JP2003328198A - Method of generating copper ion and apparatus therefor, method of producing copper sulfate and apparatus therefor, method of generating metallic ion and apparatus therefor, and method of producing acid water and apparatus therefor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To efficiently generate copper ions with a high purity. <P>SOLUTION: An ion generating tank 2 is divided into an anode chamber 21 and a cathode chamber 22 with a hydrogen ion exchange membrane 23. Gaseous hydrogen is released from the vicinity of a cathode 24 in the cathode chamber 22, and in the anode chamber 21, copper ions are eluted into the anode chamber 21 from an anode 25. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method and apparatus for producing copper ions, a method and apparatus for producing copper sulfate, a method and apparatus for producing metal ions, a method for producing ionized water and apparatus therefor, and in particular to a high purity The present invention relates to a technique suitable for generating copper ions.

[0002]

2. Description of the Related Art In order to obtain copper ions required for copper plating, a solution of copper sulfate hydrate is applied as a plating solution. There is a problem that the film characteristics of the plating layer are deteriorated by the presence of such impurities. Therefore, high purity is required for the copper sulfate as a raw material, and there is a demand for obtaining better power efficiency.
At this time, in particular, it is necessary to supply copper ions while maintaining a stable concentration and purity for a long time, and it is necessary to maintain a uniform copper ion concentration in the plating solution supplied with copper ions. .

Further, in order to supply copper ions into the plating solution, a metal copper block (copper plate, copper piece) was applied to the anode to elute the copper ions. It is necessary to mix phosphorus, and phosphorus exists as an impurity in the plating solution. However, the presence of phosphorus in copper deteriorates the film characteristics of the plating layer, and there has been a demand for improvement.

Further, recently, in a semiconductor device, by using copper having a low electric resistivity for a wiring layer, it is possible to prevent a wiring delay due to the electric resistance of the wiring and to improve a signal transmission speed in the device. Since it is possible to improve the processing speed as a result, it is considered to adopt copper (Cu) for the wiring layer in order to improve the processing speed in the semiconductor element. For that, a high-purity product was required.

In addition to copper, it is difficult to produce metal ions of metals such as silver, gold and platinum, which have a smaller ionization tendency than hydrogen, and an inexpensive and simple method has been demanded. .

The present invention has been made in view of the above circumstances and is intended to achieve the following objects. To enable efficient generation of metal ions. To enable particularly efficient generation of copper ions. In the above case, reduce impurities. To enable stable supply of copper ions. To enable the production of high-purity copper sulfate. To enable efficient supply of acidic water.

[0007]

According to the copper ion generating method of the present invention, an ion generating tank is divided into an anode chamber and a cathode chamber by a hydrogen ion exchange membrane, and hydrogen gas is released from the cathode surface in the cathode chamber. At the same time, the above problem was solved by eluting copper ions from the anode into the anode chamber in the anode chamber. In the present invention, it is desirable to store an acid solution in the anode chamber. In the present invention,
As the anode, it is possible to employ a means for placing the raw material copper inside the cage-shaped conductor. The copper ion generator of the present invention comprises an ion generating tank, a hydrogen ion exchange membrane for partitioning the inside of the ion generating tank into an anode chamber and a cathode chamber, and an electric current provided in the cathode chamber to discharge hydrogen gas from the surface. The above-mentioned problems are solved by including a cathode that operates and an anode that is provided in the anode chamber and is energized to elute copper ions into the anode chamber. An acid solution may be stored in the anode chamber of the present invention. Further, the anode may include a cage-shaped conductor and a raw material copper placed inside the conductor cage. The copper sulfate production method of the present invention divides an ion generating tank into an anode chamber and a cathode chamber with a hydrogen ion exchange membrane, and in the cathode chamber, releases hydrogen gas from the cathode surface and supplies the sulfuric acid to the anode chamber. In the above, the above problems were solved by eluting copper ions from the anode into the anode chamber and producing a copper sulfate solution in the anode chamber. In the present invention, as the anode,
It is desirable to place the raw material phosphorus-free copper inside the cage-shaped conductor. The copper sulfate manufacturing apparatus of the present invention comprises an ion generating tank, a hydrogen ion exchange membrane for partitioning the inside of the ion generating tank into an anode chamber and a cathode chamber, and an electric current provided in the cathode chamber to discharge hydrogen gas from the surface. The above-mentioned problems are solved by including a negative electrode and a positive electrode which is provided in the positive electrode chamber to which sulfuric acid is supplied and which is energized to elute copper ions into the positive electrode chamber. Further, in the present invention, it is also possible to adopt a means in which the anode has a cage-shaped conductor and a raw material non-phosphorus copper placed inside the conductor cage. The metal ion generation method of the present invention divides an ion generation tank into an anode chamber and a cathode chamber with a hydrogen ion exchange membrane, and in the cathode chamber, releases hydrogen gas from the cathode surface, and in the anode chamber, from the anode. The above problems were solved by eluting metal ions into the anode chamber. In the present invention, the anode chamber may be provided with a means for storing an acid solution or a means for placing the raw material metal inside the cage-shaped conductor as the anode. The metal ion generator of the present invention comprises an ion generation tank, a hydrogen ion exchange membrane for partitioning the inside of the ion generation tank into an anode chamber and a cathode chamber, and an electric current provided in the cathode chamber to discharge hydrogen gas from the surface. The above-mentioned problem is solved by including a cathode that operates and an anode that is provided in the anode chamber and that is energized to elute metal ions in the anode chamber. An acid solution can be stored in the anode chamber in the present invention, and the anode includes a cage-shaped conductor and a raw material metal placed inside the conductor cage. Can have. Further, as the method for producing acidic water of the present invention, the ion generation tank is divided into an anode chamber and a cathode chamber with a hydrogen ion exchange membrane, and in the anode chamber, metal ions are eluted from the anode into the anode chamber, and the cathode is used. In the chamber, it is also possible to employ a means of producing hydrogen gas by releasing hydrogen gas from the surface of the cathode. The acidic water producing apparatus of the present invention comprises an ion generating tank, a hydrogen ion exchange membrane for partitioning the inside of the ion generating tank into an anode chamber and a cathode chamber, and a metal ion in the anode chamber which is energized and energized. The above problem is solved by providing an anode that elutes with a cathode and a cathode that is provided in the cathode chamber and discharges hydrogen gas from its surface when energized, and by generating acidic water in the cathode chamber.

In the ion generating tank of the present invention, the inside thereof is divided into an anode chamber and a cathode chamber by a hydrogen ion exchange membrane, and the cathode is energized in the cathode chamber so that hydrogen ions in the cathode chamber are discharged from the vicinity of the cathode. It is released as hydrogen gas to reduce the hydrogen ion concentration in this cathode chamber. As a result, only the hydrogen ions inside the anode chamber move to the cathode chamber through the hydrogen ion exchange membrane. Therefore, the cations in the anode chamber are reduced,
By energizing the anode in the anode chamber in this state, metal ions such as copper ions can be eluted from the anode into the anode chamber to increase the metal ion concentration in the anode chamber. Here, as the anode, it is also possible to apply a plate-shaped or rod-shaped shape made of metallic copper. This makes it possible to easily produce metal ions of metals such as copper, silver, gold, and platinum that have a smaller ionization tendency than hydrogen. At the same time, it is possible to produce acidic water with hydrogen ions in the cathode chamber.

In the present invention, a hydrogen ion exchange membrane for partitioning the inside of the ion generating tank into an anode chamber and a cathode chamber, a cathode provided in the cathode chamber, and a specific configuration for realizing the above method, A configuration provided with an anode provided in the anode chamber is adopted. When this cathode is energized,
Hydrogen ions inside the cathode chamber are released as hydrogen gas. When the anode is energized, metal ions such as copper ions are eluted into the anode chamber. Further, the hydrogen ion exchange membrane is supposed to selectively permeate hydrogen ions between the electrode chambers.
Thereby, by energizing the cathode and the anode to move the hydrogen ions inside the anode chamber to the cathode chamber, hydrogen ions inside the anode chamber are reduced and metal ions such as copper ions are eluted from the anode into the anode chamber. . With this, silver, gold, platinum, etc.
Even if the metal has a smaller ionization tendency than hydrogen, the metal ion can be easily produced. At the same time, it is possible to produce acidic water with hydrogen ions in the cathode chamber.

The hydrogen ion exchange membrane may be one that selectively permeates hydrogen ions, that is, one that allows only hydrogen ions to pass without passing metal ions eluted in the anode chamber to the cathode chamber. For example, a cation resin, a hydrogen ion selective permeable membrane or the like can be applied. Also,
The cathode may be one that has low reactivity with the liquid in the cathode chamber and also has low reactivity with hydrogen. For example, Cu, Ti, C, Pb, or Ru on the surface of Ti may be used.
A structure coated with a platinum group oxide such as is applicable.

In the present invention, by storing an acid solution in the anode chamber, it is possible to stabilize the eluted metal ions and move hydrogen ions to the cathode chamber to produce metal ions such as copper. Become. Here, as the applicable acid, the kind thereof varies depending on the metal ion to be produced, but when producing copper ion, sulfuric acid, nitric acid, hydrochloric acid or the like can be applied. In the case of silver ion, nitric acid can be applied. In addition to this, hydrochloric acid and hydrocyanic acid (HCN) are also applicable.
And weak acids such as malic acid are applicable. In addition, except for the case of producing acidic water, it is preferable to store the acid solution having the same concentration as that of the anode chamber also in the cathode chamber.

Further, in the present invention, as the anode,
By adopting a configuration in which the raw material copper is placed inside the cage-shaped conductor, it becomes possible to energize the raw material copper which is eluted as copper ions as a conductor basket as a wiring, and the raw material copper is cut by the elution. , It is possible to prevent the non-energized portion from dropping to the bottom of the anode chamber, and to prevent the copper ion from being eluted so that the copper raw material becomes so small that it cannot be energized. . Here, when the wiring is directly connected to the copper plate and this is used as the anode without applying the conductor cage, more copper ions are eluted near the liquid surface and the copper plate near the liquid surface is cut. , Unreacted copper plate remains in the liquid. According to the present invention, such a situation can be prevented. Also,
The conductor cage is preferably resistant to the acid in the anode chamber, and is preferably made of, for example, stainless steel, platinum, titanium, or a structure in which the surface of Ti is coated with a platinum group oxide such as Ru. .

As the copper sulfate producing apparatus, a copper sulfate supply pipe or the like for delivering the copper sulfate solution to the outside can be provided near the bottom of the anode chamber. This makes it possible to promptly supply water or a copper sulfate solution having a higher specific gravity than the acid solution and having a higher concentration near the bottom of the anode chamber to the outside. Further, it is possible to prevent copper ions near the anode from moving rapidly to reduce the concentration of cations, prevent the limiting current in the electrode reaction from decreasing, and prevent the generation rate of copper ions from decreasing. When the supply destination of metal ions such as copper ions and copper sulfate is, for example, a plating tank or the like, a plating anode and a plating cathode for plating are provided in the plating tank to generate hydrogen ions near the plating anode. By returning to the anode chamber of the ion generating tank, metal ions such as copper ions can be continuously produced without replenishing new acid unless the raw material metal such as copper for the anode is exhausted. Further, in this case, by adding a raw material metal such as raw material copper and replenishing it in the conductor basket, it is possible to continuously produce metal ions such as copper ions, and at the same time, add an acid solution such as sulfuric acid. By supplying, copper sulfate can be continuously produced.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION A first embodiment of a copper ion generating method and apparatus therefor according to the present invention will be described below with reference to the drawings. FIG. 1 is a schematic diagram showing a copper ion generator of the present embodiment. In the figure, reference numeral 1 is a copper ion generator, and 2 is an ion generation tank.

Copper ion generator 1 in this embodiment
As shown in FIG. 1, the ion generation tank 2, a hydrogen ion exchange membrane 23 that divides the inside of the ion generation tank 2 into an anode chamber 21 and a cathode chamber 22, and a cathode ion chamber 22 are provided with electricity. It is provided with a cathode 24 that releases hydrogen gas H ₂ from the surface and an anode 25 that is provided in the anode chamber 21 and that is energized to elute copper ions Cu ²⁺ into the anode chamber 21.

The ion generating tank 2 has a box-like shape with an open upper surface, and a pipe 26 is connected to a side wall near the bottom of the ion generating tank 2 at a position of an anode chamber 22 described later, and a predetermined acid solution is stored therein. It In this embodiment, the acid solution is 90
~ 220 g / l (0.9-2.2 N with an ionization degree of 1)
It is considered to be sulfuric acid H ₂ SO ₄ in a certain degree.

The hydrogen ion exchange membrane 23 is used in the ion generating tank 2
Of the ion generating tank 2 is closely attached to the side wall and the bottom of the ion generating tank 2 facing each other.
The inside of the ion generating tank 2 is divided into an anode chamber 21 and a cathode chamber 22. The proton exchange membrane 23 is, as it were selectively permeable to hydrogen ions H ^+, is intended to act like a semi-permeable membrane, is transmitted through the water molecules and hydrogen ions H ^+, copper will be described later ions Cu Metal ions such as ²⁺ and negative ions such as sulfate ions SO ₄ ²⁻ do not permeate.

The hydrogen ion exchange membrane 23 is formed of hydrogen ions H ⁺
It is only necessary to selectively permeate, and for example, a cation resin, a hydrogen ion selective permeable membrane, or the like can be applied. As the hydrogen ion exchange membrane 23, a commercially available product may be used, and in the present embodiment, special cation membranes HSV and HSF of Selemion (registered trademark) manufactured by Asahi Glass Co., Ltd. can be applied.

The anode chamber 21 is provided near its center with an anode 25 connected to the anode side of a direct current supply device (not shown). The anode 25 is configured to include a cage-shaped conductor 25A connected to a power source and a raw material copper 25B placed inside the conductor cage 25A so as to be able to conduct electricity through the conductor cage 25A.

The conductor cage 25A is a bottomed cylindrical cage. The upper end of the conductor cage 25A is located above the liquid surface stored in the anode chamber 21 as described later, and the bottom of the conductor cage 25A efficiently elutes the copper ions Cu ²⁺ in order to elute the copper ions Cu ^2+. Is separated from the bottom of the. The inner diameter of this conductor cage 25A is the raw material copper 25 described later.
It is preferable to set the diameter larger than the diameter of B, specifically, 30 to 60 corresponding to the raw material copper 25B to be used.
It is set to about mm. In addition, the cage-shaped mesh interval size in the conductor cage 25A is the same as the conductor cage 2 when the raw material copper 25B, which is reduced by elution of copper ions Cu ²⁺ , is used as described later.
It is set so as to be able to stay within 5 A, specifically, it is set to about 6 to 10 mm. The conductor cage 25A is preferably resistant to the acid in the anode chamber 21, and for example, the surface of stainless steel, platinum, titanium, or titanium (Ti) material is coated with a platinum group oxide such as Ru. It is preferably composed of a structure or the like.

The raw material copper 25B is preferably a substantially spherical copper anode ball containing no impurities, and particularly preferably one containing no phosphorus. In addition, raw material copper 25
The diameter of B is preferably about 11 mm to 55 mm, and specifically, the diameter of 55 mm was used.

The cathode chamber 22 is provided with a cathode 24 connected to the cathode side of a DC current supply device (not shown).
The plate-shaped cathode 24 is provided vertically near the center of the cathode chamber 22, and preferably has a shape that increases the surface area in order to enhance reactivity. Further, the cathode 24 may be one having a low reactivity with an acid solution and a low reactivity with hydrogen, such as Cu, Ti, C,
A structure in which the surface of Pb or titanium (Ti) material is coated with a platinum group oxide such as Ru is applicable.

Next, the production of copper ions in the above copper ion generator will be described.

When producing copper ions, first, the ions
The inside of the generation tank 2 is filled with a sulfuric acid aqueous solution, and the conductor cage 2
Raw material copper 25B is supplied into 5A. In this state, the cathode
In the chamber 22, water molecules, sulfate ions SO_Four ^2- , Hydroxy iodide
OH^- , Undissociated sulfuric acid molecule, and hydrogen ion H⁺ But
There are water molecules and sulfate ions SO in the anode chamber 21. _Four
^2- , Hydrogen ion H⁺ , Hydroxide ion OH^- , Undissociated sulfuric acid
Molecule and trace amount of copper ion Cu²⁺Exists.

Next, from the current supply device (not shown) to the anode 25 and the cathode 24, 2 × 10 ^{+2 to} 6 × 10 ⁺² A / m
Apply ² electrolytic current. Then, in the vicinity of the surface of the cathode 24, the hydrogen ions H ⁺ in the cathode chamber 22 become hydrogen gas H ₂
Is released as. For this reason, in order to maintain the electrical neutrality of the cathode chamber 22, positive ions are transferred from the anode chamber 21 to the cathode chamber 22.
However, since the two chambers 21 and 22 are partitioned by the hydrogen ion exchange membrane 23, only the hydrogen ions H ⁺ inside the anode chamber 21 move to the cathode chamber 22. At this time, copper ions Cu ²⁺ cannot pass through and stay in the anode chamber 21. Here, the upper limit of the applied electrolysis voltage varies depending on the stirring conditions of the anolyte solution, temperature, concentration, etc.
5 It is set within a range where oxygen is not generated on the surface.

As a result, the hydrogen ion concentration in the anode chamber 21 is reduced, that is, the cations in the anode chamber 21 are reduced. In the anode 25, an electrolytic current is applied to the raw material copper 25B in contact with the conductor cage 25A via the conductor cage 25A. Positive ions in the anode chamber 21 (hydrogen ions H
⁺ ) Is reduced, by energizing the anode 25 of the anode chamber 21, the copper ions Cu ²⁺ are transferred from the anode 25 to the anode chamber 2 up to the cation concentration in the initial state before energization.
By eluting into the inside of 1, the electric neutrality in the anode chamber 21 is maintained. At this time, the magnitude of the electrolytic current applied to the anode 25 is proportional to the amount of the eluted copper ions Cu ²⁺ .

In this state, by continuing to energize the anode 25 and the cathode 24, hydrogen gas H ₂ is continuously generated from the cathode, and the hydrogen ion concentration in the cathode chamber 22 is continuously reduced. As a result, only the hydrogen ions H ⁺ inside the anode chamber 21 pass through the hydrogen ion exchange membrane 23 and the cathode chamber 2
2, the hydrogen ion concentration in the anode chamber 21, that is, the cation concentration is reduced, and as a result, the raw material copper 25B
From this, copper ions Cu ²⁺ are continuously eluted. As a result, the copper ion C, which has a smaller ionization tendency than hydrogen,
u ²⁺ can be produced.

At the same time, the raw material copper 25B is added and the conductor cage 2 is added.
By supplying into 5 A, copper ions Cu ²⁺ can be produced more continuously.

According to the copper ion generating method and its apparatus of the present embodiment, the hydrogen ion exchange membrane 23 that divides the inside of the ion generating tank 2 into the anode chamber 21 and the cathode chamber 22, and the cathode chamber 2
2 is configured to include a cathode 24 provided in the anode chamber 21 and an anode 25 provided in the anode chamber 21, and a direct current is applied to the anode 25 and the cathode 24 from a current supply device (not shown), With the cathode 24 energized, the cathode chamber 22
The internal hydrogen ion H ⁺ is released as hydrogen gas H ₂ ,
The hydrogen ion concentration in the cathode chamber 22 is reduced, only the hydrogen ions H ⁺ in the anode chamber 21 are moved to the cathode chamber through the hydrogen ion exchange membrane 23, and the cation concentration in the anode chamber 21 is reduced. As a result, copper ions C are continuously supplied from the raw material copper 25B.
u ²⁺ can be eluted.

As a result, hydrogen has a smaller ionization tendency than hydrogen.
Even if it is copper, copper ion Cu²⁺To manufacture
Is possible. Therefore, in order to dissolve the raw material copper 25B,
There is no need to mix impurities such as phosphorus with this raw material copper 25B.
Therefore, the obtained copper ion Cu ²⁺Contains impurities such as phosphorus.
Not rare, high purity copper ion Cu²⁺It is possible to get
It Therefore, it can be applied to copper wiring such as semiconductors.
High purity copper ion Cu ²⁺Can be easily obtained.

At the same time, according to this method for producing copper ions Cu ²⁺ , the anode 2 is proportional to the electrolytic current applied to the anode 25.
Since the copper ion Cu ²⁺ elutes from 5, the amount of the copper ion Cu ²⁺ to be manufactured can be easily set according to the magnitude of the electrolytic current applied.

Further, in the present embodiment, by adopting the structure in which the raw material copper 25B is placed inside the cage-shaped conductor 25A as the anode 25, the raw material copper 25B can be energized through the conductor cage 25A. In addition to being possible, even if the raw material copper 25B is reduced due to elution, it is possible to maintain the power supply and elute the raw material copper 25B to the end. For this reason, when the anode is a copper plate or the like, the copper plate is cut and the part which is not energized falls to the bottom of the anode chamber, and the copper plate becomes smaller due to elution and cannot be energized. The raw material copper can be efficiently converted into copper ions.

The copper ions Cu produced in the anode chamber 21
By sending ²⁺ to the outside through the pipe 26, an increase in the concentration of cations in the anode chamber 21 can be ^suppressed , and further copper ions Cu ²⁺ can be produced. Further, at this time, by connecting the pipe 26 near the bottom of the anode chamber 21 to a plating tank or the like, it becomes possible to rapidly supply the produced copper ions Cu ²⁺ to a predetermined location in the plating tank or the like. At this time, in the anode chamber 21, by forming a flow from the vicinity of the anode 25 to the connecting portion of the pipe 26,
Prevention more together efficiently can supply copper ions Cu ^2+, copper ions Cu ²⁺ in the vicinity of anode 25 to move rapidly to reduce the cation concentration, that limit current in the electrode reaction is reduced As a result, it is possible to prevent the generation rate of copper ions Cu ^{2+ from} decreasing.

A second embodiment of the method for producing copper sulfate and the apparatus therefor according to the present invention will be described below with reference to the drawings.

The copper sulfate manufacturing apparatus of this embodiment has substantially the same construction as the copper ion generator of the first embodiment shown in FIG.

In this embodiment, copper ions Cu ²⁺ are produced in the same manner as in the first embodiment described above,
It is possible to efficiently produce copper sulfate. at the same time,
By additionally supplying the raw material copper 25B into the conductor cage 25A and additionally supplying sulfuric acid into the anode chamber 21,
It is possible to continuously produce copper sulfate. Further, since it is not necessary to mix impurities such as phosphorus with the raw material copper 25B in order to dissolve the raw material copper 25B, the obtained copper sulfate does not contain impurities such as phosphorus, and high-purity copper sulfate can be obtained. It will be possible. Therefore, it is possible to easily obtain high-purity copper sulfate that can be applied to copper wiring of semiconductors and the like.

In the present embodiment, the anode chamber 21
The pipe 26 provided near the bottom can be used as a copper sulfate supply pipe for delivering the manufactured copper sulfate solution to the outside. This makes it possible to promptly supply water or a copper sulfate solution having a higher specific gravity than the acid solution and having a higher concentration near the bottom of the anode chamber to the outside. Further, the copper ions near the anode 25 are rapidly moved to reduce the cation concentration in the anode chamber 21 and prevent the limiting current in the electrode reaction from being reduced, thereby preventing the production rate of copper sulfate from being reduced. be able to. Further, when the supply destination of copper sulfate is, for example, a plating tank or the like, a plating anode and a plating cathode for plating are provided in the plating tank, and hydrogen ions generated near the plating anode are generated in the anode chamber of the ion generating tank. By returning to the above condition, copper ions Cu ²⁺ can be produced and copper sulfate can be continuously supplied unless the raw material copper 25B in the anode 25 is lost.

A third embodiment of the method for producing acidic water and the apparatus therefor according to the present invention will be described below with reference to the drawings.

The acidic water producing apparatus of this embodiment has substantially the same structure as the copper ion generator of the first embodiment shown in FIG.

In the present embodiment, the cathode chamber 22 is sulphurized.
Store pure water instead of acid solution. Then, the first embodiment
Similarly to the above, the anode 25 and the cathode 24 are not
An electrolytic current is applied from the flow supply device. Then, cathode 2
4 near the surface, hydrogen ions H in the cathode chamber 22⁺ But
Hydrogen gas H₂ Is released as hydrogen ion exchange
Hydrogen ion H inside the anode chamber 21 is passed through the exchange membrane 23.⁺ Is
The injury moves to the cathode chamber 22. At this time, hydrogen ion exchange
The film 23 is hydrogen ion H.⁺ To selectively permeate the
Molecule and hydrogen ion H ⁺ Only penetrates, but copper ions
Cu²⁺, And sulfate ion SO_Four ^2- Basic ions such as
It cannot pass through and remains in the anode chamber 21. By this
As a result, the hydrogen ion concentration in the cathode chamber 22 increases and the cathode chamber 2
Acidic water can be produced in 2.

In each of the above embodiments, the raw material copper 25B was placed in the conductor cage 25A of the anode 25 to elute the copper ions Cu ²⁺ . However, metals other than copper, such as silver,
By depositing any metal, including gold, platinum, and other metals having a smaller ionization tendency than hydrogen, the metal ions can be produced.

In this case, the anode 25 and the cathode 24 are illustrated.
Do not apply direct current from a current supply device.
The charged cathode 24, the hydrogen ion inside the cathode chamber 22
H ⁺ Hydrogen gas H₂ As the inside of the cathode chamber 22
The hydrogen ion concentration of
Then, hydrogen ions H in the anode chamber 21⁺ Move only to cathode chamber
Then, the concentration of cations in the anode chamber 21 is reduced, and
As a result, metal ions may be continuously eluted from the raw metal.
It will be possible.

Here, the type of acid to be applied differs depending on the metal ion to be produced, but it is applicable to sulfuric acid in the production of copper ion, and nitric acid in the case of silver ion. , Weak acids such as hydrochloric acid, hydrocyanic acid (HCN) and malic acid are applicable.

The present invention dissolves a metal in an aqueous solution by electrolysis, has a higher controllability of the dissolution rate than the conventional method, is easy to unmanned, and has a compact equipment, and a raw material and It has many advantages such as low cost of auxiliary raw materials and expectation of a refining function when dissolved. Further, when producing high-purity metal salts, a concentration step by evaporation or the like is often used, but if this concentration step or the raw material solution is replaced with this method, utility costs such as electricity, heat energy, cooling water, etc. will be dramatically increased. It is cheaper, equipment cost is compact and cheap, operation is easy and controllable, and unlike ordinary concentration, it is possible to avoid concentrating even minute amount of impurities contained in the original liquid. Inexpensive manufacturing can be expected. Further, it can be applied as a hydrogen generator by collecting the generated hydrogen.

[0045]

EXAMPLES Examples of the present invention will be described below. In this example, in the copper ion generator having the same configuration as that of the first embodiment described above, the above selemion film; HSV was selected as the hydrogen ion exchange film 23, and the raw material copper 25B was used.
As each, a DC copper ball and an OF copper ball having a diameter of 55 mm were used. In addition, the electrolytic current is 1.9.
A, 4.3A and 6.4A were selected. Here, DC copper means that phosphorus has a purity of about 99.93% and a phosphorus content of about 0.035%.
0.06% is included, and OF copper means oxygen-free copper having a purity of 99.99% or more and oxygen of 10 ppm or less. The results are shown in Table 1, FIG. 2 and FIG.

[0046]

[Table 1]

FIG. 2 is a graph showing the relationship between time and copper dissolution amount, and FIG. 3 is a graph showing the relationship between current value and copper dissolution amount.

From these results, the amount of copper dissolved is proportional to the time when an electric current is passed, the current value and the amount of copper dissolved are proportional, and there is almost no difference in the dissolved amount between DC copper and OF copper. You can see that there is no.

[0049]

According to the method and apparatus for producing copper ions, the method and apparatus for producing copper sulfate, the method and apparatus for producing metal ions, the method and apparatus for producing ionized water of the present invention, in the ion generating tank, Is divided into an anode chamber and a cathode chamber by a hydrogen ion exchange membrane, an electrolytic current is applied to the cathode and the anode, and hydrogen ions in the cathode chamber are released as hydrogen gas from the vicinity of the cathode. By reducing the concentration, only hydrogen ions inside the anode chamber are transferred to the cathode chamber through the hydrogen ion exchange membrane to reduce cations inside the anode chamber, and metal ions such as copper ions are eluted from the anode into the anode chamber. It is possible. This allows copper, silver,
Even for metals such as gold and platinum which have a smaller ionization tendency than hydrogen, the metal ions can be easily produced. At the same time, it is possible to produce the effect that acidic water can be produced by hydrogen ions in the cathode chamber. The present invention is also applicable to metals having a greater ionization tendency than hydrogen, such as Ni.

[Brief description of drawings]

FIG. 1 is a schematic diagram showing a first embodiment of a copper ion generator according to the present invention.

FIG. 2 is a graph showing the relationship between time and the amount of copper dissolved in an example of the present invention.

FIG. 3 is a graph showing a relationship between a current value and a copper dissolution amount in an example of the present invention.

[Explanation of symbols]

1 Copper ion generator 2 ion generation tank 21 Anode chamber 22 Cathode chamber 23 Hydrogen ion exchange membrane 24 cathode 25B Raw material copper 25A conductor basket 25 anode 26 Piping

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Kazuo Fujiwara             1-14-16 Kudankita 1-chome, Chiyoda-ku, Tokyo             Ceremony company Techno Oteuchi (72) Inventor Yukio Matsubara             1-14-16 Kudankita 1-chome, Chiyoda-ku, Tokyo             Ceremony company Techno Oteuchi F-term (reference) 4K021 AA01 AB25 BA04 BB03 DB18                       DB19 DB21 DB31 DC15

Claims (9)

[Claims] 1. An ion generating tank is divided into an anode chamber and a cathode chamber by a hydrogen ion exchange membrane, and hydrogen gas is released from the cathode surface in the cathode chamber, and copper ions are emitted from the anode in the anode chamber. A method for producing copper ions, characterized in that the copper ions are eluted in the anode chamber. 2. An ion generating tank, a hydrogen ion exchange membrane for partitioning the inside of the ion generating tank into an anode chamber and a cathode chamber, a cathode provided in the cathode chamber and energized to release hydrogen gas from the surface, A copper ion generator, comprising: an anode provided in the anode chamber, which is energized to elute copper ions into the anode chamber. 3. An ion generating tank is divided into an anode chamber and a cathode chamber by a hydrogen ion exchange membrane, and hydrogen gas is released from the cathode surface in the cathode chamber, and from the anode in the anode chamber supplied with sulfuric acid. A method for producing copper sulfate, characterized in that copper ions are eluted into the anode chamber to produce a copper sulfate solution in the anode chamber. 4. An ion generating tank, a hydrogen ion exchange membrane for partitioning the inside of the ion generating tank into an anode chamber and a cathode chamber, a cathode provided in the cathode chamber and energized to release hydrogen gas from the surface, A copper sulfate manufacturing apparatus, comprising: an anode which is provided in the anode chamber to which sulfuric acid is supplied and which is energized to elute copper ions into the anode chamber. 5. The apparatus for producing copper sulfate according to claim 4, wherein the anode has a raw material phosphorus-free copper. 6. An ion generating tank is divided into an anode chamber and a cathode chamber by a hydrogen ion exchange membrane, and hydrogen gas is released from the cathode surface in the cathode chamber, and metal ions are emitted from the anode in the anode chamber. A method for producing metal ions, characterized in that the metal ions are eluted in the anode chamber. 7. An ion generating tank, a hydrogen ion exchange membrane dividing the inside of the ion generating tank into an anode chamber and a cathode chamber, a cathode provided in the cathode chamber and discharging hydrogen gas from the surface by being energized. A metal ion generator, comprising: an anode provided in the anode chamber and energized to elute metal ions in the anode chamber. 8. An ion generating tank is divided into an anode chamber and a cathode chamber with a hydrogen ion exchange membrane, and in the anode chamber, metal ions are eluted from the anode into the anode chamber, and in the cathode chamber, from the cathode surface. Releases hydrogen gas,
A method for producing acidic water, which comprises producing acidic water. 9. An ion generating tank, a hydrogen ion exchange membrane for partitioning the interior of the ion generating tank into an anode chamber and a cathode chamber, and an anode provided in the anode chamber for eluting metal ions into the anode chamber by being energized. And a cathode which is provided in the cathode chamber and which is energized to release hydrogen gas from its surface, and which produces acidic water in the cathode chamber.