KR20090091260A - A method to produce function rice using mineral water produced by deep sea water - Google Patents

Abstract

A method for manufacturing a functional rice by using mineral water produced from deep sea water is provided to dip the rice plant or the rice in the mineral water from which NaCl is removed and manufacture the functional rice in which the mineral component is high is manufactured. A method for manufacturing a functional rice includes next steps. The deep sea water, the NaCl of the concentrated deep sea water or the brine which in the salt manufacturing process is produced are desalinized. The mineral water is produced. After the rice or the rice plant which dehydrate is dipped, it is dry and the functional rice is manufactured. The desalination process is selected one of the electrolytic extraction process and the freezing process. The functional material component is added to the mineral water. The functional material is a mixture of chitosan, tocopherol, taurine, lysine, protheoglycan, the chondroitin sulfate, propolis, blackgrass, the shark ointment, yeast, and enzyme.

Description

A method to produce function rice using mineral water produced by deep sea water}

The present invention relates to a method for producing functional rice, and more particularly, a functional additive is added to a mineral water obtained by removing the excess NaCl by taking the deep sea water of the deep sea layer deeper than 200m from the sea surface. Then, the present invention relates to a method of manufacturing functional rice having a high mineral content by immersing rice or rice.

In general, the manufacturing method of functional beauty in the prior art, such as ginseng, red ginseng, jujube, hamcho (鹹 草), wolfberry, pine needles, round, herb extracts such as licorice, onion, grape, plum, garlic Extracts of vegetables, extracts of teas such as green tea, black tea, extracts of mushrooms such as pine mushrooms, shiitake mushrooms, chaga mushrooms, mushrooms of mushrooms, extracts of seaweeds such as kelp, chitosan , Tocopherol, vitamins, vitamins, lysine, iron, calcium, vegetable or animal dietary fiber additives, and then, if necessary, gelatin Functional starch by coating with one kind of coating selected from starch, cyclodextrin, agar solution, gum arabic or alginic acid, and then dried. various Not to push the development of the mineral-containing functionality.

In the case of Japanese Patent Publication No. 2005-278508, a technique using functional additives and deep sea water has been proposed, but in the case of simply using deep sea water as water, there is a problem that NaCl is excessively infiltrated into functional beauty because it is excessively salty. .

Literature Information of the Prior Art

[Document 1] Republic of Korea Patent Registration No. 10-0464591 (2004.12.22)

[Document 2] Korean Patent Registration No. 10-0470189 (2005.01.26)

[Document 3] Korean Patent Registration No. 10-0521157 (2005.10.06)

[Document 4] Korean Patent Registration No. 10-0563269 (2006.03.15)

[Document 5] Republic of Korea Patent Registration No. 10-0572578 (2006.04.13)

[Patent 6] Japanese Patent Laid-Open No. 2005-278508 (2005.10.13)

An object of the present invention is to provide a method for producing a functional mineral having a high mineral content by infiltrating the mineral component into the tissue of rice using the deep sea water of the deep seabed deeper than 200m in the sea surface containing a large amount of useful mineral components .

The present invention collects the deep sea water of the deep seabed deeper than 200m from the sea surface and warms it to 20-30 ℃, and the deep sea water from which the solids are removed by the filtration process or the deep sea water is subjected to reverse osmosis filtration to demineralized water. The mineral water produced from the salt manufacturing process is mixed with the concentrated deep seawater which is not filtered in the producing process, and the mineral water is produced from the deep sea water by desalting NaCl using one of the electrodialysis, electro-extraction or freezing processes. Step and adding a functional additive to the mineral water, and immersed dehydrated after washing the rice or rice with fresh water, and then dried to produce a functional beauty.

The present invention is expected to be widely used in the production of functional non-functional ingredients that require mineral ingredients, since the deep sea water containing a variety of minerals useful for health can be manufactured with a high mineral content.

First, when examining the characteristics of deep sea water, the deep sea water is a harmful heavy metal containing various mineral components necessary for the growth of animals and plants, as shown in the following Table 1 "Analysis of Importance of Deep Sea Water and Superficial Seawater". The ingredient is contained in extremely small amounts and has a clean characteristic with low concentration of harmful microorganisms and pollutants.

Table 1 Analysis of Significant Values in Deep-sea and Superficial Seawater

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%) 2.69 2.75 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 - (㎎ / ℓ}} ) 2,836 2,627  Nutrient salts NH ₄ ⁺ ammonia nitrogen (mg / l) 0.05 0.03 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) 0.4001 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

Although the history of deep sea water use is very short, it has been developed in the field of fisheries until now, but even in non-fishing fields such as food, medical, health industry, beverage, cosmetics, soil conditioner and microbial culture. We are doing various researches.

Deep sea water is generally called deep sea water that is deeper than 200m above sea level, and unlike surface sea water, sunlight does not reach, so plankton and life cannot grow, so nutrients ( Compared with the seawater of the surface because the concentration of water is high and there is no contaminant in the surface seawater because it is not mixed with the surface seawater due to the density difference according to the water temperature. It has characteristics such as low temperature stability, cleanliness, eutrophicity, mineral balance, and maturation.

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 the seasons.

In particular, deep sea waters in the East Sea of Korea settled by dense differences in cold seawater that melted the drift ice in the Sea of Okhotsk, off the Vladivostok between Ostrov Sakhalin and Hokkaido. As the deep water flows in and blocks the Japanese archipelago and slows down, the deep seabed deeper than 300m from the sea level, the water temperature is 1 ~ 2 ℃ throughout the year, and it is off the coast of Muroto, Kouchi Prefecture, on the Hawaii or Japan Pacific coast. Compared with deep water etc., it has a characteristic low about 8-11 degreeC.

2. Cleanliness

Because it is deep in the seabed, 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 include less suspended suspended solids. 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 surface water intake systems, the adherent organisms propagate in the intake pipe, and the resistance of the pipe increases and it becomes impossible to take in water. The total number of live bacteria such as microorganisms, chlorella, etc. is characterized by a small amount from one tenth to one hundredth of the surface number.

③ chemical cleanliness

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

3. eutrophicity

Compared to surface seawater, marine deep water contains nitrogen, phosphorus, and silicic acid, which are nutrient sources for algae and phytoplankton (mainly diatoms, microorganisms with chlorophyll), which are a source of plant and plant growth. There is a characteristic that contains 10 times rich in inorganic nutrients.

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 and are accumulated in the deeper layers below. High concentrations of inorganic nutrients.

4. Characteristics of minerals

Deep ocean waters have properties that contain most of the elements present on Earth.

Although there are many important elements necessary for the growth of animals and plants, the mineral balance is said to contain extremely small amounts of deeply related to human health, such as copper and zinc, which are essential trace elements that are harmful if ingested in large quantities. There is a good character.

5. Aging

Deep sea water has a lower pH than superficial sea water (around 7.8), while the organic content is low and the deep sea water is separated from the sea water and the clusters of water molecules are kept in small groups for a long time under low pressure and high pressure. The water quality is stable with micro-clustered water.

In the present invention with reference to the accompanying drawings a method for producing a functional mineral having a high mineral content by using the characteristics that contains a variety of mineral components in the seabed deeper than 200m depth from the sea surface using the above-described principle Is the same as And in the present invention "part" indicating the ratio of mixing means parts by weight.

I. Steps to produce mineral water

1. Intake and heating treatment process

The ocean deep water of the seabed deeper than 200m from the sea level is taken out and warmed up so that the subsequent treatment can be smoothly processed.

Deep sea water intakes deep sea water from the sea floor deeper than 200m deep from the sea surface, and the intake method is to take down pipes from the ship to deeper than 200m below sea level, or install pipes from the sea surface to deep seabed deeper than 200m deep. Water is collected by pump or pipe is installed at sea level deeper than 200m from sea level, and water intake well is installed below sea level to collect water by Siphon principle.

The deep sea water withdrawal has low viscosity and high treatment efficiency, so it is inferior in treatment efficiency, so it is supplied with heat from a boiler (in summer, the surface water temperature may be used) Send to.

2. Filtration Process

In the filtration process, sand filtration (Sand filter) to remove the suspended solids (SS: Suspended solid) in the water, and then the filtered water is sent to the process to demineralize NaCl to produce mineral water.

When the filtered water is produced in the production of beverages, it is sent to the desalination production process, and the produced demineralized water is sent to the beverage production process, and the deep sea water concentrated during desalination is desalted with NaCl to produce mineral water. .

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, the filtration speed is 6 ~ 10m / hour, the effective diameter of the filter sand is 0.3 ~ 0.45 The thickness range is equal to or less than 2.0, and the uniformity factor is 2.0 or less, and the thickness of the filtrate 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.

3. Process for producing concentrated deep sea water

In the case of producing the beverage in the sand filtered filtrate in the filtration process, after the microfiltration (Ultrafiltration) or ultrafiltration (Ultrafiltration), the nanofiltration (Nanofiltration) and reverse osmosis filtration (Reverse osmosis filtration) The filtered demineralized water is sent to the beverage production process, and the concentrated deep sea water is filtered to demineralize NaCl to produce mineral water.

Microfiltration and ultrafiltration are independent of the type of filtration membrane, and the supply pressure of the pump is determined in consideration of the filtration speed and the pressure loss according to the specification of the vendor.

In microfiltration or ultrafiltration, the filtered water is treated with a water 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... … … … … … … … … … … … … … … … … … … … ①

Where 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.

In deep sea water, such as CaSO ₄ and CaCO ₃ , the solubility in water is low, so the scale is generated when concentrated, which can lower the treatment efficiency due to fouling of the membrane. The filtered water from which (CaSO ₄ , CaCO ₃ , SrSO ₄ ..., Etc.) was removed is fed to a reverse osmosis filtration process.

In the nanofiltration step, reverse osmosis sulfate ions that cause membrane clogging in the filtration step (SO ₄ ^{2 -)} in the following to remove, de-brine the sending filtered by reverse osmosis filtration step is to send the beverage production process, without being filtered and concentrated Deep ocean water is sent to the NaCl desalination process.

The membrane modules of nanofiltration and reverse osmosis filtration are tubular, hollow fiber, spiral wound, plate and plate. 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 crosslinked water-soluble vinyl polymer may be used. The membrane structure has a dense layer on one side of the membrane, and is an asymmetric membrane composed of micropores gradually from a large pore toward the inside of the membrane or toward one side of the membrane. A composite membrane having a very thin separation layer formed of another material on the dense layer of the membrane can be used, and piperazine polyamide-based composite membranes are preferred. It is not limiting.

Nanofiltration process, the sulfate ions that cause scale (Scale) generated in the reverse osmosis filtration of the post-processing (SO ₄ ^{2 -)} as is the main purpose to remove, deep ocean water from the microfiltration or ultrafiltration removal of the fine solid material in water Is sent to a nanofiltration process where the unfiltered sulfate-containing water is discharged and the filtered water is sent to reverse osmosis filtration.

Transmission sequence of the ion in the nanofiltration membrane, if the cation is ^{Ca 2 +> Mg 2 +>} Li +> Na +> K +> and NH ₄ ^+, if 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 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 the deep seawater with a salt concentration of 3.5 wt%. In the case of spiral, the membrane permeability is 0.7 to 1.4 m 3 / If m 2 · day, the membrane permeate amount is 70 to 80% of the inflow rate.

In the reverse osmosis filtration process, the deep sea water filtered in the nanofiltration process is filtered and the demineralized water is sent to a beverage production process, and the concentrated deep sea water, which is not filtered, is desalted with NaCl to produce mineral water.

When the reverse osmosis filtration process is a spiral filtration membrane, when the operating pressure is 55 to 56 kg / cm 2 and the membrane permeate is 0.5 to 0.8 m 3 / m 2 · day, the salinity of the filtered water is removed in the range of 99.0 to 99.85 wt%. Deep seawater is concentrated as 40-60% of the influent is filtered.

4. Process for producing mineral water by desalting NaCl

When the pre-treated deep sea water, concentrated deep sea water, and the brine produced in the salt manufacturing process are supplied to the deep sea water storage tank (1), the removal of excess NaCl is carried out by the monovalent cation selective exchange diaphragm and monovalent anion selection. Desalting NaCl by electrodialysis apparatus 3 using exchange diaphragm, desalting NaCl by electroextraction apparatus 14 using monovalent cation selective exchange diaphragm and monovalent anion selective exchange diaphragm or freezing While producing ice by the device, NaCl is sent to the process of desalination of NaCl selected from the process of precipitation and removal of NaCl, and the mineral water from which NaCl is removed is sent to the immersion process of the non-functional manufacturing stage.

① Desalination of NaCl by electrodialysis

In the present invention, desalination treatment is performed by desalting NaCl contained in the deep seawater pre-treated by electrodialysis apparatus, the deep seawater concentrated in the reverse osmosis filtration process, and the brine produced in the salt manufacturing process. The production of water is carried out by separating the ionic solute membrane by permeation of the direct current power supply as a driving force, and the cation exchange diaphragm separates monovalent cations having a fixed negative charge. The membrane which selectively permeates is used, and the anion exchange membrane uses the membrane which selectively permeates the monovalent anion which has a fixed electrostatic charge.

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. Pretreatment of the deep seawater supplied to the deep seawater reservoir 1 while applying a direct current from the rectifier to the cathode 5 of the chamber 7, the deep seawater concentrated without being filtered by the reverse osmosis filtration device, and salt production The brine produced in the process is supplied to the desalination chamber 10 by a deep sea water transfer pump 2 to remove NaCl in a concentration range of 400 to 800 mg / l, while a part is returned to the deep sea water storage tank 1, The number of demineralized minerals can be measured by an electric conductivity indicating switc (ECIS). h) to the immersion process by the operation of the solenoid valve (Solenoid valve (ⓢ)), the concentrated brine in the concentrated brine reservoir (12) in the salt concentration chamber (11) by the concentrated brine transfer pump (13) 11) circulating to the concentrated brine reservoir 12, Na ⁺ ions in the deep sea water penetrate the monovalent cation selective exchange diaphragm 9 by electrical attraction, and the salt concentration chamber 11 on the cathode 5 side. Cl ⁻ ions pass through the monovalent anion selective exchange diaphragm 8 to the salt concentration chamber 11 on the positive electrode side 4 so that the specific gravity of the brine concentration in the brine reservoir 12 is 12-18 °. Concentrated brine concentrated in the Be range is sent to the salt manufacturing process by operating the solenoid valve (ⓢ) by BOME (Baume indicating switch).

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 ②.

TSS (ppm) = 640 X EC (mS / cm). … … … … … … … … … … … … … … … … … … ②

 In order to increase the processing efficiency of the electrodialysis apparatus 3, 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 inversely proportional to the thickness of the diffusion layer, the monovalent anion selection in the present invention depends on the NaCl concentration in the mineral water, which is the demineralized water to be drained, and the NaCl concentration of the concentrated brine. An electrodialysis apparatus for forming a desalting chamber 10 and a salt concentration chamber 11 in which the exchange diaphragm 8 and the monovalent cation selective exchange diaphragm 9 are alternately arranged between the anode 4 and the cathode 5 ( 3) send the deep sea water of the deep sea water storage tank (1) to the desalination chamber (5) by the sea deep water transfer pump (2), remove NaCl, and then circulate some of the deep sea water storage tank (1), and concentrate the brine reservoir (12). ) Concentrated brine by the concentrated brine transfer pump (13) It is sent to the concentration chamber 11 and circulated to the concentrated brine reservoir 12. By supplying a large amount of concentrated brine passing through the salt concentration chamber 11 so that the scale component is not generated in the salt concentration chamber 11 while improving NaCl removal efficiency, it is possible to prevent scale trouble. In addition, by supplying the concentrated brine having a high NaCl concentration to the salt concentration chamber 11, the liquid resistance of the current can be reduced and the limit current density can be increased, thereby improving the processing performance of the electrodialysis apparatus 3. Can be.

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

The monovalent cation selective exchange diaphragm 9 used in the present invention is a diaphragm that selectively transmits only monovalent cations while suppressing the permeation of bivalent or higher 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 polymers such as polyvinylpyridine or graft polymers whose main chain is polystyreneimine or graft polymer whose side chains are made of polyvinyl pyridine are polystyrene, and the main chain of graft polymer is composed of cation exchange membrane. Any molecule having the same molecular structure as the main chain or the side chain can be used without limitation. Preferably, polyethylene, polypropylene, and polychloride Molecular structure with only a fixed monovalent cations in the main chain or side chain with the same molecular structure and a polymer consisting of a cation exchange membrane permeability (透過能) ^- carbonyl (Polyvinylchlorde), polystyrene (Polystyrene) or the like negatively charged R-SO ₃ Cation exchange diaphragms such as polyvinylpyridine, polyvinylamine or polyethyleneimine membranes can be used, and in particular, polystyrene-graft-ethylene imine of polystyrene-divinylbenzene-based Can be.

And 1 is selected, an anion exchange membrane (8) is a monovalent cation selected exchange membrane (9), as opposed to a power failure by a diaphragm that can be monovalent optionally replaced with only negative ions and (正電荷) R-NH ₃ ⁺ of the polymer chain ( It is fixed to the polymer chain and fixed to the membrane, so it is also called static charge membrane, and the ion exchange group is cross-linked by aliphatic hydrocarbon, and the surface of the membrane An anion exchange diaphragm in which a thin layer of a polymer material having a cation exchange group is formed on the surface, and it is preferable to perform quaternization simultaneously with crosslinking with aliphatic hydrocarbons to the monomer introduced into the exchange group. Examples of the polymer material having an exchange group include a polymer electrolyte having a cation exchange group and an insoluble polymer having a linear polymer electrolyte or a cation exchange group. For example, a polyelectrolyte having a cation exchange group having a molecular weight of 500 or more in a sulfonate such as Ligninsulfonate, a phosphate ester salt such as a higher alcohol phosphate ester, a methacrylic acid, a styrene sulfonic acid (Styrene) Phenols containing linear polymer electrolytes containing a plurality of monomer units having a carboxylic acid group (-COOH) or a sulfonic acid group (-SO ₃ H), such as sulfonic acid, and a cation exchange group. And a diaphragm for selectively exchanging monovalent anions such as an insoluble polymer having a cation exchange group such as a condensation of aldehydes with an aldehyde.

The anode 4 of the anode chamber 5 of the electrodialysis apparatus 3 is made of a corrosion-resistant material and a DSA (Dimensionally Stable Anode) electrode or a platinum plated electrode having high hydrogen and oxygen generation overvoltage. 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 is Raney nickel having 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 in order to reduce the processing efficiency due to the formation of scale or slimes such as organic matter. 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 cathode chamber 6, and the electrolyte solution (cathode chamber solution) supplied to the cathode chamber 7 is Seawater (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 concentrated brine reservoir (12) with a specific gravity of 12-18 ° Be is sent to the salt manufacturing process.

② Process for desalting NaCl by electric extraction device

The electroextraction apparatus 14 for removing excess NaCl contained in the deep sea water includes a monovalent cation selective exchange diaphragm 9 and 1 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 desalting chamber 10 separated by the anion selective exchange diaphragm 8 is installed in multiple stages, it will be described in detail with reference to the accompanying drawings.

FIG. 3 is a "process diagram for producing mineral water by removing NaCl contained in mineral brine by electroextraction." The negative electrode 5 between the positive electrode 4 and the negative electrode 5 installed inside the salt extraction chamber 15 is shown in FIG. The side by which the monovalent cation selective exchange diaphragm 9 is installed and the anode 4 by which the monovalent anion selective exchange diaphragm 8 is installed, and the isolated desalination chamber 10 is installed in multiple stages, When the NaCl contained in the mineral brine is removed by a device for removing NaCl, the salt extraction chamber 15 and the desalination chamber 10 are transferred to the deep sea water transfer pump 2 by the deep sea water stored in the deep sea water storage tank 1. The deep sea water to be supplied to the desalination chamber 10 is circulated to the deep sea water storage tank 1, and the air in the air from the blower 16 is passed through the diffuser pipe 17 installed at the bottom of the salt extraction chamber 15. While aeration, an electric field of 4-50 volts DC is applied from the rectifier. When an ectric field is formed, Na ⁺ ions contained in the deep sea water of the desalting chamber 10 by electrophoresis penetrate the monovalent cation selective exchange diaphragm 9 on the cathode 5 side to form a salt. Cl ^- ions are transferred to the extraction chamber 15, and the concentrated brine is concentrated in the BOMEDO as the Cl ^- ions pass through the monovalent anion selective exchange diaphragm 8 toward the anode 4 to the salt extraction chamber 15. When the specific gravity of Baume's Baume's hydrometer indicating switch (BIS) is concentrated to 12-18 ° Be, the solenoid valve (ⓢ: Solenoid valve) is operated to discharge the brine from the salt production process, and the desalination chamber (10 The electroconductivity of the electrical conductivity indicating switch (ECIS) installed in the NaCl-depleted mineral water line in the deep ocean water within the range of 6-12 ㎳ / cm is used to operate the solenoid valve. Send to immersion process.

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 of the deep sea water alternately according to the processing capacity. Install multiple stages in parallel.

The above-described reaction mechanism for removing NaCl from the NaCl in the deep sea water by electroextraction is as follows.

NaCl contained in mineral brine is dissociated into Na ⁺ ions and Cl ⁻ ions by hydrolysis in water as in the following reaction ③.

^{_{NaCl -H 2 O → Na + +}} Cl - ... … … … … … … … … … … … … … … … … … … ③

When 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 deep sea water in the desalting chamber 10 by electrophoresis are negative electrode (5). The monovalent cation selective exchange diaphragm (9) side passes through the monovalent cation selective exchange diaphragm (9) to the salt extraction chamber (15), and the Cl ⁻ ions pass through the monovalent anion selective exchange diaphragm (8) on the positive electrode side (4) to extract salts. As it moves to the chamber 15, NaCl is removed from the deep sea water of the desalination chamber 10.

Na ⁺ --septum-> Na ⁺ ... … … … … … … … … … … … … … … … … … … ④

Cl ^{- -} Diaphragm ^- → Cl - ... … … … … … … … … … … … … … … … … … … ⑤

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

Na ⁺ + Cl ^−- → NaCl... … … … … … … … … … … … … … … … … … … ⑥

On the anode 4 and cathode 5 sides of the salt extraction chamber 15, when the following side reactions occur, odor generation and power consumption may increase. The aeration of air through the diffuser (17) ensures that the following side reactions are suppressed as much as possible.

2Cl ⁻ → Cl _{2 ( aq )} + 2e ⁻ . … … … … … … … … … … … … … … … … … … … … ⑦

Cl _{2 ( aq )} → Cl _{2 (g)} ↑. … … … … … … … … … … … … … … … … … … … … … ⑧

Cl _{2 ( aq )} + H ₂ O → HClO _{( aq )} + HCl... … … … … … … … … … … … … … … … … ⑨

^{_{2HClO (aq) + 2H + +}} 2e - → Cl 2 (g) ↑ + 2H 2 O ... … … … … … … … … … … … ⑩

^{_{2H 2 O + 2e - → 2OH}} - + H 2 (g) ↑ ... … … … … … … … … … … … … … … … … … ⑪

At this time, the supply amount of air supplied from the blower 16 through the diffuser pipe 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 are made of flame resistant stainless steel, titanium, epoxy coating or lining of carbon steel, Lining of fiber glass reinforced plastic (FRP) is used.

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 in the electrodialysis apparatus 3.

③ Process for desalting NaCl by freezer

In the case of removing NaCl by refrigeration of NaCl contained in the deep sea water, the phase equilibrium of the H ₂ O-NaCl system according to FIG. 4 refrigeration and the state diagram when the sea water is cooled are shown in FIG. 4. Likewise, mineral salt water is supplied to the refrigerating unit with the insulated cooling coil, and the temperature of the mineral salt water in the refrigerating unit is -4 ° C (surface sea water or the original deep sea water) while circulating the refrigerant from the refrigerator through the cooling coil. Is started to freeze at -2 ℃), the sherbet ice production will begin to produce, and if the temperature continues to cool down to -11 ~ -12 ℃ semi-solid ice is produced, and further cooled to When cooled to -22 ~ -23 ℃, NaCl in mineral brine begins to be removed while producing a solid ice containing NaCl · 2H ₂ O, NaCl in the solution in the present invention when cooled to -25 ~ -26 ℃ Removed Number of minerals are produced. At this time, the specific gravity of the mineral water is 25 to 26 ° Be.

When NaCl is removed by freezing deep sea water, the mineral water produced is high in concentration. Therefore, demineralized or fresh water filtered through reverse osmosis filtration should be diluted to 3 ~ 5 ° Be.

Example 1

The positive ion 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 membrane (9: Aciplex, which selectively transmits only monovalent cations). Trademark) K-102, manufactured by Nippon Chemical Co., Ltd.) and the anion-exchange diaphragm 50, each of which has a monovalent anion selective exchange diaphragm (8: Aciplex A-102; Electrodialysis apparatus in which a multi-stage (50-stage) was alternately installed as shown in FIG. 2 between the anode (4), which is a DSA electrode coated with RuO ₂ -TiO ₂ , and the cathode (5), which is a stainless steel electrode, on a titanium plate ( 3) was prepared.

The deep seawater storage tank (1) of 50L warmed the deep seawater of Table 1 to 25 ℃ and then sand-filtered filtration water is injected, and the deep dialysis water pump (2) is a diaphragm (Diaphragm) metering pump and the electrodialysis It is supplied to the desalination chamber 10 of the apparatus 3 so that the membrane surface velocity may be 10 cm / sec, and it circulates in the marine deep water storage tank 1, and the brine of 20 liter concentrated brine storage tank 12 is diaphragm-made. The concentrated brine transfer pump 13, which is a type metering pump, is supplied to the salt concentration chamber 11 so that the linear velocity is 3 cm / sec. When applied at 4A / dm ² (applied voltage was 55 ~ 60Volt), when the conductivity value of ECIS of mineral water line was desalted to 8 ~ 10㎳ / ㎝, The analysis of material importance is shown in Table 2 below.

At this time, the specific gravity of the brine in the concentrated brine storage tank 12 was adjusted to 12 ° Be, the solution of the cathode chamber (7) was supplied to the lower portion of the cathode chamber (7) by supplying 5wt% Na ₂ SO ₄ aqueous solution at 50 kW / min Discharged to the lower portion of the anode chamber (6).

Table 2 Analysis of Significance of Demineralized Mineral Water Emissions from Electrodialysis Processes

Item Pretreated Marine Deep Water NaCl demineralized mineral water from electrodialysis      pH             7.8                  7.3  NaCl (wt%)             2.69                  0.82 Ca ^{2 +} (㎎ / ℓ)           406                392 Mg ^{2 +} (㎎ / ℓ)         1,270              1,219 K ⁺ (mg / L)           414                126 _{^{SO 4 2 - (㎎ / ℓ}} )         2,836              2,751

II. Function not manufactured

1. Pretreatment process of rice or rice

Rice and rice that can be used in the functional non-manufacturing of the present invention may use milled brown rice, white rice, or harvested and threshed rice (hell, silk). Can be used.

Brown, white rice or threshed rice is washed with fresh water (mineral water, tap water, demineralized water filtered by reverse osmosis filtration device) to remove foreign substances adhering to the surface, and then screen, breeze or bamboo It is entangled in such a long shape and naturally dehydrated in a strip that is sent to the dipping process.

2. Immersion Process

The demineralized mineral water of NaCl contained in the deep sea water is supplied to an immersion tank equipped with a heating jacket, and the water temperature is heated to a range of 35 to 45 ° C., followed by injecting treated rice or rice in a pretreatment process. After soaking for 2 to 6 hours, the mineral component penetrates into the rice tissue and is sent to a drying process.

Ginseng, red ginseng, turmeric, jujube, hamcho (구 草), gojija, pine needles, mulberry leaves, sulyeonhwa (雪 蓮花), round, licorice in the mineral water desalted NaCl contained in the deep sea water Herbal extracts such as 甘草, extracts of vegetables such as onions, grapes, plums, garlic, green tea, extracts of teas such as black tea, matsutake mushrooms, shiitake mushrooms, Grifola frondosa, agaricus ( Agaricus mushrooms, Chaga mushrooms, Sparassis crispa, Ganoderma lucidum mushrooms, Sichuan mushrooms, Mushroom extracts such as Cordyceps sinensis, Seaweeds such as kelp, Chitosan, Tocopherol, Taurine, β-glucan, SOD material, vitamins (Vitamins), lysine (Lysine), proteoglycan, Chondroitin sulfate, propolis, black vinegar, shark ointment ( 억), yeast, enzyme, blood pressure increase Add functional ingredients containing at least one of peptide, iron, calcium, vegetable fiber or animal fiber to 0.1 to 20 parts of rice or rice to add functional beauty It can also manufacture.

At this time, if the functional material ingredient does not penetrate into the rice tissue, gelatin, starch, cyclodextrin, agar solution, pectin, mannan, curd 100 g of a coating agent selected from plant gum or alginic acid, such as curdlan, cellulose derivative, xanthan gum, gum arabic, etc. 0.5-5 parts are injected and coated, followed by drying to prepare a functional beauty.

3. Drying and Packaging Process

In the immersion process, the rice or rice infiltrating minerals into the tissue of the rice is withdrawn and dried to a water content in the range of 5 to 12 wt%, and then the rice is packaged and functionally treated. To prepare, rice is milled (搗 精) and then packaged to produce a functional beauty.

The drying process is natural drying, rotary dryer, drum dryer, band dryer, vacuum dryer, infrared ray dryer, hot air dryer or hot air dryer. Drying is performed by one type of drying method in a fluidized bed dryer, and the present invention is not particularly limited to the drying method.

Example 2

200 kg of threshed rice is poured into a 500 liter plastic container, and 250 liters of mineral water produced in Example 1 is injected thereinto, soaked for 3 hours, extracted, and naturally dried to a water content of 12 wt%. The results of analysis of the main minerals magnesium, calcium, and potassium contained in the functional rice made from rice polished in rice are shown in Table 3.

Table 3 Analysis of Magnesium, Calcium and Potassium Components as Important Minerals in Functional Beauty

ingredient NaCl Mg Ca K Content (mg / kg) 748 902 292 298

As shown in Table 2, it can be seen that a functional taste containing mineral components such as calcium and magnesium can be produced while having a low salt concentration.

1 is a process chart for manufacturing functional rice using mineral water produced from deep sea water

2 is a process chart for desalting NaCl by an electrodialysis process

3 is a process chart for desalting NaCl by an electroextraction process

Figure 4 is a phase diagram of the H ₂ O-NaCl system when freezing seawater

5 is a state diagram when cooling sea water

<Explanation of symbols for main parts of drawing>

1: deep sea water reservoir 2: deep sea water transfer 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: Air diffuser ⓢ: Solenoid valve

LS: Level switch M: Motor

BI: Baume indicator

BIS: Baume indicating switch

ECIS: Electric conductivity indicating switch

Claims (3)

Producing mineral water by desalting NaCl in a process selected from deep sea water, concentrated deep sea water, or salt manufacturing process in an electrodialysis process, an extraction process, or a freezing process; Method of producing functional rice using the mineral water produced from deep sea water, characterized in that the step of washing the mineral water and then immersed dehydrated rice, and then dried to make a functional non-manufacturing step. The method of claim 1, wherein instead of immersing the dehydrated rice after washing in the mineral water, it is produced from deep sea water by immersing the dehydrated rice after washing in mineral water, and then dried and milled. Method of producing functional beauty using mineral water. According to claim 1 or 2, the mineral water in ginseng, red ginseng, turmeric (대 金), jujube, hamcho (구 草), wolfberry, pine needles, mulberry leaves, sulyeonhwa (雪 蓮花), round, licorice (甘草) Herbal medicine extracts such as, onions, grapes, plums, extracts of vegetables such as garlic, green tea (추출물), extracts of teas such as black tea, Matsutake mushroom, shiitake mushroom, leaf mushroom (Grifola frondosa), Agaricus (Agaricus) Mushrooms, Chaga, Sparassis crispa, Ganoderma lucidum, Situation mushrooms, Extracts of mushrooms such as Cordyceps sinensis, Extracts of seaweeds such as seaweed, Chitosan, Tocopherol, Taurine ( Taurine, β-glucan, SOD material, vitamins (Vitamins), lysine (Lysine), proteoglycan, Chondroitin sulfate, Propolis, black vinegar, shark ointment Yeast, Enzyme, Peptide, Iron Functional beauty by using mineral water produced from deep sea water by adding functional material ingredient mixed with at least one type among calcium, vegetable fiber or animal fiber How to prepare.

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