JP2010095737A - Oxidation device for surface of solid organic matter - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an oxidation device for the surfaces of solid organic matters using ozone water, which attains the acceleration of ozone oxidation and the suppression of ozone decomposition in combination. <P>SOLUTION: The device is provided with: a pretreatment tank 1 packed with an ozone oxidation accelerator; and an ozone treatment apparatus 2 having an ozone water treatment tank 3. The pretreatment tank 1 is filled with an ozone oxidation accelerator Q, and workpieces P are held by a plurality of fixing holders 4 capable of reciprocating between the pretreatment tank 1 and the ozone water treatment tank 3 by a driving apparatus not shown in the figure. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an apparatus for oxidizing a surface of a solid organic material such as a synthetic resin, and in particular, by an accelerated oxidation method using ozone water, it is possible to efficiently oxidize the surface of a solid organic material while suppressing waste due to ozone self-decomposition. The present invention relates to an oxidizer.

  A roughening treatment with sulfuric acid / chromic acid is performed as a pretreatment for the electroless plating of a solid organic material such as a plastic molded article. However, the waste water after the roughening treatment with sulfuric acid / chromic acid contains harmful chromium. For this reason, the wastewater containing chromium has a problem that wastewater treatment such as reduction, neutralization, and coagulation precipitation is required, and the precipitate also contains chromium and cannot be easily discarded.

  Therefore, various methods for modifying the surface of the plastic molded article by using ozone instead of the roughening treatment with chromic acid have been studied. Oxidation methods using ozone include a method in which ozone itself acts effectively as an oxidizing agent depending on the solid organic matter to be treated, and a hydroxyl radical (.OH) that has a high oxidizing power generated during the ozone decomposition process. And a method for effectively acting a radical as an oxidizing agent.

Among these methods, in the method in which ozone itself acts effectively as an oxidizing agent, it is effective to suppress the self-decomposition of ozone and to keep the ozone concentration in the reaction field high to promote the oxidation reaction. . Specifically, in order to maintain the ozone concentration high, the hydrogen ion concentration of ozone water is increased and maintained in an acidic region. This is because OH ⁻ ions and hydroxy radicals (.OH) have an effect of promoting the self-decomposition of ozone against the self-decomposition of ozone.

Therefore, for the purpose of suppressing OH ⁻ ions and hydroxy radicals (.OH), a method of oxidizing a plastic molded article using an aqueous hydrogen carbonate compound solution in which ozone is dissolved in advance has been proposed (Patent Document 1). reference).

  Moreover, after making a plating raw material contact the 1st solution containing ozone, the pre-processing method of making it contact with the 2nd solution containing an alkaline component is proposed (refer patent document 2, 3).

Furthermore, a pretreatment method has been proposed in which an ultraviolet irradiation treatment is performed while bringing a plating material into contact with an ozone solution (see Patent Documents 4 and 5).
JP 2001-131759 A JP 2004-131805 A JP 2005-68497 A JP 2004-315894 A JP 2005-68495 A

  However, the method of oxidizing the surface of a plastic molded article using ozone water disclosed in Patent Document 1 suppresses the self-decomposition of ozone by capturing radicals with an aqueous hydrogen carbonate compound solution. There is a problem that the ozone chain decomposition reaction is difficult to occur, and the plastic molded product cannot be oxidized efficiently.

  On the other hand, it is preferable to suppress the self-decomposition of ozone in order to maintain the effect for a long period of time even in a method in which radicals such as hydroxy radicals (.OH) caused by ozone effectively act as an oxidizing agent. Suppressing the self-decomposition of ozone also suppresses the generation of radicals, and is therefore not necessarily effective in terms of oxidation of the solid organic matter surface.

  Further, in the plating material pretreatment methods disclosed in Patent Documents 2 and 3, since the contact is made with the first solution containing ozone and then the contact with the second solution containing the alkali component, the plating material made of the alkali component is used. Although there is an effect of removing the embrittlement layer on the surface, the promotion of ozone oxidation may not be sufficient.

  Furthermore, in the pretreatment method of the plating material disclosed in Patent Documents 4 and 5, since the ultraviolet ray irradiation treatment is performed while the plating material is in contact with the ozone solution, hydroxy radicals (.OH) caused by ozone are efficiently removed. However, it may be difficult to maintain the effect for a long time and may not be suitable for some applications.

  Thus, conventionally, there has been no oxidation apparatus for the surface of a solid organic substance using ozone water that has both the promotion of ozone oxidation and the suppression of decomposition of ozone.

  An object of the present invention is to solve the above-described conventional problems and to provide a solid organic matter surface oxidation apparatus using ozone water that has both the promotion of ozone oxidation and the suppression of decomposition of ozone.

  In order to solve the above problems, the present invention comprises a pretreatment means for wetting the surface of a solid organic substance with an ozone oxidation accelerator, and an ozone treatment apparatus having an ozone water treatment tank, and the solid organic matter is treated with the pretreatment means. Then, a solid organic matter surface oxidizing apparatus is provided, which is immersed in an ozone water treatment tank (claim 1).

  According to the above invention (invention 1), in the pretreatment means, the surface of the solid organic substance is wetted with an ozone oxidation accelerator and is immersed in an ozone water treatment tank so as to promote the self-decomposition of the ozone. Is attached only to the surface of the solid organic matter, so that excessive self-decomposition of ozone present in the solvent in the ozone water treatment tank is suppressed, and the ozone concentration of the ozone water in the reaction tank is maintained at a sufficient value. Can do. On the other hand, the ozone oxidation promoter starts active ozone self-decomposition reaction near the surface of the solid organic matter and generates hydroxyl radicals effective for oxidation on the surface of the solid organic matter. It can be done efficiently.

  In the said invention (invention 1), it is preferable that the said ozone oxidation promoter is at least 1 sort (s) chosen from the group which consists of surfactant solution, hydrogen peroxide solution, and alkaline solution (invention 2).

  According to the said invention (invention 2), the active self-decomposition reaction of ozone can be started in the surface vicinity of solid organic substance by the effect of the hydroxy ion of these solutions.

  In the said invention (invention 1,2), the immersion tank of the said ozone oxidation accelerator solution or the spray apparatus of the said ozone oxidation accelerator solution can be used as the said pre-processing means (invention 3). According to this invention (invention 3), only the surface of the solid organic substance can be effectively wetted with the ozone oxidation accelerator solution.

  In the said invention (Invention 1-3), when the ozone generator and the ozone gas which generate | occur | produced in this ozone generator were dissolved in raw water as said ozone treatment apparatus, it was manufactured with this ozone dissolver and this ozone dissolver What has a supply means which supplies ozone water to the said ozone water processing tank can be used (Claim 4).

  According to the above invention (invention 4), since high-concentration ozone water can be supplied to the ozone water treatment tank, the surface of the solid organic matter can be efficiently oxidized, and such an effect can be obtained for a long time. Can be held.

  In the said invention (invention 4), it is preferable to have a hydrogen ion concentration adjustment means in the front | former stage or back | latter stage of the said ozone dissolving apparatus (invention 5). According to this invention (invention 5), the self-decomposition of ozone in the produced ozone water can be suppressed, and the ozone concentration can be maintained at a high concentration for a long time.

  Further, in the above inventions (inventions 4 and 5), the ozone water treatment tank is provided with an ozone water discharge mechanism, and the discharged ozone water joins the raw water side via the ozone water discharge mechanism. Preferred (claim 6).

  According to the said invention (invention 6), ozone water can be efficiently manufactured in an ozone dissolution apparatus by recovering ozone water in an ozone water treatment tank and reusing it as raw water of ozone water again.

  In the said invention (invention 1-6), it is preferable that the said ozone water processing tank has a stirring means (invention 7). According to this invention (Invention 7), the ozone concentration locally decreases due to the self-decomposition of ozone on the surface of the solid organic matter, but the vicinity of the surface of the solid organic matter is obtained by stirring the inside of the ozone water treatment tank with the stirring means. The ozone water can be replaced and maintained at a high concentration, and the attenuation of the oxidation reaction due to the self-decomposition of ozone can be suppressed.

  In the said invention (invention 1-7), it is preferable to have the defoaming mechanism of the solid organic substance surface in the said ozone water treatment tank (invention 8). According to this invention (invention 8), it is possible to prevent non-uniform oxidation of the surface of the solid to be treated due to the bubbles generated during the oxidation of ozone remaining on the surface of the solid organic matter.

  In the above invention (invention 8), at least one selected from the group consisting of water jetting means, mechanical vibration means and ultrasonic vibration means can be used as the defoaming mechanism on the surface of the solid organic matter (invention). 9). According to this invention (invention 9), the bubbles adhering to the surface of the solid organic matter can be easily and efficiently removed.

  The solid organic matter surface oxidation apparatus of the present invention comprises pretreatment means for wetting the solid organic matter surface with an ozone oxidation accelerator and an ozone treatment apparatus having an ozone water treatment tank, and after treating the solid organic matter with the pretreatment means, Since it is immersed in the ozone water treatment tank, the surface of the solid organic matter can be wetted with an ozone oxidation accelerator in the pretreatment means, and this can be immersed in the ozone water treatment tank. As a result, the pH in the ozone water treatment tank can be made acidic so that the self-decomposition of ozone can be suppressed, so that the ozone concentration can be kept high, while the oxidation of ozone that wets the surface of solid organic matter is accelerated. By virtue of the active agent, active ozone self-decomposition reaction is initiated, and hydroxyl radicals effective for oxidation are generated on the surface of the solid organic material, so that the surface of the solid organic material can be oxidized efficiently.

Embodiments of the present invention will be described below in detail with reference to the drawings.
FIG. 1 is a flowchart showing an apparatus for oxidizing a solid organic matter surface according to an embodiment of the present invention.

  In FIG. 1, an oxidation apparatus for the surface of a workpiece P made of synthetic resin, which is a solid organic substance, includes a pretreatment tank 1 filled with an ozone oxidation accelerator Q as a pretreatment means, and an ozone treatment apparatus 2 having an ozone water treatment tank 3. Is provided.

  The plurality of workpieces P are respectively held by the fixing holder 4 in the pretreatment tank 1 and can reciprocate between the pretreatment tank 1 and the ozone water treatment tank 3 by a driving device (not shown). .

  The plurality of fixing holders 4 are arranged in an ozone water treatment tank 3 to be described later so that the work P does not hinder the stirring flow of ozone water to the adjacent work P.

The ozone treatment apparatus 2 includes a PSA type oxygen concentrator 5 that concentrates oxygen in the air, and an ozone production apparatus 6 that produces ozone from oxygen concentrated in the oxygen concentrator 5. The ozone gas (O ₃ ) produced by the device 6 is supplied to the ejector 12 of the first supply line 7 described later.

  On the other hand, an acid addition device 9 as a hydrogen ion concentration adjusting means, an inlet pump 11, and an ejector 12 as an ozone dissolving device are sequentially provided in the first supply pipeline 7, and the first supply pipeline 7 7 is connected to the gas-liquid separator 13 on the downstream side of the ejector 12. The raw water W is supplied to the ejector 12 via the first supply pipe 7, and ozone water in which ozone supplied from the ozone manufacturing apparatus 6 is dissolved is manufactured by the ejector 12. A second supply pipe 8 is connected to the gas-liquid separator 13, and these constitute a supply means for the ozone water W0.

  In addition, an ozone gas discharge pipe 14 is connected to the gas-liquid separator 13. In addition, 15A and 15B are open / close valves, respectively, and 23 is an exhaust ozone gas decomposition treatment apparatus.

  Furthermore, the upper edge of the ozone water treatment tank 3 is provided with a first overflow receiving part 16 and a second overflow receiving part 17, and the ozone water W1 flowing into the first overflow receiving part 16 is Then, the water is returned to the upstream side of the acid addition device 9 in the first supply line 7 through the reflux line 18, and the first overflow receiving portion 16 and the reflux line 18 constitute an ozone water discharge mechanism.

  On the other hand, the ozone water W2 that has flowed into the second overflow receiver 17 is heat-exchanged by the heat exchanger 21 via the circulation line 19 and the circulation pump 20, and then circulates between the ozone water treatment tanks 3. Some blow.

  The ozone water treatment tank 3 is provided with a rotating impeller 22 as a stirring means at the bottom, and mechanical vibration means (not shown) that can vibrate the workpiece P as a defoaming mechanism. ) Is provided. Further, the ozone water treatment tank 3 is provided with an ozone concentration meter and a pH sensor (not shown).

  In the apparatus as described above, as the ozone oxidation accelerator Q filled in the pretreatment tank 1, an alkaline solution and a surfactant solution in which hydroxy ions exist can be used.

As the alkali, for _{example, NaOH, KOH, Na 2 CO} 3, K 2 CO 3 and the like. This alkaline solution preferably has a pH of 7 to 12 and is adjusted to a concentration such that the pH of the ozone water treatment tank 3 does not easily exceed 6, even if a small amount is mixed in the ozone water treatment tank 3.

  As the surfactant, those having a saturated hydrocarbon skeleton having 4 to 12 carbon atoms and having a structure showing alkalinity when made into an aqueous solution are preferable. If such an alkaline surfactant is used, it is not necessary to add the inorganic alkali described above separately. Specific examples of such surfactants include aliphatic monocarboxylates. Further, the hydrocarbon skeleton of the surfactant may be linear or branched.

  Furthermore, hydrogen peroxide water can also be used as the ozone oxidation accelerator Q. When hydrogen peroxide water is used as the ozone oxidation accelerator Q, it may be used in combination with the inorganic alkali as described above, or hydrogen peroxide water alone.

Further, the ozone concentration of ozone water W0 in the ozone water treatment tank 3 is preferably kept _{20mg-O 3 / L (pH5} ) ~50mg-O 3 / L (pH2). If the ozone concentration is less than 20 mg-O ₃ / L, the surface of the synthetic resin workpiece P is not sufficiently oxidized, and, for example, the adhesion of plating in a subsequent plating step or the like may be reduced, which is not preferable. . As for the upper limit, the saturated concentration of ozone cannot be exceeded.

Next, the operation of the solid organic matter surface oxidation apparatus having such a configuration will be described. First, the raw water W is supplied to the first supply pipe 7 by the inlet pump 11 and is adjusted to be acidic by the acid addition device 9. As the acid used at this time, sulfuric acid, hydrochloric acid, nitric acid, organic acid, or the like can be used. Specifically, it is preferable to adjust the pH of the raw water W to 2-5. Thus, self-decomposition of ozone water W0 produced in the ejector 12 is _{suppressed, 20mg-O 3 / L (} pH5) the ozone concentration of ozone water W0 in the ozone water treatment tank _{3 ~50mg-O 3 / L (} pH2 ) Can be maintained.

  In addition, the lower the temperature of the raw water W, the more advantageous it is to dissolve and maintain ozone at a high concentration. On the other hand, the higher the temperature, the faster the oxidation reaction rate. The temperature is preferably 20 to 40 ° C.

In parallel with this, oxygen in the air is concentrated by the PSA type oxygen concentrating device 5, ozone is then produced from the concentrated oxygen by the ozone producing device 6, and the produced ozone gas (O ₃ ) is supplied to the ejector 12. Supply.

  As a result, the ozone gas is dissolved in the raw water W by the ejector 12 and gas-liquid separation is performed by the gas-liquid separator 13 into the ozone water W0 and the exhausted ozone gas, and then the ozone water W is supplied from the second supply pipe 8 to the ozone water treatment tank 3. On the other hand, the exhausted ozone gas is decomposed by the exhausted ozone gas decomposition processing device 23 through the ozone gas exhaust pipe 14 and then exhausted.

  When the ozone water treatment tank 3 is filled with a predetermined amount of ozone water W0, the synthetic resin work P is immersed in the pretreatment tank 1 filled with the ozone oxidation accelerator Q, and the surface is exposed to the ozone oxidation accelerator. Wet with Q, then pull up the holding fixture 4 and immerse the workpiece P in the ozone water treatment tank 3. Then, since the surface of the work P is wet with the ozone oxidation accelerator Q, active self-decomposition reaction of ozone in the ozone water W0 in the ozone water treatment tank 3 is started by the effect of the hydroxy ions. As a result, since a hydroxyl radical effective for oxidation is generated on the surface of the work P, the surface of the work P can be efficiently oxidized.

  In addition, in the oxidation treatment with hydroxy radicals accompanying the decomposition of ozone, ozone is rapidly consumed on the surface of the workpiece P. Therefore, it is necessary to promptly perform mass transfer for supplying radicals into the laminar boundary layer. Therefore, it is necessary to keep the slip speed of the ozone water on the surface of the workpiece P high. Therefore, in the present embodiment, the impeller 22 is provided at the bottom of the ozone water treatment tank 3 and the ozone water in the ozone water treatment tank 3 is stirred to form a circulation flow, thereby continuously supplying ozone water in contact with the workpiece P. Thus, the oxidation by the hydroxy radical is maintained.

  Further, when the ozone water W0 prepared in advance enters the ozone water treatment tank 3 which is an open system, the gas-liquid equilibrium relationship is lost, and bubbles are generated due to the partial diffusion of ozone. In addition, since ozone that has acted on the oxidation reaction by the hydroxyl radical becomes oxygen with low solubility, oxygen bubbles are also generated. As a result, some of these bubbles generated on the surface of the workpiece P may adhere to the surface of the workpiece P and not be detached. Thus, there is a possibility that the part where the bubbles are attached may hinder the uniform oxidation treatment of the surface by the hydroxyl radical. Therefore, in the present embodiment, by providing the ozone water treatment tank 3 with mechanical vibration means that can vibrate the workpiece P as a defoaming mechanism, such bubble adhesion is avoided.

  The immersion time of the workpiece P in the ozone water treatment tank 3 as described above may be about 2 to 30 minutes although it depends on the ozone concentration of ozone water. When the surface of the workpiece P is oxidized in this way, the fixing holder 4 is pulled up, the workpiece P is removed and dried, and a desired process such as electroless plating may be performed.

  On the other hand, during the above operation, ozone water is continuously supplied from the second supply pipe 8 so that the dissolved ozone concentration of the ozone water in the ozone water treatment tank 3 does not decrease. For this reason, the ozone water W0 overflows the ozone water treatment tank 3. Therefore, the ozone water W1 that has flowed into the first overflow receiving portion 16 is recirculated to the upstream side of the acid addition device 9 of the first supply line 7 via the recirculation line 18 and reused. The ozone water W2 flowing into the overflow receiving part 17 is heat-exchanged by the heat exchanger 21 via the circulation line 19 and the circulation pump 20, and then circulated between the ozone water treatment tanks 3 and partially blown. Therefore, it is preferable to make effective use of ozone water.

  In addition, as solid organic substance used as the workpiece | work P, a synthetic resin is common, and as such a synthetic resin, if it oxidizes with ozone, it will not specifically limit, For example, ABS resin, Examples include polypropylene, polyamide, polycarbonate, polyacetal, polyester, noryl and the like. Furthermore, as long as it is oxidized by ozone, it is applicable also to solid organic substances other than a synthetic resin. The solid organic matter whose surface has been oxidized in this way is suitable as a molded article to be subjected to a plating treatment such as electroless plating because its adhesion improves when a film is formed on the surface. In particular, ABS resin is excellent in tensile strength, bending strength, impact strength, and the like, and is a synthetic resin that is most often electrolessly plated.

  As mentioned above, although one Embodiment of this invention was described in detail with reference to the accompanying drawing, this invention is not limited to the said embodiment at all, A various change implementation is possible.

  For example, as a means for wetting the surface of the workpiece P with the ozone oxidation accelerator Q, in this embodiment, it is immersed in the pretreatment tank 1, but the ozone oxidation accelerator Q liquid is sprayed with a spraying device such as a spray to The surface may be wetted with the ozone oxidation promoter Q.

  Further, the defoaming mechanism of the work P is not limited to the mechanical vibration means that can vibrate the work P, and may be an ultrasonic vibration means or a water jet means. In the case of the water jet means, the water used is more preferably deaerated water.

  EXAMPLES Hereinafter, although this invention is demonstrated further in detail based on an Example and a comparative example, this invention is not limited to the following Example at all.

<Test equipment and conditions>
A test apparatus equipped with the ozone water supply system shown in FIG. 1 was prepared. The specifications of the test apparatus were as follows.
・ Ozone water treatment tank 3: Capacity 46L (width 470mm x depth 210mm x height 470mm)
・ Pretreatment tank (alkaline treated water tank) 1: Filled with the same ozone water treatment tank 3 as alkaline surfactant (1 g / L sodium laurate dissolved in 50 g / L NaOH aqueous solution) ・ Ozone production Device 6: The generated ozone concentration is arbitrarily adjusted so that the ozone water concentration in the ozone water treatment tank 3 is 20 mg / L. Heat exchanger 21: The water temperature in the ozone water treatment tank 3 is 30 ° C. The amount of cooling water supplied to the heat exchanger 21 is adjusted as described above. ・ Acid addition device 9: Add sulfuric acid while controlling the inside of the ozone water treatment tank 3 to be pH 3.0. Work P: Vertical 50 mm for test, horizontal A test piece made of ABS resin having a thickness of 100 mm and a thickness of 3 mm was prepared.

[Example 1]
After the workpiece P was immersed in the pretreatment tank 1, it was immersed in the ozone water treatment tank 3 for 6 minutes for oxidation treatment. At this time, the ozone water in the ozone water treatment tank 3 is agitated by the impeller 22, the work P is installed in parallel to the flow of the ozone water, the single axis robot is activated, and the work P is set at an amplitude of 10 cm and a speed of 20 cm / Vibrated up and down in seconds.

  The workpiece P thus treated was washed with water and then immersed in a mixed aqueous solution set at 50 ° C. containing sodium lauryl sulfate (concentration: 50 g / L) and NaOH (concentration: 1 g / L) for 2 minutes. P was taken out and washed with water.

  Next, palladium chloride (0.1% by mass) and tin chloride (5% by mass) were dissolved in an aqueous hydrochloric acid solution (3N) to prepare a catalyst solution. And the workpiece | work P was immersed in this catalyst solution for 4 minutes. At this time, the temperature of the catalyst solution was set to 40 ° C. Then, in order to activate palladium, the workpiece | work P was immersed for 2 minutes in hydrochloric acid aqueous solution (1N) set to 50 degreeC. In this step, the catalyst was adsorbed on the workpiece P, and the workpiece P was taken out from the hydrochloric acid aqueous solution and washed with water.

  Subsequently, the workpiece P was immersed in a Ni-P chemical plating bath (plating solution) kept at 30 ° C. for 10 minutes to form a Ni—P plating film on the surface of the resin substrate of the workpiece P. Uniform deposition was confirmed on the workpiece P thus treated. At this time, the thickness of the plating film was 0.5 μm.

  Furthermore, the to-be-plated resin member which formed the copper plating film on the Ni-P plating film was obtained by immersing this plated work P in a copper sulfate electroplating bath (25 ° C.) for 40 minutes. In addition, the thickness of the film which combined the Ni-P plating film and the copper plating film was about 30 μm.

  A tensile test was performed in order to evaluate the adhesion strength of the plated film of the workpiece P (resin member to be plated) obtained as described above. In the tensile test, a test piece obtained by cutting a plating film on the workpiece P into a strip having a width of 10 mm is used as a test piece, and using this test piece, the adhesion strength of the plating film according to JIS H8630 (adhesion test method). (Kg / cm) was measured.

[Comparative Example 1]
In Example 1, the workpiece P, which was oxidized in the same manner except that it was not immersed in the pretreatment tank 1, was washed with water and electroless plated in the same manner, and uniform plating deposition was observed on the workpiece P. About 30% of the entire surface was not precipitated.

[Comparative Example 2]
In Example 1, the workpiece P that was subjected to oxidation treatment in the same manner except that the workpiece P was not immersed in the pretreatment tank 1 and the mechanical vibration was not applied to the workpiece P without starting the single-axis robot was similarly washed. When electroless plating was performed, uniform plating deposition was not observed on the workpiece P, and about 50% of the entire surface was not deposited.
The results of Example 1 and Comparative Examples 1 and 2 are shown in Table 1.

  As shown in Table 1, it is confirmed that the surface of the workpiece P can be oxidized efficiently by performing the alkali treatment before being immersed in the ozone water treatment tank 3, and the uniform plating treatment is possible. It was. It was also confirmed that the adhesion of the plating was good.

It is a flowchart which shows the oxidation apparatus of the solid organic matter surface which concerns on one Embodiment of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Pretreatment tank 2 ... Ozone treatment apparatus 3 ... Ozone water treatment tank 6 ... Ozone production apparatus 7 ... 1st supply line (ozone water supply apparatus)
8 ... Second supply pipe (ozone water supply device)
9 ... Acid addition device (hydrogen ion concentration adjusting means)
11 ... Inlet pump (ozone water supply device)
12 ... Ejector (ozone dissolving device)
13. Gas-liquid separation device (ozone water supply device)
16 ... 1st overflow receiving part (ozone water discharge mechanism)
18 ... Circulation pipe (ozone water discharge mechanism)
22 ... Impeller (stirring means)
P ... Work (solid organic matter)
W ... Raw water W0, W1, W2 ... Ozone water Q ... Ozone oxidation accelerator

Claims (9)

A pretreatment means for wetting the surface of a solid organic substance with an ozone oxidation accelerator; and an ozone treatment apparatus having an ozone water treatment tank,
An apparatus for oxidizing a surface of a solid organic matter, wherein the solid organic matter is treated by the pretreatment means and then immersed in an ozone water treatment tank.   2. The solid organic matter surface oxidizing apparatus according to claim 1, wherein the ozone oxidation accelerator is at least one selected from the group consisting of a surfactant solution, a hydrogen peroxide solution, and an alkaline solution.   3. The solid organic matter surface oxidizing apparatus according to claim 1, wherein the pretreatment means is a dipping tank for the ozone oxidation accelerator solution or a spraying apparatus for the ozone oxidation accelerator solution. 4.   The ozone treatment device includes an ozone generator, an ozone dissolver that dissolves ozone gas generated by the ozone generator in raw water, and a supply unit that supplies ozone water produced by the ozone dissolver to the ozone water treatment tank. The oxidation apparatus for the surface of a solid organic matter according to any one of claims 1 to 3, wherein   5. The solid organic matter surface oxidizing apparatus according to claim 4, further comprising a hydrogen ion concentration adjusting unit in a front stage or a rear stage of the ozone dissolving apparatus. The ozone water treatment tank is provided with an ozone water discharge mechanism,
6. The apparatus for oxidizing a solid organic matter surface according to claim 4, wherein the discharged ozone water joins to the raw water side via the ozone water discharge mechanism.   The said organic water treatment tank has a stirring means, The solid organic substance surface oxidation apparatus in any one of Claims 1-6 characterized by the above-mentioned.   The solid organic matter surface oxidation apparatus according to any one of claims 1 to 7, wherein the ozone water treatment tank has a defoaming mechanism on the surface of the solid organic matter.   9. The oxidation of the surface of the solid organic material according to claim 8, wherein the defoaming mechanism on the surface of the solid organic material is at least one selected from the group consisting of water jetting means, mechanical vibration means, and ultrasonic vibration means. apparatus.

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