KR100955004B1 - Method for producing mineral salt with mineral materials - Google Patents

Abstract

PURPOSE: A method for producing mineral salt containing mineral components is provided to manufacture the mineral salt according to specified amount by using calcium salt, salt and mineral concentrated water produced in a filtering process of deep ocean water. CONSTITUTION: A method for producing mineral salt containing mineral components comprises the following: separating concentrated water and desalinated water by passing deep sea water(10) through a reverse osmosis membrane or a nano filter membrane; separating calcium salt crystal from the water by heating and concentrating the concentrated water(20) with a first evaporator; separating mineral concentrated water in which salt is removed by heating and concentrating the concentrated water with a second evaporator; producing NF permeated water in which anion ions are removed; crystallizing mixed liquid in which the salt, the NF permeated water and the calcium salt crystal are mixed.

Description

Method for producing mineral salt with mineral ingredients {Method for producing mineral salt with mineral materials}

The present invention relates to a method for preparing mineral salts from deep sea water, and more particularly, to provide mineral salts having a desired amount of various useful mineral components contained in mineral concentrates and calcium salts, and more specifically, minerals. It is crystallized after mixing calcium salt, salt and mineral concentrated water obtained in the process of preparing water in an appropriate amount.

In general, deep sea water is deeper than 200m deep and does not reach sunlight, and because it does not reach sunlight, it is stable at a lower temperature than the surface, and inorganic nutrients such as nitrates, phosphates, and silicates required for life activities It is a marine resource with characteristics such as rich eutrophicity, low harmful artificial pollutants such as environmental hormones, very few bacteria and organic matters, and ripening aged for a long time at high pressure of 20 atm or higher.

In addition, the deep sea water has a lot of essential trace elements and minerals, and especially the main minerals (magnesium, calcium, potassium) are contained in similar to the ratio of the elemental component of the living body is known to be useful for the production of mineral water through desalination. However, in the case of seawater, Mg, Ca, K, etc., minerals useful for the human body are not removed together or the mineral balance is low by membrane filtration methods such as reverse osmosis treatment or electrodialysis by removing salts using a conventional desalination method. In order to solve this problem, the process of mixing raw seawater has a disadvantage in that the eating feeling decreases due to saltiness.

Accordingly, the Republic of Korea Patent Publication No. 2009-0061174, as shown in Figure 1, through the deep seawater 10 through the reverse osmosis membrane, the concentrated water 20 including the ionic component and the permeate (30) from which the ionic component is removed Obtaining; Separating the calcium salt (25) crystals by heating and concentrating the concentrated water by using a first concentrator; Heating and concentrating the concentrated water 40 (separated water) from which the calcium salt has been removed using a second concentrator and filtering to obtain a liver water 50 from which the salt 45 is removed; Dissolving the calcium salt (25) in permeate (30) to produce a mixed solution (60), and passing the mixed solution through an anion exchange resin to obtain filtered water (70) from which anions (65) in the mixed solution are removed; And mixing the filtered water (70) passed through the anion exchange resin and the brine (50) to obtain mineral water (80). The manufacturing method is described.

However, the above-described deep ocean mineral water production method is the primary and secondary sulfate worsen a sense of ingestion in order concentrator (SO ₄ ^2-) and chloride ion (Cl ^-), but to remove the anions, such as getting the guard 50 , The still water 50 is still contained in a large amount of negative ions, and because of this, the mineral water thus prepared still has a bad eating feeling.

On the other hand, salt is generally prepared by evaporating water from seawater using solar heat or an evaporator. Therefore, if a separate additive is not used during the preparation of salt, the composition of salt is necessarily the same as that of seawater. Salt, on the other hand, is essential for food and cooking. However, sodium chloride, the main component of salt, is known to adversely affect adult diseases such as high blood pressure, and thus, demand for mineral salts with low sodium chloride and high mineral content is increasing.

Korean Patent Laid-Open Publication No. 2006-0029945 as a prior art for producing mineral salts, as shown in Figure 2, storing the brine or sea water in the storage tank (1) and then the cartridge filter (3) through the supply pump (2) Pass the pre-treatment to remove impurities, supply the pre-treated brine to the nanofiltration system (5) through a high-pressure pump (4), and a large amount of monovalent ionic components such as Na + and Cl-passed through the nano-filtration system (5) Separating the permeated water and minerals that do not pass through the nanofiltration system (5) into concentrated water containing a large amount, the concentrated water is introduced into the evaporator (6), heated and evaporated to concentrate, minerals that are evaporated residues It describes a technique for forming a salt containing a large amount in the lower portion. Thus, by treating the brine with a nanofiltration membrane, the content of sodium and chlorine ions in the brine is relatively reduced, and at the same time, a low salt mineral salt containing a large amount of mineral components useful for the human body such as magnesium and calcium can be obtained.

However, in this technique, when the concentrated water is concentrated by evaporation with the evaporator 6, calcium sulfate (CaSO ₄ ) is first precipitated, and then sodium chloride (NaCl) is precipitated, and magnesium (Mg) is added to the remaining mineral concentrate (salt water). ) And only potassium (K) ions will be included (see Figure 1). Thus, when the precipitated sodium chloride (NaCl) is used as the mineral salt, it is possible to obtain concentrated salt with high purity but does not include various mineral components, and when the remaining mineral concentrate is used as the mineral salt, sodium chloride (NaCl) It does not include, if the filtrate after the precipitate of calcium sulfate is a mineral salt has a disadvantage that does not contain a calcium component. Furthermore, when the filtrate before the precipitation of calcium sulfate is used as the mineral salt, since the concentrated water to be evaporated and concentrated is prepared as the mineral salt, there is a problem in that the amount of useful mineral components included in the mineral salt cannot be adjusted. .

Accordingly, the present invention utilizes calcium salts, salts and mineral concentrates obtained in the process of heating concentrated and filtered marine deep water or concentrated water thereof, and various useful mineral components included in the mineral concentrate and calcium salt. The goal is to provide mineral salts with the desired amount.

In addition, the present invention is to provide a method that can significantly reduce the anion, especially sulfate ions contained in the mineral concentrated water, to produce a mineral salt with improved eating feeling. In addition, the present invention is to provide a mineral salt containing magnesium (Mg ^{2 +} ) and potassium (K ⁺ ), which are useful for the human body with anion removal, in an optimally suitable ratio (about 3: 1) for the human body. In addition, the present invention is to provide a method that can be used in the production of mineral salts only after removing the anion to reduce the eating odor from the calcium salt separated in the mineral concentrate production process, increase the soft eating sensation.

The present invention for achieving the above object, the step of passing the deep sea water through a reverse osmosis membrane or Nano Filter (Nano Filter) membrane to separate the concentrated and demineralized water; Heating and concentrating the concentrated water with a first evaporator to separate calcium salt crystals; Heating and concentrating the concentrated water from which the calcium salt crystals are separated by a second evaporator, and separating the salts from the concentrated mineral water from which the salts are removed; And crystallizing the mixed solution in which the salt, the mineral concentrated water, and the calcium salt crystals are mixed.

Another embodiment of the present invention comprises the steps of passing the deep ocean water through a reverse osmosis membrane or a Nano Filter (NF) membrane to be separated into concentrated and demineralized water; Heating and concentrating the concentrated water with a first evaporator to separate calcium salt crystals; Heating and concentrating the concentrated water from which the calcium salt crystals are separated by a second evaporator, and separating the salts from the concentrated mineral water from which the salts are removed; The demineralized water and the mineral concentrated water are mixed to produce mineral concentrated dilution water, and the mineral concentrated dilution water is passed through a nano-filter (NF) membrane having a negative ion. Obtaining the removed NF permeate; And it may be a method for producing a mineral salt containing a mineral component, comprising the step of crystallizing the mixed solution of the salt and NF permeated water and calcium salt crystals.

In addition, the present invention comprises the steps of mixing the calcium salt crystals with demineralized water to obtain mixed dissolved water, and electrolytic dialysis of the mixed dissolved water to obtain calcium dissolved water from which anions have been removed; The crystallization of the mixed solution of the salt, NF permeate and calcium salt crystals may be characterized in that the mixed solution of the salt, NF permeate and calcium dissolved water is crystallized.

In addition, in the above-described production method, the crystallization of the mixed solution may be performed while controlling the size of the crystal in accordance with the time for circulating the mixed solution in a cooling tube.

Specific details of other embodiments are included in the detailed description and the drawings.

The present invention described above obtains calcium salts, salts and mineral concentrates in the process of heating and concentrating deep sea water or concentrated water thereof and filtering the calcium salts, salts, and mineral concentrates in an appropriate amount ratio. By mixing and crystallizing, it is possible to provide a mineral salt having a desired amount of various useful mineral components contained in mineral concentrate and calcium salt.

In addition, the present invention by passing the mineral concentrated water through the nano-filtration (Nano Filter: NF) membrane, by significantly removing the anions contained in the mineral concentrated water, can produce a mineral salt with improved eating feeling It works. In addition, the present invention does not pass the mineral concentrated water through the NF membrane as it is, in particular by mixing the mineral concentrated water with demineralized water in a specific ratio to obtain mineral concentrated dilution water, and then passing the mineral concentrated dilution water through the NF membrane, Along with the removal of negative ions, it is possible to adjust the ratio of magnesium (Mg ²⁺ ) and potassium (K ⁺ ), which are useful minerals in the human body, to an optimal state (about 3: 1). In addition, the present invention by diluting the calcium salt separated in the process of producing mineral concentrate water to remove the anion to reduce the feeling of eating by electrodialysis, thereby providing a method that can be used only in the production of mineral salts calcium ions to increase the soft eating feeling can do.

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

Figure 3 is a flow chart for explaining a method for producing a mineral salt containing a mineral component using mineral concentrate in accordance with a preferred embodiment of the present invention, Figure 4 is NF permeation in accordance with another preferred embodiment of the present invention It is a flowchart explaining the method of manufacturing the mineral salt containing a mineral component using water.

As shown here, the present invention relates to a method for producing a mineral salt containing an optimal ratio of mineral components (Mg, K, Ca, etc.) useful to the human body using deep sea water.

The overall process of the present invention may first undergo a pretreatment process in which the deep seawater 110 is pretreated with MF (fine filtration membrane) and / or UF (ultrafiltration membrane) to remove insoluble components and organic matter in the deep water. Then, the pre-treated deep water 110 is passed through a reverse osmosis membrane (RO membrane) or nanofiltration membrane (NF membrane) to obtain the concentrated water 120 and the demineralized water 130. Subsequently, the concentrated water 120 is subjected to a vacuum concentration process by MED (multi-utilization method) and TVR (thermal steam recompression method), thereby separating and crystallizing calcium salt 125 and sodium chloride 145 sequentially. Mineral concentrated water (150) containing magnesium (Mg) and potassium (K) ions is obtained. Thus, the separated crystallized calcium salt 125 and sodium chloride 145 and the separated mineral concentrate water 150 are mixed in appropriate amounts, respectively, and then crystallized to obtain mineral salts.

Specifically, the present invention, before permeating the deep seawater 110 to the reverse osmosis membrane, in order to remove the suspended solids and organic matter present in the deep seawater 110, MF (precision membrane) and / or UF (ultraviolet) The pretreatment process may be performed using a pretreatment membrane composed of a filtration membrane. Both the microfiltration membrane and the ultrafiltration membrane are filtered according to the molecular size or the types of substances that can be filtered depending on the molecular size. Usually the pore size of the microfiltration membrane is about 0.1-10 μm and the filterable materials are suspensions and suspended solids. In addition, in the case of the ultrafiltration membrane, the pore size is about 20 ~ 1000A is the size that can filter to bacteria and yeast. By going through this pretreatment process, the reverse osmosis membrane can be protected and the recovery rate can be kept constant.

The present invention passes the deep water 110 subjected to the pretreatment through the reverse osmosis membrane or the nanofiltration membrane to obtain the concentrated water 120 and the demineralized water 130. When passing through the reverse osmosis membrane, the concentrated water 120 including the ionic component and the demineralized water 130 from which the ionic component is removed can be obtained. In addition, in the case of passing through the nanofiltration membrane, monovalent ions such as Na + and Cl- are removed (excluded) because 40-50% cannot pass through the nanofiltration membrane, whereas divalent ions such as Ca + 2 and Mg + 2 are removed. About 70-98% of the minerals are removed (excluded) because they do not pass through the nanofiltration membrane, so that monovalent ions such as Na + and Cl- are reduced, and a lot of minerals useful for the human body such as Ca + 2 and Mg + 2 Concentrated water 120 can be obtained. For example, the deep water 110 may be permeated through a reverse osmosis membrane (RO membrane) at a pressure of 50 to 60 kg / cm ³ to prepare the primary demineralized water and the primary concentrated water 120. In addition, the second demineralized water 130 and the second concentrated water may be obtained by passing the first demineralized water through the reverse osmosis membrane (RO membrane). Here, the secondary concentrated water can be recycled to the deep sea water 110 by the cooling crystal tube during the decontamination process.

The concentrated water 120 is concentrated by heating with a first evaporator and filtered to separate the calcium salt 125 crystals, and the concentrated separated water 140 in which the calcium salt 125 crystals are separated by a second evaporator is heated to concentrate. And filtering to obtain the mineral concentrated water 150 from which the salt 145 has been removed. Since each of the minerals contained in the deep sea water 110 has its own solubility, by adjusting the specific gravity through the vacuum concentration process, it is possible to extract each of the minerals according to their solubility. As shown in Table 1 below, by applying heat to the concentrated water 120 to evaporate, it can be seen that the amount of precipitated minerals varies as the specific gravity of the concentrated water 120 is adjusted. First of all, a small amount of Fe ₂ O ₃ is precipitated, and then all Ca salts (CaCO ₃ and CaSO ₄ ) and sodium chloride (NaCl, salt), MgCl ₂ , MgSO ₄ , and KCl contained in the deep water 110 are sequentially Precisely or simultaneously.

[Table 1: Precipitation (g / L) during evaporation of seawater]

Specific gravity (Be) Volume (cc) Fe ₂ O ₃ CaCO ₃ CaSO ₄ MgSO ₄ MgCl ₂ NaCl NaBr KCl 3.4 1000 7.1 533 0.003 0.0642 11.5 316 Trace 14.0 245 Trace 16.75 190 0.0550 0.5600 20.60 145.5 0.5620 22.00 131.0 0.1480 25.00 112.0 0.1600 26.25 95.0 0.1508 0.0040 0.0078 3.2614 27.00 64.0 0.1476 0.0130 0.0356 9.6500 28.50 39.0 0.0700 0.0260 0.0444 7.8960 0.0728 32.30 30.0 0.0144 0.0174 0.0150 2.6240 0.0358 32.40 23.0 0.0254 0.0240 2.2720 0.0518 35.0 16.2 0.5382 0.0274 1.4040 0.0620 Total precipitation 0.0030 0.1172 1.7488 0.6240 0.1532 27.1074 0.2224 Remaining amount in mineral concentrated water 1.8548 3.1640 0.5885 0.3300 0.5335 Sum 0.0030 0.1172 1.7488 2.4788 3.3172 27.695 0.5524 0.5335

In the present invention, in concentrating and filtering the concentrated water 120 in this manner, CaSO ₄ is applied to the concentrated water 120 by applying a vacuum concentration process consisting of MED (multiple application method) and TVR (thermal steam recompression method). And NaCl. Currently, there are several methods of vacuum concentration. MSF (multi-stage evaporation method) that converts seawater into steam after condensation by flashing to release steam instantly, and evaporation by latent heat exchange between steam condensing inside pipe and concentrated brine flowing out of the pipe and lowering pressure in the container There is a method such as MED (multiple utility). In particular, MED has the advantage of allowing evaporation without additional effects after the first steam injection. The present invention installs a TVR (thermal vapor recompression method) in addition to the MED (multi-utility method) method, inhales some of the steam generated from the low pressure effect by using high pressure steam, mixes with high pressure steam, and compresses After that, the heat was recycled to further increase efficiency.

In the multi-effect vacuum evaporation method according to the present invention, the steam generated in the first evaporator boiler acts as a heating source of the next utility evaporator, becomes a condensed water by cooling condensation, and becomes fresh water, and the steam generated in the second evaporator. Is the next source of heat in the evaporator to evaporate the concentrated water inside the evaporator. At this time, it is possible to reduce the energy required to evaporate the concentrated water by lowering the boiling point by vacuum reduced pressure, in the present invention used a TVR (thermal vapor recompression method) method in a more improved manner. In the TVR (Heat Steam Recompression Method), the high-pressure steam through the first stage evaporator is converted to low pressure steam, which maximizes energy efficiency by reusing the steam that has been recompressed through the heat ejector. .

In the energy sector, MSF (Stage Evaporation) requires about 126 х 10 ⁵ to 144 х 10 ⁵ J to produce one tonne of fresh water, whereas for MED-TVR it is about 54 х 10 ⁵ to 72 х 10 ⁵ J. Energy is needed. Comparing the above values, MED-TVR can achieve energy efficiency of about 2.3 times compared to MSF. Also, GOR (Evaporator's performance indicator indicating the amount of evaporator when steam is added, Kg) When comparing freshwater / Kg steam), MSF is about 8 ~ 12 and MED-TVR is about 12 ~ 16.

The calcium salt (125) crystals produced during the vacuum concentration process contain calcium, which is an important component useful for the human body, and the present invention together with the sodium chloride (NaCl, salt) crystals separated in the vacuum concentration process. Mineral salt may be prepared by mixing with mineral concentrate water 150 or NF permeated water 180 to be described later.

Here, another feature of the present invention is to prepare the mineral concentrated dilution water 170 by mixing the demineralized water 130 and the mineral concentrated water 150, the nano-filter (Nano Filter: NF) membrane 175 to concentrate the mineral Passing the dilution water 170 to obtain an NF permeated water 180 from which anions (sulphate ions: SO ₄ ^2- , chlorine ions: Cl ⁻ ) in the mineral concentrated dilution water 170 are removed. have.

According to the prior art, as shown in Figure 1, by mixing the mineral concentrated water (50) obtained by separating the anion with the primary and secondary concentrator in the filtered water (70) passed through the anion exchange resin to produce mineral water have. However, in this case, the mineral concentrate 50 obtained by separating anions with a concentrator still contains a large amount of anions, and thus the mineral salts thus prepared may also have a poor eating feeling.

As the experimental results of the present inventors, as can be seen in the following examples, the anion is separated from the amount of sulfate ion (SO ₄ ^2- ) contained in the primary concentrated water 20 (5,404mg / L) In the mineral concentrate 50 obtained, a significant amount (37,852 mg / L) of sulfate ions (SO ₄ ^2- ) was included, and the inventors of the present invention concentrated the mineral concentrate 150 in demineralized water 130 to solve this problem. Mixing with to obtain a mineral concentrated dilution water 170, it was passed through the NF film 175 to significantly reduce the negative ions.

The NF membrane 175 is generally one of the pretreatment membranes used in the pretreatment of raw water, but the present inventors apply it to the mineral concentrate 150 to remove anions, and to pass the NF membrane 175 to this purpose. Previously, mineral concentrated water 150 was mixed with demineralized water 130 to obtain mineral concentrated dilution water 170, which was then passed through NF film 175. As described above, the mineral concentrated water 150 is mixed with the demineralized water 130 to obtain the mineral concentrated dilution water 170, but there is also a function for preventing the NF film 175 having a fine size hole from being blocked. This is because when the mineral enriched dilution water 170 passes through the NF membrane 175, the ratio of Mg and K, which are useful to the human body, along with anion removal can be adjusted closer to the ideal 3: 1. The ratio of mixing the demineralized water 130 and the mineral concentrated water 150 is preferably 4: 1 or more, and in particular, the present inventors have a weight ratio of the demineralized water 130 and the mineral concentrated water 150 to 6: 1 or 7: 1 or more. It was confirmed that it is most preferable to mix and prepare more demineralized water.

In addition, the present invention used the NF membrane 175 to remove the negative ions contained in the mineral concentrated dilution water 170, the NF membrane 175 basically does not separate the ions by the action of electrical force The anion contained in the mineral concentrated dilution water 170 is separated by physical pressure. In particular, in the present invention, by using the NF film 175 having a negative ion, the negative ions contained in the NF film 175 are electrically charged to the negative ions contained in the mineral concentrated dilution water 170. By pushing the repulsive force so as not to pass through the NF film 175, only the anion (sulfate ion and chlorine ion) was removed and the cation (magnesium and potassium) contained NF permeated water 180. For this purpose, it is preferable that the surface of the NF film 175 is treated with a negative ion, and a negative ion is formed on the surface thereof.

The present inventors also considered using a conventional anion exchange resin in order to remove anions from the mineral concentrate water 150, but an anion exchange resin is an exchanger such as an amine group, an ammonium group, and the like to remove anions originally. It is contained in the form of granules, which is not suitable for removing the anion to the highly concentrated mineral concentrated water 150. In addition, the anion exchange resin had to be added to the regenerant separately in order to remove the negative ions trapped therein, there was a disadvantage in that the exchanger and the like included in the granular form to be replaced at regular intervals.

In still another aspect of the present invention, the calcium salt 125 crystals are mixed with demineralized water 130 to obtain mixed dissolved water 160, and the mixed dissolved water 160 is electrodialysis 165 to remove anions. Obtaining the calcium dissolved water 166 may be further included.

This is by diluting the calcium salt 125 separated in the process of producing mineral concentrate 150 and removing anion (for example, sulfate ion (SO ₄ ^2- )) which reduces the eating sensation by electrodialysis (165) method. In addition, only calcium ions (Ca ²⁺ ), which increase soft eating, are used for the manufacture of mineral salts.

In general, in Japan, OI (O Index, water taste index) defines the delicious water conditions, where the delicious water conditions are the more Ca (calcium), K (potassium), SiO ₂ (silicon dioxide) and Mg ( Magnesium), SO ₄ (sulfuric acid) is less the water taste is excellent. In the case of calcium and potassium, the water taste is softened to improve the taste, and in the case of sulfuric acid, it not only gives a bitter taste, but also combines with calcium to reduce calcium.

In the present invention, in order to selectively remove the sulfate ions that worsen the taste of water, in the mineral salt manufacturing process, the sulfuric acid ions in the calcium dissolved water (166) and the NF permeated water (180), which is a mineral inflowing process, and the NF process. Each of the ED (electrodialysis) was removed to prepare a more delicious salt.

In the ED (electrodialysis) group 165 used in the present invention, an anode and a cathode are installed at both ends thereof, and an anion permeable membrane and a cationic permeable membrane are intersected therebetween, and when a voltage is supplied to both electrodes, the cation and the anion are removed. A device capable of doing this was used. That is, the anion moves through the anion permeable membrane toward the anode and the cation moves through the cation permeable membrane toward the cathode to separate the cation and the anion contained in the mixed dissolved water 160. Thus, in the case of mixed dissolved water 160 according to the invention, for example CaSO ₄ (calcium sulfate) dissolved water, Ca ⁺ (calcium) ions pass through the cation permeable membrane and SO ₄ ^2- (sulfate) ions are anions By passing through the permeable membrane to the anode to selectively remove sulfate ions and the like, calcium dissolved water 166 containing only calcium ions can be obtained.

Then, the present invention crystallizes the mixed liquid mixture of the mineral concentrated water 150 or NF permeated water 180, calcium salt 125 or calcium dissolved water 166, and sodium chloride 145 obtained as described above. By doing so, mineral salt is prepared.

That is, the mineral concentrated water 150 or NF permeated water 180 contains Mg and K (contained in a ratio of about 3: 1), and in the case of magnesium, MgCl ₂ (magnesium chloride) and MgSO ₄ (magnesium sulfate) ) And potassium is present in the form of KCl (potassium chloride). In addition, the calcium salt 125 contains Ca ⁺ (calcium) ions, and in particular, the dissolved calcium 166 removes SO ₄ ^2- (sulfuric acid) ions, which reduces the taste of water, and increases the taste of Ca. ^{Only +} (calcium) ions are included.

Thus, the present invention by mixing the mineral concentrated water 150 or NF permeated water 180, calcium salt 125 or calcium dissolved water 166 to the sodium chloride 145, various and useful mineral components Amounts can be prepared with mineral salts.

The method of obtaining the salt by crystallizing the mixed pressure solution may be obtained by a general method of evaporating and heating the mixed solution to crystallize it. Preferably, the crystallization of the mixed liquid is suitably crystallized while controlling the size of the crystal in accordance with the time for circulating the mixed liquid in a cooling tube. That is, the mineral concentrated water 150 or the NF permeated water 180, the calcium salt 125 or the calcium dissolved water 166, and the sodium chloride 145 are respectively or sequentially injected into the cooling crystal tube and mixed, By repeating the process of circulating the mixed mixture for a certain time, the crystal size of the mineral salt can be adjusted as desired. Sodium chloride 145 begins to be granulated in the evaporation concentrator, but because the particle size is fine and the mineral content is not high, the particle size of the mineral salt can be adjusted through the mixing process in the cooling crystal tube.

The invention may be better understood by the following examples, which are intended for purposes of illustration of the invention and are not intended to limit the scope of protection defined by the appended claims.

Example 1 Concentration and Desalination of Deep Sea Water Through RO Process

Depth of deep ocean water is treated with two stages of pretreatment consisting of a micro filter with a pore size of 0.5 μm and a micro filter of 1 μm (Material: Polyvinylidene fluoride (PVDF)), followed by a primary RO membrane (Material: Poolyamide (PA)). Company: Woongjin Chemical) to obtain primary concentrated water and primary demineralized water. Then, the first demineralized water was transferred to a second RO membrane (material: Polyamide (PA), manufacturer: Woongjin Chemical) to separate the second demineralized water and the second concentrated water. The mineral concentrations contained in the raw water (deep water), pretreated water, demineralized water, and concentrated water in each process are shown in Table 2 below.

[Table 2: Mineral concentrations in raw water (deep water), demineralized water and concentrated water]

division Deep water Pretreatment water Primary concentrated water Primary demineralized water 2nd demineralized water Na (mg / L) 10,800 10,800 20,572 35 0.3 Mg (mg / L) 1,300 1,300 2,479 One 0 Ca (mg / L) 456 456 870 0.3 0 K (mg / L) 414 414 789 1.3 0 SO4 (mg / L) 2,833 2,833 5,404 One 0 Cl (mg / L) 22,370 22,370 42,625 56 0.4 B (mg / L) 5.12 5.12 8.1 0.42 0.27

As shown in Table 2, when comparing the mineral concentration of the deep water and the pre-treated water as raw water, the mineral content did not change, and in the case of secondary demineralized water, the content of all minerals including sodium (Na) was removed by 99% or more. In the first concentrated water, all the minerals were concentrated about 2 times as compared to the raw water. Among them, sulfate ions (SO ₄ ^2- ) contained 5,404 mg / l.

Example 2 Separation of Calcium Salts and Salts Using MED-TVR (Multi-Effect Vacuum Evaporation Method-Thermal Steam Recompression Method)

The primary concentrated water obtained in Example 1 was concentrated at about 70 ° C. until the specific gravity of the first evaporator became about 24 to 25 ° Be in a first evaporator to precipitate CaSO ₄ . The remaining filtrate was transferred to the second evaporator, and the second evaporator was concentrated at about 60 ° C. until the specific gravity was about 31 to 33 ° Be to precipitate NaCl, and the amount produced about 5 g when 1 L was evaporated. . The remaining filtrate when NaCl was precipitated and the mineral concentrate contained in NaCl precipitate was separated using a centrifuge. The main components of the mineral concentrate thus produced are magnesium salts and calcium salts, which are mixed with the precipitated NaCl during the mineral salt manufacturing process described later.

Example 3: Preparation of NF Permeate Using Dilute Mineral Concentrated Water and NF Membrane (Nano Filter)

The mineral concentrated water separated in Example 2 was mixed with secondary demineralized water obtained in Example 1 to prepare mineral concentrated dilution water. The mixing ratio of mineral concentrated water and secondary demineralized water is as shown in Table 3 below. Table 3 below shows the mineral content of the mineral concentrated dilution water mixed according to the mineral concentration number and ratio.

As shown in Table 3, the mineral concentrated water contained 37,852 mg / L of sulfate ion (SO ₄ ^2- ), which was included in the primary concentrated water 20 (SO ₄ ^2- ). It can be seen that the amount is significantly more than the amount (5,404mg / ℓ).

Table 3: Mineral Content of Mineral Concentrated Water and Mineral Concentrated Dilution Water]

division Na (mg / L) Mg (mg / L) Ca (mg / L) K (mg / L) SO ₄ (mg / L) Cl (mg / L) Mineral concentrate 22630 67428 0 20136 37852 269578  Demineralized water: Mineral concentrated water 4: 1 4316 13060 0 4044 7428 42378 5: 1 3521 10883 0 3370 6190 35315 6: 1 3157 9329 0 2889 5306 30270 7: 1 2698 8163 0 2528 4643 26486

Then, the mineral concentrated dilution water mixed with the demineralized water and the mineral concentrated water in the ratio of 4: 1 to 7: 1 was passed through the NF membrane containing anion to obtain NF permeated water. As the NF film used in this example, a nano filter (Woongjin Chemical, NE-4040-70) whose surface was treated with anion was used. The mineral content contained in the ratio-enriched NF water thus obtained is as shown in Table 4 below.

Table 4: Mineral Content of NF Permeate

division Na (mg / L) Mg (mg / L) Ca (mg / L) K (mg / L) SO ₄ (mg / L) Cl (mg / L)  Demineralized water: Mineral concentrated water 4: 1 4601 10849 N.D 4463 1162 39079 5: 1 3109 8620 N.D 3602 1218 30175 6: 1 3009 6888 N.D 2836 1196 24271 7: 1 2124 6916 N.D 2595 1135 26783

That is, Table 3 is the mineral content contained in the mineral concentrated dilution water before the NF membrane permeation, Table 4 is the mineral content contained in the NF permeate water after the NF membrane permeation. As shown in Table 3 and Table 4, the content of Cl and SO ₄ was significantly reduced before and after the permeation of the NF membrane, in particular, the content of SO ₄ can be confirmed that up to 80% or more removed compared to before and after the NF membrane permeation. This is believed to be the result of the greater removal of sulfate ions having a higher molecular weight by anions formed on the surface of the NF film.

In addition, the ratios of magnesium (Mg) and potassium (K) in NF permeated water for mineral concentrated dilution waters with a ratio of 4: 1, 5: 1, and 6: 1 of demineralized water and mineral concentrated water were 2.43: 1, 2.39, respectively. : 1 and 2.43: 1, but the ratio of magnesium (Mg) and potassium (K) in the NF permeate to mineral concentrated dilution water with the ratio of desalted water and mineral concentrated water is 7: 1, which is 2.67. It can be seen that similarity.

Example 4 Calcium Dissolved Water Preparation by Electrodialysis

The calcium sulfate (CaSO ₄ ) salt precipitated according to Example 2 was mixed with secondary demineralized water of Example 1 to prepare calcium sulfate dissolved water, which was then placed in an electrodialysis machine, and the electrodialyzer was operated at a voltage of 40V. A constant current was sent to separate Ca ²⁺ (calcium ion) and SO ₄ ^2- (sulfate ion). Table 5 shows the change in the content of calcium and sulfate ions over time after electrodialysis.

[Table 5: Contents of Calcium Ion and Sulfate Ion by Electrodialysis from Calcium Sulfate Dissolved Water to Calcium Dissolved Water]

Mineral content operating time (min) Ca (mg / L) SO ₄ (mg / L) Voltage (V) Early 0 725 40 60 2 692 40 120 86 319 40 180 150 117 40 240 295 40 40

As shown in Table 5, by the electrodialysis according to the present invention it was possible to obtain a calcium dissolved water finally removed about 95% sulfate ions.

Example 5 Preparation of Mineral Salts Using a Cooling Crystal Tube

NaCl precipitated according to Example 2, mineral concentrated water according to Example 2, and calcium dissolved water according to Example 4 were mixed in an appropriate amount to prepare mineral salts having a balanced mineral balance.

That is, the NaCl precipitated according to Example 2 was transferred to a cooling crystal tube having a temperature of about 10 to 15 ° C. (see FIG. 5), and then mixed with the mineral concentrated water and the calcium dissolved water thereafter, about 15 Stir for ˜20 hours. Cold water reactor of the cooling crystal tube recycled the secondary concentrated water to improve energy efficiency. Then, the mixed salt made by mixing in the cooling crystal tube was transferred to the early stage to evaporate the water in the mixed salt, thereby producing the mineral salt according to the present invention.

Table 6 below shows the content of each mineral component in the mineral salt thus prepared.

Table 6: Mineral Components in Mineral Salts

NaCl (%) Mg (%) Ca (%) K (%) SO4 (%) Before mineral mixing 95.2 0.23 0.12 0.18 0.49 After mineral mixing 90.5 0.75 0.58 0.83 0.13

There is a big difference between the mineral content of salt and the mineral content after mixing before mineral concentrate and calcium dissolved water are mixed.

After mixing, salinity decreased from 95% to 90%, while magnesium increased about 4 times, calcium 5 times, potassium 5 times, and sulfate ion decreased 4 times. In particular, it can be confirmed that the taste of mineral salts can be improved by rapidly decreasing the bitter sulfate ion.

On the other hand, while the present invention has been shown and described with respect to certain preferred embodiments, the invention is variously modified and modified without departing from the technical features or fields of the invention provided by the claims below It will be apparent to those skilled in the art that such changes can be made.

The present invention can provide mineral salts having various and useful mineral components in desired amounts.

1 is a flow chart for explaining a deep seawater mineral water manufacturing method for improving the eating feeling through the adjustment of mineral components and ion exchange according to the prior art,

Figure 2 is a flow chart for explaining a low salt mineral salt manufacturing method according to the prior art,

3 is a flowchart illustrating a method for preparing a mineral salt containing a mineral component using mineral concentrate according to an embodiment of the present invention,

4 is a flowchart illustrating a method of preparing a mineral salt containing a mineral component using NF permeable water according to another preferred embodiment of the present invention.

5 is a photograph showing an example of a cooling crystal tube for producing mineral salts according to the present invention.

Claims (4)

delete Passing the deep ocean water through a reverse osmosis membrane or a nano filter (NF) membrane to separate the concentrated and demineralized water; Heating and concentrating the concentrated water with a first evaporator to separate calcium salt crystals; Heating and concentrating the concentrated water from which the calcium salt crystals are separated by a second evaporator, and separating the salts from the concentrated mineral water from which the salts are removed; The demineralized water and the mineral concentrated water are mixed to prepare a mineral concentrated dilution water, and the mineral concentrated dilution water is passed through a nano filter (NF) membrane having a negative ion. Obtaining the removed NF permeate; And Crystallization of the mixed solution of the salt, NF permeated water and calcium salt crystals, comprising the step of producing a mineral salt containing a mineral component. The method of claim 2, And mixing calcium salt crystals with demineralized water to obtain mixed dissolved water, and electrolytic dialysis of the mixed dissolved water to obtain calcium dissolved water from which anions are removed. Crystallizing the mixed solution of the salt, NF permeate and calcium salt crystals crystallizes the mixed solution of the salt, NF permeate and calcium dissolved water crystallization method of the mineral salt containing a mineral component. The method of claim 2, Crystallizing the mixed solution is a method of producing a mineral salt containing a mineral component, characterized in that the crystallization while adjusting the size of the crystals in accordance with the time to circulate the mixture in the cooling tube.

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