KR100887519B1 - A method to concentrate organic matter and a mineral ingredient from deep-ocean water or bottom of the sea depths bedrock water - Google Patents

Abstract

The present invention relates to a method for concentrating organic matter and minerals from deep seawater or deep sea bedrock. More specifically, the present invention relates to cosmetic and cosmetic water, soap, bath water, and pharmaceuticals from deep sea water or deep sea bedrock. It relates to a method of concentrating organic and mineral components.

To this end, the present invention, the step of desalting NaCl of the concentrated water discharged from the reverse osmosis filtration process in the process of producing a beverage by taking the deep sea water or the deep sea bedrock of deep seabed deeper than 200m from the sea surface, Firstly, the desalted water subjected to NaCl desalination is concentrated in a second reverse osmosis filtration process, and the organic and mineral components are concentrated in a second step of evaporation and concentration. There is this.

Deep sea water, organic matter, minerals, concentration, desalination, reverse osmosis filtration, electroextraction, electrodialysis

Description

A method to concentrate organic matter and a mineral ingredient from deep-ocean water or bottom of the sea depths bedrock water}

1 is a process chart for concentrating organic matter and minerals from deep sea water

2 is a diagram illustrating the desalination mechanism by the electroextraction method

3 is a desalination process chart by the electroextraction method

4 is a desalination process chart by electrodialysis

<Explanation of symbols for main parts of drawing>

One; Brine reservoir 2; Brine Transfer Pump

3; Salt extraction apparatus 4; Salt extraction chamber

5; Desalting chamber 6; anode

7; Negative electrode 8; Anion exchange diaphragm

9; Monovalent cation selective exchange diaphragm 10; Diaphragm supporter

11; Blower 12; Diffuser

13; Electrodialysis apparatus 14; Anode chamber

15; Cathode chamber 16; Salt concentration room

17; Concentrated brine reservoir 18; Concentrated brine transfer pump

Ⓢ; Solenoid valve LS; Level switch

BIS; Baume's hydrometer indicating switch

ECIS; Electric conductivity indicating switch

The present invention relates to a method for concentrating organic matter and minerals from deep seawater or deep sea bedrock, and more specifically, in the process of preparing a beverage by taking the deep sea water or deep sea bedrock of deep seabed deeper than 200m from the sea surface. The present invention relates to a method of concentrating organic matter and minerals by desalting concentrated brine discharged from the reverse osmosis filtration process without being filtered, followed by secondary reverse osmosis filtration and evaporation and concentration.

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 the sun so that plankton and life do not proliferate. Due to the high concentration and the difference in density due to the water temperature, there is almost no contaminant present in the surface seawater because it is not mixed with the surface seawater, and it has low temperature stability and low concentration of suspended solids when compared with the surface seawater. Mineral balance characteristics with a very low level of contaminants, harmful bacteria and organic matters, rich in nutrients, which are very important for plant growth, and balanced minerals. Under long periods of high pressure and low temperature, the clusters of water molecules are small grouped for a long time, so that the surface tension is low and the permeability is good. Analysis of the aged sex (熟 成 性) major components which are known to have properties such, is contained in the deep sea water and surface sea water is equal to the contents of Table 1.

          Table 1, Analysis of Principal Components of Deep Sea Water and Surface Sea Water

         division       Ulleungdo Hyunpo Koji Prefecture Murodo, Japan 650m deep sea water Surface waters 374m deep sea water  Surface waters  General Item  Water temperature (℃)  0.5  23  11.5  20.3  pH  7.15  8.1  7.98  8.15  DO dissolved oxygen (mg / l)  6  8  7.80  8.91  TOC Total Organic Carbon (mg / l)   1.023  1.547  0.962  1.780 COD _Mn (mg / L)  0.2  0.6    -    -  Soluble evaporation residue (mg / l)  37,000   -  47,750  37,590  M-alkalido (mg / l)    -   -  114.7  110.5  Main element  Cl chloride ion (wt%)  3.41 with NaCl  3.40 with NaCl  2.237  2.192  Na sodium (wt%)  1.080  1.030  Mg magnesium (mg / l)  1,320  1,280  1,300  1,310  Ca calcium (mg / L)  393  403  456  441  K potassium (mg / L)  380  356  414  399  Br Cancel (mg / L)  65   -  68.8  68.1  Sr Strontium (mg / L)  9.9   -  7.77  7.61  B boron (mg / L)  4.7   -  4.44  4.48  Ba barium (mg / l)  0.01   -  0.044  0.025  F Fluorine (mg / l)  1.2   -  0.53  0.56 SO ₄ ^2- sulfate ion (mg / l)  2,630   -  2,833  2,627  Nutrient salts NH ₄ ⁺ ammonia nitrogen (mg / l)  0.05   -  0.05  0.03 NO ₃ ^- Nitrogen Nitrate (mg / l)  0.28  0.04  1.158  0.081 PO ₄ ^3- phosphate (mg / l)  0.16  0.026  0.177  0.028  Si silicon (mg / l)  2.8  0.44  1.89  0.32  Trace element  Pb lead (μg / ℓ)  0.11   -  0.102  0.087  Cd cadmium (µg / l)  0.05   -  0.028  0.008  Cu copper (µg / l)  0.26   -  0.153  0.272  Fe iron (㎍ / ℓ)  0.20   -  0.217  0.355  Mn manganese (㎍ / ℓ)  0.45   -  0.265  0.313  Ni nickel (µg / l)  0.36   -  0.387  0.496  Zn zinc (µg / l)  0.45   -  0.624  0.452  As arsenic (㎍ / ℓ)  0.04   -  1.051  0.440  Mo molybdenum (µg / l)  7.60   -  5.095  5.565  Cr chromium (µg / l)  0.021   - Number of bacteria  Number of live bacteria (dog / ml)    0  520   0  540  E. coli count (pcs / ml)   voice  voice    voice    voice

As shown in Table 1, the deep ocean water contains various minerals necessary for the growth of living organisms, and although scientifically accurate evidence has not yet been proved, recent research shows that deep sea water B. In deep-sea bedrock, marine microorganisms such as Pseudoalteromonas denitrificans, and Alteromonas macleodii, proliferate macrophages. It is known to excrete organic substances such as Cycloprodigiosin hydrochloride, which is effective for Atopic dermatitis, as metabolites, and it is also known as crustaceans. From fish, sugars such as trehalose and chitosan, which are excellent in moisture retention, From the alginate (Alginic acid) and total organic carbon, as shown in the organic oligomer (Oligomer) state to excrete such organisms in Table 1; can contain about 1㎎ / ℓ to (TOC Total organic carbon) standard.

The organic matter contained in the deep sea water has been found to be effective in the growth of living organisms and effective in atopic dermatitis, and is used in cosmetics, bath water, and the like. Is also published.

Conventional techniques for concentrating organic substances and minerals contained in deep seawater or deep sea bedrock have not been investigated.However, Phytomer of France freeze-dried deep seawater in Bretagne. (Freeze drying) is concentrated to produce a powder (Powder) bath, but there is a problem with high NaCl concentration and high operating costs.

Therefore, the present invention proposes a method of desalination from concentrated brine without filtering in reverse osmosis filtration process of beverage production in deep seawater or deep sea bedrock, and then concentrates organic and mineral components.

It is an object of the present invention to provide a method for concentrating NaCl desalted organics and minerals from concentrated brine without filtering in reverse osmosis filtration of beverage preparation in deep seawater or deep sea bedrock.

In order to achieve the above object, the present invention, in the process of producing a beverage by ingesting deep seawater or deep sea bedrock, desalting NaCl in concentrated brine without filtering from reverse osmosis filtration, desalination The first step is to concentrate the brine in the second reverse osmosis filtration process, the first concentrated organic material and mineral components in the second evaporation, concentration step is characterized in that the organic material and minerals finally concentrated.

The present invention is to collect the deep sea water or deep sea bedrock of deep seabed deeper than 200m from the sea surface and warmed to 20 ~ 30 ℃ sand filtration, precision filtration Prefiltration by one or two or more combinations of Microfiltration, Ultrafiltration, and Nanofiltration, and then sent to the first reverse osmosis filtration process. The present invention relates to a method for concentrating an organic substance and a mineral component from brine concentrated without being filtered, as described in detail below with reference to the accompanying drawings.

I. Desalination of brine

From the sea surface, the deep seawater or deep seawater of deep seabed deeper than 200m is collected, warmed and pretreated and sent to the first reverse osmosis filtration process. When the brine is supplied to the brine storage tank (1), the brine is stored in the brine by one of the following desalination treatment methods by the electroextraction method and desalination treatment method by the electrodialysis method. Desalting the NaCl component contained.

1. Desalination Treatment by Electro Extraction

In the present invention, the salt extraction apparatus 3 by the electroextraction method is provided with a desalination chamber 5 between the anode 6 and the cathode 7 inside the salt extraction chamber 4 as shown in FIG. 5) an anion exchange diaphragm 8 is formed on the positive electrode 6 side to transmit all anions, and a monovalent cation selective exchange diaphragm 9 penetrates the monovalent cation on the negative electrode 7 side. When the capacity is large, as shown in Fig. 3, the desalination chamber 5 is alternately provided with a plurality of stages between the anode 6 and the cathode 7.

In other words, the anion exchange diaphragm 8 used in the present invention uses an anion exchange diaphragm 8 that permeates all monovalent and divalent or more anions, and the cation exchange diaphragm monovalent cation selectively transmits only monovalent cations. The selective exchange diaphragm 9 is used to remove (demineralize) the monovalent salt NaCl and sulfate ions (SO ₄ ^{2 −} ) contained in the brine.

In the desalination method according to the electroextraction method of the present invention, an anion exchange diaphragm 8 between the anode 6 and the cathode 7 is used in the salt extraction chamber 4 as shown in FIG. , The cation selective exchange diaphragm is a salt extraction chamber of the brine storage tank (1) by the brine transfer pump (2) to the desalination apparatus by an electroextraction method composed of a desalting chamber (5) separated using a membrane that transmits only monovalent cations. (4) supplies deep seawater or deep sea bedrock to the seawater, and supplies the brine from the brine reservoir (1) to the desalination chamber (5) by the brine transfer pump (2) and returns it to the brine reservoir (1) while direct current When electricity is applied, the salt contained in the brine of the desalting chamber 5 is removed (desalting) by the following electrochemical reaction mechanism (Mechanism).

The salts contained in the brine in the desalting chamber 5 are ionized by the hydrolysis reaction as in the reaction formula ①.

^{㎜X ⇔ ㎜ + + X m -} ... … … … … … … … … … … … … … … … … … … … … … ①

Where M ⁺ is a monovalent cation (Na ⁺ , K ⁺ ..., Etc.), X ^{m −} is all anions (Cl ⁻ , Br ⁻ , SO ₄ ^2−, etc.) and m is the valence of the anion.

The monovalent cation (M ⁺ ) contained in the brine of the desalting chamber (5) passes through the monovalent cation selective exchange diaphragm (9) on the side of the cathode (7), and moves to the salt extraction chamber (4), as shown in Scheme (2). All anions (X ^{m −} ) are transferred to the salt extraction chamber 4 through the anion exchange diaphragm 8 on the anode 6 side as in the reaction equation ③.

Mm ⁺ (desalting chamber)-monovalent cation selective exchange membrane → mm ⁺ (salt extraction chamber). … … ②

X ^{m -} (desalting chambers) - anion-exchange membrane → X ^{m -} (extraction chamber salt) ... … … … … … … ③

As a result, the monovalent cation (M ⁺ ) and all the anions (X ^{n −} ) contained in the brine in the desalting chamber 5 pass through the diaphragm and are extracted and removed by the salt extraction chamber 4 as shown in Scheme ④ and desalted.

^{㎜ + + X m - → ㎜X} ... … … … … … … … … … … … … … … … … … … … … … ④

A salt extraction device (3) or an electrodialysis device (13) using a monovalent cation selective exchange diaphragm (9) through which cations selectively permeate only monovalent ions and an anion exchange diaphragm (8) through which all anions permeate When the sulfate ion (SO ₄ ^{2 −} ), which is a monovalent cation and a divalent ion, is removed from the brine, sulfates such as CaSO ₄ bonded with sulfate ions in the brine in the desalting chamber 5 are removed as sulfate ions are removed. It is characterized by the combination of chlorine ions (Cl ⁻ ) of) to calcium chloride (CaCl ₂ ).

CaSO ₄ + 2NaCl → CaCl ₂ + Na ₂ SO ₄ ... … … … … … … … … … … … … … … … ⑤

This phenomenon of changing the composition of the hydrous is called selective permeability of ions.

In this case, since CaCl ₂ has a high solubility, there is no problem of generating scale due to calcium salt.

As described in the above description, the salt extracting apparatus 3 is characterized in that the salt contained in the brine in the desalting chamber 5 has the anode chamber 14 and the cathode chamber at both ends of the electrodialysis apparatus 13. The electrolysis reaction (15) does not occur at all, and the salt extraction chamber (4) is separated and removed (condensed) in the original salt state, so that no current is required as the salt is decomposed, and the anode (6) Since the distance between the cathode 7 and the cathode 7 can be set close to each other, since a small voltage is applied at an applied voltage of 3 to 6 volts, the power consumption is low.

In the desalination process of FIG. 3, the anode 6 and the cathode 7 are alternately provided with multiple stages in the salt extraction chamber 4 by a desalination apparatus by an electroextraction method, and the anode Between (6) and cathode (7), anion exchange diaphragm (8) uses a diaphragm with no surface modification to permeate all anions, and cation selective exchange diaphragm selectively It is a process chart of the salt extraction apparatus 3 by the electroextraction method comprised by the desalination chamber 5 isolate | separated using the diaphragm whose surface was modified so that it could permeate | transmit.

When the brine that is not filtered in the first reverse osmosis filtration process in the beverage production process is introduced into the brine storage tank (1), the brine transfer pump (2) is supplied to the salt extraction chamber (4) of the salt extraction device (3) It is also supplied to the desalination chamber 5 and circulated to the brine reservoir 1.

While blowing the air in the air from the blower 11 through the diffuser 12, 3 to 10 volts of direct current is applied from the rectifier, and the electric field inside the desalination chamber 5 is removed. ), The cation (+) contained in the brine in the desalting chamber (5) by electrophoresis passes through the monovalent cation selective exchange membrane (9) toward the cathode (7) to extract the salt. In the salt extraction chamber 4, the anion (-) is transferred to the salt extraction chamber 4 while passing through the anion exchange diaphragm 8 at the anode 6 side. When the Bomedo specific gravity control switch (BIS; Baume's hydrometer indicating switch) reaches 10-20 ° Be, the concentrated concentrated brine is operated by operating a solenoid valve (ⓢ). To be discharged.

The desalted water in which the NaCl is removed from the brine in the desalination chamber 5 and the decontaminated water is desalted in the electric conductivity value range of 6-20 kV / cm in the electric conductivity indicating switch (ECIS) of the saline line is a solenoid valve ( Ⓢ) is sent to the second reverse osmosis filtration process.

At this time, the supply amount of air supplied from the blower 11 through the diffuser 12 is such that the intensity of aeration is 1.2 to 2.0 air (m 3) / tank volume (m 3).

The monovalent cation selective exchange diaphragm 9 is a diaphragm that selectively transmits only monovalent cations while suppressing divalent or more multivalent cation permeation. The polystyrene-divinylbenzene-based main chain ( Main side: The side chain and polyethyleneimine or polyvinyl pyridine to the load electrode film in which the negative charge R-SO ₃ ^- is fixed to the main chain. Graft polymer such as Polyvinylpyridine or an ion exchange membrane composed of a graft polymer whose main chain is polystyrene as a side chain of polyethyleneimine or polyvinyl pyridine, and the main chain of the graft polymer is formed from the main chain or side chain of the cation exchange diaphragm. Any structure having the same molecular structure can be used without limitation. Preferably, polyethylene, polypropylene, polyvinyl chloride, poly Styrene (polystyrene) or the like negatively charged R-SO ₃ ^- for a fixed cation-exchange membrane the main chain or the side chain (側鎖) with the same molecular structure and a polymer consisting of a monovalent cation only permeability of the molecular structure of polyester having a (透過能) Cation selective exchange membranes such as polyvinylpyridine, polyvinylamine or polyethyleneimine membranes may be used, in particular polystyrene-graft-ethylene imine of polystyrene-divinylbenzene. Can be.

The anion exchange diaphragm 8 which permeates all anions is fixed to the polymer chain of the base material by immobilizing primary and tertiary amines or ammonium groups on the membrane and amination to introduce cations. A membrane is used that does not modify the surface of the membrane to selectively permeate monovalent anions to the surface of the entire membrane.

Salt extraction chamber (4) and desalination chamber (5) are made of flame resistant stainless steel, titanium, polyvinyl chloride (PVC), polyethylene (PE), and SBS (Styrene-Butadiene-Styrene Block Copolymer). Polypropylene (PP), Fiber glass reinforced plastic (FRP), Bakelite, Ebonite, Epoxy coating or lining of carbon steel, Glass Lining of fiber glass reinforced plastic (FRP).

The material of the negative electrode (7) plate is lined with Rainy nickel on a steel sheet of high hydrogen generating overvoltage, and is made of flameproof stainless steel or titanium plate. , The anode (6) plate is a DSA coated with TiO ₂ -RuO ₂ coated on a titanium plate, which is a material having excellent corrosion resistance and high oxygen and chlorine generation overvoltage. ; Dimensionally Stable Anode electrode.

The diaphragm supporter 9 for supporting the diaphragm is a synthetic resin such as viscose rayon or nylon having a thickness of 1 to 10 mm outside the anion exchange diaphragm 8 and the monovalent cation selective exchange diaphragm 9. Is fixed on nonwoven fabric of flame resistant stainless steel, titanium, PVC, PE, SBS, PP, FRP, bakelite, and ebony by a porous sheet or lattice.

Example 1

Take the deep sea water as shown in Table 1, heat it to 25 ℃, perform ultrafiltration of sand filtration and spiral wound type, and filter the filtrate with FI (Fouling index) value of 3.2 to Japan Toray Co., Ltd. (東 レ 株 式) Spiral Reverse Osmosis of High Pressure Reverse Osmosis Membrane Model No. SU-810 from Toray Corporation of Japan by supplying the filtered filtrate with a pressure of 20 kg / cm 2 G using a spiral nanofiltration membrane of Model No. SU-610. When the membrane permeate was 0.72m 3 / m 2 · day by supplying pressure to the membrane at 60 kg / cm 2 G using a permeate membrane, the membrane permeate amount was 52% of the influent flow rate. Analysis of the main components of the brine is shown in Table 2.

     Table 2 Analysis of Principal Components of Filtrate and Brine in First Reverse Osmosis Filtration

           Item      Demineralized water     Unfiltered saline   pH        6.2         7.9  Total Organic Concentration (TOC; mg / l)        nil         2.01 Na ⁺ (mg / L)       38.7    21,470 Cl ^- (㎎ / ℓ)       71.6    52,540 Ca ^{2 +} (㎎ / ℓ)        0.6       856 Mg ^{2 +} (㎎ / ℓ)        1.9     2,445 K ⁺ (mg / L)        1.7       822 _{^{SO 4 2 - (㎎ / ℓ}} )        4.7     2,368

Example 2

While supplying the unfiltered brine discharged from the first reverse osmosis filtration process of Example 1 to the brine storage tank 1 having a capacity of 4 m 3 / hour 10 m 3, the specification of the salt extraction device was reduced, and the desalting chamber 5 had a capacity. 0.1 m3 (25 mm x 1,000 mm x 4,000 mm) x 11 chambers, the capacity of the salt extraction chamber 4 is 4.2 m3 (875 mm x 1200 mm x 4,000 mm), and the anode is TiO ₂ on a 1,000 mm x 1200 mm titanium plate. -3 x 6 sheets of RuO ₂ -coated DSA electrode, 3 x 6 sheets of 1,000 mm x 1,200 mm titanium plate electrode, and the anion exchange membrane 8 on the positive side 6 are manufactured by Asahi Kasei Co., Ltd. 11 monolithic cation selective exchange diaphragms 9 on the negative electrode 5 side were prepared using 11 sheets of Aciplex A-101 3,600 mm × 1,000 mm, and Aciplex K-102 3,600 mm × 1,000 of Asahi Kasei Co., Ltd. In the salt extraction device (3) consisting of a desalting chamber (5) using 11 sheets of mm size, the brine of the salt storage tank (1) having a capacity of 10 m3 is injected into the salt extraction chamber (4) by the brine transfer pump (2). Flow rate of 4㎥ / hr In order to supply the desalination chamber (5) to the brine storage tank (1) and return it to the brine reservoir (1), a 4.5 volt direct current is applied from the rectifier. When the deionized water was discharged at 8 kW / cm, the main component analysis of demineralized water was as shown in Table 3, and the applied current was 58 amperes (Ampere).

Table 3, Analysis of Major Components of Demineralized Salt after Desalination by Electro-Extraction

                Item             ingredient        pH (hydrogen ion concentration)                7.8        TOC (Total Organics Concentration; mg / l)                2.0        Sodium (Na; mg / l)              552.6        Chlorine (Cl; (mg / L))            9,361.1        Calcium (Ca; mg / L)              813.2        Magnesium (Mg; mg / l)            2,322.7        Potassium (K; mg / l)               20.3 A sulfate ion _{^{(SO 4 2 -; ㎎ /}} ℓ)               82.3

2. Desalination treatment by electrodialysis

In the desalination process by electrodialysis of the salt contained in the brine, when the direct current is applied from the rectifier, the ionic solute is separated by membrane permeation using the potential difference of the direct current as a driving force. The same cation exchange diaphragm as the salt extraction device 3 described above uses a monovalent cation selective exchange diaphragm 9 that selectively transmits monovalent ions, and the anion exchange diaphragm is an anion exchange diaphragm that transmits all anions ( 8).

The electrodialysis apparatus 13 is a desalting chamber 5 and a desalting chamber separated by a monovalent cation selective exchange diaphragm 9 penetrating only a monovalent cation and an anion exchange diaphragm 8 penetrating all anions as shown in FIG. 4. (5) The salt concentration chambers 16 alternately provide a plurality of stages in a row, and the anode chambers 14 at both ends have an anode 6 therebetween. The cathode chamber 15 has a structure in which a cathode 7 is provided.

The brine from the brine reservoir (1) is supplied to the desalination chamber (5) of the electrodialysis apparatus (13) by the brine transfer pump (2) and returned to the brine reservoir (1), and the concentrated brine in the concentrated brine reservoir (17) is concentrated. A direct current from the rectifier to the positive electrode 6 of the positive electrode chamber 14 and the negative electrode 7 of the negative electrode chamber 15 is supplied to the salt concentration chamber 16 by the brine transfer pump 18 and returned to the concentrated brine storage tank 17. When electricity is applied, Na ⁺ and K ⁺ , which are monovalent cations contained in the brine in the desalting chamber 5, are applied to the monovalent cation selective exchange diaphragm 9 on the negative electrode 7 side by electrical attraction. Permeate to the salt concentration chamber 16, where all anions (X ^{m -} X is an anion, m is the number of anion valences) are passed through the anion exchange diaphragm 8 on the anode 6 side to 16, while the salt and sulfate ions contained in the brine in the desalting chamber 5 are concentrated by the salt concentration chamber 16, the brine in the desalting chamber 5 is desalted. Lee.

In this case, the electrolyte solution of the cathode chamber 15 and the anode chamber 14 may use deep sea water, but in order to suppress corrosion of the anode 6 while preventing the generation of chlorine (Cl ₂ ) gas in the anode 6. 3-10 wt% Na ₂ SO ₄ The aqueous solution is supplied to the cathode chamber 15, and the electrolyte solution discharged from the cathode chamber 15 is supplied to the anode chamber 14.

When the brine that is not filtered in the first reverse osmosis filtration process is supplied to the brine storage tank (1), the brine transfer pump (2) is supplied to the desalting chamber (5) of the electrodialysis apparatus (13) to the brine storage tank (1) The anode 6 of the anode chamber 14 while feeding the concentrated brine from the concentrated brine reservoir 17 to the salt concentration chamber 16 by the concentrated brine transfer pump 18 and returning it to the concentrated brine reservoir 17. When a direct current is applied to the cathode 7 of the cathode chamber 15 from the rectifier, the monovalent cation in the brine of the desalination chamber 5 forms the monovalent cation selective exchange diaphragm 9 by electrical attraction. The permeate is transferred to the salt concentration chamber 16 on the negative electrode 7 side, and all the anions pass through the anion exchange diaphragm 8 to the salt concentration chamber 16 on the positive electrode 6 side and concentrated brine reservoir 17 The concentrated brine concentrated in the range of 10 ~ 20 ° Be in the range of bomedo is solely controlled by Baume's hydrometer indicating switch (BIS). Operate the nose valve (ⓢ) to the salt manufacturing process, and the salt is desalted in the brine in the desalination chamber (5) and the electrical conductivity of the electroconductivity indicating switch (ECIS) installed in the brine return line is 6 Demineralized water desalted in the range of ˜20 μs / cm is sent to a second reverse osmosis filtration process by operating a solenoid valve.

When the concentrated brine of the concentrated brine reservoir 17 is circulated and supplied to the salt concentration chamber 16 by the concentrated brine transfer pump 24, the monovalent cation in the brine is caused by the electrical attraction to the monovalent cation selective exchange diaphragm (9). Permeate into the salt concentration chamber 16 on the cathode 7 side, and all the anions pass through the anion exchange diaphragm 8 to the salt concentration chamber 16 on the anode 6 side to concentrate salts. The concentrated brine concentrated in the brine concentration in the concentrated brine storage tank (17) 10 ~ 20 ° Be is sent to the salt manufacturing process by operating the solenoid valve (ⓢ) by the BME dome specific gravity indicating controller (BIS).

The electrodialysis apparatus 13 preferably increases the current density as large as possible in 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 in the diffusion layer. Since the thickness of the diffusion layer is inversely proportional to the thickness of (iii), it depends on the salt concentration in the demineralized water to be drained and the salt concentration of the concentrated brine. Brine transfer to the electrodialysis apparatus (13) forming a desalting chamber (5) and a salt concentrating chamber (16) arranged alternately between the anode (6) and the cathode (7) and the anion exchange diaphragm (8). Concentrated brine is sent to the salt concentration chamber 16 by the concentrated brine transfer pump 24 to circulate after desalting and sent to the desalination chamber 5 by the pump 2 to improve the salt concentration efficiency. Scale components are not produced in the salt concentration chamber (16). When a large amount of concentrated brine passing through the rock salt concentration chamber 16 is supplied, scale trouble can be prevented reliably, and the salt resistance of the current is supplied by supplying the concentrated salt water with a high salt concentration to the salt concentration chamber 16. Since the limit current density can be increased, the processing performance of the electrodialysis apparatus 13 can be improved.

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 13, the flow rate supplied to the desalting chamber 5 is a membrane line. The desalted water desalted in a speed range of 10 to 30 cm / sec is returned to the brine storage tank 1, and the flow rate of the concentrated brine supplied to the salt concentration chamber 16 has a membrane surface velocity of 1 to 1. The concentrated brine is returned to the concentrated brine reservoir 17 so that the 3 cm / sec range is maintained.

The monovalent cation selective exchange diaphragm 9 and the anion exchange diaphragm 8 used in the electrodialysis apparatus 13 use the same diaphragm as the diaphragm of the salt extraction apparatus 3 described above.

The anode 6 of the anode chamber 14 of the electrodialysis apparatus 13 is made of a corrosion-resistant material and a DSA (Dimensionally Stable Anode) electrode or a platinum plated electrode having a high hydrogen and oxygen generation overvoltage. The solution passed through the cathode chamber 15 is injected to suppress the generation of chlorine and oxygen on the surface of the anode 6, and the cathode 7 has high hydrogen generation overvoltage (Ranney nickel). Or a stainless steel steel plate, and the monovalent cation selective exchange diaphragm 9 closest to the cathode chamber 28 uses a hydrogen ion impermeable membrane or a monovalent anion permeable membrane. It is preferable to reduce the amount of hydrogen ions generated on the surface of the cathode 7 to improve power efficiency and reduce odor.

In addition, in the salt concentration chamber 16, 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 (7) so that the attached scale and slime are detached.

Concentrated brine concentrated in the range of 10-20 ° Be in the brine storage tank (17) of the electrodialysis process is sent to the salt manufacturing process by operating the solenoid valve (ⓢ) by the Bomedo specific gravity indication controller (BIS). .

Example 3

The monovalent cation selective exchange diaphragm 9 having an effective conduction area of 236 mm (length) x 220 mm (width) of 0.2 mm has a monovalent cation that allows only Japan to pass through monovalent cations. The Aciplex K-102 manufactured by Isa Chemical Co., Ltd., and the anion exchange diaphragm (8) is a DSA coated with RuO ₂ -TiO ₂ on 50 sheets of Aciplex A-101 of Asai Chemical Co., Ltd. on a titanium plate. A 50 L salt storage tank of the desalination chamber 5 of the electrodialysis apparatus 13 in which multiple stages (50 stages) are alternately installed between the anode 16, which is an electrode, and the cathode 17 of a stainless steel electrode, as shown in FIG. 1) was supplied with unfiltered brine at 25 ° C. in the first reverse osmosis filtration process of Example 1, followed by a membrane velocity with a brine feed pump (2), a diaphragm type metering pump. It is supplied to the desalination chamber 24 so that the degree is 10 cm / sec, and it circulates in the brine storage tank 1, and the brine of the 20 liter concentrated brine storage tank 28 is diaphragm-type metering pump. Concentrated salt water feed pump 18 to the film speed is myeonseon 3㎝ / sec presented salt concentration chamber (16) and concentrated salt water reservoir (1), the DC electric current density is 3~4A / dm ² from the rectifier fed to a rotational The main component analysis of demineralized demineralized water when desalination was performed at the electric conductivity value of 8 kV / cm in the conductivity indicator controller (ECIS) of the brine circulation line was applied. Same as 4

At this time, the specific gravity of the concentrated brine in the concentrated brine storage tank 18 was adjusted by 12 ° Be, the cathode chamber solution is discharged to the top by supplying 5wt% Na ₂ SO ₄ aqueous solution to the bottom of the cathode chamber 15 at 50 kW / min To the lower portion of the anode chamber 14.

Table 4, Analysis of Major Components of Demineralized Salt after Desalination by Electrodialysis

                Item             ingredient        pH (hydrogen ion concentration)                7.8        TOC (Total Organic Matter Concentration; mg / l)                2.0        Sodium (Na; mg / l)              650.2        Chlorine (Cl; (mg / L))            9,586.7        Calcium (Ca; mg / L)              818.6        Magnesium (Mg; mg / l)            2,362.7        Potassium (K; mg / l)               28.3 A sulfate ion _{^{(SO 4 2 -; ㎎ /}} ℓ)              102.3

II. Concentrating the organic and mineral components of the desalted demineralized water in the second reverse osmosis filtration process

When the desalted salt is desalted in the desalting method by the electroextraction method and the desalting method by the electrodialysis method, it is supplied to the reverse osmosis filtration process, and the permeation rate of the permeate is in the range of 95 to 99%. Filtration to concentrate organic and mineral components.

The filtered filtrate is sent to the drinking water production process to be used for beverage production.

At this time, the operating pressure of the reverse osmosis filtration process is operated at a low pressure of 5 to 20 atm because salt is removed and the osmotic pressure is low.

And the material and form of the reverse osmosis filtration membrane may be the same as the first reverse osmosis filtration membrane, but it is preferable to use a low pressure reverse osmosis membrane because it is operated at a low pressure.

In addition, the characteristics of the present invention, by sending the filtered water filtered in the second reverse osmosis filtration process to the beverage production process can be treated with a drink, there is also an advantage that can improve the beverage production yield.

Example 4

When the demineralized water desalted in Example 2 was used at a reverse pressure osmosis filtration device of Example 1 at an operating pressure of 12㎏ / ㎠G and supplied at 6㎥ / hour, the filtered water was discharged at 5.8㎥ / hour, The concentrated water concentrated without filtration was discharged at 0.2㎥ / hour, and the main component analysis of the discharged concentrated water is shown in Table 5 below.

Table 5 Analysis of Principal Components of Concentrated Water Concentrated in Secondary Reverse Osmosis Filtration Process

                Item             ingredient        pH (hydrogen ion concentration)                7.82        TOC (Total Organic Concentration; mg / l)               60.0        Sodium (Na; mg / l)           16,495.1        Chlorine (Cl; (mg / L))          279,709.7        Calcium (Ca; mg / L)           24,347.2        Magnesium (Mg; mg / l)           69,541.6        Potassium (K; mg / l)              606.0 A sulfate ion _{^{(SO 4 2 -; ㎎ /}} ℓ)            2,464.1

III. The step of concentrating highly organic and mineral components in the evaporation and concentration process of the first concentrated organic matter

In the second reverse osmosis filtration process, the deep seawater or the deep seabed with concentrated organic matter and minerals is further reduced in volume, and when highly concentrated, vacuum evaporation is performed at 40 ° C. or lower so as not to decompose the organic matter. Lyophilization produces deep sea water with a high concentration of organics and minerals.

The organic and mineral components contained in the deep sea water are found to be used in various fields such as cosmetics, medicine, food and feed additives because they are found to contain various substances useful for skin and growth of organisms. .

As described above, the present invention has an effect of improving the production yield of beverages in the case of concentrating the organic matter and mineral components from the brine discharged from the process of taking the deep sea water or the deep sea bedrock water to produce a beverage. And because it can concentrate the mineral component is expected to have an effect that is widely applied to the process for producing beverages from deep sea water.

Claims (3)

When the deep seawater or seabed deep rock water is collected and unfiltered brine enters the brine reservoir (1) during the first reverse osmosis filtration process of the beverage production process, the brine is transported. A pump (2) is supplied to the salt extraction chamber (4) and the desalting chamber (5) of the salt extraction unit (3) and circulated to the brine storage tank (1), and air from the blower (11) to the air diffuser (12). While aeration through the application of a 3 to 10 volts DC electricity from the rectifier (印 加) to the salt extraction chamber (4) When the concentration of bomedo of concentrated brine reaches 10 to 20 ° Be discharged to the salt manufacturing process Desalination with demineralized water in which the salt is removed from the brine in the desalination chamber (5) so that the electrical conductivity of the brine line is desalted in the range of 6-20 mW / cm, Deep sea water or seabed, characterized in that the demineralized water is supplied to the reverse osmosis filtration membrane of the second reverse osmosis filtration process to filter the permeate in the range of 95 to 99% to concentrate organic and mineral components. Concentrates organics and minerals from deep rock water. The salt extraction chamber 4 and the desalination of the salt extraction apparatus 3 to the brine transfer pump 2 when the unfiltered brine flows into the brine reservoir 1 in the first reverse osmosis filtration process. Instead of supplying to the chamber 5, the brine transfer pump 2 is supplied to the desalination chamber 5 of the electrodialysis apparatus 13 and returned to the brine storage tank 1, and the concentrated brine of the concentrated brine storage tank 17. Is supplied to the salt concentration chamber 16 by the concentrated brine transfer pump 18 and returned to the salt brine storage tank 17, and rectifiers are supplied to the anode 6 of the anode chamber 14 and the cathode 7 of the cathode chamber 15. The concentrated brine concentrated in the range of 10-20 ° Be in the brine concentration of the concentrated brine reservoir 17 by direct current was applied to the salt manufacturing process, and the demineralized salt desalted in the desalination chamber 5 was secondary. A method for concentrating organic matter and minerals from deep ocean water or deep sea bedrock by sending to reverse osmosis filtration. The method of claim 1 or 2, wherein in the second reverse osmosis filtration process, when the deep seawater or the deep seawater with concentrated organic matter is highly concentrated, vacuum evaporation or lyophilization is performed at 40 ° C. or lower so as not to decompose the organic matter. To concentrate organics and minerals from deep ocean water or deep sea bedrock.

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