KR20100009781A

KR20100009781A - A method to make a mineral adjusting agent using produced bittern from deep sea water, and method to use the same

Info

Publication number: KR20100009781A
Application number: KR1020080070567A
Authority: KR
Inventors: 서희동
Original assignee: 서희동
Priority date: 2008-07-21
Filing date: 2008-07-21
Publication date: 2010-01-29

Abstract

PURPOSE: A method for manufacturing mineral adjusting agent and a method using the same are provided to make the mineral adjusting agent having good tastes and freshness while producing salt by concentrating deep sea water. CONSTITUTION: A method for manufacturing mineral adjusting agent includes the following steps of: removing NaCl contained in salt water while producing ices; adjusting the brine in which NaCl is removed with a calcium agent to a 2~6 level of mineral balance; and agitating one component selected among citric acid, tartaric acid, succinic acid, malic acid, fumaric acid, fumarate, gluconic acid, gluconic acid salt, lactic acid with the brine. The calcium agent is selected among calcium citrate, calcium lactate, calcium pantothenate, calcium gluconate and calcium chloride.

Description

A method to make a mineral adjusting agent using produced bittern from deep sea water, and method to use the same}

The present invention relates to a method of making a mineral regulator and a method of using the same, and more particularly, to produce salt by concentrating deep sea water in the deep seabed deeper than 200m deep in sea level It also relates to a method of making mineral regulators using the brine produced as a by-product, and to using them for mineral adjustment in food processing, water and beverages.

In general, the adjustment of the mineral content of conventional food or beverages, when using deep seawater directly, there is a problem in that the taste is poor because the mineral balance is not appropriate, but contains a large amount of NaCl, nanofiltration of the deep seawater of the following document 1 Although a method of preparing a mineral modifier added with calcium, organic acid and non-reducing sugar to the number of minerals selectively removed NaCl by a process combining and electrodialysis has been proposed, there is a problem of high manufacturing cost and high facility cost with low concentration. .

Literature Information of the Prior Art

[Document 1] Republic of Korea Patent Registration No. 10-0819210 (2008.03.28)

The present invention is to take the deep sea water deeper than 200m deep from the sea surface containing various mineral components to produce fresh water and salt while freezing treatment of by-products produced by by-products, food processing, The aim is to provide a method of making mineral regulators for the adjustment of mineral components in water and beverage preparation.

The present invention relates to a method of making a mineral regulator for adjusting mineral components in food and beverages, and a method of using the same, wherein the deep sea water of a deep seabed deeper than 200 m in the sea surface is found. Concentrating the water to produce salt by producing frozen salt (Bittern) as a by-product while producing salt to remove the NaCl component is produced, by adding calcium agent to the NaCl component is removed mineral balance (Mineral adjusting the balance, and then adding a mineral acid that produces metal complex salt and non-reducing sugars to make a mineral regulator, and the mineral regulator It is characterized by consisting of the steps used for processing, water and beverages.

The present invention can be widely used as a mineral regulator of food processing, water and beverages because it can produce a mineral regulator at a low cost by using a by-product of the brine while producing salt by concentrating the deep sea water to produce salt and excellent taste and refreshing effect It is expected to be.

First of all, the characteristics of deep ocean waters are generally referred to as deep ocean waters, which are deeper than 200 m above sea level, and are called deep ocean waters. Because plankton and life cannot grow because sunlight does not reach, the concentration of nutrients is high and it is not mixed with surface seawater due to the density difference according to the water temperature. Therefore, the deep ocean water is characterized by the mineral characteristics and erosion of various mineral components which are useful for the growth of animals and plants without the harmful miscellaneous bacteria present in the surface sea water, as shown in the following Table 1. While there is a characteristic of being benign, there are characteristics such as low temperature stability, cleanliness, and maturation.

Table 1 Analysis of Significant Values in Surface Seawater and Deep Sea Water

division Ulleungdo Hyunpo 650m deep sea deep water Surface waters General Item Water temperature (℃) 1.2 20.3 pH 7.8 8.15 DO dissolved oxygen (mg / l) 6 8 TOC Organic Carbon (mg / L) 0.962 1.780 COD _Mn (mg / L) 0.2 0.6 Soluble evaporation residue (mg / l) 47,750 37,590 M-alkalido (mg / l) 114.7 110.5 Main element NaCl (wt%) 2.75 2.69 Mg magnesium (mg / l) 1,270 1,280 Ca Calcium (mg / L) 406 405 K potassium (mg / L) 414 399 Br Clear (mg / L) 68.2 68.1 Sr Strontium (mg / L) 7.76 7.61 B boron (mg / l) 4.45 4.48 Ba barium (mg / l) 0.044 0.025 F Fluorine (mg / L) 0.52 0.56 SO ₄ ² ^- sulfate ion (mg / l) 2,836 2,627 Nutrient salts NH ₄ ⁺ ammonia nitrogen (mg / l) 0.050 0.030 NO ₃ ^- Nitrogen Nitrate (mg / l) 1.158 0.081 PO ₄ ³ ^- phosphate (mg / l) 0.177 0.028 Si silicon (mg / l) 2.800 0.320 Trace element Pb lead (μg / ℓ) 0.110 0.087 Cd cadmium (㎍ / ℓ) 0.050 0.008 Cu copper (㎍ / ℓ) 0.260 0.272 Fe iron (㎍ / ℓ) 0.230 0.355 Mn manganese (µg / l) 0.265 0.313 Ni nickel (µg / l) 0.360 0.496 Zn zinc (μg / ℓ) 0.450 0.452 As Arsenic (㎍ / ℓ) 0.401 0.440 Mo molybdenum (µg / l) 5.110 5.565 Cr chromium (µg / l) 0.020 - Number of bacteria Number of live bacteria (dog / ml) 0 520 E. coli count (pcs / ml) voice voice

The history of deep sea water use is short, and various researches have been conducted in the non-fishery areas such as food, medicine, health industry, beverages, and cosmetics, starting with the fishery field. same.

1. Low temperature safety

While the surface temperature of surface seawater fluctuates greatly with the seasons, deep ocean waters are stable at low temperatures without changing the water temperature with seasons.

In particular, deep sea waters in the East Sea of Korea settled by dense differences in cold seawater that melted drift ice in the Sea of Okhotsk, off the coast of Vladivostok between Ostrov Sakhalin and Hokkaido. As the deep water flows in and blocks the Japanese archipelago, it slows down the water, and the water depth is deeper than 300m from the sea level. The water temperature is 1 ~ 2 ℃ throughout the year, off the coast of Muroto in Kouchi Prefecture, Hawaii or Japan. Is about 8 to 11 ° C lower than deep ocean water.

2. Cleanliness

Because it is deep, it is difficult to receive pollution from river water and air on land, and there are few chemicals, pollutants and bacteria.

① physical cleanliness

Physical cleanliness is said to be less suspended matter and suspended matter, and deep sea water contains less suspended solids than surface seawater.

② biological cleanliness

The biggest problem in the intake of seawater is the propagation of adherent organisms.In general, in the surface seawater intake system, the adherent organisms propagate in the intake pipe. The total number of viable microorganisms, such as (pathogenic) microorganisms and chlorella, is less than one tenth to one hundredth of the surface water.

③ chemical cleanliness

Since deep seawater does not mix with contaminated surface waters, it is not contaminated with so-called environmental pollutants such as dioxins, PCBs, organic chlorine compounds, and organic tin.

3. eutrophicity

Deep sea water has abundant nutrients such as nitrogen, phosphate, and silicate needed for plant growth in inorganic deep sea water, which are about 5 to 10 times higher than surface sea water. There is a characteristic.

At sea levels deeper than 150 m above sea level, the amount of light is less than 1%, and at further depths, phytoplankton are unable to photosynthesize, so nutrients are not consumed by phytoplankton, but sink and accumulate in the deeper layers below, resulting in inorganic nutrients. The concentration of is high.

4. Characteristics of minerals

Sea water contains more than 70 kinds of elements, and deep sea water has such characteristics.

Although there are many important elements necessary for the growth of animals and plants, they are necessary, but very small amounts of deeply related to human health, such as copper and zinc, essential trace elements that are harmful to intake in large quantities, are contained. .

5. Aging

The deep sea water has a lower pH than the superficial sea water (pH 7-8), and the organic deep water is separated from the sea water and matured as stable water under low temperature and high pressure for a long time.

Concentration of the composition of the raw water (Bittern) produced as a byproduct while concentrating the deep sea water to produce the salt is slightly different depending on the method of producing the salt, but produced by evaporating the deep sea water from the salt salt to precipitate the salt (析出) The composition of the main components of the brine produced by primary evaporation and second evaporation of seawater by electrodialysis, which is a purified water and ion exchange membrane method, is shown in Table 2.

Table 2 Composition of main components of the brine (wt%)

Kind of guard NaCl KCl MgCl ₂ MgSO ₄ MgBr ₂ CaCl ₂ Gansu Produced in Salt Farm 2 to 11 2 to 4 12-21 2-7 0.2 to 0.4 - Seawater produced by ion exchange membrane method 1 to 8 4 to 11 9-21 - 0.5 to 1 2 to 10

NaCl contained in the brine has a salty taste, magnesium (MgCl ₂ , MgSO ₄ ) bitter taste, potassium (KCl) sour taste to drop the water taste, whereas calcium component to soften the taste of water to taste There are characteristics that make it good.

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

Index of health (KI) = Ca-0.87 Na... … … … … … … … … … … … … … … … … … ②

Therefore, it is preferable that the mineral regulator used for drinking water or food is prepared by adding a calcium agent in a ratio of calcium (Ca) / magnesium (Mg) weight ratio of 2 or more.

It is also necessary to add nonreducing saccharides such as trehalose and sucrose to mask metal odors caused by minerals. In addition, organic acids such as citric acid, tartaric acid, malic acid, and lactic acid may be added to improve the precipitation and absorption efficiency of minerals. There is a need.

In the present invention, the measurement of the specific gravity of the solution to determine the concentration of salinity is measured by Baume's hydrometer, and the Baume degree (° Be) of the Baume hydrometer is measured in the liquid to measure the specific gravity of the liquid. It is the numerical value of the scale when it is opened, and the heavy bomedo for heavy liquids which is heavier than the specific gravity of water and the light bomedo for light liquids which are lighter than the specific gravity of water Among them, the heavy liquid solution has pure water at 0 ° Be, the 15% saline solution at 15 ° Be, and has 15 equal divisions between them, and the hard liquid solution has 10% saline solution at 0 ° Be. Pure water is made into 10 degree Be, and the division which divided | divided into 15 equal parts between them is graded.

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

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 brine used in the present invention is not particularly limited to those in which the composition of the brine according to the decontamination method is slightly different, and as described above, the brine produced by-products by concentrating the deep sea water to produce salt is used in bittern. Since there is a characteristic that contains a variety of minerals will be described in detail how to make a mineral regulator to adjust the mineral components in food processing, water and beverages using the brine as follows.

I. Producing the brine from which the NaCl component is removed

1. The process of producing brine from deep sea water

The deep sea water was collected and warmed to 20 ~ 30 ℃, and the sand filtration, micro filtration or ultra filtration was performed alone or in combination with two or more processes. After removing suspended solids (SS), concentrated brine, concentrated brine from the electrodialysis or electroextraction unit, and deep sea water from the frozen brine while producing nanofiltration and reverse osmosis filtration to produce ice water. When the brine or the deep sea water is evaporated by solar heat and wind in heating evaporation, vacuum heating evaporation, and solar salt, the specific gravity of the brine reaches 25 ° Be, and as shown in FIG. 1, the salt begins to precipitate. Continue to evaporate the brine to 32-34 ° Be to separate the precipitated salt and produce the remaining liquid constituent.

In the present invention, the composition of the brine is somewhat different according to the decontamination method of concentrating the deep sea water to produce salt as shown in Table 2, but the present invention is not particularly limited to the difference of the composition of the brine according to the decontamination method.

The composition of the brine is somewhat different as shown in Table 2 depending on the production method. In particular, the brine produced from brine concentrated by electrodialysis has the characteristic that CaCl ₂ is contained, and the brine produced from brine concentrated by natural salt or heat evaporation has MgSO ₄ .

2. Process of removing NaCl contained in water

Removal of NaCl contained in the brine produced in the deep sea water is a step of removing NaCl by an electrodialysis apparatus using a monovalent cation selective exchange membrane and a monovalent anion selective exchange membrane, a monovalent cation selective exchange membrane, and 1 The removal of NaCl by the electroextraction apparatus using anion selective exchange diaphragm or the process of freezing the brine by precipitation and removal of NaCl while producing ice to remove the NaCl. Produce the removed guard.

end. Process of removing NaCl by electrodialysis device

In the present invention, the removal of NaCl contained in the brine by the electrodialysis apparatus 3 is performed by separating the ionic solutes by membrane permeation using the potential difference of the direct current power as a driving force. The monovalent cation selective exchange diaphragm 9 selectively transmits a monovalent cation having a fixed negative charge, and the monovalent anion selective exchange diaphragm 8 has a fixed static charge. An ion exchange membrane is used which selectively permeates monovalent anions.

The electrodialysis apparatus 3 suppresses scale troubles and improves the NaCl removal efficiency while increasing the limit current density to improve the treatment efficiency. The cation selective exchange diaphragm 9 is alternately arranged in a row between the anode 4 and the cathode 5, and the anode 4 and the cathode of the anode chamber 6 at both ends are arranged. While applying the direct current to the cathode 5 of the chamber 7 from the rectifier, the water supplied to the water storage tank 1 is supplied to the desalination chamber 10 by the water transport pump 2 so that the salt concentration is 400. The NaCl is removed in the range of ~ 800 mg / l while some are returned to the water storage tank (1), and the desalted water is returned to the solenoid valve (ⓢ) by an electric conductivity indicating switch (ECIS). To the mineral reaction tank, and the concentrated brine of the concentrated brine storage tank 12 to the salt concentration chamber (11). When supplied to the salt concentration chamber 11 by the concentrated brine transfer pump 13 and circulated to the concentrated brine reservoir 12, Na ⁺ ions in the brine penetrate the monovalent cation selective exchange diaphragm 9 by electrical attraction. NaCl is removed while moving to the salt concentration chamber 11 on the cathode 5 side, and Cl ⁻ ions pass through the monovalent anion selective exchange diaphragm 8 to the salt concentration chamber 11 on the anode side 4. The concentrated brine concentrated in the range of 18 to 20 ° Be in the concentrated brine reservoir 12 operates a solenoid valve (ⓢ) by a BME (Baume indicating switch) to discharge the concentrated brine. .

In this case, the electrical conductivity is an index indicating the degree of conductivity of the aqueous solution, and the salt concentration in water is a unit. The unit is S / m (Siemens / m) corresponding to the inverse of the electrical resistivity of the aqueous solution. The relationship between (EC) and soluble salts (TSS) in water is shown in the following equation ③.

TSS (ppm) = 640 X EC (mS / cm). … … … … … … … … … … … … … … … … … … ③

The electrodialysis apparatus 3 preferably increases the current density as much as possible within the range below the limit current density in order to increase the processing performance, but the limit current density is proportional to the salt concentration, and the diffusion layer. Since the thickness of the diffusion layer is inversely proportional to the thickness of (iii), it depends on the salinity concentration in the brine which is discharged demineralized water and the salinity concentration of the concentrated brine. The water storage tank in the electrodialysis apparatus 3 which forms the desalination chamber 10 and the salt concentration chamber 11 which arranged the monovalent cation selective exchange diaphragm 9 alternately between the anode 4 and the cathode 5 ( The brine of 1) is sent to the desalination chamber (5) to the desalination chamber (5) to remove NaCl, and then partially circulated, and the concentrated brine is sent to the salt concentration chamber (11) by the concentrated brine transfer pump (13) to circulate. In the salt concentration chamber (11) while improving NaCl removal efficiency Supplying a large amount of concentrated brine passing through the salt concentration chamber 11 so that the kale component is not produced can prevent scale trouble, and supply the concentrated salt solution with a high NaCl concentration to the salt concentration chamber 11 to supply the current solution. Since the resistance decreases, the limit current density can be increased, and thus the processing performance of the electrodialysis apparatus 3 can be improved.

In order to improve electrodialysis efficiency and to suppress scale trouble by increasing the amount of current passing by increasing the limit current density in the electrodialysis apparatus 3, the flow rate supplied to the desalination chamber 10 is the membrane surface linear velocity. The liver water from which NaCl was removed in the range of 10 to 30 cm / sec is returned to the water storage tank 1, and the flow rate of the concentrated brine supplied to the salt concentration chamber 11 has a membrane surface velocity of 1 to 3 cm. The concentrated brine is returned to the concentrated brine reservoir 12 so that the / sec range is maintained.

Scale is generated in the ion exchange diaphragm of the electrodialysis apparatus 3, and the treatment efficiency can be reduced due to fouling of the membrane. Therefore, CaSO ₄ , CaCO ₃ , SrSO ₄ ... In order to suppress the generation of scale as much as possible, an ion exchange diaphragm is used, in which divalent or more ionic materials are poorly permeable and selectively transmit only monovalent ionic materials.

The monovalent cation selective exchange diaphragm 9 used in the present invention is an exchange diaphragm which selectively permeates only a monovalent cation while suppressing the permeation of bivalent or more polyvalent cations, and is a polystyrene-divinylbenzene. The side chain of polyethyleneimine or poly is attached to the negatively charged membrane that fixes negative charge -SO ₃ ^- to the main chain of the system. Graft polymer (Polyvinylpyridine), etc. Graft polymer (Polyvinylpyridine) or graft polymer whose main chain is a polystyrene pyridine side chain made of polyethyleneimine or polyvinyl pyridine, the graft polymer is a main chain of the cation exchange membrane Any structure having the same molecular structure as the side chain can be used without limitation. Preferably, polyethylene, polypropylene, and polyvinyl chloride (Po) are used. A molecule having only a monovalent cation permeable to the main chain or side chain having the same molecular structure as a polymer composed of a cation exchange membrane immobilized with negatively charged R-SO ₃ ^- on lyvinylchlorde, polystyrene, etc. Cation exchange membranes such as polyvinylpyridine, polyvinylamine or polyethyleneimine membranes having a structure may be used, and in particular, polystyrene-graft-ethylene imine of polystyrene-divinylbenzene Can be used.

And a monovalent anion selected exchange membrane (8) is a monovalent cation selected exchange membrane (9), as opposed to a power failure by a diaphragm which is capable of exchanging one selects an anion and (正電荷) R-NH ₃ ⁺ of the polymer chain (Polymer It is also fixed to the chain and fixed to the membrane, so it is also called a static charge membrane, and the ion exchange groups are crosslinked by aliphatic hydrocarbons, An anion exchange membrane in which a thin layer of a polymer material having a cation exchange group is formed on the surface. It is preferable to crosslink and quaternize the monomer introduced into the exchange group with an aliphatic hydrocarbon. Examples of the polymer material having an exchange group include a polymer electrolyte having a cation exchange group, a linear polymer electrolyte, an insoluble polymer having a cation exchange group, and the like. Sulfonate such as Liginsulfonate, Phosphate ester salts such as higher alcohol phosphate esters, etc.Polymer electrolytes having a cation exchange group with a molecular weight of 500 or more, methacrylic acid, styrene sulfonic acid Linear polymer electrolyte containing a large number of monomer units having a carboxylic acid group (-COOH) or a sulfonic acid group (-SO ₃ H) such as), a phenol and an aldehyde including a cation exchange group. A membrane for selectively exchanging monovalent anions such as an insoluble polymer having a cation exchange group such as a condensed stream is used.

The anode 4 of the anode chamber 6 of the electrodialysis apparatus 3 is a corrosion-resistant material and has a high chlorine and oxygen generating overvoltage (DSA) electrode or a platinum plated electrode. The solution passed through the cathode chamber 7 is injected to suppress the generation of chlorine and oxygen on the surface of the anode 4, and the cathode 5 has a high hydrogen generation overvoltage. Or a stainless steel sheet, and the monovalent cation selective exchange diaphragm 9 closest to the cathode chamber 7 uses a hydrogen ion impermeable membrane or a monovalent anion permeable membrane. The amount of hydrogen ions generated on the surface of the cathode 5 may be reduced to improve power efficiency and reduce odor.

In addition, in the salt concentration chamber 11, a polarity switching device is installed in the rectifier to prepare a scale or slimes such as organic matter, thereby reducing processing efficiency. Switch the power of (5) to detach the attached scale and slime.

The electrolyte solution of the electrode chamber is supplied to the cathode chamber 7 to supply the electrolyte solution discharged from the cathode chamber 7 to the anode chamber 6, and the electrolyte solution (cathode chamber solution) supplied to the cathode chamber 7 is Sea water or deep sea water may be used, but 3-10 wt% Na ₂ SO ₄ Using an aqueous solution can suppress corrosion of the electrode and generation of chlorine (Cl ₂ ) gas in the anode 4.

Concentrated brine in the brine reservoir 12 discharges the brine concentrated in the range of 18 ~ 20 ° Be (sent to the salt manufacturing process).

I. Process of removing NaCl by electric extraction device

The electroextraction apparatus 14 for removing excess NaCl contained in the brine has a monovalent cation selective exchange diaphragm 9 and a monovalent anion between the anode 4 and the cathode 5 in the salt extraction chamber 15. Regarding the removal of NaCl by electric extraction in which the desalination chamber 10 isolated by the selective exchange diaphragm 8 is installed in multiple stages, it will be described in detail with reference to the accompanying drawings.

3 is a process chart for removing NaCl contained in the brine by electric extraction. Between the positive electrode 4 and the negative electrode 5 installed inside the salt extraction chamber 15, the negative electrode 5 is monovalent cation selective exchange. NaCl contained in the water by electric extraction consisting of a multi-stage installation of the desalination chamber 10 isolated by the diaphragm 9 and the positive electrode 4 on the anode 4 side. In the case of removing NaCl contained in the brine by a device for removing the salt, the seawater of the brine storage tank 1 is supplied to the desalination chamber 10 by the brine transfer pump 2 and circulated to the brine storage tank 1, Alternatively, the deep sea water is supplied to the salt extraction chamber 15, and the air from the blower 16 is aerated from the rectifier while aerated through the diffuser 17 installed below the salt extraction chamber 15. Electrophores are applied when direct current is applied to form an electric field. Na ⁺ ions contained in the brine in the desalting chamber 10 are permeated through the monovalent cation selective exchange diaphragm 9 on the negative electrode 5 side to the salt extraction chamber 15. Cl ^- ions pass through the monovalent anion selective exchange diaphragm 8 on the anode side 4 to the salt extraction chamber 15, whereby the concentrated brine is concentrated in the Baume's hydrometer indicating switch (BIS). When the specific gravity of Bomedo is concentrated in the range of 12 to 20 ° Be, the solenoid valve (ⓢ: Solenoid valve) is operated to discharge the concentrated brine by the salt manufacturing process, and NaCl is removed from the brine in the desalting chamber (10). The electroconductivity of the electric conductivity indicating switch (ECIS) installed in the line is in the range of 6-12 ㎳ / cm, and the NaCl-free water is sent to the mineral reactor by operating the solenoid valve.

The desalination chamber 10 between the anode 4 and the cathode 5 in the salt extraction chamber 15 of the electric extraction device 14 for removing NaCl contained in the brine is alternately depending on the processing capacity. ) Install multiple stages in parallel.

The above-described reaction mechanism for removing NaCl by electro extraction from NaCl in the brine is as follows.

NaCl contained in the brine is dissociated into Na ⁺ ions and Cl ⁻ ions by hydrolysis in water as shown in the following reaction formula ⑤.

_{^{NaCl -H 2 O → Na + +}} Cl - ... … … … … … … … … … … … … … … … … … … ⑤

When a direct current is applied from the rectifier to the positive electrode 4 and the negative electrode 5 to form an electric field inside the desalination chamber 10, the Na ⁺ ions contained in the brine in the desalting chamber 10 by electrophoresis are negative electrode 5. The monovalent cation selective exchange diaphragm 9 on the side passes through the salt extraction chamber 15, and the Cl ⁻ ion penetrates through the monovalent anion selective exchange diaphragm 8 on the anode side 4 to the salt extraction chamber. As it moves to (15), NaCl is removed from the brine in the desalting chamber (10).

Na ⁺ --septum-> Na ⁺ ... … … … … … … … … … … … … … … … … … … ⑥

Cl ^{- -} Diaphragm ^- → Cl - ... … … … … … … … … … … … … … … … … … … ⑦

Na ⁺ ions and Cl ⁻ ions transferred to the salt extraction chamber 15 are in situ in the original NaCl state.

Na ⁺ + Cl ^−- → NaCl... … … … … … … … … … … … … … … … … … … ⑧

On the positive electrode 4 and the negative electrode 5 side, when the following side reactions occur, odor generation and power consumption may increase, so air in the air is blown from the blower (Air blower) 16 (Diffuser: 17) Aeration to ensure that the following side reactions are suppressed as much as possible.

2Cl ⁻ → Cl ₂ ₍ _aq ₎ + 2e ⁻ . … … … … … … … … … … … … … … … … … … … … ⑨

Cl ₂ ₍ _aq ₎ → Cl ₂ _(g) ↑. … … … … … … … … … … … … … … … … … … … … … ⑩

Cl ₂ ₍ _aq ₎ + H ₂ O → HClO ₍ _aq ₎ + HCl... … … … … … … … … … … … … … … … … ⑪

_{^{2HClO (aq) + 2H + +}} 2e - → Cl 2 (g) ↑ + 2H 2 O ... … … … … … … … … … … … ⑫

_{^{2H 2 O + 2e - → 2OH}} - + H 2 (g) ↑ ... … … … … … … … … … … … … … … … … … ⑬

At this time, the supply amount of air supplied from the blower 16 through the diffuser 17 is such that the aeration intensity (Intensity of aeration) is 1.2 to 2.0 air (m 3) / tank volume (m 3).

The electroextractor 14 and the desalination chamber 10 may be made of flame resistant stainless steel, titanium, epoxy coated or lining carbon steel, or glass. Lining fiber glass reinforced plastic (FRP).

The positive electrode 4, the negative electrode 5, the monovalent anion exchange diaphragm 8 and the monovalent cation exchange diaphragm 9 use the same ones as the electrodialysis apparatus 3.

All. Process of removing NaCl by freezing

In the case of removing NaCl by freezing NaCl contained in the brine, as shown in FIG. 4 "Phase diagram of H ₂ O-NaCl system according to freezing of brine," When supplied to the refrigerating unit, the refrigerant is circulated through the cooling coil and the temperature of the water in the refrigerating unit is lowered, and the sherbet ice starts to be produced (the temperature at which ice is produced varies depending on the concentration of salt in the water). in a), when the still cooled at a temperature fall when the -11~-12 ℃ and the semi-solid state of ice production, the more cooling is cooled to a temperature of -22~-23 ℃ which the NaCl · 2H ₂ O-containing solid state As ice is produced, NaCl in the brine begins to be removed, and in the present invention, when cooled in the range of -23 to -25 ° C, the NaCl is removed from the solution. At this time, the specific gravity of the bomedo is 25 to 26 ° Be.

Example 1

The desalted water filtered through deep osmosis filtration of the deep sea water in Table 1 is sent to the beverage manufacturing process, and the unfiltered brine is sent to the Cheonil Salt Cell (天日鹽田池), where the specific gravity of the short-selling water is concentrated in the range of 20 ~ 23 ° Be. Although the specific gravity was heated and evaporated to 32 ° Be, the salt was precipitated, and the composition of the remaining water, which is the remaining liquid, was as shown in Table 3.

Table 3 Analysis of Principal Components of Residual Water from Preliminary Concentrated Water-Solution Cells by Precipitating and Evaporating Salt by Heating and Evaporating to 32 ° Be

ingredient NaCl KCl MgCl ₂ MgSO ₄ Moisture and other ingredients Concentration of components (wt%) 5.6 2.3 16 5.3 70.8

As shown in Fig. 2, the cation exchange diaphragm having a thickness of 236 mm (length) x 220 mm (width) of 0.2 mm in the effective conduction area is monovalent cation selective exchange selectively transmitting only monovalent cations. Diaphragm (9: Aciplex (registered trademark) K-102, manufactured by Nippon Chemical Co., Ltd.) and the anion exchange diaphragm are monovalent anion selective exchange diaphragms (8: Aciplex A-102, Japan). 50 sheets each of which is made up of 25 desalting chambers (10) and 25 salt concentration chambers (11), and the anode (4) of the anode chamber (6) is made of RuO ₂ -TiO ₂ on a titanium plate. The coated DSA electrode was used, and the cathode 5 was supplied to the electrodialysis apparatus 3 made of stainless steel, and to the 50 L water storage tank 1, and the water supply pump, which is a diaphragm type metering pump. (2) It is supplied to the desalination chamber 10 so that the linear velocity is 10 cm / sec, and it circulates to the water storage tank 1 The brine of the concentrated brine reservoir 12 of 20 L was supplied to the salt concentrate chamber 11 so that the linear velocity was 3 cm / sec by the concentrated brine transfer pump 14 which is a diaphragm-type metering pump. DC current was applied from the rectifier at a current density of 3 to 4 A / dm ² (at this time, the applied voltage was 55 to 60 Volt), and the conductivity value of the conductivity indicator controller (ECIS) in the mineral brine circulation line was 10. When NaCl was removed at ˜12 dl / cm, the main component analysis values of NaCl-removed liver were as shown in Table 4 below.

At this time, 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 7 to be discharged to the upper portion of the cathode chamber 6.

Table 4 Analysis of Principal Components of NaCl-Depleted Grafts

ingredient NaCl KCl MgCl ₂ MgSO ₄ Moisture and other ingredients Concentration of components (wt%) 0.52 0.28 15.8 5.2 78.2

II. Steps to Make a Mineral Modifier

Injecting one type of calcium agent from calcium citrate, calcium lactate, calcium pantothenate, calcium gluconate or calcium chloride into the NaCl-removed liver water Adjust the mineral balance to the weight ratio of Ca / Mg in the range of 2 to 6, and then add citric acid, citrate, tartaric acid, tartarate, succinic acid, and pumpkin 5-15 parts by weight of one selected from a salt acid, malic acid, malic acid, fumaric acid, fumaric acid, fumaric acid, gluconic acid, gluconate, lactic acid or lactic acid salt, 5-15 parts by weight of one of sucrose or trehalose is added and stirred to form a mineral regulator.

In addition, the NaCl-removed brine itself can be used as a mineral regulator for cost savings.

In addition, one type of calcium agent may be injected into calcium chloride (Calcium citrate), Calcium lactate, Calcium pantothenate, Calcium gluconate, or Calcium chloride. What adjusted the mineral balance in the range of 2-6 weight ratio of Ca / Mg can also be used as a mineral regulator.

Example 2

Ca / Mg weight ratio by injecting 5.64 kg of calcium chloride dihydrate (CaCl ₂ · 2H ₂ O, Ca content 27 wt%) into 10 kg (Mg content of 5.08 wt%) of NaCl-reduced brine produced in Example 1 When the mineral balance was adjusted to A3, 1 kg of citric acid and 1 kg of sucrose were injected and stirred to dissolve to form a mineral regulator. The composition of the main minerals was as shown in Table 5 below.

Table 5 Analysis of Major Mineral Components of Mineral Modifiers

ingredient Sodium (Na) Potassium (K) Magnesium (Mg) Calcium (Ca) Moisture and other ingredients Concentration of components (wt%) 0.20 0.15 5.08 15.25 79.32

III. Use of mineral modifiers in food and beverages

The mineral regulator is added to the demineralized water desalted by adding seawater or deep sea water to be used as water for beverages and food processing processes, and also used as mineral additives in food processing processes.

If the deep sea water is used to make the demineralized water into the beverage, the hardness is adjusted in the range of 50 to 100 mg / l, and the water is used in the liquor manufacturing process in the range of 250 to 1,000 mg / l.

Example 3

After warming the deep sea water at 25 ° C., the mineral modifier produced in Example 2 was injected into demineralized water obtained by performing microfiltration, nanofiltration, first reverse osmosis filtration, and second reverse osmosis filtration to remove salt. Drinking water adjusted to 82mg / L was supplied to 10 panelists by drinking mineral water of D- company on the market. The results were as shown in Table 6 below.

Table 6 Results of comparing and tasting the beverages made in Example 3 with those sold on the market (unit: person)

Item very good. good. same. Can not do it. Very bad flavor 8 2 - - - Refreshing feeling 7 3 - - - Comprehensive Evaluation 8 2 - - -

As shown in Table 6 above, the mineral adjuster prepared in the present invention is added to the demineralized water after desalination of the deep sea water to adjust the hardness (adjustment of mineral components), and has a better taste and refreshing feel than mineral water sold on the market. It turned out to be.

1 is a change in concentration of various salts according to the specific gravity of the concentrated water by the concentration of deep sea water

Figure 2 is a process chart for removing NaCl contained in the liver by electrodialysis

Figure 3 is a process for removing NaCl contained in the water by electroextraction

Figure 4 is a phase diagram of the H ₂ O-NaCl system according to the freezing of brine

1: water storage tank 2: water transportation pump

3: electrodialysis device 4: anode

5: cathode 6: anode chamber

7: cathode chamber 8: monovalent anion selective exchange diaphragm

9: monovalent cation selective exchange diaphragm 10 desalting chamber

11: salt concentration room 12: concentrated brine reservoir

13: concentrated brine transfer pump 14: salt extraction device

15: Salt Extraction Room 16: Air Blower

17: diffuser ⓢ: Solenoid valve

pHIS: pH indicating switch M: Motor

LS: Level switch BI: Baume indicator

BIS: Baume indicating switch

DOI: Dissolved oxygen indicator

ECIS: Electric conductivity indicating switch

Claims

In the production of mineral regulators to adjust minerals in food processing, water and beverages,

Concentration of deep sea water to produce NaCl by removing electrolytic dialysis device using monovalent cation selective exchange diaphragm and monovalent anion selective exchange diaphragm. The process of removing NaCl selected from the process of removing NaCl by the electroextraction device using the valent cation selective exchange diaphragm and the monovalent anion selective exchange diaphragm or the precipitation and removal of NaCl while producing ice by freezing the brine. Producing a brine from which NaCl contained in the brine is removed,

Injecting one type of calcium agent from calcium citrate, calcium lactate, calcium pantothenate, calcium gluconate or calcium chloride to the NaCl-removed liver water Adjust the mineral balance to the weight ratio of Ca / Mg in the range of 2 to 6, and then add citric acid, citrate, tartaric acid, tartarate, succinic acid, and pumpkin Acid salt, malic acid, malic acid, malic acid, malic acid, malic acid, fumaric acid, fumaric acid, gluconic acid, gluconate, lactic acid or lactate 5-15 parts by weight of the kind, and 5-15 parts by weight of one of sucrose or trehalose, and stirring and dissolving to form a mineral regulator A method of making mineral regulators using the brine produced from layered water.

In the processing of minerals in food processing, water and beverages, NaCl contained in the by-products produced by the production of salt by concentrating deep sea water to produce salts and monovalent cation selective exchange diaphragm and 1 The process of removing NaCl by electrodialysis using an anion selective exchange diaphragm, the process of removing NaCl by an electroextraction apparatus using a monovalent cation selective exchange diaphragm and a monovalent anion selective exchange diaphragm, or by freezing the ice A method of removing one of NaCl selected from the processes of precipitation and removal of NaCl during production.

In the processing of minerals in food processing, water and beverages, NaCl contained in the by-products produced by the production of salt by concentrating deep sea water to produce salts and monovalent cation selective exchange diaphragm and 1 The process of removing NaCl by electrodialysis using an anion selective exchange diaphragm, the process of removing NaCl by an electroextraction apparatus using a monovalent cation selective exchange diaphragm and a monovalent anion selective exchange diaphragm, or by freezing the ice A step of removing NaCl selected from the process of precipitation and removal of NaCl while producing a step of producing a salt water from which NaCl contained in the water is removed;

Injecting one type of calcium agent from calcium citrate, calcium lactate, calcium pantothenate, calcium gluconate or calcium chloride to the NaCl-removed liver water Method of using a mineral adjuster in which the mineral balance is adjusted in the range of 2 to 6 weight ratio of Ca / Mg.

A method of using a mineral modifier selected from claim 1, 2 or 3 as a mineral modifier in a beverage, water in a food processing process or a food processing process.