KR20060078594A - The manufacture method of the mineral adjustment agent, drinking water, table salt and bittern from deep sea water - Google Patents

Abstract

The present invention relates to a method for preparing mineral regulators, salts, liver water and beverages from deep sea water, and more particularly, to prepare mineral regulators for the preparation of food and beverages using various mineral components contained in deep sea water. It is to present a method of making salt and water and beverages.

To this end, the present invention is to take the deep sea water of 200m or less of the seabed depth and pre-treatment such as warming treatment, microfiltration treatment, small grouping of water molecules and mineral activation treatment at 20 ~ 30 ℃.

The pre-treated deep sea water is removed from the first nanofiltration process, and then sent to the first reverse osmosis process, and the demineralized water, which is filtered water, is sent to the drinking water manufacturing process, and the concentrated concentrated brine is sent to the second nanofiltration process. The filtered brine is sent to the salt manufacturing process, and the first concentrated mineral water is diluted with demineralized water from the first reverse osmosis filtration process to the third nanofiltration process. The water is sent to the first electrodialysis process.

In the first electrodialysis process, a monovalent cation selective exchange diaphragm and a monovalent anion selective exchange diaphragm are alternately installed between the anode and the cathode in an electrodialysis apparatus to remove salts of monovalent ions. A cation exchange diaphragm that penetrates cations and a monovalent anion selective exchange diaphragm that only penetrate monovalent anions are sent to a second electrodialysis device with alternating multiple stages between the anode and cathode to produce concentrated mineral water from which sulfate ions have been removed. Then, the monovalent cation selective exchange diaphragm and the monovalent anion selective exchange diaphragm are sent to a third electrodialysis apparatus in which multiple stages are alternately installed between the positive electrode and the negative electrode, thereby producing concentrated mineral water in which salts are finally removed.

In the third electrodialysis process, non-reducing disaccharides are supplied by supplying calcium agent to concentrated mineral water from which salt and sulfate ions have been removed and adjusting the mineral balance in the range of Ca / Mg weight ratio of 2-6. The liquid mineral regulator is prepared by adding the sugar alcohol, which is sent to a drying process to evaporate water to prepare a solid mineral regulator.

The brine discharged from the second and third nanofiltration processes and the first and third electrodialysis processes may include a cation exchange diaphragm penetrating all the cations and a monovalent anion selective exchange diaphragm selectively penetrating only the monovalent anion between the anode and the cathode. In the fourth electrodialysis process in which alternating stages are installed, concentrated brine containing a large amount of mineral components is made, followed by evaporation and crystallization processes to dehydrate and dry the precipitated salts while evaporating moisture to remove the mineral components. While preparing a large amount of salt, dehydrated water is prepared.

Demineralized water from the fourth electrodialysis process and demineralized water discharged from the first reverse osmosis process are converted to polyboric acid by converting the boron compound in water to polyboric acid in the pH adjustment process, and then sent to the second reverse osmosis filtration process. The filtered water is neutralized, and then adjusted to hardness using a mineral regulator, and then sterilized to prepare a beverage.

Deep sea water has very low levels of contaminants, harmful germs and organics, and sunlight does not reach 200 m or below, so the water temperature is much lower than superficial sea water. Rich in nutrients such as nitrates, phosphates and silicon, which are rich in eutrophication, and clusters of water molecules under long periods of time under high pressure, resulting in a small grouping of water molecules, making them less permeable. Maturity modifiers because they contain the essential microelements necessary for the growth of organisms such as calcium, magnesium, iron, zinc, sodium, etc., and mineral properties with good mineral balance. It is expected to be widely used in the manufacture of salt, salt water and drinking water.

Deep sea water, mineral conditioners, salt, water, beverages, nanofiltration, reverse osmosis filtration. Electrodialysis

Description

The manufacture method of the mineral adjustment agent, drinking water, table salt and bittern from deep sea water}

1 is a manufacturing process chart of mineral regulator from deep sea water

2 is a salt and water production process chart

Figure 3 is a beverage production process

4 is a process for small grouping and mineral activation of water molecules

5 is a process for desalting salt (NaCl) in mineral saline by the first electrodialysis apparatus

6 is a process chart for concentrating mineral components of mineral water and removing sulfate ions by a second electrodialysis apparatus;

7 is a process for desalting salts contained in concentrated mineral water by a third electrodialysis apparatus;

8 is a process for preparing a mineral modifier by mixing calcium and additives

9 is a process chart for concentrating the salt of brine by the fourth electrodialysis apparatus

10 is a process diagram of evaporating water into atmospheric air to precipitate salt, followed by dehydration and drying to prepare salt and brine.

11 is a process diagram of evaporating water with hot air to precipitate salt, followed by dehydration and drying to prepare salt and brine.

12 is a process for preparing a beverage by adjusting the pH adjustment, neutralization and minerals in the beverage production process

13 is a precipitation rate of various salts according to the specific gravity change when concentrating the seawater at 35 ℃

14 is a precipitation rate of various salts according to the specific gravity change when concentrating the seawater at 80 ℃

15 is a change chart of the concentration of various salts according to the specific gravity of the concentration function due to the concentration of seawater

Fig. 16 is a relational chart of precipitation amounts of salts in the concentration of seawater;

17 is a change in concentration of the salt contained in the electrodialysis process

18 is a relational diagram of seawater, hydrous water, and cramps

19 is a model diagram of clusters of water molecules;

<Description of the symbols for the main parts of the drawings>

One; Electronic treatment tank 2; electrode

3; Insulator 4; Stainless steel sheet

5; Foundation concrete structure 6; grounding

7; Constant voltage generator (electron charger)

7a; Variable resistor 7b; grounding

7c; Primary winding 7d; Iron core

7e; Secondary winding 8; Intermediate Treatment Tank

9; Magnetizer feed pump 10; Constant Voltage Conduit Magnetizer

11; Small group reservoir 12; Small group transfer pump

13; Mineral brine reservoir 14; Mineral Saline Transfer Pump

15; A first electrodialysis apparatus 16; anode

17; Cathode 18; Anode chamber

19; Cathode chamber 20; Monovalent anion selective exchange diaphragm

21; Monovalent cation selective exchange membrane 22; Cation exchange diaphragm

23; Anion exchange diaphragm 24; Desalination Room

25; Salt concentrate chamber 26; Demineral Room

27; Mineral concentration chamber 28; 1st circulating brine reservoir

29; First brine circulation pump 30; Mineral water reservoir

31; Mineral water transfer pump 32; Second electrodialysis device

33; Concentrated mineral circulating water storage tank 34; Concentrated Mineral Water Circulation Pump

35; Concentrated mineral water reservoir 36; Concentrated Mineral Water Transfer Pump

37; Third electrodialysis apparatus 38; Second circulation brine reservoir

39; Second brine circulation pump 40; Additive mixer

41; Stirrer 42; Heating jacket

43; Thermal insulation 44; Mineral regulator transfer pump

45; Cooler 46; Brine reservoir

47; Brine transfer pump 48; 4th electrodialysis device

49; Third circulation brine reservoir 50; 3rd brine circulation pump

51; Concentrated brine reservoir 52; Concentrated brine transfer pump

53; Salt bath 54; Salt Lake Rake

55; Evaporation tower 56 by atmospheric air; Spray nozzle

57; Exhaust fan 58; Return concentrated brine reservoir

59; Concentrated brine return pump 60; Precipitation Salt Conveyor

61; Dehydration reservoir 62; Dehydration Feed Pump

63; Blower 64; Burner

65; Heat exchanger 66; Evaporation Tower by Hot Air

67; Demister 68; pH adjustment tank

69; pH adjusting tank stirrer 70; Second reverse osmosis filtration process pump

71; Neutralization tank 72; Neutralization tank stirrer

73; Mineral regulator supply pump 74; Mineral regulator

75; Mineral regulator stirrer 76; Sterilization Process Supply Pump

pH: Hydrogen ion ⓢ: Solenoid valve

pHIS; PH indicating switch

FI; Flow indicator BI: Bumedo indicator

BIS: Baume indicating switch

ECIS: Electric conductivity indicating switch

TT; Temperature transmitter

TIC; Temperature indicating controller

The present invention relates to a method for preparing mineral regulators, salts, liver water and beverages from deep sea water, and more particularly, to prepare mineral regulators for the preparation of food and beverages using various mineral components contained in deep sea water. It relates to a method of making salt and soda and beverages.

Deep sea water is generally called deep sea water of less than 200m, and unlike seawater on the surface, because of the lack of sunlight, plankton and living organisms do not proliferate, so the concentration of nutrients is high. As there is no contaminant present in surface seawater because it is not mixed with seawater, low temperature stability, cleanliness, eutrophicity, mineral balance characteristics, and ripening There are characteristics such as sex, and the details are shown in Table 1.

                      Table 1 Characteristics of deep sea water

  Low temperature stability While the surface water temperature fluctuates greatly with the seasons, deep ocean waters are stable at low temperatures with little fluctuations in the water temperature.    Cleanliness Deep ocean water is deep and difficult to be polluted by terrestrial river water and air, and there are very few chemicals, bacteria, organisms and suspensions.   Eutrophication The deep ocean water is deep in the sunlight and does not have photosynthesis. Compared with surface sea water, it contains many inorganic nutrients such as nitrogen, phosphorus, and silicic acid, which are necessary for the growth of living organisms.   Mineral properties Deep sea water contains a variety of essential minerals and is characterized by low impurities.    Aging Deep sea water matures over a long period of time under high pressure, and the clusters of water molecules are small grouped, so that the surface tension is low, and the permeability is high, and the thermal conductivity is high.

Deep sea water contains about 5 to 10 times more inorganic nutrients than no surface water, and contains no more than 70 kinds of minerals. There is a characteristic that component is included, and the analysis value of deep seawater and surface seawater is shown in Table 2 below.

                Table 2 Component Analysis of Deep Sea Water and Surface Sea Water

            Item   Deep ocean water     Surface seawater      General item Water temperature (℃) 9 16.5-24.0 pH 7.59 7.85 DO dissolved oxygen (mg / l) 7.80 8.91 TOC Organic Carbon (mg / L) 0.962 1.780 Soluble evaporation residue (mg / l) 40750 37590 M-alkalido (mg / l) 114.7 110.5        Major element Cℓ chloride ion (wt%) 2.237 2.192 Na sodium (wt%) 1.080 1.030 Mg magnesium (wt%) 0.130 0.131 Ca Calcium (mg / L) 456 441 K potassium (mg / L) 414 399 Br Clear (mg / L) 68.8 68.1 Sr Strontium (mg / L) 7.77 7.61 B boron (mg / l) 4.44 4.48 Ba barium (mg / l) 0.044 0.025 F Fluorine (mg / L) 0.53 0.56 SO₄ (mg / ℓ) 2833 2627    Nutrients NH₄ ammonia nitrogen (mg / l) 0.05 0.03 NO₃Nitrate nitrate (mg / ℓ) 1.158 0.081 PO₄ phosphate (mg / ℓ) 0.177 0.028 Si silicon (mg / l) 1.89 0.32       Trace elements Pb lead (μg / ℓ) 0.102 0.087 Cd cadmium (㎍ / ℓ) 0.028 0.008 Cu copper (㎍ / ℓ) 0.153 0.272 Fe iron (㎍ / ℓ) 0.217 0.355 Mn manganese (µg / l) 0.265 0.313 Ni nickel (µg / l) 0.387 0.496 Zn zinc (μg / ℓ) 0.624 0.452 As Arsenic (㎍ / ℓ) 1.051 0.440 Mo molybdenum (µg / l) 5.095 5.555  Number of bacteria Number of live bacteria (dog / ml) 10² 10³ to 10⁴

Note: The above analysis is based on the analysis of the deep seawater and surface seawater of 374m below the east side of Murodo Lighthouse in Kochi Prefecture, Japan.

As mentioned above, deep sea water has a very low level of contaminants, harmful germs and organics, low temperature stability, rich in nutrients, which are very important for plant growth, and long-term under high pressure. Over time, clusters of water molecules have been subpopulated into small groups and matured with water with good permeability due to low surface tension, calcium, magnesium, iron, zinc, sodium, etc. There are mineral properties that contain essential trace elements necessary for living things.

The constituent elements of the human body are 65% oxygen, 18% carbon, 10% hydrogen, 3% nitrogen, and important minerals: 1.5-2.1% calcium, 0.8-1.2% phosphorus, 0.3-0.4% potassium, 0.25-0.3% sulfur In addition to 0.15 to 0.2% sodium, 0.15 to 0.2% chlorine and 0.05 to 0.1% magnesium, trace minerals include iron 0.006%, zinc 0.002%, selenium 0.0003%, manganese 0.0003%, copper 0.00015%, urethra 0.00004%, other molybdenum, Cobalt, chromium, etc. are present in ultra trace amounts.

For adults, the daily requirement of minerals is calcium 600-700 mg, phosphorus 700 mg, potassium 2000 mg, sodium 1.5 g, magnesium 250-320 mg and trace minerals iron 10-12 mg, zinc 10-12 mg, copper 1.6 to 1.8 mg, manganese 3.0 to 4.0 mg, urethral 150 μg, selenium 45 to 60 μg, molybdenum 25 to 30 μg, and chromium 30 to 35 μg.

In particular, the lack of calcium among the mineral components can cause osteoporosis, the lack of calcium (Ca) is the most problematic problem, the required calcium intake is 600 ~ 700 ㎎ / day, magnesium is 250 ~ 320 ㎎ / day of calcium and magnesium It is preferable to ingest by weight ratio 2 or more.

In beverages or food NaCl shall remind the salty taste, magnesium (MgCl _2, MgSO ₄₎ is a potassium (KCl) the bitter taste, the acidity, sulfate ion (SO ₄ ^{2 -)} dropped mulmat to remind the the acidity (酸味) On the other hand, the calcium component is characterized by softening the taste of water to improve the taste of water.

And in the case of drinking water, the water taste index (OI) of the following formula ① (OI) is 2.0 or more, the taste is good, the health index (KI) of the following formula ② is known to be good for health water 5.2 or more.

Mulmat index (OI) = (Ca + K + SiO 2) / (Mg + SO 4 2 -) ... … … … … … … … … ①

Ca- 0.87Na, index of health (KI). … … … … … … … … … … … … … … … … … … ②…

Therefore, in the case of mineral modifiers used in beverages and foods, it is preferable that the calcium (Ca) / magnesium (Mg) weight ratio is manufactured at a ratio of 2 or more.

However, deep seawater is NaCl concentration and the sulfate ion (SO ₄ ^{2 -)} is the concentration of the problems that the concentration is contained higher by about three times compared to calcium (Ca) nopeumyeonseo of magnesium (Mg).

Therefore, in order to manufacture a high quality mineral regulator using deep sea water, excess salt and sulfate ions must be removed, and the mineral balance should be adjusted at a ratio of Ca / Mg of 2 or more.

In other words, deep sea water has the characteristics of minerals in terms of manufacturing mineral regulators, cleanliness without contaminants and microorganisms, eutrophication with large amounts of nutrients, and minerals containing various minerals necessary for the human body, but NaCl, KCl, SO ₄ ^{2 -} Since there is a problem that the concentration of magnesium is higher than the calcium content in the presence of excess, mineral preparation should be removed to remove the NaCl, KCl, SO ₄ ^{2 -} and then adjust the weight ratio of Ca / Mg to 2 or more. .

Salts are different from each other according to the manufacturing method, the importance of the salt is shown in Table 3 below.

                   Table 3 Importance Table by Salt Types

    Item   Thousand Sun Salt  Gas salt  Remanufacture   Ion exchange membrane concentrate   NaCl (wt%)    80-85    99      88     99.2-99.7   Ca (wt%)     0.2     0.1   0.1-0.15     0.03-0.05   Mg (wt%)    0.5-1.0     0.2   0.2-0.5     0.013-0.035 SO ₄ (wt%)    1.0-1.5     0.4   0.4 ~ 0.8     0.13-0.15   K (wt%)    0.1-0.17     0.1     0.1     0.01 ~ 0.02

Examining the minerals contained in salts in Table 3, there is a problem that salts other than natural salts are not healthy salts because they contain less minerals.

Salt produced from deep sea water contains no environmental pollutants compared to salt produced from surface sea water, but Pb, Cd, Cu, As… It does not have a high concentration of harmful heavy metals, such as calcium and magnesium because it contains a variety of minerals useful for the human body has the characteristics that can produce a good quality salt for health.

Therefore, the present invention provides a method for producing a salt having a high concentration of minerals, without producing a salt with high purity of NaCl as in the past ion exchange concentrated salt.

The composition of the brine varies considerably depending on the method and conditions of salt production.In the case of salt production in salt farms, the amount of magnesium sulfate precipitated in the summer is higher than that produced in the winter when the temperature is low. The concentration of magnesium sulfate is lowered in the brine produced in, which is called wintering.

Calcium chloride (CaCl ₂ ) is present in the liver water produced in the ion exchange diaphragm salt with high potassium content and no magnesium sulfate, and the composition of the salt water according to the salt preparation method is shown in Table 4 below.

              Table 4 Composition of Salt Water According to Salt Preparation Method (wt%)

  Kind of guard  NaCl  KCl MgCl ₂ MgSO ₄ MgBr ₂ CaCl ₂   Remarks    Salt salt 2 to 11 2 to 4 12-21  2 to 7 0.2 to 0.4   - Magnesium sulfate Ion exchange diaphragm salt water 1 to 8 4 to 11 9-21    - 0.5 to 1 2 to 10 Calcium chloride system

In addition, when reviewing the deep sea water in terms of beverage production, there are the following problems.

① deep sea water is aged under the mineral and the low temperature and high pressure for a long period of time at depths below 200m NMR ^{(Nuclear magnetic resonance; NMR) 17} O - NMR half value width - ¹⁷ O NMR half value width of the value of the common tap water in 75~80Hz Although the group of water molecules is smaller than the value of 130 ~ 150Hz, Lourdes and Evian in France, Nordenau in Germany and Nana in India Mineral water, such as Nadana and Tracote, Mexico, has a higher nuclear magnetic resonance ¹⁷ O-NMR half width than 60 to 70㎐, so the water taste is slightly lower than that of famous mineral water.

② The deep sea water contains boron compounds in the range of 4-5 mg / l. However, it is difficult to treat the drinking water below 0.3mg / l by the simple nanofiltration, reverse osmosis filtration and electrodialysis.

③ The weight ratio of Ca / Mg should be 2 or more to improve the taste of water and mineral balance. The mineral balance is suitable for deep sea water. The Ca / Mg weight ratio is in the range of 0.3 to 0.35, and the magnesium content is much higher than that of calcium. As such, the mineral balance of Ca / Mg must be adjusted.

In the case of Japanese Patent Publication No. 2004-65196, demineralized water is used as an adjusting agent for mineral beverages. However, since magnesium (Mg) is about three times higher than calcium (Ca) and sulfate ions have not been removed, there is a problem that water taste and mineral balance are not good and minerals are not concentrated at all. In case of moving and not using in the field, there is a problem of high transportation and packaging costs.

Japanese Patent Publication No. 2006-6168 discloses a method for masking the taste by adding trehalose to mineral water produced by concentrating and desalting mineral water, seawater or deep seawater, but mineral balance is appropriate. There is a problem that cannot be adjusted.

In Japanese Patent Laid-Open No. 2005-52130 and Japanese Patent Laid-Open No. 2002-369671, in order to solve the problem of boron contained in the above-described deep sea water, fresh water and fresh water collected from the deep water of the deep sea water and streams are used. ), A method of mixing water such as mineral water, tap water, and the like has been proposed, but such a beverage has a problem in that it can not fully exhibit the characteristics of deep sea water.

In Japanese Patent Application Laid-Open No. 2004-65196, the treatment was performed while adjusting the conductivity to less than 10 mW / cm in an electrodialysis apparatus using a membrane that selectively permeates only monovalent ions. Was less than 0.2 mg / l, and there was a problem that the concentration of Mg ion was higher than that of Ca ion, and in the case of JP-A-238515, seawater was treated by adjusting the electrical conductivity by electrodialysis. However, this method also did not solve the above problems.

The method of reverse osmosis filtration treatment with Amberlite resin of Japanese Patent Publication No. 2002-361246 and Japanese Patent Publication No. 2001-300264 for removing boron compound is carried out in the final stage of reverse osmosis process by three stage reverse osmosis filtration. Although a method of adjusting the pH has been proposed, these also have problems such as mineral balance, small grouping of water molecules and redox potential values have not been properly solved.

In the case of Korea Patent Publication No. 10-2006-0031791, warm and pre-filtration of deep sea water for drinking water production, and then positive and negative ions to selectively exchange monovalent ions for concentrated mineral brine in reverse osmosis filtration after nanofiltration In the second electrodialysis apparatus using the monovalent anion selective exchange membrane and the cation exchange diaphragm which permeate all the cations, the calcium ion and the additive are added to the removal of the sulfate ion in the primary electrodialysis process using the selective exchange membrane. for the manufacture of mineral modifiers CaSO the salt when hayeoteul adjust the mineral balance of a high hardness (500㎎ / ℓ or more) due to highly salty have not been removed and the problem is to drop or flavor, containing calcium in the ocean water ₄ by using the precipitate settled to the packaging and facility cost is high problem of precipitate process to the CaSO ₄ If you use the process has problems such that it takes a lower concentration of mineral modifiers packaging costs and transportation costs high.

Conventional salt production methods for deep sea water in the case of Japanese Patent Application Laid-Open No. 10-150947 do not require heating and produce concentrated brine at room temperature. As it grows, there is a problem that salt production is restricted according to the climate and weather conditions. The method of preparing salt by taking deep seabed rock water is also concentrated in room temperature in Japan Patent Publication No. 2004-52449. The method of precipitating the crystallized salt by heating also does not solve the above problem.

In the present invention, the Bomedo (° Be) of the Baume's hydrometer showing the specific gravity of the seawater is expressed as a numerical value of the scale when the Bomedo hydrometer is floated in the liquid to measure the specific gravity of the liquid, rather than the specific gravity of the water. There are heavy heavy bomedoes for heavy liquids and light bomedos for light liquids that are lighter than the specific gravity of water. Among them, pure liquids are pure water. Is 0 ° Be, 15% saline is 15 ° Be, and the division is divided into 15 equal parts. For the liquid solution, 10% saline is 0 ° Be, and pure water is 10 ° Be. In addition, the interval between them is divided into 15 equal parts, and since BOME (° Be) is approximated with salt concentration (wt%) in the case of sea water, it is widely used as a measure of concentration.

The relationship between the Bume (° Be) and the specific gravity (d) of the liquid is

For heavy media that has a specific gravity of liquid greater than that of water

d = 144.3 / (144.3- ° Be). … … … … … … … … … … … … … … … … … ③

In the case of an alarm field where the specific gravity of the liquid is lower than the specific gravity of the water

d = 144.3 / (134.3 + ° Be). … … … … … … … … … … … … … … … … … ④

The electrical conductivity measured by the electric conductivity indicating switch (ECIS) is an indicator of the degree of conduction of an aqueous solution by conducting electricity. The unit represents the salt concentration in water. The unit is the inverse of the electrical resistivity of the aqueous solution. Corresponding Siemens / meter, the relationship between the electrical conductivity (EC) and the total soluble salt (TSS) in water is given by the following equation (5).

TSS (ppm) = 640 X EC (mm / cm). … … … … … … … … … … … … … … … ⑤

The double salinity concentration (NaCl ppm) can be estimated simply by the following equation ⑥.

Salinity concentration (NaCl ppm) = 552 x EC (cc / cm) -200. … … … … … … … … … ⑥

The conductivity value is expressed in units of millimenss / meter, or microsiemens / centimeter, which is an international system of units, and ㎳ / m = 10 μs / cm (or 10 μmhos / cm).

The present invention is to provide a method for producing salt and water and drinking water while preparing a mineral regulator by injecting calcium agent and additives in the deep water of the sea to remove the salt and sulfate ions in order to solve the above problems There is a purpose.

In order to achieve the above object, the present invention is to remove the salt and sulfate ion by pretreatment step such as warming treatment, pretreatment filtration, small grouping of water molecules and mineral activation treatment, withdrawal of deep sea water at 200 m or less depth And concentration of mineral components, removal of salts and sulfate ions by electrodialysis and concentration of mineral components, preparing mineral regulators, preparing salt and brine from discharged brine, using demineralized water and mineral regulators It is characterized by consisting of steps to prepare a beverage.

The present invention relates to a method for producing salt and liver water and beverages while preparing mineral modifiers that can be used in food, feed and beverages by using minerals contained in deep sea water. Same as

I. Pretreatment stage

1. Intake and warming process

In the pretreatment process, the deep sea water of 200m or less in depth is collected and warmed so that the subsequent treatment can be smoothly processed.

In FIG. 1, the deep sea water is taken from the deep seabed of 200 m or less, and the intake method is to take the pipe down to 200 m or less from the ship's bottom, or install the pipe to the sea level 200 m or less, and then take it with a pump. Or, pipes are installed up to 200m below sea level, and the intake wells are installed below sea level to take water according to siphon principle.

The deep sea water collected in the sump is low in temperature and high in viscosity, resulting in low treatment efficiency. Therefore, it is heated to 20 ~ 30 ℃ by receiving heat from boiler (in summer, you can use the surface water temperature). It is sent to the electronic treatment water tank (電子 소 理 水槽; 1) of the small grouping treatment and mineral activation treatment process.

Even if the treatment efficiency is slightly reduced, if the small grouping and mineral activation treatment of water molecules are omitted in order to reduce the facility cost, the warmed treatment is sent to the pretreatment filtration process.

2. Small grouping and mineral activation process of water molecules

When the deep sea water heated to 20 ~ 30 ℃ is supplied to the electronic treatment tank 1, it is magnetized by high voltage constant voltage treatment, constant voltage conductive tube magnetizer (10) or permanent magnet. After treatment, small groups of water molecules are clustered, treated with microclustered water, and the surface tension and viscosity are lowered to activate minerals and then sent to a pretreatment filtration process.

In the high pressure constant voltage treatment and the constant voltage conductive tube magnetizer 10, a combination of the magnetization treatment and the small group of water molecules and the activation treatment of the mineral component are performed in the electronic treatment tank of the deep sea water heated to 20 to 30 ° C. (1), and the high voltage AC constant voltage is applied from the constant voltage generator 7 to the electrode 2 by applying a voltage of 3,000 to 5,000 Volt (field strength of 0.3 to 15 KV / m) and a current of 0.4 to 1.6 μA. When the electrostatic fields of + and-are alternately applied to water molecules for 4 to 10 hours alternately around (2), this causes the water molecules themselves to vibrate and rotate repeatedly, When the hydrogen bond is partially broken, it is sent to the intermediate treatment water storage tank (8), and is sent to the magnetizer supply pump (9) to the constant voltage conductive tube magnetizer (10) and wound into a coil (0.5) to 5 V wound on the conductive tube. When applying AC or DC low voltage in the range, magnetization process occurs. To enable a mineral component, and then, some nuclear magnetic resonance and electron transport to the treatment tank (1) (核磁氣共鳴; Nuclear magnetic resonance, NMR) half value width (半値幅) for ¹⁷ O-NMR of this 48~60㎐ It is treated with microclustered water in the range, and then sent to the small-sized water storage tank 11 and sent to the pretreatment filtration process by the small-sized water transfer pump 12.

The flow rate sent from the intermediate treatment water storage tank 8 to the magnetizer supply pump 9 to the constant voltage conductive tube magnetizer 10 and returned to the electronic treatment water tank 1 is 1 to 4 times the inflow water flow rate.

The small grouped water thus produced is treated with reduced water having a high alkaline oxidation frequency with a high energy Oxidation Reduction Potential (ORP) value in the range of +100 to -200 Hz.

The voltage applied to the electrode 2 of the electronic treatment tank 1 in the constant voltage generator 7 is adjusted in accordance with the values of pHI (7.4-7.8) and ORPI (+100 kPa or less) installed in the intermediate treatment water reservoir 8. do.

The material of the electrolytic treatment tank 1 is made of stainless steel, and the stainless steel electrode 2 filled with charcoal having high conductivity is inside. To the bottom of the insulator (3) of polyethylene (polyethylene), polyvinyl chloride (PVC), Styrofoam (Styrofoam) is selected and installed, the lower part of the insulator (3) is a conductor and corrosion-resistant material A steel sheet 4 is installed between the foundation concrete structures 5, and the stainless steel sheet 4 is grounded 6 to the ground.

The constant voltage conductive tube magnetizer 10 has an alternating current in the range of 0.5 to 5 V in a coil wound around a cylindrical tube of insulating material such as synthetic resin (PVC, PE, styrene resin, etc.), ebonite, FRP, and Bakelite. Alternatively, when a low voltage of direct current is applied, a magnetic field is formed inside the coil, and when water (fluid) is passed therein, the water is treated as a small group of water and the mineral component dissolved in the water Is activated.

Instead of the constant voltage conductive tube magnetizer 10, a permanent magnet magnetized in the range of 12,000 to 15,000 G (Gauss) may be provided.

When the capacity of the treated water is large, the electronic treatment tank 1 in which the electrode 2 network of stainless steel filled with charcoal is embedded is treated by installing multiple stages.

As in the present invention, when the group of the water molecules by the high-voltage constant voltage treatment and the magnetizer is small grouped and treated with the small group water, the surface tension and the viscosity of the water are reduced and the penetration force is reduced. As the filtration efficiency improves in the filtration process, various mineral components are activated by magnetization, and when ingested, minerals having excellent absorption rate are generated.

However, even if the treatment efficiency is slightly reduced, in order to reduce the facility cost, the small grouping of the water molecules and the mineral activation treatment may be omitted, and the warmed treatment may be sent to the pretreatment filtration process for treatment.

3. Pretreatment Filtration Process

The pretreatment filtration process removes suspended solids (SS) by filtration through sand filtration, micro filtration or ultra filtration alone or a combination of two or more processes. Next, it is sent to the first nanofiltration process.

In this case, if the beverage, salt, and brine are not prepared, the first nanofiltration process, the reverse osmosis filtration process, the second nanofiltration process, and the third nanofiltration process, which describe deep seawater subjected to pretreatment, will be omitted. It is sent to the mineral brine storage tank 13 of the process to prepare a mineral regulator.

At this time, the filtration pressure is determined in consideration of the pressure loss of the filter and the pressure loss of the pipe according to the operating conditions.In the case of sand filtration, the filtration speed is 6-10 m / hour, and the effective diameter of the filter sand Is 0.3 to 0.45 mm, the uniformity factor is 2.0 or less, and the thickness of a fibrous layer is 0.5 to 1.0 m.

At this time, if the turbidity of the deep ocean water taken is 2 mg / ℓ or less, it is not necessary to sand filtration.

Micro-filter and Ultra-filter are not limited to the type of filtration membrane, and the supply pressure of the pump is decided by considering the filtration speed and the pressure loss according to the vendor's specifications. do.

In microfiltration or ultrafiltration, filtration treats the water's fouling index (FI) in the range of 2-4.

The FI value is a numerical value representing the fine turbidity concentration in the target water and is expressed by the following equation.

FI = (1-T ₀ / T ₁₅ ) x 100/15... … … … … … … … … … … … … … … … … … … … ⑦

T ₀ is the time required for filtration of the first 500 ml of sample water when the sample water was filtered under pressure of 0.2 MPa using a 0.45 μm microfiltration membrane, and T ₁₅ was filtered for 15 minutes in the same state as T _0. It is time required for filtration of 500 ml of sample water after that.

II. Salt and Sulfate Ion Removal and Mineral Concentration by Membrane Filtration

Film salt by filtration and the sulfate ions removed as mineral concentrate is first nanofiltration (Nano- filtration) sulfate ions which cause clogging of the membrane in step (SO ₄ ^{2 -)} in the removal of the then fed to the first reverse osmosis step tuyeogwa The filtered demineralized water is sent to the beverage production process, the unfiltered and concentrated mineral brine is sent to the second nanofiltration process, and the filtered brine is sent to the salt manufacturing process, and the unfiltered mineral water is sent to the first reverse osmosis filtration process. Diluted with demineralized water and sent to the third nanofiltration process, the filtered brine is sent to the salt manufacturing process, the concentrated mineral water is sent to the first electrodialysis process.

The membrane modules of nanofiltration and reverse osmosis filtration are tubular, hollow fiber, spiral wound, flat plate and Any form such as a frame may be used, and the material of the film is not particularly limited.

As the material of the nanofiltration membrane, polyamide-based, polypiperazineamide-based, polyesteramide-based, or cross-linked water-soluble vinyl polymers can be used. Is an asymmetric membrane composed of a dense layer on one side of the membrane, which is composed of micropores gradually from a large pore toward the inside of the membrane or toward the membrane on one side, or a dense layer of such an asymmetric membrane. A composite membrane having a very thin separation functional layer formed of another material may be used. A piperazine polyamide composite membrane is preferable, but the material and structure of the membrane are not particularly limited in the present invention. .

1. First Nanofiltration Process

First nanofiltration in the process in a reverse osmosis filtration of the post-treatment scale (Scale) sulfate ion that causes the generation (SO ₄ ^{2 -)} as is the main purpose to remove, deep ocean water, removing the suspended solids in the water in the pre-filtering step Is sent to the nanofiltration process to discharge unfiltered sulfate-ion-containing water and to send the filtered desulfurized-ion mineral salt to the first reverse osmosis process.

Transmission sequence of the ion in the nanofiltration membrane, if the cation is ^{Ca 2 +> Mg 2 +>} Li +> Na +> K +> NH 4 + and, in the case of the anion is _{^{SO 4 2 - »HCO 3 ->}} F -> _{^{Cl -> Br -> NO 3}} -> and SiO _2, a sulfate ion (SO ₄ ^{2 -),} if the it is difficult to permeate than Mg ^{+ 2} and Ca ^{+ 2.}

In the first nanofiltration process, the supply pressure is 15 to 20 kg / cm 2, which is lower than the osmotic pressure of 25 kg / cm 2 of deep seawater with a salt concentration of 3.5 wt%. In the case of spiral, the membrane permeability is 0.7 to 1.4. When m 3 / m 2 · day, the membrane permeate amount becomes 70 to 80% of the inflow rate.

Example 1

The deep sea water as shown in Table 2 is warmed to 25 ° C., and then injected into the electronic treatment tank 1 of the step of small grouping of water molecules, and a high-pressure alternating voltage is applied from the constant voltage generator 7. A voltage of 3,500 Volt (electric strength 1.2 KV / m) and a current of 0.5 μA were applied to the electrode 2 for 5 hours, and then sent to the intermediate treatment water storage tank 8, followed by a constant voltage conductive tube to the magnetizer supply pump 9. The half-width of ¹⁷ O-NMR of nuclear magnetic resonance was 52㎐, which was sent to the firearm 10 and applied to the coil wound on the conductive tube by applying direct current of 0.6V range to magnetization. Sludge of model number SU-610, a cross-linked polyamide material manufactured by Toray Industries, Ltd., of Toray Co., Ltd. Membrane permeate by supplying pressure to the membrane at 20㎏ / ㎠G using nanofiltration membrane When the amount was 1.2㎥ / ㎡ · day, the permeate amount of the membrane became 80% of the inflow, and the analysis of the importance of unfiltered sulfate-ion-containing water and filtered desulfurized-ion-mine water is shown in Table 5 below. .

Table 5 Analysis of Significant Values of Unfiltered Sulfate-Ioned Water and Filtered Desulfurized-ion Mine Saline by Nanofiltration

 Item      Pre-treated deep sea water (raw water)         Filtrated Desulphate Ion Mineral Saline    Unfiltered sulfate-containing water      pH        7.80         7.24          7.82 Na ⁺ (mg / L)   10,800    9,650     15,400 Cl ^- (㎎ / ℓ)   22,370   17,300     42,650 Ca ^{2 +} (㎎ / ℓ)      456      338        928 Mg ^{2 +} (㎎ / ℓ)    1,300    1,060      2,260 K ⁺ (mg / L)      414      355        650 _{^{SO 4 2 - (㎎ / ℓ}} )    2,833      319     12,890  B (mg / L)        4.44        4.10          5.80

As shown in Table 5, nanofiltration of deep sea water resulted in almost no removal of boron compounds, 28.5% Na, 41% calcium (Ca) and 35% magnesium (Mg). However, more than 90% of sulfate ions were removed.

2. First reverse osmosis filtration process

In the first reverse osmosis filtration process, the desulfurization ion mineral saline with primary removal of sulfate ions in the first nanofiltration process is used for the purpose of concentrating low concentration mineral brine and demineralizing brine. When supplied to the filtration membrane, the operating pressure is supplied to the filtration membrane at 50 to 70 kg / cm 2, and the filtered demineralized water is sent to the beverage production process, and the concentrated mineral brine is sent to the second nanofiltration process.

When the filtration membrane of the first reverse osmosis filtration process is a spiral filtration membrane, when the operating pressure is 55 to 56 kg / ㎠ and the membrane permeate is 0.5 to 0.8 ㎥ / ㎡ The mineral brine is concentrated while 40-60% of the influent is filtered.

Example 2

Desulfurized ion mineral saline, filtered filtrate in the first nanofiltration of Example 1, was cross-linked polyamide-based composite membrane in a high pressure reverse osmosis membrane of Toray Corporation of Japan. The membrane permeate was 52% of the influent when the membrane permeate was 0.72㎥ / ㎡ · day using a spiral reverse osmosis membrane of model No. SU-810. At this time, the main component analysis of filtered demineralized water and concentrated non-filtered concentrated brine are shown in Table 6 below.

Table 6 Analysis of Principal Components of Demineralized Water, Filtrate, and Unconcentrated Concentrated Mineral Saline in the First Reverse Osmosis

 Item  Influent Water (Desulfurized Ion Mineral Salt)   Filtered demineralized water  Concentrated brine      pH        7.24         7.20       7.28 Na ⁺ (mg / L)    9,650       38.7    20,063 Cl ^- (㎎ / ℓ)   17,300       71.6    35,478 Ca ^{2 +} (㎎ / ℓ)      338        0.6       703 Mg ^{2 +} (㎎ / ℓ)    1,060        1.9     2,206 K ⁺ (mg / L)      355        1.7       737 _{^{SO 4 2 - (㎎ / ℓ}} )      319        3.7     1,584  B (mg / L)        4.1        1.8         6.6

As shown in Table 6, most of the substances were removed highly by 99% or more in deep osmosis, but the boron compound was 1.8 mg / l and the removal rate was very low, below 80%. Since it was doubled, it could not be used for beverage production by itself.

When the small grouping process of the water molecule group was omitted in the pretreatment step, the membrane permeability fell to 0.68㎥ / ㎡ · day when the operating pressure was supplied to the membrane at the same pressure at 60㎏ / ㎠G. It was reduced to 46% of the inflow.

3. Second Nano Filtration Process

In the second nanofiltration process, the mineral salt concentrated in the first reverse osmosis process is separated into salts having monovalent ions, and the mineral components (polyvalent ions) are concentrated.

The second nanofiltration is filtered while adjusting the pressure so that 75-85% of the concentrated mineral brine is pressurized at 50 to 60 kg / cm2 in the first reverse osmosis filtration to the separation membrane of the second nanofiltration process. The brine is sent to the salt manufacturing process, and the mineral brine with a relatively concentrated mineral content is sent to the third nanofiltration process.

In the second nanofiltration process, the operating pressure is adjusted so that the flow rate of the brine to be filtered is in the range of 75 to 85% of the inflow flow rate. The pressure varies depending on the filtration membrane, but is slightly higher than the osmotic pressure of the deep seawater 25 kg / cm 2. It becomes -30 kg / cm <2>.

At this time, in the case of the spiral filtration membrane, the membrane permeate amount is in the range of 1.5 to 2.0 m 3 / m 2 · day.

Example 3

In the first reverse osmosis filtration process of Example 2, the flow rate of the brine filtered by installing the SU-210 nanofiltration membrane of Toray Japan Co., Ltd. was installed on the concentrated mineral brine side where the pressure was discharged at 60 kg / cm 2 G. As a result of concentrating the minerals while adjusting the discharge pressure to be 80% of the flow rate (the pressure was 27 kg / cm 2 G), the analysis values of the important components of the brine and the concentrated mineral water are shown in Table 7 below. In this case, the membrane permeation amount was 1.25 m 3 / m 2 · day.

Table 7 Analysis of Significant Values of Brine and Filtrate Concentrated Mineral Water in the Second Nanofiltration Process

  Item Concentrated mineral brine discharged from the first reverse osmosis filtration process Brine filtered in the second nanofiltration process Mineral water concentrated without filtration in the second nanofiltration process      pH        7.28         7.24         7.30 Na ⁺ (mg / L)   20,063    18,423    26,623 Cl ^- (㎎ / ℓ)   35,478    30,600    54,990 Ca ^{2 +} (㎎ / ℓ)      703       264     2,459 Mg ^{2 +} (㎎ / ℓ)    2,206       690     8,270 K ⁺ (mg / L)      737       654     1,069 _{^{SO 4 2 - (㎎ / ℓ}} )    1,584       376     6,416

As shown in Table 7, in the second nanofiltration process, more than 73.5% of monovalent ions, Na ⁺ , 71% of K ⁺ , and 69% of Cl ⁻ were permeated through the membrane, while calcium ions (divalent ions) ( Ca ^{2 +)} was 30%, a magnesium (Mg ^{2 +)} was 25%, and sulfate ion (SO ₄ ^{2 -)} was 19% of the transmission, without the filtrate and a concentrated mineral side, 2 to the concentration of the ions relative While highly concentrated, monovalent ions were also concentrated at the same time.

4. Third Nano Filtration Process

In the third nanofiltration process, the mineral brine concentrated in the second nanofiltration process is diluted with demineralized water discharged from the first reverse osmosis filtration process, and then nanofiltration is performed to efficiently concentrate the mineral component of divalent or more ions. .

Concentration of mineral salts shared by mineral constituents of monovalent ions and divalent or higher polyvalent ions by nanofiltration results in better separation of salts due to better permeability of monovalent salts in the filtered water than mineral constituents of polyvalent ions. The non-filtered side concentrates relatively many minerals that are polyvalent ions, but also salts that are monovalent ions.

When the mineral brine shared by the monovalent ions and the polyvalent ions is repeatedly concentrated by nanofiltration, comparing the case of Example 1 and Example 2 described above, when the concentration is repeated, the polyvalent ions are concentrated more than the monovalent ions. However, salts (NaCl), which are monovalent ions, are also concentrated, and when the concentration of salts, which are monovalent ions, is high, there is a problem that the concentration efficiency of polyvalent ions is lowered.

In addition, when the concentration of salts of monovalent ions in mineral salts increases, the operating pressure must be increased to improve the separation efficiency.However, nanofiltration simply changes the pressure conditions because it is impossible to operate the upper operating pressure above 30㎏ / ㎠. It is not possible to efficiently concentrate minerals alone.

Thus, in the third nanofiltration process, 1 to 2 times the demineralized water of the first reverse osmosis process is diluted with mineral brine concentrated in the second nanofiltration process, and then the operating pressure is supplied to the filtration membrane at 20 to 30 kg / ㎠. The brine, which is filtered water, is sent to the salt production process, and the concentrated mineral brine is sent to the mineral brine storage tank 13 of the first electrodialysis process.

If the dilution ratio of the demineralized water is more than 2 times to improve the concentration efficiency of mineral components, the concentration of salt in the filtered water is low, so the concentration cost is high in the salt manufacturing process, and there is no economical effect. This is also an economic problem, it is preferable to use a dilution factor of 2 or less.

In addition, if the concentration efficiency of salts and minerals decreases slightly, in order to reduce the facility investment cost, the third nanofiltration process is omitted, and the mineral salt storage tank of the first electrodialysis process is replaced with the mineral brine concentrated in the second nanofiltration process (13 Send to).

Example 4

SU of Japan Toray Co., Ltd. was diluted by mixing and diluting the demineralized water discharged from the first reverse osmosis filtration process with the same ratio (1: 1 ratio) to the mineral brine concentrated in the second nanofiltration process of Example 3. When the nanofiltration process using the -210 filter membrane was supplied to the filter membrane at a pressure of 28㎏ / ㎠G, the analysis of the important components of the filtered water and the unconcentrated mineral brine was as shown in Table 8.

At this time, the membrane permeated water was 1.27m 3 / m 2 · day, the flow rate of the filtered water was 84% of the inflow flow rate, and the flow rate of the concentrated water was 16%.

Table 8 Analysis of Significant Values of Brine and Filtrate Concentrated Mineral Water in the Third Nanofiltration Process

   Item Mineral saline mixed with mineral salt concentrated in the second nanofiltration process and demineralized water discharged in the first reverse osmosis filtration at a ratio of 1: 1. Brine filtered in the third nanofiltration process Mineral water concentrated without filtration in the third nanofiltration process      pH                7.26         7.24        7.30 Na ⁺ (mg / L)           13,330    12,700   16,638 Cl ^- (㎎ / ℓ)           27,530    24,910   47,183 Ca ^{2 +} (㎎ / ℓ)            1,230       337    5,920 Mg ^{2 +} (㎎ / ℓ)            4,136       886   21,200 K ⁺ (mg / L)              535       497      735 _{^{SO 4 2 - (㎎ / ℓ}} )            3,210       460   17,650

As shown in Table 8, in the third nanofiltration process, more than 80% of monovalent ions such as Na ⁺ , 78% of K ⁺ , and 76% of Cl ⁻ penetrated the membrane, whereas calcium ions of divalent ions ( Ca ^{2 +)} was 23%, a magnesium (Mg ^{2 +)} and 18% sulfuric acid ion (SO ₄ ^{2 -)} is a mineral side it concentrate not filtered, while 12% of the transmission 2 is carried out the concentration of the ion example 2 compared to the Ca ^{2 +} was 2.4 times, Mg ^{+ 2} concentration has been 2.56 times, while the monovalent ions Na ⁺ was reduced to 1.6 times.

As described above, in the present embodiment, when monovalent ions and polyvalent ions coexist, separation by nanofiltration increases the concentration of monovalent ions and dilutes with dilute water to concentrate the separation to improve the separation efficiency. It became.

III. Salt and Sulfate Ion Removal and Mineral Concentration by Electrodialysis

Treatment of mineral brine by electrodialysis concentrates the concentrated brine discharged from the first nanofiltration process, the first reverse osmosis process, and the second and third nanofiltration processes while removing salt and sulfate ions to a higher degree. The purpose is to prepare purified mineral water.

In the case of preparing mineral modifiers without preparing the water and salt from deep sea water, the first nanofiltration process, the first reverse osmosis process, and the second and third nanofiltration processes are omitted, and the filtered water in the pretreatment process Deep water is supplied to the mineral brine storage tank 13 of the first electrodialysis process.

1. First electrodialysis process

The cation exchange diaphragm 21 of the first electrodialysis process includes a monovalent cation selective exchange diaphragm 21 that selectively transmits only monovalent cations and an anion exchange diaphragm 20 that selectively transmits monovalent anions. An object of the present invention is to lower the concentration of salt (NaCl) contained in the mineral saline by the first electrodialysis apparatus 15 in which multiple stages are alternately provided between the anode 16 and the cathode 17.

The first electrodialysis apparatus (15) is applied with a direct current from a rectifier, and the ionic solute penetrates the membrane by means of electrophoresis as a driving force by electrophoresis. The monovalent cation selective exchange diaphragm 21 selectively transmits only the monovalent cation having a fixed negative charge, and the monovalent anion selective exchange diaphragm 20 has a fixed static charge. Separating salts of monovalent ions contained in mineral water from mineral components of polyvalent ions using a diaphragm selectively penetrating only a monovalent anion having

When the concentrated mineral brine discharged from the second nanofiltration process and the third nanofiltration process is supplied to the mineral brine storage tank 13, the monovalent cation selective exchange diaphragm 21 and the monovalent anion are supplied by the mineral brine transfer pump 14. The selective exchange diaphragm 20 is supplied to the desalting chamber 24 of the first electrodialysis apparatus 15 in which the multistage is alternately installed between the anode 16 and the cathode 17 to supply minerals. While returning to the brine storage tank 13, the brine of the first circulation brine storage tank 28 is supplied to the salt concentration chamber 25 by the first brine circulation pump 29 to circulate to the first circulation brine storage tank 28 When direct current is applied from the rectifier, the cations contained in the mineral saline in the desalting chamber 24 are caused by the electrical attraction to the monovalent cation (Na ⁺ , K ^+, etc.) on the cathode 17 side. Selective permeation of (21) is transferred to the salt concentration chamber 25, the anion is selected from the monovalent anion of the positive electrode 16 Electrical of: (Electric conductivity indicating switch ECIS) (such as Cl ^{- -,} Br) only is selectively permeable to go to the salt concentration chamber 25 to the electrical conductivity indicating controller of the mineral salt water line a ring diaphragm 20, a monovalent anion When the conductivity is in the range of 6 to 15 ㎳ / cm, the solenoid valve is operated to send to the mineral water reservoir 30, and the specific gravity of the first circulation brine reservoir 28 is in the range of 12 to 18 ° Be. Concentrated brine is sent to the brine reservoir 46 of the salt manufacturing process by operating a solenoid valve (ⓢ) with a Baume indicating hydrometer (BIS).

When the water level of the first circulation brine reservoir 28 drops, the solenoid valve (ⓢ) is operated by a level switch (LS) installed in the first circulation brine reservoir 28 using demineralized water or deep sea water of the drinking water manufacturing process as water. Supply.

In order for the first electrodialysis apparatus 15 to increase the processing performance, it is preferable to increase the current density as much as possible within the range below the limit current density, but the limit current density is proportional to the salt concentration. Since the thickness of the diffusion layer is constant, since the thickness of the diffusion layer is constant, it depends on the concentration of salt in the mineral water to be drained and the concentration of brine. In the present invention, the monovalent cation selective exchange diaphragm 21 And a monovalent anion selective exchange diaphragm 20 in the first electrodialysis apparatus 15 formed of the desalination chamber 24 and the salt concentration chamber 25 which are alternately arranged between the anode 16 and the cathode 17. The concentrated mineral brine discharged from the two-nanofiltration process or the third nano-filtration process is sent to the desalination chamber 24 by the mineral brine transfer pump 14, and after the desalination treatment, a part is circulated to the mineral brine storage tank 13, The brine of the circulation brine reservoir 28 is the first brine circulation pump The salt concentration chamber 25 is sent to the salt concentration chamber 25 and circulated to the first circulation salt water storage tank 28 to improve desalination and salt concentration efficiency while preventing scale components from being generated in the salt concentration chamber 25. Supplying a large amount of brine to the water supply can prevent scale trouble, and supply salt water having a high salt concentration to the salt concentration chamber 25, thereby reducing the liquid resistance of the current. Since the current density can be increased, the processing performance of the first electrodialysis apparatus 15 can be improved.

In the first electrodialysis apparatus 15, the limit current density is increased to increase the amount of energization, so that the flow rate supplied to the desalination chamber 24 in order to improve the electrodialysis efficiency and suppress scale troubles is determined by the membrane surface velocity ( The demineralized mineral water is returned to the mineral brine storage tank 13 so that the flatness is within the range of 5 to 20 cm / sec. The flow rate of the brine supplied to the salt concentration chamber 25 is 2 to the membrane surface velocity. The brine is returned to the first circulation brine reservoir 28 so that the 5 cm / sec range is maintained.

In the case of not producing beverages or salts, the concentrated mineral salts discharged from the second and third nanofiltration processes are not supplied. It supplies to (13) and processes it similarly to the above-mentioned content.

The monovalent cation selective exchange diaphragm 21 used in the present invention is an exchange membrane that selectively permeates only a monovalent cation while suppressing divalent or more multivalent cation permeation, and is a polystyrene-divinylbenzene. Side chains and polyethyleneimine in a load-carrying film that holds a negative charge R-SO ₃ ^- in the main chain of the Or a graft polymer such as polyvinylpyridine or a graft polymer whose main chain is polystyrene or a side chain of polystyrene pyridine. As long as the main chain has the same molecular structure as the main chain or the side chain of the cation exchange diaphragm, it can be used without limitation. Preferably, polyethylene, polypropyl (polypropylene), polyvinyl chloride (Polyvinylchlorde), polystyrene (polystyrene) or the like negatively charged R-SO ₃ ^- create a fixed monovalent cations in the main chain or the side chain (側鎖) having a polymer molecular structure consisting of a cation exchange membrane permeability Cation selective exchange diaphragms such as polyvinylpyridine, polyvinylamine or polyethyleneimine membranes having a molecular structure of (透過 能) can be used, and in particular, polystyrene-divinylbenzene-based polystyrene Graft-ethylene imine may be most preferably used.

The monovalent anion selective exchange diaphragm 20 is a membrane capable of selectively exchanging only monovalent anions, as opposed to the monovalent cation selective exchange diaphragm 21. The surface of the membrane is modified to selectively permeate monovalent anions to the surface of the positively charged membrane into which a cation is introduced by immobilizing tertiary amine or ammonium groups on the membrane. In the membrane treated, the ion exchange groups are cross-linked by aliphatic hydrocarbons, and a thin layer of a polymer material having a cation exchange group is formed on the surface of the membrane. As anion exchange diaphragm, it is preferable to perform crosslinking and quaternization at the same time of crosslinking with aliphatic hydrocarbon to the monomer introduced into the exchanger, and a polymer material having a cation exchange group as a polymer material having a cation exchange group. Molecular weights such as insoluble polymers such as sulphates and linear polymer electrolytes or cation exchange groups, specifically, sulfonates such as Ligninsulfonate and phosphate ester salts such as higher alcohol phosphate esters. Polymer electrolyte having 500 or more cation exchange groups, monomer having carboxylic acid group (-COOH) or sulfonic acid group (-SO ₃ H) such as methacrylic acid, styrene sulfonic acid A membrane that selectively exchanges only monovalent anions with a linear polymer electrolyte containing a large number of units, an insoluble polymer having a cation exchange group such as a condensation of phenols and aldehydes including a cation exchange group, and the like. do.

The anode 16 of the anode chamber 18 of the first electrodialysis apparatus 15 is made of TiO ₂ -RuO on a titanium plate having a high corrosion resistance and high chlorine and oxygen generation overvoltage. ₂ is injected into the solution passing through the cathode chamber 19 by using a DSA (Dimensionally stable anode) electrode or a platinum plated electrode to suppress the generation of chlorine and oxygen on the surface of the anode 16, the cathode (17) uses Ranney nickel or stainless steel sheet with high hydrogen generation overvoltage, and the cation exchange diaphragm closest to the cathode chamber 19 is a hydrogen ion impermeable membrane. It is preferable to reduce the amount of hydrogen ions generated on the surface of the negative electrode 17 by using a thin film or monovalent anion selective exchange diaphragm 20 to improve power efficiency and reduce odor.

In case the scale is attached in the salt concentration chamber 25 and the treatment efficiency is reduced, a polarity switching device is installed in the rectifier to switch the power of the positive electrode 16 and the negative electrode 17 to be attached. Allow the scale to detach.

The electrolyte solution of the electrode chamber is supplied to the cathode chamber 19 to supply the electrolyte solution discharged to the cathode chamber 18, and the electrolyte solution (cathode chamber solution) supplied to the cathode chamber 19 is seawater (deep sea water). 3-10 wt% Na ₂ SO ₄ Using an aqueous solution can suppress corrosion of the electrode and generation of chlorine (Cl ₂ ) gas at the anode 16.

Example 5

The cation exchange diaphragm having an effective conduction area of 236 mm (length) x 220 mm (width) of 0.2 mm has a monovalent cation selective exchange diaphragm 21 which selectively transmits only monovalent cations. (Registered trademark) K-102, manufactured by Japan Chemical Co., Ltd.) and Anion Exchange Diaphragm are monovalent anion selective exchange membranes (20; Aciplex A-102, manufactured by Japan Chemical Co., Ltd.) that selectively permeate only monovalent anions, respectively. First electrodialysis, in which 50 sheets were alternately provided with multi-stage (50-stage) between the anode 16, which is a DSA electrode coated with RuO ₂ -TiO ₂ , and the stainless steel electrode, which was coated with 50 sheets, as shown in FIG. Into the desalination chamber 24 of the apparatus 15, a 50 L mineral brine storage tank 13 was supplied with a concentrated brine of 26 ° C., which was not filtered in the third nanofiltration process of Example 4, and then, diaphragm type. Desalting so that the linear velocity is 10 cm / sec with the mineral salt water transfer pump 14, which is a fixed-quantity pump. Supplied to (24) and circulated to the mineral brine storage tank (13), and the brine from the 20 l of the first circulating brine storage tank (28) with a first brine circulation pump (14), which is a diaphragm type metering pump, has a linear velocity of 3 cm / It supplied to the salt concentration chamber 25 for the first time, and circulated to the 1st circulating brine storage tank 28, DC electric current was applied from the rectifier with a current density of 3-4 A / dm <^2> (at this time, the applied voltage was 55-60V). ) When the electroconductive value of ECIS of mineral salt circulation line is desalted to 10-12∼ / ㎝, the analysis value of demineralized mineral water is shown in Table 9.

At this time, the specific gravity of the brine in the first circulating brine storage tank was adjusted by 12 ° Be, the cathode chamber solution is discharged to the upper portion by supplying 5wt% Na ₂ SO ₄ aqueous solution to the lower portion of the cathode chamber 19 at 50 kW / min Feed into the bottom of the chamber (18).

Table 9 Analysis of Significant Values of Demineralized Mineral Water Emitted from the First Electrodialysis Process

  Item Mineral water (influent water) concentrated without filtration in the third nanofiltration process Demineralized mineral water discharged from the first electrodialysis process      pH              7.30                  7.28 Na ⁺ (mg / L)         16,638              4,992 Ca ^{2 +} (㎎ / ℓ)          5,920              5,800 Mg ^{2 +} (㎎ / ℓ)         21,200             20,770 K ⁺ (mg / L)            735                221 _{^{SO 4 2 - (㎎ / ℓ}} )         17,650             17,480

2. Second Electrodialysis Process

In the second electrodialysis step, the purpose is to remove sulfate ions and to concentrate mineral components.

The second electrodialysis apparatus 32 includes a cation exchange diaphragm 22 that transmits all cations and a cation exchange diaphragm 22 that transmits all cations. ), An electrodialysis apparatus in which multiple stages are alternately installed between the cathode and the cathode 17 is applied.

In the first electrodialysis process, when the mineral water from which salts are removed from the mineral brine is supplied to the mineral water storage tank 30, the cation exchange diaphragm 22 and the monovalent ions that can penetrate all cations by the mineral water transfer pump 31 are provided. The positive electrode 16 and the negative electrode from the rectifier in the second electrodialysis apparatus 32 in which the monovalent anion selective exchange diaphragm 20 that selectively permeates only alternately is provided between the positive electrode 16 and the negative electrode 17. Supplying a direct current to the 17 to the demineralization chamber 26 and circulated to the mineral water storage tank 30, the concentrated mineral water in the concentrated mineral circulation water storage tank 33 to the concentrated mineral water circulation pump (34) When supplied to the mineral concentration chamber 27 and circulated to the concentrated mineral circulating water storage tank 33, all the cations (mineral components) of the demineralized chamber 26 passes through the cation exchange diaphragm 22 on the negative electrode 17 side. will be taken to mineral concentrate chamber 27, anions are monovalent ions (Cl ^-, Br ^-, etc. ) Is passed through the monovalent anion selective exchange diaphragm 20 on the anode side 16 to the mineral concentration chamber 27 so that the electrical conductivity of the ECIS of the mineral water line is 400 to 1,000 mW /. If the cm range is sent to the beverage production process by operating the solenoid valve (ⓢ), if the concentration of bomedo of concentrated mineral water in the concentrated mineral circulating water storage tank 33 is concentrated in the 26 ~ 33 ° Be range of the bomedo weight indicator controller ( BIS) to operate the solenoid valve (ⓢ) is sent to the concentrated mineral water storage tank 35 of the third electrodialysis process.

In the first electrodialysis process, when the desalination treatment is carried out by supplying the concentrated mineral brine in the second nanofiltration process and the third nanofiltration process, since the concentration is high, the electrical conductivity is good, and thus the sufficient desalination treatment is performed in the first electrodialysis process. It is sent to the concentrated mineral water storage tank 35 of the third electrodialysis process, so the desalination process of the third electrodialysis process is omitted because it is no longer needed to be desalted, and is sent to the additive mixer 40 of the additive mixing process.

The cation exchange diaphragm 22 used in the second electrodialysis apparatus 32 is negatively charged to the main chain of polystyrene-divinylbenzene-based R-SO _3. ^- a fixed and a load conductor film (負荷電膜) to the film surface 1 is attached to the cationic polyelectrolyte such as polyethyleneimine (polyethyleneimine) a foil layer (薄層狀) (Coating) in order to selectively transmit only the cation in which or Using a cation exchange diaphragm that is not bonded and modified, a membrane capable of transmitting all cations is used.

The anion exchange diaphragm uses the same monovalent anion selective exchange diaphragm 20 as the anion exchange diaphragm of the first electrodialysis apparatus 15.

In the second electrodialysis apparatus 32, the anode 17 and the cathode 17 are the same as those of the first electrodialysis apparatus 15.

Example 6

The second electrodialysis apparatus 31 is a cation exchange diaphragm 22 capable of permeating all the cations in the first electrodialysis apparatus 15 of Example 5 without modification of the surface of the cation exchange diaphragm. The experiment was carried out using an electrodialysis apparatus of the same specifications except for using.

The cation exchange diaphragm having an effective conduction area of 236 mm (length) x 220 mm (width) of 0.2 mm has a cation exchange diaphragm (22; Aciplex® K-101, Japan). Products) and 50 anion exchange membranes (20; Aciplex A-102, manufactured by Nippon Chemical Co., Ltd., Japan) which selectively transmits only monovalent anions. RuO ₂ -TiO ₂ 50 L of the demineralized chamber 26 of the second electrodialysis apparatus 32 in which multiple stages (50 stages) were alternately installed as shown in FIG. 6 between the anode 16 coated DSA and the cathode 17 of stainless steel. After supplying the mineral water at 26 ° C. desalted in Example 5 to the mineral water storage tank 30 of the present invention, the linear velocity was 10 cm when the mineral water transfer pump 31 was a diaphragm-type metering pump. To the demineralization chamber (26) to circulate to the mineral water storage tank (30), and to store 20 liter of concentrated mineral circulation water When the concentrated mineral water of (33) is blocked by the concentrated mineral water circulation pump (34), which is a diaphragm type metering pump, it is supplied to the mineral concentration chamber (27) such that the linear velocity is 3 cm / sec and circulated to the concentrated mineral circulation water storage tank (33). DC current was applied from the rectifier at a current density of 3 to 5 A / dm2 (at this time, the applied voltage was 45 to 52 V). The conductivity value of the conductivity indicator controller (ECIS) in the mineral water circulation line was 600 to 650 kW. Analysis of the importance of mineral water concentrated in the concentration of 31 ~ 32 ° Be of the concentration of blemedo in the concentrated mineral circulating water storage tank (32) while discharged the sulfate-containing water in the range / cm range.

In this case, the cathode chamber solution was supplied with a 5 wt% Na ₂ SO ₄ aqueous solution at 50 kV / min to the lower portion of the cathode chamber 19 to be discharged to the upper portion of the cathode chamber 18.

Table 10 Analysis of Significant Values of Concentrated Mineral Water Concentrated in Second Electrodialysis Process

 Item Demineralized mineral water discharged from the first electrodialysis process Concentrated mineral water in the second electrodialysis process      pH          7.28             7.26 Na ⁺ (mg / L)      4,992        24,960 Ca ^{2 +} (㎎ / ℓ)      5,800        29,025 Mg ^{2 +} (㎎ / ℓ)     20,770       103,850 K ⁺ (mg / L)        221         1,103 _{^{SO 4 2 - (㎎ / ℓ}} )     17,480           320

3. The third electrodialysis process

In the third electrodialysis process, as in the first electrodialysis process, the monovalent cation selective exchange diaphragm 21 and the anion exchange diaphragm selectively penetrate only monovalent anions as the cation exchange diaphragm selectively permeate monovalent anions. Concentration of salinity (NaCl) in the same electrodialysis apparatus as the first electrodialysis apparatus 15 in which the anion selective exchange diaphragm 20 was alternately provided with a plurality of stages between the anode 16 and the cathode 17. The purpose is to remove them highly.

When mineral salts with low concentration, such as deep sea water pre-filtered, are introduced into the first electrodialysis process, desalination treatment results in lower electrical conductivity and lower desalination efficiency. As the temperature increases and the temperature rises, the concentration of mineral salts with low concentration, such as deep sea water pre-filtered in the first electrodialysis process, is limited to desalination. Only after desalting can the salt be treated highly in mineral brine.

When the concentrated mineral water concentrated in the second electrodialysis apparatus 32 flows into the concentrated mineral water storage tank 35, it is sent to the desalination chamber 24 of the third electrodialysis apparatus 37 by the concentrated mineral water transfer pump 36. While circulating through the concentrated mineral water storage tank 35, the brine of the second circulation brine storage tank 38 is discharged into the salt concentration chamber 25 by the second brine circulation pump 39 and circulated to the second circulation brine storage tank 38. While applying a direct current from the rectifier to the anode 16 and the cathode 17, the monovalent cations (Na ⁺ , K ⁺ ) in the desalting chamber 24 is the monovalent cation selective exchange diaphragm 21 on the cathode 17 side. the transmission to be taken to salt concentration chamber (25), a monovalent anion (Cl ^-, Br ^-) is a positive electrode 16 side of monovalent salt concentration chamber 25 then passes through an anion selected exchange membrane 20 of the When the salt contained in the mineral water of the desalting chamber 24 is removed and the salt is removed in the electric conductivity of the electric conductivity indicator controller (ECIS) in the range of 0.4 to 3 kW / cm, the sole Concentrated mineral water from which salt and sulfate ions have been removed by operating the nose valve (ⓢ) is sent to the additive mixer 40, and the brine of the second circulation brine storage tank 38 is the BME specific gravity of the BOME. The solenoid valve (ⓢ) is actuated and sent to the salt manufacturing process while adjusting to 12 to 18 ° Be.

The monovalent cation selective exchange diaphragm 21, the monovalent anion selective exchange diaphragm 20, the anode 16, the cathode 17 and all other structures used in the third electrodialysis apparatus 37 are the first electrodialysis apparatus. Same as (15).

When the desalination treatment is carried out by receiving concentrated mineral brine in the 2nd nanofiltration process and the 3rd nanofiltration process in the first electrodialysis process, the conductivity is good because the salt concentration is high. Therefore, even if the desalination efficiency is slightly reduced, in order to reduce the facility cost, the third electrodialysis process is omitted, and the concentrated mineral water concentrated in the second electrodialysis process is sent to the additive mixer 40 of the additive mixing process.

In addition, when used as a mineral modifier in the foliar fertilizer or compost manufacturing process in crops, the additive mixing process described later is omitted since the addition of calcium and additives does not require the adjustment of mineral balance and formation of complex compounds. The concentrated mineral water from which the salt and the sulfate ion are removed in the third electrodialysis process is used as a crude mineral regulator.

Example 7

The third electrodialysis apparatus 37 was experimented with the same electrodialysis apparatus with all the specification conditions of the first electrodialysis apparatus 15 of Example 5.

The cation exchange diaphragm having an effective conduction area of 236 mm (length) x 220 mm (width) of 0.2 mm has a monovalent cation selective exchange diaphragm (21; Aciplex K-102, Japan) that selectively permeates only monovalent cations. Manufactured by Kogyo Co., Ltd.) and the anion exchange diaphragm were 50 sheets of monovalent anion selective exchange diaphragm (20; Aciplex A-102, manufactured by Nippon Chemical Co., Ltd., Japan) which selectively permeate only monovalent anions. The DSA electrode coated with RuO ₂ -TiO ₂ on the plate and the cathode 17 are desalination chambers of the third electrodialysis apparatus 37 in which multiple stages (50 stages) are alternately installed as shown in FIG. 24) was supplied to the concentrated mineral water storage tank 35 of 50 l concentrated mineral water of 26 ℃ concentrated in the second electrodialysis process of Example 6, and then to the concentrated mineral water transfer pump 36, a diaphragm type metering pump It is supplied to the desalination chamber 24 so that the membrane surface velocity becomes 10 cm / sec and circulated to the concentrated mineral water storage tank 35. , 20 L of the second circulating brine reservoir 38 is supplied to the salt concentration chamber 25 so that the linear velocity is 3 cm / sec when the brine is blocked by the second brine circulation pump 39 which is a diaphragm type metering pump. While circulating through the brine reservoir 38, direct current is applied from the rectifier at a current density of 4 to 5 A / dm ² (at which the applied voltage is 38 to 42 V). The conductivity indicator controller (ECIS) of the concentrated mineral water circulation line When the decontamination treatment was carried out at 5 ~ 6㎳ / ㎝, the analysis value of the demineralized concentrated mineral water is shown in Table 10.

At this time, the specific gravity of the brine in the second circulating brine storage tank 38 was adjusted by 12 ° Be, the cathode chamber solution is supplied 5wt% of Na ₂ SO ₄ aqueous solution to the bottom of the cathode chamber 19 at 50 kW / min discharged to the top What was supplied to the lower part of the anode chamber 18.

Table 10 Analysis of Significant Values of Demineralized Mineral Water Emitted from the Third Electrodialysis Process

  Item Concentrated mineral water in the second electrodialysis process Concentrated mineral water with no salt and sulfate ions removed in the third electrodialysis process      pH              7.26               7.25 Na ⁺ (mg / L)         24,960             482 Ca ^{2 +} (㎎ / ℓ)         29,025          28,965 Mg ^{2 +} (㎎ / ℓ)        103,850         103,032 K ⁺ (mg / L)          1,103              22 _{^{SO 4 2 - (㎎ / ℓ}} )            320             284

※ Note: The total disolved solid (TDS) of concentrated mineral water without salt and sulfate ions was 583,230 mg / l.

Ⅳ, step of preparing a mineral regulator

When the concentrated mineral water from which salt and sulfate ions have been removed is supplied to the additive mixer 40, the calcium agent and the additive are supplied to supply a heat source from a boiler, and then heated to a temperature indicating controller (TIC) at 40 to 80 ° C. While stirring with a stirrer (41) to dissolve the calcium agent and additives to react with the mineral component, and then sent to the cooler (45) to cool to room temperature to prepare a liquid mineral regulator, in the case of commercializing the solid mineral regulator in the evaporation process The water is evaporated to prepare a solid mineral regulator.

When the concentrated mineral water from which salt and sulfate ions have been removed is supplied to the additive mixer 40, the calcium agent is supplied in a Ca / Mg weight ratio of 2 to 6 to adjust the mineral balance.

The type of calcium agent to be injected is made of materials containing a lot of calcium, such as bones of animals such as bovine bone, eggshells, shells of oyster shells, and coral reefs. Calcium chloride (CaCl ₂ ), Calcium Lactate, Calcium Lactate, Calcium Carbonate (CaCO ₃ ), Citric Acid, prepared by dissolving powders calcined at ~ 1,200 ° C and dissolved in 3-10 wt% aqueous HCl solution. Calcium Citrate, Calcium Gluconate, Calcium Glycerophosphate, Calcium Phosphate, Calcium Lignosulfonate, Calcium sorbate, Calcium silicate ), Calcium acetate (Calcium Acetate), calcium carboxymethyl cellulose (Calcium Carboxymethylcellulose), calcium alginate (Calcium Alginate), or a mixture of two or more kinds thereof is used.

Additives should be free from side effects, such as inhibiting aging and denaturation of foods, inhibiting mating and malting, inhibiting decomposition of lipids, suppressing odor, and improving absorption efficiency of minerals. When used in beverages, non-reducing disaccharides, which have the effect of not deteriorating or denatured when they are preserved for a long time while masking the taste of metal due to mineral ingredients, improve taste. Sucrose, Trehalose, Nonreducing Sugar Alcohol Maltitol, Xylitol, Sobitol, Erythitol, Lactitol, One or two or more kinds of mannitol are supplied at a ratio of 0.01 to 0.4 times by weight to the total dissolved solids (TDS) content.

The above additives include citric acid, succinic acid, tartaric acid, malic acid, fumaric acid, oxaluccinic acid and lactic acid, which produce mineral salts and complexes. One or a mixture of two or more kinds of (lactic acid) may be mixed with the additive in the range of 3 to 15 wt%.

The stirring is performed by dissolving the flow rate (Q) / volume (V) at 180 to 360 RPM for 0.5 to 2 hours at a stirring time (retention time) in the range of 1 to 5 minutes with a propeller stirrer to dissolve and react the calcium agent and the additive.

The material of the stirrer 41 uses one kind of salt-resistant stainless steel, titanium, and bronze alloys.

In the case of preparing a solid mineral modifier, a high temperature liquid phase mineral modifier prepared in the additive mixing and mineral activation steps is sent to an evaporation process to evaporate water to prepare a solid phase mineral modifier.

The method of evaporating the mineral conditioner in the liquid state is carried out by evaporation of moisture by solar heat and wind in the evaporation basin as in the salt production of hot water, and dried to produce powder by hot air drying, or 60 to 90 ° C. Water is evaporated by a spray dryer with hot air to prepare a solid mineral conditioner in powder form.

In the drying process, care should be taken to evaporate and dry the moisture at 60 ~ 90 ℃ below 90 ℃ because the weak components of heat may be decomposed if the water is evaporated above 100 ℃.

Example 8

In the third electrodialysis process, oyster shell was roasted at 20 kg in concentrated mineral water from which salt and sulfate ions were removed, and then dissolved in hydrochloric acid solution. Calcium chloride (CaCl ₂ ) was the main component. Then, 1.4 kg of calcium agent having 35 wt% calcium content was added to add a weight ratio of Ca / Mg to about 2.5. Then, 6 kg of sucrose and 0.2 kg of citric acid were added thereto, followed by heating and stirring at 60 ° C. for 1 hour. To prepare a liquid mineral regulator.

Ⅴ. Steps to prepare salt and brine

Salt production method in the present invention proposes a salt production method with a high mineral content in order to fully exhibit the characteristics of the various mineral components contained in the deep sea water.

1. Fourth electrodialysis process

In the fourth electrodialysis process, the cation exchange diaphragm 22 transmits all cations, and the anion exchange diaphragm comprises a monovalent anion selective exchange diaphragm 20 that selectively transmits only monovalent anions. It is an electrodialysis device with multiple stages installed alternately between (17) and its purpose is to concentrate with brine containing a large amount of minerals while removing the sulfate ions which make acid taste deteriorate.

The fourth electrodialysis apparatus 48 for concentrating salts and minerals and removing sulfate ions is a cation exchange diaphragm 22 that can penetrate all cations and an anion exchange diaphragm that monovalent anions selectively penetrate only monovalent anions. The same electrodialysis apparatus as the second electrodialysis apparatus 32 in which the selective exchange diaphragm 20 is alternately provided with multiple stages between the anode 16 and the cathode 17 is applied.

When the brine is supplied to the brine reservoir 46 in the second and third nanofiltration processes, only the cation exchange diaphragm 22 and the monovalent ions selectively penetrate all cations by the brine transfer pump 47. The positive electrode 16 and the negative electrode 17 from the rectifier in the fourth electrodialysis apparatus 48 in which the monovalent anion selective exchange diaphragm 20 is permeately alternately provided between the positive electrode 16 and the negative electrode 17. While supplying a DC current to the desalination chamber (24) and circulated to the brine storage tank 46, the brine of the third circulation brine storage tank (49) to the salt concentration chamber (25) by the third brine circulation pump (50) When supplied and circulated to the third circulation brine storage tank 49, all cations (salts and all mineral components) in the desalting chamber 24 pass through the cation exchange diaphragm 22 on the negative electrode 17 side and the salt concentration chamber 25 ) to be moved, the anion is a monovalent ion (Cl ^-, Br ^-, etc.) only to the salt concentration of the first side of the anode 16 transmits the selected anion exchange membrane (20) The electroconductivity of the brine electric conductivity indicator controller (ECIS) is moved to (25) to operate the solenoid valve (ⓢ) in the range of 2 ~ 12㎳ / ㎝ to the beverage production process, the third circulation brine storage tank (49) When the concentration of the bomedo concentration of brine is concentrated in the range of 12-20 ° Be, the solenoid valve (ⓢ) is operated by the bomedo specific gravity control controller (BIS) and sent to the concentrated brine storage tank 51.

The cation exchange diaphragm 22, the monovalent anion selective exchange diaphragm 20, the positive electrode 16, the negative electrode 17, and all the structures used for the fourth electrodialysis apparatus 48 and all the structures same.

In the salt production of the present invention, the concentration of the primary brine in the fourth electrodialysis process the cation exchange diaphragm 22 and all the positive ions permeate monovalent anion selective exchange diaphragm 20 that only penetrates the monovalent anion. By applying an electrodialysis apparatus in which multiple stages are alternately installed between the 16 and the cathode 17, Na ⁺ , K ⁺ , Ca ^{2 +} , Mg ^{2 +} , Fe ^{2 +} , Fe ^{3 in} the brine of the desalting chamber 24. ⁺ , Zn ^{2 +} ... And all cations are moved to the cathode 17 side of the salt concentration chamber 25 and the anion is Cl, such as ^-, Br ^- and monovalent anion s 1 is transmitted through the selected anion exchange membrane 20, such as a positive electrode (16 ) See the salt concentration chamber 25 on the side to separate the salt concentration, so sO ₄ ^2, the salt concentration chamber ⁽²⁵⁾ of a polyvalent anion (多價) such as is almost non-existent.

So salt with high solubility, because it was present in the CaSO ₄ The sulfate ion has low solubility in water, the salt water does not have a sulfate ion-existent during the concentrated brine of salt concentration chamber (25) by following the ⑧ reaction of (CaCl ₂ It is present in the form of), the salt and the brine produced in the present invention is characterized by a high calcium content compared to the general natural salt.

CaSO ₄ + MgCl ₂ → CaCl ₂ + MgSO ₄ ... … … … … … … … … … … … ⑧

When the reaction occurs as shown in the above reaction formula (8), and the concentration of the function as shown in the "concentration gradient of the salt contained in the electrodialysis process" of Figure 17, the change occurs to the salt with a high content of CaCl ₂ .

The anion exchange diaphragm 20 through which all the anions pass through the monovalent anion selective exchange diaphragm 20 through which only the monovalent anions selectively permeate only the monovalent ions pass through the anion exchange diaphragm 48 of the fourth electrodialysis apparatus 48 ( It can also be changed to 23).

In the fourth electrodialysis apparatus 48, the purpose of using the monovalent anion selective exchange diaphragm 20 that transmits only monovalent anions is to exclude sulfate ions contained in the brine. In order to remove highly sulfate ions from the demineralized water used for beverage production even though the quality is somewhat reduced, the surface of the membrane may not be modified instead of the monovalent anion selective exchange diaphragm 20 of the fourth electrodialysis apparatus 48. It is used to replace the anion exchange membrane (23) that transmits all the anions that are not anion exchange membrane.

2. Process of evaporation and crystallization, dehydration and drying of the precipitated salt-manufacturing salt and water by packing and inspection

In the precipitation of salt by evaporation concentration, a process of evaporating moisture by atmospheric air is applied to summer in summer, and moisture by heating air in winter or rainy season. The same process as FIG. 11 for evaporating is applied.

Iii. Process of evaporating water into atmospheric air to precipitate salt and then dehydrating and drying to produce salt and brine

In the case of evaporation of salt by evaporation, the evaporation of water by atmospheric air is concentrated in the range of 12 ~ 20 ° Be in the range of Bumedo in the first electrodialysis process, the third electrodialysis process and the fourth electrodialysis process. When the brine is supplied to the concentrated brine storage tank 51, the concentrated brine is concentrated over the top of the salt extraction tank 53 by the concentrated brine transfer pump 51 (concentrate the concentrated brine supplied to the return concentrated brine storage tank 58). Evaporation tower by atmospheric air by the exhaust fan 57 while spraying the concentrated brine and compressed air conveyed by the brine conveying pump 59 through the spray nozzle 56 to the top of the evaporation tower 55 by atmospheric air together (55) The overflowed water, which sucks dry air in the atmosphere from the lower part and flows in countercurrent contact with concentrated brine, evaporates the water in the concentrated brine, and flows to the salt precipitation tank 53 and overflows to the upper part. Sent to brine reservoir (58), and then Water is evaporated while the brine conveying pump 59 is conveyed to the upper part of the evaporation tower 55 by atmospheric air, and the water content is shown in FIG. 13 "Deposition rate of various salts according to specific gravity change in the concentration of seawater at 35 ° C". At the temperature of 35 ° C., NaCl begins to precipitate when the specific gravity of Bomedo reaches 25.8 ° Be. When the precipitated salt (NaCl) precipitates under the salt precipitation tank 53, the salt precipitate tank 53 is formed by the salt precipitation tank lake 54. ) Collected in the bottom portion of the cone (Cone) and supplied to the dehydration process by the precipitation salt feed screw conveyor (60), the dehydration filtrate is sent to the dehydration filtrate storage tank (61), the dehydrated salt is sent to a drying process to dry the salt Manufacture.

When the dehydration liquid discharged from the dehydration process is supplied to the dehydration liquid storage tank 61, the dehydration liquid transfer pump 62 is returned to the upper portion of the evaporation tower 55 by atmospheric air, and the dehydration liquid storage tank 61 is depleted in the dehydration liquid storage tank 61. When the specific gravity is 30 ~ 32 ° Be, the solenoid valve (ⓢ) is operated by the BOMEI specific gravity indication controller (BIS) to package the discharged water (苦 汁) to manufacture the product.

Since the various mineral components are contained in the brine produced here, it can be sent to the concentrated mineral water storage tank 35 of the 3rd electrodialysis process and used for manufacture of a mineral regulator.

In order to improve the spraying efficiency of the injection nozzle 56, the compressed air is supplied at a pressure of 1 to 6 kg / cm &lt; 2 &gt; on the upstream side, and a mass ratio of air and liquid is supplied at a ratio of 1.1 to 1.2.

The structure of the evaporation tower 55 by atmospheric air is the same as that of the cooling tower of an industrial plant, and the material is made of preservative wood, fiber glass reinforced plastic (FRP), slate, and the like. Specifications, operation and design conditions are the same as the process of the evaporation tower 66 by hot air air described later.

2. Process diagram of evaporating water with hot air to precipitate salt, followed by dehydration and drying to produce salt and brine

During the winter season when the temperature is low or when the humidity is high, the brine concentrated in the brine concentration range of 12-20 ° Be in the first electrodialysis process, the third electrodialysis process and the fourth electrodialysis process is concentrated in the brine reservoir 51. When supplied, the concentrated brine is overflowed over the top of the salt extraction tank 53 by the concentrated brine transfer pump 52, and the concentrated brine supplied to the return concentrated brine storage tank 58 is conveyed by the concentrated brine transfer pump 59. The air supplied from the blower 63 is heated by the burner 64 while the concentrated brine and compressed air are sent to the upper part of the evaporation tower 66 by hot air air and sprayed through the spray nozzle 56. When supplied downward to the bottom through the hot air, the evaporated water is released to the atmosphere through the demister 67 while countercurrently contacting the hot air, and the concentrated brine in which the water is evaporated and concentrated is concentrated in the center well of the salt extraction tank 53. In the concentration of seawater at 80 ° C. As shown in the precipitation rate of various salts according to the medium change, salt (NaCl) starts to precipitate when the specific gravity of Bumedo reaches 25.8 ° Be at 80 ° C, and when the precipitated salt precipitates, the salt precipitation tank lake (54 Collected by the lower center cone portion) and supplied to the dehydration process by the precipitation salt feed screw conveyor (60), the dehydration filtrate is sent to the dehydration filtrate storage tank (61), the dehydrated salt is sent to a drying process to dry to prepare a salt. .

When the dehydration liquid discharged from the dehydration process is supplied to the dehydration liquid storage tank 61, it is returned to the center well of the salt-precipitation tank 53 by the dehydration liquid transfer pump 62, and dewatered in the dehydration liquid storage tank 61. If the specific gravity of the filtrate in the filtrate is in the range of 30 to 32 ° Be, the solenoid valve (ⓢ) is operated by the BOME to control the discharged water to manufacture the product.

Here too, the brine may be commercialized in the brine itself or sent to the concentrated mineral water storage tank 35 of the third electrodialysis process for use in the preparation of the mineral regulator.

The material of the evaporation tower 66 by hot air is preferably flame retardant titanium or stainless steel. However, in consideration of economic efficiency, FRP (Fiber reinforced plastics) resin or epoxy resin ( Epoxy resin may be lined or coated.

In order to improve the spraying efficiency of the injection nozzle 56, the compressed air is supplied at a pressure of 1 to 6 kg / cm &lt; 2 &gt; on the upstream side, and a mass ratio of air and liquid is supplied at a ratio of 1.1 to 1.2.

The heating of the air supplied from the blower 63 uses heavy oil, light oil, liquid natural gas (LNG), liquid petroleum gas (LPG), etc. in the burner 64, and the temperature of the hot air air is 120 to 400 ° C. The temperature of the wet air exhausted to the atmosphere through the demister 67 is set to 60 to 80 ° C. In the evaporation tower 66 by hot air, the drying evaporation proceeds only with the constant drying, and the concentrated brine discharged to the salt-precipitation tank 53 at the bottom is 80 ° C. or lower so that the weak components are not thermally decomposed. The evaporation tower 66 by hot air is designed.

The flow rate of the brine stream of the salt-precipitation tank 53 flows into the conveyance concentrated brine storage tank 58, and the conveyance concentration brine of the concentrated brine transfer pump 59 is 2 to the flow rate of the concentrated brine supplied to the evaporation tower 66 by hot air. The flow rate is 4 times.

The flow rate of the hot air air supplied from the blower 63 required for drying evaporation is determined by reducing the heat loss by 5-10% to the value obtained from the enthalpy and the material balance of the device entrance.

When the flow rate of the hot air air supplied from the blower 63 is determined, the tower diameter of the evaporation tower 66 by the hot air air shall have a flow rate of the hot air air of 3 to 5 m / sec.

The angle α of the lower cone of the evaporation tower 66 by hot air is designed to be 10 ° ≤α≤60 °, and the ratio of the diameter of the discharge part (D。) and the diameter of the tower (D) ) Is designed in the range of 0.3≤D。 / D≤0.7.

The salt-precipitation tank 53, the conveyed concentrated brine storage tank 58, and the dehydration liquid storage tank 61 are made of epoxy coated on reinforced concrete, or titanium or flame-resistant stainless steel or steel sheet with FRP resin or epoxy resin. Lining or coating can also be used.

The diameter of the salt-precipitation tank 53 has a solid load of 60-90 kg / m 2 · day of precipitation salt, a depth of 3-4 m, and a slope of the bottom of the bottom in the range of 1.5 / 10 to 2.5 / 10. To be designed).

The salt-precipitation tank rake 54 also uses the above-described flame-retardant material or coated with an epoxy resin on a steel sheet, and the rotation speed is 0.02 to 0.05 rpm, and the power of the speed reducer is equal to the diameter of the salt-precipitation tank 53. The torque is determined by taking into account the state of the precipitated salt.

Concentrated brine return pump (59), precipitated salt transfer screw conveyor (60), dehydration feed pump (62) and the dehydrator is made of titanium or flame resistant stainless steel, all brine piping is titanium, flame resistant stainless steel, PE ( Polyethylene) and PVC (Poly vinyl chloride) resin tubes are used.

When the concentrated brine having evaporated moisture from the evaporation towers 55 and 66 is sent to the salt-precipitation tank 53, the concentrated brine is evaporated and concentrated as shown in FIGS. When Be becomes NaCl starts to precipitate, the evaporation is continued and the concentration of the Bumedo of the concentrated brine is 30 ~ 32 ° Be MgCl ₂ precipitates, and then MgBr ₂ also precipitates (dehydrated) in the present invention In the filtrate storage tank 61, when the specific gravity of the dememorated filtrate is 30 to 32 ° Be, the brine is discharged to produce salt having a low bromine concentration.

Example 9

The brine discharged from the second nanofiltration process of Example 3 and the brine discharged from the third nanofiltration process of Example 4 were concentrated by the same electrodialysis apparatus as in Example 6 to concentrate the salts of the brine.

The cation exchange diaphragm having an effective conduction area of 236 mm (length) x 220 mm (width) of 0.2 mm is composed of a cation exchange diaphragm (22; Aciplex K-101, manufactured by Nippon Chemical Co., Ltd.) that transmits all cations. anion exchange membranes are monovalent anion selective only one is selected, the anion exchange membrane for transmitting a (20; Aciplex a-102, Japan旭化成工業株式會社product) to the positive electrode sheet 50 respectively 16 is RuO ₂ -TiO a titanium plate ₂ coated DSA electrode and negative electrode 17 are 50 L of salt water in the desalting chamber 25 of the fourth electrodialysis apparatus 48, in which multiple stages (50 stages) are alternately installed between stainless steel electrodes as shown in FIG. After supplying the brine filtered in the second nanofiltration process of Example 3 and the brine at 26 ° C. filtered in the third nanofiltration process of Example 3, the brine transfer pump 47 which is a diaphragm type metering pump. ) To the desalination chamber 24 so that the linear velocity is 10 cm / sec. When the concentrated brine of the three-circulating brine reservoir 49 is blocked by the third brine circulation pump 50, which is a diaphragm-type metering pump, it is supplied to the salt concentration chamber 25 so that the linear velocity is 3 cm / sec. ), The DC current is applied from the rectifier at a current density of 12 to 15 A / dm2 (at this time, the applied voltage was 55 to 60 V), and the conductivity value of the conductivity indicator controller (ECIS) of the salt water circulation line is 4 to The demineralized water desalted at 6 kW / cm produced brine with a concentration of 18 ° Be in the Bomedo specific gravity of the third circulation saline reservoir 49.

In this case, the cathode chamber solution was supplied with a 5 wt% Na ₂ SO ₄ aqueous solution at 50 kV / min to the lower portion of the cathode chamber 19 to be discharged to the upper portion of the cathode chamber 18.

In the above-mentioned fourth electrodialysis apparatus 48, the concentrated brine was evaporated and concentrated by hot air at 130 ° C., and the decomposed salt having a specific gravity of Bomedo in the range of 26 to 32 ° Be was dehydrated, followed by 120 ° C. hot air. The results of analysis of the importance of the dried salt produced and the discharged water from the dehydration liquid are shown in Table 11 below.

Table 11 Analysis of Significant Values of Salts and Salts Prepared in Salt Manufacturing Process (Unit: wt%)

     Ingredient Item    NaCl    KCl MgCl ₂ CaCl ₂ MgBr ₂ MgSO ₄    Salt   88.20   0.15    7.88    2.91    0.1    Nil    bittern    4.20   7.50   15.80    5.20    0.75    Nil

Ⅵ. Steps to prepare a drink

1. pH adjustment and second reverse osmosis filtration process

Boron is contained in the deep sea water in the form of boric acid (H ₃ BO ₃ ) while it is contained in the range of 4-5 mg / l, and the particle size is small, with an ion radius of 0.23 Å. Is less than 0.3mg / l of drinking water and difficult to treat, and also has a dissociation constant pKa of about 9, which is almost undissolved in seawater and hardly exists in an ionic state. Since the treatment is difficult to treat the drinking water below 0.3mg / l even by the electrodialysis method, the boric acid is converted into a polyboric acid in the gel state by treating the pH with an alkali of 9-11. The boron compound is then removed by reverse osmosis filtration.

When boric acid in water is subjected to alkali treatment, it is converted into polyboric acid in gel state by the reaction of ⑨ as follows.

B (OH) ₃ + OH ^_ → [B (OH) ₄ ] ^- → [B ₃ O ₃ (OH) ₄ ] ^- → [B ₄ O ₅ (OH) ₄ ] ^2- → [B ₅ O ₆ (OH ) ₄ ] ^- … ⑨

When the demineralized water filtered in the first reverse osmosis filtration process and the demineralized water removed in the fourth electrodialysis process are supplied to the pH adjusting tank 68, the alkali agent (NaOH) is supplied to the pH indicating switch (pHIS). The boron compound was converted into polyboric acid by stirring with a pH adjusting tank stirrer 69 while injecting in the range of ˜11, and then the operating pressure was increased to 5-25 kg / cm 2 by the second reverse osmosis filtration feed pump 70. The boron compound-containing water, which was not filtered and supplied to the reverse osmosis membrane, was discharged to its original position below 200m after the neutralization treatment, and the filtered water, which is the deboron water filtered under the drinking water standard of 0.3 mg / l, was neutralized. Send to 70.

Since the inflow water flowing into the second reverse osmosis filtration process contains little salt, the membrane permeability of the spiral filtration membrane is 0.6 to 1.2 m 3 / m 2 even though the operating pressure is operated at a low pressure in the range of 5 to 25 kg / cm 2. In this case, the boron compound is filtered to the drinking water standard value of 0.3 mg / l or less.

In the second reverse osmosis process, even when the pH is supplied in an alkaline state of 9 to 11, scales such as CaCO ₃ and CaSO _{4 which} generate scale are removed in the nanofiltration process and the first reverse osmosis process. It doesn't matter.

The stirring method is a propeller type stirrer, which is stirred at 180 to 360 rpm for 20 to 40 minutes. The material is stainless steel or bronze.

Example 10

In the first reverse osmosis filtration step of Example 2, demineralized water, which was filtered water, was adjusted to pH 9.5 in a pH adjustment step to convert the boron compound in water into the form of polyboric acid, followed by Toray Corporation of Japan. Low pressure reverse osmosis membrane of model No. SU-710 using spiral reverse osmosis membrane of SU-710 and supplying pressure to the membrane at 20㎏ / ㎠G, the membrane permeation volume is 0.72㎥ / ㎡ The concentration of boron (B) in the filtrate (deboron water) was measured to be 82%, and the concentration of boron (B) in the drinking water was treated below 0.3 mg / L of the drinking water.

2. Neutralization process

In the second reverse osmosis filtration process, when the filtered water, which is deboronized water, from which the boron compound has been removed, is supplied to the neutralization tank 71, it is stirred with a neutralization tank stirrer 72 while supplying 5-10 wt% aqueous hydrochloric acid (HCl) solution to give a hydrogen ion concentration. The pH is adjusted to a drinking water reference value of 5.8 to 8.5 with an indicator controller (pHIS) and then sent to the mineral regulator (74) with a mineral regulator supply pump (73).

Stirring method is a propeller-type stirrer for 20 to 40 minutes stirring at 180 ~ 360rpm, the material is stainless steel or bronze.

3. Mineral adjustment and beverage production process

In the neutralization process, when the pH is adjusted to 5.8 to 8.5, which is a beverage standard value, and supplied to the mineral regulator 74 with the mineral regulator supply pump 73, the mineral regulator prepared in the mineral manufacturing process is stirred with the mineral regulator stirrer 75 while being stirred. The hardness is adjusted to a range of 50 to 1,000 mg / l with the conductivity indicator controller (ECIS), and then sent to the sterilization process by a sterilization process supply pump 76 for sterilization at a high temperature of 120 to 135 ° C. for 0.5 to 10 minutes or ultraviolet sterilization. The treated beverages are sent to a container filling process and filled into containers (cans or plastic bottles), then inspected and packaged and shipped as beverages.

Stirring method of the mineral mixer 74 is a propeller-type stirrer and stirred for 20 to 40 minutes at 180 to 360 rpm, and the material is stainless steel or bronze.

Example 11

In the second reverse osmosis filtration process of Example 10, the pH of the filtrate (deboron water), which was finally treated with the boron compound below the drinking water quality standard, by adding 10 wt% aqueous hydrochloric acid (HCl) solution to neutralize the pH to 7.3, The water quality analysis results of the mineral regulator prepared in the above were injected while adjusting the conductivity in the electric conductivity indication controller (ECIS) in the range of 250∼260㎲ / ㎝.

Table 13 Analysis of Water Quality of Drinking Water Prepared by Injecting Mineral Modifier into Filtrate Water (Deboron Water) in Secondary Reverse Osmosis Filtration

   Item  Filtrate of Second Reverse Osmosis Membrane  Manufactured beverages  Remarks (Water Standard)          pH           8.2     7.3    5.8 to 8.5  Conductivity (㎲ / ㎝)         210   255 ¹⁷ O-NMR (㎐)          53    53 Redox potential value (㎷)          62    60  Hardness (mg / ℓ)          14.8   210.7  300 or less Na ⁺ (mg / L)          28.96    32.62  200 or less (WHO standard) Cl ^- (㎎ / ℓ)          50.82    57.24  250 or less Ca ^{2 +} (㎎ / ℓ)           0.86    42.30 Mg ^{2 +} (㎎ / ℓ)           3.08    16.90 K ⁺ (mg / L)           0.98     1.10 SiO _{2 (mg / L)}           0.25     2.26 _{^{SO 4 2 - (㎎ / ℓ}} )           3.32     5.20  200 or less  B (mg / l)           0.12     0.13    0.3 or less

Reviewing the results of processing of the information in Table 13 Index of good mulmat of the above-mentioned formula ① (OI) = (Ca + K + SiO ₂₎ / (Mg + SO ₄ ^{2 -),} the value of is (42.30 + 1.10 + 2.26) /(16.90 + 5.20) = 2.04, which is greater than or equal to 2.0 for the good water index, and the index of health (KI) in formula ② = Ca- 0.87Na = 42.30 -0.87 × 32.62 = 13.92, which is greater than or equal to 5.2 for the mineral balance. Has been properly adjusted, the redox potential has been properly treated to +120 mA, and the ¹⁷ O-NMR value of the half width of nuclear magnetic resonance is 53 mA, resulting in the small grouping of water molecules to produce high quality beverages. It turned out to be possible.

In addition, the concentration of boron (B) was also treated to 0.13 mg / L, which is 0.3 mg / L or less of drinking water standard value.

As described above, according to the present invention, since the deep ocean water contains various mineral components necessary for the growth of animals and plants without being contaminated with harmful pollutants, salts and sulfate ions contained in excess are contained. The mineral regulator prepared by mixing insufficient calcium and non-reducing disaccharides or sugar alcohol additives can be widely used as mineral regulators in food and beverages. Because of its superior properties compared to mineral water, it is expected to be widely used in the preparation of mineral regulators, salts and salt water and beverages from deep sea water.

Claims (16)

I. Pretreatment stage 1. Intake and heating process In the pretreatment process, deep sea water of 200 m or less is collected and warmed to 20 to 30 ° C., and sent to an electronic treatment tank (電子 處理 水槽; 1) of small groups of water molecules and mineral activation treatment. 2. Small grouping and mineral activation process of water molecules When the deep sea water warmed to 20 to 30 ° C. is supplied to the electronic treatment tank 1, a high-voltage alternating constant voltage is supplied to the electrode 2 from the constant voltage generator 7 to 3,000 to 5,000 Volts (field strength of 0.3 to 15 KV / m). A voltage of 0.4 and 1.6 μA is applied and an electrostatic field of + and-is alternately repeated around the electrode 2 and applied to the water molecules for 4 to 10 hours to seal the water molecules. When the hydrogen bond is partially broken, it is sent to the intermediate treatment water storage tank (8), and is sent to the magnetizer supply pump (9) to the constant voltage conductive tube magnetizer (10) and wound into a coil (0.5) to 5 V wound on the conductive tube. When a low voltage of alternating current or direct current is applied, magnetization occurs to activate the mineral component, and then some of them are returned to the electronic treatment tank 1 to carry out a nuclear magnetic resonance (NMR). a microclustered water);) of the ¹⁷ O-NMR half-intensity width (半値幅) number of sub-groups of the 48~60㎐ range (小集團水of Convenient then, is sent to the sub-group number of the storage tank (11) produces beams with pre-filtering step by the sub-group transfer pump (12). 3. Pretreatment Filtration Process The pretreatment filtration process uses sand filtration, micro filtration or ultra filtration alone or a combination of two or more processes to filter the water FI (Fouling index) in the range of 2 to 4. After treatment, it is sent to the first nanofiltration process. II. Salt and Sulfate Ion Removal and Mineral Concentration by Membrane Filtration 1. First Nanofiltration Process In the first nanofiltration process, the supply pressure is 15-20 kg / cm 2, which is lower than the osmotic pressure of 25 kg / cm 2 of the deep seawater with a salt concentration of 3.5 wt%, and the unfiltered sulfate-containing water is discharged, and sulfuric acid is discharged. The desulfurized ion mineral saline, which is filtered water with ions removed, is sent to the first reverse osmosis filtration process. 2. First reverse osmosis filtration process In the first nanofiltration process, when the desulfurized ion mineral salt solution from which the primary sulfate ion is removed is supplied to the first reverse osmosis process, the demineralized water is supplied to the filtration membrane at an operating pressure of 50 to 70 kg / cm 2, and the filtered demineralized water is used to produce the beverage. The concentrated brine is sent to the second nanofiltration process. 3. Second Nano Filtration Process The second nanofiltration is filtered while adjusting the pressure so that 75-85% of the concentrated mineral brine is pressurized at 50 to 60 kg / cm2 in the first reverse osmosis filtration to the separation membrane of the second nanofiltration process. The brine is sent to the salt manufacturing process, and the mineral brine with a relatively concentrated mineral content is sent to the third nanofiltration process. 4. Third Nano Filtration Process After diluting with 1 ~ 2 times the demineralized water discharged from the first reverse osmosis filtration process to the mineral brine concentrated in the 2nd nanofiltration process, supplying it to the filtration membrane at 20 ~ 30㎏ / ㎠, It is sent to the manufacturing process, the concentrated mineral brine is sent to the mineral brine storage tank 13 of the first electrodialysis process. III. Salt and Sulfate Ion Removal and Mineral Concentration by Electrodialysis 1. First electrodialysis process When the concentrated mineral brine discharged from the second nanofiltration process and the third nanofiltration process is supplied to the mineral brine storage tank 13, the monovalent cation selective exchange diaphragm 21 and the monovalent anion are supplied by the mineral brine transfer pump 14. The selective exchange diaphragm 20 is supplied to the desalting chamber 24 of the first electrodialysis apparatus 15 in which the multistage is alternately installed between the anode 16 and the cathode 17 to supply minerals. While returning to the brine storage tank 13, the brine of the first circulation brine storage tank 28 is supplied to the salt concentration chamber 25 by the first brine circulation pump 29 to circulate to the first circulation brine storage tank 28 When direct current is applied from the rectifier, the cations contained in the mineral saline in the desalting chamber 24 are transferred to the monovalent cations (Na ⁺ , K) by the electrical attraction force. ⁺ etc.) and to selectively transmit only by going to the salt concentration chamber 25, the anion is the anode 16 side of the monovalent anion selected Of: (Electric conductivity indicating switch ECIS) (such as Cl ^{- -,} Br) only selectively transmitted through the salt is be taken to the concentrate chamber 25 to break mineral salt conductivity not tense the line a ring diaphragm 20, a monovalent anion When the conductivity is in the range of 6 to 15 ㎳ / ㎝, the solenoid valve is operated to send to the mineral water storage tank 30 and the specific gravity of the bamedo of the first circulation salt storage tank 28 is 12-18 ° Be. Concentrated brine is sent to the brine reservoir 46 of the salt manufacturing process by operating a solenoid valve (ⓢ) with a Baume indicating switch (BIS). 2. Second Electrodialysis Process In the first electrodialysis process, when the mineral water from which salts are removed from the mineral brine is supplied to the mineral water storage tank 30, the cation exchange diaphragm 22 and the monovalent ions that can penetrate all cations by the mineral water transfer pump 31 are provided. The positive electrode 16 and the negative electrode from the rectifier in the second electrodialysis apparatus 32 in which the monovalent anion selective exchange diaphragm 20 that selectively permeates only alternately is provided between the positive electrode 16 and the negative electrode 17. Supplying a direct current to the 17 to the demineralization chamber 26 and circulated to the mineral water storage tank 30, the concentrated mineral water in the concentrated mineral circulation water storage tank 33 to the concentrated mineral water circulation pump (34) When supplied to the mineral concentration chamber 27 and circulated to the concentrated mineral circulating water storage tank 33, all the cations (mineral components) of the demineralized chamber 26 passes through the cation exchange diaphragm 22 on the negative electrode 17 side. will be taken to mineral concentrate chamber 27, anions are monovalent ions (Cl ^-, Br ^-, etc. ) Is passed through the monovalent anion selective exchange diaphragm 20 on the anode side 16 to the mineral concentration chamber 27 so that the electrical conductivity of the ECIS of the mineral water line is 400 to 1,000 mW /. When the cm range is reached, the solenoid valve (ⓢ) is operated and sent to the beverage production process. When the concentration of bomedo of concentrated mineral water in the concentrated mineral circulating water storage tank 33 is concentrated in the range of 26 to 33 ° Be, the bomedo gravity indicator controller By operating the solenoid valve (ⓢ) (BIS) is sent to the concentrated mineral water storage tank 35 of the third electrodialysis process. 3. The third electrodialysis process When the concentrated mineral water concentrated in the second electrodialysis apparatus 32 flows into the concentrated mineral water storage tank 35, it is sent to the desalination chamber 24 of the third electrodialysis apparatus 37 by the concentrated mineral water transfer pump 36. While circulating through the concentrated mineral water storage tank 35, the brine of the second circulation brine storage tank 38 is discharged into the salt concentration chamber 25 by the second brine circulation pump 39 and circulated to the second circulation brine storage tank 38. While applying a direct current from the rectifier to the anode 16 and the cathode 17, the monovalent cations (Na ⁺ , K ⁺ ) in the desalting chamber 24 is the monovalent cation selective exchange diaphragm 21 on the cathode 17 side. the transmission to be taken to salt concentration chamber (25), a monovalent anion (Cl ^-, Br ^-) is a positive electrode 16 side of monovalent salt concentration chamber 25 then passes through an anion selected exchange membrane 20 of the When the salt contained in the mineral water of the desalting chamber 24 is removed and the salt is removed in the electric conductivity of the electric conductivity indicator controller (ECIS) in the range of 0.4 to 3 kW / cm, the sole Concentrated mineral water from which salt and sulfate ions have been removed by operating the id valve (ⓢ) is sent to the additive mixer 40, and the brine of the second circulation brine storage tank 38 is the BME specific gravity of the BOME. The solenoid valve (ⓢ) is actuated and sent to the salt manufacturing process while adjusting to 12 to 18 ° Be. Ⅳ, step of preparing a mineral regulator When concentrated mineral water from which salt and sulfate ions have been removed is supplied to the additive mixer 40, bones of animals such as bovine bone, eggshells, shells of oyster shells, coral reefs, etc. Calcium chloride (CaCl ₂ ) and calcium lactate prepared by dissolving a powder containing a large amount of calcium, such as (瑚 礁), at calcination at 800 to 1,200 ° C, and dissolving the powder in 3-10 wt% aqueous HCl solution Calcium Lactate, Calcium Carbonate (CaCO ₃ ), Calcium Citrate, Calcium Gluconate, Calcium Glycerophosphate, Calcium Phosphate, Calcium Lignosulfonate, Calcium sorbate, Calcium silicate, Calcium Acetate, Calcium Carboxymethylcellulose, Calcium Alginate, or a calcium agent mixed with two or more Mg weight ratio is in the range of 2 to 6 By adjusting the mineral balance, and by using sucrose, nonreducing disaccharide, or trehalose, and nonreducing sugar alcohol, maltitol. ), Xylitol, sorbitol, sorbitol, erythitol, lactitol, mannitol, or one or two or more of these additives. It is supplied in a ratio of 0.01 to 0.4 times by weight to the content of solids) and supplied with a heat source from a boiler, and stirred with a stirrer 41 while heating to 40 to 80 ° C. using a temperature indicating controller (TIC). Dissolve the calcium agent and additives to react with the mineral component, and then send to the cooler 45 to cool to room temperature to prepare a liquid mineral regulator, or a high temperature liquid mineral regulator in the salt production In this evaporation sheet, the crystals deposited by evaporating moisture by solar heat and wind are hot-air dried to prepare powder, or by spray dryer with hot air at 60-90 ° C. By evaporation to prepare a powdered solid mineral regulator. A method for producing a mineral regulator from deep sea water by the above-described treatment step. The method of claim 1, wherein the mineral regulator is prepared from deep ocean water by a step of omitting the small grouping of the water molecules and the mineral activation treatment and sending the heated treatment to a pretreatment filtration process. The method of claim 1, wherein a mineral regulator is prepared from deep sea water by a process in which an electronic treatment tank 1 in which a stainless steel electrode 2 net filled with charcoal is incorporated is provided with multiple stages. Way. The method of claim 1, wherein the mineral regulator is prepared from deep sea water by a process in which a permanent magnet magnetized in the range of 12,000 to 15,000 G (Gauss) is installed in place of the constant voltage conductive tube magnetizer (10). The method of claim 1, wherein when the beverage and the salt are not prepared, pretreatment filtration omits the first nanofiltration process, the reverse osmosis filtration process, the second nanofiltration process, and the third nanofiltration process, and the first electrodialysis process. A method of producing a mineral regulator from deep sea water by a process sent to the mineral brine storage tank (13). The method of claim 1, wherein the third nano filtration step is omitted when the facility investment cost is to be reduced even if the concentration efficiency of the salt and mineral components decreases slightly, and the mineral brine concentrated in the second nano filtration step is replaced by the first electrodialysis step. A method of producing a mineral regulator from deep sea water by a process sent to the mineral brine reservoir (13). The method according to claim 1, wherein the third electrodialysis step is omitted in order to reduce the facility cost even if the desalination efficiency decreases slightly, and the concentrated mineral water concentrated in the second electrodialysis step is sent to the additive mixer 40 of the additive mixing step. A process for producing a mineral regulator from deep sea water by a process. The method of claim 1, wherein the mineral regulator is prepared from deep sea water by sending the brine produced in the salt production process to the concentrated mineral water storage tank (35) of the third electrodialysis process. According to claim 1, Citric acid, Succinic acid, Tartaric acid, Malic acid, Fumaric acid, Oxalic acid (Oxalsuccinic acid) to form mineral salts and complex compounds in the additive ), A method for producing a mineral regulator from deep sea water by mixing a single or two or more kinds of lactic acid in the range of 3 to 15wt% with additives. When the concentrated mineral water from which salt and sulfate ions are removed in the third electrodialysis process of claim 1 is used as a mineral regulator in the foliar fertilizer or compost manufacturing process, the additive mixing process is used. Omitted, the concentrated mineral water from which the salt and sulfate ions produced in the third electrodialysis process is removed as a crude mineral regulator. Preparation of salt using brine discharged from the second nanofiltration process, the third nanofiltration process of claim 1, the first electrodialysis process and the third electrodialysis process 1. Fourth electrodialysis process When the brine is supplied to the brine reservoir 46 in the second and third nanofiltration processes, only the cation exchange diaphragm 22 and the monovalent ions selectively penetrate all cations by the brine transfer pump 47. The positive electrode 16 and the negative electrode 17 from the rectifier in the fourth electrodialysis apparatus 48 in which the monovalent anion selective exchange diaphragm 20 is permeately alternately provided between the positive electrode 16 and the negative electrode 17. While supplying a DC current to the desalination chamber (24) and circulated to the brine storage tank 46, the brine of the third circulation brine storage tank (49) to the salt concentration chamber (25) by the third brine circulation pump (50) When supplied and circulated to the third circulation brine storage tank 49, all cations (salts and all mineral components) in the desalting chamber 24 pass through the cation exchange diaphragm 22 on the negative electrode 17 side and the salt concentration chamber 25 ) to be moved, the anion is a monovalent ion (Cl ^-, Br ^-, etc.) only to the salt concentration of the first side of the anode 16 transmits the selected anion exchange membrane (20) The deionized water from which salts and minerals are removed in the range of 2 ~ 12㎳ / ㎝ of electroconductivity indicator controller (ECIS) of brine is sent to the beverage production process by operating solenoid valve (ⓢ). When the concentration of the bomedo of the brine concentrated in the third circulation brine reservoir 49 is concentrated in the range of 12 to 20 ° Be, the solenoid valve (ⓢ) is operated by the bomedo gravity control controller (BIS) to the concentrated brine reservoir 51. send. 2. Process diagram of evaporating moisture into atmospheric air to precipitate salt, followed by dehydration and drying to prepare salt and brine In the first electrodialysis process, the third electrodialysis process, and the fourth electrodialysis process, the concentrated brine supplied to the concentrated brine reservoir 51 with concentrated brine having a specific gravity in the range of 12 to 20 ° Be is concentrated brine transfer pump. (51), the concentrated brine and compressed air conveyed by the concentrated brine return pump (59) together with the concentrated brine supplied to the conveying concentrated brine storage tank (58) by overflowing the upper portion of the salt extraction tank (53) While spraying through the spray nozzle 56 to the upper part of the evaporation tower 55 by air, the exhaust fan 57 sucks dry air in the atmosphere from the lower part of the evaporation tower 55 by the atmospheric air, and makes countercurrent contact with concentrated brine ( After evaporating the water in the concentrated brine while flowing, the overflowed water that flows to the salt precipitation tank 53 and overflows to the upper portion is sent to the return concentrated brine storage tank 58, and then, by the concentrated brine return pump 59. While conveying to the upper part of the evaporation tower 55 by atmospheric air When the salt (NaCl) precipitated by evaporation of the powder is precipitated under the salt precipitation tank 53, the salt is collected by the salt precipitation tank rake 54 into the cone portion of the bottom center of the salt precipitation tank 53, and then the precipitation salt feed screw conveyor 60 is formed. By supplying to the dehydration process by the dehydration liquid is reported to the dehydration liquid storage tank (61), the dehydrated salt is sent to a drying process to produce salt by the drying process. 12. The monovalent anion selective exchange diaphragm of the fourth electrodialysis apparatus 48 according to claim 11, in the case where the salt to be produced contains sulfuric acid salts and the quality thereof is somewhat deteriorated, in order to remove sulfuric acid ions in the demineralized water used for beverage production highly. (20) A method of producing salt by a step of replacing with anion exchange membrane (23) that transmits all anions instead. 12. The brine concentrate according to claim 11 is concentrated in the range of 12 to 20 ° Be in the first electrodialysis process, the third electrodialysis process, and the fourth electrodialysis process during the low temperature winter season and the high humidity season. Concentrated brine supplied to the brine storage tank 51 is a concentrated brine transfer pump 52, the concentrated brine supplied to the return concentrated brine storage tank (58) by overflowing the upper portion of the salt extraction tank 53 concentrated brine return pump The air supplied from the blower 63 is blown by the burner 64 while sending the concentrated brine and compressed air conveyed by the 59 together to the upper part of the evaporation tower 66 by hot air air and spraying it through the spray nozzle 56. When supplied downward through the heated heat exchanger (65), the evaporated water is released to the atmosphere through the demister (67) while countercurrently contacting the hot air air, and the concentrated brine evaporated is concentrated in the salt-precipitation tank ( When the precipitated salt precipitates in the center well of 53) Collected by the salt extraction tank rake (54) to the lower central cone portion and supplied to the dehydration process by the precipitation salt feed screw conveyor 60, the dehydration liquid is sent to the dehydration liquid storage tank 61, the dehydrated salt is sent to the drying process A method of producing salt by a drying process. When the dehydration liquid discharged from the dehydration process of claim 11 is supplied to the dehydration liquid storage tank 61, the dehydration liquid from the dehydration liquid storage tank 61 while being conveyed to the upper portion of the evaporation tower 55 by atmospheric air by the dehydration liquid feed pump 62. A method of manufacturing a water-based product by packaging the water discharged by operating the solenoid valve (ⓢ) by the BOMET specific gravity indication controller (BIS) when the specific gravity of the filtrate reaches 30 to 32 ° Be. When the dehydration liquid discharged from the dehydration process of claim 13 is supplied to the dehydration liquid storage tank 61, the dehydration liquid storage tank 61 is returned to the center well of the salt extraction tank 53 by the dehydration liquid feed pump 62. Method for manufacturing the water-based product by packaging the water discharged by the operation of the solenoid valve (ⓢ) by the BME when the Bomedo specific gravity of the dehydration solution is in the range of 30 ~ 32 ° Be. Demineralized water discharged from the reverse osmosis filtration process of claim 1 and the fourth electrodialysis process 1. pH adjustment and second reverse osmosis filtration process When the demineralized water filtered in the first reverse osmosis filtration process and the demineralized water removed in the fourth electrodialysis process are supplied to the pH adjusting tank 68, the alkali agent (NaOH) is supplied to the pH indicating switch (pHIS). The boron compound was converted into polyboric acid by stirring with a pH adjusting tank stirrer 69 while injecting in the range of ˜11, and then the operating pressure was increased to 5-25 kg / cm 2 by the second reverse osmosis filtration feed pump 70. The boron compound-containing water, which was not filtered and supplied to the reverse osmosis membrane, was discharged to its original position below 200m after the neutralization treatment, and the filtered water, which is the deboron water filtered under the drinking water standard of 0.3 mg / l, was neutralized. Send to 70. 2. Neutralization process In the second reverse osmosis filtration process, when the filtered water, which is deboronized water, from which the boron compound has been removed, is supplied to the neutralization tank 71, it is stirred with a neutralization tank stirrer 72 while supplying 5-10 wt% aqueous hydrochloric acid (HCl) solution to give a hydrogen ion concentration. The pH is adjusted to a drinking water reference value of 5.8 to 8.5 with an indicator controller (pHIS) and then sent to the mineral regulator (74) with a mineral regulator supply pump (73). 3. Mineral adjustment and beverage production process In the neutralization process, when the pH is adjusted to the drinking water standard value of 5.8 to 8.5 and is supplied to the mineral regulator supply pump 73 with the mineral regulator supply pump 73, the mineral regulator prepared in the mineral manufacturing process is supplied and stirred with the mineral regulator stirrer 75. While the hardness is adjusted to a range of 50 to 1,000 mg / l with an ECS controller, the sterilization process is supplied to a sterilization process by a sterilization process supply pump 76 for 0.5 to 10 minutes at a high temperature of 120 to 135 ° C. Drinking water sterilized by UV sterilization is sent to a container filling process, filled into a container (can or plastic bottle), packaged after inspection, and then released into a beverage.

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