WO1998017845A1

WO1998017845A1 - Electrolyzer

Info

Publication number: WO1998017845A1
Application number: PCT/JP1997/003809
Authority: WO
Inventors: Fumio Hine; Teruki Takayasu; Tomoyoshi Asaki; Yukio Arai; Yoichi Kamegaya; Masahisa Komiya
Original assignee: Ishifuku Metal Industry Co., Ltd.; Showa Co., Ltd.
Priority date: 1996-10-24
Filing date: 1997-10-22
Publication date: 1998-04-30
Also published as: TW391991B

Abstract

A feeder is constituted with a corrosion resisting conductive metal which is disposed in a divided manner between a lead base and an anode substrate, bonded fixedly to the lead base, and brought into contact with the anode substrate so that a sufficient electric conductivity is secured with respect to both the lead base and the anode substrate. A stable and sufficient electric conductivity concerning a current flowing from the lead base to the anode substrate is secured.

Description

Description Technical field

TECHNICAL FIELD The present invention relates to an electrolytic apparatus used for producing copper foil by a tin plating, a zinc plating, and an electroplating method on a steel sheet to which a large current flows.

Background art

In recent years, in an electric-plating areas, zinc plated or tin-plated to _c steel current density has been high summer with high speed plating, in the manufacture of a metallic foil, or the like by the electric-plating method,

A high plating current density of 30 to 25 OA dm ² is employed. In addition, it is required to obtain a metal foil by plating on a large-sized band-shaped material having a width of 500 to 200 mm or by electroplating. Therefore, in order to obtain a plating film of such a large-sized material, the electrolytic device used must be large. In the production of electroplated products and metal foil, the demand for higher quality of these products is increasing, and the distance between the anode and the cathode must be increased in order to make the current distribution more uniform when manufacturing the products. There is a demand for an electrolysis apparatus that can minimize the variation in the temperature.

The anodes of large electrolyzers operated at such a high current density have been mainly made of low-cost lead or lead alloy, which is easy to process. However, the lead or lead alloy of the anode material melts or corrodes due to electrolysis, resulting in a change in the shape of the anode surface. There are a number of problems, including the risk of product quality degradation due to contamination of the electrolyte with lead, etc., and the need for environmental measures to prevent lead contamination.

In order to solve the problem of lead or lead alloy of these anode materials, conductive metal materials such as copper, iron, aluminum, lead, and tin are used as core materials, and these core materials are used as corrosion-resistant conductive metals such as titanium plates. Attempts have been made to use electrolytic devices that use an anode in which an anode substrate made of a corrosion-resistant conductive metal such as titanium is coated on a composite substrate coated with a metal and an anode substrate coated with an electrode catalyst is detachably attached. . In these attempts, the cost of manufacturing the composite substrate is high, and it is difficult to process the arc-shaped inner surface 加工 processing of the current-carrying part, especially in an electrolytic device where the anode requires an arc-shaped inner surface. There were many problems, such as the need for complicated processing, costing, poor processing accuracy, and poor power distribution. In addition, the anode of the electrolysis device has a lead base made of lead or a lead alloy, and the lead base is coated with a corrosion-resistant conductive metal such as titanium and an electrode catalyst, and the anode base is fixed with a corrosion-resistant conductive metal screw. Attempts have also been made to attach using bolts and nuts. This method had the following problems.

1) Because the lead base is soft,

• Since the screw cannot be screwed directly to the lead base with a strong force, the contact resistance increases, resulting in poor electrical connection.

In addition, the size and structure of mechanical members (for example, those using corrosion-resistant conductive metal nuts and bolts) that allow the anode substrate to be detachably attached to the lead substrate are limited, and the mechanical members have sufficient current carrying capacity. Or welding may occur,

• Repeated removal of the anode substrate damages the lead substrate where the current flows from the lead substrate to the anode substrate, reduces the contact area, causes abnormal heat generation due to energization, and consequently results in poor energization.

· Repeated removal of the anode substrate damages the surface of the lead substrate facing the cathode at regular intervals, lowers the mounting accuracy of the anode substrate, and causes uneven electrode spacing.

2) Due to the properties of lead or lead alloy, the surface of the lead substrate gradually oxidizes with contact with the electrolyte, increasing the contact resistance at the point where current flows from the lead substrate to the anode substrate, resulting in poor current conduction. Or abnormal heat generation.

In particular, in an electrolytic device in which the anode has an arc-shaped inner surface, the above-mentioned problem is conspicuous due to the complexity of the structure.

It solves the problems of electrolytic devices using lead and lead alloy anodes and conventional composite substrate anodes.

Disclosure of the invention

In order to solve the above problems according to the present invention,

In an electrolytic device that can maintain an electrolytic solution between an anode and a cathode,

The anode is

A) a lead base made of lead or a lead alloy, which has a current-carrying terminal from the outside and has a surface facing the cathode at regular intervals;

A) an anode substrate made of a corrosion-resistant conductive metal, which is detachably mounted on a surface of a lead substrate, is provided so as to face the cathode at regular intervals, and a surface facing the cathode is coated with an electrode catalyst;

Ii) Divided between the lead substrate and the anode substrate, fixedly joined to the lead substrate and contacted with the anode substrate so as to ensure sufficient electrical conductivity with both the lead substrate and the anode substrate. Feeder made of conductive metal with corrosion resistance

An electrolysis device is provided, comprising:

Further, in order to solve the above-mentioned problems according to the present invention,

The anode is

A) a lead base made of lead or a lead alloy, having a current-carrying terminal from the outside and having a surface facing the cathode at regular intervals;

B) Divided on the surface of the lead base to ensure sufficient electrical conductivity with the lead base A feeder made of a corrosion-resistant conductive metal fixedly attached to the lead base; and ゥ) a feeder detachably attached to the feeder and provided to face the cathode at regular intervals; An electrolysis apparatus, comprising: a power supply body and an anode substrate made of a corrosion-resistant conductive metal connected so as to ensure sufficient electric conductivity. You.

One lead base

The lead substrate according to the present invention can use lead or a lead alloy conventionally used as an anode.

As the lead alloy, an alloy of tin, silver, indium, bismuth, calcium, antimony, or the like can be used.

The surface of the lead substrate is subjected to plane processing or arc-shaped inner surface processing according to the shape of the cathode so as to face the cathode at regular intervals. The lead base has a hole for mounting the anode base or the power supply, as necessary.

If an electrolytic device equipped with a lead or lead alloy anode is currently used, the anode material can be modified and used as a lead base in the present invention. In the modification of the lead or lead alloy, the thickness required to mount the anode base and the power supply according to the present invention is cut, and if necessary, a through hole for mounting the anode base and the power supply is provided. By providing them, the lead base of the present invention can be obtained. The precision of the through-hole provided in the lead base does not require special high precision, and it is used in the present invention if the precision at which the drilling can be performed is obtained even at the site where the electrolytic device is installed. Can be used as a lead base.

One anode substrate

The material of the anode substrate according to the present invention is made of a corrosion-resistant conductive metal such as titanium, tantalum, niobium, and zirconium, or an alloy containing these as a main component. The anode substrate is plate-shaped, is divided into a plurality as necessary, and has a mounting structure with a mechanism that can be attached to and detached from the lead substrate, and the surface facing the cathode is a platinum group metal, an alloy thereof, and / or an alloy thereof. An electrode catalyst mainly composed of an oxide or an electrode medium mainly composed of a base metal oxide such as cobalt oxide, tin oxide, manganese oxide or the like is coated, and on the back surface, a current is supplied from the power supply to the anode substrate. To supply power for The bending of the anode base when the anode base is attached to the lead base damages the electrode catalyst layer coated on the surface. The mounting of the anode substrate should be as flexible as possible. Therefore, especially when the anode substrate is mounted on a lead substrate having an arc-shaped inner surface, it is desirable that the anode substrate also has a similar arc shape.

The contact point between the anode substrate and the power supply body is coated with a platinum group metal as a main component, if necessary, to reduce the contact resistance. A coating thickness of submicrometer to several micrometers is sufficient.

An example of a specific structure for detachably connecting the anode substrate to the surface of the lead substrate according to the present invention is as follows.

The lead base has a through hole, the anode base has a rod passing through the through hole, and a female screw or a male screw is attached to the rod on the back surface of the lead base, whereby the positive The polar base is detachably connected to the lead base.

, The lead base has a through hole, a rod is provided in the through hole, the rod is fixed on the back surface of the lead base, the anode base has a hole, and a male screw is formed in the hole of the anode base from the front side of the lead base. That is attached to the rod via a lead, whereby the anode substrate is detachably connected to the lead substrate.

The rod used to attach the anode substrate to the lead substrate may be any shape, such as circular, square or polygonal. The rod is provided with a screw to remove the anode substrate. Used for construction. The member used for the mounting mechanism of the anode substrate may be any material having corrosion resistance and mechanical strength, such as the same corrosion-resistant conductive metal or corrosion-resistant ceramic as the anode substrate. Normally, titanium material is suitable in terms of workability, cost, corrosion resistance and the like.

Electricity is supplied from the lead substrate to the anode substrate via a power supply. The feeder is divided between the lead base and the anode base, and is evenly arranged. The anode base and the feeder come into contact with each other by the tightening pressure for mounting the anode base to the lead base, and the contact point is a current-carrying part. Becomes It should be noted that it is not always necessary to electrically insulate the lead substrate and the anode substrate at locations other than the current-carrying location with the power supply. However, it is necessary to provide insulation in the following cases. The insulation can be made of a corrosion-resistant resin material, and by installing it in the mechanism that attaches the anode substrate to the lead substrate, the energizing circuit is interrupted, and welding and other problems occur when the anode substrate attachment mechanism is energized. Can be prevented from being caused by the current supply.

• When the resistance of the current-carrying circuit formed from the lead substrate to the anode substrate is lower than the resistance of the circuit via the power feeder.

· When welding or abnormal heat generation occurs in the mounting mechanism of the anode substrate.

Further, specific structures for detachably connecting the power supply body and the anode base according to the present invention include the following.

• A hole is formed in the anode substrate, a female screw is provided in the power supply, and a male screw is screwed from the cathode side with the female screw of the power supply through the hole in the anode substrate, and the anode substrate is detachably connected to the power supply. thing.

Provide a hole in the lead base, provide a hole in the power supply body, provide a hole in the anode base, insert a male screw from the cathode side or the hole side of the lead base into the hole in the power supply body and the hole in the anode base, and insert the nut. The anode base is detachably connected to the power feeder.

• Make a hole in the lead base, make a hole in the power feeder, make a female screw in the anode base, An anode base screw is detachably connected to a power feeder by screwing a male screw from the hole side with a female screw of the anode base via a hole in the feeder.

• A hole is formed in the lead base, a hole is formed in the feeder, and the anode base has a rod that penetrates the hole in the feeder. A male screw or a female screw is provided at the tip of this rod, and the anode is inserted from the hole side of the lead base. The base is detachably connected to the power feeder.

The same corrosion-resistant conductive metal as that of the anode base is used for the screws, nuts, and rods used to attach the feeder to the anode base.

Electricity is supplied from the lead substrate to the anode substrate via a power supply. It is desirable that the power feeder is divided between the lead base and the anode base and arranged uniformly.

One feeder

The role of the power feeder

The role of the power supply according to the present invention is as follows.

1) Stable and sufficient current supply from the lead substrate to the anode substrate.

2) Prevent damage to the surface of the soft lead base facing the cathode at regular intervals due to repeated removal of the anode base.

3) Support the anode substrate so that the cathode and the anode substrate face each other at regular intervals.

4) Removably attach the anode substrate to the power supply.

——Material of feeder——

The material of the power supply according to the present invention may be a corrosion-resistant conductive metal such as titanium, tantalum, niobium, or zirconium, or an alloy containing these as a main component, or a clad of the above-described corrosion-resistant conductive metal and lead or a lead alloy. Can be used. When a cladding material is used, at least the portion that comes into contact with the anode substrate and becomes a current-carrying part must be made of a corrosion-resistant conductive metal.

Power supply body when the anode substrate is detachably attached to the power supply body The power supply according to the present invention is divided and arranged between a lead base and an anode base. When the lead base has an arc-shaped inner surface or when an extremely large current flows, the feeders are uniformly distributed in an island shape or gap to ensure stable and sufficient electric conductivity and current carrying capacity. Place without. The shape of the power supply may be any shape, but a structure and strength that allow the anode base to be detachably attached to the power supply are required, and at the contact portion between the power supply and the anode base, Welding due to energization must be avoided. To avoid welding, it is necessary to secure a contact area according to the magnitude of the current flowing through the contact part. If the current in the contact area is high, a power supply shall be provided so that a large contact area can be secured according to the current. Usually, the shape of the power supply is plate-like, similar to the anode substrate, and the size or shape of the plate is changed to adjust the contact area with the anode substrate. Normally, more stable electrical conductivity can be maintained by coating at least one of the contact surfaces between the power supply and the anode substrate with a platinum group metal as a main component. The coating thickness is sufficient if the sub-micrometer to several micrometer is sufficient. _C- 1-1 When the anode substrate is detachably mounted on the lead substrate,

The power supply according to the present invention is divided between the lead base and the anode base. When the lead base has an arc-shaped inner surface or when an extremely large current flows, it is necessary to arrange the feeders uniformly in an island shape to ensure stable and sufficient electric conductivity and current carrying capacity. Especially desirable. The shape of the power supply may be any shape, but welding at the contact portion between the power supply and the anode substrate due to energization must be avoided. To avoid welding, it is necessary to secure a contact area according to the magnitude of the current flowing through the contact. If the current in the contact area is high, a power feeder is provided so that a large contact area can be secured according to the current. Usually, the shape of the power supply is plate-like, similar to the anode substrate, and the size of the plate is changed to adjust the contact area with the anode substrate. At least one of the contact surfaces between the power supply and the anode substrate is coated with platinum group metal as the main component. W

As a result, more stable electrical conductivity can be maintained. A coating thickness of submicrometer to several micrometers is sufficient.

The power feeder should be provided in the form of an island in the vicinity of the mechanism where the anode base is attached, so that the contact pressure at the current-carrying point between the feeder and the anode base is increased, and the contact resistance is reduced. It is more desirable.

In order to ensure stable and sufficient electrical conductivity from the power supply to the anode substrate,

• It is possible to secure the shape and size of the power feeder suitable for energizing the anode substrate and supporting the anode substrate.

· By energizing the power supply and the anode substrate, the contact area and contact pressure necessary for energization can be secured,

• There must be a space where power feeders can be divided evenly so that power distribution can be evenly distributed. By providing the power supply between the lead base and the anode base, this space can be easily secured.

——About the support——

In addition, when the power feeders are mounted in a dispersed manner, a support (strip) for maintaining the predetermined shape of the anode base in a part of the space where the power feeder is not mounted, in order to keep the distance between the anode base and the cathode constant. Attach as necessary. The material of the support is a material that has corrosion resistance to the electrolytic solution. If the support does not deform so as not to impair the function as a support, the conductor is an insulator. You may. Specific materials include a corrosion-resistant conductive metal similar to that of the power feeder, a synthetic resin such as a fluorinated resin, an acrylic resin, and an epoxy resin, and a natural polymer such as rubber and a processed material thereof (hard rubber. Ebonite, etc.). The support is attached to the lead base or anode base by screws or the like. Fixed connection between the power feeder and the lead base.

In the connection between the power supply body and the lead base according to the present invention, a fixed connection with the lead base is performed so as to ensure sufficient electric conductivity. The term “fixed joining” refers to a mechanism that can remove the anode base when the anode base and the lead base are joined, but has a high electrical conductivity mounting mechanism that does not require removal of the power feeder.

By providing a fixed connection between the power supply and the lead base, it is possible to perform various types of joints that have excellent electrical conductivity and a large current carrying capacity, and that the electrical connection is stable. Permanent treatment can be done without waste so that The power supply according to the present invention is mounted on a lead base and fixedly joined as follows. · The power feeder is attached to the lead base by welding. It is more desirable that the power feeder is welded to the surface of the lead base.

• The lead base has a through hole, and the power feeder has a rod of corrosion resistant conductive metal penetrating the through hole, and on the back of the lead base, a female or male screw of the corrosion resistant conductive metal is attached. And the power feeder is fixedly joined to the lead base. The internal and external threads attached to the rod are connected to the lead base via corrosion-resistant conductive metal washers.

• In the case where the power feeder is connected to the lead base using a female screw or male screw, it is more desirable to weld each of the connecting members to ensure stable electrical conductivity. For example, welding of a rod provided on a power supply body to a power supply body, welding of a female screw or a male screw attached to the rod, welding of a female screw or a male screw to a washer, welding of a washer to a lead base, and the like. Brazing welding using a lead alloy with a low melting point is also an effective method of welding the lead base to the power feeder and welding the lead base to the washer. When performing brazing welding, the welding surface of the corrosion-resistant conductive metal requires special activation treatment. Welding of the corrosion-resistant conductive metal used for covering the power supply, anode substrate, lead substrate, etc. is performed in an inert atmosphere such as an argon gas atmosphere, argon gas seal, or vacuum atmosphere. W

Welding is performed in the air. Welding methods include fusion welding methods such as plasma arc welding, TIG welding, and laser welding, welding methods such as forging welding, friction welding, and brazing methods. In the case of pressure welding and brazing using a low-melting brazing material, it is possible even in air.

· Furthermore, it is also effective to separately prepare a member made of corrosion-resistant conductive metal, weld the member to a lead base, and join one of the members to a power feeder to form an energizing circuit.

Permanent treatment of joints to ensure stable electrical conductivity

The fixed connection between the power supply and the lead base makes it possible to eliminate the following permanent treatment of the joint to ensure stable electrical conductivity. For example, if the lead base and the corrosion-resistant conductive metal of the power feeder are not welded together, the following method is used as a permanent measure to prevent poor current flow due to infiltration of the electrolyte into the joint. Is raised.

1) Coating treatment of the joint with corrosion resistant resin.

2) Welding of lead base and corrosion-resistant conductive metal is a difficult process. On the other hand, by heating the joint and compressing the corrosion-resistant conductive metal of the power supply while softening the lead or lead alloy, it is possible to easily obtain a mating state where the electrolyte does not penetrate, and remove the crimping force. The joined state can be maintained as long as it does not exist. Treatment by this method.

3) When the lead base material is a lead alloy, a lead plate is sandwiched between the joint between the lead base and the corrosion-resistant conductive metal of the power feeder, and strong crimping is applied so that the corrosion-resistant conductive metal can sufficiently deform the lead plate. However, a bonding state in which the electrolyte does not penetrate can be easily obtained. Treatment by this method.

If the feeder is removed each time the anode substrate is removed, the permanent treatment of the joint to ensure stable electrical conductivity described above loses its function, Waste of performing the treatment again will occur. ,

Position Adjustment of Anode Substrate by Eleven Feeders

By changing the height of the power feeder attached between the lead base and the anode base, the mounting position of the anode base with respect to the electrode spacing can be adjusted. The height of the feeder can be adjusted by inserting a 扳 having a desired thickness made of the same material as that used for the feeder between the feeder and the anode base. Inserting a plurality of stacked plates is not preferable because it increases the contact resistance. In this way, by adjusting the position of the anode substrate, fine adjustment of the electrode interval can be partially performed. As a result, the distance between the electrodes as a whole can be secured uniformly, and the quality of products manufactured by electrolysis can be further improved.

Lead-based coatings

If electrolysis is continued for a long time, the electrode catalyst coated on the anode substrate deteriorates, and the anode potential increases. When the lead substrate is in contact with the electrolyte, there is a problem that lead and the like are eluted from the lead substrate as the anode potential increases. Coating the lead base with a corrosion-resistant resin, rubber or corrosion-resistant metal is an effective means to solve this problem. As the resin having corrosion resistance, fluorinated resin, epoxy resin or acrylic resin reinforced with glass fiber or carbon fiber can be used. As the corrosion-resistant metal, titanium, tantalum, niobium, zirconium, or an alloy containing these as a main component can be used.

Action

The electrolytic device according to the present invention has the following effects by having the above structure.

1) The effect of separately providing the structure for mounting the anode substrate to the lead substrate and the structure for conducting electricity from the lead substrate to the anode substrate was obtained.

2) The effect of providing the current-carrying structure using the power feeder between the lead base and the anode base was obtained. 3) As a result, the effect of creating a bonding structure and a bonding mechanism that can easily secure stable and sufficient air conductivity from the lead substrate to the anode substrate was obtained.

4) The mechanism for attaching and detaching the anode substrate to and from the lead substrate was simplified, and the effect of miniaturization was obtained.

5) The effect of easily adjusting the distance between the cathode and the anode with high accuracy was obtained.

6) The effect of easily using the lead or lead alloy used as the anode was obtained.

7) The effect of easily coating the lead base to prevent the electrolyte from coming into direct contact with the lead base was obtained.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 is an external view showing an example of a plate-shaped anode according to a preferred embodiment of the present invention.

FIG. 2 is a plan view showing an example of a plate-shaped anode according to a preferred embodiment of the present invention.

FIG. 3 is a sectional view showing an example of a flat plate-shaped anode according to a preferred embodiment of the present invention.

FIG. 4 is an external view showing an example of an arc-shaped inner surface anode according to a preferred embodiment of the present invention. FIG. 5 is a plan view showing an example of an arc-shaped inner surface anode according to a preferred embodiment of the present invention. FIG. 6 is a cross-sectional view showing an example of an arc-shaped inner surface anode according to a preferred embodiment of the present invention. FIG. 7 is a partial cross-sectional view showing an example of an arc-shaped inner surface anode according to a preferred embodiment of the present invention.

FIG. 8 is a partial cross-sectional view showing an example of a flat anode according to the present invention.

FIG. 9 is a partial cross-sectional view showing an example of the arc-shaped inner surface anode of the present invention.

FIG. 10 is an external view showing an example of a plate-shaped anode according to a preferred embodiment of the present invention. Figure 1 1 is a partial sectional view _c Figure 1 2 shows an example of an anode of a flat plate in accordance with a preferred embodiment of the present invention, external view c Figure 1 showing an example of an anode of an arc-shaped inner surface in accordance with a preferred embodiment of the present invention 3 is a plan view showing an example of an arc-shaped inner surface anode according to a preferred embodiment of the present invention.c FIG. 14 is a cross-sectional view showing an example of an arc-shaped inner surface anode according to a preferred embodiment of the present invention. FIG. 15 is a partial cross-sectional view showing an example of an anode on the inner surface of a circular arc shape according to the preferred embodiment of the present invention.

FIG. 16 is a partial cross-sectional view in which an anode substrate and a power supply are mounted on a lead substrate having another structure according to the present invention.

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described in detail by showing specific examples of the present invention.

One-plate anode 20—

FIG. 1 shows the appearance of an anode 20 having a flat plate shape in an electrolytic apparatus according to a preferred embodiment of the present invention. FIG. 2 shows a partial plan view of FIG. FIG. 3 is a cross-sectional view of FIG. Anode for electrolysis with a circular arc inner surface 20

FIG. 4 shows the appearance of an anode 20 having an arc-shaped inner surface in an electrolytic device according to a preferred embodiment of the present invention. FIG. 5 is a plan view of FIG. FIG. 6 is a cross-sectional view of FIG. FIG. 7 is a partially enlarged sectional view of FIG. FIG. 8 and FIG. 9 are partial cross-sectional views in which the anode base 2 and the power supply 3 are attached to a lead base 1 having another structure according to the present invention.

Detailed Description of Example of One-Plate Electrolytic Anode 20

FIGS. 1, 2 and 3 show an electrolysis apparatus according to a preferred embodiment of the present invention, in which the anode 20 includes a plate-shaped lead base 1, an anode base 2, a power supply 3, and the like.

The lead substrate 1 is a flat plate-shaped alloy made of lead and tin having through-holes for mounting the current-carrying terminals 13 and the anode substrate 2 and the power supply 3 from the outside.

An externally threaded titanium rod 4 is welded to the back surface of the anode substrate 2 made of titanium divided into three parts. A mechanism in which the titanium rod 4 passes through the holes provided in the power feeder 3 and the lead base 1 made of titanium, and the anode base 2 can be attached and detached by the nut 5 of the titanium via the titanium 6 on the back side of the lead base 1. And is fastened to the lead base 1. By tightening the nut 5, the electric current between the power feeder 3 and the electrode base 2 is reduced. The required contact pressure is obtained. The surface of the anode substrate 2 is coated with an electrode catalyst of a iridium oxide component.

A titanium feeder 3 divided into three and provided with holes is uniformly arranged around a titanium rod 4 extending from the anode base 2 between the lead base 1 and the anode base 2. On the back side of the power supply body 3, a titanium rod 7 with an external thread whose screw portion is coated with platinum is provided by welding. The titanium rod 7 passes through a hole in the lead base 1 provided separately from the titanium rod 4 of the anode base, and is coated with platinum through a titanium washer 9 welded to the lead base 1 with a lead-tin alloy. After being tightened by the nut 8, the washer 9 and the nut 8, and the nut 8 and the titanium rod 7 are welded using a lead-tin alloy. By these joining processes, the power feeder 3 and the lead base 1 are fixedly joined.

In the space between the anode substrate and the lead substrate, a support 10 made of a fluorinated resin is arranged to support the anode substrate and keep the distance from the cathode constant with high accuracy.

The main energizing circuit in this embodiment is energized from the energizing terminal 13, passes through the lead base 1, the washer 9, the bolt 8, the titanium rod 7, the power supply 3, and reaches the anode base 2. The lead base 1 to the power feeder 3 form an energized circuit fixedly mounted. In addition, a sufficiently large contact area and contact pressure are secured in the contact portion between the anode base 2 and the power supply 3, and each contact surface is coated with platinum, so that the contact resistance is greatly reduced.

As described above, the anode of the electrolysis apparatus of the present embodiment forms a stable and sufficient electric conduction circuit between the lead base and the anode base so that the contact resistance does not increase for a long period of time, A current can be stably supplied to the anode substrate 2. In addition, there is no danger of welding between the titanium rod 4 and the nut 5 in the mechanism for removing the anode substrate. In addition, the power supply 3 can prevent the lead substrate surface from being damaged by repeated removal of the anode substrate. Detailed Description of Embodiment of Electrolytic Anode 20 Having One Circular Inner Inner Surface FIG. 4, FIG. 5, FIG. 6, and FIG. 7 show a lead base 1, an anode base 2, a power supply 3, etc. Fig. 4 shows an anode 20 having an arc-shaped inner surface according to a preferred embodiment of the invention. Note that the thickness dimensions of the anode substrate 2, the power supply 3, and the support 10 in FIG. 4 are exaggerated. The lead base 1 is an alloy made of lead and silver having an arc-shaped inner surface provided with a through hole for mounting the current-carrying terminal 13 and the anode base 2 from the outside.

The anode substrate 2 is divided into 18 sheets, and is made of a titanium plate having the same arc inner surface shape as the lead substrate 1. On the back surface of the anode base 2, a titanium rod 4 having an external thread is provided by welding. The titanium rod 4 passes through the hole provided in the lead base 1, and the anode base 2 is fastened to the lead base 1 by a nut 5 using a titanium nut 5 through a titanium washer 6 on the back side of the lead base 1. Installed. By tightening the nut 5, a contact pressure necessary for energizing the power supply body 3 and the electrode base 2 can be obtained. The surface of the anode substrate 2 is coated with an electrode catalyst containing iridium oxide, and the surface of the anode substrate 2 that contacts the power supply 3 is coated with platinum.

Disc-shaped power feeder made of clad material of titanium and lead-silver alloy 3 Force Lead-tin alloy is fixedly welded to the surface of the hole around the lead base 1 using a lead-tin alloy . The titanium surface of the power feeder 3 in contact with the anode substrate 2 is coated with platinum. Further, in the space between the anode base 2 and the lead base 1, a titanium support 10 for supporting the anode base 2 and keeping the distance from the cathode constant with high precision is attached to the anode base 2. , Has been placed.

The anode of the electrolysis apparatus according to the present embodiment is supplied with electricity from the conducting terminals 13, passes through the lead base 1 and the power supply 3, and is supplied with power to the anode base 2. As a result, an energizing circuit having sufficient electric conductivity was secured between the lead base and the anode base, and stable energization was ensured for a long period of time. As a result, the titanium rod 4 and nut The occurrence of welding with G5 also disappeared. Also, the power supply 3 can prevent the surface of the lead substrate from being damaged due to the removal of the anode substrate. Further, the power supply body 3 and the support body 10 support the anode base 2, and the anode base 2 can maintain a predetermined arc-shaped inner surface shape, so that a uniform electrode interval can be secured.

FIG. 8 is a partial sectional view of another plate-shaped anode 20 according to the present invention. A boss with a hole is provided on the back surface of the anode substrate 2, and is attached to the lead substrate in a detachable manner using titanium female fasteners 11 and titanium male screws 12. Power is supplied to the anode base 2 from a titanium power feeder 3 welded to a lead base. In the space between the anode base 2 and the lead base 1, a titanium support 10 for supporting the anode base 2 and keeping the distance between the anode base 2 and the cathode high and accurate and constant is arranged.

FIG. 9 shows another anode 20 having an arc-shaped inner surface according to the present invention. A titanium externally threaded rod 4 is welded to the anode substrate 2 and is detachably attached to the lead substrate using the externally threaded rod 4, a fluorinated resin mesh 6 and a titanium nut 5. ing. Power is supplied to the anode base 2 by a titanium feeder 3 provided between the anode base 2 and the lead base 1, and the energization circuit from the mounting mechanism of the anode base 2 is cut off by the hash 6. I have. An externally threaded rod 7 is welded to the power supply 3, and the externally threaded rod 7 penetrates a hole in the lead base and is fastened by a titanium nut 8 and a washer 9. Inserting a lead plate between washer 9 and lead base 1 and tightening nut 8 prevent the electrolyte from entering the fixed joint between titanium washer 9 and lead base 1. An increase in contact resistance due to oxidation of the lead base 1 is prevented. The titanium rod 7 and the nut 8 are welded to stabilize the power supply from the lead base 1 to the power supply 3. The titanium rod 7 has a cross-sectional area that can secure a current carrying capacity to the anode substrate 2.

Next, the present invention will be described in more detail by showing other specific examples of the present invention. FIG. 10 shows the appearance of the anode 120 having a flat plate shape in the electrolytic apparatus according to the preferred embodiment of the present invention.

FIG. 11 shows a partial cross-sectional view of FIG.

Anode with inner surface of one circular arc 1 2 0—

FIG. 12 shows the appearance of an anode 120 having an arc-shaped inner surface in an electrolysis apparatus according to a preferred embodiment of the present invention.

FIG. 13 is a plan view of FIG.

FIG. 14 is a cross-sectional view of FIG.

FIG. 15 is a partially enlarged sectional view of FIG.

FIG. 16 is a partial cross-sectional view in which the anode substrate 102 and the power supply 103 are attached to a lead substrate 101 having another structure according to the present invention.

Detailed Description of Example of One Plate Electrolytic Anode 120

FIGS. 10 and 11 show an electrolysis apparatus according to a preferred embodiment of the present invention, in which the anode 120 has a plate-shaped lead base 101, an anode base 102, a power feeder 103, and the like. The lead substrate 101 shown in the figure is a flat plate-shaped alloy having through holes for mounting the current-carrying terminals 113 from the outside, the anode substrate 102 and the power feeder 103, and is made of an alloy composed of lead and tin. The power feeder 103 is an 8 mm thick titanium plate divided into four, and has a through hole for mounting on the lead base 101 and an anode base 102 for mounting the anode base 102 with the flathead screw 114. An internal thread is provided. The power feeder 103 is tightened with titanium female screw 1 1 1 and male screw 1 1 2 and attached to the lead base 101, then the female screw 1 1 1 flange and lead base 1 1 Was welded.

The anode substrate 102 is a titanium plate having a thickness of 3 mm divided into two, and has a through hole for attaching to the power feeder 103 with a countersunk titanium screw 114, facing the cathode. The mating surface was coated with an electrode catalyst made of iridium oxide, and the back surface was coated with platinum to reduce the current-carrying contact resistance with the feeder 103.

In the present embodiment, the main energizing circuit is energized from the energizing terminal 113, the lead base 101, the female threaded fastener 111, the male screw 111, the boss of the power source 103, the power source 110, and Through 0 3, the anode substrate 102 is reached. The lead base 101 to the power feeder 103 form a fixedly connected energized circuit. The contact portion between the anode substrate 102 and the power supply body 103 has a sufficiently large contact area and contact pressure, and each contact surface is coated with platinum to greatly reduce contact resistance. .

In addition, the lead base 1 and the female threaded fastener 1 1 1 in contact with the electrolyte were covered with an epoxy resin coating 1 15 containing glass fiber to prevent the elution of trace amounts of lead components into the electrolyte. .

As described above, the anode 120 of the electrolytic apparatus of the present example has a stable and sufficient electric conductivity between the lead substrate 101 and the anode substrate 102 such that the contact resistance does not increase for a long period of time. Thus, an energizing circuit having the following formula was formed, and it was possible to stably energize the anode substrate 102. In addition, there is no possibility of occurrence of welding in the mechanism for removing the anode substrate 102. Further, the power supply body 103 can prevent the surface of the lead substrate 101 from being damaged by the repeated removal of the anode substrate 2.

Detailed Description of Embodiment of Electrolytic Anode 120 Having One Arc-Shaped Inner Surface

FIGS. 12, 13, 14, and 15 show an arc shape according to a preferred embodiment of the present invention, including a lead base 101, an anode base 102, a power feeder 103, and the like. An anode 120 having an inner surface is shown.

The thicknesses of the anode substrate 102 and the power feeder 103 in FIG. 12 are exaggerated and the countersunk screws 114 are omitted.

The lead base 101 attaches the energized terminal 113 from the outside and the anode base 102 Is an alloy made of lead and silver having an arc-shaped inner surface with a through hole for it.

The anode substrate 102 is a titanium plate having a thickness of l mm and divided into 18 pieces, and is made of a titanium plate having the same arc-shaped inner surface shape as the lead substrate 101. The anode substrate 102 has a through hole for attachment to the power supply 103 by means of a countersunk screw 114. The surface facing the cathode is coated with an electrode catalyst containing iridium oxide. The surface of the anode substrate 102 in contact with was coated with platinum.

The power feeding body 103 is made of a titanium plate having a thickness similar to that of the anode substrate 102 and having a thickness of 5 mm divided into 18 pieces. On the back surface of the power supply body 103, a titanium rod 107 with an external thread is provided by force welding. The titanium rod 107 passed through the hole provided in the lead base 101, and the titanium nut 105 through the titanium washer 106 on the back side of the lead base 101. 03 is attached to the lead base 101. The washer 106 was joined to the lead base 101 by welding.

The anode 120 of the electrolysis apparatus of this embodiment is energized from the current-carrying terminal 113, and the lead base 101, washer 106, nut 105, titanium rod 107, power feeder 103 Power is supplied to the anode substrate 102 through the fastening portion of the plate screw 114. As a result, between the lead substrate 101 and the anode substrate 102, a current-carrying circuit having sufficient electric conductivity was secured, and stable current could be secured for a long period of time. As a result, the removal of the anode substrate 2 became easy. In addition, the power supply body 103 can prevent the lead substrate 1 from being damaged by the removal of the anode substrate.

The following effects were obtained when the anode of the electrolytic device according to the present invention had the above structure.

1) Stable and sufficient electrical conductivity from the lead substrate to the anode substrate was obtained easily.

2) The mechanism for attaching and detaching the anode base to the lead base can be simplified and downsized. The effect was obtained.

3) The effect of protecting the surface of the lead base, which is soft and susceptible to damage, and greatly affects the electrode spacing, was obtained.

4) The effect of easily adjusting the distance between the cathode and the anode with high accuracy was obtained.

5) Lead or lead alloy used as the anode was easily and inexpensively used.

6) The effect of facilitating coating of the lead base to prevent the electrolyte from coming into direct contact with the lead base was obtained.

From the above effects, the following comprehensive effects were obtained.

Anode bases coated with an electrode catalyst on a corrosion-resistant conductive metal such as titanium, which has excellent performance, can be used easily and at low cost without compromising the performance of large electrolysis equipment operated at high t and current density. Now you can.

Claims

The scope of the claims .

1. In an electrolytic device that can maintain an electrolytic solution between the anode and the cathode,

The anode is

A) an anode substrate made of a corrosion-resistant conductive metal, which is detachably mounted on the surface of the lead substrate and is provided so as to face the cathode at regular intervals, and the surface facing the cathode is covered with an electrode catalyst; When,

ゥ) The lead base and the anode base are divided and arranged, and both the lead base and the anode base are fixedly joined to the lead base so as to secure sufficient electric conductivity. A feeder made of a corrosion-resistant conductive metal in contact with the anode substrate;

An electrolysis device comprising:

2. The electrolytic device according to claim 1, wherein the lead base and the power supply body are welded.

3. The electrolytic device according to claim 2, wherein the surface of the lead base and the power supply body are welded.

4. The lead base has a through hole, the power supply body has a rod passing through the through hole, and a female screw or a male screw is attached to the rod on the back surface of the lead base, The electrolytic device according to claim 1, wherein a body is fixedly joined to the lead base.

5. The lead base has a through hole, the anode base has a rod passing through the through hole, and a female screw or a male screw is attached to the rod on the back surface of the lead base. Therefore, the anode substrate is detachably connected to the lead substrate.

6. The lead base has a through hole, a rod is provided in the through hole, the rod is fixed on the back surface of the lead base, the anode base has a hole, and A male screw is attached to the rod through a hole in the anode base, whereby the anode base is connected to the lead base. 2. The electrolytic device according to claim 1, wherein the electrolytic device is detachably connected to the panel.

7. The electrolytic cell according to claim 1, wherein a current-carrying circuit from the lead substrate to the anode substrate is blocked by a corrosion-resistant insulating material so as not to be formed in a mechanism for removing the anode substrate.

8. The electrolytic device according to claim 1, wherein the power supply body is made of a clad material of a corrosion-resistant conductive metal and lead or a lead alloy.

9. The electrolytic apparatus according to claim 1, wherein at least one surface of the power supply body and the anode base body in contact with each other is coated with a platinum group metal.

10. The electrolytic device according to claim 1, wherein the electrocatalyst coated on the anode substrate mainly comprises a platinum group metal, an alloy thereof, and / or an oxide or base metal oxide thereof.

1 1. The electrolytic apparatus according to claim 1, wherein the lead substrate in contact with the electrolytic solution is coated with a corrosion-resistant resin, rubber, or a corrosion-resistant metal.

1 2. In an electrolytic device that can maintain an electrolytic solution between the anode and the cathode,

The anode is

A) a feeder made of a corrosion-resistant conductive metal fixedly attached to the lead base so as to be divided and arranged on the surface of the lead base and to secure sufficient electrical conductivity with the lead base; It is detachably attached to the lined electric body, is provided so as to face the cathode at regular intervals, and a surface facing the cathode is coated with an electrode catalyst so that sufficient electric conductivity with the power supply body is secured. An electrolytic apparatus comprising: a connected anode substrate made of a corrosion-resistant conductive metal.

1 3. The electrolytic device according to claim 12, wherein the lead base and the power supply body are welded.

1 4. The lead base has a through hole, and the power supply body has a rod penetrating through the through hole ^; on the back surface of the lead base, a female screw or a male screw is provided on the rod, 13. The electrolytic device according to claim 12, wherein a power supply body is attached to the lead base.

1 5. The lead base has a through hole, a rod is provided in the through hole, the rod is fixed on the back surface of the lead base, the power supply body has a hole, and a male screw is a hole in the power supply body. 13. The electrolytic device according to claim 12, wherein the power supply is attached to the lead base through the rod.

1 6. The lined electric body has a female screw hole, the anode base has a through hole, a male screw is tightened into the female screw hole through the through hole, and the anode base is detachably attached to the power feeder. 13. The electrolysis device of claim 12, which is installed.

17. The electrolytic apparatus according to claim 12, wherein at least one surface of the power supply body and the anode substrate that is in contact with each other is coated with a platinum group metal.

18. The electrolytic device according to claim 12, wherein the electrode catalyst coated on the anode base is mainly composed of a platinum group metal, an alloy thereof, or an oxide or a base metal oxide thereof.

1 9. The electrolytic apparatus according to claim 12, wherein the lead base in contact with the electrolytic solution is coated with a corrosion-resistant resin, rubber, or a corrosion-resistant metal.