%), calcium ion is 0.400 g (Ca2 +, 0.04%), potassium ion is 0.38 g (K +, 0.04%), bicarbonate ion is 0.14 g (HCO3-, 0.01%) As the main component ion is 3.4% dissolved, the remaining 0.1% is dissolved in trace metals, and a total of 92 dissolved substances are known to exist in seawater.

In particular, deep ocean water is a seawater that exists at a depth of 200m or more, where sunlight does not reach, and it is separated by the ocean physical structure that is far from the coast and does not mix with the atmosphere or surface water (river water) due to surface and water temperature and density difference. In addition, deep ocean water is known to be a marine water resource that has been kept clean for a long time because it is structurally blocked from contaminating inflow sources such as human origin chemical pollutants (organic compounds such as pathogens and fertilizer pesticides). In particular, deep sea water contains various minerals such as zinc, selenium, and manganese, as well as four major minerals (magnesium, calcium, potassium, and sodium), which are known to be useful as natural mineral raw materials through water quality control desalination. have.

Deficiency and excess of minerals cause various diseases and inhibit physical and mental development, it is important to maintain the mineral balance in the body. Minerals such as calcium, magnesium and potassium are one of the five major nutrients required by humans as important elements that play a role in body composition and function of the body. Among the minerals, calcium (calcium, Ca ²⁺ ) is ^responsible for bone and tooth formation, muscle, nerve and heart function, blood coagulation, etc., deficiency constipation, osteoporosis, developmental disorders, spasms, cavities, nerves Symptoms such as anxiety occur.

Magnesium (Magnesium, Mg ^{2 +} ) performs functions such as energy production, nervous function control, and the promotion of vitamin B and E metabolism.In deficiency, heart disease, hypertension, nephrolithiasis, insomnia, arrhythmia, hypotension, loss of appetite, muscle pain, Anemia and the like. Potassium (potassium, K ⁺ ) performs functions such as intracellular acid group balance control, moisture control, nerve function maintenance, cellular function preservation, vasodilation, and oxygen supply to the brain, and deficiency of arrhythmia, loss of appetite, and muscle spasms. , Constipation, fatigue, asthenia, hypoglycemia, etc. occur.

Minerals contained in seawater (deep ocean water) can be a very useful source of minerals for modern people whose mineral balance is compromised due to poor dietary habits and environmental pollution. However, since seawater contains a significant amount of salt (NaCl), there is a problem that potassium, calcium, magnesium, and the like, which are useful mineral components, are removed together during desalination to remove salt.

Seawater desalination methods include evaporation, reverse osmosis and electrodialysis. The evaporation method utilizes the principle of evaporating seawater to evaporate the solvent and retain the solute.The reverse osmosis membrane method removes salt by using an ionic substance dissolved in water as a membrane and passes only pure water. In the electrodialysis method, anion membranes and cationic membranes are alternately arranged, and a DC voltage is applied to electrodes positioned at both ends of the anion membrane and the cationic membrane to remove cations and anions, thereby obtaining pure fresh water.

In addition, the conventional method of extracting minerals from seawater was to extract minerals from seawater by separating the mineral salts such as calcium salts and magnesium salts by evaporating and concentrating seawater (deep water). However, when these desalination methods are used, it is difficult to efficiently separate calcium and magnesium from various mineral components included in seawater, and the recovery rate of the mineral components is low and energy is consumed. In addition, the mineral salts extracted by the above desalination and mineral extraction methods do not remove ions, chlorine ions (Cl-) and sulfate ions (SO ₄ ^2- ), but combine with cations to form salts. When dissolving mineral water, it is impossible to manufacture high hardness mineral water with hardness above 400 because chlorine ions and sulfate ions, which are the criteria for drinking water quality, are redissolved.

Korean Patent Registration No. 10-732066 discloses an efficient extraction method of high purity minerals from deep ocean water using low temperature vacuum crystallization method, and Korean Patent Registration No. 10-0885175 discloses deep seawater using a pressure-controlled steam recompression evaporation system. Disclosed is a method for preparing mineral water using evaporation crystallization to separate mineral salts and using such minerals. In addition, Korean Patent Laid-Open Publication No. 2001-102137 discloses desalination of seawater into a concentrated solution containing water, essential minerals such as magnesium, calcium, iron, and vitamins, and the like, and then the concentrated solution itself is separated into this separated water, or Separately, a method of preparing a beverage by adding essential mineral components such as water-soluble magnesium, calcium, and iron obtained from seawater concentrate, and providing a beverage for improving the health function obtained are disclosed. Korean Registration No. 10-06630840 relates to a method for producing a hardened mineral mixed beverage from deep seawater or subterranean seawater and a manufacturing apparatus for producing the same, a) taking deep seawater or subterranean seawater and pretreating Filtration through a nanofiltration membrane to produce nanofiltration production water having reduced divalent ions; b) preparing the reverse osmosis production water in which monovalent ions are reduced by the reverse osmosis membrane of the nanofiltration production water filtered in step a); c) filtering the nanofiltration production water filtered in step a) with a secondary nanofiltration membrane to prepare a high hardness mineral concentrated water in which divalent ions are concentrated; It is disclosed a composition consisting of a step d) mixing the reverse osmosis production water prepared in step b) and the mineral concentrated water prepared in step c). However, the above prior art produces an alkali water having a hydrogen ion concentration (pH) of 10 to 13 by adjusting the amount of current when producing alkaline water, which is a technical feature of the present invention, and produces an alkaline water having a hydrogen ion concentration of 10 to 13 In the sedimentation tank to produce calcium salts and magnesium salts for each pH does not disclose the composition of sedimentation separation does not start.

The present invention removes chlorine ions and sulfate ions from seawater or deep sea water and separates and extracts useful minerals such as calcium, magnesium and potassium, and at the same time increases the recovery rate of useful mineral constituents to reduce the energy while increasing the purity of mineral salts. The present invention relates to an efficient separation extraction method and a method for producing a high hardness mineral beverage meeting the drinking water quality standard using the same.

In order to solve the above problems, the present invention generates precipitates of calcium salts and magnesium for each hydrogen ion concentration in alkaline water adjusted by hydrogen ion electrolysis method (pH) from sodium water (sea deep water) in the precipitation tank Separation from chlorine and sulfate ions provides a method for producing high-purity, high-quality mineral beverages suitable for drinking water quality standards, while reducing energy salt production energy costs.

The method for producing mineral salts according to the present invention can separate and extract high purity mineral calcium salts and magnesium salts from seawater or deep sea water with low cost energy, and separate the mineral salts, chlorine and sulfate ions into the water quality standards for drinking water. It is possible to produce suitable high hardness mineral water, and to efficiently produce mineral raw materials of various products including useful minerals such as calcium and magnesium in seawater.

1 is an overall process diagram showing a method for preparing mineral salts and mineral water in the electrolytic alkaline water of the present invention.
2 is a schematic diagram of a membrane-free electrolysis device for generating electrolyzed water for generating electrolyzed water and adjusting hydrogen ion concentration (pH).
Figure 3 is a sedimentation separation tank for separating the mineral salt produced in the hydrogen ion concentration adjusted alkaline water.
Figure 4 is a process chart combining the NF-RO-ED process and MVR-precipitation separation process for improving the mineral salt production yield.
5 shows a membrane-free electrolysis device for generating electrolytic water.
Figure 6 shows the structure of each part of the membrane-free electrolysis device for generating electrolytic water.
Figure 7 shows the concentration changes of magnesium and calcium in the mineral salts formed for each hydrogen ion concentration.
Figure 8 shows the XRD Spectrum (@pH = 10) of the mineral salt formed by adjusting the hydrogen ion concentration.

In order to achieve the object of the present invention, the present invention is to adjust the pH in alkaline water produced by electrolysis of seawater (deep sea water or concentrated water) to produce magnesium salt and calcium salt precipitate to concentrate and separate the natural mineral food raw material and It relates to a method for producing mineral-added raw materials of deep sea water to eat.

1) pre-treatment of seawater or deep seawater to produce concentrated water and produced water by primary treatment;

2) preparing an acidic water and an alkaline water by electrolyzing the concentrated water;

3) electrolysis in the production of alkaline water to adjust the amount of current to produce an alkaline water of hydrogen ion concentration (pH) 10 to 13;

4) producing alkaline water having a hydrogen ion concentration of 10 to 13 to separate and precipitate calcium salt and magnesium salt for each pH in the precipitation tank;

5) mixing the separated calcium salt and magnesium salt to prepare a useful mineral salt in which calcium and magnesium are adjusted;

6) The present invention relates to a method for producing a mineral beverage having high hardness mineral beverage and mineral content (magnesium: calcium) adjusted by dissolving the useful mineral salt of 5) in the production water of 1).

In addition, the pretreatment of step 1) may be any one or more selected from sand filtration, rapid filtration membrane, micro filter (MF), immersion membrane filter (SMF), and ultra filter (UF), and the primary treatment is reverse osmosis membrane. In addition to the production of concentrated water and production water using (RO), it can be selected in the process of producing production water and mineral concentrated water using electrodialysis membrane and NF-RO membrane.

In the step 2), after the first treatment of reverse osmosis membrane (RO) or electrodialysis membrane, electrolyzed concentrated water to prepare acidic and alkaline water, instead of concentrated water, raw water of seawater or deep seawater or concentrated water using NF-RO. And it may further comprise the step of preparing acidic water and alkaline water after electrolysis using mineral concentrated water produced by the reduced pressure evaporation distillation method.

In the method for preparing mineral salt adjusted mineral component according to one embodiment of the present invention, a method of preparing mineral supplement beverage may be added by dissolving citric acid or orange extract in the production water of step 6).

On the other hand, in the mineral beverage production method according to an embodiment of the present invention, by producing a by-product in the step of producing an alkaline water of hydrogen ion concentration (pH) 10 to 13 by adjusting the amount of current when the alkaline water of step 3) The acidic water can be transformed into a step that can be used as a disinfectant.

As another embodiment, the mineral supplement tablet or powder product may be added by adding citric acid, vitamin preparation, orange powder, etc. to a useful mineral salt preparation method of adjusting calcium and magnesium concentrations by mixing calcium salt and magnesium salt of step 5). It can be modified by the manufacturing method of.

In addition, the production of concentrated water in step 1) includes preparing first concentrated water and primary produced water by passing seawater or deep sea water through a reverse osmosis membrane (RO) after pretreatment; By passing the first concentrated water back to the ion exchange membrane (ED) it can be made to produce a high concentration of the second concentrated water, characterized in that the amount of current flowing during the electrolysis of step 2) is 50-260 mA.

In addition, the concentrated water of step 1) is a pre-treatment process using a nano-filter (NF), ultra-filter (UF) membrane to remove only sulfate ions (SO4) and the remaining sodium, magnesium, calcium, potassium, chlorine ions are permeated The produced water can be concentrated again by filtration through a reverse osmosis membrane (RO), dissolving one or more extracts selected from citric acid, plant or fruit extracts and 5) useful mineral salts in the produced water of step 1) A method for producing a mineral beverage in which the components of the calcium salt are adjusted can be provided.

Hereinafter, the present invention will be described in detail with reference to the accompanying drawings.

1 is an overall process diagram showing a method for preparing mineral salts and mineral water in the electrolytic alkaline water of the present invention, Figure 2 is a diaphragm electrolysis device for generating electrolytic water for the production of electrolytic water and hydrogen ion concentration (pH) adjustment The schematic diagram of the is shown. In addition, the mineral water of the present invention is meant to include bottled water and various beverages, the method of producing mineral water of the present invention by passing the seawater (sea deep sea water) through the primary RO (reverse osmosis membrane) after pretreatment, the primary concentrated water and primary Preparing a production water and passing the first concentrated water through ED (ion exchange membrane) to produce a second concentrated water of high concentration.

The flow of the whole process of the present invention is pre-treatment of seawater or deep seawater (filtered by sand filtration, rapid filtration membrane, micro filter (MF), immersion membrane filter (SMF), ultra filter (UF), etc.), RO (reverse osmosis membrane) Concentrated and produced water by passing through NF-RO membrane (nano filter-reverse osmosis composite membrane), electrodialysis membrane (ED) and electrolyzed concentrated water as it is, ED (ion dialysis membrane) or MVR (reduced vapor recompression) The concentrated water is re-concentrated by the evaporation method to prepare a high concentrated water and electrolyzed to prepare acidic water and alkaline water (FIG. 1).

Acidic and alkaline water are prepared by electrolyzing concentrated water and concentrated water with a membrane-free decomposition device for producing electrolytic water. In the production of alkaline water, the current amount is adjusted to adjust the pH of the alkaline water to produce mineral salts with different calcium and magnesium components adjusted for each pH (FIG. 2).

Alkaline Hydrogen Ion Concentration According to Current of Electrolyte Hydrogen ion concentration (pH) Ammeter A-meter (mA) pH = 10 50-150 pH = 11 160-200 pH = 12 200-260 pH = 13 > 260

Figure 3 shows a sedimentation separation tank for separating the mineral salt produced in the hydrogen ion concentration adjusted alkaline water.

By controlling the hydrogen ion concentration of the electrolyzed alkaline water of seawater or deep sea water concentrated water, it is possible to produce mineral salts with different composition of calcium and magnesium content at each pH, which is then transferred to the settling tank to precipitate the generated salts. Separated with deep water concentrate.

Since the volume of the sedimentation tank is about 100 liters and is conical, the mineral salt precipitate formed is collected at the bottom of the conical bottom of the sedimentation tank. The sedimentation tank without disturbing the mineral salt deposited on the bottom by using the supernatant removal discharge device 15 cm above the conical bottom of the sedimentation tank. The seawater or the deep seawater was separated from the concentrated water (Fig. 3).

Mineral precipitates separated in the sedimentation tank were centrifuged using a centrifuge, dried in a hot air dryer, and then powdered to prepare mineral salts. For mineral salts dried by pH, magnesium: calcium ratio 0.01-0.4 at pH 10 or less, magnesium: calcium ratio 0.4-1.8 at pH 11, magnesium: calcium ratio 1.8-3.8 at pH 12, magnesium: calcium ratio at pH 13 and above The separation of calcium and magnesium occurs between 3.8 and 40.72.

Composition of sea salt or deep sea mineral salt (based on water temperature of 20 ℃) unit  pH = 10 pH = 11 pH = 12 pH = 13 Sodium (Na) % 1.20 1.61 0.86 1.09 Magnesium (Mg) % 9.24 21.02 26.75 30.68 Calcium (Ca) % 23.01 11.92 7.19 4.42 Potassium (K) % 0.12 0.11 0.05 0.09 Chloride (Cl) % 3.32 3.03 3.22 3.13 Sulphate (SO ₄ ^{2 -)} % 1.63 1.53 1.52 1.62 ^{_{Carbonate (CO 3 2 -) &}} Hydroxide (OH) % 61.48 60.79 60.42 58.92

At this time, the anions of mineral salts are mostly carbonate or hydroxide ions, so they are separated from chlorine and sulfate ions, which are water quality standards. As described above, mineral salts having different concentrations of magnesium to calcium are prepared by mixing and adjusting mineral salts having different magnesium and calcium concentrations according to hydrogen ion concentration (pH).

Preparation of Mineral Salts with Adjusted Mineral Contents by Mixing Mineral Salts by Hydrogen Ion Concentration Mg Ca Mg / Ca  Calcium mineral salt @ pH = 10 9.24 23.01 0.40  Magnesium Mineral Salts @ pH = 13 30.68 4.42 6.9  @ pH10 (23%) + @ pH13 (77%) 25.7 8.7 3.0

For example, a calcium salt having a purity of 90% or more, a mineral salt having a magnesium to calcium ratio in the range of 0.1 to 50, a magnesium salt having a magnesium concentration of 98% or more, and the like are prepared. Mix the calcium salts, calcium / magnesium mixed salts, magnesium salts, and the like with the mineral salts of which the mineral content is adjusted, and then mix it with citric acid powder, vitamin powder, fruit extract powder, green tea powder, etc. Manufacture.

By mixing calcium salt, calcium / magnesium mixed salt, magnesium salt, etc. prepared by hydrogen ion concentration, mineral salt with adjusted mineral content is dissolved in demineralized water to produce high hardness mineral water with hardness up to 1200 with calcium and magnesium composition adjusted. Manufacture. Since mineral salts have already been separated and removed from the ions of drinking water quality standards such as sodium ions, boron ions, chlorine ions, and sulfate ions when mineral salts are manufactured, the hard mineral mineral water prepared using these mineral salts is Prepare high hardness mineral bottled water that meets drinking water quality standards.

 In addition to citric acid, orange extracts, green tea extracts, various plant or fruit extracts, and the like with demineralized water during the manufacturing process, mineral-enriched mineral mixed drinks can also be prepared.

Composition and Comparison of Water Quality Standards of Hardened Mineral Water Using Mineral-Adjusted Salts division ingredient unit Mineral demineralized water according to the present invention (based on hardness 4,353) Mineral demineralized water prepared by conventional methods
(Based on hardness 3,721) High hardness mineral water produced by the present invention (based on 1,000 hardness) Marine deep water quality standards Elemental ingredient Sodium (Na) mg / L 14 600 3.0 - Magnesium (Mg) mg / L 790 801 182 - Calcium (Ca) mg / L 440 167 101 - Potassium (K) mg / L N.D. 160 N.D. - Hazardous Effects Nitrate mg / L N.D. N.D. N.D. 10 Boron (B) mg / L 0.04 0.029 0.0203 1.0 Arsenic (As) mg / L 0.003 0.0002 0.001 0.05 Lead (Pb) mg / L 0.002 0.0002 0.0003 0.05 Selenium (Se) mg / L 0.03 - 0.008 0.01 Mercury (Hg) mg / L N.D. N.D. N.D. 0.001 Chromium (Cr) mg / L 0.003 0.0006 0.001 0.05 Cadmium (Cd) mg / L 0.0002 0.0002 0.00004 0.005 Barium (Ba) mg / L 0.007 - 0.002 - strontium mg / L 0.08 0.05 0.01 4.0 or less Aesthetically Affecting Substances Copper (Cu) mg / L 0.014 0.00023 0.003 1.00 Hydrogen ion concentration (pH) mg / L 7.5 - 7.5 5.8-8.5 Zinc (Zn) mg / L 0.055 0.004 0.013 1.00 Iron (Fe) mg / L 0.015 0.0073 0.003 0.30 Manganese (Mn) mg / L 0.002 0.0002 0.001 0.30 Aluminum (Al) mg / L 0.017 0.0002 0.004 0.20 Chlorine Ion (Cl) mg / L 629 2630 145 250 A sulfate ion (SO ₄ ^{2 -)} mg / L 107 1598 25 250 Hardness
(Hardness) mg / L 4,353 3,721 1,000 1,200 Hazardous Effects Organic Substances Volatile component mg / L N.D. N.D. N.D. N.D. Pesticide Ingredients mg / L N.D. N.D. N.D. N.D. microbe Common bacteria mg / L N.D. N.D. N.D. N.D. Coliform mg / L N.D. N.D. N.D. N.D.

ND (not detected): not detected

In the pretreatment process of the present invention, only the sulfate ions (SO ₄ ^2- ) are removed using the nanofilter (NF) and ultrafilter (UF) membranes, and the remaining salts (sodium, magnesium, calcium, potassium, chlorine ions, etc.) are permeated. Filtration of the water through the reverse osmosis membrane comprises the steps of preparing concentrated water wherein only SO ₄ ^2- is removed and the remaining salts (sodium, potassium, calcium, magnesium, etc.) are concentrated.

Although the conventional reverse osmosis membrane process is simple, the concentration of the concentrated water is low, and there are problems such as the inclusion of sulfate ion (SO ₄ ^2- ) in the concentrated water, and the ion exchange membrane process (ED) uses the concentration of the reverse osmosis membrane. It can be higher than the process, but there were problems of purity such as mineral separation. In order to solve these two problems and increase the production yield, a process of manufacturing a high-efficiency mineral salt and high hardness mineral water is performed by combining a nano filter membrane (NF)-reverse osmosis membrane (RO)-electrodialysis membrane (ED) process. Figure 4 shows a process diagram combining the NF-RO-ED process and MVR-precipitation separation process for improving the mineral salt production yield.

The production water from which sulfate ions were removed through the first nanofilter membrane was obtained, and the high purity production water (demineralized water) and the concentrated water from which more than 7% of sulfate ions were removed through the second reverse osmosis membrane process, and the ED (ion exchange membrane) was thirdly manufactured. The process produces a concentrated water of at least 14% with (SO ₄ ^2- ) removed. The concentrated water is evaporated and crystallized through MVR (Decomposition Evaporation Distillation Method), and the purified supernatant with high concentration of magnesium is separated and purified to prepare mineral concentrated water (hardness of 100,000 or more). In addition, by adjusting the hydrogen ion concentration (pH) by electrolyzing 14-30% concentrated liquid produced through ion exchange membrane (ED) process and separating and extracting calcium, magnesium, etc. among mineral components through the precipitation separation method Selectively separating and preparing high-purity mineral salts (calcium salt, magnesium salt, calcium / magnesium component ratio adjusting mineral salt) and mixing the prepared high-purity mineral salt with demineralized water to prepare mineral water.

The quality of the water produced depends on how much sulfate ions (SO ₄ ^2- ) are contained, the desalination and the balance of potassium, calcium and magnesium content. By installing the NF process, highly concentrated water with significantly reduced sulfur content could be used for mineral extraction, and it can be seen that only a part of calcium crystallization remains as mineral concentrated water during the crystallization process. The elimination of sulfate ions has the advantage that there is no inconvenience to crystallize and re-dissolve calcium during the crystallization process. In addition, it is possible to adjust the mineral composition through the precipitation separation process through electrolysis, so that potassium, calcium and magnesium can be adjusted arbitrarily, so that it is possible to manufacture mineral salts with balanced minerals suitable for the purpose. Production of suitable mineral water is possible.

The method for preparing the mineral salt and the mineral water of the present invention includes preparing a mineral salt by electrolyzing the secondary concentrated water and adjusting and crystallizing the mineral (calcium, magnesium, potassium) component using a precipitation separation system. . Existing evaporative concentration methods include direct evaporation (flat type) by generating direct thermal energy and indirect evaporation using steam, and indirect evaporation using steam (Mechanical Vapor Recompressor) method. There is a way to maximize energy efficiency. In order to prepare mineral salts by evaporating concentrated water, energy of 10,750,000kcal of flat type, 5,750,000kcal of steam type, 1,380,000kcal of multistage vacuum type and 500,000kcal of MVR method is used.

MVR method is used for steam input-evaporative concentration-mechanical recompression (temperature rise)-evaporative concentration-mechanical recompression (temperature rise)-evaporative concentration. By re-compressing the temperature through compression, almost infinite repetition is possible at low energy costs.

However, the energy consumed in the electrolysis sedimentation process consumes about 1.0 kw, which translates into 1,700 kcal. Compared to the MVR method which is estimated to require the minimum energy, the electrolytic sedimentation method can be used to drastically reduce the energy required during the mineral salt manufacturing process.

Hereinafter, the Example of each process of this invention is described.

Example 1 Adjusting Hydrogen Concentration (pH) Through an Electrolysis Process

The electrolyzed water generator consists of a control panel for electrolyzed water generation, electrolyzed water generating diaphragm electrolysis tank, seawater and concentrated water supply line, circulation pump, alkaline and acidic water generating tank, strong aliphatic and strong acidic water discharge line, and water level sensor of the tank. have. FIG. 5 shows a membrane-free electrolytic decomposition device for generating electrolyzed water, and FIG. 6 shows each part structure of the membrane-free electrolytic decomposition device for producing electrolytic water.

It is better to raise the minimum level sensor as the strong alkali is required in the electrolytic device. If the device requires a pH above 13, the ammeter must be at least 260 mA before it can be produced. However, if the minimum water level is too low, the amount of waste water discarded after the operation setting time will be large, and much time is required to increase the ammeter value. On the contrary, if the minimum water level sensor is placed too high, the amount of water discarded is small, so the amount of supplemental water is small, and the amount of chlorine ions taken from the septum may be less and the pH value may be lowered. The pH value can be adjusted according to the amount of current as follows.

If you set the operation time of the electrolyzer to 30 minutes and the time interval for entering the metering pump to 10 minutes, the device operates after 30 minutes of operation. The metering pump is operated three times in 30 minutes and produces about 400 ml of alkaline water at one time.

Example 2: Separation of Mineral Salts Using Precipitation Tank

By controlling the hydrogen ion concentration of the electrolyzed alkaline water of seawater or deep sea water concentrated water, it is possible to produce mineral salts with different composition of calcium and magnesium content at each pH, which is then transferred to the settling tank to precipitate the generated salts. Separated with deep water concentrate. The volume of the sedimentation tank is about 100 liters, and the upper part is cylindrical and the lower part is conical. The mineral salt precipitates are collected at the bottom of the conical bottom of the sedimentation tank. Separate from the concentrated seawater or the deep seawater of the sedimentation tank without disturbing the mineral salts.

In particular, by installing an inverted U-shaped tube in the middle of the lower cone of the sedimentation tank and connecting it to the supernatant outlet, the supernatant is discharged to the inlet of the inverted U-tube tube by opening the cock of the supernatant outlet. By adjusting the height of the inverted U tube, it is possible to adjust the depth of the supernatant according to the amount of sediment. In addition, by making a rod that can be installed stir on the outside of the sedimentation tank using the stir system to make the reaction of the mineral salt in the precipitation tank. The resulting mineral salts collect at the bottom of the conical bottom of the sedimentation tank and can be easily recovered through the sedimentation outlet. Figure 3 shows a sedimentation separation tank for separating the mineral salt produced in the hydrogen ion concentration adjusted alkaline water.

Example 3: Composition of Mineral Salts by pH (pH)

Mineral precipitates separated in the sedimentation tank were centrifuged using a centrifuge, dried in a hot air dryer, and then powdered to prepare mineral salts. The mineral salt produced and separated and dried at pH 10 was 9.24% of magnesium and 23.1% of calcium. Most of the minerals formed as magnesium / calcium ratio 0.4 were calcium. At pH 11, the mineral salt formed consisted of 21% magnesium and 12% calcium, with a magnesium / calcium ratio of 2.0. Mineral salts formed at pH 12 consisted of 26.7% magnesium and 7.2% calcium, with a magnesium: calcium ratio of 3.7. At pH 13, the mineral salt formed was 30.7% magnesium, 4.4% calcium, and the magnesium: calcium ratio was 7.0, resulting in the separation of calcium and magnesium, accounting for 82% of the total cationic minerals.

The concentration change of magnesium and calcium with pH in the mineral salt formed by adjusting the hydrogen ion concentration is shown in FIG. 7. Magnesium increased with increasing hydrogen ion concentration from 10 to 13, while calcium concentration decreased. Therefore, by adjusting the hydrogen ion concentration (pH) of the alkali water it was possible to adjust the ratio of magnesium and calcium in the mineral salt produced.

The mineral salts produced were analyzed for mineral mineral crystals using a Multi purpose X-ray Diffractometer (MP-XRD). The analysis conditions were X-ray power of 45 KV / 30mA, Scan Mode of θ / 2θ, and Scan range of 10-100 deg (2θ). Since most of the mineral crystals formed are in the form of calcium carbonate, magnesium hydroxide and calcium hydroxide, they are mostly separated from chlorine and sulfate ions, which are water quality standards for drinking water (FIG. 8).

As a result, the concentration of chlorine ions in the constituents of the mineral salts is 3%, and the concentration of sulfate ions is 1%. Therefore, when preparing drinking spring water by using mineral salts adjusted with mineral content according to the hydrogen ion concentration, chlorine and sulfate ions were removed, and thus high hardness water was produced while meeting drinking water quality standards. Figure 8 shows the XRD Spectrum (@pH = 10) of the mineral salt formed by adjusting the hydrogen ion concentration.

Example  4: Preparation of mineral salt powder and tablets by adjusting calcium and magnesium components

As described above, the mineral salts having different magnesium and calcium concentrations were mixed and adjusted according to hydrogen ion concentration (pH) to prepare mineral salts in which the concentration ratio of magnesium to calcium was adjusted. For example, magnesium having a Mg / Ca ratio of 0.40 formed at a hydrogen ion concentration (pH) of 10 and a calcium calcium salt of 23% as a main component and magnesium having a Mg / Ca ratio of 6.9 at a hydrogen ion concentration (pH) of 13 are magnesium By mixing 77% of the mineral salts, it was possible to prepare a mineral salt having a magnesium content of 25.7%, a calcium content of 8.7%, and a Mg / Ca ratio of 3.0.

In addition, by mixing the above-described calcium mineral salts, calcium / magnesium mixed mineral salts, magnesium mineral salts and the like, the mineral salts with the mineral content adjusted are mixed with citric acid powder, vitamin powder, fruit extract powder, green tea powder and the like (tablet) Or it could be manufactured in powder fabric.

Example 5: Preparation of high hardness mineral water using mineral salt

Adjusted mineral content by adjusting Mg / Ca ratio to 2.0 by mixing calcium salts, calcium / magnesium mixed salts and magnesium salts prepared for each hydrogen ion concentration. 10.0 grams of mineral salts were dissolved in 1 liter of demineralized water (hardness 80). Up to 4,350 demineralized brine was prepared. This is again diluted with 2 liter demineralized water to produce 3 liters of hard mineral mineral water.

Since the mineral salts have already been separated and removed from the ions of drinking water quality standards such as strontium, boron ions, chlorine ions, and sulfate ions when the mineral salts are manufactured, the hard mineral mineral water prepared by dissolving these mineral salts in demineralized water is eaten up to a hardness of 1,000 or more. It satisfies the water quality standards prescribed by the Water Management Act. Drinking water quality standards are shown in Table 4.

In addition to citric acid, orange extracts, green tea extracts, various plant or fruit extracts, and the like with demineralized water during the manufacturing process, it is also possible to prepare mineral-enriched mineral mixed drinks.

High-purity mineral calcium salts and magnesium salts can be separated and extracted from seawater or deep sea water at low cost, and mineral salts, chlorine ions, and sulfate ions can be separated to produce high-hardness mineral drinks that meet the drinking water quality standards. . In addition, it is possible to efficiently produce mineral raw materials of various products including useful minerals such as calcium and magnesium in sea water, thereby creating added value of related industries based on beverages and minerals.

Claims (14)

a) pretreatment of seawater or deep seawater, followed by primary treatment to produce concentrated water and produced water;
b) electrolyzing the concentrated water to prepare alkaline water and alkaline water between 10 and 13 in pH;
c) precipitating and separating the alkaline water having a hydrogen ion concentration of 10 to 13 by precipitation of calcium salt and magnesium salt for each pH in a precipitation tank;
d) mixing the separated calcium salt and magnesium salt in a predetermined ratio to prepare a useful mineral salt in which calcium and magnesium are adjusted;
e) a method of producing a mineral beverage, wherein the components of magnesium salt and calcium salt are adjusted by dissolving the useful mineral salt of step d) in the production water of step a).
The method of claim 1, wherein the primary treatment of step a) is a reverse osmosis membrane (RO) treatment step, electrodialysis membrane treatment step, NF-RO membrane treatment process using any one or more methods selected from the manufacturing process of mineral drink Way
The method of claim 1, wherein the pretreatment of step a) uses any one or more methods selected from sand filtration, rapid filtration membrane, micro filter (MF), immersion membrane filter (SMF), and ultra filter (UF). How to prepare drinks
The method of claim 1, wherein the alkaline water having a pH of 10 to 13 prepared by electrolysis in step b) is produced by controlling the amount of current.
The method of claim 4, wherein the amount of current is 50-260 mA.
According to claim 1, wherein the concentrated water used for the electrolysis of step b) is from seawater or deep sea water, concentrated water using NF-RO or NF-RO-ED, mineral concentrate produced by vacuum evaporation Method for producing a mineral beverage, characterized in that using any one or more selected
According to claim 1, wherein the concentrated water production of step a) after the pre-treatment of seawater or deep sea water through a reverse osmosis membrane (RO) to produce a primary concentrated water and primary production water; Method for producing a mineral beverage, characterized in that the first concentrated water again passed through the ion exchange membrane (ED) to produce a second concentrated concentrated water of high concentration
The method of claim 1, wherein the concentrated water of step a) is subjected to pretreatment using a nanofilter (NF) or ultrafilter (UF) membrane to remove only sulfate ions (SO4) and to remove the remaining sodium, magnesium, calcium, potassium, chlorine. Method for producing a mineral beverage, characterized in that the ion permeated production water is again filtered through a reverse osmosis membrane (RO)
The method according to claim 1, wherein the constant ratio of step d) is a magnesium / calcium ratio of 0.01-40.72.
a) pretreatment of seawater or deep seawater, followed by primary treatment to produce concentrated water and produced water;
b) electrolyzing the concentrated water to prepare alkaline water and alkaline water between 10 and 13 in pH;
c) precipitating and separating the alkaline water having a hydrogen ion concentration of 10 to 13 by precipitation of calcium salt and magnesium salt for each pH in a precipitation tank;
d) mixing the separated calcium salt and magnesium salt in a predetermined ratio to prepare a useful mineral salt in which calcium and magnesium are adjusted;
e) a method of preparing a mineral beverage in which the magnesium salt and calcium salt components are adjusted by dissolving at least one extract selected from citric acid, plant or fruit extract and useful mineral salt of step d) in the production water of step a).
Mineral beverage prepared by the method of any one of claims 1 to 10
a) pre-treating the seawater or deep sea water by any one or more methods selected from sand filtration, rapid filtration membrane, micro filter (MF), immersion membrane filter (SMF), and ultra filter (UF);
b) preparing pre-treated seawater or deep seawater into concentrated and produced water using any one or more methods selected from reverse osmosis membrane (RO) treatment, electrodialysis membrane treatment and NF-RO membrane treatment;
c) electrolyzing the concentrated water to produce acidic water and alkaline water between 10 to 13 hydrogen ion concentration (pH);
d) a method for producing sterilized sterilized water, characterized in that the step of separating the acidic water separately
The method according to claim 12, wherein the amount of current used in the electrolysis of step b) is 50-260 mA.
Disinfectant sterilized water, which is produced by any one of claims 12 to 13.

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