JP5115504B2 - Gas reaction treatment method - Google Patents

Description

The present invention relates to a gas reaction treatment method, more particularly Ruga scan reaction treatment method using ozone or ozone-containing gas as a gas. Hereinafter, in the present specification, pure ozone gas and ozone-containing gas are collectively referred to as ozone gas.

  Ozone gas is widely used as a pretreatment for electroless plating for the purpose of hydrophilizing the resin surface or forming a passive state for strengthening the stainless steel surface (see, for example, JP-A-63-250468). Open 2000-31637).

  In the conventional reaction treatment method of the object to be treated with ozone gas, the reaction tank is opened, the object to be treated is installed in the ozone reaction tank, the ozone reaction tank is sealed, and then the ozone gas is vented from the vent inlet in the ozone reaction tank. Start the reaction.

  In addition, as an operation after the ozone gas reaction treatment, the supply gas to the ozone reaction tank is changed from ozone gas to an inert gas (nitrogen, etc.), the ozone gas is purged, the ozone reaction tank is opened, and the object to be processed Take out. The reason why the ozone gas is purged with an inert gas is to prevent the ozone gas from leaking to the outside when the ozone reaction tank is opened and having a great influence on the surroundings.

JP-A 63-250468 JP 2000-31637 A

  In the above prior art, when the ozone reaction tank is opened and the object to be processed is taken out and replaced with the next object to be processed, the time for replacing all ozone gas in the ozone reaction tank once with an inert gas, or newly regenerating ozone gas. It takes extra filling time to fill. When the ozone concentration in the gas reaction tank is low, the reaction is slow, so that the treatment object cannot be treated to a predetermined extent unless the treatment time is lengthened accordingly. Therefore, when processing a large amount of objects to be processed one after another, it takes time and is not efficient.

  The present invention provides a gas reaction apparatus and a gas reaction treatment method capable of efficiently performing a treatment by shortening the time for replacing a gas into a gas reaction vessel when reacting a gas and an object to be treated in a reaction vessel. For the purpose.

The gas reaction treatment method of the present invention uses a gas reaction apparatus having an ozone gas supply unit, an ozone gas storage unit that stores ozone gas from the ozone gas supply unit, and an ozone reaction unit that makes the object to be processed and ozone gas contact with each other. In the gas reaction processing method, the ozone gas supply unit is capable of supplying pressurized ozone gas, and after exhausting the ozone gas storage unit, storing the pressurized ozone gas from the ozone gas supply unit in the ozone gas storage unit And a step of placing an object to be treated in the ozone reaction section, exhausting the ozone reaction section, and then supplying pressurized ozone gas from the ozone gas storage section to the ozone reaction section, and then supplying ozone gas from the ozone gas supply section. A step of directly supplying the ozone reaction section, and a step of performing a gas purge by supplying nitrogen gas to the ozone reaction section after completion of the reaction. , Then, it is characterized in that a step of taking out the object to be processed from the ozone reaction section.

According to gas reaction treatment method of the present invention, because it can be of a predetermined short time the atmosphere in the gas reaction section by pressurized supply gas to the gas reaction portion, efficiently processing object gas Reaction treatment can be performed.

In addition, according to this invention , the pressurized gas can be supplied to a gas reaction part from a gas storage part, and the atmosphere in a gas reaction part can be made into a predetermined thing in a very short time.

According to the present invention , the atmosphere in the gas reaction part can be rapidly made predetermined by exhausting the gas in the gas reaction part to make the gas reaction part have a negative pressure.

It is a systematic diagram of the gas reaction apparatus which concerns on embodiment. It is a systematic diagram of the gas reaction apparatus which concerns on embodiment. It is a systematic diagram of the gas reaction apparatus which concerns on embodiment. It is a systematic diagram of the gas reaction apparatus which concerns on a comparative example. It is a graph which shows the ozone concentration change in the reaction part.

  Hereinafter, the present invention will be described in more detail.

  In the gas reaction apparatus of the present invention, the object to be treated and the gas are brought into contact with each other in the gas reaction part, and the pressurized gas is supplied into the gas reaction part. It is.

  As the pressurized supply means, one that stores pressurized gas and reduces the volume to supply the gas to the gas reaction tank is suitable.

  In the present invention, it is preferable that an exhaust gas treatment device for detoxifying the gas flowing out from the ozone reaction section is provided. The ozone gas detoxification means is not particularly limited as long as it is an apparatus that can reduce the concentration to a level that does not cause a problem even if ozone gas is released to the outside, and a catalyst-supported activated carbon, a thermal decomposition apparatus, an ultraviolet decomposition apparatus, or the like can be used.

  The gas reaction processing method of this invention processes a to-be-processed object using this gas reaction apparatus. Examples of the object to be treated include metals, synthetic resins, ceramics, plant-based materials, animal-based materials, and composite materials thereof. As the gas, ozone gas is suitable.

  The supply amount of the reaction gas such as ozone gas, the ozone concentration, etc. may be set according to how far the object to be processed is desired.

  What is necessary is just to select the time to hold a to-be-processed object in a reaction part according to the magnitude | size of a to-be-processed object and a reaction part, the characteristic of a to-be-processed object, etc.

  Hereinafter, embodiments will be described with reference to the drawings.

  1 to 3 are system diagrams of a gas reaction apparatus according to an embodiment, respectively.

  First, the gas reactor shown in FIG. 1 will be described.

  This gas reactor treats an object to be processed with an ozone gas supply unit 1, an ozone gas storage unit 3 that compresses and stores ozone gas supplied from the ozone gas supply unit 1, and an ozone gas supplied from the ozone gas storage unit 3. An ozone reaction section (hereinafter also referred to simply as a reaction section) 5, gas treatment devices 8 and 10 for detoxifying ozone, a pump 12 for suction and exhaust, and the like.

Ozone gas supply unit 1 through the pipe 2 provided with a valve V ₁ is connected to the ozone gas reservoir 3, the ozone gas reservoir 3 is connected to the reaction section 5 via a pipe 4 provided with a valve V ₂ . Incidentally, the ozone gas supply unit 1 is connected directly to the reaction section 5 via a pipe 6 provided with a valve V _3. Further, the ozone gas reservoir 3, a gas processing device 8 via a pipe 7 having a relief valve V _R is connected. When ozone gas pressure in the reservoir 3 is equal to or greater than the set pressure of the relief valve V _R, ozone gas leaks from the reservoir 3 to the gas treatment device 8, and that ozone gas pressure in the reservoir 3 is not always exceed the set pressure Become.

  The reaction unit 5 has an entry / exit port (not shown) for an object to be processed. Needless to say, the lid of the doorway is configured to be hermetically sealed. The reaction unit 5 is provided with an air release valve (not shown). This air release valve is opened only when air is allowed to flow into the reaction section 5, and is closed at other times.

The reaction unit 5 is connected to a gas treatment apparatus 10 through a pipe 9 having a valve V _4. The gas processing apparatus 10 is connected to an exhaust pump 12 via a pipe 11, and is configured so that the gas in the reaction unit 5 can be exhausted by the exhaust pump 12 via the gas processing apparatus 10.

  The ozone gas supply unit 1 preferably has an ozone production unit composed of an oxygen supply source and an ozone generator. In order to pressurize and supply the ozone gas to the ozone gas storage unit 3, it is preferable to have a power source such as a compressor or to keep the oxygen gas of the ozone raw material at a high pressure.

  The material of the ozone gas storage unit 3 is preferably a material such as stainless steel that has as low a reactivity as possible with the reaction gas. In order to reduce the reactivity to ozone gas, the inner surface of the ozone gas storage unit 3 may be previously subjected to a surface treatment such as coating or passive film treatment.

  The volume of the ozone gas storage unit 3 is preferably larger than the ozone reaction unit 5 and preferably about 1.5 to 10 times the volume of the reaction unit 5. The internal pressure of the ozone gas storage unit 3 is set to be larger than that of the ozone reaction unit 5. This is to increase the ozone concentration of the ozone gas flowing into the ozone reaction section 5 and the pressure in the ozone reaction section.

  Although there is no restriction | limiting in particular in the shape of the ozone gas storage part 3, In order to store compressed gas, a cylindrical shape is preferable from a safety surface.

Further, the ozone gas storage unit 3 is configured to have a variable volume, and it is preferable to alternately store and discharge ozone gas by changing the volume of the ozone gas storage unit. Specifically, the storage unit is a bellows. Examples are a structure (lantern shape) and a syringe structure. In the this reservoir, inflated gradually allowed to flow into ozone gas, after entering the specified amount of the reaction gas, when opening the valve V ₂ leading to the reaction section by contracting the reservoir with power simultaneously, ozone gas reservoir The ozone gas in the part can be discharged to the reaction part. When the pressurized ozone gas is not supplied to the ozone reaction part, the supply of the ozone gas is stopped when the internal pressures of the ozone gas storage part and the ozone reaction part become equal. Note that either the pressure type or the variable volume type may be used, or both may be used in combination. For example, when a variable volume type ozone gas storage unit is used, the volume initially increases with the inflow of ozone gas. However, when ozone gas is allowed to flow beyond the upper limit of the volume, the gas is compressed in the ozone gas storage unit.

  The material of the ozone reaction part 5 is preferably a material that is as low in reactivity as possible with ozone gas.

  The shape of the ozone reaction part 5 is not particularly limited as long as it has a structure in which an object to be processed can be installed inside, but is preferably one having no useless space.

  Moreover, it is preferable that the ozone reaction part 5 is pressure-reduced and becomes a negative pressure before supplying ozone gas from the ozone gas storage part 3. FIG. For this purpose, for example, the inside of the ozone reaction unit 3 is preferably exhausted by the exhaust pump 12. For this reason, it is desirable for the ozone reaction part to have a strength that can withstand negative pressure caused by exhaust.

  Next, a preferred example of a method for ozone-treating an object to be treated using the gas reaction apparatus of FIG. 1 will be described.

The valve V ₁ is opened, the valves V ₂ and V ₃ are closed, ozone gas is supplied from the ozone gas supply unit 1 to the ozone gas storage unit 3, and ozone gas having a predetermined pressure is stored in the ozone gas storage unit 3.

Also, after inserting an object to be processed in the reaction unit 5, and the valve V ₄ is opened, the exhaust pump 12 is operated to evacuate the reaction unit 5 to a predetermined pressure or less.

Thereafter, the valve V ₄ is closed, the valve V ₂ is opened, and ozone gas is supplied from the ozone gas storage unit 3 into the reaction unit 5. The gas pressure in the reaction part 5 rises rapidly. After the gas pressure in the reaction unit 5 rises to a specified value, the valve V ₂ is closed, the valves V ₃ and V ₄ are opened, and ozone gas is directly supplied from the ozone gas supply unit 1 to the reaction unit 5 to react. The exhaust gas is supplied to the gas processing device 10 to be processed and discharged from the pipe 11. At this time, the exhaust pump 12 may be stopped or operated at a low speed. The internal pressure of the reaction unit 5 adjust to a desired value by adjusting the gas supply conditions and valve V ₄ to the reaction section.

  After the object to be treated and ozone gas are brought into contact with each other in the reaction unit 5 for a predetermined time, the exhaust pump 12 is operated, and the atmosphere release valve provided in the reaction unit 5 is opened to exhaust the ozone gas in the reaction unit 5. . Thereafter, the object to be processed is taken out from the reaction part 5, the object to be processed of the next lot is inserted into the reaction part 5, and then the atmosphere release valve is closed, and the next ozone treatment process is started.

  In addition, it is preferable to supply ozone gas from the ozone gas supply part 1 to the ozone gas storage part 3 while taking out and inserting this to-be-processed object.

FIG. 2 is a system diagram of a gas reaction apparatus according to another embodiment. In this embodiment, to directly connect the ozone gas reservoir 3 and the pipe 11, bypass pipe 13 is provided with a valve V _5. The other structure of FIG. 2 is the same as that of FIG. 1, and the same code | symbol has shown the same part.

When the object to be processed is processed using the gas reactor shown in FIG. 2, the valve V ₅ is opened and the valves V ₁ and V ₂ are closed prior to the start of the first ozone treatment step. 12 is operated, the ozone gas storage part 3 is exhausted to about −0.1 MPa, and the gas in the storage part 3 is discharged. Thereafter, the valve V ₅ is closed, the valve V ₁ is opened, ozone gas is supplied from the ozone gas supply unit 1 to the ozone gas storage unit 3, and ozone gas having a predetermined pressure is stored in the ozone gas storage unit 3. Thereafter, the first ozone treatment is performed in the same procedure as the gas reaction apparatus of FIG. The second and subsequent ozone treatment procedures are the same as in FIG.

  According to the gas reactor shown in FIG. 2, since the gas in the ozone gas storage unit 3 is discharged prior to the first ozone treatment step, the ozone gas is stored from a state in which there is almost no gas in the ozone gas storage unit 3. It is possible to store ozone gas with high purity in the ozone gas storage unit 3 in a short time.

  FIG. 3 is a system diagram of a gas reaction apparatus according to still another embodiment of the present invention.

In this embodiment, the ozone gas supply unit 1 is configured to supply nitrogen gas from a nitrogen source 1b such as a nitrogen cylinder and oxygen gas from an oxygen source 1c such as an oxygen cylinder to the ozone generator 1a. Yes. The nitrogen source 1b is to allow supplying the nitrogen gas into the reaction section 5 via a pipe 14 having a valve V _6. The reaction unit 5 is provided with an ozone concentration meter 5a.

  The other structure of FIG. 3 is the same as that of FIG. 1, and the same code | symbol has shown the same part.

The process of processing the object to be processed by the gas reaction apparatus in FIG. 3 is different from that in FIG. upon, and the valve V ₆ is opened, the nitrogen source 1b by supplying nitrogen gas and in that so as to purge the ozone gas into the reaction section 5, other procedures are the same as in the case of Figure 1.

  Although not shown, in the gas reaction apparatus of FIG. 2, nitrogen may be supplied to the reaction unit 5 from a nitrogen source, and the ozone gas in the reaction unit 5 may be purged with nitrogen gas.

  When the inside of the reaction part 5 when taking out the object to be processed from the reaction part 5 is a nitrogen atmosphere instead of air, the inside of the reaction part 5 can be kept at a low humidity and a high cleanliness. Moisture and dirt react with ozone and cause unevenness in the processability of the workpiece. By eliminating these by purging with clean nitrogen, there is an advantage that the stability of the treatment can be increased.

Hereinafter, examples and comparative examples will be described.
<Example 1>
In the gas reactor shown in FIG. 3, an ozone generator 1a manufactured by Sumitomo Precision Industries, Ltd. was used. As the gas sources 1c and 1b, an industrial oxygen cylinder and an industrial nitrogen cylinder were used, and the ozone generator 1a was supplied by mixing oxygen and nitrogen so that nitrogen would be 0.5% vol. The tank of the ozone gas storage unit 3 is made of SUS304 having a volume of 50 L (diameter: 36 cm, height: 50 cm), and the inner surface is subjected to electrolytic polishing surface treatment. The tank of the ozone reaction section 5 is made of 15 L (cylindrical shape having a diameter of 20 cm and a height of 48 cm) made of SUS304, and the inner surface is subjected to surface treatment of electrolytic polishing. The gas treatment devices 8 and 10 for treating the exhausted ozone gas were SUS304 cylindrical columns packed with 10 L of “Secard MR-4” manufactured by Shinagawa Kasei Co., Ltd. as an ozone decomposition catalyst.

  The processing procedure is as follows.

  Three ABS resin pieces (50 mm × 100 mm × 3 mm) were placed in the ozone reaction tank 5 as objects to be processed.

Next, the valves V ₂ and V ₃ were closed, the valve V ₄ was opened, and the inside of the ozone reaction tank 5 was exhausted by the exhaust pump 12 to a negative pressure of about −0.10 MPa.

Further, the valve _{V 1} is opened, the ozone gas of an ozone concentration 300 g / Nm ³ from the ozone generator 1a is supplied to the ozone gas reservoir 3 at a rate of 12NL / min, the pressure in the ozone gas reservoir is 0.20MPa The ozone gas storage tank was continuously ventilated (30 minutes).

Next, the exhaust pump 12 is stopped, the valve V ₁ is closed, V ₂ is opened, and ozone gas that has been pressurized and stored in the ozone gas storage tank is instantaneously supplied to the ozone reaction tank. The pressure was about 0.15 MPa. Then, the valve _{V 2} closed, and the _{V 3} opened, and fed directly by the 12NL / min ozone gas from the ozone generator 1a to the ozone reaction unit 5 through a pipe 6.

After a lapse (in the 3 min in this case) is predetermined processing time by the valve V ₃ is closed, the valve V ₆ is opened, venting the reaction unit 5 and nitrogen gas at a rate of about 12NL / min The ozone gas remaining in the ozone reaction tank was purged.

After confirming that the ozone concentration in the ozone reaction tank was 0.1 g / Nm ³ or less, the object to be treated was taken out of the ozone reaction tank, and the contact angle of the object to be treated was measured. The results are shown in Table 1.
<Comparative Example 1>
Using the gas reactor shown in FIG. 4, the same object to be treated as in Example 1 was subjected to ozone treatment.

The gas reactor shown in FIG. 4 is the same as the gas reactor shown in FIG. 3, except that the ozone gas storage unit 3, the gas processing device 8, the exhaust pump 12, and the pipes 2 and 4 are omitted, and the ozone gas from the ozone generator 1a is piped. It is made to supply directly to the reaction part 5 via only. Each device used is the same as in the first embodiment. Note that, as a direct drive and an ozone generator 1a and the gas processing apparatus 10, the pipe 15 is provided with a valve V _7. Under normal conditions the valve V ₇ is closed.

An ozone gas having the same ozone concentration as that of Example 1 was sent from the ozone generator 1a to the pipe 6 at the same supply speed and supplied to the reaction unit 5. Three minutes after the start of supply of ozone gas, valve V ₃ is closed, valve V ₆ is opened, nitrogen gas is supplied from nitrogen source 1b to reaction unit 5 to purge ozone gas, and the object to be treated is taken out. The contact angle of this workpiece was measured. The results are shown in Table 1.
<Comparative example 2>
The workpiece was treated under the same conditions as in Comparative Example 1 except that the treatment time was 4 minutes, and the contact angle was measured. The results are shown in Table 1. FIG. 5 shows the change over time in the ozone concentration in the reaction section 5 in Example 1 and Comparative Examples 1 and 2.

＜考察＞
同じ処理時間の実施例１と比較例１では、実施例１の方が十分にオゾン処理されていることが認められる。比較例１のフローで実施例と同等の処理性能を得るには、比較例２の結果から、処理時間を１分半程増やす必要があることが認められた。

<Discussion>
In Example 1 and Comparative Example 1 having the same processing time, it is recognized that Example 1 is sufficiently ozone-treated. In order to obtain the processing performance equivalent to that of the example in the flow of Comparative Example 1, it was recognized from the result of Comparative Example 2 that the processing time needs to be increased by about one and a half minutes.

  As apparent from FIG. 5, in Example 1, the ozone concentration in the ozone reaction tank can be set to a desired concentration in a short time as compared with Comparative Examples 1 and 2, so that the ozone gas storage is performed before the ozone gas treatment. If it is performed during the process, the total processing time per time can be shortened.

1 Ozone gas supply unit 3 Ozone gas storage unit 5 Ozone reaction unit

Claims (1)

Ozone gas supply unit, and the ozone gas reservoirs that store ozone gas from said ozone gas supply unit, the gas reaction treatment method using gas reaction apparatus having an ozone reaction portion contacting the object to be processed and the ozone gas,
The ozone gas supply unit state, and are capable of supplying pressurized ozone gas,
After exhausting the ozone gas storage part, storing the pressurized ozone gas from the ozone gas supply part in the ozone gas storage part;
A step of putting an object to be treated in the ozone reaction section, exhausting the ozone reaction section, and then supplying pressurized ozone gas from the ozone gas storage section to the ozone reaction section;
Thereafter, supplying ozone gas directly from the ozone gas supply unit to the ozone reaction unit;
After completion of the reaction, supplying nitrogen gas to the ozone reaction part and performing a gas purge;
Thereafter, a step of removing the object to be processed from the ozone reaction part;
A gas reaction treatment method comprising:

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