KR20110111340A - Method for producing drinking water from deep sea water - Google Patents

Abstract

The present invention relates to a method for producing a beverage from deep sea water, and more particularly, by taking the deep sea water of the deep seabed deeper than 200 m deep from the sea surface, and supplying a mineral modifier to the fresh water after electroextraction and reverse osmosis to adjust the hardness It relates to a method of producing a beverage.
To this end, the present invention, in the production of beverages from deep sea water deeper than 200m deep in the sea surface, the pre-treatment step of producing the pre-treated marine deep water by taking the deep sea water and warming treatment, pre-treatment, the pre-treated sea First desalination step of desalting deep water by electroextraction, supplying alkali agent to the desalting step, adjusting pH to 9-11, converting boric acid to polyboric acid, and then producing fresh water by reverse osmosis In the step, the neutralizing agent by injecting the neutralizing agent into the fresh water, it is characterized by consisting of the step of producing a beverage by adjusting the hardness in the range of 50 ~ 1,000mg / ℓ by injecting a mineral regulator.

Description

Method for producing drinking water from deep sea water

The present invention relates to a method for producing a beverage from deep sea water, and more particularly, by taking the deep sea water of the deep seabed deeper than 200 m deep from the sea surface, and supplying a mineral modifier to the fresh water after electroextraction and reverse osmosis to adjust the hardness It relates to a method of producing a beverage.

In general, the production method of drinking water from deep sea water is the first desalination treatment by primary reverse osmosis or electrodialysis after pretreatment such as warming, pretreatment filtration, and then the second reverse osmosis to produce fresh water. Drinking water is produced by adjusting the hardness by injecting a mineral regulator, but the method by primary reverse osmosis or electrodialysis has a problem in that the production cost of the drink is high due to high power consumption.

In order to solve the above problems, a method of producing a beverage by adjusting the hardness by demineralizing the primary salt by the electroextraction method of Document 1, and then injecting a mineral regulator into the demineralized water which is the filtered water subjected to the second reverse osmosis filtration. Although the method of primary desalination is proposed by alternately installing the positive and negative electrodes between the desalination chambers, the chlorine (Cl _{2) may} be caused by side reactions in the salt extraction chambers due to the close distance between the electrodes. ), Gaseous generation such as chlorine dioxide (ClO ₂ ), oxygen (O ₂ ), hydrogen (H ₂ ) is severe, and there is a problem of large air pollution and power consumption.

Patent Document 1 Republic of Korea Patent Publication No. 10-2008-0003248 (2008.01.07)

The present invention is to provide a method for producing a beverage by mixing the mineral deepener in the fresh water after the first desalination treatment by the deep extraction of the deep sea water by the electric extraction method without the generation of odor gas while low power consumption It is an object of the present invention.

The present invention, in the production of beverages from deep sea water deeper than 200m deep from the sea surface, the pre-treatment step of producing the pre-treated marine deep water by taking the deep sea water and warming treatment, pre-treatment filtration, the deep sea water First desalting step of desalting by electroextraction, supplying alkali agent to the desalting step to adjust pH to 9-11, converting boric acid to polyboric acid, and producing fresh water by reverse osmosis , Neutralizing the fresh water by injecting a neutralizing agent, and then injecting a mineral modifier to adjust the hardness to a range of 50 to 1,000 mg / l to produce a beverage.

The present invention, the first desalination treatment by the electric extraction method after the pre-treatment, such as warm water treatment, pre-treatment of the deep sea water has a low power consumption characteristics, while the second reverse osmosis filtration can be operated at low pressure to produce a drink at a low production cost It is expected to be widely used for the production of beverages from deep sea water.

1 is a process chart for producing a beverage from deep sea water
2 is an explanatory diagram of a desalting mechanism of deep sea water by electroextraction;
3 is a desalination apparatus using electric extraction of deep sea water

The present invention relates to a method for desalination by ingesting deep sea water, and more specifically, to warm and purify deep sea water with a depth of seabed deeper than 200 m at sea level. Neutralize freshwater, filtered water obtained by reverse osmosis of boric acid with poly boric acid by adjusting the pH to 9-11 after primary desalination by electroextraction. After the treatment, the method of producing the drink by adjusting the hardness with the mineral adjuster is presented.

Deep sea water is generally called deep sea water that is deeper than 200m above sea level, and unlike surface water, sunlight does not reach, so plankton and living organisms do not proliferate. Due to the difference in density, there is no contaminant present in surface seawater because it is not mixed with surface seawater, so it has low temperature stability, less pollutants, no harmful bacteria and organic matters compared to surface seawater. ), Rich in nutrients, rich in inorganic nutrients, which are very important for plant growth, well balanced properties of various minerals, and ripening aged for a long time under high pressure and low temperature. have.

The deep sea water contains about 5 to 10 times more inorganic nutrients than the surface sea water without any contaminants and harmful germs, and is especially important for calcium, magnesium, iron, zinc, sodium, etc. There are more than 70 kinds of elements, and various minerals are included. The analysis values of deep seawater and surface seawater are shown in Table 1 below.

Depth analysis of deep sea and surface seawater division Murodo, Koji Prefecture, Japan  374m deep sea water  Surface waters Work
half
term
neck  Water temperature (℃)  11.5  20.3  pH  7.98  8.15  DO dissolved oxygen (mg / l)  7.80  8.91  TOC Organic Carbon (mg / L)  0.962  1.780 COD _Mn (mg / L)    -    -  Soluble evaporation residue (mg / l)  47,750  37,590  M-alkalido (mg / l)  114.7  110.5 week
Yo
won
small  Cl chloride ion (wt%)  2.237  2.192  Na sodium (wt%)  1.080  1.030  Mg magnesium (mg / l)  1,300  1,310  Ca calcium (mg / L)  456  441  K potassium (mg / L)  414  399  Br Cancel (mg / L)  68.8  68.1  Sr Strontium (mg / L)  7.77  7.61  B boron (mg / L)  4.44  4.48  Ba barium (mg / l)  0.044  0.025  F Fluorine (mg / l)  0.53  0.56 SO ₄ ^{2 -} sulfate ion (mg / l)  2,833  2,627 spirit
amount
salt
Liu 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)  1.89  0.32 beauty
Amount
won
small  Pb lead (μg / ℓ)  0.102  0.087  Cd cadmium (µg / l)  0.028  0.008  Cu copper (µg / l)  0.153  0.272  Fe iron (㎍ / ℓ)  0.217  0.355  Mn manganese (㎍ / ℓ)  0.265  0.313  Ni nickel (µg / l)  0.387  0.496  Zn zinc (µg / l)  0.624  0.452  As arsenic (㎍ / ℓ)  1.051  0.440  Mo molybdenum (µg / l)  5.095  5.565  Cr chromium (µg / l) Fungus
Number  Number of live bacteria (dog / ml) 0 540  E. coli count (pcs / ml) voice voice

In general, desalination of deep seawater or superficial seawater is carried out by prefiltration by microfiltration or ultrafiltration, followed by nanofiltration and reverse osmosis. Osmosis filtration is used to remove salts from deep seawater and surface seawater, or electrodialysis and reverse osmosis using ion exchange membranes are mainly applied.However, nanofiltration and reverse osmosis The method by the administration section has a problem that there is no economical problem and high maintenance cost due to the membrane replacement cost due to fouling of the membrane due to the low recovery rate of 40 to 60% while operating at high pressure. I) Altitude is high because the solution resistance increases rapidly in the electric conductivity value of 6 ~ 12㎳ / ㎝ or less. There is a desalination process difficult.

Thus, in the present invention, while supplying deep sea water to a multistage desalting chamber separated by a diaphragm between the anode and the cathode in the salt extraction chamber, direct current is applied to the anode and the cathode from the rectifier to form an electric field. Salts (NaCl, KCl, MgSO ₄ , MgCl ₂ , CaSO ₄ , MgBr ₂ ..., Etc.) contained in the deep seawater in the desalting chamber are extracted into the salt extraction chamber as the salts of the original state by electrophoresis. By applying a low voltage and a current by a desalting apparatus (referred to as "electric extraction desalting apparatus" in the present invention) to remove by means of the first desalting treatment in a state of low power consumption, then a low pressure of 2 ~ 10㎏ / ㎠ By reverse osmosis, we propose a desalination method with low operating and maintenance costs.

In the present invention, the Bumedo (° Be) of the Bumedo hydrometer (° Be) representing the specific gravity of the deep sea water is expressed as a numerical value of the scale when the Bumedo hydrometer is floated in the liquid to measure the specific gravity of the liquid, 15 ° saline is 15 ° Be and 15% is divided between them. Bomedo (° Be) approximates the salt concentration (wt%) for deep sea water. (I) it is widely used as a measure of concentration.

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

The electrical conductivity measured in the electric conductivity indicating switch (ECIS) is an indicator of the degree of conduction of an aqueous solution by conducting electricity, and the unit represents the salt concentration in water. The unit is the inverse of the electrical resistivity of the aqueous solution. Corresponding Siemens / meter, the relationship between the electrical conductivity (EC) and the total soluble salt (TSS) in water is given by the following equation (2).

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

The double salinity concentration (NaCl ppm) can be estimated simply by the following equation (3).

Salinity concentration (NaCl ppm) = 552 x EC (cc / cm) -200. … … … … … … … … … (3)

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

The present invention is to take the deep sea water of the seabed deeper than 200m deep from the sea surface, and then subjected to warming treatment and pre-treatment, and then desalted by the first electroextraction method, after adjusting the secondary pH to 9-11, reverse osmosis It relates to a method of producing desalination by desalting by the administration section, and producing a drinking water using the fresh water, which will be described in detail with reference to the accompanying drawings.

Ⅰ. Pretreatment stage

1. Intake and warming process

In the pretreatment process, the deep sea water of the seabed deeper than 200m deep from the sea surface is taken out and warmed so that the subsequent treatment can be smoothly processed.

Deep sea water is taken from deep seabeds deeper than 200m deep from the sea surface, and the intake method is piped down to deep seabeds deeper than 200m below sea level, or pipes are installed to deep seabed deeper than 200m deep from sea level. The water is pumped or the pipe is installed from the sea level to the sea floor deeper than 200m deep, and the water intake well is installed deeper than the sea level to take water according to the siphon principle.

The deep sea water collected in the sump is low in temperature and high in viscosity, resulting in low treatment efficiency, so it is supplied with heat from a boiler (in summer, the surface water temperature may be used), and then warmed to 20 to 30 ° C. Send to fair

2. Pretreatment Filtration Process

The pretreatment filtration process removes suspended solids (SS) by filtration through sand filtration, micro filtration or ultra filtration alone or a combination of two or more processes. Next, it is sent to the pre-treated deep sea water storage tank (1) of the desalination process by the electroextraction method.

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

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

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

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

The FI value is a numerical value representing the fine turbidity concentration in the target water, and is expressed by the following equation (4).

FI = (1-T ₀ / T ₁₅ ) x 100/15... … … … … … … … … … … … … … … … … … … … (4)

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

II. First desalination step

The present invention, in order to solve the problem of high power consumption when the desalination treatment of seawater or deep sea water with an electrodialysis apparatus or reverse osmosis filtration apparatus, the anode 8 and the cathode 9 in the salt extraction chamber (3) It relates to a desalination apparatus by electric extraction in which a desalting chamber (4) separated by a cation exchange diaphragm (5) and an anion exchange diaphragm (6) is installed in a plurality of stages. As follows.

The present invention, in order to solve the problem of high power consumption when desalination of the deep sea water by electrodialysis or reverse osmosis filtration device, the cation between the anode (8) and the cathode (9) inside the salt extraction chamber (3) The desalination apparatus by electroextraction in which the desalination chamber 4 separated by the exchange diaphragm 5 and the anion exchange diaphragm 6 is installed in multiple stages will be described in detail with reference to the accompanying drawings. .

FIG. 2 is an explanatory view of a desalting mechanism of deep sea water by the electroextraction method. The negative electrode 9 is a cation exchanger between the positive electrode 8 and the negative electrode 9 installed inside the salt extraction chamber 3. The deep seawater is primary by an "extraction desalination apparatus" consisting of the diaphragm 5 and the anode 8 provided with an anion exchange diaphragm 6 and an isolated desalination chamber 4 with multiple stages. Desalting treatment.

The deep seawater to be pretreated is supplied to the storage tank 1, and the deep seawater to be supplied to the salt extraction chamber 3 and the desalination chamber 4 by a transfer pump 2, and the deep seawater to be supplied to the desalination chamber 4 is While circulating to the storage tank 1, aeration of air in the air from the blower 10 through the diffuser 11, 4 to 50 volts of direct current from the rectifier is applied to the electric field. When the electric field is formed, the cations (Na ⁺ , K ⁺ , Ca ^{2 +} , Mg ^{2 +} , Fe ^{2 +} , Fe ³⁺ ) contained in the deep sea water of the desalting chamber 4 by electrophoresis. , Zn ^{2 +} ..., Etc.) are transferred to the salt extraction chamber 3 by passing through the cation exchange diaphragm 5 on the cathode 9 side, and anion (Cl ⁻ , Br ⁻ , NO ₃ ⁻ , SO ₄ ^{2 − _{, HCO 3 -, CO 3 2}} -, HPO 4 2 -, PO 4 3 - ... and so on) is concentrated as it moves to the anode (8) an anion exchange membrane (6) transmitted by salt extraction chamber 3 to the side brine Is produced and sent to the salt manufacturing process The salts contained in the deep sea water are firstly desalted.

The concentration of brine in the salt extraction chamber (3) is the amount of deep ocean water that flows in such a way that the Bomedo specific gravity of the Baume's hydrometer indicating switch (BIS) installed in the salt extraction chamber (3) is 12 to 20 ° Be. Adjust it.

The desalted water in which the salt is removed from the deep seawater in the desalination chamber 4 and the deionized water in the electric conductivity indicating range (ECIS) installed in the demineralized water line is in the range of 6-12 mW / cm operates the solenoid valve. To discharge the first desalted water.

In the actual desalination apparatus for deep sea water, the cathode 9 side inside the salt extraction chamber 3 has a cation exchange diaphragm 5 as shown in FIG. 8) The anion exchange diaphragm 6 is provided to install an isolated desalting chamber 4 between the anode 8 and the cathode 9 in multiple stages, and this is alternately repeated depending on the processing capacity. The desalination chamber (4) is applied to the desalination unit by the electric extraction, by supplying the deep sea water of the storage tank (1) to the salt extraction chamber (3) and the desalination chamber (4) by the transfer pump (2), and applying direct current electricity from the rectifier. When the electric field is formed in the desalination apparatus, the salt contained in the desalination chamber 4 is extracted into the salt extraction chamber 3 by electrophoresis, and the desalination treatment is performed.

In the first desalination treatment of the salt contained in the deep sea water, the deep sea water of the storage tank 1 is transferred to the desalting apparatus subjected to the desalination treatment by electric extraction to the salt extraction chamber 3 and the desalination chamber 4 by a transfer pump 2. The deep sea water supplied to the desalination chamber 4 is conveyed to the storage tank 1 while supplying air from the blower 10 to the diffuser 11 installed below the salt extraction chamber 3 to aeration. When a direct current of 4 to 50 volts is applied from the rectifier to the positive electrode 8 and the negative electrode 9 to form an electric field in the desalination chamber 4, electrophoresis is performed. The cations contained in the deep seawater of the desalting chamber 4 pass through the cation exchange diaphragm 5 on the cathode 9 side and move to the salt extraction chamber 3, and the anion is an anion exchange diaphragm on the anode 8 side. While passing through (6) to the salt extraction chamber (3), the concentrated brine from the salt extraction chamber (3) is the ratio of the supply of the deep sea water flowing in The concentrated brine is discharged by the salt manufacturing process while operating the solenoid valve (ⓢ) so that the specific gravity of the BIS in the BIS range is 12 to 20 ° Be. The desalted water is removed and the deionized water of the electroconductivity indicator controller (ECIS) in the demineralized water line is in the range of 6-12㎳ / ㎝. The solenoid valve (ⓢ) is operated. After adjustment, it is sent to reverse osmosis filtration process.

The desalting chamber 4 is installed between the anode 8 and the cathode 9 in the salt extraction chamber 3 of the desalination apparatus of the deep sea water according to the treatment capacity. Alternately install multiple stages.

The electrochemical reaction mechanism in which the salt in the deep sea water described above is desalted by the "desalting apparatus by electroextraction" is as follows.

In the case of NaCl among the salts contained in the deep sea water, Na ⁺ ions and Cl ^- ions are dissociated in the deep sea water by hydrolysis reaction as in the following reaction formula (5).

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

When a direct current is applied from the rectifier to the anode 8 and the cathode 9 to form an electric field inside the desalination chamber 4, the electrophoresis causes cations such as Na ⁺ ions contained in the deep sea water in the desalination chamber 4. The silver penetrates the cation exchange diaphragm 5 on the cathode 9 side and moves to the salt extraction chamber 3, and anion such as Cl ⁻ ions penetrates the anion exchange diaphragm 6 on the anode 8 side to salt The salts (NaCl, KCl, CaSO ₄ , CaCO ₃ , MgCl ₂ , MgSO ₄ , MgBr ₂ , SrSO ₄ ..., Etc.) are removed (desalted) from the deep sea water of the desalting chamber 4 while moving to the extraction chamber ₃ . In the case of NaCl, reviewing the reaction mechanism is as follows.

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

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

Na ⁺ ions and Cl ⁻ ions transferred to the salt extraction chamber 3 are in situ in the original NaCl state.

Na ⁺ + Cl ⁻ —H ₂ O → NaCl... … … … … … … … … … … … … … … … … … … (8)

On the anode 8 and cathode 9 sides, if the following side reactions occur, odor generation and power consumption may increase. Therefore, air from the blower 10 may be diffused into the air. 11) aeration through the following side reactions (副 反 최대한) to the maximum suppressed.

2Cl ⁻ → Cl _{2 ( aq )} + 2e ⁻ . … … … … … … … … … … … … … … … … … … … (9)

Cl _{2 ( aq )} → Cl _{2 (g)} ↑. … … … … … … … … … … … … … … … … … … … … 10

Cl _{2 ( aq )} + H ₂ O → HClO _{( aq )} + HCl... … … … … … … … … … … … … … … … … (11)

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

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

At this time, the supply amount of air supplied from the blower 10 through the diffuser 11 is such that the aeration intensity (Intensity of aeration) is 1.2 to 2.0 air (m 3) / tank volume (m 3).

A feature of the present invention is that the salinity (NaCl, etc.) does not occur at all in the deep sea water of the desalting chamber 4 as compared to the desalination method by electrolysis or electrodialysis. The salt is applied from the rectifier to the anode 8 and the cathode 9 by direct current to form an electric field. By electrophoresis, cations (Na ^+, etc.) penetrate the cation exchange diaphragm 5 on the cathode 9 side. Is moved to the salt extraction chamber (3), anion (Cl ^- etc.) passes through the anion exchange diaphragm (6) on the positive electrode (8) side to the salt extraction chamber (3) to the state of the original salt It is characterized by low power consumption because current is not consumed by salt decomposition because it is extracted and removed during the reaction.

Salt extraction chamber (3) and desalination chamber (4) are made of flame resistant stainless steel, titanium, epoxy coated (coated) or lined with carbon steel, or glass. Lining fiber glass reinforced plastic (FRP).

The negative electrode plate 6 is made of steel plate of high hydrogen generation overvoltage, which is made of lined with Raney nickel, or flame-resistant stainless steel or titanium plate. , The anode (8) plate is coated with TiO ₂ -RuO ₂ on a titanium plate, which is made of a material with high corrosion resistance and high oxygen and chlorine generation overvoltage. It uses a dimensionally stable table (DSA) electrode.

Remove all monovalent salts (NaCl, KCl, KBr, etc.) and polyvalent salts (多 價 鹽, MgCl ₂ , MgSO ₄ , CaSO ₄ , FeCl ₂ , FeCl ₃ , SrSO ₄ , etc.) contained in deep ocean water In the case of desalination of the deep water, the cation exchange diaphragm 5 on the cathode 9 side uses a cation exchange diaphragm that permeates all cations, and the anion exchange diaphragm 6 on the positive electrode 8 side includes all anions. An anion exchange diaphragm is used.

However, even if the desalination efficiency is slightly reduced, the asbestos, nylon, polypropylene, and polyvinylidene fluoride are similarly disposed in the diaphragm on the anode 8 side and the cathode 9 side in consideration of economical efficiency. vinylindene fluoride, polyolefin, polyethylene, polyester, polyester, hexafluoropropylene, polyfluoroolefin, tetrafluoroethylene (TFE: Tetrafluoroethylene), polytetrafluoroethylene (PTFE: Polytetrafluoroethylene), one kind of membrane may be used.

When the NaCl component contained in the deep ocean water is removed to produce mineral water containing a large amount of divalent or more minerals for use in agricultural water, the salts contained in the deep ocean water When only the monovalent cation is removed without removing the mineral component as a cation, a monovalent cation selective exchange diaphragm that selectively permeates only the monovalent cation through the cation exchange diaphragm 5 on the negative electrode 9 side is used.

The one contained in the deep sea water cations (Na ^+, K ⁺⁾ and sulfate ions (SO ₄ ^{2 -)} to the case of producing the removed number of mineral, an anion exchange membrane (5) on the side of the anode (8) is all the anions The permeable anion exchange membrane is used, and the cation exchange membrane 5 on the cathode 9 side uses a membrane in which only monovalent cations are exchanged selectively.

The sulfate ions (SO ₄ ^{2 -)} in the deep sea water is in the form of calcium chloride (CaCl ₂₎ by the reaction of calcium ions (14), such as (Ca ^{2 +)} is as follows: As to sulfate ions are removed existed as CaSO ₄ In the presence of water, mineral water having a high calcium content is produced.

CaSO ₄ + MgCl ₂ → CaCl ₂ + MgSO ₄ ... … … … … … … … … … … … … … … (14)

The monovalent cation selective exchange diaphragm used in the present invention is an exchange membrane that selectively permeates only monovalent cations while suppressing divalent or more multivalent cation permeation, and is based on a polystyrene-divinylbenzene system. Side chains and polyethyleneimine or polyvinyl chloride in the load-carrying membranes that hold the negative charge R-SO ₃ ^- in the main chain. Graft polymers such as polyvinylpyridine or graft polymers whose main chains are polystyrene with side chains made of polyethyleneimine or polyvinyl pyridine. As long as it has the same molecular structure as the main chain or the side chain of the cation exchange diaphragm, it can be used without limitation. Preferably, polyethylene, polypropylene Only monovalent cations permeate into the main chain or side chain with a polymer molecule structure composed of a cation exchange diaphragm immobilized with negative charge R-SO ₃ ^- on propylene, polyvinyl chloride, polystyrene, etc. Monovalent cation selective exchange diaphragms such as polyvinylpyridine, polyvinylamine or polyethyleneimine membranes having a molecular structure of Polystyrene-graft-ethylene imine may be most preferably used.

In contrast to monovalent cation selective exchange diaphragms, monovalent anion selective exchange diaphragms are membranes capable of selectively exchanging only monovalent anions and are classified from primary to tertiary amines in the polymer chain of a substrate. The surface of the membrane was modified to selectively permeate monovalent anions to the surface of the positively charged membrane in which (Amine) or ammonium groups were fixed to the membrane and aminated to introduce a cation. Anion exchange diaphragm in which the ion exchange group is bridge | crosslinked by aliphatic hydrocarbon, and the thin film layer of the polymeric material which has a cation exchange group is formed in the membrane surface part. It is preferable to perform quaternization at the same time of crosslinking with an aliphatic hydrocarbon to the monomer introduced into the exchanger (Monomer), and a polymer having a cation exchange group as a polymer material having a cation exchange group. It is a molecular weight 500 such as an insoluble polymer having an electrolyte, a linear polymer electrolyte, or a cation exchange group. Monomer unit having a carboxylic acid group (-COOH) or a sulfonic acid group (-SO ₃ H) such as a polymer electrolyte having a cation exchange group, a methacrylic acid, and styrene sulfonic acid A membrane that selectively exchanges only monovalent anions with a linear polymer electrolyte containing a large number of units, an insoluble polymer having a cation exchange group such as a condensation of phenols and aldehydes including a cation exchange group is used.

The cation exchange diaphragm which permeates all cations is a load-electrode membrane which fixes negatively charged R-SO ₃ ^- in the main chain of a polystyrene-divinylbenzene system. In order to selectively permeate monovalent cations to the surface of the membrane selectively, a cationic polymer electrolyte such as polyethyleneimine is coated or bonded in a thin layer to perform a modification process. Cation exchange membranes are used.

In addition, the anion exchange diaphragm penetrating all anions is a positively charged membrane in which a cation is introduced by amination by immobilizing primary to tertiary amines or ammonium groups in the polymer chain of the substrate to the membrane. The membrane which does not modify the membrane surface is used so that a monovalent anion may permeate selectively on the surface of a denser.

The diaphragm supporter 7 is flame resistant stainless steel or titanium on the outside of the cation exchange diaphragm 5 and the anion exchange diaphragm 6 on a nonwoven fabric made of synthetic resin such as viscose rayon or nylon having a thickness of 1 to 10 mm. It is supported by a porous plate or grid plate.

In the desalting apparatus as shown in FIG. 3, the anode 8 inside the salt extraction chamber 3 having a capacity of 3.6 m 3 (840 mm × 1,200 mm × 4,000 mm) has TiO ₂ -RuO ₂ on a 1,000 mm × 1,200 mm titanium plate. Two sheet-coated DSA electrodes were installed, and the cathode 9 had two 1,000 mm × 1,200 mm titanium plate electrodes alternately installed, and a cation exchange diaphragm between each anode 8 and the cathode 9. (5) The Aciplex K-101 of Asahi Kasei Co., Ltd., Japan, the deionization chamber using Aciplex A-101 of the company (4) capacity of 0.1 ㎥ (25 mm x 1,000 mm x 4,000 mm) In a desalting apparatus equipped with three sheets x 3, the deep seawater with a salt concentration of 3.45 wt% in the storage tank 1 was transferred to the salt extraction chamber (3). ) Is supplied so that the specific gravity of brine in concentrated brine is maintained in the range of 12-14 ° Be, and 2-15 m / hr is supplied to the desalination chamber, and 5 to 15 volts of direct current electric current is supplied from the rectifier to each cathode and anode. is it The results of measuring the current and salinity removal rate were as shown in Table 2 below.

Desalination Test Report by Electro-Extraction of Deep Sea Water Voltage applied (Volt) 5 10 15 Ampere  32.8   46.5   71.4 Salt concentration in treated deep sea water (wt%)    0.84     0.31     0.08 Desalination Rate (%)  75.7   91.0   97.7

(Note: The theoretical applied current is 1,347A for desalination by electrolysis up to 0.1wt% of 1Ton / hr of deep seawater with a salt content of 3.45wt%.)

As shown in Table 1, it can be seen that the desalination of deep sea water by the "desalination apparatus by electroextraction" of the present invention has less power consumption than the desalination by conventional electrodialysis.

III. Steps to produce fresh water

Deep sea water contains boron in the range of 4-5 mg / l and is present in the form of boric acid (H ₃ BO ₃ ). Since the particle size is small as the ion radius is 0.23Å, the drinking water standard is 0.3 by simple reverse osmosis. It is difficult to treat it in mg / l or less, and the dissociation constant pKa value is about 9, which is almost undissolved in the deep ocean water and hardly exists in the ionic state. Also, it is difficult to treat the drinking water below 0.3mg / l, so that the pH is treated with 9 ~ 11 alkali, and the boric acid is converted to polyboric acid in the gel state. The boron compound is removed by reverse osmosis filtration.

When boric acid in water is subjected to alkali treatment, it is converted into polyboric acid in a gel state by the following reaction (15).

B (OH) ₃ + OH ^_ → [B (OH) ₄ ] ^- → [B ₃ O ₃ (OH) ₄ ] ^- → [B ₄ O ₅ (OH) ₄ ] ^2- → [B ₅ O ₆ (OH ) ₄ ] ^- … (15)

In the desalination process by the electro-extraction method, if the demineralized water is first supplied to the pH adjusting tank 21, the pH of the alkali agent (NaOH) is injected into the pH range of 9-11 using a pH indicating control switch (pHIS). The boron compound was converted to polyboric acid by stirring with the adjusting tank stirrer 22, and then supplied to the reverse osmosis filtration process, and the operating pressure was supplied to the reverse osmosis filtration membrane by the supply pump 23 to the reverse osmosis filtration membrane. The concentrated water containing the boron compound is neutralized and discharged to the original position deeper than 200m from the sea surface, and fresh water, which is filtered water filtered under the drinking water standard of 0.3mg / l, produces fresh water. .

At this time, the operating pressure of the feed pump supplied to the reverse osmosis membrane of the reverse osmosis filtration process is supplied at 5 to 25 kg / cm 2, and the operating pressure is 5 to 25 kg / since the concentration of salt is low in the feed water supplied to the reverse osmosis filtration process. Even when operating at a low pressure in the range of cm 2, the membrane permeation amount of the spiral filtration membrane is operated at 0.6 to 1.2 m 3 / m 2 · day, in which the boron compound is filtered below the drinking water standard of 0.3 mg / l.

In the reverse osmosis filtration process, scale generation is not a problem because the materials such as CaCO ₃ , CaSO ₄ , and SrSO ₄ , which produce scales, are removed in the desalting process by the electroextraction method even when the pH is supplied in an alkaline state of 9-11. Do not.

The stirring method of the pH adjustment process is a propeller type stirrer, which is stirred at 180 to 360 rpm for 20 to 40 minutes, and the material is made of stainless steel or bronze.

In the desalination process by the electroextraction method of Example 1, the applied voltage was operated at 10 volts to convert the boron compound in the form of polyboric acid by adjusting the pH to 9.5 in the pH dehydration process. Then, the pressure was supplied to the membrane at 10 kg / cm 2 G using a spiral reverse osmosis membrane of Toray Corporation of Japan, low pressure reverse osmosis membrane, model number SU-710, and the membrane permeation amount was 0.72m 3 / m 2. The amount of permeated water was 82.3% of the amount of influent when the work was done, and the analysis values of the main components of the filtered water (deboron water) are shown in Table 3, and the concentration of boron (B) was 0.12 mg / l. 0.3 mg / L or less was used to produce beverages.

Analysis of Major Components of Filtrate in Reverse Osmosis Filtration Process         ingredient         Content (mg / ℓ)           Sodium (Na)             67.6 Chloride ion (Cl ^-)            116.3           Magnesium (Mg)              2.7           Calcium (Ca)              1.1           Potassium (K)              3.3           Boron (B)              0.12 Nitrate (NO ₃ ^-)              0.02           Phosphate              0.04 Silicate Silicate (SiO ₂ )              0.2           Evaporation residue             206           General bacteria           Within the standard           Escherichia coli           Not detected

Ⅳ. Steps to produce beverages

1. Neutralization and Mineral Adjustment Process

Fresh water, which is filtered water in the reverse osmosis filtration process, is injected with acid (HCl, H ₂ SO _4, etc.) as a neutralizing agent to neutralize the pH to 5.8 to 8.5, which is the standard value of drinking water, and then supplied with mineral modifier to provide hardness. Is adjusted to a range of 50 to 1,000 mg / L.

Neutralization and mineral adjustment may be performed simultaneously in the same reactor, and mineralization may be sequentially performed after neutralization treatment, and the stirring method may be performed using a propeller type stirrer at 180 to 360 rpm for 20 to 40 minutes. The material is stainless steel or bronze.

The mineral modifier may be a commercially available mineral modifier, and the type of mineral modifier is not particularly limited, but the salt concentration is concentrated by concentrating the deep sea water in the depth of the seabed deeper than 200 m in the sea level in the range of 32 to 34 ° Be. Trehalose or sucrose, which is a non-reducing sugar, was adjusted to a Ca / Mg weight ratio in the range of 2 to 6 by injecting calcium agent into the produced Bittern. It is preferable to adjust the hardness using the mineral regulator prepared by adding.

2. Beverage Production Process

In the neutralization and mineral adjustment process, the pH was neutralized to 5.8 to 8.5, and then the mineral water was supplied to adjust the hardness to the range of 50 to 1,000 mg / L. The water was sterilized, and then the container was filled and packed, It is inspected and shipped as a beverage product.

The sterilization treatment is one of known high temperature heat sterilization treatment, ultraviolet irradiation treatment or pretreatment treatment.

Edison Co., Ltd. produced from Kochi Muroto deep sea water, while neutralizing the pH to 7.3 by adding 5 wt% aqueous hydrochloric acid (HCl) solution to the filtrate in reverse osmosis of Example 2. Water quality of the mineral adjuster of Co., Ltd.) was adjusted to 250 kW / cm, and the UV sterilized water was analyzed as shown in Table 4 below.

Water quality analysis value of drinking water Item Manufactured beverages Remarks (the standard of drinking water) pH    7.3    5.8 to 8.5  Conductivity (㎲ / ㎝) 250 -  Hardness (mg / ℓ) 250  300 or less Na ⁺ (mg / L)   32  200 or less (WHO standard) Cl ^- (㎎ / ℓ)   61  250 or less Ca ^{2 +} (㎎ / ℓ)   52 - Mg ^{2 +} (㎎ / ℓ)  16 - K ⁺ (mg / L)    1.2 - SiO _{2 (mg / L)}    2.4 - _{^{SO 4 2 - (㎎ / ℓ}} )    5.6 200 or less  B (mg / l)    0.12    0.3 or less

As shown in the contents of Table 4, the concentration of boron (B) was treated to 0.12 mg / l with a drinking water standard value of 0.3 mg / l or less.

1: reservoir 2: transfer pump
3: salt extraction chamber 4: desalting chamber
5: cation exchange membrane 6: anion exchange membrane
7: diaphragm supporter 8: anode
9: cathode 10: air blower
11: diffuser ⓢ: Solenoid valve
BIS: Baume's hydrometer indicating switch
ECIS: Electric conductivity indicating switch

Claims (1)

In the production of drinking water from deep sea water,
The deep seawater is warmed to 20 to 30 ° C., and then filtered by combining one or more filtration processes from a filtration process consisting of sand filtration, micro filtration or ultra filtration. (Suspended solid) pretreatment step of treating with filtered water,
Filtrate water in the pretreatment step is provided with a plurality of alternating anodes 5 and cathodes 6 in the salt extraction chamber 3, and a diaphragm between these anodes 5 and 6 cathodes. The deep seawater is supplied to the salt extraction chamber 3 and the desalting chamber 4 to the desalting apparatus by electric extraction composed of a plurality of desalting chambers 4 separated by (7), and is supplied to the desalting chamber 4. The pre-treated deep sea water is returned to the storage tank 1, while supplying air from the blower 9 to the diffuser 10 and aeration, applying direct current electric current from the rectifier to remove salts contained in the deep sea water in the desalting chamber 4. First desalination step of desalination,
The alkaline agent is injected into the demineralized water desalted in the first desalting step in the range of 9 to 11, and then supplied to the reverse osmosis filtration process to discharge the filtered boron compound-containing water after neutralization treatment, and the boron compound is 0.3 mg / l. Producing fresh water which is filtered water filtered below;
Neutralizing the pH to 5.8 to 8.5 by supplying a neutralizer to the fresh water, and then supplying a mineral regulator to sterilize, container filling and packaging treatment, inspection of water to adjust the hardness in the range of 50 ~ 1,000 ㎎ / ℓ Method for producing a beverage from deep sea water, characterized in that consisting of a step of producing a beverage.

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