KR100944538B1 - Method for producing high hardness mineral water containing mineral using sea water - Google Patents

Abstract

PURPOSE: A method for producing mineral water with high hardness containing mineral using sea water is provided toefficiently and inexpensively separate the mineral of high purify by removing chlorine ions and sulfate ions, and to manufacture various products including the minerals. CONSTITUTION: A method for producing mineral water with high hardness containing mineral using sea water comprises the following steps: manufacturing first concentrated water and first permeated water by passing sea water through a first reverse osmosis membrane; evaporating and crystallizing the first concentrated water with a multi-stage vacuum evaporation system; separating the crystallized minerals according to kinds of the minerals; manufacturing second concentrated water; making the first mineral concentrated water; making the second mineral concentrated water in which chlorine ions and sulfate ions are removed with a water-splitting electrodialyzer; and mixing and diluting the second mineral concentrated water with second permeated water.

Description

Method for producing high hardness mineral water containing mineral using sea water}

The present invention relates to the production of mineral-containing high hardness mineral water from which seawater is treated to remove sulfate and chlorine ions.

In general, a method of preparing fresh water by treating seawater (including deep seawater) includes an evaporation method, a reverse osmosis membrane method, and an electrodialysis method. Either way, the water produced has been limited in its use due to the nature of the raw water and the component properties of the water produced. Among them, the most important thing that determines the difference is the mineral content and the amount thereof.

However, the above methods are not easy to manufacture the water according to the consumer's requirements and legal standards because the minerals are not freely controlled and the legal regulations on the composition of the minerals are difficult.

In particular, drinking water and deep sea water to be eaten are strictly regulated in their content and amount because they are ingested as drinking water by humans. Among them, chlorine and sulfate ions are representative. According to the water quality standards of the current drinking water management law, chlorine ions are not more than 250mg / L, sulfate ions are not more than 200mg / L. The hardness of drinking water is 300mg / L, the drinking spring water is 500mg / L, and the deep sea water is 1200mg / L, so it can contain a large amount of minerals, but this is due to the regulation of chlorine and sulfate ions, which are representative anions. If not removed, mineral water of more than 200 hardness is not easy to manufacture.

Deep sea water to be eaten is made from deep water as a raw material. Deep sea water means seawater that is located at a depth of 200m or more, which is not reached by sunlight as defined by the Law on Development and Management of Deep Sea Water. Deep sea water is defined as deep water, which does not produce organic matter by photosynthesis and does not generate vertical mixing in winter. These deep sea waters are rich in nutrients containing inorganic nutrients necessary for life activities, cleanliness free from chemical contamination, low temperature stability with little change in temperature, It is a marine resource that has characteristics such as maturation matured over a long period of time at a pressure of 20 atm and higher. ), It is widely used in the medical field (atopic skin treatment). In particular, since the deep sea water contains four minerals (magnesium, calcium, potassium, sodium), various mineral components such as zinc, selenium and manganese, it is known to be useful for the production of mineral water through desalination. However, due to regulations on chlorine and sulfate ions, it is difficult to produce high hardness mineral water without removing them.

Minerals are one of the five nutrients required by humans, and play a role in body composition, body function control, and the like. Deficiency and excess of minerals inhibit physical and mental development and cause various diseases, so it is important to maintain the mineral balance in 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 Anxiety may occur, and symptoms such as hypercalcemia, calcium deposition in the joints or kidneys may occur when taken in conjunction with vitamin D. Magnesium (Magnesium, Mg ²⁺ ) performs the functions of energy production, nervous function control, vitamin B, E metabolism, etc.In deficiency, heart disease, hypertension, nephrolithiasis, insomnia, arrhythmia, hypotension, loss of appetite, muscle pain, Anemia and the like, and overdose is dangerous for patients with renal dysfunction. Potassium (potassium, K ⁺ ) performs functions such as regulating intracellular acid group balance, controlling water, maintaining nerve function, preserving cellular function, expanding blood vessels, and supplying oxygen to the brain, and deficiency of arrhythmia, loss of appetite, and muscle spasms. , Constipation, fatigue, asthenia, hypoglycemia, etc., and overdose is dangerous for patients with renal failure.

Mineral components contained in the deep sea water is 100% water soluble, there is an advantage that it is easy to absorb in the body. Therefore, minerals contained in deep sea water can be a very useful mineral source for modern people whose mineral balance is broken by poor diet and environmental pollution.

Therefore, it is important to make mineral water that contains a lot of minerals but economically and efficiently removes chloride and sulfate ions.

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. In addition, it is divided into cation and anion, and these ions have various characteristics such as monovalent ions and divalent ions, so that it is not easy to separate and extract them individually.

The desalination method of seawater is generally known as evaporation method, reverse osmosis membrane method, electrodialysis method, etc. The evaporation method uses a principle of evaporating seawater to evaporate the solvent water and retain the solute, and reverse osmosis membrane method The ionic substance dissolved in seawater is filtered by using a membrane (semi-permeable membrane) that excludes dissolved ionic substances and only pure water passes.The electrodialysis method alternately arranges an anionic membrane and a cationic membrane, and then It is a method of obtaining pure fresh water by applying DC voltage to electrodes located at both ends of membrane and cationic membrane to remove cations and anions.

However, when these desalination methods are used, in some cases, even if the content of the mineral content is satisfied or even if the mineral is contained, the composition ratio is unbalanced, making it difficult to produce the desired water. In addition, since it is difficult to efficiently separate the various mineral components contained in the sea water, the recovery rate of the mineral component is low, and it also has a disadvantage that it is difficult to remove chlorine ions and sulfate ions from the included minerals.

Korean Patent No. 10-732066 discloses a method for efficiently extracting high purity minerals from deep ocean water using low temperature vacuum crystallization, and Korean Patent No. 10-695671 discloses a method for producing calcium hydrogen carbonate using deep sea water. However, practical methods for economically producing high hardness mineral water have not been developed while chlorine and sulfate ions are selectively and efficiently removed.

The present invention has been made in accordance with the requirements as described above, the present invention is to provide a method for the efficient separation and extraction of minerals from sea water and a method for producing mineral-hardened mineral water by removing chlorine and sulfate ions from the separated and extracted minerals will be.

In order to solve the above problems, the present inventors use minerals by separating high purity minerals from deep sea water using low energy costs and removing chlorine and sulfate ions using nano membranes, bipolar membranes, ion exchange membranes, and the like. High hardness mineral water has been produced.

According to the present invention, high-purity minerals can be separated from seawater with low-cost energy, and efficient production of various products including minerals from which chlorine and sulfate ions have been removed is possible.

In order to achieve the object of the present invention, the present invention

1) preparing the first concentrated water and the first permeated water by passing the deep ocean water through a first RO (reverse osmosis membrane) after pretreatment;

2) separating and extracting the mineral by evaporating the primary concentrated water through a multi-stage evaporation concentration system,

3) separating the minerals by type through the evaporation crystallized minerals through a particle size separator,

4) preparing the secondary permeate and the secondary concentrated water by passing the primary permeate of step 1) through the secondary RO (reverse osmosis membrane);

5) mixing the mineral extracted and extracted in step 3) with the second RO (reverse osmosis membrane) permeate to make a primary mineral concentrate,

6) preparing a secondary mineral concentrated water from which the chlorine and sulfate ions are removed by using the hydrolysis electrodialysis apparatus using the bipolar membrane and the ion exchange membrane as the primary mineral concentrated water prepared in step 5),

7) making the differentiated secondary mineral concentrated water from which sulfate ions have been removed by passing the primary mineral concentrated water prepared in step 5) through the nanomembrane,

8) to a method for producing mineral-containing hard mineral water comprising the step of mixing the secondary mineral concentrated water prepared in step 6) or step 7) with the secondary RO (reverse osmosis membrane) permeated water produced in step 4) It is about.

Method for producing mineral water according to an embodiment of the present invention may further include the step of recycling the second concentrated water of step 4) back to the first RO process.

The method for preparing mineral water according to one embodiment of the present invention may further include the step of crystallizing by spray-drying the residual liquid remaining after the particle size separation in step 3) to crystallize even a small amount of minerals.

In the method for producing mineral water according to an embodiment of the present invention, the pretreatment of the deep sea water of step 1) is sand filtration, rapid filtration membrane, micro filter (MF), nano filter (NF), or ultra filter (UF) filtration It may be performed through, but is not limited thereto.

In the method for producing mineral water according to one embodiment of the present invention, the particle size separator of step 3) may be a vibration screen of 20 to 500 mesh.

Hereinafter, the present invention will be described in more detail.

1 is an overall process diagram showing a method for producing mineral water of the present invention. The flow of the whole process of the present invention is the first step after the pretreatment of the sea water (including deep sea water) (sand filtration, rapid filtration membrane, micro filter (MF), nano filter (NF), ultra filter (UF), etc.) Through the RO (reverse osmosis membrane), the first concentrated water and the first permeated water (demineralized water) are prepared, and the first concentrated water is highly concentrated and crystallized through a multi-stage evaporation concentration system, and the mineral salts having different components are separated by using a particle size separator. How to separate and extract the minerals. The primary permeate (demineralized water) passes through a secondary RO (reverse osmosis membrane) to produce a secondary permeate (high purity demineralized water) and a low concentration of secondary concentrated water. The separated and extracted minerals are mixed and diluted in secondary permeated water to make primary mineral concentrated water. The prepared primary mineral concentrate is converted into a secondary mineral concentrate by removing chlorine and sulfate ions using a hydrolysis electrodialysis apparatus using a bipolar membrane and an ion exchange membrane. In addition, primary mineral concentrated water is used to make secondary mineral concentrated water from which sulfate ions have been removed using a nanomembrane. The secondary mineral concentrated water thus prepared is mixed and diluted in the secondary RO (reverse osmosis membrane) permeated water according to the mineral composition ratio to prepare high hardness mineral water. The secondary concentrated water is sent to the primary RO for recycling.

Mineral water of the present invention is meant to include bottled water (eating water, deep sea water to eat, etc.) and various beverages.

The method for producing mineral water of the present invention includes a primary mineral concentrated water production process and a secondary mineral concentrated water production process using a nanomembrane.

Passing the prepared primary mineral concentrated water through the nano-membrane can be obtained a secondary mineral concentrated water from which SO ₄ ^{2 -} has been removed.

It influences the quality of the produced mineral water, sulfuric acid ions (SO ₄ ^{2 -) -} depends on whether the whether and how jeokeunga desalination, and potassium, calcium, magnesium content of the balance of the chloride ion (Cl). A sulfate ion (SO ₄ ^{2 -),} chloride ion (Cl ^-) in order to remove the film by using nano requires a complicated process is made efficient removal of sulfate ions (SO ₄ ^2-), which sulfate ion (SO ₄ ^{2 -)} It is considered that the ion size is larger than other ions as these divalent ions.

Primary mineral concentrates can be prepared in various combinations. It can be made with only calcium from the extracted minerals, or it can be made with mixed magnesium and potassium concentrates.

It is economical to use nanomembrane to make secondary mineral concentrates in which only sulfate ions (SO ₄ ^2- ) are removed from the primary mineral concentrates. The nanomembrane process can be operated at an economical cost like the RO (reverse osmosis membrane) process.

A sulfate ion (SO ₄ ^{2 -)} and chloride ion (Cl ^-) is difficult only by nano-film process to make the number of the secondary mineral concentrate is removed together. This is because sulfate ions (SO ₄ ^2- ) are difficult to pass through the nano-membrane due to the large size of ions, but chlorine ions (Cl ⁻ ) pass easily like other ions. Therefore, a sulfate ion (SO ₄ ^{2 -)} and chloride ion (Cl ^-) in order to remove together is more efficient than the method of using a bipolar membrane and electrodialysis.

Recently, water-splitting electrodialysis is attracting attention as an efficient process for producing acid / base. The bipolar membrane is a type of membrane combined with a cation exchange layer and an anion exchange layer and plays a key role in the hydrolysis electrodialysis process. Bipolar membranes have unique electrochemical properties that decompose water molecules into hydrogen and hydroxide ions under reverse bias conditions. Thus, chemical and biological processes can produce acids / bases without the generation of by-products.

The bipolar film production method can be divided into four types. The first method is to combine a commercially available cation / anion exchange membrane, and the second method is to prepare a bipolar membrane in the form of a single sheet. The third method is casting on the existing commercial film. Finally, it can be divided into manufacturing method by continuous coating method.

<Water decomposition process by bipolar membrane>

The first method was attempted early in the development of bipolar membrane, and it can be divided into loose overlapping method and hot pressing or introduction of adhesive polymer.However, bipolar membrane manufactured by this method has low physicochemical stability and resistance to water decomposition. It has a high disadvantage and is rarely used at present. Recently, second and third single-sheet bipolar membranes and bipolar membranes manufactured by casting have been mainly developed, and polymer catalysts (eg, Carboxylic acid, Secondary / tertiary amines) and Research into the introduction of inorganic catalysts (eg metal hydroxide / oxide) is underway.

As can be seen from the above figure, bipolar membrane can decompose water into H ⁺ and OH ^- by applying more than 0.83V which is the theoretical decomposition voltage of water. Bipolar membrane cation and anion exchange layer and a bias layer in the reverse order of the combined type (Reverse Bias), i.e., hydrogen ions of water molecules in a state where the negative electrode cation-exchange layer of bipolar membrane, the anion-exchange layer faces the positive electrode (H ⁺ ) and hydroxide ions (OH ^- Parts by).

The water decomposition process using bipolar membrane is more effective than the existing electrolytic water dissociation method used to generate acid / base. Conventional electrolytic processes using water decomposition reactions at electrodes require very large electrode areas, resulting in low current efficiency and low energy efficiency. On the contrary, the water decomposition process using the bipolar membrane is easy to scale up. The major difference is that the decomposition of water is caused by the bipolar membrane, not the electrode. Therefore, there is no problem of contamination of the electrode generated when water is decomposed by the electrode, and a large electrode area is not required. In particular, even when a plurality of membranes are overlapped, there is no need for Kankan to install the electrodes. Therefore, the number of electrodes can be drastically reduced because the electrodes need to be installed at both ends after installing several membranes.

In particular, the electrical efficiency is remarkably high because the decomposition of water is made by the bipolar membrane, not the power of electricity. Table 1 compares the energy values of the water decomposition by the electrode and the water decomposition process by the bipolar membrane.

[Table 1] Comparison of energy of water decomposition by electrode and water decomposition electrodialysis apparatus by bipolar membrane

division △ U-Electric Voltage Difference ΔG-reversible free enthalpy required for water decomposition Water decomposition by electrode ΔU = 2.056 V ΔG = 0.0551kwh / mol Water decomposition by bipolar membrane ΔU = 0.828 V ΔG = 0.0221 kwh / mol

The method for producing mineral water of the present invention includes a method for producing mineral-containing high hardness mineral water through a multi-stage evaporation system.

In order to produce mineral water, it is important to separate and extract the minerals. There may be a variety of methods to separate and extract minerals. Representative examples include electrodialysis and evaporation. Electrodialysis methods are not easy to selectively and quantitatively separate minerals. It is also difficult to extract all the ingredients required. This is because the types of ions vary and the characteristics of the ions are complicated. Simple evaporation can extract all the minerals contained in the seawater, but the separation is difficult and also difficult to perform smoothly due to the various characteristics and differences of the minerals.

Therefore, a multi-stage evaporation method that takes into account the properties of minerals and the physical properties of seawater is needed, not just evaporation. This multi-evaporation method is important to proceed in harmony with the mineral separation extraction technology. Furthermore, as the concentration of seawater increases, its concentration and density increase, which necessitates facility capacity considering energy input and evaporation.

[Table 2] Concentration experiment of seawater (Donghae University Press, Marine Chemistry)

division  Precipitate Volume (ml) Density (weight) Weight (g) Iron oxide (Fe ₂ O ₃ ) Calcium Carbonate (CaCO ₃ ) Calcium Sulfate (CaSO ₄ ) Sodium Chloride (NaCl) Magnesium Sulfate (MgSO ₄ ) Magnesium Chloride (MgCl ₂ ) Sodium bromide (NaBr) Potassium Chloride (KCl) Total (g) sea water 1000 1.0245 1025 function 457.3 1.0531 481.6 0.0008 0.0619 0.0627 371.4 1.0748 399.1 0.0004 0.0210 0.0214 242.7 1.0958 265.9 trace 0.0018 0.0018 198.1 1.1238 217.0 0.0082 0.3353 0.3435 151.3 1.1500 174.0 0.0087 0.4308 0.0078 0.0168 0.4641 118.5 1.1864 140.6 0.0127 0.2486 trace 0.0053 0.0141 0.2807 Mother liquor 100.0 1.2176 121.8 0.0751 0.0839 0.0050 0.0181 trace 0.1820 83.5 1.2219 102.2 0.0753 4.8465 0.0710 0.1189 0.0034 5.1151 66.1 1.2253 81.0 0.0550 5.1887 0.0379 0.0836 trace 0.0173 5.3825 44.4 1.2358 54.9 0.0483 6.2577 0.0712 0.1227 0.0089 0.0221 6.5259 26.0 1.2512 32.5 0.0396 5.6609 0.1251 0.2254 0.0058 0.0513 6.1081 15.9 1.2924 20.6 0.0116 2.6256 0.0837 0.1975 0.0068 0.0406 2.9658 bittern 8.0 1.3056 10.4 1.0966 1.1784 0.4221 0.0268 0.2417 2.9659 Precipitate total 0.0012 0.1143 1.3196 25.7599 1.5854 1.2191 0.0433 0.3764 30.4192 Residual salt in mother liquor 0 0 0 0.0521 0.4972 2.2271 0.0595 0.3357 3.1716 Sum 0.0012 0.1143 1.3196 25.8120 2.0826 3.4462 0.1028 0.7121 33.5908

When the seawater is evaporated and concentrated, evaporation and crystallization are performed as shown in Table 2 above. Therefore, it is important to operate a multi-stage evaporative concentration system that reflects these characteristics.

When seawater is concentrated through RO (reverse osmosis membrane), the concentration of concentrated water is about 1.04. When this is concentrated in the first stage evaporator, as the concentration proceeds, calcium carbonate starts to crystallize. Calcium carbonate does not melt well once it is crystallized, so it is not easy to dissolve and use it as a raw material for mineral water. In addition, even when salt is put in food does not melt well. Therefore, it is better to separate and extract it and use it for other purposes than the raw material of mineral water. In addition, since it is a cause of the scale if it is left as it is, separating and extracting helps to enhance the operation efficiency of the facility.

At the end of the evaporation and extraction of the calcium carbonate crystals, the concentration of concentrated seawater reaches 1.08. At this time, it is transferred to a two-stage evaporation system to proceed with evaporation. From this, calcium sulfate is crystallized. In this case, high purity calcium sulfate separated from calcium carbonate can be obtained. Calcium sulfate is better to be used as a mineral raw material of mineral water because its solubility is higher than that of calcium carbonate. In case of making mineral water containing calcium, separated calcium sulfate is used as raw material.

By the end of the crystallization of calcium sulfate in the secondary evaporation system, the concentration of concentrated seawater reaches about 1.18. At this time, it is moved to the third evaporator to proceed with evaporation. From here, the crystallization of calcium sulfate is almost over and the crystallization of sodium chloride begins. Crystallization of sodium chloride continues until the specific gravity reaches 1.3.

When the specific gravity reaches 1.3, magnesium begins to crystallize. It is necessary to evaporate the magnesium until the crystallization of magnesium progresses to some extent in order to make the salt containing a large amount of minerals, but when magnesium is included in the salt, the salt has a bitter taste and is not yet crystallized. Magnesium is the main component of liquid (nigari), which is a mineral liquid that can be used for various purposes, such as mineral water and tofu production.

In the third evaporator, the salt is extracted and the remainder is separated with mineral liquid. Since the size of the salt particles varies depending on how the third evaporator is designed and operated, the third evaporator can be operated in various forms such as a flat method according to the target particle size of the salt.

The method for producing mineral water of the present invention includes the step of separating the mineral crystals evaporated crystallized by mineral type through a particle size separator. That is, the present invention relates to a method of separating and extracting crystallized mineral (calcium, sodium, magnesium, potassium, etc.) salts and mineral liquids through a vibrating screen (sieve) corresponding to the concentration and crystallization particle size.

As the seawater is concentrated, crystallization of various minerals occurs, and crystals are formed in order of calcium carbonate, calcium sulfate, sodium chloride, magnesium sulfate, magnesium chloride, and potassium chloride. This crystallization order is formed sequentially or simultaneously in order from low to high solubility of each crystal salt.

In the method of separating and concentrating primary mineralized water through evaporation and spray drying, the mineral is crystallized according to the concentration as the evaporation proceeds, and the particle size of each crystallized mineral is different. That is, a method of separating and extracting the crystallized mineral salts (calcium, sodium, magnesium, potassium, etc.) and the mineral liquid through a vibrating screen (sieve) corresponding to the concentration and crystallization particle size.

In order to separate mineral salts and mineral liquids, a particle size separator suitable for the mineral to be crystallized is operated for each evaporator. Of course, in the case of connecting the nets of different sizes in multiple stages, it is possible to continuously separate the particles. Passing the concentrated liquid through the multi-stage vibrating screen (mesh) causes the vibration screen to be caught according to each size, and the remaining liquid is forced out to the bottom and reconcentrated. When crystallized, the screen is separated and extracted. .

The method for producing mineral water of the present invention includes a step of completely separating and extracting a small amount of minerals after crystal separation and extraction of representative minerals calcium, sodium, magnesium, potassium, etc. into crystals through spray drying.

The process of spray drying the remaining small amounts of minerals is much simpler and more efficient than crystallizing through evaporative concentrations to small amounts. In other words, attempting to crystallize the residue to 100% evaporates problems such as sticking inside the equipment, denatured by heat, difficulty in extracting transport, and limiting the continuity of the system. Crystallization and extraction of large amounts of minerals and small amounts of minerals are more efficient than evaporating and concentrating all residual liquids.

The spray drying method may be either nozzle type or disk rotation type. If it is a large-capacity treatment, disk rotation is advantageous, and small amount is suitable for nozzle type.

In the method for preparing mineral water and mineral salts of the present invention, the separated mineral salts and mineral liquids are mixed with secondary permeate to form primary mineral concentrates, and the nano-membrane or water-splitting electrodialysis (WSED) process. Preparing mineral water, for example, drinking bottled water (eating water, deep sea water, etc.) and beverages from which anion sulfate and chlorine ions are removed.

After the seawater is subjected to a pretreatment process, the first RO (reverse osmosis membrane) process is produced to prepare the first concentrated water and the first permeated water. The primary concentrated water is introduced into a multi-stage evaporation system to separate mineral salts and mineral liquids through an evaporation crystallization process. The primary permeate is introduced into a secondary RO (osmotic membrane) process to produce secondary permeate and secondary concentrated water. Separately prepared minerals and mineral liquids are mixed and diluted in secondary permeate to make primary mineral concentrate. Through producing the primary mineral to be concentrated nano membrane (NF membrane) SO ₄ ^{2 -} removing ions or water-splitting electrodialysis (WSED; Water-Splitting Electrodialysis) chloride ions by introducing a process (Cl ^-) and sulfate ions ( SO ₄ ^2- ) is removed together to prepare a secondary mineral concentrate. Secondary mineral concentrated water is mixed and diluted with secondary permeate (demineralized water) at a suitable ratio to prepare a mineral water containing high hardness.

Hereinafter, the present invention will be described in detail by way of examples. However, the following examples are merely to illustrate the invention, but the content of the present invention is not limited by the following examples.

Example 1 Removal of Sulfate Ion Using a Nanomembrane

As shown in Table 3, sulfate ions were removed using a nanofilm (NF membrane). In the case of using a nano-membrane, it is possible to prepare a variety of mineral concentrated water from which the sulfate ion component is removed, thereby producing high hardness mineral water. In particular, since sulfate ions worsen the taste of water and lead to acidification of the water, it is important to remove the mineral water in order to make delicious hard water. When minerals are separated and extracted, mixed and diluted with RO (reverse osmosis membrane) permeated water (demineralized water) and then passed through the nanomembrane (NF membrane), sulfate ions are prevented from passing through the membrane due to their ionic properties. Most other ions will pass through. This process produces mineral concentrates from which sulfate ions have been removed. Table 3 shows the results of experiments in which raw seawater was passed through a nanomembrane (NF membrane).

[Table 3] Water Quality Results of Seawater Treated with Nanofilm (NF Film) (Unit: mg / L)

division enemy NF membrane permeate salt 10,127 10,900 potassium 364 436 calcium 388 191 magnesium 1,241 653 Chlorine Ion 15,433 17,100 Sulfate ion 2,790 48 all 30,343 29,328

In the results of Example 1, it can be seen that when the nano-membrane (NF film) is used, more than 98% of sulfate ions are removed. Using nano-membrane (NF membrane) can remove sulfate ions not only in seawater, but also in a combination of various minerals such as calcium mineral water and magnesium mineral water. Thus, after making the concentrated mineral water from which sulfate ions have been removed and mixing it with RO (reverse osmosis membrane) permeated water (demineralized water), high hardness mineral water from which sulfate ions are removed can be produced.

According to the Drinking Water Management Act, the regulation value of sulfate ion is set. Currently, it is regulated to 200mg / L, so even if you want to make high-quality mineral water, you cannot make it. I can make it. It also has the advantage of improving the taste of water by removing sulfate ions.

Example 2 Removal of Sulfuric Acid and Chlorine Ion by Water Decomposition Electrodialysis System

Sulfate ions and chlorine ions were removed by a hydrolysis electrodialysis apparatus. 5 is a photograph of the actual hydrolysis electrodialysis apparatus. When mineral concentrated water flows into the water-dissolving electrodialysis apparatus using bipolar membrane and ion exchange membrane as shown in the figure below, anions such as chlorine ion and sulfate ion are gathered in one place according to the characteristics of the membrane and hydrogen ions (H ⁺ ) produced by the bipolar membrane. In combination with an acidic group such as sulfuric acid or hydrochloric acid. On the other hand, the cations such as magnesium, calcium, potassium, sodium, etc. are gathered in one place according to the properties of the membrane and are combined with the hydroxyl ions (OH ⁻ ) produced by the bipolar membrane to be alkalized.

<Sulfation Ion and Chlorine Ion Removal by Hydrolysis Dialysis Using Bipolar Membrane and Ion Exchange Membrane>

Bipolar membranes used in electrolysis electrodialysis apparatuses undergo water decomposition in bipolar membranes, unlike water decomposition processes by electrodes. Therefore, there is no contamination of the electrode and a large heat transfer area is not necessary. In the case of installing a plurality of electrodes, it is convenient to install only one electrode at both ends instead of installing several electrodes, and electrical efficiency is much higher than water decomposition by electrodes as shown in Table 1 above. In addition, the RO (reverse osmosis membrane) permeate water is added to both sides of the bipolar membrane to manage the purity of the generated mineral water.

It is possible to produce a variety of mineral water according to the type of mineral water to be added, and it is possible to produce a mineral water of high hardness despite the regulation of sulfate and chlorine ions, which are regulated by the drinking water management law. According to the water quality standards of the current drinking water management law, chlorine ions are not more than 250mg / L, sulfate ions are not more than 200mg / L. The hardness of the drinking water is 300mg / L, the drinking spring water is 500mg / L, and the deep sea water is 1200mg / L, which can contain a large amount of minerals, but this is due to the regulation of chlorine and sulfate ions, which are representative anions. Without effective removal, mineral water with a hardness of 200 mg / L is not easy to manufacture. As in the above embodiment, when the cations are combined with hydroxyl ions and alkalinized from the removal of chlorine and sulfate ions, the content of sulfate and chlorine ions is not regulated, thereby making it possible to prepare high hardness mineral water.

< Example  3> Multi-stage vacuum evaporation method  Mineral extraction by

Minerals were extracted by multi-stage vacuum evaporation. 3 is a manufacturing experiment to develop a multi-stage vacuum evaporation system, Figure 4 is a photograph producing a product using a real multi-stage vacuum evaporation system. The evaporation system lowers the boiling point of seawater by applying vacuum, so seawater evaporates at low temperatures. Therefore, the energy required to evaporate seawater can be reduced. As seawater is concentrated by evaporation, the concentration of dissolved minerals gradually increases, and above saturation concentrations, the dissolved ions begin to crystallize.

This evaporation system can be made in one evaporator, but it is much more effective if it is operated in multiple stages depending on the concentration and specific gravity and the minerals to be produced. In the case of one evaporator there is a problem that the minerals are crystallized. Of course, selective separation is possible at the same time in the particle size separator, but other minerals have the same particle size, and the operating conditions may vary depending on the concentration of the minerals. It can be said that it is much more efficient to install and operate the evaporator by the step of crystallization of minerals.

<Separation extraction of minerals by multi-stage vacuum evaporation method>

The figure above shows the results that can be obtained by evaporating 100 tons of seawater into a multi-stage vacuum evaporator. As the 100 tons of seawater go through each evaporation step, the specific gravity and the minerals produced are different. As the minerals crystallized according to specific gravity, it is effective to operate the evaporation system in multiple stages, and it also helps to solve the scale problem caused by the first crystallization of calcium carbonate.

The multi-stage evaporation system is energy efficient and easy to control because the energy input amount can be determined according to the characteristics of the seawater at each stage. In addition, the vacuum can increase energy efficiency and reduce mineral destruction and scale formation due to high temperature evaporation. If the vacuum is about 600mmHg, the boiling point is lowered below 60 ℃. By lowering the boiling point, the energy input can be reduced by that difference. In addition, due to evaporation at low temperatures, it is possible to reduce the physicochemical change and scale of minerals due to high temperatures.

< Example  4> evaporated crystallized minerals Particle size separator  Separating by mineral type through

In order to selectively separate and extract the mineral crystallized in the course of the concentration was separated using a vibration screen according to the size of the particles. 6 is an actual vibration screen picture. Magnesium salt, sodium chloride salt, calcium salt, etc. were separated according to the particle size of the crystal salt using a vibrating screen (Table 4). The average particle size of the magnesium salt was 263 μm, the average particle size of the sodium chloride salt was 175 μm, and the average particle size of the calcium salt was 7.73 μm. Magnesium salts, sodium chloride salts and calcium salts were separated using multiple vibrating screens having pore sizes of 180 μm, 125 μm and 38 μm using the average particle size difference of these mineral salts.

[Table 4] Particle Size and Separation Mesh Size of Minerals

division Particle size (㎛) Mesh size Remarks Magnesium salt 263.23 80 180 μm Sodium chloride salt 175.08 115 125 μm Calcium salt 7.73 400 38 μm

* In case of calcium, it is possible to extract with 38㎛ net because the mass is larger than individual particle size due to the tangling and bonding property.

Therefore, magnesium salts, sodium chloride salts, and calcium salts separated using the network according to the crystal grain size well exhibit the component characteristics of each salt.

BRIEF DESCRIPTION OF THE DRAWINGS It is the whole process drawing which shows the manufacturing method of the mineral containing high hardness mineral water of this invention.

2 is a photograph of preparing concentrated water and permeate using RO (reverse osmosis membrane).

Figure 3 is an evaporation concentration and mineral separation extraction experiment carried out to develop the manufacturing apparatus of the present invention.

4 is a photograph of a device for extracting minerals by a multi-stage vacuum evaporation method using concentrated water.

Figure 5 is a photograph of the sulfate and chlorine ion removal device using a hydrolysis electrodialysis apparatus.

6 is an actual vibration screen picture.

Claims (5)

1) preparing the first concentrated water and the first permeated water by passing the seawater through the first reverse osmosis membrane after pretreatment; 2) evaporating and crystallizing the primary concentrated water using a multi-stage vacuum evaporation system; 3) separating the minerals by type through the particle size separator of the evaporated crystallized minerals; 4) passing the first permeate water through a second reverse osmosis membrane to prepare a second permeate water and a low concentration secondary water; 5) mixing the mineral separated in step 3) with the second reverse osmosis membrane permeated water to make primary mineral concentrated water; 6) preparing a secondary mineral concentrated water from which chlorine and sulfate ions are removed by using the hydrolysis electrodialysis apparatus using the bipolar membrane and the ion exchange membrane as the primary mineral concentrated water prepared in step 5); 7) mixing and diluting the secondary mineral concentrated water prepared in step 6) with the secondary reverse osmosis membrane permeated water. 1) preparing the first concentrated water and the first permeated water by passing the seawater through the first reverse osmosis membrane after pretreatment; 2) evaporating and crystallizing the primary concentrated water using a multi-stage vacuum evaporation system; 3) separating the minerals by type through the particle size separator of the evaporated crystallized minerals; 4) passing the first permeate water through a second reverse osmosis membrane to prepare a second permeate water and a low concentration secondary water; 5) mixing the mineral separated in step 3) with the second reverse osmosis membrane permeated water to make primary mineral concentrated water; 6) passing the primary mineral concentrated water prepared in step 5) through the nano-membrane to make the secondary mineral concentrated water from which sulfate ions have been removed; 7) mixing and diluting the secondary mineral concentrated water prepared in step 6) with the secondary reverse osmosis membrane permeated water. [Claim 3] The mineral-containing hard mineral water of claim 1 or 2, further comprising spray-drying the remaining liquid after separation of the particle diameter in step 3) to crystallize and crystallize even a small amount of minerals. Manufacturing method. The pretreatment of the deep sea water of step 1) is performed by sand filtration, rapid filtration membrane, micro filter (MF), nano filter (NF), or ultra filter (UF) filtration. Method for producing a mineral-containing high hardness mineral water, characterized in that. The method of claim 1 or 2, wherein the particle size separator of step 3) is a method for producing mineral-containing high hardness mineral water, characterized in that the vibration screen of 20 to 500 mesh.

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