WO2006132160A1 - 液体のpH調整方法およびpH調整装置 - Google Patents
液体のpH調整方法およびpH調整装置 Download PDFInfo
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- WO2006132160A1 WO2006132160A1 PCT/JP2006/311124 JP2006311124W WO2006132160A1 WO 2006132160 A1 WO2006132160 A1 WO 2006132160A1 JP 2006311124 W JP2006311124 W JP 2006311124W WO 2006132160 A1 WO2006132160 A1 WO 2006132160A1
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/4618—Devices therefor; Their operating or servicing for producing "ionised" acidic or basic water
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F2001/46133—Electrodes characterised by the material
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/005—Processes using a programmable logic controller [PLC]
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/06—Controlling or monitoring parameters in water treatment pH
Definitions
- the present invention relates to a liquid pH adjusting method and a pH adjusting device.
- an object of the present invention is to provide a novel pH adjusting method and a pH adjusting device capable of adjusting the pH of a solution with a simple device.
- the first method of the present invention for adjusting the pH of a liquid comprises:
- the conductivity can be increased.
- the second method of the present invention for adjusting the pH of the liquid is:
- an ion adsorbing electrode (E1) containing a conductive substance (C1) capable of adsorbing ions, and a counter electrode By applying a voltage so as to cause electrolysis of water at the counter electrode, at least a part of the ions (L) is adsorbed to the conductive material (C1) and hydrogen is generated at the counter electrode.
- the aqueous solution (A) is an aqueous solution in which a salt is dissolved, and the conductive substance (CI'C2) capable of adsorbing the ions may be activated carbon. May be included.
- the first device of the present invention for adjusting the pH of a liquid is capable of adsorbing ions, a container, an ion-adsorbing electrode (E1) containing a conductive substance (C1) that can adsorb ions, and An ion-adsorbing electrode (E2) containing a conductive material (C2), a counter electrode, and a voltage applying means;
- the second device of the present invention for adjusting the pH of the liquid includes a container, an ion adsorption electrode (E1) containing a conductive substance (C1) capable of adsorbing ions, a counter electrode, and a voltage.
- E1 ion adsorption electrode
- C1 conductive substance capable of adsorbing ions
- counter electrode a conductive substance capable of adsorbing ions
- voltage a voltage
- the third device of the present invention for adjusting the pH of the liquid includes a container, an ion adsorption electrode (E1) containing a conductive substance (C1) capable of adsorbing ions, a counter electrode, and a voltage. And in an aqueous solution (A) containing at least one kind of ions (L) other than hydrogen ions and hydroxide ions, between the ion-adsorbing electrode (E1) and the counter electrode, water is added at the counter electrode.
- aqueous solution (A) containing at least one kind of ions (L) other than hydrogen ions and hydroxide ions between the ion-adsorbing electrode (E1) and the counter electrode, water is added at the counter electrode.
- the method of the present invention it is possible to easily adjust the pH of the liquid, and it is also possible to produce only an acidic aqueous solution or only an alkaline aqueous solution.
- an acidic aqueous solution and an alkaline aqueous solution can be prepared simultaneously. is there. Further, according to the method of the present invention, it is possible to change the pH with a small amount of electricity.
- the method of the present invention can be an alkaline aqueous solution having a pH of 8 to 12 or a pH of 6 if water containing ions equivalent to tap water is used. It is possible to make an acidic aqueous solution of pH2.
- FIG. 1A and FIG. 1B are diagrams schematically showing an example of the method of the present invention for adjusting the pH of a solution.
- FIG. 2A and FIG. 2B are diagrams schematically showing another example of the method of the present invention for adjusting the pH of a solution.
- FIG. 3 is a diagram schematically showing another example of the method of the present invention for adjusting the pH of a solution.
- FIG. 4A, FIG. 4B and FIG. 4C are diagrams schematically showing another example of the method of the present invention for adjusting the pH of a solution.
- FIG. 5A, FIG. 5B and FIG. 5C are diagrams schematically showing another example of the method of the present invention for adjusting the pH of a solution.
- FIG. 6 is a diagram schematically showing another example of the method of the present invention for adjusting the pH of a solution.
- FIG. 7 is a diagram schematically showing another example of the method of the present invention for adjusting the pH of a solution.
- FIG. 8 is a diagram schematically showing another example of the method of the present invention for adjusting the pH of a solution.
- FIG. 9A and FIG. 9B are diagrams schematically showing the structure of the electrodes used in the examples.
- FIG. 10 is a diagram schematically showing the structure of another electrode used in the example.
- the pH adjustment method of the present invention is a method for adjusting the pH of a liquid.
- This method includes step (i) and step (ii).
- step (i) in an aqueous solution (A) containing at least one ion (L) other than hydrogen ions and hydroxide ions, an ion-adsorbing electrode (C1) containing a conductive substance (C1) capable of adsorbing ions ( Between the E1) and the ion adsorption electrode (E2) containing the conductive substance (C2) capable of adsorbing ions, the ion adsorption electrode (E1) becomes the anode (the ion adsorption electrode (E2) is Apply voltage.
- Step (i) is performed in a state where both the ion adsorption electrodes (E1) and (E2) are immersed in the aqueous solution (A).
- the ion adsorption electrode (E1) or the ion adsorption electrode (E2) is displaced in a liquid containing water (hereinafter sometimes referred to as “aqueous liquid” t).
- aqueous liquid a liquid containing water
- the pH of the aqueous liquid is changed by applying a voltage between the other and the counter electrode.
- Step (ii) is performed in a state where the two electrodes to which a voltage is applied are both immersed in an aqueous liquid.
- a voltage is applied so that water is electrolyzed at the counter electrode.
- the voltage application in the pH adjustment method of the present invention may be performed by a constant voltage method or a constant current method.
- the constant current method it becomes possible to control the pH over a long processing time.
- the applied voltage at that time is not more than a voltage at which an electric potential of a level is obtained so that little electrolysis of water occurs in the ion adsorption electrode.
- the applied voltage is a DC voltage
- the flowing current is a DC current.
- the voltage may be a pulse voltage or a pulse current, or an AC voltage or an AC current may be applied. Including processes.
- the potential of the counter electrode needs to be a potential at which electrolysis of water occurs.
- the voltage applied between the counter electrode and the ion-adsorbing electrode must take into account the IR drop due to the liquid resistance between the electrodes. Therefore, in order to realize fast processing, it is preferable that the voltage applied between the counter electrode and the ion-adsorbing electrode is larger than 2V.
- Gas generation in the ion adsorption electrode is likely to occur when the resistance of the conductive material (activated carbon or the like) of the ion adsorption electrode is large. If the resistance of the conductive material is high, the IR drop becomes large, and the potential of the portion already attached with ions may reach the potential of water electrolysis, resulting in poor current efficiency. In this case, if the current density is lowered, the force processing that can be normally performed with less polarization takes time. In order to solve this problem, it is preferable to arrange the current collector appropriately so that the resistance is higher than the resistance of the liquid between the electrodes in the ion adsorption electrode, and no part is generated.
- the internal resistance of the ion adsorption electrode is preferably as low as possible, but at least a portion where the internal resistance is higher than the resistance of the liquid between the ion adsorption electrode and the counter electrode is not formed in the ion adsorption electrode. It is desirable to make it. By using such an electrode, even if the current density is increased, the polarization difference on the surface of the activated carbon can be reduced, and the number of points that partially reach the decomposition potential of water can be reduced, so that the current efficiency can be increased.
- the ion adsorption electrode is an electrode capable of reversibly adsorbing and releasing ions.
- the ion adsorption electrode for example, an electrode that forms an electric double layer on the surface by adsorbing ions in a solution can be used.
- This electric double layer is constituted by the surface charge of the conductive material (C1 'C2) and the ions attracted to the surface charge.
- the ions constituting the electric double layer have a charge opposite to the surface charge of the conductive material adsorbed by the ions. For example, anion is adsorbed when the surface charge is positive, and cations are adsorbed when the surface charge is negative.
- the conductive material (C1 'C2) capable of adsorbing ions a conductive material having a large specific surface area can be used.
- carbon can be used, and among these, active carbon is a specific surface area. Is preferably used because of its large size.
- the first and second ion adsorption electrodes are It may include activated carbon fiber cloth, which may include agglomerated granular activated carbon to form a conductive sheet, or agglomerated granular activated carbon and conductive carbon to form a conductive sheet. Moreover, you may include the activated carbon block obtained by hardening activated carbon particle.
- the specific surface area of the large specific surface area conductive material for example, 1500m 2 / g ⁇ 2500m 2 / g range derconnection may be of.
- Examples of the activated carbon fiber cloth include activated carbon fiber cloths manufactured by Nippon Kainol Co., Ltd. (product numbers such as ACC-5092-15, ACC-5092-20, and ACC-5092-25).
- the conductive substance (C1'C2) may be a porous conductive substance. Also conductive material
- a substance used for an electrode of a liquid-flow capacitor may be applied.
- a typical example of the conductive substance (C1 'C2) is a porous carbon material (eg, activated carbon).
- the specific surface area of the conductive material (C1′C2) may be 900 m 2 / g or more.
- the upper limit of the specific surface area is not particularly limited, but may be, for example, 2500 m 2 Zg or less.
- a conductive material having a smaller specific surface area can also be used.
- a conductive material having a specific surface area of 300 m 2 Zg or more can be used.
- “specific surface area” is a value measured by the BET method using nitrogen gas.
- the liquid resistance can be made low and uniform by making the electrode into a flat plate shape.
- a flat electrode can be formed by fixing a conductive material containing granular activated carbon on a current collector metal foil with a binder.
- the conductive material may include conductive carbon such as acetylene black.
- an electrode is formed using an activated carbon fiber cloth formed of activated carbon fiber, the electrode can be obtained simply by attaching fine wires. This electrode allows the ions in the solution to easily pass through, so that the ion concentration and pH of the solution can be homogenized. Therefore, the use of this electrode can improve the speed of producing an acidic aqueous solution or an alkaline aqueous solution.
- wiring for current collection may be formed on the sheet.
- metal wiring can be used.
- the metal constituting the wiring is selected from the group consisting of Al, Ti, Ta and Nb. At least one.
- the metal that coats the metal include at least one metal (including an alloy) selected from the group consisting of Au, Pt, Pd, and Rh.
- a saddle electrode that easily generates hydrogen gas or oxygen gas during electrolysis of water is used.
- an electrode having Pt on its surface is used.
- an electrode having a metal surface coated with Pt such as an electrode coated with Ti or Nb with Pt, may be used.
- the material constituting the ion adsorption electrode and the material constituting the counter electrode may be the same or may be changed depending on whether the pH of the liquid is increased or decreased.
- the counter electrode has an actual surface area (surface area measured by a BET method or the like) of 10 times or less (for example, 5 times or less) of its apparent surface area (surface area of the outer shape).
- a counter electrode examples include a general metal electrode and a graphite electrode.
- conductive material C1 'C2 is a at its actual surface area (surface area measured by the BET method) is, the observed force only the surface area of the upper (table area of the outer shape) of 10 4 times or more May be.
- the aqueous solution (A) contains at least one ion (L) in addition to protons (H +) and hydroxide ions (OH-).
- the ion (L) includes one or both of at least one cation (L +) other than a proton and at least one anion (L—) other than a hydroxide ion. That is, the aqueous solution (A) is an aqueous solution containing one or both of a cation (L +) and an anion (L ⁇ ), for example, an aqueous solution in which a salt is dissolved.
- the anion (L—) becomes a conductive substance (C1). Adsorbed and cations (L +) are adsorbed on the conductive substance (C2).
- the salt dissolved in the aqueous solution (A) is not particularly limited, and examples thereof include sodium chloride, sodium chloride, potassium sulfate and the like.
- An example of the aqueous solution (A) is tap water.
- the ion concentration of the aqueous solution (A) can be easily increased by a method such as dissolving a necessary amount of salt.
- the aqueous liquid used in the step (ii) is the aqueous solution in the step (i) ( A) may be used.
- the ion-adsorbing electrodes (El) and (E2) are the aqueous solution of step (i).
- Step (ii) is performed in the state immersed in (A).
- the aqueous liquid treated in the step (ii) is a liquid containing water, for example, a liquid containing 50% by mass or more (for example, 80% by mass or more or 90% by mass or more) of water.
- a typical example of an aqueous liquid is water or an aqueous solution.
- the aqueous liquid in step (ii) may be different from the aqueous solution (A) treated in step (i).
- this case will be described with an example.
- the conductive substance (C1) adsorbs at least one kind of anion (L—) contained in the ions (L).
- step (ii) a voltage is applied between the ion adsorption electrode (E1) and the counter electrode so that the ion adsorption electrode (E 1) is a force sword, whereby the conductive substance (C1) The anion (L-) adsorbed on the liquid is released into the liquid and hydrogen ions are generated at the counter electrode to reduce the pH of the liquid.
- FIG. 1A An example of the process of the first example is schematically shown in FIG. First, as shown in FIG. 1A, in the tank 10, an ion adsorption electrode 11 containing a conductive substance (C1) capable of adsorbing ions, an ion adsorption electrode 12 containing a conductive substance (C2) capable of adsorbing ions, The first counter electrode 13 and the second counter electrode 14 are immersed in an aqueous solution 20 in which salt is dissolved (hatching is omitted).
- the tank 10 includes an inlet 1 for introducing a liquid into the tank 10 and an outlet 2 for discharging the liquid from the tank 10.
- the aqueous solution 20 is an aqueous sodium chloride solution. However, it may be an aqueous solution in which one or more other salts are dissolved! /.
- a DC voltage is applied between the ion adsorption electrode 11 and the ion adsorption electrode 12 so that the ion adsorption electrode 11 becomes an anode.
- a salt anion CD is adsorbed on the conductive material of the ion adsorption electrode 11 and a salt cation (Na +) is adsorbed on the conductive material of the ion adsorption electrode 12.
- the voltage is It is preferable that the voltage does not cause water electrolysis, and since an IR drop occurs in the voltage applied between the electrodes, a voltage higher than the theoretical electrolysis of water is applied between the electrodes. However, water electrolysis does not always occur. When setting the voltage, this IR drop (voltage drop) is taken into consideration if necessary (the same applies to the following voltage application).
- Liquid 30 is a liquid whose pH is adjusted, and is water or an aqueous solution.
- a direct current is applied between the ion adsorbing electrode 11 and the first counter electrode 13 so that the ion adsorbing electrode 11 becomes a force sword. Shed.
- anions adsorbed by the conductive substance of the ion adsorption electrode 11 CD is released into the liquid 30 and hydrogen ions (H +) and oxygen gas are generated at the first counter electrode 13.
- the liquid 30 becomes hydrochloric acid and the pH of the liquid 30 is reduced, and the voltage applied at this time is preferably a voltage that does not generate hydrogen gas from the ion adsorption electrode 11.
- This method is a method for producing an acidic solution.
- the conductive substance (C2) adsorbs at least one cation (L +) contained in the ions (L).
- step (ii) the ion adsorption electrode (E2) is interposed between the ion adsorption electrode (E2) and the counter electrode.
- FIG. 2A An example of the manufacturing process of the second example is schematically shown in FIG. First, the process of FIG. 2A is the same as the process of FIG. 1A.
- Liquid 30 is a liquid whose pH is adjusted, and is water or an aqueous solution.
- a current is applied between the ion adsorption electrode 12 and the second counter electrode 14 by applying a voltage so that the ion adsorption electrode 12 becomes an anode.
- the cations adsorbed by the conductive substance of the ion adsorption electrode 12 are released into the liquid 30 and at the same time, hydroxide ions (OH—) and hydrogen gas are generated at the second counter electrode 14.
- the voltage applied at this time is preferably a voltage at which oxygen gas is not generated from the ion adsorption electrode 12.
- this method is a method for producing an alkaline solution.
- two counter electrodes may be provided as one.
- the counter electrode which is not limited to the shape of the counter electrode, may be a net-like, porous, or linear electrode.
- Figure 3 shows an example using only one net-like counter electrode.
- a voltage is applied between one of the ion adsorption electrodes 11 and 12 and the counter electrode 15.
- the solution in the tank may be replaced and step (ii) of the method of the second example may be performed. Then, after performing the method of the second example, the solution in the tank may be replaced and step (ii) of the method of the first example may be performed. In this way, it is possible to produce an acidic solution and an alkaline solution alternately by one ion adsorption.
- step (i) of the first example and the step (ii) of the second example are performed separately.
- the conductive substance (C1) adsorbs at least one anion (L—) contained in the ions (L), and the conductive substance (C2) force S ions (L ) Adsorbs at least one cation (L +) contained in).
- the ion adsorption electrode (E1) is a force sword between the ion adsorption electrode (E1) and the first counter electrode in the first liquid containing water. Apply voltage so that As a result, the anion ( ⁇ ) adsorbed on the conductive material (C1) is released into the first liquid, and hydrogen ions are generated at the first counter electrode. including the step of reducing the pH (step (ii-a)).
- the ion-adsorbing electrode (E2) serves as an anode between the ion-adsorbing electrode (E2) and the second counter electrode in the second liquid containing water.
- step (ii) of the third example is schematically shown in FIG.
- the tank 10 is separated into the tank 10a and the tank 10b by the partition wall 41 as shown in FIG. 4B.
- the first liquid 30a is disposed in the tank 10a
- the second liquid 30b is disposed in the tank 10b.
- the partition wall 41 is a partition wall that does not allow ions to pass therethrough.
- the partition wall 41 is a partition wall that can be disposed in a container in which the liquid to be treated is disposed.
- the step (ii) described in the first example is performed in the tank 10a.
- the step (ii) described in the second example is performed in the tank 10b.
- the acidic aqueous solution and the alkaline aqueous solution may be produced simultaneously or separately.
- an inlet 1 and an outlet 2 may be formed in each tank.
- the partition may be a partition 51 serving as both the first counter electrode 13 and the second counter electrode 14.
- the process of FIGS. 5A to 5C is the same as the process of FIGS. 4A to 4C except that the partition wall 51 that also serves as the first counter electrode 13 and the second counter electrode 14 is used.
- the acidic aqueous solution and the alkaline aqueous solution may be produced simultaneously or separately.
- the partition wall that also serves as the electrode may be a partition wall 61 through which hydrogen atoms pass, as shown in FIG.
- the partition wall 61 through which hydrogen atoms pass is used, the hydrogen generated on one surface of the partition wall 61 when the alkaline aqueous solution is prepared passes through the partition wall 61 and the surface of the partition wall 61 on the side where the acidic aqueous solution is prepared. Are released as hydrogen ions. Therefore, the generation of hydrogen gas and oxygen gas can be suppressed by the amount of hydrogen ions that have passed through the partition wall 61.
- the partition wall 61 through which hydrogen atoms pass for example, an iron sheet coated with Pt, or coated with Pt Nb sheet and Pd sheet.
- the second pH adjustment method of the present invention includes the following steps (I) and (ii).
- the aqueous solution (A) containing at least one ion (L) other than hydrogen ions and hydroxide ions contains a conductive substance (C1) capable of adsorbing ions.
- a voltage between the ion adsorption electrode (E1) and the counter electrode at least a part of the ions (L) is adsorbed on the conductive substance (C1).
- Step (I) is performed in a state where both the ion adsorption electrode and the counter electrode are immersed in the aqueous solution (A).
- step (II) in a liquid containing water (aqueous liquid), by applying a voltage between the ion adsorption electrode and the counter electrode, the ions (L) adsorbed on the conductive substance Is released into the liquid and hydrogen or hydroxide ions are generated at the counter electrode to change the pH of the liquid.
- Step (II) is performed in a state where both the ion adsorption electrode and the counter electrode are immersed in an aqueous liquid.
- step (ii) a voltage is applied so that water is electrolyzed at the counter electrode.
- the ion adsorption electrode, the counter electrode, the aqueous solution (A), the aqueous liquid treated in the step (II), and the voltage application method are the same as those in the first pH adjustment method described above.
- step (I) and step (II) may be performed in the same solution or in different liquids.
- Step (I) of the second pH adjustment method may be the following third pH adjustment method.
- the pH of the aqueous solution (A) is increased in the step (I) Can reduce the pH of aqueous liquids.
- the pH of the aqueous solution (A) can be reduced in step (I), and the pH of the aqueous liquid can be increased in step (ii).
- step (II) Te reduces P H of the aqueous liquid, contact the step (I), Te, ion-adsorbing electrode (E1) is the anode between the counter electrode ion-adsorbing electrode (E1) By applying a voltage so as to become, at least one kind of anion ( ⁇ ) contained in the ion (L) is adsorbed on the conductive substance (C 1).
- step (ii) a voltage is applied between the ion adsorption electrode (E1) and the counter electrode so as to be a ion adsorption electrode (E1) force sword.
- the anion ( ⁇ ) adsorbed in 1) is released into the aqueous liquid and hydrogen ions are generated at the counter electrode. In this way, the pH of the aqueous liquid is reduced.
- step (II) when the pH of the aqueous liquid is increased in the step (II), the ion adsorption electrode (E1) is interposed between the ion adsorption electrode (E1) and the counter electrode in the step (I). By applying a voltage so that) becomes a force sword, at least one cation (L +) contained in the ion (L) is adsorbed on the conductive substance (C1).
- step (II) a voltage was applied between the ion-adsorbing electrode (E1) and the counter electrode so that the ion-adsorbing electrode (E1) became an anode, thereby adsorbing the conductive material (C1). Releases cations (L +) into aqueous liquid and generates hydroxide ions at the counter electrode. In this way, the pH of the aqueous liquid is raised.
- a conductive substance (C1) capable of adsorbing ions in an aqueous solution (A) containing at least one ion (L) other than hydrogen ions and hydroxide ions is used.
- a voltage between the ion-adsorbing electrode (E1) and the counter electrode so that water is electrolyzed at the counter electrode, at least a part of the ions (L) is adsorbed on the conductive substance (C1).
- it includes a step of changing the pH of the aqueous solution (A) by generating hydrogen ions or hydroxide ions at the counter electrode.
- the ion adsorption electrode, the counter electrode, the aqueous solution (A), and the voltage application method are the same as those in the first pH adjustment method described above.
- the cation (L +) in the aqueous solution (A) is adsorbed to the ion adsorption electrode by applying a voltage so that the ion adsorption electrode becomes a force sword. And oxygen gas and hydrogen ions are generated at the counter electrode. In this way, the pH of the aqueous solution (A) is reduced.
- the ion-adsorbing electrode 12 and the counter electrode 14 are immersed in an aqueous solution 20 in which a salt (salt sodium salt) is dissolved in a tank 10. Then, a voltage is applied between the ion adsorption electrode 12 and the counter electrode 14 so that the ion adsorption electrode 12 becomes a force sword, and the cation (sodium ion) is adsorbed on the ion adsorption electrode 12. At this time, at the counter electrode 14, water is electrolyzed to generate oxygen gas and hydrogen ions. In this way, the aqueous solution 20 becomes an acid (hydrochloric acid) aqueous solution, and the pH of the aqueous solution 20 is reduced.
- a salt salt sodium salt
- the aqueous solution 20 can be replaced with another liquid to raise the pH of the liquid.
- a voltage is applied to the ion adsorption electrode and the counter electrode so that the ion adsorption electrode 12 becomes an anode.
- positive ions sodium ions
- hydrogen gas and hydroxide ions are generated at the counter electrode. In this way, the pH of the liquid to be processed can be raised.
- the ion-adsorbing electrode 11 and the counter electrode 13 are immersed in an aqueous solution 20 in which a salt is dissolved in a tank 10. Then, a voltage is applied between the ion adsorbing electrode 11 and the counter electrode 13 so that the ion adsorbing electrode 11 becomes an anode, and the anion (chlorine ion) is adsorbed on the ion adsorbing electrode 11. At this time, water is electrolyzed at the counter electrode 13 to generate hydrogen gas and hydroxide ions. In this way, the aqueous solution 20 becomes an aqueous solution of alkali (sodium hydroxide), and the pH of the aqueous solution 20 rises.
- alkali sodium hydroxide
- the aqueous solution 20 may be replaced with another liquid to reduce the pH of the liquid.
- a voltage is applied to the ion adsorption electrode and the counter electrode so that the ion adsorption electrode 11 becomes a force sword.
- anions chlorines
- oxygen gas and hydrogen ions are generated at the counter electrode. In this way, the pH of the liquid to be treated can be reduced.
- the amount of ions adsorbed and released in the conductive substance may be detected by measuring the amount of charge flowing through the electrode.
- the accumulated charge determines the amount of hydrogen ions or hydroxide ions, so the pH can be adjusted by the charge.
- the amount of ions that can be adsorbed on the ion-adsorbing electrode is measured in advance, the amount of charge flowing through the electrode is monitored to absorb the electrode. It can be detected that the amount of attached ions has reached the vicinity of the saturation amount.
- the amount of ions that can be adsorbed on the ion adsorption electrode can be measured by, for example, voltammetry.
- the amount of ions adsorbed on the conductive material may be detected by measuring the potential of the ion adsorption electrode. If the ions adsorbed on the conductive material exceed the saturation amount, the potential of the ion adsorption electrode changes to the potential at which water is electrolyzed. Therefore, by monitoring the potential change, it can be detected that the ions adsorbed on the ion adsorption electrode have reached the saturation amount.
- the potential of the ion adsorption electrode can also determine the potential difference between the reference electrode and the ion adsorption electrode.
- the potential of the ion adsorption electrode changes by adsorbing ions.
- the potential increases with adsorption of the anions, and when the oxygen generation potential is exceeded, more current is consumed to generate oxygen gas.
- the potential decreases with the adsorption of cations, and when the potential falls below the hydrogen generation potential, more current is consumed for hydrogen gas generation. Therefore, the saturated adsorption amount of the ion adsorption electrode can be obtained by detecting that the ion adsorption charge amount or ion adsorption amount has reached a certain value, and at that time, the ion adsorption amount is initialized.
- the pH adjustment method of the present invention when the pH is changed excessively, the voltage application direction is reversed, that is, the anode and the force sword are switched.
- the pH may be adjusted by applying pressure.
- the pH adjustment method of the present invention can be used as a method for preparing at least one aqueous solution selected from an acidic aqueous solution and an alkaline aqueous solution in another aspect.
- the method for reducing the pH can be used as a method for producing an acidic aqueous solution or a method for neutralizing an alkaline aqueous solution.
- the method for increasing the pH can be used as a method for producing an alkaline aqueous solution or a method for neutralizing an acidic aqueous solution.
- the present invention is a method for increasing the pH of a solution using an ion-adsorbing electrode on which cations are adsorbed and a counter electrode.
- the present invention is a method for reducing the pH of a solution using an ion adsorption electrode on which anion is adsorbed and a counter electrode.
- An example of the first pH adjustment method of the present invention includes (1) a first ion-adsorbing electrode including a first conductive material having a large specific surface area, and a second conductive material having a large specific surface area.
- a second ion-adsorbing electrode containing the first ion-adsorbing electrode and an anode between the first ion-adsorbing electrode and the second ion-adsorbing electrode.
- the second conductive material of the second ion adsorption electrode (2) By applying a voltage so that the negative ion of the salt is adsorbed to the first conductive material of the first ion adsorption electrode, the second conductive material of the second ion adsorption electrode (2) in a liquid containing water, either one of the first ion adsorption electrode or the second ion adsorption electrode and a counter electrode; Adjusting the pH of the liquid by applying a voltage therebetween.
- An example of the second pH adjustment method of the present invention is as follows. (1) A salt is dissolved between the first ion-adsorbing electrode containing the first conductive material having a large specific surface area and the first counter electrode. The first conductive material of the first ion adsorption electrode is immersed in an aqueous solution and a voltage is applied between the first ion adsorption electrode and the first counter electrode. A step of adsorbing ions of the salt; and (2) applying a voltage between the first ion adsorption electrode and the first counter electrode in a liquid containing water. Releasing the ions from the ion-adsorbing electrode into the liquid and generating hydrogen ions or hydroxide ions at the first counter electrode to adjust the pH of the liquid.
- An example of the third pH adjustment method of the present invention is an aqueous solution in which a salt is dissolved in the first ion-adsorbing electrode containing the first conductive material having a large specific surface area and the first counter electrode.
- the salt ions are applied to the first conductive material of the first ion adsorption electrode by applying a voltage between the first ion adsorption electrode and the first counter electrode.
- adjusting the pH of the aqueous solution by generating hydrogen ions or hydroxide ions at the first counter electrode.
- the pH adjusting device of the present invention is a device for carrying out the above pH adjusting method of the present invention. For this reason, redundant explanations may be omitted for the matters described in the explanation of the pH adjustment method.
- this apparatus can be used as an apparatus for producing an acidic aqueous solution and Z or an alkaline aqueous solution, or can be used as a neutralizing apparatus for an acidic solution and / or an alkaline aqueous solution.
- An outline of the configuration of an example of the apparatus of the present invention is shown in FIGS.
- the second and third pH adjusters of the present invention comprise a container, an ion adsorption electrode (E1) containing a conductive substance (C1) capable of adsorbing ions, a counter electrode, and a voltage application means.
- the ion adsorption electrode (E1) can be arranged in the container.
- the voltage applying means applies a voltage between the ion adsorption electrode (E1) and the counter electrode.
- the container is not particularly limited as long as it can hold an aqueous salt solution, an acidic aqueous solution, or an alkaline aqueous solution.
- This container preferably includes a mechanism for facilitating replacement of the liquid in the container.
- the container preferably includes an inlet for allowing liquid to flow into the container and an outlet for discharging the liquid in the container.
- an electrolytic cell with an inlet and an outlet, a continuous treatment of the liquid is possible.
- batch processing of liquid is facilitated by providing valves at each of the inlet and outlet.
- the ion adsorption electrode and the counter electrode As the ion adsorption electrode and the counter electrode, the above-described ion adsorption electrode and the counter electrode can be used.
- a DC power source such as a constant current power source or a constant voltage power source can be used. These may be used in combination with a timer, a coulomb meter, or a pH meter to adjust the pH. For example, you can use a combination of a constant current power source and a timer !, or a constant current power source or a constant voltage power source with a coulomb meter and a Z or pH meter.
- the second and third pH adjusters are, for example, the devices shown in Figs. Tank 10 in Figures 7 and 8 corresponds to the container.
- the second pH adjuster adjusts the pH of the liquid by performing the steps of the second pH adjusting method described above. That is, the second pH adjuster performs the step (I) and the step (ii) described above.
- the third pH adjuster adjusts the pH of the liquid by performing the steps of the third pH adjusting method described above.
- a constant current power source and a timer may be used in combination to detect the amount of ions adsorbed on the ion adsorption electrode and the amount of ions adsorbed and released on the ion adsorption electrode.
- a constant voltage power source and a coulomb meter may be used in combination, or a constant current power source or a constant voltage power source and a coulomb meter and Z or a reference electrode may be used in combination.
- the reference electrode may be based on the hydrogen generation potential or the oxygen generation potential when water (for example, neutral water) is electrolyzed with a minute current using the water electrolysis electrode.
- the first pH adjusting device of the present invention further includes an ion adsorption electrode (E2) including a conductive substance (C2) capable of adsorbing ions in addition to the above-described device.
- the voltage application means applies a voltage between at least two electrodes in which the group force composed of the ion adsorption electrode (E1), the ion adsorption electrode (E2), and the counter electrode is also selected.
- the ion adsorption electrode (E2) the ion adsorption electrode described above can be used.
- An example of this apparatus is the apparatus shown in FIGS.
- This first pH adjusting device adjusts the pH of the liquid by performing the steps of the first pH adjusting method described above. That is, the first pH adjuster performs the above-described step (i) and step (ii).
- the counter electrode may include a first counter electrode and a second counter electrode.
- the voltage application means applies a voltage between at least two electrodes selected from the group force consisting of the ion adsorption electrode (E1), the ion adsorption electrode (E2), the first counter electrode, and the second counter electrode. .
- a voltage is applied between two ion adsorption electrodes or between an ion adsorption electrode and a counter electrode.
- step (ii) including step (ii-a) and step (ii-b) can be performed.
- At least one aqueous solution selected from an acidic aqueous solution and an alkaline aqueous solution may be prepared!
- the apparatus of the present invention may further include a partition for separating the liquid to be treated.
- This partition can be arranged in the container.
- the partition described above Can be used.
- the step (ii-a) and the step (ii) including the step (ii-b) can be performed separately or simultaneously.
- the first to third pH adjusters of the present invention may each include a control device for performing each step.
- a known control device including an arithmetic processing unit and a memory unit can be applied to such a control device.
- the memory unit records the program for executing each process and the pH target value. This control device controls the voltage applied to the electrode based on the target value of pH (and the input value of each sensor force if necessary).
- the liquid may be processed continuously, or the liquid may be processed in a notch manner.
- the notch method means that the liquid in the container is processed without substantially replacing the liquid in the container during one process.
- the aqueous solution (A) in the container is usually discharged and another liquid is introduced into the container.
- the aqueous solution in the container is not added or discharged until the processing is completed, but if the replacement of the liquid in the container is not substantially performed until the processing is completed, this is a batch-type processing.
- aqueous solution even if a small amount of aqueous solution is added or discharged so as not to affect the treatment, it falls under the notch method. For example, even if 20% or less (for example, 10% or less, 5% or less, or 1% or less) of an aqueous solution in a container is added or discharged during processing, it can be regarded as a patch method. .
- each of the two steps may be performed by a notching process, or while the liquid is continuously flowing. You can go through the treatment (liquid treatment).
- Batch processing Z batch processing, batch processing Z liquid flow processing, liquid flow processing Z batch processing, liquid flow processing Z liquid flow processing may be mentioned as a combination of the processing methods of [Previous process] / [After process] .
- the amount of ions adsorbed and released in the conductive material may be detected by measuring the amount of charge flowing through the electrode.
- the amount of ions adsorbed on the conductive substance (C1′C2) may be detected by measuring the potential of the ion adsorption electrode ( ⁇ 1 ⁇ ⁇ 2).
- the pH of the present invention may further include a pH meter.
- at least one aqueous solution selected from an acidic aqueous solution and an alkaline aqueous solution may be prepared by the pH adjusting device of the present invention.
- the activated carbon cloth used in the following examples is activated carbon fiber cloth manufactured by Nihon Kynol Co., Ltd. (Product No .: ACC-5092-25, basis weight 100 to 130 gZm 2 , thickness about 0.5 mm, odor adsorption amount 1850 to 210 Omg / g).
- the specific surface area of the activated carbon fiber cloth is about 2000 m 2 / g or more.
- an activated carbon cloth of approximately 5cm x 6cm is prepared, and 9 lb of Ti coated Pt is attached to this activated carbon cloth 9 la, and activated carbon electrode (ion adsorption electrode) 91 was made. Moreover, the activated carbon electrode 92 was produced by the same method. Also, Ti electrodes were coated with Pt to produce counter electrodes 93 and 94.
- the activated carbon electrodes 91 and 92 were disposed between the counter electrode 93 and the counter electrode 94 as shown in FIG. 9B, and placed in a box-shaped container having an internal volume of 100 ml.
- 80 ml of an aqueous NaCl solution having a concentration of 0. OlmolZ liters was placed.
- an acidic aqueous solution (an acidic aqueous solution containing NaCl) was discharged from the tank, and the tank was thoroughly washed with tap water, and then 80 ml of tap water was placed in the tank. Then, an activated carbon electrode having adsorbed sodium ions was used as an anode, a counter electrode was used as a force sword, and a current of 120 seconds was applied at 120 mA to prepare an alkaline aqueous solution. The pH of the resulting alkaline aqueous solution is 11.04.
- a current collector coated with Pt on Ti was attached to a 3cm x 5cm activated carbon cloth to produce an activated carbon electrode.
- a Ti electrode was coated with Pt to produce a counter electrode.
- the activated carbon electrode and the counter electrode were opposed to each other with a separator interposed therebetween, and placed in a box-shaped container having an internal volume of 50 ml.
- a nylon mesh was used for the separator (the same applies to the following examples).
- a current collector coated with Pt on Ti was attached to a 3cm x 5cm activated carbon cloth to produce an activated carbon electrode.
- a Ti electrode was coated with Pt to produce a counter electrode.
- the activated carbon electrode and the counter electrode were opposed to each other with a separator interposed therebetween, and placed in a box-shaped container having an internal volume of 15 ml. Further, 10 ml of NaCl aqueous solution having a concentration of 0.1 molZ was placed in the container.
- the activated carbon electrode is used as an anode
- the counter electrode is used as a force sword
- a current of 60 mA is passed between both electrodes for 500 seconds
- chlorine ions are adsorbed on the activated carbon electrode.
- the NaCl aqueous solution in the container was discharged to wash the container, and the solution in the container was replaced with tap water.
- the polarity was changed, that is, the current was passed with the activated carbon electrode as the force sword and the counter electrode as the anode to produce an acidic aqueous solution.
- three experiments were performed with different amounts of current and energization time.
- the activated carbon electrode is used as a force sword
- the counter electrode is used as an anode
- a current of 60 mA is passed between both electrodes for 400 seconds to adsorb sodium ions to the activated carbon electrode. It was.
- the NaCl aqueous solution in the container is discharged to clean the container, The solution inside was replaced with tap water.
- the polarity was changed, that is, an activated carbon electrode was used as an anode and a counter electrode was used as a force sword to pass an electric current to prepare an alkaline aqueous solution.
- three experiments were performed with different amounts of current and energization time.
- a 3 cm x 5 cm activated carbon cloth was attached with a current collector coated with Pt on Ti to produce an activated carbon electrode.
- a Ti electrode was coated with Pt to produce a counter electrode.
- the activated carbon electrode and the counter electrode were placed opposite each other with a separator in between, and placed in a box-type container having an internal volume of 50 ml, and 40 ml of an acidic aqueous solution of pH 4.8 prepared in Example 1 was injected into this container.
- a counter electrode was produced in the same manner as in Example 1. Next, the activated carbon electrode and the counter electrode are opposed to each other with a separator in between, and placed in a box-shaped container with an internal volume of 50 ml, and 40 ml of tap water is placed in the container. [0127] Thereafter, with the activated carbon electrode as a force sword and the counter electrode as an anode, a current was passed between the electrodes at a constant current of 60 mA for 60 seconds to adsorb cations on the activated carbon electrode, and oxygen was generated at the counter electrode. This operation was repeated 5 times.
- an alkaline aqueous solution was prepared by using the activated carbon electrode as an anode and the counter electrode as a force sword, and passing a current at a constant current of 60 mA between the electrodes for 10 seconds.
- the prepared alkaline aqueous solution is discharged, and tap water is again put into the container.
- the activated charcoal electrode is used as an anode
- the counter electrode is used as a power sword
- a current of 60 mA is applied between the two electrodes for 10 seconds.
- an alkaline aqueous solution was repeatedly prepared by using the cation first adsorbed on the activated carbon electrode.
- the container has an internal volume of about 100ml, and a container with a structure that can be divided into two 50ml rooms by inserting a partition (metal plate) in the middle of the container was prepared.
- a partition metal plate
- a Pt-plated plate on both sides of the Ti plate was used.
- the activated carbon electrode (3cm X 5cm activated carbon cloth) in the container.
- 80 ml of an aqueous NaCl solution having a concentration of 0.1 ImolZ liter was placed in the container.
- a 50 mA current was passed for 300 seconds to adsorb chlorine ions to the anode and adsorb sodium ions to the force sword.
- one activated carbon electrode was taken out and attached to one surface of the partition wall via a separator.
- the other activated carbon electrode was taken out and attached to the other surface of the partition wall via a separator.
- This partition wall (metal plate) was set in a container. Then, an acidic aqueous solution is made with the activated carbon electrode on which chlorine ions are adsorbed and the partition wall (also serving as the counter electrode), and an alkaline aqueous solution is made with the activated carbon electrode on which sodium ions are adsorbed and the partition wall (also serving as the electrode for water electrolysis). It was.
- the water to be treated was continuously flowing water.
- the side that produces the acidic aqueous solution had a current of 60 mA and the amount of flowing water was lOOmlZ, and the side that produced the alkaline aqueous solution had the amount of current of 60 mA and the amount of flowing water was 240 mlZ.
- the treatment was performed for 1 minute.
- the resulting alkaline aqueous solution had a pH of 9.3, and the acidic aqueous solution had a pH of 5.2.
- Counter electrode Z separator Z activated carbon electrode Z separator Z counter electrode Z separator Z activated carbon electrode / Separator / counter electrode group was prepared.
- the counter electrode described in Example 1 was used as the counter electrode.
- the activated carbon electrode was prepared by attaching a current collector similar to FIG. 9A to an activated carbon cloth (3 cm ⁇ 5 cm).
- the prepared electrode group was placed in a container having a volume of 50 ml, and 40 ml of tap water was further added. Then, the counter electrode was a force sword, the activated carbon cloth was the anode, and an electric current was applied to produce an alkaline aqueous solution. At this time, five kinds of experiments (Conditions 1 to 5) were performed by changing the amount of electric current and the processing time while keeping the amount of charge (coulomb amount) constant.
- the structure of the current collector of the electrode is the same as that shown in Fig. 10, that is, the structure in which the wiring for collecting current around the activated carbon cloth is arranged (however, one activated carbon cloth is provided).
- An electrode group similar to the electrode group was fabricated. Using this electrode group (Condition 6), an alkaline aqueous solution was prepared in the same manner as described above.
- an electrode group similar to the above-described electrode group was produced except that the structure of the current collector of the electrode was the structure shown in Fig. 10 and two activated carbon cloths were stacked. Using this electrode group (Condition 7
- the present invention relates to a method for adjusting pH, a method for producing an acidic solution, a method for producing an alkaline solution, an acid solution, It can be used for neutralizing neutral solution, neutralizing alkaline solution, and apparatus for carrying out these methods.
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- Life Sciences & Earth Sciences (AREA)
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Abstract
Description
Claims
Priority Applications (4)
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JP2006536911A JP3994417B2 (ja) | 2005-06-08 | 2006-06-02 | 液体のpH調整方法およびpH調整装置 |
US11/921,717 US20090205975A1 (en) | 2005-06-08 | 2006-06-02 | Method for adjusting ph of liquid and ph adjustor |
EP06756945.9A EP1889813B1 (en) | 2005-06-08 | 2006-06-02 | Method for adjusting ph of liquid and ph adjustor |
CN200680020189.4A CN101193822B (zh) | 2005-06-08 | 2006-06-02 | 液体的pH调节方法以及pH调节装置 |
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JP2005168711 | 2005-06-08 | ||
JP2005-168711 | 2005-06-08 | ||
JP2006007945 | 2006-01-16 | ||
JP2006-007945 | 2006-01-16 |
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WO2006132160A1 true WO2006132160A1 (ja) | 2006-12-14 |
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PCT/JP2006/311124 WO2006132160A1 (ja) | 2005-06-08 | 2006-06-02 | 液体のpH調整方法およびpH調整装置 |
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US (1) | US20090205975A1 (ja) |
EP (1) | EP1889813B1 (ja) |
JP (1) | JP3994417B2 (ja) |
CN (1) | CN101193822B (ja) |
WO (1) | WO2006132160A1 (ja) |
Cited By (7)
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WO2009157388A1 (ja) * | 2008-06-23 | 2009-12-30 | 有限会社ターナープロセス | 殺菌方法および殺菌装置 |
US8529737B2 (en) | 2008-03-25 | 2013-09-10 | Tanah Process Ltd. | Portable device for regulating hardness of drinking water |
JP2014127466A (ja) * | 2012-12-26 | 2014-07-07 | Kazuhiro Hayashi | 電解液中の電極間の物質移動過程は電圧印加で促進 |
WO2015093094A1 (ja) * | 2013-12-19 | 2015-06-25 | シャープ株式会社 | 機能水生成器 |
JP2015529542A (ja) * | 2012-06-27 | 2015-10-08 | コーニンクレッカ フィリップス エヌ ヴェ | カチオンおよびアニオンを含む溶液を調製する装置および方法 |
JP2016509529A (ja) * | 2012-12-26 | 2016-03-31 | コーニンクレッカ フィリップス エヌ ヴェKoninklijke Philips N.V. | pH調整器、pH調整器を含む装置及びpHを調整する方法 |
JP2018515321A (ja) * | 2014-12-26 | 2018-06-14 | コーニンクレッカ フィリップス エヌ ヴェKoninklijke Philips N.V. | UpAセルのpH制御方法 |
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CN101291880B (zh) * | 2005-09-27 | 2011-09-07 | 棚氏处理有限公司 | 离子浓度调整方法及离子浓度调整装置 |
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WO2016150928A1 (en) * | 2015-03-26 | 2016-09-29 | Koninklijke Philips N.V. | Controlling regeneration of an electrode in unidirectional ph adjustment of water |
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Also Published As
Publication number | Publication date |
---|---|
CN101193822A (zh) | 2008-06-04 |
JP3994417B2 (ja) | 2007-10-17 |
EP1889813B1 (en) | 2014-09-17 |
CN101193822B (zh) | 2013-06-12 |
EP1889813A4 (en) | 2009-12-23 |
JPWO2006132160A1 (ja) | 2009-01-08 |
US20090205975A1 (en) | 2009-08-20 |
EP1889813A1 (en) | 2008-02-20 |
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