WO2008023778A1

WO2008023778A1 - Plating solution regenerating apparatus and method of regenerating plating solution

Info

Publication number: WO2008023778A1
Application number: PCT/JP2007/066402
Authority: WO
Inventors: Kentaro Suzuki; Kei Yuki; Fumio Aoki
Original assignee: Jfe Steel Corporation
Priority date: 2006-08-21
Filing date: 2007-08-17
Publication date: 2008-02-28
Also published as: MY140064A; US20090078577A1

Abstract

A plating solution regenerating apparatus for electroplating, comprising a circulation tank, a sludge removing unit, a concentrating unit, an iron compound crystallizing unit, an iron compound separating unit, an iron compound re-dissolving unit, an iron ion removing unit, a piping started with the circulation tank and sequentially connecting these units so that the recited order agrees with the downstream direction, a piping connecting the iron ion removing unit to the circulation tank, a piping connecting the iron compound separating unit to the circulation tank, and a flow channel changing unit connected to the circulation tank and disposed at at least one interspace selected from the group consisting of the interspace between the sludge removing unit and the concentrating unit, the interspace between the concentrating unit and the iron compound crystallizing unit and the interspace between the iron compound crystallizing unit and the iron compound separating unit. This apparatus is capable of removing sludge and iron contents from the plating solution used in electroplating of steel strip to thereby regenerate the plating solution. Further, by the use of this apparatus, continuous operation of electroplating can be maintained without lowering of the utilization rate of the sludge removing unit even when the operation of unit for iron contents removal is halted.

Description

Technical data Plating solution regenerating equipment and plating solution regenerating method

The present invention relates to a regenerating apparatus and a regenerating method that can be used for electric plating of steel strips and that can recycle the liquor. Background art

To continuously apply electric plating (for example, electric tin plating, electrochromium plating, electrozinc plating, copper electroplating, etc.) to the steel strip, the electrolyte liquid is stored in the plating tank. While running the steel strip in the liquid, a voltage is applied using the steel strip as a cathode and a plated metal (for example, tin, chromium, zinc, copper, etc.) disposed opposite the copper strip as an anode. The tinned steel strip is also called tinplate, but in the following, a copper strip that has been electroplated will be referred to as an electroplated steel strip.

In the operation with electric plating, sludge is mixed into the electrolyte liquid stored in the plating tank (hereinafter referred to as plating solution). Here, sludge refers to an agglomerated metal oxide that floats or precipitates in the plating solution. For example, in the case of tin plating

Sn (0H) ₄ etc. becomes sludge. If the sludge in the plating solution increases, problems related to quality such as sleeves will occur.

Therefore, various techniques for removing sludge in the plating solution from the plating tank have been studied. For example, Japanese Patent Laid-Open No. 62-74486 describes a technique for separating and removing sludge using a centrifuge. However, since the viscosity of sludge is often high, not only a powerful centrifuge is required to enable sludge separation, but also sludge separation takes a long time.

Japanese Patent Application Laid-Open No. 2004-59940 describes a technique for precipitating and removing sludge using a precipitation tank. However, since it takes a long time to settle sludge, it is usually necessary to install a large number of precipitation tanks in order to shorten the processing time. Moreover, not only sludge, but also plating metal ions and iron ions exist in the moistening liquid. Of these ions, metal ions that form a plating layer on the steel strip surface (for example, tin ions, chromium ions, zinc ions, copper ions, etc.) do not need to be removed. However, iron ion dissolves when the copper strip reacts with the components of the plating solution and impairs the electrolytic properties of the plating solution, leading to deterioration in the quality of the plating layer covering the surface of the steel strip. However, the removal of iron ions is not considered in both of the above technologies.

In order to regenerate and use the plating solution while continuously applying metal plating to the steel strip, not only sludge in the plating solution but also iron ions must be removed from the plating tank. Since it is difficult to remove sludge and iron ion at the same time with a single device, it is necessary to divide the process of removing sludge and the process of removing iron ions, and to perform a series of these processes continuously. . In order to do so, it is necessary to arrange dedicated removal devices in series and operate them at the same time to continuously supply the plating solution to each device.

When the sludge removal device and the iron ion removal device are placed in series in this way to regenerate the plating solution, if any of the devices fails, the entire plating solution regeneration process is completed. There is no choice but to stop and the productivity of the electric steel strip is reduced. The present invention removes sludge and iron from the plating solution used for electroplating of steel strips, making the plating solution reusable and improving the productivity of electroplated steel strips. An object is to provide an apparatus and a reproduction method. Disclosure of the invention

The present invention relates to a circulation tank, a sludge removal device, a concentration device, an iron compound crystallization device, an iron compound separation device, an iron compound remelting device, an iron ion removal device, and these circulation tanks as a base. Piping connecting the devices in order so that the description order is in the downstream direction, piping connecting the iron ion removal device to the circulation tank, piping connecting the iron compound separation device to the circulation tank, and the sludge The circulation tank is at least one place selected from the group consisting of a removal device and the concentrator, between the concentrator and the iron compound crystallizer, and between the iron compound crystallizer and the iron compound separator. A plating solution regenerating apparatus for electroplating having a flow path changing device connected to It is to be noted that, in this wet solution regenerating apparatus, it is preferable that the flow path changing device is provided between the sludge removing device and the concentrating device. Alternatively, it is preferable that the flow path changing device is provided between the concentrating device and the iron compound crystallizing device. Alternatively, it is preferable that the flow path changing device is provided between the iron compound crystallizing device and the iron compound crystal 1 device. In any of the above plating solution regeneration apparatuses, it is more preferable to further include a flow path changing device connected to the circulation tank between the iron compound redissolving device and the iron ion removing device.

Furthermore, the present invention is a slick regenerator that makes it possible to reuse the plating solution used for electroplating a steel strip, the circulation tank storing the staking solution, and the circulation tank A sludge removing device for removing sludge in the squeezed liquid supplied from the squeezed solution, a squeezed solution concentrating device for concentrating the squeezed solution supplied from the sludge removing device, and a squeezed solution concentrating device. An iron analysis apparatus for cooling the plating solution to precipitate an iron compound, and an iron separation apparatus for separating the iron compound from the plating solution supplied from the iron analysis apparatus and re-dissolving it in water And an iron content removing device that removes the iron ion of the re-dissolved solution supplied from the iron content separating device by ion exchange resin, and the plating solution is fed from the plating solution concentrating device to the circulation tank. Channel change It is also a tandem liquid regenerating apparatus characterized by having an additional apparatus.

Further, the present invention provides the plating solution regenerating apparatus according to any one of the above, wherein the concentration apparatus, the iron compound crystallization apparatus, the iron compound separation apparatus, the iron compound remelting apparatus, and the iron ion removing apparatus. When stopping at least one device selected from the group consisting of: upstream of the upstream upstream stop device, and between the sludge removal device and the concentrator, between the concentrator and the iron compound crystallizer, And an operation method of the plating solution regenerating apparatus that switches the flow path of the plating solution to the circulation tank at at least one point selected from the group consisting of the iron compound crystallizing device and the iron compound separating device.

In this method for operating the sag regenerator, at least one device selected from the group consisting of the iron compound crystallization device, the iron compound separation device, the iron compound redissolving device, and the iron ion removing device is used. When stopping, upstream from the most upstream stop device, and between the sludge removal device and the concentrator, between the concentrator and the iron compound crystallizer, It is preferable to switch the flow path of the plating solution to the circulation tank at at least one point selected from the group consisting of the iron compound crystallizer and the iron compound separator. Alternatively, when stopping at least one device selected from the group consisting of the iron compound separation device, the iron compound redissolving device, and the iron ion removing device, upstream of the most upstream stop device, and the sludge A plating solution at least one selected from the group consisting of a removing device and the concentrating device, between the concentrating device and the iron compound crystallizing device, and between the iron compound crystallizing device and the iron compound separating device. It is preferable to switch the flow path to the circulation tank.

In any of the above-described methods for operating the plating solution regenerating device, when the iron ion removing device is stopped, the flow path of the resolving solution between the iron compound remelting device and the iron ion removing device. It is further preferable to further switch to the circulation tank.

In any of the above-described methods for operating the plating solution regenerating apparatus, the plating solution is preferably an electroplating solution containing tin methanesulfonate.

Furthermore, the present invention provides a plating solution regeneration method for reusing a plating solution used for electroplating a steel strip, and supplying the plating solution stored in a circulation tank to a sludge removal device. After removing sludge in the plating solution, the plating solution is supplied to a plating solution concentrating device to concentrate the plating solution, and then the plating solution is supplied to the iron analysis output device. Then, iron in the plating solution is precipitated as an iron compound, and the plating solution is supplied to an iron separation device to separate the iron compound. The separated iron compound is redissolved in water and re-dissolved. The re-dissolved solution is supplied to an iron content removing device, and iron ions are removed by ion exchange resin while the iron compound is removed by the iron content separating device and the iron content removed. The re-removed iron ion is removed by an apparatus While the demolition liquid is fed to the circulation tank, when the operation of the iron analyzing device, the iron content separation device or the iron content removal device is stopped, the metal solution concentration device is transferred to the circulation tank. This is also a method for regenerating the simmering liquid characterized by feeding the liquid. Brief Description of Drawings FIG. 1 is a flow diagram showing an example of an apparatus for removing sludge and iron ions by applying the present invention.

FIG. 2 is a flow diagram illustrating another apparatus for removing sludge and iron ions by applying the present invention.

FIG. 3 is a flow diagram illustrating another apparatus for removing sludge and iron ions by applying the present invention.

FIG. 4 is a flowchart showing the apparatus used for comparison. BEST MODE FOR CARRYING OUT THE INVENTION

The plating solution used when applying electrical plating to steel strips contains plated metal ions and has electrical conductivity. Sludge and iron ions are inevitably mixed into the plating solution with the operation of electric plating. If sludge or iron ions are mixed in the plating solution, it adversely affects the properties of the steel strip surface and the electrolytic properties of the plating solution. is there.

The present invention is applied to electrical plating such as tin plating, chromium plating, zinc plating, and copper plating. In particular, it is preferable to apply sludge to iron tin that has a problem of iron ions. In addition, tin plating is preferably applied to plating solutions such as methanesulfonic acid bath, halogen bath, and phenolsulfonic acid bath. In particular, since the pH of a methanesulfonic acid bath is low and iron is easily dissolved, the present invention is preferably applied to a methanesulfonic acid bath. The case where the present invention is applied to a tin methanesulfonate plating solution will be described below.

In the present invention, the plating solution stored in the plating tank is temporarily stored in the circulation tank, and the plating solution is fed to a device for removing sludge and iron ions. Furthermore, after removing sludge and iron ions, the regenerated plating solution is returned to the circulation tank and then circulated in the plating tank.

FIG. 1 is a flowchart showing an example of a procedure for removing sludge and iron ions by applying the present invention. Although FIG. 1 shows an example in which the pump 9 is arranged on the outlet side of the circulation tank 1, the position and number of the pumps 9 are appropriately set according to the flow rate of the fitting liquid 10 or the specifications of each device described later. It ’s fine. The plating tank is not shown. The plating solution 10 is supplied from the circulation tank 1 to the sludge removal device 2. Sludge removal device 2 removes sludge in plating solution 10 and uses conventionally known devices such as filters, filter presses, and centrifuges. However, considering the sludge viscosity and particle size, it is preferable to use a filter press.

On the outlet side (downstream) of the sludge removal device 2, valves 13 a and 13 b and pipes connected to the circulation tank are disposed as the flow path conversion device 13. When a series of devices to be described later operate, the valve 13b is closed and the valve 13a is opened. Therefore, the plating solution .10 is supplied from the sludge removal device 2 to the plating solution concentrating device 3. Plating solution concentrating device 3 is for concentrating the fitting solution 10, and it is preferable to use a device capable of vaporizing water by heating or vacuum distillation. This concentration facilitates precipitation of the iron compound 11 in the iron compound crystallizer 4 (also referred to as an iron analyzer) described later. The ratio of concentrating the plating solution 10 in the plating solution concentrating device 3 may be appropriately set according to the flow rate of the plating solution 10 or the specifications of each device described later. However, excessive concentration increases the amount of heat energy consumed, leading to increased costs. In the case of tin methanesulfonate plating solution, the standard concentration is about 4 times the concentration of methanesulfonic acid in the plating solution 10 supplied from the sludge remover 2.

In the present invention, the plating solution 10 is concentrated after removing sludge in the plating solution 10. The reason is that if the plating solution 10 with the sludge mixed therein is supplied to the plating solution concentrating device 3, it will be difficult to remove iron thereafter.

FIG. 1 shows an example in which valves 13a and 13b are arranged as components of the flow path conversion device 13. However, the flow path conversion device 13 used in the present invention is not limited to a valve, and a conventional flow of fluid can be obtained. Equipment used to change the path (for example, a valve opening / closing device) can be used.

The soaking solution 10 concentrated in the plating solution concentrating device 3 is supplied to an iron compound crystallizing device 4 (also called an iron analyzing device). In the iron compound crystallizer 4, the plating solution 10 is cooled to deposit iron compound 11 (in the case of tin methanesulfonate plating solution, iron methanesulfonate). Iron methanesulfonate is one in which the steel strip reacts with methanesulfonic acid, a component of the plating solution. In this iron compound crystallizer, plating metal ions '' (That is, tin ions) Only the iron compound 11 is precipitated while maintaining the state dissolved in the fitting solution 10. Therefore, the cooling condition of the plating solution 10 in the iron compound crystallizer 4 is set to be intermediate between the temperature at which the iron compound is precipitated and the temperature at which the plated metal compound (that is, the tin compound) is precipitated. For example, in the case of a tin methanesulfonate plating solution, it should be set between the precipitation temperature of iron methanesulfonate and the precipitation temperature of tin methanesulfonate (about 14 ° C).

Next, the plating solution 10 and the iron compound 11 are supplied from the iron compound crystal device 4 to the iron separator 5. The iron content separation device 5 comprises an iron compound separation device 6 and an iron compound re-dissolution device 7. The iron compound 11 (in the case of tin methanesulfonate plating solution, iron methanesulfonate) is used as the plating solution. It is separated from 10 and redissolved in water. As the iron compound separator 6, conventionally known devices such as filters and centrifuges are used. However, because sludge has already been removed in this process, the viscosity of the mixture of plating solution 10 and iron compound 11. has decreased, and the specific gravity of iron compound 11 (ie, iron methanesulfonate) must be relatively high. Therefore, it is preferable to use a centrifuge.

The iron compound 11 is separated by the iron compound separator 6 and the scum 10 is fed to the circulation tank 1.

On the other hand, the iron compound 11 is supplied to the remelting device 7. The re-dissolution apparatus 7 re-dissolves the iron compound 11 (that is, iron methanesulfonate) in water, and uses a water tank or the like in which water is fff distilled. Here, water refers to water that does not contain methanesulfonic acid, such as distilled water, ion exchange water, tap water, and industrial water. Hereinafter, an aqueous solution in which iron compound 11 (that is, iron methanesulfonate) is redissolved is referred to as redissolved solution 12.

The re-dissolution liquid 12 is supplied from the re-dissolution apparatus 7 to the iron ion removal apparatus 8 (also called iron removal apparatus). The iron ion removing device 8 replaces the iron ions in the re-dissolved liquid 12 with protons, so that the iron ions are adsorbed and removed from the re-dissolved liquid 12 by the ion exchange resin. The lysing liquid component (ie, methanesulfonic acid) is regenerated in the re-dissolved liquid 12 from which iron ions have been removed, and the re-dissolved liquid 12 is sent to the circulation tank 1. In this way, sludge and iron ions are removed from the used plating solution 10 stored in the circulation tank 1 and regenerated, and the retentate solution 10 is returned to the recirculation tank 1 and further returned to the plating tank. Has been recycled. ..

In addition, at least one facility selected from the group consisting of a plating solution concentrator 3, an iron compound crystallizer 4, an iron compound separator 6, an iron compound remelting device 7, and an iron ion removal device 8 must be When stopping the operation for inspection or other reasons, open the valve 13b of the flow path conversion device 13 and close the valve 13a. As a result, the plating solution 10 is fed from the sludge removing device 2 to the circulation tank 1. In other words, the sludge removal device 2 removes sludge even when a series of devices related to the removal of iron from the plating liquid concentrator 3 to the iron ion removal device 8 or a part of them are stopped. Therefore, the continuous operation of electric plating can be maintained by supplying the liquid 10 to the circulation tank 1. FIG. 2 is a flowchart showing another example of the apparatus of the present invention. Specifically, the flow path conversion device 13 of FIG. 1 is provided on the outlet side (downstream) of the methicine liquid concentration device 3. Similar to the operation in FIG. 1 described above, when a series of devices are operating, the valve 13b is closed and the valve 13a is opened.

However, at least one facility selected from the group consisting of an iron compound crystallizer 4, an iron compound separator 6, an iron compound redissolver 7, and an iron ion remover 8 should be used for reasons such as periodic inspection. When the operation is stopped, the valve 13b of the flow path converter 13 is opened and the valve 13a is closed. As a result, the plating solution 10 is fed from the fitting solution concentrator 3 to the circulation tank 1. In other words, even when a series of devices related to the removal of iron from the iron compound crystallizer 4 to the iron ion removal device 8 'or part of its operation is stopped, the sludge removal device 2 uses the liquid 10 By removing the sludge and concentrating it in the plating solution concentrating device 3, the stencil solution 10 is fed to the circulation tank 1 so that the continuous operation with electric plating can be maintained.

FIG. 3 is a flowchart showing another example of the apparatus of the present invention. Specifically, the flow path converter 13 in FIG. 1 is provided on the outlet side (downstream) of the iron compound crystallizer 4. Similar to the operation in FIG. 1 described above, when a series of devices are operating, the valve 13b is closed and the valve 13a is opened. However, if the operation of at least one facility selected from the group consisting of the iron compound separator 6, the iron compound remelter 7, and the iron ion remover 8 is stopped due to a failure or periodic inspection, Open the valve 13b of the liquid flow path converter 13 and close the valve 13a. As a result, the plating solution 10 is fed from the iron compound crystallizer 4 to the circulation tank 1. In other words, even when a series of devices related to the removal of iron compounds from the iron compound separation device 6 to the iron ion removal device 8 or a part of them are stopped, the sludge removal device 2 uses the sludge solution 10 to the sludge. The plating solution concentrating device 3 concentrates the solution, and the iron compound crystallizing device 4 feeds the plating solution 10 in which the iron compound is deposited to the circulation tank 1, thereby Continuous operation can be maintained. In this case, iron compound deposits are mixed in the plating solution in the circulation tank 1, but dissolve in the circulation tank 1, so there is no problem in the operation of electric plating.

As described above, the present invention includes the sludge removing device 2 and the plating solution concentrating device 3, the plating concentrating device 3 and the iron compound crystallizing device 4, and the iron compound crystallizing device 4 and the A plating solution regenerating apparatus for electroplating, having a flow path changing device 13 connected to the circulation tank at at least one location selected from the group consisting of iron compound separators 6, its operating method, and electroplating liquid It is a playback method.

Therefore, the plating solution regenerating apparatus according to the present invention has three flow path changing devices 13 installed in advance in all of the above three locations, or two flow path changing devices 13 of the above three locations. Needless to say, the technical scope also includes those that have been selected and installed in advance. By using these devices, the valves of the flow path changing device 13 suitable for the desired operation method can be appropriately switched to regenerate the electroplating solution.

Further, in any of the above-described plating solution regenerators of the present invention, a remelt solution flow path changing device 14 connected to the circulation tank is provided between the iron compound remelting device 7 and the iron ion removing device 8. I prefer to have more.

That is, on the outlet side (downstream) of the redissolving device 7, it is preferable that valves 14 a, 14 b and pipes connected to the circulation tank are arranged as the flow converting device 14 for the redissolved liquid. Figure 3 shows an example of such an installation. When the iron ion remover 8 is in operation, close the knob 14b and open the valve 14a. Therefore, normally, the redissolving liquid 12 is supplied from the redissolving apparatus 7 to the iron ion removing apparatus 8.

On the other hand, when the operation of the iron ion removal device 8 is stopped due to equipment failure or periodic inspection, the valve 14b of the flow path conversion device 14 for re-dissolved liquid is opened and the valve 14a is closed. As a result, the redissolved liquid 12 is fed from the remelting device 7 to the circulation tank 1. In other words, even when the iron ion removal device 8 stopped operating, the sludge was removed from the solution 10 by the sludge removal device 2, the iron compound was precipitated, and then the iron compound was dissolved in water. By supplying the re-dissolved liquid 12 to the circulation tank 1, it is possible to maintain continuous operation with electric plating.

Although the example in which the valves 14a and 14b are disposed as components of the re-dissolved liquid flow path conversion device 14 used in the present invention has been shown, the flow path conversion device 14 used in the present invention is not limited to the valve, The equipment used to change the flow path of the fluid (eg, a valve opening / closing device) can be used.

In any of the plating solution regenerators of the present invention, either one of the plating solution flow channel conversion device 13 and the redissolving liquid flow channel conversion device 14 may be used, or both may be used in combination. good.

It should be noted that the above description is merely an example of the embodiment of the present invention relating to the tin methanesulfonate plating solution, and various modifications are made depending on the type of plating metal and the components of the plating solution. Can do.

As described above, according to the present invention, the plating solution can be regenerated by removing sludge and iron from the plating solution used for electroplating. Furthermore, in this slick regenerator, continuous operation of electrical scum can be maintained without lowering the operating rate of the sludge remover even when the equipment related to iron removal stops operating. . Therefore, it is possible to improve the productivity of electric steel strips. Example 1 The plating solution that was installed in the tin steel strip production line and used in the tank was sent to the circulation tank. The plating solution is a tin methanesulfonate plating solution, and sludge, iron ions, and tin ions are inevitably mixed in the plating solution as the tin steel strip is manufactured. The plating solution was regenerated using the apparatus shown in Flowchart 1.

As shown in FIG. 1, the plating solution 10 was supplied from the circulation tank 1 to the sludge removal device 2 to remove the sludge. The sludge remover 2 used a filter press. In normal operation, the valve 13b of the flow path changing device 13 arranged on the outlet side of the sludge removal device 2 is closed, the valve 13a is opened, and the plating solution 10 is transferred from the sludge removal device 2 to the slag solution concentration device 3. Supplied. In the plating solution concentrator 3, the plating solution 10 was distilled under reduced pressure to evaporate water, and concentrated so that the concentration of methanesulfonic acid in the plating solution 10 supplied from the sludge removal device 2 was four times. Concentrated in the plating solution concentrating device 3 was supplied to the iron compound crystallizing device 4 and cooled to 14 ° C. to precipitate iron methanesulfonate. Next, the plating solution 10 and the precipitate were supplied to the iron compound separator 6 in the iron separator 5. The iron methanesulfonate precipitated in the iron compound separator 6 was separated from the plating solution 10. As the iron compound separator 6, a centrifuge or the like was used. The plating solution 10 from which the iron methanesulfonate 11 was separated by the iron compound separator 6 is fed to the circulation tank 1, while the iron methanesulfonate 11 is supplied to the iron compound redissolving device 7 and iron methanesulfonate 11 Was dissolved in industrial water. The obtained re-dissolved liquid 12 was supplied to the iron ion removal device 8, and the iron ions were adsorbed on the ion exchange resin. Re-dissolved liquid 12 from which iron ions had been removed was sent to circulation tank 1.

In addition, when stopping the operation of at least one of the plating solution concentrator 3, the iron compound crystallizer 4, the iron compound separator 6, the iron compound remelter 7, and the iron ion remover 8, the flow path must be changed. The valve 13b of the device 13 was opened, the valve 13a was closed, and the plating solution 10 was fed from the sludge removal device 2 to the circulation tank 1. This is an invention example.

-On the other hand, as a comparative example, the used liquor solution was regenerated with the apparatus shown in the flow chart 4. Since this apparatus is the same as the normal operation of the invention example, its description is omitted. However, METSUKI Solution Concentrator 3, Iron Compound Crystallizer 4, Iron Compound Separator 6, Iron Compound Remelter When the operation of at least one of 7 and the iron ion removal device 8 was stopped, the entire regeneration process of the plating solution 10 was stopped.

For the inventive example and the comparative example, the production line for the tin strip was operated for 12 months, and the operating rate of the sludge removal device 2 was investigated. During the last 12 months, there was a situation in which the operation of equipment related to iron removal had to be stopped.

As a result, the operating rate of the sludge removal apparatus 2 was 100% in the inventive example, whereas it was 50% in the comparative example. Therefore, in the inventive example, the productivity of the tin steel strip was improved compared to the comparative example. Example 2

It was installed in the tin steel strip production line and used in a slag tank. The plating solution is a tin methanesulfonate plating solution, and sludge, iron ions, and tin ions are inevitably mixed in the plating solution as the tin steel strip is manufactured. The plating solution was regenerated using the apparatus shown in Flowchart 2.

As shown in FIG. 2, the plating solution 10 was supplied from the circulation tank 1 to the sludge removal device 2 to remove the sludge. The sludge remover 2 used a filter press. Since the sludge was removed, the liquor 10 was supplied to the moist liquid concentrator 3. In the plating solution concentrating device 3, the fitting solution 10 was distilled under reduced pressure to vaporize water, and concentrated so as to be four times the methanesulfonic acid concentration of the plating solution 10 supplied from the sludge removal device 2. In normal operation, the valve 13b of the flow path changing device 13 arranged on the outlet side of the plating solution concentrator 3 is closed, the valve 13a is opened, and the concentrated plating solution 10 is applied to the plating solution concentrator 3 force and iron. It supplied to the compound crystallizer 4. The concentrated soaking solution 10 was cooled to 14 ° C. with an iron compound crystallizer 4 to precipitate iron methanesulfonate. Next, the plating solution 10 and the deposit were supplied to the iron compound separator 6 in the iron separator 5. The iron methanesulfonate precipitated in the iron compound separator 6 was separated from the plating solution 10. As the iron compound separator 6, a centrifuge or the like was used. The plating solution 10 from which iron compound separator 11 has been separated by iron compound separator 6 is fed to circulation tank 1, while iron methanesulfonate 11 is fed to iron compound redissolver 7 to provide iron methanesulfonate 11 Dissolved in industrial water. The obtained re-dissolved liquid 12 was supplied to the iron ion removal device 8, and the iron ion was adsorbed on the ion exchange resin. Re-dissolved liquid 12 from which iron ions had been removed was sent to circulation tank 1.

When stopping the operation of at least one of the iron compound crystallizer 4, the iron compound separator 6, the iron compound remelting device 7, and the iron ion removal device 8, open the valve 13b of the flow path changing device 13, The valve 13a was closed, and the plating solution 10 was fed from the plating solution concentrating device 3 to the circulation tank 1. This is an invention example.

On the other hand, as a comparative example, the used liquor was regenerated with the apparatus shown in the flow chart 4. Since this apparatus is the same as the normal operation of the invention example, its description is omitted. However, when the operation of at least one of the iron compound crystallizer 4, the iron compound separator 6, the iron compound redissolver 7, and the iron ion remover 8 is stopped, the entire reprocessing of the plating solution 10 must be performed. Stopped.

For the inventive example and the comparative example, the production line for the tin strip was operated for 12 months, and the operating rates of the sludge removal device 2 and the squeeze liquid concentrating device 3 were investigated. During the last 12 months, there was a situation where the operation of equipment related to iron removal had to be stopped.

As a result, the operating rate of the sludge removal apparatus 2 was 100% in the inventive example, whereas it was 50% in the comparative example. The operating rate of the plating solution concentrator 3 was 45% in the comparative example, compared with 95% in the inventive example. Therefore, in the inventive example, the productivity of the tin steel strip was improved compared to the comparative example. Example 3

The plating solution that was installed in the tin steel strip production line and used in the tank was sent to the circulation tank. The plating solution is a tin methanesulfonate plating solution, and sludge, iron ions, and tin ions are inevitably mixed in the plating solution as the tin steel strip is manufactured. The plating solution was regenerated using the apparatus shown in Flowchart 3.

As shown in FIG. 3, the plating solution 10 was supplied from the circulation tank 1 to the sludge removal device 2 to remove the sludge. The sludge remover 2 used a filter press. Since the sludge was removed, the liquor 10 was supplied to the moist liquid concentrator 3. Plating solution concentrator 3 The fitting solution 10 was distilled under reduced pressure to evaporate water and concentrated to 4 times the methanesulfonic acid concentration of the plating solution 10 supplied from the sludge removal device 2. Concentrated in the plating solution concentrating device 3 was supplied to the iron compound crystallizing device 4 and cooled to 14 ° C. to precipitate iron methanesulfonate. Next, in normal operation, the valve 13b of the flow path changing device 13 disposed on the outlet side of the iron compound crystallizer 4 is closed, the valve 13a is opened, and the plating solution 10 and the precipitate are crystallized from the iron compound. The iron was supplied from the device 4 to the iron compound separation device 6 in the iron separation device 5. The iron methanesulfonate precipitated in the iron compound separator 6 was separated from 10 forces of the plating solution. As the iron compound separator 6, a centrifuge or the like was used. The plating solution 10 separated from the iron methanesulfonate 11 by the iron compound separator 6 is fed to the circulation tank 1, while the iron methanesulfonate 11 is supplied to the iron compound redissolving device 7 and the iron methanesulfonate 11 Was dissolved in industrial water. In normal operation, the valve 14b of the re-dissolution liquid flow path changing device 14 arranged on the outlet side of the iron compound re-dissolution device 7 in the iron separator 5 is closed, the valve 14a is opened, and the re-dissolution liquid 12 is removed. The iron compound redissolving device 7 was supplied to the iron ion removing device 8. In the iron ion removal device 8, iron ions were adsorbed on the ion exchange resin. Re-dissolved liquid 12 from which iron ions had been removed was sent to circulation tank 1.

When stopping the operation of at least one of the iron compound separation device 6, the iron compound remelting device 7, and the iron ion removal device 8, open the valve 13b of the flow path changing device 13, and close the valve 13a. The plating solution 10 was fed from the iron compound crystallizer 4 to the circulation tank 1. In particular, when the operation of only the iron ion removal device 8 is stopped, the valve 13b of the flow path changing device 13 is closed and the valve 13a is opened, and at the same time, the valve 14b of the redissolved liquid flow changing device 14 is opened. The valve 14a was closed, and the re-dissolved liquid 12 was fed from the iron compound re-dissolver 7 to the circulation tank 1. This is an invention example.

On the other hand, as a comparative example, since the same use as that of the inventive example was performed, the attached solution was regenerated by the apparatus shown in the flow chart 4. Since this apparatus is the same as the normal operation of the invention example, its description is omitted. However, when the operation of at least one of the iron compound separation device 6, the iron compound redissolving device 7, and the iron ion removal device 8 was stopped, the entire regeneration treatment of the plating solution 10 was stopped. For the inventive example and the comparative example, the production line for the tin strip was operated for 12 months, and the operating rates of the sludge remover 2 and the iron compound crystallizer 4 were investigated. During the last 12 months, there was a situation in which the operation of equipment related to iron removal had to be stopped.

As a result, the operating rate of the sludge removal apparatus 2 was 100% in the inventive example, whereas it was 50% in the comparative example. In addition, the availability factor of the iron compound crystallizer 4 was 90% in the inventive example, whereas it was 40% in the comparative example. Therefore, in the inventive example, the productivity of the tin steel strip was improved compared to the comparative example. Industrial applicability

With the apparatus and method of the present invention, the plating solution can be regenerated by removing sludge and iron from the stencil used for electroplating copper strips. Moreover, with the apparatus of the present invention, even when the apparatus related to the removal of iron stops operating, it is possible to maintain the continuous operation of electric plating without lowering the operating rate of the sludge removal apparatus. Therefore, it is possible to improve the productivity of steel plating steel strips and contribute widely to industry.

Claims

The scope of the claims

1. Circulation tank;

• Sludge removal equipment;

.Concentrator;

'Iron compound crystallizer;'

.Iron compound separation equipment;

'Iron compound remelting equipment;

'Iron ion removal device;

• Piping that connects these devices in sequence so that the above described order is in the downstream direction from the circulation tank;

• piping connected from the iron ion removal device to the circulation tank;

• piping from the iron compound separator to the circulation tank; and

At least one location selected from the group consisting of the sludge removal device and the concentrator, the concentrator and the iron compound crystallizer, and the iron compound crystallizer and the iron compound separator Flow path changing device connected to the circulation tank

A plating solution regenerator for electroplating.

2. The plating solution regenerating apparatus according to claim 1, wherein the flow path changing device is provided between the sludge removing device and the concentrating device.

3. The plating solution regenerating apparatus according to claim 1, wherein the flow path changing device is provided between the concentrating device and the iron compound crystallizing device.

4. The plating solution regenerating apparatus according to claim 1, wherein the flow path changing device is provided between the iron compound crystallizing device and the iron compound separating device.

5. The plating solution regenerating apparatus according to any one of claims 1 to 4, further comprising a flow path changing device connected to the circulation tank between the iron compound remelting device and the iron ion removing device.

6. A plating solution regenerating apparatus that makes it possible to reuse the plating solution used for electroplating the steel strip, the circulation tank storing the plating solution, and the mesh supplied from the circulation tank. Sludge removal device that removes sludge in the attached liquor, and the sludge removal. A plating solution concentrating device for concentrating the plating solution supplied from a device, an iron analyzing and extracting device for cooling the plating solution supplied from the plating solution concentrating device to precipitate an iron compound, and the iron An iron separation device that separates the iron compound from the plating solution supplied from the analysis device and re-dissolves it in water, and an iron ion of the re-dissolution solution supplied from the iron separation device is used as an ion exchange resin. And an iron content removing device that removes the iron solution, and a flow path changing device that feeds the metal solution from the metal solution concentrating device to the circulation tongue.

7. When stopping at least one device selected from the group consisting of the concentrating device, the iron compound crystallizing device, the iron compound separating device, the iron compound redissolving device, and the iron ion removing device, Upstream from the stop device, and between the sludge removal device and the concentrating device, between the concentrating device and the iron compound crystallizing device, and between the iron compound crystallizing device and the iron compound separating device. The method of operating a plating solution regenerating apparatus according to claim 1, wherein the plating solution flow path is switched to the circulation tank at at least one location selected from the group.

8. When stopping at least one device selected from the group consisting of the iron compound crystallizing device, the iron compound separating device, the iron compound redissolving device, and the iron ion removing device, it is upstream from the most upstream stop device. And between the sludge removing device and the concentrating device, between the concentrating device and the iron compound crystallizing device, and between the iron compound crystallizing device and the iron compound separating device. 2. The method for operating a plating solution regenerating apparatus according to claim 1, wherein the plating solution flow path is switched to the circulation tank at least at one location.

9. When stopping at least one device selected from the group consisting of the iron compound separation device, the iron compound redissolving device, and the iron ion removing device, upstream of the most upstream stop device, and the sludge A plating solution at least one selected from the group consisting of a removing device and the concentrating device, between the concentrating device and the iron compound crystallizing device, and between the iron compound crystallizing device and the iron compound separating device. The method for operating the plating solution regenerating apparatus according to claim 1, wherein the flow path of the plating solution is switched to the circulation tank.

10. When the iron ion removing device is stopped, the flow path of the redissolved liquid is further switched to the circulation tank between the iron compound redissolving device and the iron ion removing device.

10. A method for operating the plating solution regenerating apparatus according to 9.

11. The method for operating a plating solution regenerating apparatus according to any one of claims 7 to 9, wherein the plating solution is an electroplating solution containing tin methanesulfonate.

12. In the method of reclaiming scouring liquid that can be used to apply electrical staking to the steel strip, the squeezing liquid stored in the circulation tank is supplied to the sludge removal device to recycle the scouring liquid. After removing the sludge in the sachet, supply the squeeze solution to the squeeze solution concentrator to concentrate the squeeze solution, and then supply the squeeze solution to the iron analyzer. Iron is deposited as an iron compound, and further, the plating solution is supplied to an iron separator to separate the iron compound. The separated iron compound is redissolved in water to form a re-dissolved solution, The re-dissolved liquid is supplied to the iron content removing device and iron ions are removed by the ion exchange resin, while the iron solution from which the iron compound is removed by the iron content separating device and the iron content removing device The re-dissolved liquid from which the iron ions have been removed is added to the circulating tank. On the other hand, when the operation of the iron analyzer, the iron separator, or the iron remover is stopped, the plating solution is supplied from the plating solution concentrator to the circulation tank. Shimmering liquid regeneration method.