KR20080092572A - A method to produce electrolysis oxidation water and electrolysis reduction water from deep sea water - Google Patents

Abstract

Provided is a method for producing electrolytic oxidized water as well as electrolytic reduced water using the desalinated water and desalinated mineral water after obtaining desalinated water and desalinated mineral water by collecting deep seawater from a water depth of 200 m or lower and desalinating the seawater, thereby removing NaCl excessively contained in the seawater. A method for producing electrolytic oxidized water and electrolytic reduced water from deep seawater comprises: a pre-treatment step including a water collecting and heating process of collecting deep seawater from a water depth of 200 m or lower and heating the collected deep seawater to a temperature of 20 to 30 deg.C, and a pre-treating filtration process of passing the heated deep seawater through one or more of a sand filter, a micro-filtration filter and a ultra-filtration filter to remove suspended solids from the deep seawater, and perform a nano-filtration treatment of the suspended solid-removed deep seawater; a desalination step including a first reverse osmosis filtration process of filtering the nano-filtered water through a reverse osmosis filtration membrane, a pH adjusting process of supplying an alkali agent into the filtered water to adjust a pH of the filtered water to a range of 9 to 11, a second reverse osmosis filtration process of supplying the pH-adjusted filtered water to a second reverse osmosis filtration membrane, and an electrodialysis process of supplying concentrate from the first reverse osmosis filtration process to a desalination chamber of an electrodialyzer to return the concentrate to an electrodialyzer supply water storage tank, supplying brine of a brine storage tank to a salt concentration chamber to return the brine to a brine storage tank, sending concentrated brine of the brine storage tank to a salt production process, and sending desalinated mineral water to an anode chamber of an electrolyzer of the electrolysis process; and a production step of the electrolytic oxidized water and electrolytic reduced water including an electrolysis process of applying a DC electricity to an anode of the anode chamber and a cathode of a cathode chamber to produce alkaline reduced water and acidic oxidized water from the filtered water of the second reverse osmosis filtration process, thereby produce the electrolytic reduced water and electrolytic oxidized water respectively from the alkaline reduced water and acidic oxidized water.

Description

A method to produce electrolysis oxidation water and electrolysis reduction water from deep sea water}

1 is a process chart for producing electrolytic oxidized water and electrolytic reduced water from deep sea water

2 is a process diagram of the electrodialysis apparatus

3 is electrolysis process chart

<Explanation of symbols for main parts of drawing>

1: electrodialysis equipment supply tank 2: electrodialysis equipment supply pump

3: electrodialysis device 4: anode

5: cathode 6: anode chamber

7: cathode chamber 8: anion exchange diaphragm

9: cation exchange diaphragm 10: desalination chamber

11: salt concentration room 12: brine reservoir

13: brine transfer pump 14: electrolysis device

15: anode chamber 16: cathode chamber

17: anode 18: cathode

19: diaphragm 20: electrolytic oxidation water storage tank

21: electrolytic oxidation water transfer pump 22: electrolytic reduction water storage tank

23: electrolytic reduction water transfer pump ⓢ: Solenoid valve

LS: Level switch FI: Flow indicator

pHI: pH indicator M: Motor

pHIS: pH indicating switch

ORPI: Oxidation reduction potential indicator

ORPIS: Oxidation reduction potential indicating switch

The present invention relates to a method for producing electrolytic oxidized water and electrolytic reduced water, and more particularly, to collect deep sea water of 200 m or less and warm it to 20 to 30 ° C. After pre-filtration and filtration, the concentrated water, which was not filtered in the first reverse osmosis filtration process, was sent to the electrodialysis process, and the demineralized mineral water desalted with NaCl was electrolyzed. The electrolytic oxidation water is sent to the anode chamber of 電 分解 工程, and the filtered water filtered in the first reverse osmosis process is sent to pH adjustment process to adjust the pH to 9-11. The present invention relates to a method for producing electrolytic reduced water by sending the filtered water from which the boron compound is removed to the process and sent to the cathode chamber of the electrolysis process.

Deep sea water is generally called deep sea water of 200m or less, and unlike the surface waters, it is not exposed to sunlight, so plankton and living organisms do not proliferate. There is almost no contaminant present in surface seawater because it is not mixed with surface seawater due to the density difference according to the low density, and low temperature stability, low concentration of suspended solids and low concentration of pollutants and pollutants compared to surface seawater. Minerals with very low purity of bacteria and organic matter, rich in nutrients and inorganic minerals which are very important for plant growth. Balance characteristics and high pressure low temperature clusters of water molecules are small grouped for a long time, so the surface tension is small, so the permeability is good. It is known that the properties such as the aging property (熟 成 性) Aging with water, deep sea water, and analysis of the main components contained in the sea surface is equal to the contents of Table 1.

In addition, deep sea water contains a variety of minerals necessary for the growth of living organisms, and recent studies have shown that deep sea water contains marine microorganisms Jude Arteronamonas denitrificans and Arteromonas macleodyne. (Alteromonas macleodii) and other metabolites such as cycloprodigiosin hydrochloride, which activate macrophage proliferation and are effective in atopic dermatitis. And sugars such as trehalose and chitosan that are highly moisturizing from fish such as crustaceans, and alginic acid and algae from seaweeds. There are properties that contain substances useful for the same skin care.

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

         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

Deep ocean water of 200 m or less in depth does not reach sunlight, and therefore, photosynthesis by algae or aqueous plants is not performed in the deep ocean water. It is a general opinion. As such, it is thought that there is almost no organic substance in the deep ocean currents, but it contains minerals at a higher concentration than in surface seawater, and these minerals are scarce to be easily found in the current diet. It also contains minerals. In addition, it was found that many organic substances were dissolved in this deep ocean water. Therefore, these dissolved organic substances are highly likely to have cellular activity, and these components can be obtained, and high cellular activity, specifically fibroblast energy metabolism and proliferation active substance (增殖 活性 物質: 纖維) Immune cell activators, such as skin cell activators, and eosinophils, can be obtained. Such fibroblast energy metabolism and proliferation active substances are effective for preventing skin aging or improving the function of aged skin, and such eosinophils are known to be highly useful as therapeutic agents for allergic diseases such as atopy.

As described above, deep sea water has been found to be useful for the growth of living organisms and effective in atopic dermatitis, and is used in cosmetics, bath water, and the like, and in recent years, such substances also contain microelements that have anticancer activity. It is announced.

Thus, in the present invention, the above-described characteristics of deep sea water can be used for electrolytic oxidation water and alkali reducing drinking water which can be used in foliar spray, cosmetic water, and sterilizing water in bath water, crops and horticultural crops. The present invention proposes a method for economically producing electrolytic reduced water.

Conventional techniques for simultaneously producing electrolytic reduced water and electrolytic oxidized water from deep sea water have not been investigated. As a method of preparing electrolytic oxidized water, Japanese Patent Laid-Open No. 2002-153874 discloses electrolysis of an aqueous solution in which sodium chloride is dissolved in deep sea water. Primary alkaline water is produced on the cathode side and primary oxidized water is produced on the anode side, and the primary alkaline water and primary oxidized water are mixed in a sealed state, and the mixed solution is electrolyzed again to generate secondary alkaline water and secondary oxidized water. The method for producing sterilizing water using this secondary oxidized water as sterilizing water is presented, but since the salt content is high by using the deep sea water which has sterilizing power but is not desalted, foliar spraying agent for sterilization of pests of crops and mineral supply (葉面 撒布 劑) has a problem that can not be used.

In the present invention, the Bomedo (° Be) of the Baume's hydrometer showing the specific gravity of the seawater is expressed as a numerical value of the scale when the Bomedo hydrometer is floated in the liquid to measure the specific gravity of the liquid, rather than the specific gravity of the water. Heavy bomedoes for heavy liquids and light bomedoes for light liquids that are lighter than the specific gravity of water. Among them, pure liquids are pure water. 0 ° Be, 15% saline solution to 15 ° Be, with 15 divisions between them. For liquid solution, 10% saline solution to 0 ° Be and pure water to 10 ° Be. The scale is divided into 15 equal parts between them, and BOME (° Be) is widely used as a measure of concentration because seawater approximates salt concentration (wt%).

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

For heavy media that has a specific gravity of liquid greater than that of water

d = 144.3 / (144.3- ° Be). … … … … … … … … … … … … … … … … … ①

In the case of an alarm field where the specific gravity of the liquid is lower than the specific gravity of the water

d = 144.3 / (134.3 + ° Be). … … … … … … … … … … … … … … … … … ②

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

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

The double salinity concentration (NaCl ppm) can be estimated simply by the following equation (4).

Salinity concentration (NaCl ppm) = 552 x EC (cc / cm) -200. … … … … … … … … … ④

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 provides a method for simultaneously producing electrolytic reduced water and electrolytic oxidation water using demineralized water and demineralized mineral water desalted from NaCl contained in excess by taking deep ocean water of 200 m or less in order to solve the above problems. It is an object of the present invention to.

In order to achieve the above object, the present invention is to take a deep sea water of 200m or less depth of water, consisting of pre-treatment step, desalination step, electrolytic oxidation water and electrolytic reduction water production step, each step is made of the following steps sequentially It is characterized by

The present invention is to take the deep sea water of 200m or less depth of water, consisting of pre-treatment step, desalination step, the production step of electrolytic oxidation water and electrolytic reduced water, each step is to produce electrolytic oxidation water and electrolytic reduced water in which each of the following processes sequentially It relates to a method, described in detail below with reference to the accompanying drawings.

I. Pretreatment stage

1. Intake and warming process

Deep sea water of 200m or less in depth is collected and warmed to 20 ~ 30 ℃ for subsequent treatment to be sent to pretreatment filtration process.

Deep sea water is taken in from the depth of the sea below 200m, and the intake method is to take the pipe down to 200m below the seabed, or to install the pipe to the depth of 200m below the seabed or with the pump. Piping up to a depth of 200m or less is provided so that the intake well is installed below the sea level, and the water is collected according to the siphon principle.

The deep sea water collected in the sump is warmed to 20 ~ 30 ℃ because of its low viscosity and high treatment efficiency.

The heating method may be supplied with heat from a boiler, or may use surface water in the summer.

2. Pretreatment Filtration Process

The warmed deep seawater is sand filtration (Sand filter), micro filtration (micro filter), ultra filtration (限 外 濾過: Ultra filter) alone or a combination of two or more of the FI (Fouling index) of water suspended solids a value of 2 to 4 range (SS: suspended solid) the removal and then, to the nanofiltration treatment sulfate ion (SO ₄ ^{2 -)} which the membrane clogging (Fouling) problems in reverse tuyeogwa removed and then the desalination Sent to the first reverse osmosis filtration process.

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, Ultra-filter and Nanofiltration are not limited to the type of filtration membrane, and pumps are considered in consideration of filtration speed and pressure loss according to vendor's specifications. Determine supply pressure of pump).

The FI value is a numerical value representing the fine turbidity concentration in the target water and is expressed by the following equation ⑤.

FI = (1-T ₀ / T ₁₅ ) × 100/15... … … … … … … … … … … … … … … … ⑤

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 the time required for the filtration of 500 ml of sample water later.

The warmed deep ocean water is sand filtration, fine filtration, ultrafiltration alone or a combination of two or more of the deep sea water is removed from the suspended solids in the range of 2 to 4 FI (Fouling index) value of water Is sent to the nanofiltration process.

In the case of omitting the nanofiltration process to reduce the facility cost, the warmed deep ocean water is filtered through sand filtration, microfiltration, and ultrafiltration alone or a combination of two or more thereof to obtain a FI (Fouling index) value of 2 As long as the suspended solids have been removed in the range of -4, ocean deep water is sent to the first reverse osmosis process.

When the above-mentioned sand filtration, microfiltration, ultrafiltration alone or a combination of two or more of the filtration to remove the suspended solids in the range of 2 to 4 FI (Fouling index) value of water, and then supplied to Nanofiltration , supply pressure of the salt concentration of 3.5wt% was supplied to the nanofiltration membrane by the osmotic pressure of 25 atmospheres (atm) 15 to 20 low pressure (atm) than the deep ocean water, without being filtered, sulfate ion (SO ₄ ^{2 -)} a large amount of Sulfate-containing water is discharged and the filtered filtrate is sent to the first reverse osmosis process.

In the nanofiltration process, the supply pressure is 15-20 atmospheres (atm), which is lower than the osmotic pressure 25 atmospheres (atm) of the deep seawater with a salt concentration of 3.5wt%. In this case, the membrane permeate amount is 80 to 90% of the inflow rate.

When the feed pressure is supplied to the nanofiltration membrane at 15 to 20 atm, the permeate amount of the membrane is 0.7 to 1.4 m 3 / m 2 · day for the spiral membrane, and the membrane permeability is 80 to 85% of the influent flow rate.

Nanofiltration is a pressure-driven membrane separation process in which particles or polymers of less than 2 nm are blocked. Nanofiltration membranes use membranes having a diameter of 1 to 2 nm between the ultrafiltration membrane and the reverse osmosis membrane.

Transmission sequence of the ion in the nanofiltration membrane, if the cation is ^{Ca 2 + ≥Mg 2 +> Li} +> Na +> K +> and NH ₄ ^+, if the anion is _{^{SO 4 2 - »HCO 3 ->}} F - ^{> Cl -> Br -> NO} 3 -> and SiO _2, a sulfate ion (SO ₄ ^{2 -),} if the it is difficult to permeate than Mg ^{+ 2} and Ca ^{+ 2.}

In the nanofiltration process, the solubility is low, such as CaCO ₃ , CaSO ₄ , and SrSO ₄ dissolved in the deep sea water, and the membrane is formed during filtration in the first reverse osmosis filtration process. send the filtered water to remove) a primary reverse process tuyeogwa ^-) is turned on ⁽² SO ₄ sulfuric acid in order to suppress as much as possible the phenomenon.

The module shape of the nanofiltration membrane is any shape such as tubular, hollow fiber, spiral wound, and plate and frame. May be used, and the material of the film is not particularly limited.

However, in the present invention, the nanofiltration membrane has a high passing rate of monovalent ions (Na ⁺ , K ⁺ ), and can block bivalent or more ions (Aromatic polyamide: Poly-p-phenyleneterephthalamide, Poly-m-phenyleneisophthalamide) Preference is given to using a countdown membrane.

Example 1

After warming the deep seawater of Table 1 to 25 ° C and pretreating the FI value to 3.2 by ultrafiltration, the model number SU- of cross-linked polyamide made by Toray Corporation of Japan When the membrane permeate was 1.2 m 3 / m 2 · day by supplying pressure to the membrane at 20 kg / cm 2 G using a spiral nanofiltration membrane of 610, the membrane permeate amount was 82% of the inflow rate. The analysis values of the main components of the mineral water and the filtered desulfurized ionized water were as shown in Table 2 below.

Table 2 Analysis of Principal Components of Water Quality Before and After Nanofiltration

 Item Pretreated Marine Deep Water (Raw Water) Desulphurized Water Salt (filtration)  % Removal      pH        7.80         7.24      - Na ⁺ (mg / L)   10,800    9,650     10.65 Cl ^- (㎎ / ℓ)   22,370   17,300     22.66 Ca ^{2 +} (㎎ / ℓ)      456      338     25.88 Mg ^{2 +} (㎎ / ℓ)    1,300    1,060     18.46 K ⁺ (mg / L)      414      355     14.25 _{^{SO 4 2 - (㎎ / ℓ}} )    2,833      608     78.54  B (mg / L)        4.44        4.43       0.23

As shown in Table 2, nano-filtration of deep sea water resulted in almost no removal of boron compounds. The removal rate of salts, calcium, magnesium, etc. was as low as 10-26%, but the sulfate ion was 78.54%. It was quite high.

II. Desalination stage

1. First Reverse Osmosis Filtration Process

When the filtered water filtered in the nanofiltration is supplied to the first reverse osmosis filtration process, the filtered water is supplied to the reverse osmosis membrane at 50 to 60 atmospheres (atm), and the filtered filtrate is sent to the pH adjustment process, and is discharged without being filtered. The brine is sent to an electrodialysis process.

In this case, in the case of the spiral reverse osmosis membrane, the membrane permeate water is operated at 0.5 to 0.8 m 3 / m 2 · day to remove the filtered filtrate in the range of 99.0 to 99.85 wt% of salt.

Reverse osmosis membrane (RO membrane) is a kind of filtration membrane that has the property of passing water and not penetrating water other than water such as ions or salts. The pore size is generally about 2 nanometers (nm: 10 ^-9). m) Below, the structure of the membrane is hollow fiber membrane, spiral membrane, tubular membrane, and the material of the membrane is cellulose acetate, aromatic polyamide, Polyvinyl alcohol, polysulfone, and the like.

Asymmetric membrane made of a skin layer without pores of cellulose acetate and a support layer on sponge, a hollow fiber membrane made of an improved cellulose acetate membrane, and a nonwoven fabric A porous film made of polysulfone was formed on a fabric, and then an aromatic polyamide was interfacially polymerized on its surface to form a dense layer having a thickness of 1 mm or less. Although there exist a film | membrane, such as a spiral type | mold which made a composite membrane into the flat membrane, in this invention, the form and material of a membrane are not specifically limited.

Example 2

Desulfuric acid ionized salt, which is filtrate filtered in the nanofiltration of Example 1, is a model of a crosslinked polyamide-based composite membrane in a high pressure reverse osmosis membrane of Toray Corporation of Japan. When the membrane was supplied with a pressure of 60 kg / cm 2 G using a spiral reverse osmosis membrane of SU-810 and the membrane permeate was 0.72 m 3 / m 2, the membrane permeate was 50% of the influent. The analysis values of the main components of the filtered water and the concentrated brine concentrated without filtration are shown in Table 3 below.

Table 3 Analysis of Principal Components of Filtrate and Concentrated Water in Primary Reverse Osmosis

 Item Influent Water (Desulphurized Salt Water) Filtrate (Demineralized Water) Unconcentrated concentrated water      pH        7.24         7.20          7.38 Na ⁺ (mg / L)    9,650       36.2     19,259.8 Cl ^- (㎎ / ℓ)   17,300       71.0     34,525.2 Ca ^{2 +} (㎎ / ℓ)      338        0.6        671.4 Mg ^{2 +} (㎎ / ℓ)    1,060        1.8      2,114.2 K ⁺ (mg / L)      355        1.6        706.3 _{^{SO 4 2 - (㎎ / ℓ}} )      608        3.6        104.3  B (mg / L)        4.43        1.8          7.1

As shown in Table 3, most of the substances were removed highly by 99% of deep seawater in reverse osmosis, but the boron compound was 1.8 mg / l and the removal rate was very low, below 60%. It was not possible to use it for beverage production because it exceeded 6 times.

2. pH adjustment process

When the filtered water filtered in the first reverse osmosis filtration step is supplied to the pH adjustment step, one of NaOH, NaHCO ₃ and Na ₂ CO ₃ is supplied as an alkali agent to adjust the pH to a range of 9-11. The boric acid component is treated with polyboric acid and sent to the secondary reverse osmosis process.

Boric acid in water is converted to polyboric acid in the gel state by the reaction of ⑥ as alkali treatment.

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 ] ^- … ⑥

The operating condition of the pH adjustment step is that the pH adjustment method is performed by injecting alkali into the demineralized water of the first reverse osmosis step while stirring with a propeller stirrer of 180 to 360 RPM (rotational speed) for 15 to 30 minutes. Adjust to 9-11.

3. Second Reverse Osmosis Filtration Process

When the pH is adjusted to 9-11 in the pH adjustment process and supplied to the secondary reverse osmosis process, the operating pressure is supplied to the secondary reverse osmosis membrane at 10 to 20 atmospheres (atm). Silver was operated at 0.6 to 0.8 m3 / m 2 · day, and the unfiltered boron-containing water was discharged after neutralization treatment, and the deboron water filtered at boron concentration below 0.3 mg / l, which is the drinking water standard, was used in the cathode chamber of the electrolysis process (16 Send to).

In the second reverse osmosis process, even when the pH is supplied in an alkaline state of 9 to ₁₁ , scale generation is not a problem since the materials such as CaCO ₃ and CaSO _{4 which} generate scale are removed in the nanofiltration process.

Example 3

The filtrate filtered in the first reverse osmosis of Example 2 was adjusted to pH 9.5 in the pH adjustment step to convert the boron compound in water into the form of polyboric acid, and then manufactured by Toray Industries, Ltd. Low Pressure Reverse Osmosis Membrane Using the spiral reverse osmosis membrane of Model No. SU-710, the pressure was supplied to the membrane at 25㎏ / ㎠G, and the membrane permeation rate was 0.72㎥ / ㎡ · day and the membrane permeation rate was 82% of the inflow rate. When the concentration of boron (B) in the filtered water (deboron water) was measured, 0.12 mg / l of boron in the drinking water was treated at 0.3 mg / l or less, so that it could be used as a reducing alkaline beverage.

4. Electrodialysis Process

The electrodialysis apparatus (3) separates ionic solutes by membrane permeation using a potential difference of direct current power applied from a rectifier as a driving force, as shown in FIG. The cation exchange diaphragm 9 selectively transmits only monovalent cations having a fixed negative charge, and the anion exchange diaphragm 8 selectively only monovalent anions having a fixed electrostatic charge. The ion-exchange diaphragm which permeate | transmits is comprised between the anode 4 and the cathode 5 alternately, and arranged in a single row | line | stage.

When the concentrated water discharged without filtration in the first reverse osmosis filtration process is supplied to the electrodialysis apparatus supply water storage tank 1 of the desalination process, the desalination chamber of the electrodialysis apparatus 3 by the electrodialysis apparatus supply pump 2 ( 10) and return to the electrodialysis apparatus supply water storage tank (1), the brine of the brine storage tank 12 to the salt concentration chamber (11) by the brine transfer pump 13 to the brine storage tank (12) When direct current is applied from the rectifier to the positive electrode 4 and the negative electrode 5, monovalent cations such as Na ⁺ and K ⁺ contained in the brine of the desalination chamber 10 pass through the cation exchange diaphragm 9. The monovalent anion, such as Cl ⁻ , moves to the salt concentration chamber 11, passes through the anion exchange diaphragm 8, and moves to the salt concentration chamber 11, where the BME (Bome) ratio of the brine reservoir 12 is indicated. Brine concentrated in the range of 18 ~ 20 ° Be of the switch has a solenoid valve (ⓢ). Demineralized mineral water which is sent to the forging process and desalted with electroconductivity value of electric conductivity indicating switch (ECIS) installed in the filtrate line is 6-12㎳ / ㎝, is operated by solenoid valve. Decomposition process It is sent to the anode chamber 15 of the electrolysis device 14.

And when the water level of the brine reservoir 12 falls, the filtered water of the second reverse osmosis filtration process is supplied to the water level controller (Level switch: LS) installed in the brine reservoir 12 as water by the operation of the solenoid valve (ⓢ).

The electrodialysis apparatus 3 preferably increases the current density as much as possible within the range below the limit current density in order to increase the processing performance, but the limit current density is proportional to the salt concentration, Since the thickness of the diffusion layer is inversely proportional to the thickness of (iii), it depends on the salt concentration and the concentration of the brine in the drained mineral water, and according to the present invention, the cation exchange diaphragm 9 and the anion exchange diaphragm 8 ) Is discharged from the first reverse osmosis filtration process to the electrodialysis apparatus 3 which forms the desalination chamber 10 and the salt concentration chamber 11 which are arranged alternately between the anode 4 and the cathode 5. The concentrated water is sent to the desalination chamber (10) as an electrodialysis device supply pump (2), and NaCl is desalted, and some are circulated to the electrodialysis device supply water storage tank (1), and the brine in the brine storage tank (12) is a brine transfer pump. It is sent to the salt concentration chamber 11 by (13), and it circulates.

By supplying a large amount of brine which passes through the salt concentration chamber 11 so that scale components are not produced in the salt concentration chamber 11 while improving the desalination and salt concentration efficiency, it is possible to prevent scale troubles. By supplying saline with a high salt concentration, the liquid resistance of the current is reduced, so that the limit current density can be increased, and thus the treatment performance of the electrodialysis apparatus 3 can be improved.

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

Deep sea water has low solubility in water such as CaSO ₄ and CaCO _3, and when concentrated, scale is generated, which can reduce the treatment efficiency due to fouling of the diaphragm. Multivalent ionic materials (CaSO ₄ , CaCO ₃ , MgCl ₂ , MgSO ₄ , SrSO ₄ ...) And sulfate ions were removed first, and CaSO ₄ , CaCO ₃ , SrSO was removed in the electrodialysis apparatus (3). ₄ . In order to suppress the generation of scale as much as possible, the ion-exchange diaphragm which uses a divalent or more ionic substance and which permeate | transmits only the monovalent ionic substance selectively is used.

The cation exchange diaphragm 9 used in the present invention is a diaphragm which selectively transmits only a monovalent cation while suppressing divalent or more multivalent cation permeation, and is mainly composed of polystyrene-divinylbenzene. Side chains and polyethyleneimine or polyvinyl pyridine in the negatively charged membrane that holds the negatively charged R-SO ₃ ^- in the main chain Graft polymer such as Polyvinylpyridine or Graft polymer whose main chain is polystyrene with side chains of polyethylenimine or polyvinyl pyridine.The main chain of graft polymer is the main chain of cation exchange diaphragm or Any structure having the same molecular structure as the side chain can be used without limitation. Preferably, polyethylene, polypropylene, and polyvinyl chloride (P) are used. olyvinylchlorde), polystyrene (polystyrene) or the like negatively charged R-SO ₃ ^- create a fixed monovalent cations in the main chain or side chain with the same molecular structure and a polymer consisting of a cation exchange membrane permeability (the molecular structure of polyester having a透過能) Cation exchange diaphragms such as polyvinylpyridine, polyvinylamine or polyethyleneimine membranes can be used, and in particular, polystyrene-graft-ethylene imine based on polystyrene-divinylbenzene can be most preferably used. have.

The anion exchange diaphragm 8 is a diaphragm capable of selectively exchanging only monovalent anions as opposed to the cation exchange diaphragm 9 to fix the static charge R-NH ₃ ⁺ to the polymer chain. In addition, since the static charge is fixed to the membrane, it is also called a static charge membrane. The ion exchanger is crosslinked by aliphatic hydrocarbons, and the cation exchanger is formed on the surface of the membrane. An anion exchange diaphragm in which a thin layer of a polymer material having a high molecular weight is formed, and it is preferable to perform quaternization simultaneously with crosslinking with an aliphatic hydrocarbon to a monomer introduced into the exchanger. Examples thereof include a polymer electrolyte having a cation exchange group, an insoluble polymer having a linear polymer electrolyte or a cation exchange group, and specifically, lignin sulfonic acid. Sulfonate salts such as Liginsulfonate, phosphate ester salts such as higher alcohol phosphate esters, and the like, such as polymer electrolytes having a cation exchange group having a molecular weight of 500 or more, such as methacrylic acid and styrene sulfonic acid Phenols and aldehydes including a linear polymer electrolyte containing a large number of monomer units having a carboxylic acid group (-COOH) or a sulfonic acid group (-SO ₃ H), and a cation exchanger. The diaphragm which selectively exchanges monovalent anions, such as an insoluble polymer which has a cation exchange group like condensation, is used.

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

In addition, in the salt concentration chamber 11, a scale is attached to the rectifier in order to reduce the processing efficiency, so that a polarity switching device is installed in the rectifier to switch the power of the positive electrode 4 and the negative electrode 5 to be attached. Allow the scale to detach.

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

In the electrodialysis apparatus 3 described above, the concentrated brine is sent to the salt manufacturing process, and the mineral water desalted by monovalent ions (NaCl and KCl) is sent to the anode chamber 15 of the electrolysis apparatus 14.

NaCl desalted mineral water contains calcium (CaSO ₄ , CaCO ₃ ), magnesium (MgSO ₄ , MgCl ₂ ), potassium (KCl) and other trace minerals.

Example 4

The cation exchange diaphragm having a thickness of 0.2 mm of 236 mm (length) x 220 mm (width) of the brine concentrated without filtration in the first reverse osmosis filtration process of Example 2 was 1 Monovalent cation exchange membranes 21 (Aciplex® K-102, manufactured by Japan Chemical Co., Ltd.) and anion exchange membranes that selectively permeate only valent cations and monovalent anion exchange membranes selectively permeate only monovalent anions ( 20; FIG between Aciplex a-102, Japan旭化成工業株式會社product) of each 50 sheets of the RuO ₂ -TiO ₂ in the titanium plate a DSA electrode, a positive electrode (cathode 4) as stainless strong poles (5 coated) In the first reverse osmosis filtration process of Example 2 to the desalination chamber 10 of the electrodialysis apparatus 3 in which multiple stages (50 stages) were alternately installed as in 3 to 50 L of electrodialysis apparatus feed water storage tanks 1 After supplying concentrated concentrated water at 25 ° C., which was not filtered, the diaphragm type metering pump The membrane is fed into the desalination chamber 10 so that the linear velocity is 10 cm / sec with the electrodialysis apparatus supply pump 2, and is circulated to the electrodialysis apparatus supply water storage tank 1, and the 20 liter brine storage tank ( When the salt water of 12) is blocked by the salt water feed pump 13, which is a diaphragm-type metering pump, it is supplied to the salt concentration chamber 11 so that the linear velocity becomes 3 cm / sec. When applied at a density of 3 to 4 A / dm ² (applied voltage was 55 to 60 Volt), the electroconductive value of the conductivity indicator controller (ECIS) in the mineral water circulation line was desalted to 6 to 8 mW / cm. Analysis of main components of demineralized mineral water was as shown in Table 4 below.

At this time, the specific gravity of the brine in the brine storage tank 12 was adjusted to 12 ° Be, the cathode chamber solution is discharged to the upper by supplying 5wt% Na ₂ SO ₄ aqueous solution to the lower portion of the cathode chamber 7 at 50 kW / min Feed into the bottom of the seal (6).

Table 4 Analysis of Principal Components of Demineralized Mineral Water in Electrodialysis Process

  Item Demineralized mineral water discharged from the electrodialysis process   pH                   7.28 Na ⁺ (mg / L)                  19.2 Ca ^{2 +} (㎎ / ℓ)                 682.4 Mg ^{2 +} (㎎ / ℓ)                2110.3 K ⁺ (mg / L)                   0.8

III. Steps for producing electrolytic oxidized water and electrolytic reduced water

1. Electrolysis process

The demineralized mineral water desalted in the electrodialysis process is supplied to the anode chamber 15 of the electrolysis device, and the filtered water filtered in the second reverse osmosis process is supplied to the cathode chamber 16. When 3 to 20 volts of direct current electricity is applied from the rectifier to the anode 17 of the anode chamber 15 and the cathode 18 of the cathode chamber 16, the electrolytic oxidation water in the anode chamber 15 Generated, and electrolytic reduced water is produced in the cathode chamber (16).

When alkaline reduction water is generated by applying direct current electric current from the rectifier so that the value of the ORP of the cathode chamber 16 is in the range of -250 to -100 kV, the alkaline reducing water is generated into the electrolytic reduction water storage tank 22. Send to produce electrolytic reduced water.

The electrolytic reduced water of the electrolytic reduced water storage tank 22 is sent to the electrolytic reduced water transfer process to the electrolytic reduced water transfer pump 23.

At this time, the oxidation reduction potential (ORP) of the anode chamber 15 is a value of +800 to +1,200 kPa, when the direct current is applied from the rectifier to generate an acidic electrolytic oxidation water, the electrolytic oxidation water storage tank 20 To produce electrolytic oxidation water.

The electrolytic oxidation water of the electrolytic oxidation water storage tank 20 is sent to the electrolytic oxidation water transfer process to the electrolytic oxidation water transfer pump 21.

The electrolytic oxidation water produced here is sterilizing and contains a large amount of minerals, so it can be used in foliar sprays, bath water, etc., and electrolytic reduced water can be used for the production of alkaline beverages.

At this time, the electrochemical reaction mechanism (Mechanism) occurring in the electrolysis process is as follows.

Water-containing salts are hydrolyzed as follows.

^{_{H 2 O ⇔ 2H + + OH}} - ... … … … … … … … … … … … … … … … … … ⑦

_{^{M a X b ⇔ aM b +}} + bX a - ... … … … … … … … … … … … … … … … … … ⑧

Where M is Na, K, Ca, Mg, Fe, Zn... Cation material such as Cl, Br, CO ₃ , SO ₄ . An anion material such as, a is the number of cation (+) valence, b is the number of anion (-) valence.

1) Reaction in anode chamber 35

^{_{H 2 O → 2H + + [}} O] (aq) + 2e - → 1 / 2O 2 (g) ↑ + 2e - ... … … … … … … ⑨

Here, [O] _{( aq )} means active oxygen dissolved in an aqueous solution, and O _{2 (g)} ↑ means oxygen released to the atmosphere in a gas (Gas) state when an excessive current is applied. .

^{_{bX a - → X b (aq}} ) + be - → X b (g) ↑ + be - ... … … … … … … … … … ⑩

In the case of X ^{a -} is Cl ^- ion, considering the electrolytic reaction is as follows.

^{_{2Cl - → Cl 2 (aq)}} + 2e - → Cl 2 (g) ↑ + 2e - ... … … … … … … … … … ⑪

Here, Cl _{2 ( aq )} means chlorine dissolved in an aqueous solution, Cl _{2 (g)} ↑ means chlorine released to the atmosphere in the gas state when an excess current is applied.

2) Solution reaction in the anode chamber 15

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

2) Reaction in cathode chamber 16

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

Here, [H] _{( aq )} means active hydrogen dissolved in water, and H _{2 (g)} ↑ means hydrogen generated in a gaseous state when an excessive current is applied.

^{M a + + aOH - → M} (OH) a ... … … … … … … … … … … … … … … … … ⑭

When M ^{a +} is Na ⁺ ion, considering the electrolytic reaction is as follows.

Na ^{+ +} OH ^- → NaOH ... … … … … … … … … … … … … … … … … … … … ⑮

The electrolysis device 14 is made of PVC (Poly vinyl chlorite), PE (Polyethylene), PP (Polypropylene), ABS resin (Acrylonitrile butadiene styrene copolymer), butadiene resin (Bakelite) ), Ebonite and Acrylic resin can be used.

The anode 17 of the anode chamber 15 is made of a corrosion resistant material and is subjected to baking coating of RuO ₂ -TiO ₂ on a titanium plate with high chlorine and oxygen generation overvoltage. One dimensionally stable anode (DSA) electrode or a platinum plated electrode is used.

The cathode 18 of the cathode chamber 16 is made of Ranney nickel or stainless steel sheet with high hydrogen generation overvoltage.

The diaphragm 19 is an exchange membrane that selectively permeates only monovalent cations while suppressing the permeation of divalent or higher polyvalent cations. The main chain of the polystyrene-divinylbenzene system is a main chain. Grafts such as polyethyleneimine or polyvinylpyridine have side chains on the side of the negatively charged membrane, which holds the negatively charged R-SO ₃ ⁻ in the chain. An ion exchange membrane synthesized from a graft polymer or a graft polymer whose main chain is polyethyleneimine or a polystyrene pyridine side chain is a polystyrene. The cation exchange membrane, which is the main chain of the graft polymer, has the same molecular structure as the main chain or side chain. It can be used without limitation, and preferably, polyethylene, polypropylene, polyvinyl chloride, polystyrene Negatively charged R-SO ₃ in ^- a fixed monovalent cation man gaji molecules the permeability (透過能) in the main chain or side chain with the same molecular structure and a polymer consisting of a cation exchange membrane structure of polyvinylpyridine (Polyvinylpyridine), poly Membranes modified with a cationic resin such as vinylamine or polyethyleneimine may be used, and in particular, polystyrene-graft-ethylene imine of polystyrene-divinylbenzene may be most preferably used. .

In the case of using the diaphragm 39 that simultaneously transmits a bivalent or higher multivalent cation, multivalent ions such as Ca, Sr, Mg, Fe, and Fe move to the cathode chamber 16 to form a cathode. (18) The use of the diaphragm 19 that permeates polyvalent ions should be avoided because scales are generated in the plate, which increases electrical resistance and lowers processing efficiency.

Example 5

The size of the anode chamber 16 is 1,000 mm (length) × 500 mm (width) × 1,000 mm (depth), and the size of the cathode chamber 15 is also 1,000 mm (length) × equal to the size of the anode chamber 16. Isolated with a diaphragm (19) of Nafion-115 perfluorosulfonic acid Nafion-Resin from Dupont between 500 mm (width) x 1,000 mm (depth) In addition, the anode 17 uses a DSA electrode baked-coated TiO ₂ -RuO ₂ on a titanium plate of 800 mm (width) x 1,000 mm (height) x 5 mm (thickness), and the cathode 18 is 800 mm. Example 3 As an anode chamber 15 of an electrolytic decomposition apparatus 14 using an electrode lined with a Raney nickel 3 mm thick on a steel plate having a width × 1,000 mm (height) × 10 mm (thickness) The filtered water filtered in the second reverse osmosis filtration process of 0.73 ㎥ / hr is supplied, and the desalted mineral water desalted in the electrodialysis process of Example 4 is supplied to the cathode chamber 15 at a flow rate of 1 ㎥ / hr. 8 to 10 volts straight from the rectifier In the cathode chamber 16, a redox potential was applied to produce an electrolytic reduced water in the range of -200 to -210 ㎷ and sent to the electrolytic reduced water storage tank 22 in the cathode chamber 16, and in the anode chamber 15, the redox potential ( ORP) value produced electrolytic oxidation water in the range of +1,020 to +1,030 Pa and sent to the electrolytic oxidation water storage tank 20.

At this time, the pH of the cathode chamber 16 was 12.6 to 12.8, and the pH of the anode chamber 15 was operated in the range of 2.3 to 2.5.

As described above, the present invention contains various mineral components and organic substances useful in deep sea water of 200 m or less in depth, and desalted water and demineralized minerals desalted with NaCl components contained in excess using such deep sea water. Since high-quality electrolytic oxidation water and electrolytic reduction water can be produced simultaneously with water, it is expected to have an effect that can be widely used in the production of electrolytic oxidation water and electrolytic reduction water.

Claims (1)

A method of producing electrolytic oxidized water and electrolytic reduced water, wherein the deep sea water having a depth of 200 m or less is taken out, and comprises a pretreatment step, a desalination step, and an electrolytic oxidation water and an electrolytic reduced water, each step being performed sequentially. I. Pretreatment stage 1. Intake and warming process Deep sea water with a depth of 200m or less is collected, warmed to 20 ~ 30 ℃ and sent to the pretreatment filtration process. 2. Pretreatment Filtration Process The warmed deep seawater is sand filtration (Sand filter), micro filtration (micro filter), ultra filtration (限 外 濾過: Ultra filter) alone or a combination of two or more of the FI (Fouling index) of water After removing the suspended solids (SS) in the range of 2 to 4, the nanofiltration is sent to the first reverse osmosis process. II. Desalination stage 1. First Reverse Osmosis Filtration Process When the filtered water filtered in the nanofiltration is supplied to the first reverse osmosis filtration process, the filtered filtrate is supplied to the reverse osmosis membrane is sent to the pH adjustment process, and the concentrated water discharged without filtration is sent to the electrodialysis process. 2. pH adjustment process When the filtered water filtered in the first reverse osmosis filtration process is supplied to the pH adjustment process, alkali (Alkali) agent is supplied to adjust the pH to a range of 9-11, and the boric acid component in the water is treated with polyboric acid for secondary reverse osmosis filtration. Send to fair 3. Second Reverse Osmosis Filtration Process When the pH is adjusted to 9-11 in the pH adjustment step and supplied to the second reverse osmosis membrane, the boron-containing water which is not filtered by being supplied to the second reverse osmosis membrane is discharged after neutralization treatment, and the boron concentration is the drinking water standard value. The deboron water filtered at 0.3 mg / l or less is sent to the cathode chamber 16 of the electrolysis process. 4. Electrodialysis Process When the concentrated water discharged without filtration in the first reverse osmosis filtration process is supplied to the electrodialysis apparatus supply water storage tank 1 of the desalination process, the desalination chamber of the electrodialysis apparatus 3 by the electrodialysis apparatus supply pump 2 ( 10) and return to the electrodialysis apparatus supply water storage tank (1), the brine of the brine storage tank 12 to the salt concentration chamber (11) by the brine transfer pump 13 to the brine storage tank (12) The direct current from the rectifier is applied to the positive electrode 4 and the negative electrode 5, so that the specific gravity of the Baume indicating switch (BIS) of the brine reservoir 12 is concentrated in the range of 18 to 20 ° Be. The brine is sent to the salt manufacturing process by operating a solenoid valve, and desalination is carried out with an electric conductivity value of 6 to 12 kW / cm of the electric conductivity indicating switch (ECIS) installed in the filtrate line. Demineralized mineral water operates solenoid valve. And it sends it to the anode chamber 15 of the electrolytic process the electrolytic device 14. III. Steps for producing electrolytic oxidized water and electrolytic reduced water 1. Electrolysis process The demineralized mineral water desalted in the electrodialysis process is supplied to the anode chamber 15 of the electrolysis device, and the filtered water filtered in the secondary reverse osmosis process is supplied to the cathode chamber 16. The redox potential of the cathode chamber 16 is applied by applying a DC electric current of 3 to 20 volts from the rectifier to the anode 17 of the anode chamber 15 and the cathode 18 of the cathode chamber 16. Applying a direct current electric current from the rectifier so that the value of (ORP) is in the range of -250 to -100 kV, and alkali reduced water is produced, it is sent to the electrolytic reduced water storage tank 22 to produce electrolytic reduced water, and the anode chamber 15 Oxidation reduction potential (ORP) of the value of the acidic electrolytic oxidized water in the range of +800 ~ + 1,200㎷ is generated and sent to the electrolytic oxidation water storage tank 20 to produce electrolytic oxidized water.

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