JP2001158987A - Alkaline permanganate solution electrolytic regeneration equipment - Google Patents

Abstract

(57) [Problem] To provide an alkaline permanganate solution electrolytic regenerating apparatus having a further improved regenerating efficiency than that proposed by the present applicant and already patented. SOLUTION: An anode 2 of a honeycomb type cylindrical body is disposed in a tank body into which an alkali permanganate solution flows, and a part of the surface of the cylindrical body is electrically disconnected by a rod-shaped conductor at the center of each cylindrical body. A cathode coated with a conductor was arranged, the area ratio between the cathode and the anode was set to 1:40 to 1: 1000, and the tank body was connected to a desmear treatment tank by a circulation circuit having a liquid circulation pump. In the alkaline permanganate solution electrolytic regenerating apparatus, a plurality of cuts are made in the side surface of each cylindrical body constituting the anode 2, and a part of the side surface is projected inside the cylindrical body using these cuts. 2a and convex portions 2b protruding outward were formed alternately.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrolytic regeneration apparatus for converting a manganate into a permanganate, and more particularly, to an apparatus for electrically oxidizing manganate generated in an alkaline permanganate solution. And a regenerating apparatus for regenerating permanganate.

[0002]

2. Description of the Related Art Generally, a corrosive solution used in a processing step for manufacturing a printed circuit board is an alkaline solution containing permanganate as an oxidizing agent. It is known that acid salt precipitates accumulate as degraded wounds, resulting in a reduced capacity of the corrosive fluid. For example, in a manufacturing process of a multilayer wiring printed circuit board, a connection failure occurs when a resin (smear) melted by frictional heat generated by drilling adheres to a cross section of an inner layer circuit in a hole. Therefore, in order to remove this smear, the smear is removed using an alkali permanganate solution.However, by treating the printed circuit board, the permanganate changes to manganate, and further reaction occurs If it proceeds, it will become manganese dioxide sludge.

Accordingly, several methods have been found to regenerate permanganate at the manganate stage so as not to generate sludge of manganese dioxide. As the method, a method using a regenerating agent (US Pat.
No. 852) Single-cylinder electrode-type electrolytic regenerator (as shown in FIG. 6, a cathode cylinder 62 is provided in the center of a pair of porous cylinders 61 and an anode rod 63 around it) No. 1,294,882) is known.

However, sludge is simultaneously generated in the conventional method using a regenerant, and the electrolytic regeneration efficiency with respect to electric current is 10 to 15 in a single-tube electrode type electrolytic regeneration apparatus.
%, And the regeneration efficiency is improved in the partition electrode type electrolytic regeneration device, but the solution to be regenerated on the anode side and the aqueous solution of the alkali metal hydroxide on the cathode side are gradually mixed. However, the reproduction efficiency was poor and the reproduction efficiency was poor.

Accordingly, the present applicant has proposed an invention which solves the above-mentioned problem, and has already obtained a patent (Japanese Patent No. 283).
No. 5811). The invention of this application is disclosed in Japanese Patent No. 2835811
Therefore, specific examples of the invention will be described with reference to FIGS.

[0006] The configuration of the apparatus for regenerating manganate to permanganate according to the above-mentioned patent invention is such that a plurality of electrodes comprising a cathode 1 and an anode 2 are placed in a tank body 3 into which an alkali permanganate solution flows. In an electrolytic regenerator installed opposite to the immersion state, the cathode 1 is composed of a rod-shaped conductor, a part of its surface is covered with a non-conductor ₁₁ , and the anode 2 is formed of a plurality of (square) cylindrical bodies. A cathode 71 is provided at the center of the cylindrical body and the anode 2 is formed.
And the cathode 1 are disposed in close proximity to each other, the area ratio between the cathode 1 and the anode 2 is set to 1:40 to 1: 1000, and the tank body 3 is supplied to the desmear treatment tank 4 containing the alkali permanganate solution 5 by a liquid circulation pump. 6 and a return path 8 are connected by piping (see FIG. 7).

[0007] What cathode 1 is a rod-shaped electrode made of conductive material such as copper, which partially coated (TM. Hereinafter the same. Polytetrafluoroethylene DuPont) non conductor 1 _1, such as Teflon , For example, total length 1000 mm
In this example, a Teflon-coated portion (non-conductive portion) 43 mm and a non-coated portion (conductive portion) 7 mm are alternately formed over 850 mm below a copper rod having a diameter of 3 mm. I have.

A plurality of cathodes 1 penetrate through fitting holes 14 of a plastic support plate 10 made of Teflon or the like, are connected and supported by a copper- (minus) connection plate 21, and are screwed to a honeycomb-shaped anode 2. A connecting rod 20 having a hole is welded, and its tip end is fixed with a nut 19 through the fitting hole 15 of the support plate 10 (see FIGS. 8 and 9). In addition, anode 2
Has a honeycomb shape in which a plurality of circular or square cylindrical bodies are assembled, and the cathode 1 is arranged at the center of each cylindrical body (see FIG. 11).

The connecting rod 20 and the -connecting plate 21 are connected to each terminal with a-+ connecting cable connected to the rectifier 9 so that the support plate 10 can properly maintain the electrodes of the cathode 1 and the anode 2. The support plate 10
Are integrated into the upper lid 30 (FIGS. 10 and 11).
reference).

As shown in FIG. 11, the supporting plate 10 is provided with fitting holes 14 and 15 for connecting and connecting the connecting rods 20 of the bar-shaped cathode 1 and the anode 2, respectively. Although the connection cable is connected to the connection rod 1 and the connection rod 20, the connection rod may be connected to the end of each rod via a terminal strip. The rod-shaped cathode 1 is fixed to the connection plate 21 with a nut 12 and is incorporated in the support plate 10.

Reference numeral 19 in FIG. 11 is used for fixing the connecting rod 20 with a mounting nut. 7 and 9, reference numeral 25 denotes a sludge discharge valve, reference numerals 26, 27, and 28 denote control valves, and reference numeral 29 denotes an electrode cover which is provided on the support plate 10 as necessary. Reference numeral 30 denotes an upper cover body, which bolts the support plate 10 and the connection plate 21 to the support tank body 3.

In this case, the electrolytic regeneration at 100 A for 32.5 hours under the initial conditions shown in Table 3 in the example of FIG. 7 was as follows. Analysis of the solution in the tank resulted in potassium permanganate 44.71 g / l potassium manganate 5.52 g / l, 9288 g permanganate compared to the initial stage.
(I.e., 25.24 g / l) while manganate decreased by 8721 g / l (i.e., 23.70 g / l).

[0013]

[Table 3]

In addition, the electrolytic regeneration efficiency with respect to the current at the manganate concentration was as shown in Table 4. Therefore, an electrolytic regeneration efficiency of about 50% can be obtained up to a manganate concentration of 15 g / l. Further, since the equilibrium point of the manganate concentration by electrolytic regeneration is suppressed to a low concentration of 5 g / l, sludge of manganese dioxide generated by further reaction from the manganate can be suppressed.

[0015]

[Table 4]

As described above, the present invention is intended to easily eliminate these conventional disadvantages, and has provided a regenerating apparatus for remarkably improving the efficiency of electrolytic regeneration from manganate to permanganate.

[0017]

In the case of the electrolytic regeneration apparatus according to the above-mentioned patent invention, although the regeneration efficiency is greatly improved as compared with the conventional one, it is only 50% at the maximum, so that the regeneration efficiency is further improved. Is required.

An object of the present invention is to provide an apparatus for electrolytically regenerating an alkaline permanganate solution which has a further improved regeneration efficiency than that proposed by the present applicant and already patented.

[0019]

To solve the above problems, the following means are employed. That is, in the present invention, an anode of a honeycomb-type cylindrical body is arranged in a tank body into which an alkaline permanganate solution flows, and a part of the surface is partially covered with a rod-shaped conductor at the center of each cylindrical body. A cathode coated with an electric conductor is arranged, the area ratio between the cathode and the anode is set to 1:40 to 1: 1000, and the tank body is connected to a desmear treatment tank by a circulation circuit having a liquid circulation pump. In the alkaline permanganate solution electrolytic regeneration apparatus, a plurality of cuts are made in the side surface of each cylindrical body constituting the anode, and a concave portion in which a part of the side surface is projected inside the cylindrical body using these cuts. And convex portions protruding outward are formed alternately.

[0020]

With the above construction, an alkaline permanganate solution containing manganate generated by electro-oxidation is placed in the tank body, and when current is applied while the positive and negative electrodes are immersed, The solution in the tank can be circulated in and out of the honeycomb-shaped cylinder through the unevenness formed by using the notch on the side face of the honeycomb-shaped cylinder serving as the anode, so that the electrolytic regeneration action is improved and permanganic acid is improved. Salt regeneration efficiency can be increased.

[0021]

Embodiments of the present invention will be described below with reference to the drawings. Since the alkaline permanganate solution electrolytic regeneration apparatus according to the present invention is an improvement of the invention of Japanese Patent No. 2835811 by the present applicant, only the improvements will be described, and the other parts will be described in the section of the prior art. The parts described above will be referred to, and the same or corresponding members will be denoted by the same reference numerals and description thereof will be omitted. 1 to 5
Is the improvement of the alkaline permanganate solution electrolytic regenerating apparatus according to the present invention over the conventional apparatus, that is, the anode 2
FIG. 1 is an exploded perspective view of the anode 2, FIG. 2 is a plan view, FIG. 3 (a) is a cross-sectional view taken along line AA of FIG. 2, (b) is a cross-sectional view taken along line BB, FIG. FIG. 5 is a diagram showing a modification of the anode.

As shown in FIG. 1, the anode 2 is formed of a honeycomb cylindrical body, and a plurality of cuts are formed on the side of each cylindrical body. The concave portions 2a and the convex portions 2b are formed by projecting the portions alternately inside and outside the cylindrical body. FIG. 2A shows the anode 2 of FIG.
Is a sectional view taken along line AA, and FIG. 2B is a sectional view taken along line BB. In this example, the plate thickness t of the anode 2
= 1 mm, length l = 400 mm, length L1 of recess 2a =
10 mm, the length L2 of the convex portion 2b is 7.5 mm, and the width W between the top surface of the concave portion 2a and the top surface of the convex portion 2b is 8 mm.

The anode 2 is set as in the conventional example shown in FIG. 7 and compared with the conventional example in FIG. An alkaline permanganate solution containing manganate generated by electro-oxidation, that is, a test solution shown in Table 1 is allowed to flow, and a DC voltage is applied between the cathode 1 and the anode 2 to cause a current to flow. And the regeneration efficiency with respect to the electric current was measured from the concentration analysis every two hours. The regeneration efficiency with respect to the current is defined as the regeneration efficiency of 100 g when the regeneration amount of permanganate after 1 hour at a current of 1 A is 5.9 g.
%.

[0024]

[Table 1]

The results are shown in Table 2.

[0026]

[Table 2]

From the results shown in Table 2, it was confirmed that the electrolytic regeneration apparatus according to the improved type has a higher electrolytic regeneration efficiency by 5% to 20% than the conventional electrolytic regeneration apparatus of the present invention. Was done. The reason for this is that since each cylinder of the conventional anode was a straight body, liquid circulation inside and outside the cylinder was not so much possible, so that the electrolytic regeneration efficiency was at most 50%. A plurality of cuts were made, and using these cuts, a concave portion having a part of the side surface protruding inside the cylindrical body and a convex portion protruding outward were formed alternately. Thus, the solution could be circulated, and the electrolytic regeneration efficiency was improved.

In the above embodiment, the concave portion 2a and the convex portion 2b
Are projected to the inside and outside of the tube like a Kamaboko roof, but may be a concave portion 2a ′ and a convex portion 2b ′ as shown in FIG. 4, or a concave portion 2a ″ as shown in FIG.
The projection 2b '' may be used. Further, in the above embodiment, the anode 2 is a honeycomb-type cylinder, but is not limited thereto.
Even in the case of a cylinder, a square tube, or the like, a similar cut can be made in the side surface to form irregularities, thereby improving the reproduction efficiency.

[0029]

As described above, according to the present invention,
Since the electrolytic regeneration efficiency of permanganate with respect to the electric current is extremely good, the number of electrolytic regeneration devices can be reduced, so that the cost can be reduced and the sludge of manganese dioxide can be reduced.

[Brief description of the drawings]

FIG. 1 is a perspective view showing an embodiment of an anode section of an alkaline permanganate solution electrolytic regeneration apparatus according to the present invention.

FIG. 2 is a plan view of an anode.

3A is a cross-sectional view taken along line AA of FIG. 2, FIG.
Is a sectional view taken along line BB.

FIG. 4 is a modified example of the anode side surface, (a) is a schematic side view,
(B) is a schematic sectional view along the line CC.

FIG. 5 is a schematic side view of a modification of the side surface of the anode, and FIG. 5B is a schematic cross-sectional view taken along line CC of FIG.

FIG. 6 is a perspective view of a conventional electrolytic regeneration device.

FIG. 7 is a system explanatory diagram of the electrolytic regenerating apparatus which is the patent invention of the present applicant.

FIG. 8 is a plan view of the electrode shown in FIG. 7;

FIG. 9 is a partially cut-away side view of FIG. 8;

FIG. 10 is an exploded perspective view of a cathode section.

FIG. 11 is an exploded perspective view of an anode unit.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Cathode 2 Anode 2a Concave part 2b Convex part 3 Tank main body 4 Desmear processing tank 5 Alkaline permanganate solution 6 Liquid circulation pump 7 Path 8 Return path 9 Rectifier 10 Support plate 20 Connection rod 21-Connection plate 30 Top cover

Continued on the front page (72) Inventor Hiromi Shono 4-1-1, Motofujisawa, Fujisawa-shi, Kanagawa Prefecture Ebara Electric Industry Co., Ltd. (72) Inventor Kazunori Senbiki 4-1-1, Motofujisawa, Fujisawa-shi, Kanagawa Stock F term (reference) of Ebara Densan 4K011 AA13 CA04 CA05 CA11 DA08 4K021 AB15 AB18 BA01 BC02 BC03 CA02 CA10 DC15 EA03

Claims (1)

[Claims] An anode of a honeycomb type cylindrical body is disposed in a tank body into which an alkali permanganate solution flows, and a part of the surface of the cylindrical type cylindrical body is electrically disconnected by a rod-shaped conductor. Along with disposing a cathode coated with a conductor, the cathode and the anode are configured to have an area ratio of 1:40 to 1: 1000,
And in the alkaline permanganate solution electrolysis regeneration apparatus in which the tank body is connected to a desmear treatment tank by a circulation circuit having a liquid circulation pump, a plurality of cuts are made in the side surface of each cylindrical body constituting the anode, and these cuts are made. An alkaline permanganate solution electrolytic regenerating apparatus characterized in that concave portions each having a part of the side surface protruding inside the cylindrical body and convex portions each protruding outward are alternately formed by utilizing the method.