KR100887520B1 - A concentration method of the organic matter from deep sea water or deep sea rock-floor water - Google Patents

Abstract

The present invention relates to a method for concentrating organic matter from deep seawater or deep sea bedrock, and more particularly, to a method for concentrating organic matter that can be used for manufacturing water, such as cosmetics and lotion, soap, bath water and pharmaceuticals, from deep sea water. will be.

To this end, the present invention, the step of desalting the concentrated water discharged from the reverse osmosis filtration process in the process of preparing a beverage by taking the deep sea water or the deep sea bedrock water of the deep seabed deeper than 200m from the sea surface, desalination treatment The desalted water was first concentrated in a second reverse osmosis filtration process, and the first concentrated organic material was characterized by consisting of highly concentrated organic matter in a second evaporation and concentration process.

Deep sea water, organic matter, concentration, desalting, reverse osmosis, electroextraction, electrodialysis

Description

A concentration method of the organic matter from deep sea water or deep sea rock-floor water}

1 is a process chart for concentrating organic matter 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 Room

5; Desalting chamber 6; anode

7; Negative electrode 8; Anion exchange diaphragm

9; Cation 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 of concentrating organic matter from deep sea water, and more particularly, it is not filtered from a reverse osmosis process in the process of preparing a beverage by taking deep sea water or deep sea bedrock water deeper than 200 m from the sea surface. After desalting the concentrated brine discharged, the present invention relates to a method for concentrating organic matter by secondary reverse osmosis, 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, and the surface tension is low, so that the water penetrates with good permeability. 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 main components of deep sea and surface seawater

         division       Ulleungdo Hyunpo Murodo, Koji Prefecture, 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 studies have shown that deep ocean water or In deep-sea bedrock, marine microorganisms such as Pseudoalteromonas denitrificans, and Alteromonas macleodii, are responsible for the proliferation of macrophage. It is known to activate and excrete organic substances such as Cycloprodigiosin hydrochloride, which is effective in atopic dermatitis, as metabolites, and fish such as crustaceans. Sugars such as trehalose and chitosan, which are highly moisturizing, From the species, organic compounds such as alginic acid are excreted, and oligomer (organic) organic matter is contained in the total organic carbon (TOC) as shown in Table 1, about 1 mg / l.

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, etc. In recent years, among these organic matters, trace elements that have anticancer activity (Oligoelement Is also published.

Conventional techniques for concentrating organic matter contained in deep seawater or deep sea bedrock have not been investigated, and in the present invention, organic matter is extracted from concentrated brine without filtering in reverse osmosis of beverage preparation in deep seawater or seabed deep seawater. Let us present a method of concentration.

It is an object of the present invention to provide a method for concentrating organic matter from concentrated brine without filtering in reverse osmosis filtration process of beverage production process in deep sea water 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 seabed rock water, desalting the concentrated brine without filtering from reverse osmosis, secondary desalted water The first step of concentrating in reverse osmosis filtration process, the first concentrated organic material is characterized in that consisting of the step of finally concentrating the organic material in the second evaporation and concentration process.

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 process. Concentration of the organics from the brine, concentrated, brine without sending, described in detail by the accompanying drawings as follows.

I. Desalination of brine

From the sea surface, the deep seawater or deep seawater of deep seabed deeper than 200m is collected, warmed and pre-filtered and sent to the first reverse osmosis process. Is supplied to the brine reservoir (1), it is contained in the brine by one of the following desalination treatment methods by the electroextraction method and desalination treatment method by the electrodialysis method. Desalination is done.

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 penetrating all anions on the anode 6 side, and a cation exchange diaphragm 9 penetrating all the cations on the negative electrode 7 side, and the processing 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 and the cation exchange diaphragm 9 used in the present invention include monovalent salts (NaCl, KCl, KBr, etc.) and polyvalent salts (MgCl ₂ , MgSO ₄ ) contained in saline. , CaSO ₄ , FeCl ₂ , FeCl ₃ , SrSO ₄ ..., Etc.), a diaphragm capable of removing (desalting) all of them is used.

In the desalination method according to the electroextraction method of the present invention, the anion exchange diaphragm 8 between the positive electrode 6 and the negative electrode 7 in the salt extraction chamber 4, as shown in FIG. The cation exchange diaphragm 9 supplies the deep seawater or subsea deep rock water to the salt extraction chamber 4 to the desalination apparatus by an electroextraction method composed of a desalting chamber 5 isolated using a diaphragm penetrating all cations. When the brine of the reservoir 1 is supplied to the desalination chamber 5 by the brine transfer pump 2 and returned to the brine reservoir 1, DC electricity is applied from the rectifier, and the electrochemical reaction mechanism (Mechanism) is as follows. ), The salt contained in the brine of the desalting chamber 5 is removed (desalting).

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

^{MmXn ⇔ mM n + + nX m} - ... … … … … … … … … … … … … … … … … … … … … … ①

Where M ^{n +} is all cations, X ^{m −} is all anions, m is the valence of the anion, and n is the valence of the cation.

All cations (M ^{n +} ) contained in the brine of the desalting chamber (5) pass through the cation exchange diaphragm (9) on the negative electrode (7) side to the salt extraction chamber (4), as shown in reaction equation (2), and all the anions (X). ^m- ) moves to the salt extraction chamber 4 through the anion exchange diaphragm 8 on the anode 6 side as in the reaction formula ③.

mM ^{n +} (desalting chamber)-cation exchange diaphragm → mM ^{n +} (salt extraction chamber). … … … … … … ②

nX ^m- (demineralization chamber)--anion exchange diaphragm → nX ^m- (salt extraction chamber). … … … … … … ③

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

^{mM n + + nX m - →} MmXn ... … … … … … … … … … … … … … … … … … … … … … ④

As described in the above description, the present invention is characterized in that the salt contained in the brine in the desalting chamber 5 occurs in the anode chamber 14 and the cathode chamber 15 at both ends of the electrodialysis apparatus 13. The electrolytic reaction does not occur at all, and the salt extraction chamber 4 is separated (extracted) and concentrated in the state of the original salt, so that the salt is decomposed and consumed. Since the distance of the power supply can be set close to each other, the power consumption is low because the applied voltage is applied at a low voltage of 3 to 6 volts.

In the desalination process of FIG. 3, the anode 6 and the cathode 7 are alternately provided with a plurality of stages in the salt extraction chamber 4 by a desalination apparatus by an electroextraction method. The anion exchange diaphragm 8 between the cathode 6 and the cathode 7 uses a diaphragm that does not modify the surface to allow all anions to pass through, and the cation exchange diaphragm 9 permeates all cations. It is a process chart of the salt extraction apparatus 3 by the electroextraction method which consists of the desalination chamber 5 isolate | separated using the diaphragm which did not modify the surface so that it might be possible.

When the brine that is not filtered in the first reverse osmosis filtration in the beverage production process flows into the brine storage tank (1), the brine transfer pump (2) is supplied to the salt extraction chamber (4) of the salt extraction unit (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 cations (+) contained in the brine in the desalting chamber (5) by electrophoresis penetrate through the cation exchange diaphragm (9) on the negative electrode (7) side and the salt extraction chamber (4). And the anion (-) passes through the anion exchange diaphragm 8 at the anode 6 to the salt extraction chamber 4, where the concentration of salt in the salt extraction chamber 4 is concentrated. When the Bomedo specific gravity of BIS (Baudme's hydrometer indicating switch) reaches 10-12 ° Be, the solenoid valve (ⓢ; Solenoid valve) is operated to discharge the concentrated brine to the salt manufacturing process. .

Demineralized water in which the salt is removed from the brine in the desalination chamber 5 and the decontaminated water of the electroconductivity value switch of the electric conductivity indicating switch (ECIS) in the brine line is in the range of 5 to 15 kV / cm is a solenoid valve (ⓢ ) To the secondary reverse osmosis process.

At this time, it is important to note that if the specific density of the BME of the concentrated brine in the brine extraction chamber (BIS) exceeds 12 ° Be, the material such as CaSO ₄ , SrSO ₄ , CaCO ₃ precipitates and scales. Because of the possibility of generating scale, the Bume gravity should be operated below 12 ° Be.

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 cation exchange diaphragm 9 which permeates all cations has a load fixed to the negative charge R-SO ₃ ^- in the main chain of the polystyrene-divinylbenzene system. In order to selectively permeate only monovalent cations to the diaphragm surface through the entire membrane, a cationic polymer electrolyte such as polyethyleneimine can be coated or bonded in a thin layer to modify it. Untreated cation exchange diaphragms are used.

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

Alternatively, the cation exchange diaphragm 9 and the anion exchange diaphragm 8 on the anode 6 side and the cathode 7 side are the same asbestos, nylon, polyamide, polyfluoroolefin, Polyethylene, Polypropylene, Polyolefin, Polyester, Polytetrafluoroethylene, Polyvinindene fluoride, Hexafluoropropylene And a copolymer membrane of tetrafluoroethylene (TFE) and tetrafluoroethylene may be used.

Salt extraction chamber (4) and desalination chamber (5) are made of flame resistant stainless steel, titanium, polyvinyl chloride (PVC), polyethylene (PE), styrene-butadiene-styrene block copolymer (SBS), and polypropylene (PP). ), FRP (Fiber glass reinforced plastic), Bakelite, Ebonite, Epoxy coating or lining of carbon steel, Glass fiber reinforced plastic ( Lining of FRP; Fiber glass reinforced plastic

The material of the negative electrode (7) plate is a line of steel plate with high hydrogen generation overvoltage (Raney nickel) lining (flame resistant stainless steel, 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 nonwoven fabric made of synthetic resin such as viscose rayon or nylon having a thickness of 1 to 10 mm outside the anion exchange diaphragm 8 and the cation exchange diaphragm 9. It is supported and fixed by flame resistant stainless steel, titanium, PVC, PE, SBS, PP, FRP, bakelite, or ebonite with one kind of porous plate or grating plate.

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) High pressure reverse osmosis membrane of Toray Corporation of Japan was supplied with filtered water from which the sulfate ion (SO ₄ ^2- ) was removed by supplying pressure to the membrane at 20 kg / cm 2 G using the spiral nanofiltration membrane of Model No. SU-610. The membrane permeate was 52% of the influent when the membrane permeate was 0.72㎥ / ㎡ · day using a spiral reverse osmosis membrane of model number SU-810 and the pressure was supplied to the membrane at 60㎏ / ㎠G. Analysis of the major components of the demineralized and unfiltered saline is shown in Table 2 below.

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

           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 10 m 3 at 4 m 3 / hr, the specification of the salt extraction device, 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 1,000 mm x 1200 mm TiO ₂ -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 diaphragm 8 on the anode 6 side are manufactured by Asahi Kasei Co., Ltd. 11 sheets of Aciplex A-101 of 3,600 mm × 1,000 mm size were used, and the cation exchange diaphragm 9 of the cathode 5 side was made of Aciplex K-101 of 3,600 mm × 1,000 mm size of Asahi Kasei Co., Ltd. Into the salt extraction device (3) consisting of a desalting chamber (5) using 11 sheets, the brine of the brine storage tank (1) having a capacity of 10 m 3 is injected into the salt extraction chamber (4) with a brine transfer pump (2), and 4 m 3 Desalting chamber (5) at flow rate of / hr The concentrated brine in the salt extraction chamber (4) discharged the specific gravity at 12 ° Be while supplying 12 ° Be of specific gravity to the brine reservoir while supplying it to the brine reservoir (1) while feeding it to the brine reservoir (1). When demineralized water was discharged at / cm, the main component analysis values of demineralized water were as shown in Table 3, and the applied current was 52 amperes (Ampere).

Table 3 Analysis of Principal Components of Demineralized Water after Desalination by Electro Extraction

                Item             ingredient        pH (hydrogen ion concentration)                7.8        TOC (Total Organic Concentration; mg / l)                2.0        Sodium (Na; mg / l)              579.7        Chlorine (Cl; (mg / L))            1,431.2        Calcium (Ca; mg / L)               32.4        Magnesium (Mg; mg / l)               92.5        Potassium (K; mg / l)               22.2 A sulfate ion _{^{(SO 4 2 -; ㎎ /}} ℓ)               89.5

2. Desalination treatment by electrodialysis

In the desalination process by electrodialysis of the salts 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 power as a driving force. The diaphragm 9 permeate | transmits all the cations which have a fixed negative charge, and the anion exchange diaphragm 8 uses the ion exchange diaphragm which permeate | transmits all the anions which have a fixed static charge.

The electrodialysis apparatus 13 is between the desalting chamber 5 and the desalting chamber 5 separated by a cation exchange diaphragm 9 penetrating all cations and an anion exchange diaphragm 8 penetrating all anions as shown in FIG. 4. The salt concentration chamber 16 alternately arranges multiple stages in a row, and the anode chamber 14 at both ends has an anode 6. 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, all cations (M ^{n +} ; M is cation and n is the number of cation valences) contained in the brine in the desalting chamber 5 are cation exchanged toward the cathode 7 by electrical attraction. The membrane 9 penetrates into the salt concentration chamber 16, and all anions (X ^m- ; X is an anion and m is the number of anion valences) are penetrated through the anion exchange diaphragm 8 toward the anode 6 side. The salt contained in the brine in the desalination chamber 5 while being moved to the salt concentration chamber 16 is concentrated in the desalination chamber 5 while moving to the salt concentration chamber 16. Desalting is processed.

At this time, the electrolyte solution of the cathode chamber 15 and the anode chamber 14 may use the deep sea water, but in order to suppress the corrosion of the anode 6 while preventing the generation of chlorine (Cl ₂ ) gas at the anode 6. Na ₂ SO ₄ aqueous solution of -10 wt% 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 unfiltered brine is supplied to the brine storage tank 1 in the first reverse osmosis filtration process, the brine transfer pump 2 is supplied to the desalination chamber 5 of the electrodialysis apparatus 13 to the brine storage tank 1. Conveying the concentrated brine from the concentrated brine storage tank 17 to the salt concentration chamber 16 through the concentrated brine transfer pump 18 and conveying the concentrated brine to the concentrated brine storage tank 17 while conveying it to the anode 6 of the anode chamber 14; When direct current is applied to the cathode 7 of the cathode chamber 15 from the rectifier, all cations in the brine of the desalination chamber 5 penetrate through the cation exchange diaphragm 9 by electrical attraction and the cathode 7 B) specific gravity of the concentrated brine reservoir (17) is transferred to the salt concentration chamber (16) side and all the anions pass through the anion exchange diaphragm (8) to the salt concentration chamber (16) side of the anode (6). Concentrated brine condensed in this range of 10 to 12 ° Be is controlled by solenoid valves by Baume's hydrometer indicating switch (BIS). (Ⓢ) is sent to the salt manufacturing process, the salt is desalted in the brine in the desalination chamber (5) the value of the electrical conductivity of the electric conductivity indicating switch (ECIS; Electric conductivity indicating switch) installed in the brine return line is 5 ~ 15 Demineralized water desalted in the range of ㎝ / cm is sent to a second reverse osmosis process by operating a solenoid valve.

When the concentrated brine of the concentrated brine storage tank 17 is circulated and supplied to the salt concentration chamber 16 by the concentrated brine transfer pump 24, the cations in the brine penetrate the cation exchange diaphragm 9 by electrical attraction to the cathode ( 7) is transferred to the salt concentration chamber 16 on the side, and the anion passes through the anion exchange diaphragm 8, and moves to the salt concentration chamber 16 on the anode 6 side, whereby the salt is concentrated and concentrated brine storage tank 17 Concentrated brine concentrated in the range of 10 ~ 12 ° Be of Bumedo is sent to salt manufacturing process by operating solenoid valve (ⓢ) by Bomedo.

The electrodialysis apparatus 13 preferably increases the current density as large as possible within the range of the limit current density in order to increase the processing performance. However, 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 i), it depends on the salt concentration in the demineralized water to be drained and the salt concentration of the concentrated brine. Thus, in the present invention, the cation exchange diaphragm 9 and the anion exchange diaphragm 8 The desalination chamber is connected to the desalination chamber 5 and the electrodialysis apparatus 13 forming the salt concentration chamber 16, which are alternately arranged between the anode 6 and the cathode 7. Part 5 is circulated after desalination by sending to (5), and the concentrated brine is sent to the salt concentration chamber 16 by the concentrated brine transfer pump 24 to circulate the salt concentration efficiency while improving the salt concentration efficiency. Salt concentration so as not to produce in the salt concentration chamber 16 Supplying concentrated brine to the storage chamber 16 in a large amount can prevent scale troubles, and the supply of concentrated salt solution having a high salt concentration to the salt concentration chamber 16 reduces current resistance. Since the current density can be increased, the processing performance of the electrodialysis apparatus 13 can be improved.

The flow rate supplied to the desalination chamber 5 is the membrane surface velocity in order to improve the electrodialysis efficiency while increasing the amount of energization by increasing the limit current density in the electrodialysis apparatus 13 to suppress scale troubles. The demineralized water desalted in the range of 10-30 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 3 cm /. Concentrated brine is returned to the concentrated brine reservoir 17 to maintain the second range.

The cation exchange diaphragm 9 used in the present invention is a failure in which a negative charge R-SO ₃ ⁻ is fixed to a main chain of a polystyrene-divinylbenzene system. hamak (負荷電膜) use, and the anion exchange membrane (8) is a cation exchange membrane (3), as opposed to exchange the anion membrane into the electrostatic charge (正電荷) with R-NH ₃ ⁺ of the polymer chain (polymer chain Monovalent ions such as NaCl and KCl, using a diaphragm that can pass through bivalent or higher polyvalent ions using a positive charge membrane that fixes static charge to the membrane. Of course, a diaphragm capable of desalting even more than one divalent salt such as MgCl ₂ and MgSO ₄ is used.

In other words, using an ion-exchange membrane that selectively permeates only monovalent ions deconcentrates only the salts of monovalent ions such as NaCl, so that the multivalent mineral salts cannot be concentrated. Ion exchange diaphragms should be used.

The anode 6 of the anode chamber 14 of the electrodialysis apparatus 13 uses a corrosion-resistant material and a dimensionally stable anode (DSA) electrode or a platinum-plated electrode having high chlorine and oxygen generation overvoltage. Injecting the solution through the cathode chamber 15 to suppress the generation of chlorine and oxygen on the surface of the anode (6), the cathode (7) is Raney nickel with high hydrogen generation overvoltage ) Or a cation exchange diaphragm 9 closest to the cathode chamber 28 using a stainless steel sheet, and using a hydrogen ion impermeable membrane or a monovalent anion permeable membrane. 7) It is better to reduce the generation of hydrogen ions on the surface to improve the power efficiency and reduce the occurrence of odor.

In addition, in the salt concentration chamber 16, a polarity switching device is installed in the rectifier in preparation for the generation of scales or slimes such as organic matters to reduce the processing efficiency. ) And the cathode 7 are switched so that the attached scale and slime are detached.

Concentrated brine concentrated in the range of 10-12 ° Be in the brine reservoir 17 of the electrodialysis process is sent to the salt manufacturing process by operating the solenoid valve (ⓢ) by the BOMET specific gravity indication controller (BIS). .

Example 3

The effective conduction area of 236 mm (length) × 220 mm (width) 0.2 mm thickness The cation exchange diaphragm 9 is Japan's Asai Kasei Co., Ltd. which penetrates all cations. Anion exchange diaphragm 8 is an anode (16) which is a DSA electrode coated with RuO ₂ -TiO ₂ on a titanium plate of 50 sheets of Aciplex A-101 of Asai Kasei Co., Ltd., respectively. 4 in a salt storage tank 1 of 50 L in a desalting chamber 5 of an electrodialysis apparatus 13 in which multiple stages (50 stages) are alternately installed between the anode and the stainless steel cathode 17 as shown in FIG. 1 After supplying the brine at 25 ° C discharged without filtration in the reverse osmosis filtration process, desalination was carried out with a brine transfer pump (2), a diaphragm type metering pump, so that the linear velocity was 10 cm / sec. Concentrated brine transfer pump which is supplied to the chamber 24 and circulated to the brine storage tank 1, and the brine of the 20 liter concentrated brine storage tank 28 is a diaphragm type metering pump. When the plug 18 is blocked, it is supplied to the salt concentration chamber 16 so as to have a linear velocity of 3 cm / sec and circulated to the concentrated brine storage tank 1, while applying a direct current from the rectifier to a current density of 3 to 4 A / dm ² . (At this time, the applied voltage was 55 ~ 60 Volt.) When the electroconductive value of ECIS of salt water circulation line was desalted to 8㎳ / ㎝, the analysis of the main components of demineralized demineralized water was shown in Table 4 below. same.

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 Principal Components of Demineralized Water after Desalination by Electrodialysis

                Item             ingredient        pH (hydrogen ion concentration)                7.8        TOC (Total Organic Concentration; mg / l)                2.0        Sodium (Na; mg / l)              644.1        Chlorine (Cl; (mg / L))            1,590.0        Calcium (Ca; mg / L)               36.2        Magnesium (Mg; mg / l)              102.7        Potassium (K; mg / l)               24.7 A sulfate ion _{^{(SO 4 2 -; ㎎ /}} ℓ)               99.5

II. Concentrating Organics

When the desalted water is desalted in the desalting method by the electroextraction method and the desalting method by the electrodialysis method, it is supplied to the second reverse osmosis filtration process, and is supplied to the reverse osmosis filtration membrane, and the permeability of the permeate is filtered in the range of 95 to 99.5%. The filtered filtrate is sent to the drinking water production process for use in the production of beverages, and 0.5 to 5% of the deep seawater or the deep seabed rock water where organic matter is concentrated without being filtered.

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

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

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

Example 4

The filtered water was discharged at 5.92m3 / hour when the demineralized water desalted in Example 2 was supplied at 6㎥ / hour using the reverse osmosis filtration device of Example 1 at an operating pressure of 8㎏ / ㎠G, and not filtered. Concentrated water without concentration was discharged to 0.08㎥ / hour, the main component analysis of the discharged concentrated water is shown in Table 5.

Table 5 Analysis of Major Components of Concentrated Water in the Second Reverse Osmosis Filtration Process

                Item             ingredient        pH (hydrogen ion concentration)                7.82        TOC (Total Organic Concentration; mg / l)              148.2        Sodium (Na; mg / l)           41,303.6        Chlorine (Cl; (mg / L))          101,973.0        Calcium (Ca; mg / L)            2,357.1        Magnesium (Mg; mg / l)            6,729.4        Potassium (K; mg / l)            1,581.8 A sulfate ion _{^{(SO 4 2 -; ㎎ /}} ℓ)            6,511.1

III. High concentration of organic matter in the evaporation and concentration process of the first concentrated organic matter

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

The organic matter contained in the deep sea water is found to be used in various fields such as cosmetics, medicine, food and feed additives because it is found that it contains a variety of materials useful for skin and growth of organisms.

As described above, in the present invention, when the organic matter is concentrated from the brine discharged from the process of preparing deep drink by taking deep sea water, it is possible to concentrate the useful organic matter while improving the production yield of the drink. It is expected that there will be an effect that is widely applied to the process for producing beverages from deep water.

Claims (3)

When the deep seawater or seabed deep rock water is collected and the unfiltered brine is supplied to the brine reservoir 1 in the first reverse osmosis filtration process, the brine transfer pump 2 It is supplied to the salt extraction chamber 4 and the desalination chamber 5 of the salt extraction apparatus 3, circulated to the brine storage tank 1, and the air installed in the air from the blower 11 to the salt extraction chamber 4 is installed. Concentrated brine concentrated in the brine extraction chamber (4) with a concentration of 10 to 12 ° Be by applying 3 to 10 volts of direct current electricity from the rectifier while aeration through the engine (12). Discharged to the manufacturing process, the salt is removed from the brine in the desalting chamber (5) to desalination of the brine with demineralized water in the range of 5 to 15 kW / cm electrical conductivity of the brine line, Supplying the demineralized water to the reverse osmosis membrane of the second reverse osmosis filtration process, and the filtered water filtered in the range of 95% to 99.5% of the permeate was sent to a drinking water manufacturing process, concentrating the organics with the concentrated organic matter, which was not filtered. Method for concentrating organic matter from deep seawater or deep sea bedrock, characterized in that consisting of The salt extraction chamber 4 and the desalination chamber of the salt extraction apparatus 3 are supplied to the brine storage pump 1 when the unfiltered brine is supplied to the brine storage tank 1 in the first reverse osmosis filtration process. Instead of supplying to (5), the brine transfer pump (2) is supplied to the desalination chamber (5) of the electrodialysis apparatus (13) and returned to the brine reservoir (1), and the concentrated brine of the concentrated brine reservoir (17) is transferred. The concentrated brine transfer pump 18 is supplied to the salt concentration chamber 16 and conveyed to the concentrated brine storage tank 17 from the rectifier to the anode 6 of the anode chamber 14 and the cathode 7 of the cathode chamber 15 from the rectifier. Concentrated brine with a specific gravity in the range of 10-12 ° Be in the concentrated brine reservoir (17) by applying direct current electricity is sent to the salt manufacturing process, and the salt is desalted in the brine in the desalination chamber (5) to brine. The deionized water desalted in the range of 5 ~ 15 를 / ㎝ of electric conductivity in the conveying line is sent to the second reverse osmosis filtration process to concentrate organic matter. A method for concentrating organic matter from deep ocean water or deep sea bedrock characterized in that The method according to claim 1 or 2, wherein when the organic material is highly concentrated, the organic material is concentrated from deep ocean water or deep sea bedrock by vacuum evaporation or lyophilization at 40 ° C. or lower so that the organic material is not decomposed.

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