JP5213601B2 - Circulating ozone water generation method and circulating ozone water production apparatus - Google Patents

Description

  The present invention relates to a circulating ozone water generation method and a circulating ozone water production apparatus using a pump. More specifically, the ozone water concentration is more stable, the ozone water concentration is high, and the circulation is inexpensive. The present invention relates to an ozone water generation method and a circulating ozone water production apparatus.

  Ozone treatment in which ozone gas is brought into contact with a solution to treat the solution has long been used for treating various solutions including water treatment of sewers. Moreover, in recent years, it has come to be used widely from the middle water supply to the water supply. Recently, ozone water obtained by dissolving ozone in pure water has been widely used for wet cleaning of semiconductors and liquid crystals.

  However, in semiconductors and liquid crystals, it is often required to keep the ozone water concentration stable and always kept at a high concentration, which is still insufficient and produces water with a stable ozone water concentration over a long period of time. It was difficult.

  In addition, the ozone water concentration in the actual cleaning tank fluctuated greatly because the attenuation of the ozone water concentration changed greatly depending on how the ozone water was made.

  For this reason, the ozone water concentration supplied from the apparatus is used for cleaning semiconductors and the like with a margin by supplying it at a much higher concentration than actually required.

  In addition, it is natural that the ozone water concentration has a margin from the site where it is actually used, and even if the ozone water concentration is high, there is no problem in the current cleaning of semiconductors. I have been.

  However, this does not mean that the degree of cleaning of the surface of the article to be cleaned is constant, and when used for forming a protective oxide film, there is a difference in the thickness of the oxide film due to the difference in ozone water concentration. It sometimes happened.

  Furthermore, in today's use of ozone water, it is used not only for decomposing organic substances, but also for removing metal on the substrate, generating a protective oxide film, and cleaning after patterning. As it comes to be, the limitation of the ozone water concentration range has become stricter.

  Recently, as the wiring pitch of semiconductors has become narrower, the quality of pure water used therein has become a problem, and very clean pure water has been required. The quality of such pure water has a specific resistance approaching the limit of 18.24 MΩcm, and TOC and general metal contamination are required to have a purity up to the detection limit.

  As described above, as the purity of pure water becomes higher, ozone water generation using the pure water has noticeably fluctuated fluctuations in the concentration of ozone water that seems to depend on the quality of the pure water. In general, as the purity of pure water increases, the ozone water concentration tends to decrease.

  Therefore, recently, when generating ozone water, carbon dioxide gas is added to pure water to make carbonated pure water, and then ozone gas is added to generate carbonated ozone water, or carbon dioxide gas is added to pure water. A method of injecting ozone gas to generate carbonated ozone water has come to be used.

The ozone water to which carbonic acid is added is not affected by the TOC in the pure water, so that a very high concentration of ozone water can be easily obtained, and the concentration of the generated ozone water is also extremely attenuated. Since the attenuation due to the distance to the cleaning tank is small, high-concentration ozone water can be obtained in the cleaning tank (for example, Patent Document 1).
JP 2003-145181 A

  However, all the methods for generating ozone water to which carbonic acid is added require a step of adding carbon dioxide gas to pure water, and there are problems such as an increase in production cost.

  The present invention solves the above-mentioned problems of the prior art, can effectively use the generated ozone gas, makes the ozone water concentration more stable, makes the ozone water concentration high, and is inexpensive. An object of the present invention is to provide an ozone water generation method and a circulating ozone water production apparatus.

  In order to solve the above-described problems and achieve the object, the present invention is configured as follows.

The invention according to claim 1 is a circulating ozone water generation method in which ozone water is circulated by a pump, ozone gas and pure water are injected in the middle thereof to dissolve ozone gas and generate ozone water.
Apart from the ozone water circulation line that circulates ozone water, it has an ozone gas contact mechanism,
Supplying exhaust ozone gas discharged by generation of ozone water to the ozone gas contact mechanism;
The dissolving discharge ozone ozone gas contact mechanism wherein contacting the exhaust ozone gas and pure water supplied by it in pure water,
A circulating ozone water producing method characterized that you supplying ozone water obtained by dissolving the exhaust ozone gas through the ozone gas contact mechanism with the ozone water circulation line.

According to a second aspect of the present invention, the structure in which the pure water becomes the ozone water through the ozone gas contact mechanism has a film formed of a fluororesin,
Claim Meanwhile wherein the pure water, and introducing the exhaust ozone gas to the other penetration into the exhaust ozone gas the pure water through the membrane, wherein said a structure pure water to the ozone water 1. A circulating ozone water generation method according to 1.

According to a third aspect of the present invention, the ozone gas concentration and / or ozone gas concentration of the ozone gas injected into the circulating ozone water is calculated by measuring the ozone gas concentration of the exhaust ozone gas once used. It is controlled, It is the circulation type ozone water production | generation method of Claim 1 or Claim 2 characterized by the above-mentioned.

The invention according to claim 4 is an ozone gas amount of the ozone gas that is calculated and injected into the circulating ozone water by measuring the concentration of ozone water that has become ozone water by the ozone gas contact mechanism, and / or The circulating ozone water generation method according to claim 1 or 2, wherein the ozone gas concentration is controlled.

Invention of Claim 5 has the ozone water circulation line which circulates ozone water with a pump, inject | pours ozone gas and a pure water in the middle, the circulation type ozone water which melt | dissolves ozone gas and produces | generates ozone water In manufacturing equipment,
Apart from the ozone water circulation line that circulates ozone water, it has an ozone gas contact mechanism ,
Supplying exhaust ozone gas discharged by generation of ozone water to the ozone gas contact mechanism;
Dissolving the waste ozone gas in pure water is contacted with the exhaust ozone gas and pure water supplied by the ozone gas contact mechanism,
The circulating ozone water producing apparatus is characterized in that ozone water in which the exhaust ozone gas is dissolved is supplied to the ozone water circulation line through the ozone gas contact mechanism.

In the invention according to claim 6 , the structure in which the pure water becomes the ozone water through the ozone gas contact mechanism has a film formed of a fluororesin,
Claim Meanwhile wherein the pure water, and introducing the exhaust ozone gas to the other penetration into the exhaust ozone gas the pure water through the membrane, wherein said a structure pure water to the ozone water 5. The circulating ozone water production apparatus according to 5 .

The invention according to claim 7 is an ozone water concentration measuring means for measuring the concentration of ozone water that has become the ozone water by the ozone gas contact mechanism,
Control means for controlling the ozone gas amount and / or ozone gas concentration of the ozone gas injected into the ozone water circulation line by calculating based on the measured ozone water concentration;
The circulating ozone water production apparatus according to claim 5 or 6 , characterized by comprising:

The invention according to claim 8 is an ozone gas concentration measuring means for measuring the exhaust ozone gas concentration of the ozone gas once used,
Control means for controlling the ozone gas amount and / or ozone gas concentration of the ozone gas injected into the ozone water circulation line by calculating based on the measured ozone gas concentration;
The circulating ozone water production apparatus according to claim 5 or 6, characterized by comprising:

  With the above configuration, the present invention has the following effects.

In the first and fifth aspects of the invention, pure water is supplied to the ozone water that circulates as ozone water through the ozone gas contact mechanism, so that ozone water having a stable concentration can always be obtained. Also, safe and energy-saving high-concentration ozone water can always be produced. Furthermore, it is possible to obtain an apparatus that generates ozone water having a stable concentration over a long period of time. Further, the ozone gas supplied to the ozone gas contact mechanism is exhaust ozone gas that has been used once, and the generated ozone gas can be used effectively, thereby saving energy.

In the second and sixth aspects of the invention, ozone gas can be dissolved in pure water and the pure water can be made into ozone water with a simple structure using a film formed of a fluororesin.

In the inventions according to claim 3 and claim 7 , by controlling the ozone gas amount and / or ozone gas concentration of ozone gas injected into the circulating ozone water based on the ozone gas concentration of exhaust ozone gas once used, A stable concentration of ozone water can be obtained, and the occurrence of abnormalities in the ozone gas processing section can be prevented, which is also a safety measure.

In the inventions according to claims 4 and 8 , the ozone gas amount and / or the ozone gas concentration of the ozone gas injected into the circulating ozone water is controlled based on the ozone water concentration that has become ozone water by the ozone gas contact mechanism. Therefore, it is possible to obtain ozone water having a stable concentration at all times, and to prevent occurrence of abnormality in the ozone gas processing unit, which is a safety measure.

Hereinafter, embodiments of the circulating ozone water generating method and the circulating ozone water producing apparatus of the present invention will be described. The embodiment of the present invention shows the most preferable mode of the present invention, and the present invention is not limited to this.
FIG. 1 is a conceptual diagram of circulating ozone water generation by a general pump, and FIG. 2 is a conceptual diagram in which an ozone gas contact mechanism is incorporated in pure water supplied by circulating ozone water generation according to an embodiment of the present invention. FIG. FIG. 3 is a conceptual diagram in which an ozone water contact mechanism, ozone gas concentration measuring means, and control means are incorporated in the pure water supplied in the generation of circulating ozone water according to the embodiment of the present invention. FIG. 4 is a conceptual diagram in which the ozone water contact mechanism, the ozone water concentration measuring means, and the control means are incorporated into the pure water supplied in the generation of circulating ozone water according to the embodiment of the present invention.

  In FIG. 1, the circulation type ozone water generation has an ozone water circulation line R <b> 1 for circulating ozone water 1, and the ozone water 1 is circulated by a circulation pump 4. The pure water 3, the ozone gas 7, and the ozone gas mixing mechanism 5 exist on the inlet side of the circulation pump 4, and have injection lines R2 and R3 for injecting the ozone gas 7 and the pure water 3 in the middle of the ozone water circulation line R1. The circulated ozone water 1 is diluted with pure water 3, mixed with ozone gas 7 by the ozone gas mixing mechanism 5, further mixed by the circulation pump 4 to become ozone water 1, and then introduced into the gas separation tank 6. It is burned.

  In the gas separation tank 6, ozone water and ozone gas are separated. The ozone water 1 is circulated to the ozone water circulation line R 1 by the circulation pump 4, and is discharged from the gas separation tank 6 and supplied as discharge ozone water 2. . The ozone gas that has not become ozone water in the gas separation tank 6 is processed in the ozone gas processing section 9 via the conduit 8 as the exhaust ozone gas 1A.

  Naturally, the major factors that determine the ozone water concentration of the discharged ozone water 2 are the amount of ozone gas and the ozone gas concentration, but the quality of pure water is greatly related. Here, the pure water has a specific resistance of 1/100 to 1/200 MΩcm, while having a specific resistance of 1 MΩcm or more by removing metal contamination therein.

  In FIG. 2, an ozone gas contact mechanism 10 is provided in the middle of the conduit 8 for the exhaust ozone gas 1A. The ozone gas contact mechanism 10 is disposed in the injection line R3. After contacting the pure water 3, the exhaust ozone gas 1A 9, and the pure water 3 becomes supply ozone water 11 by the ozone gas contact mechanism 10.

  In this way, the exhaust ozone gas 1A and the pure water 3 are supplied to the ozone gas contact mechanism 10 of the injection line R3, and the supply ozone water 11 is supplied via the ozone gas contact mechanism 10 from the injection line R3 to the ozone water circulation line R1. Is done. The exhaust ozone gas 1A supplied to the ozone gas contact mechanism 10 is ozone gas that has been used once. In this embodiment, the exhaust ozone gas 1A separated by the gas separation tank 6 is used. However, the ozone gas is not limited to the one separated by the gas separation tank 6 as long as it is once used.

  The structure in which the pure water 3 becomes the supply ozone water 11 through the ozone gas contact mechanism 10 has a film 10a in which the ozone gas contact mechanism 10 is formed of a fluororesin, and is in one chamber 10b partitioned by the film 10a. The pure ozone 3 is introduced into the other chamber 10c, and the exhaust ozone gas 1A is dissolved in the pure water 3 through the membrane 10a to make the pure water 3 into the supplied ozone water 11.

  In this way, the exhaust ozone gas 1A and the pure water 3 become the supply ozone water 11 through the ozone gas contact mechanism 10 and are supplied from the injection line R3 to the ozone water 1 circulating through the ozone water circulation line R1, thereby producing the gas. The discharged ozone water 2 discharged from the separation tank 6 is ozone water with a stable concentration at all times, and is safe and energy-saving high-concentration ozone water can always be generated. Furthermore, it is possible to obtain an apparatus that generates ozone water having a stable concentration over a long period of time.

  Further, the ozone gas supplied to the ozone gas contact mechanism 10 is an ozone gas once used with the exhaust ozone gas 1A that has not become ozone water in the gas separation tank 6, and the generated ozone gas can be used effectively, thereby saving energy. is there.

  Further, the ozone gas contact mechanism 10 has a simple structure using a film 10a formed of a fluororesin, and the exhaust ozone gas 1A can be dissolved in the pure water 3 so that the pure water 3 can be used as the supply ozone water 11.

  In FIG. 3, an ozone gas contact mechanism 10 is provided in the middle of the exhaust ozone gas conduit 8, and after contacting the pure water 3, the exhaust ozone gas 1 </ b> A is processed by the ozone gas processing unit 9. The pure water 3 becomes supply ozone water 11 by the ozone gas contact mechanism 10.

  An ozone gas concentration measuring means 12 for measuring the ozone gas concentration is attached to the conduit 8 of the exhaust ozone gas 1A, and the measurement information of the ozone gas concentration is sent to the control means 20. The control means 20 calculates based on the measured ozone gas concentration to control the ozone gas amount and / or the ozone gas concentration of the ozone gas 7.

  Thus, the discharge discharged from the gas separation tank 6 is performed by calculating the ozone gas concentration of the exhaust ozone gas 1A and controlling the ozone gas amount and / or the ozone gas concentration of the ozone gas 7 injected into the ozone water circulation line R1. The ozone water 2 is always ozone water having a stable concentration, and the exhaust ozone gas 1A also has a stable concentration, so that the occurrence of an abnormality in the ozone gas processing unit 9 can be prevented and also serves as a safety measure.

  In FIG. 4, an ozone gas contact mechanism 10 is provided in the middle of the conduit 8 of the exhaust ozone gas 1 </ b> A, and after contacting the pure water 3, the exhaust ozone gas 1 </ b> A is processed by the ozone gas processing unit 9. The ozone gas contact mechanism 10 is configured in the same manner as the embodiment of FIG. 3, and the pure water 3 becomes the supply ozone water 11 by the ozone gas contact mechanism 10.

  In addition, ozone water concentration measuring means 13 for measuring the concentration of ozone water that has become the supply ozone water 11 by the ozone gas contact mechanism 10 is attached to the injection line R <b> 3, and the measurement information of the ozone water concentration measurement is sent to the control means 30. The control means 30 calculates based on the measured ozone water concentration and controls the ozone gas amount and / or the ozone gas concentration of the ozone gas 7 injected into the ozone water circulation line R1.

  In this way, by calculating based on the ozone water concentration that has become the supply ozone water 11 and controlling the ozone gas amount and / or ozone gas concentration of the ozone gas 7 injected into the ozone water circulation line R1, the gas separation tank 6 The discharged ozone water 2 to be discharged is ozone water having a stable concentration at all times, and the exhaust ozone gas 1A has a stable concentration, so that the occurrence of abnormality in the ozone gas processing section 9 can be prevented, which is also a safety measure.

  Next, although the Example of the circulation type ozone water manufacturing apparatus concerning this invention is described, this Example does not limit this invention.

( Comparative Example 1 )
10 L / min pure water was supplied to generate ozone water. The amount of ozone gas supplied was 3 L / min, and the ozone gas concentration was 250 mg / L.

  When the same amount of ozone water as the supplied pure water was taken out, the ozone water concentration was 33 mg / L.

( Example 1 )
Ozone water was generated under the same conditions as in Comparative Example 1 except that an ozone gas contact mechanism was provided in the supplied pure water and exhausted ozone gas was introduced.

The ozone water concentration was 45 ppm, which was 1.3 times higher than that of Comparative Example 1 .

( Comparative Example 2 )
Ozone water was generated under the same conditions as in Comparative Example 1 . The ozone water concentration was also 33 mg / L.

( Example 2 )
Under the same conditions as in Comparative Example 1, an ozone gas measuring mechanism was attached to the exhaust ozone gas conduit, and the amount of ozone gas supplied was adjusted so that the ozone water concentration was the same as in Comparative Example 1 . The amount of ozone gas was 2 L / min, and the amount of ozone gas supplied could be reduced to 2/3.

  As described above, according to the present invention, ozone water having a stable concentration can always be obtained. Moreover, it is safe and energy-saving high-concentration ozone water can always be generated. Furthermore, it has become possible to obtain an apparatus that generates ozone water having a stable concentration over a long period of time.

  The present invention can be applied to a circulating ozone water generation method and a circulating ozone water production apparatus using a pump, can effectively use the generated ozone gas, stabilize the ozone water concentration, Is high in concentration and inexpensive.

It is a conceptual diagram of the circulation type ozone water production | generation by a general pump. It is the conceptual diagram by which the ozone gas contact mechanism was integrated in the supply pure water by the circulation type ozone water production | generation concerning this Embodiment. It is a conceptual diagram in which the ozone water contact mechanism, the ozone gas concentration measuring means, and the control means are incorporated into the pure water supplied in the circulation type ozone water generation according to the embodiment of the present invention. It is a conceptual diagram in which the ozone water contact mechanism, the ozone water concentration measuring means, and the control means are incorporated into the pure water supplied in the circulation type ozone water generation according to the embodiment of the present invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Ozone water 2 Discharged ozone water 3 Pure water 4 Circulation pump 5 Ozone gas mixing mechanism 6 Gas separation tank 7 Ozone gas 8 Conduit 9 Ozone gas processing part 10 Ozone gas contact mechanism 11 Supply ozone water 12 Ozone gas concentration measurement means 13 Ozone water concentration measurement means 20, 30 Control means

Claims (8)

In the circulating ozone water generating method of circulating ozone water with a pump, injecting ozone gas and pure water in the middle to dissolve ozone gas and generating ozone water,
Apart from the ozone water circulation line that circulates ozone water, it has an ozone gas contact mechanism,
Supplying exhaust ozone gas discharged by generation of ozone water to the ozone gas contact mechanism;
The dissolving discharge ozone ozone gas contact mechanism wherein contacting the exhaust ozone gas and pure water supplied by it in pure water,
Circulating ozone water generating method characterized that you supplying ozone water obtained by dissolving the exhaust ozone gas through the ozone gas contact mechanism with the ozone water circulation line. The structure in which the pure water becomes the ozone water through the ozone gas contact mechanism has a film formed of a fluororesin,
Claim Meanwhile wherein the pure water, and introducing the exhaust ozone gas to the other penetration into the exhaust ozone gas the pure water through the membrane, wherein said a structure pure water to the ozone water circulating ozone water generating method according to 1. The ozone gas amount of the ozone gas injected into the circulating ozone water and / or the ozone gas concentration is controlled by measuring an ozone gas concentration of the exhaust ozone gas once used. The circulating ozone water production | generation method of Claim 1 or Claim 2 . By measuring the concentration of ozone water converted into ozone water by the ozone gas contact mechanism, the amount of ozone gas and / or the ozone gas concentration of the ozone gas injected into the circulating ozone water is calculated and calculated. The circulating ozone water generating method according to claim 1 or claim 2 . In the circulating ozone water production apparatus that has ozone water circulation line that circulates ozone water with a pump, and injects ozone gas and pure water in the middle to dissolve ozone gas and generate ozone water,
Apart from the ozone water circulation line that circulates ozone water, it has an ozone gas contact mechanism ,
Supplying exhaust ozone gas discharged by generation of ozone water to the ozone gas contact mechanism;
Dissolving the waste ozone gas in pure water is contacted with the exhaust ozone gas and pure water supplied by the ozone gas contact mechanism,
A circulating type ozone water production apparatus , wherein ozone water in which the exhaust ozone gas is dissolved is supplied to the ozone water circulation line through the ozone gas contact mechanism. The structure in which the pure water becomes the ozone water through the ozone gas contact mechanism has a film formed of a fluororesin,
Claim Meanwhile wherein the pure water, and introducing the exhaust ozone gas to the other penetration into the exhaust ozone gas the pure water through the membrane, wherein said a structure pure water to the ozone water 5. The circulating ozone water production apparatus according to 5. Ozone water concentration measuring means for measuring the concentration of ozone water that has become the ozone water by the ozone gas contact mechanism;
Control means for controlling the ozone gas amount and / or ozone gas concentration of the ozone gas injected into the ozone water circulation line by calculating based on the measured ozone water concentration;
The circulating ozone water production apparatus according to claim 5 or 6 , characterized by comprising: Ozone gas concentration measuring means for measuring the ozone gas concentration of the exhaust ozone gas once used;
Control means for controlling the ozone gas amount and / or the ozone gas concentration of the ozone gas to be calculated and injected into the ozone water circulation line based on the measured ozone gas concentration;
The circulating ozone water production apparatus according to claim 5 or 6, characterized by comprising: