JPS606717B2 - Oxidation decomposition equipment - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an oxidative decomposition device that treats pollutants contained in various liquids to be treated such as river water, industrial wastewater, and domestic wastewater by oxidizing and decomposing them. related to equipment.

Conventionally, as an oxidative decomposition device for pollutants contained in various liquids to be treated such as river water, industrial wastewater, domestic wastewater, etc., a device using a PO02 electrode made of a titanium material with Pb02 as an anode has been known. However, in this thin case, for example, the second
As shown by A in the figure, when chemical steel plating waste liquid with a COD of 13000 (side) is circulated and treated under conditions of a treatment liquid volume of 10㎆, room temperature, and 10V-2A, the COD value decreases to a value close to zero. It takes approximately 70 minutes to complete the COD
It has the disadvantage that the decomposition rate is very slow.

It is an object of the present invention to provide an oxidative decomposition apparatus which has an extremely rapid oxidative decomposition rate when oxidatively decomposing contaminants in various liquids to be treated, and which improves the drawbacks of the above-mentioned known techniques. In order to achieve the above-mentioned object, according to the present invention, a main anode and a main cathode are arranged in an electrolytic cell, and various liquids to be treated such as river water, industrial wastewater, domestic wastewater, etc. are placed in the electrolytic cell. In an oxidative decomposition apparatus that is loaded and conducts a current between the main anode and the main cathode, thereby oxidizing and decomposing contaminants contained in the liquid to be treated, the main anode in the electrolytic cell is A diaphragm is arranged at a position to form an anode chamber together with the main anode, and powdery or granular manganese dioxide is loaded into the anode chamber, and the powdery or granular manganese dioxide is electrically insulating powder. The method is characterized in that the anode is mixed with a similar substance and loaded into the anode chamber.

Hereinafter, the present invention will be explained in detail using the accompanying drawings.

Figure 1 shows a specific example of the device according to the invention. 1 is an electrolytic cell.

A main anode 5 and a main cathode 6 (made of graphite, for example) are disposed, for example, on opposite side walls of the electrolytic cell. The main anode 5 in the electrolytic cell 1 is placed between the main anode 5 and the main cathode 6 facing each other.
A diaphragm 2 is placed in a position facing the main anode 5 to form an anode chamber 4, and a mixture 3 of powdery or granular manganese dioxide and an electrically insulating granular material to be described later is filled into the anode chamber 4. , whereby mann dioxide is loaded into the electrolytic cell so as to be in contact with the main anode.

Regarding the arrangement of the above mixed particulate matter group, there are lengths and shorts in the series of the manganese dioxide (electrically conductive particulate matter) group from the main electrode plates 5 and 6, and the longer the distance in the direction of the opposite electrode, the higher the electrical resistance value. In addition, manganese dioxide (electrically conductive particulate matter) is mixed with electrically insulating particulate matter and arranged in such a way that the contact between manganese dioxide (electrically conductive particulate matter) is not completely broken, and this arrangement forms the electrode reaction surface. Moreover, the surface of each electrically conductive particulate material (manganese dioxide) can participate in the reaction with the same polarity as the main electrode Itama, 6 without causing a bipolar phenomenon.In order to achieve such advantages, The size, proportion, materials, etc. of the electrically conductive particulate matter and the electrically insulating particulate material may be determined to optimal conditions according to the characteristics of the electrolytic solution and other conditions. Electrolytic diaphragm: ion exchange membrane, synthetic resin plate with many pongee holes that do not allow powdery or granular manganese dioxide 3 to pass through, ceramic plate, terracotta plate, synthetic delicate cloth, wooden board such as plum wood, etc. Use nets, etc. be able to.

Further, the powdery or granular manganese dioxide 3 described above preferably has an average particle size of about 3 to 5, but the present invention is not limited to this particle size, and "any particle size may be used." can.

The manganese dioxide 3 is used by mixing it with electrically insulating particulate materials such as glass beads, silica gel, synthetic resin particles, ion exchange resin particles, ceramic particles, etc. in a ratio of 1:1, for example. Using the oxidative decomposition apparatus of the present invention as described above,
In order to carry out the electrode reaction, a potential difference is applied between the main electrodes 596 by an external power source, and the solution to be treated is introduced into the space where the particulate material is placed in a batchwise or continuous manner and allowed to pass therethrough.

By passing it in this way, the oxidation reaction is effectively carried out in the anode chamber 4. There are many reaction systems affected by this, but ``For example, in the anodic reaction,
○ Mi 12H++ day 20X05 10th 20-→XO prison 12
H+ (in the formula, x represents a halogen element.

) Ruu - Ichisa → S20 Zero - Mn.

Seiichi-e→Mn. Hyōjiyo + 10th mother's day 20th solar eclipse → Xr's 1118th 10P is the 11th ~ pb40 Mn2 11th → Mn4f OXy saddle n Carrier as V5 10th mother Mn218 Ce40, Czu10, etc. Oxidation of organic compounds using
Kolbe reaction: decomposition of organic cyanide halides, and others.

In addition, if we measure the increase in electrode area by simply bringing a group of electrically conductive particulate matter (manganese dioxide) into contact with the main electrode plate, the electrically conductive particulate matter on the side closer to the counter electrode will be smaller than the internal electrically conductive particulate matter. The material is extremely highly polarized and as a result, the reaction is intense on the electrically conductive particulate material near the counter electrode, resulting in a high current density - without significantly increasing the electrode area.

Therefore, in the present invention, by appropriately blending an electrically insulating particulate material group into the electrically conductive particulate material group to be brought into contact, the series of electrically conductive particulate materials from the main electrode is lengthened and shortened, and a distance is created in the direction of the opposite electrode. Considering that the electrical resistance value increases as the length of the electrical resistance increases, the electrochemical reaction proceeds almost evenly on the entire electrically conductive particulate material group. What must be noted here is that if a large number of electrically insulating particulate materials are mixed and arranged to the point where the contact between the electrically conductive particulate materials is completely cut off, the electrically conductive particulate materials The above-mentioned bipolar phenomenon is induced, and the oxidation-reduction reaction proceeds at both ends of the same particle.In the apparatus of the present invention constructed in this manner, various processing solutions to be processed are placed in the electrolytic cell 1. ? is loaded and a current of 10V-2 to 4A is applied between the main anode 5 and the main cathode 6 at room temperature, the contaminants contained in the liquid to be treated are quickly removed (for example, within 40 to 12 hours). Processed by oxidative decomposition.

The liquid to be treated by the apparatus of the present invention may include river water, industrial wastewater such as chemical steel plating waste, chemical nickel plating waste, pulp waste, soap waste, fish and shellfish processing waste, etc. These are wastewater, etc., and various types of wastewater, and the pollutants contained in these treated liquids are diverse, such as metal ions and organic substances.

Hereinafter, the present invention will be explained in more detail with reference to Examples.

Example 1 Using the apparatus shown in FIG.
5 kg of a mixture of powdered or granular manganese dioxide and glass beads (mixing ratio 1:1) was loaded so as to be in contact with the main anode 5.

Such an electrolytic cell of the device of the present invention! When 10 times of chemical copper coating waste liquid with a COD of approximately 12,000 (willow) was filled into the chamber as the liquid to be treated 7 and the circulation treatment was performed under the conditions of room temperature and current of 10V-2A, the COD value was determined after approximately 4 field hours. has fallen to almost zero.

(This state is indicated by B (broken line) in FIG. 2.) This reduction in processing time is due to the following reason.

That is, in the present invention, as mentioned above, manganese dioxide (
Since we mixed glass beads (electrically insulating particulate materials) with electrically conductive particulate materials at a mixing ratio of 1:1 to form a series of electrically conductive particulate materials from the main electrode, the total Electrochemical reactions proceed almost uniformly on the group of air-conducting particulate materials, significantly expanding the electrode surface area, that is, the reaction field, and improving processing efficiency. For comparison, titanium material P
When a similar experiment was conducted using a conventional device using the b02 electrode as an anode, the results shown by the solid line (curve) A in FIG. 2 were obtained.

That is, in the conventional apparatus, it took approximately 700 hours of processing time to reduce the COD value to zero. Second
As is clear from the figure, the processing time of the apparatus of the present invention is much faster compared to the conventional apparatus.

Example 2 Using the apparatus of the present invention shown in FIG. 1, 10k9 of a mixture of powdered or granular manganese dioxide with an average particle size of 3 to 5 and glass beads (mixing ratio i:1) was placed in the anode chamber 4. It was loaded so as to be in contact with the anode 5.

As the diaphragm 2, a synthetic resin plate with many pongee holes was used. First, 20% of CODIOOOO (skin) chemical steel plating waste liquid was added as the treatment liquid 7 into the electrolytic bath 1 of the apparatus of the present invention.
When the treatment was carried out under the conditions of "normal temperature" and a current of 10 V and 40 A, the COD value decreased to almost zero after only about 4 steps had passed. (This state is shown in Figure 3. show.
) Furthermore, when chemical nickel plating waste liquid with a COD of 50,000 (blood) was treated using the same equipment and conditions as described above, the COD value decreased to zero after only 12 feeding hours.

(See FIG. 3) The reason for this is the same as in Example 1. As described above, the apparatus of the present invention can treat contaminants in various types of treatment liquids extremely quickly, and is extremely useful in practice.

[Brief explanation of the drawing]

Fig. 1 shows a specific example of the apparatus of the present invention, and Fig. 2 shows a graph of comparative experimental data of COD processing using the apparatus of the present invention and a conventional apparatus. The graph is shown. 1... Electrolytic cell, 2... Separate, 3...
・Mixture of powdered or granular manganese dioxide and electrically insulating granular material, 4... anode chamber, 5... main anode,
6... - Half cathode, 7... He treatment solution. Shigeru 1 drawing, 2 drawings, 2 drawings

Claims (1)

[Claims] 1. Consists of a main anode and a main cathode arranged in an electrolytic cell. Various liquids to be treated such as river water, industrial wastewater, domestic wastewater, etc. are loaded into the electrolytic cell, and a current is applied between the main anode and the main cathode. In an oxidative decomposition device that oxidizes and decomposes contaminants contained in the liquid to be treated by applying electricity, a diaphragm is disposed in a position facing the main anode in the electrolytic cell, A chamber is formed, and powdered or granular manganese dioxide is charged into this anode chamber, and the powdered or granular manganese dioxide is mixed with an electrically insulating powdery substance and charged into the anode chamber. Oxidation decomposition equipment.