JP2021085038A - Metal surface treatment system - Google Patents

Abstract

To provide a metal surface treatment system that can continuously be operated.SOLUTION: There is provide a metal surface treatment system 1 comprising a treatment solution tank 2, a recovery device 3 that recovers a treatment solution from the treatment solution tank, a separation device 4 that separates an oil component contained in a recovered treatment solution recovered in the recovery device, a metal ion removal device 5 that removes a metal ion present in the oil separation treatment solution removed of the oil component in the separation device, and a regenerated treatment solution supply device 6 that returns the regenerated treatment solution removed of the metal ion in the metal ion removal device to the treatment solution tank, which separation device removes the oil component from the recovered treatment solution by using buoyancy of the oil component contained in the recovered treatment solution.SELECTED DRAWING: Figure 1

Description

The disclosure in this application relates to a metal surface treatment system used for alumite treatment, chemical polishing treatment, and the like.

An alumite treatment that forms an aluminum oxide film on the aluminum surface is known. The alumite treatment is carried out for the purpose of improving the corrosion resistance and wear resistance of aluminum, and adding decoration and other functions. In general, alumite treatment uses sulfuric acid or the like as an electrolytic solution and electrolyzes aluminum with aluminum as an anode to electrochemically oxidize the surface of aluminum, and aluminum oxide Al ₂ O ₃ (also called alumina). Produces a film. As a device for performing alumite treatment, a device for flattening the surface of the oxide film while forming a film of aluminum oxide (see Patent Document 1), and an anion in order to improve the film formation rate on the product surface. A device provided with a mechanism for efficiently supplying to the surface of a product (see Patent Document 2) and the like are known.

Further, a chemical polishing treatment for smoothing a metal surface by immersing a metal such as aluminum in a chemical polishing liquid containing an acid such as nitric acid without using electricity is also known.

Japanese Unexamined Patent Publication No. 7-90688 Japanese Unexamined Patent Publication No. 4-80395

By the way, in the case of alumite treatment or chemical polishing treatment, it may be referred to as "treatment liquid" in the electrolytic solution or chemical polishing liquid for alumite treatment (hereinafter, when the electrolytic solution and the chemical polishing liquid are combined, it may be referred to as "treatment liquid"). It is important to control the concentration of the acid and the concentration of metal ions such as dissolved aluminum (hereinafter, also referred to as "metal ions") dissolved in the treatment liquid by electrolysis or chemical polishing. For example, in the case of alumite treatment, when the concentration of metal ions in the electrolytic solution increases, the conductivity of the electrolytic solution decreases, and the viscosity of the electrolytic solution increases, resulting in loss of heat dissipation, which is fatal to "burn alumite". Quality defect.

Therefore, when operating the metal surface treatment system, management is performed so that the acid concentration and the metal ion concentration in the treatment liquid are constant.

In the conventional management of the treatment liquid, the acid is replenished as necessary after confirming the current acid concentration by analyzing the treatment liquid on a regular basis. However, for metal ions, after periodically analyzing the treatment liquid, a predetermined amount of treatment liquid is withdrawn from the treatment liquid tank, fresh water (acid if necessary) is replenished, the mixture is circulated for a certain period of time, and the metal ions are analyzed again. We are checking the concentration. Therefore, each time a series of liquid exchange operations for controlling the concentration of metal ions is performed, the metal surface treatment system is stopped, and there is a problem that the operating rate of the metal surface treatment system is significantly reduced.

The disclosure in this application was made in order to solve the above-mentioned problems, and as a result of diligent research, (1) it is necessary to remove the oil component in the treatment liquid in advance before removing the metal ion. However, at that time, if a filter is used, clogging due to oil components occurs, and as a result, it is difficult to continuously operate the metal surface treatment system due to regular replacement of the filter. (2) On the other hand, from the treatment liquid tank. By using a separation device that removes the oil component from the recovery treatment liquid by utilizing the buoyancy of the oil component contained in the recovered recovery treatment liquid, the oil component can be continuously removed from the recovery treatment liquid, and as a result. , Newly found that the metal surface treatment system can be operated continuously.

That is, the purpose of the disclosure in this application is to provide a metal surface treatment system capable of continuous operation.

The disclosure in this application relates to the metal surface treatment systems described below.

(1) A metal surface treatment system, wherein the metal surface treatment system is
With the treatment liquid tank,
A recovery device that recovers the treatment liquid from the treatment liquid tank, and
A separation device that separates the oil components contained in the recovery treatment liquid recovered by the recovery device, and a separation device.
A metal ion removing device for removing metal ions in an oil separation treatment liquid from which oil components have been separated by the separating device, and a metal ion removing device.
A regeneration treatment liquid supply device for returning the regeneration treatment liquid from which metal ions have been removed by the metal ion removal device to the treatment liquid tank, and a treatment liquid supply device.
Including
The separation device removes the oil component from the recovery treatment liquid by utilizing the buoyancy of the oil component contained in the recovery treatment liquid.
Metal surface treatment system.
(2) The separation device
A recovery treatment liquid tank for storing the recovery treatment liquid and
A first discharge port formed in the recovery treatment liquid tank and discharging the oil separation treatment liquid,
A second discharge port formed in the recovery treatment liquid tank and discharging an oil component floating above the recovery treatment liquid, and a second discharge port.
Including
The second discharge port is formed in the recovery treatment liquid tank on the upper side in the direction of gravity from the first discharge port.
The metal surface treatment system according to (1) above.
(3) The metal ion removing device is
Ion exchange resin or
Ion exchange membrane,
including,
The metal surface treatment system according to (1) or (2) above.
(4) The metal ion removing device is
A resin tower filled with ion exchange resin and
A first reservoir connected to the separation device and the resin tower,
A second reservoir connected to the resin tower and
including,
The metal surface treatment system according to (1) or (2) above.
(5) The regeneration treatment liquid supply device includes a pipe, and one end of the pipe is connected to the resin tower.
The metal surface treatment system according to (4) above.
(6) Two or more of the treatment liquid tanks are provided.
The metal surface treatment system according to any one of (1) to (5) above.

The metal surface treatment system disclosed in the present application can continuously operate the metal surface treatment system by using an oil component separating device utilizing the buoyancy of the oil component.

FIG. 1 is a diagram showing an outline of a first embodiment of a metal surface treatment system. FIG. 2 is a schematic cross-sectional view showing an example of the separation device 4. 3A to 3D show a procedure of an example of removing metal ions by a chromatographic separation method using a metal ion removing device 5. FIG. 4 is a diagram showing an outline of a second embodiment of the metal surface treatment system.

Hereinafter, each embodiment of the metal surface treatment system will be described in detail with reference to the drawings. In the present specification, members having the same type of function are designated by the same or similar reference numerals. Then, the repeated description of the members with the same or similar reference numerals may be omitted.

(First Embodiment)
The metal surface treatment system 1a according to the first embodiment will be described with reference to FIG. FIG. 1 is a diagram showing an outline of a metal surface treatment system 1a. The metal surface treatment system 1a shown in FIG. 1 includes at least a treatment liquid tank 2, a recovery device 3, a separation device 4, a metal ion removal device 5, and a regeneration treatment liquid supply device 6.

The treatment liquid tank 2 is filled with the treatment liquid L. When the metal surface treatment system 1a is used as the alumite treatment system, the treatment liquid tank 2 is filled with the electrolytic solution L. When the metal surface treatment system 1a is used as an alumite treatment system, although not shown, an anode and a cathode are arranged in the treatment liquid tank 2, an alumite treatment member is connected to the anode, and the anode and the cathode are connected. By applying electricity to the aluminum oxide, a film of um can be formed on the surface of the alumite-treated member. As the electrolytic solution L, an electrolytic solution known in the field of alumite treatment such as sulfuric acid can be used. When the metal surface treatment system 1a is used as a chemical polishing treatment system, the treatment liquid tank 2 may be filled with a known chemical polishing liquid.

The recovery device 3 is not particularly limited as long as the treatment liquid L can be recovered from the treatment liquid tank 2 and the recovered treatment liquid, which is the recovered treatment liquid, can be sent to the separation device 4. The recovery device 3 can be formed by, for example, a pipe 31 connecting the treatment liquid tank 2 and the separation device 4, a pump (not shown), or the like.

The separation device 4 separates the oil component contained in the recovery treatment liquid recovered by the recovery device 3. A metal such as aluminum, which is a member to be treated, is usually surface-treated after being washed, but an oil component that cannot be completely washed is released from the surface of the member to be treated into the treatment liquid L during the surface treatment. The separation device 4 separates the free oil component.

The separation device 4 is not particularly limited as long as the oil component can be removed from the recovery treatment liquid by utilizing the buoyancy of the oil component contained in the recovery treatment liquid. FIG. 2 is a schematic cross-sectional view showing an example of the separation device 4. In the example shown in FIG. 2, the separation device 4 has a recovery processing liquid tank 41 for storing the recovery treatment liquid L1 and a first discharge port 42 for discharging the oil separation treatment liquid L2 from which the oil component O is separated from the recovery treatment liquid L1. A second discharge port 43 for discharging the oil component O suspended near the surface of the recovery treatment liquid L1 is included at least. The second discharge port 43 is formed in the recovery treatment liquid tank 41 on the upper side in the gravity direction (Z) from the first discharge port 42. Therefore, the oil component O contained in the recovery treatment liquid L1 floats above the recovery treatment liquid tank 41 due to buoyancy, so that the oil component O is discharged from the second discharge port 43, and the oil separation treatment liquid L2 from which the oil component O has been removed is discharged. It can be discharged from the first discharge port 42. Further, when the first discharge port 42 is formed above the bottom surface of the recovery treatment liquid tank 41 in the gravity direction (Z), foreign substances such as fine metal particles contained in the recovery treatment liquid L1 can also be separated by gravity.

The recovery processing liquid tank 41 may form a guide member 44 that guides the floating of the oil component O, if necessary. The number of guide members 44 is not particularly limited, but at least one guide member 44 has one end 44a fixed to the wall surface of the recovery treatment liquid tank 41 below the gravity direction (Z) of the first discharge port 42, and the other end. It is desirable that 44b is formed so as to be inclined upward from one end 44a in the direction of gravity (Z). By arranging the guide member 44 as described above, the oil component O near the first discharge port 42 is guided by the guide member 44 and floats in the direction away from the first discharge port 42. Therefore, the possibility that the oil component O is discharged from the first discharge port 42 is reduced.

The pipe 31 of the recovery device 3 can be connected to the recovery treatment liquid tank 41 by preventing the recovery treatment liquid L1 flowing from the pipe 31 into the recovery treatment liquid tank 41 from flowing in the directions of the first discharge port 42 and the second discharge port 43. There are no particular restrictions on where to connect. Alternatively or additionally, the pipe 31 is connected so that the recovery treatment liquid L1 flowing from the pipe 31 into the recovery treatment liquid tank 41 does not directly flow in the directions of the first discharge port 42 and the second discharge port 43. A shielding member 45 may be formed in the recovery treatment liquid tank 41 near the portion. In the example shown in FIG. 2, one end 45a of the shielding member 45 is fixed to the wall surface 41a of the recovery processing liquid tank 41 on the upper side in the gravity direction (Z) from the vicinity of the connecting portion of the pipe 31, and the other end 45b is fixed to one end of the shielding member 45. It is arranged at an angle so as to be below the gravity direction (Z) from 45a. Therefore, the recovery treatment liquid L1 poured into the recovery treatment liquid tank 41 flows in the direction of the bottom surface 41b of the recovery treatment liquid tank 41. Although not shown, one end 45a of the shielding member 45 may be fixed to the upper surface 41c of the recovery processing liquid tank 41.

The metal ion removing device 5 is not particularly limited as long as it can remove the metal ion component in the oil separation treatment liquid L2 from which the oil component O has been separated by the separating device 4. For example, an apparatus including an ion exchange resin that adsorbs metal ions, an ion exchange membrane, or the like can be used.

An example of the metal ion removing device 5 will be described with reference to FIGS. 1, 2 and 3A to 3D. In the example shown in FIGS. 3A to 3D, the metal ion removing device 5 is connected to a resin tower 51 filled with an ion exchange resin, a first reservoir 52 connected to the separation device 4 and the resin tower 51, and the resin tower 51. The procedure of the example which includes the 2nd reservoir 53 and removes the dissolved metal ion by the chromatographic separation method is shown.

The chromatographic separation method is a method for separating acid ions and metal ions by utilizing the difference in affinity between the ion exchange resin and the acid ions and metal ions contained in the treatment liquid. The feature of this method is that it has a simple structure in which the ion exchange resin is filled in the resin tower 51, so that it is less affected by impurities as compared with other separation methods using a membrane, and the running cost is also low. ..

In the chromatographic separation method, first, the oil separation treatment liquid L2 in which the oil component O is separated by the separation device 4 is stored in the first reservoir 52. In the first reservoir 52, the amount of the oil separation treatment liquid L2 to be sent to the resin tower 51 is adjusted. Then, as shown in FIG. 3A, the oil separation treatment liquid L2 stored in the first reservoir 52 is sent to the resin tower 51 by a liquid feeding means such as air. The moving speed of the metal ion in the resin tower 51 is higher than that of the acid ion. Therefore, in the resin tower 51, (1) a water fraction in which metal ions and acid ions are separated, (2) a fraction containing a large amount of metal ions, and (3) a fraction containing a large amount of acid ions are fed in this order. Be liquid. In the step shown in FIG. 3A, the water fraction from which the (1) metal ion and acid ion that flowed out first from the resin tower 51 are separated is stored in the second reservoir 53 (water return step).

Next, as shown in FIG. 3B, after (1) storing the water fraction in which the metal ion and the acid ion are separated in the second reservoir 53, the valve (not shown) is switched to (2) the metal. Discard the ion-rich fraction (waste liquid step). By the disposal step, the metal ions in the oil separation treatment liquid L2 can be concentrated and then disposed of. The waste liquid step of FIG. 3B is stopped in a state where the fraction containing a large amount of (3) acid ions stays in the resin tower 51.

Next, as shown in FIG. 3C, the (1) water fraction from which the metal ion and the acid ion stored in the second reservoir 53 are separated is returned to the first reservoir 52 via the resin tower 51 (return stock solution step). ). At the time of the return stock solution step, the same amount of water as the oil separation treatment liquid L2 discarded in the waste liquid step shown in FIG. 3B is added to (1) the water fraction from which the metal ion and the acid ion are separated. .. By adding the same amount of water as the discarded separation treatment liquid L2, the amount of the treatment liquid L circulating in the metal surface treatment system can be made constant. When the recovery treatment liquid L1 is also discharged from the second discharge port 43 of the separation device 4 in addition to the floating oil component O, the same amount of water as the discharged recovery treatment liquid L1 is added to (1) metal ions. And acid ions may be added to the separated water fraction. During the water return step shown in FIG. 3A, the fraction containing a large amount of (3) acid ions is located on the connection side of the resin tower 51 with the second reservoir 53. Therefore, when the water fraction from which (1) metal ions and acid ions are separated from the second reservoir 53 is returned to the resin tower 51, most of the fractions first discharged from the resin tower 51 contain acid ions. Not included. Therefore, in the return stock solution step, the predetermined amount first discharged from the resin tower 51 is returned to the first reservoir 52.

Finally, as shown in FIG. 3D, the valve (not shown) is switched to remove the metal ions and the acid ion concentration is increased. Return to. The regeneration treatment liquid supply device 6 is not particularly limited as long as the regeneration treatment liquid can be returned to the treatment liquid tank 2, and may be formed by a pipe, a pump, or the like. The above series of operations may be performed manually, or may be automatically controlled by providing a control unit (not shown).

According to the procedure shown in FIGS. 3A to 3D, metal ions can be removed from the treatment liquid L circulating in the metal surface treatment system, and acid ions can be recycled. As for the concentration of acid ions in the circulating treatment liquid L, the sampling inspection of the treatment liquid L may be performed periodically as in the conventional case, and an acid may be added as necessary. In addition, the concentration of metal ions may also be sampled and inspected periodically to adjust the number of times metal ions are removed as shown in FIGS. 3A to 3D.

3A to 3D show an example of a chromatographic separation method using an ion exchange resin as the metal ion removing device 5. Alternatively, as the metal ion removing device 5, the device may be used by an electrolysis method using an ion exchange membrane or a diffusion dialysis method using an ion exchange membrane. The electrolysis method or the diffusion dialysis method may be carried out according to a known procedure.

Since the metal surface treatment system according to the first embodiment includes a separation device using the buoyancy of the oil component, it is not necessary to replace the filter or the like. Therefore, a small amount of the treatment liquid L in the treatment liquid tank 2, for example, about 0.01 to 1.0% of the treatment liquid L is recovered at predetermined intervals and metal ions are removed to form the treatment liquid tank 2. It has the effect that even one can operate continuously.

Further, in the metal surface treatment system according to the first embodiment, most of the acid ions can be reused. Therefore, the amount of acid such as sulfuric acid used can be reduced and the manufacturing cost can be reduced as compared with the conventional operation of exchanging the treatment liquid at predetermined time intervals. Further, unlike the conventional case, the treatment liquid L from which the metal ions have been removed can be circulated. Therefore, conventionally, when the treatment liquid is discarded, it is neutralized by using caustic soda, but the amount can be significantly reduced, so that the manufacturing cost can be reduced. Furthermore, since a predetermined amount of treatment liquid can be collected regularly and metal ions can be removed, the performance of the treatment liquid can be made more uniform, so that defective products due to alumite burning and the like can be reduced and quality can be improved (surface roughness). The pod thickness and color tone become uniform.) In addition, since the oil component separating device can be continuously operated, the metal ion removing device can also be continuously operated, so that the metal ion removing device can be miniaturized, and as a result, the metal surface treatment system can be miniaturized.

(Second Embodiment)
The metal surface treatment system according to the second embodiment will be described with reference to FIG. FIG. 4 is a diagram showing an outline of the metal surface treatment system 1b according to the second embodiment.

In the first embodiment, there was only one treatment liquid tank 2. On the other hand, in the second embodiment, two or more treatment liquid tanks 2 are provided, and the recovery device 3 can recover the treatment liquid from each of the two or more treatment liquid tanks 2a to 2e, and the treatment liquid is regenerated by the metal ion removing device. It is the same as the first embodiment except that the regenerated treatment liquid can be returned to the respective treatment liquid tanks 2a to 2e. Therefore, in the second embodiment, the points different from those in the first embodiment will be mainly described, and the repetitive description of the matters explained in the first embodiment will be omitted. Therefore, it goes without saying that the matters explained in the first embodiment can be adopted in the second embodiment even if they are not explicitly explained in the second embodiment.

In the second embodiment, a plurality of treatment liquid tanks 2 are formed, but the same device can be used for the separation device 4 and the metal ion removal device 5. Therefore, the metal surface treatment system can be miniaturized. Further, the variation in the acid concentration and the amount of metal ions in the treatment liquid in each treatment liquid tank 2 can be reduced. Therefore, even if the metal surface is treated in different treatment liquid tanks 2a to 2e, the variation in quality can be reduced.

The metal surface treatment system 1 disclosed in this application enables continuous operation. Therefore, it is useful for the metal surface treatment industry.

1, 1a to 1b ... Metal surface treatment system, 2 ... Treatment liquid tank, 3 ... Recovery device, 31 ... Pipe, 4 ... Separation device, 41 ... Recovery treatment liquid tank, 41a ... Recovery treatment liquid tank wall surface, 41b ... Recovery Bottom surface of the treatment liquid tank, 41c ... Top surface of the recovery treatment liquid tank, 42 ... First discharge port, 43 ... Second discharge port, 44 ... Guide member, 44a ... One end of the guide member, 44b ... The other end of the guide member, 45 ... Shielding member, 45a ... One end of the shielding member, 45b ... The other end of the shielding member, 5 ... Metal ion removing device, 51 ... Resin tower, 52 ... First reservoir, 53 ... Second reservoir, 6 ... Regenerative treatment liquid supply device , L ... Treatment liquid, L1 ... Recovery treatment liquid, L2 ... Oil separation treatment liquid, O ... Oil component

Claims (6)

It is a metal surface treatment system, and the metal surface treatment system is
With the treatment liquid tank,
A recovery device that recovers the treatment liquid from the treatment liquid tank, and
A separation device that separates the oil components contained in the recovery treatment liquid recovered by the recovery device, and a separation device.
A metal ion removing device for removing metal ions in an oil separation treatment liquid from which oil components have been separated by the separating device, and a metal ion removing device.
A regeneration treatment liquid supply device for returning the regeneration treatment liquid from which metal ions have been removed by the metal ion removal device to the treatment liquid tank, and a treatment liquid supply device.
Including
The separation device removes the oil component from the recovery treatment liquid by utilizing the buoyancy of the oil component contained in the recovery treatment liquid.
Metal surface treatment system. The separation device
A recovery treatment liquid tank for storing the recovery treatment liquid and
A first discharge port formed in the recovery treatment liquid tank and discharging the oil separation treatment liquid,
A second discharge port formed in the recovery treatment liquid tank and discharging an oil component floating above the recovery treatment liquid, and a second discharge port.
Including
The second discharge port is formed in the recovery treatment liquid tank on the upper side in the direction of gravity from the first discharge port.
The metal surface treatment system according to claim 1. The metal ion removing device
Ion exchange resin or
Ion exchange membrane,
The metal surface treatment system according to claim 1 or 2. The metal ion removing device
A resin tower filled with ion exchange resin and
A first reservoir connected to the separation device and the resin tower,
A second reservoir connected to the resin tower and
including,
The metal surface treatment system according to claim 1 or 2. The regeneration treatment liquid supply device includes a pipe, and one end of the pipe is connected to the resin tower.
The metal surface treatment system according to claim 4. Two or more of the treatment liquid tanks are provided.
The metal surface treatment system according to any one of claims 1 to 5.

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