JP2010017633A - Apparatus for producing hydrogen-dissolved water and method for producing hydrogen-dissolved water using the apparatus, and washing device for electronic component or for instrument for manufacturing electronic component - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing hydrogen-dissolved water, from which hydrogen peroxide and oxygen have been removed, without degassing. <P>SOLUTION: The method for producing hydrogen-dissolved water includes the catalytic reaction process for removing hydrogen peroxide and oxygen from water to be treated containing hydrogen peroxide and oxygen by using a reaction producing water from hydrogen peroxide and a reaction producing water from oxygen and hydrogen in presence of a platinum group metal catalyst. The method further includes the hydrogenation process for adding hydrogen, consumed in the catalytic reaction process, beforehand to the water to be treated without degassing the water to be treated. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to an apparatus for producing hydrogen-dissolved water, a production method using the same, and a cleaning apparatus for an electronic component or an electronic component production instrument.

  In the manufacturing process of an electronic component such as an LSI, a process of processing an object to be processed having a fine structure is repeated. And cleaning for the purpose of removing fine particles, organic matter, metal, natural oxide film, etc. adhering to the surface of the processing object such as wafers and substrates, and achieving and maintaining a high degree of cleanliness will maintain product quality. And is important for yield improvement. This cleaning is performed using, for example, a cleaning solution such as a sulfuric acid / hydrogen peroxide solution mixed solution or a hydrofluoric acid solution, and rinsing with ultrapure water is performed after the cleaning. High purity is required for ultrapure water and chemicals supplied for cleaning such as rinsing. In recent years, the number of cleanings has increased due to miniaturization of semiconductor devices, diversification of materials, and complexity of processes.

  In general, for the production of ultrapure water, an ultrapure water production apparatus including a pretreatment system, a primary pure water system, and a secondary pure water system (subsystem) is used. The role of each system in the ultrapure water production system is as follows. The pretreatment system is a process for removing suspended substances and colloidal substances contained in raw water by, for example, coagulation sedimentation or sand filtration. The primary pure water system uses, for example, an ion exchange resin or a reverse osmosis (RO) membrane to remove the ionic components and organic components of the raw water from which suspended substances have been removed by the pretreatment system. This is a process for obtaining water. The subsystem is a process for producing ultrapure water by further increasing the purity of the primary pure water obtained by the primary pure water system using, for example, an ultraviolet oxidizer, a cartridge polisher (CP), an ultrafiltration device or the like. It is. The rinsing using the ultrapure water obtained in this way has a problem that a thin oxide film is formed on the wafer surface due to dissolved oxygen in the ultrapure water. In order to solve this point, there has been proposed a method of cleaning, such as rinsing, using hydrogen-dissolved water in which hydrogen gas is dissolved in ultrapure water from which dissolved oxygen has been removed by degassing (for example, patents). Reference 1). Methods for removing dissolved oxygen in water include adding hydrogen to water and reacting in the presence of a palladium (Pd) catalyst (for example, Patent Documents 2 and 3), or adding a reducing agent such as hydrogen. And a method of reacting in the presence of a Pd catalyst is disclosed (for example, Patent Document 4).

  In order to achieve a total organic carbon (TOC) concentration of ultrapure water below a set value, a step of decomposing and removing organic substances in water by irradiating ultraviolet rays having a wavelength of around 185 nm by an ultraviolet oxidation device is provided. In this ultraviolet irradiation, water molecules are also oxidized, and hydrogen peroxide which is an oxidizing substance is generated. That is, the hydrogen-dissolved water contains hydrogen peroxide derived from ultrapure water. When such hydrogen-dissolved water is used as washing water, the object to be washed may be oxidized.

As a method for removing hydrogen peroxide in water, a method for removing hydrogen peroxide in water using a Pd catalyst is known. For example, a method of using a Pd catalyst supported on an anion exchange resin (for example, Patent Document 5) or a method of using platinum group metal nanocolloid particles such as Pd supported on a carrier (for example, Patent Document 6). It is disclosed. Also, as a method for producing hydrogen-dissolved water from which dissolved hydrogen peroxide and oxygen are removed, after degassing ultrapure water and removing gas components containing oxygen, hydrogen is dissolved and further treated with a Pd catalyst device. Then, hydrogen peroxide is decomposed and treated with an impurity removing device to produce hydrogen-dissolved water (for example, Patent Document 7).
Japanese Patent No. 3296405 JP-A-5-269306 Japanese Patent No. 3224037 Japanese Patent No. 2988290 JP-A-62-35838 JP 2007-185587 A Japanese Patent No. 4109455

However, in the invention of Patent Document 7, since the gas component containing oxygen is removed by the degassing device and hydrogen is dissolved, the hydrogen-dissolved water production apparatus is enlarged, and the equipment investment and the running cost are increased. Become.
SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a method and an apparatus for producing hydrogen-dissolved water from which hydrogen peroxide and oxygen are removed without degassing.

  The method for producing hydrogen-dissolved water of the present invention uses a reaction for producing water from hydrogen peroxide and a reaction for producing water from oxygen and hydrogen in the presence of a platinum group metal catalyst to produce hydrogen peroxide and oxygen. In the method for producing hydrogen-dissolved water having a catalytic reaction step of removing hydrogen peroxide and oxygen from the water to be treated, the hydrogen consumed in the catalytic reaction step is pretreated without degassing the water to be treated. It has the hydrogenation process added to water, It is characterized by the above-mentioned. It is preferable to measure the dissolved hydrogen concentration of hydrogen-dissolved water after the hydrogenation step and the catalyst reaction step, and to control the amount of hydrogen added in the hydrogenation step by feeding back the measured value. After that, a secondary hydrogen addition step of adding hydrogen to the water to be treated may be further included. In the hydrogen addition step, the hydrogen-dissolved water obtained in the secondary hydrogen addition step is added to the water to be treated. May be. In the hydrogenation step, hydrogen may be added to the water to be treated under a pressure condition higher than atmospheric pressure, and in the secondary hydrogenation step, hydrogen is added to the water to be treated under pressure condition higher than the atmospheric pressure. May be.

  The apparatus for producing hydrogen-dissolved water of the present invention is filled with a hydrogen addition means for adding hydrogen to the water to be treated without degassing the water to be treated containing hydrogen peroxide and oxygen, and a platinum group metal catalyst. A reaction layer having water formed therein, water to be treated to which hydrogen has been added by the hydrogenation means, and a reaction for generating water from hydrogen peroxide in the presence of the platinum group metal catalyst and oxygen And catalytic reaction means for removing hydrogen peroxide and oxygen from the water to be treated using a reaction for generating water from hydrogen.

  The cleaning device for an electronic component or an electronic component manufacturing apparatus (hereinafter also referred to as an electronic component or the like) according to the present invention can perform the treatment without degassing the treatment water containing hydrogen peroxide and oxygen. A hydrogen addition means for adding hydrogen to the water, and a reaction layer filled with a platinum group metal catalyst, water to be treated to which hydrogen has been added by the hydrogen addition means is passed through the reaction layer, and the platinum group Catalytic reaction means for removing hydrogen peroxide and oxygen from water to be treated using a reaction for generating water from hydrogen peroxide and a reaction for generating water from oxygen and hydrogen in the presence of a metal catalyst, and the catalytic reaction And means for cleaning the electronic component or the electronic component manufacturing apparatus with hydrogen-dissolved water from which hydrogen peroxide and oxygen have been removed.

  According to the method and apparatus for producing hydrogen-dissolved water of the present invention, hydrogen-dissolved water from which hydrogen peroxide and oxygen have been removed can be obtained without degassing.

  Hereinafter, although an embodiment is given and explained about the present invention, the present invention is not limited to this.

(First embodiment)
A first embodiment of the present invention will be described with reference to FIG. FIG. 1 is a schematic view of a cleaning device (hereinafter simply referred to as a cleaning device) 8 for electronic components and the like according to the first embodiment of the present invention. As shown in FIG. 1, the cleaning device 8 includes an ultrapure water manufacturing device 12, a hydrogen-dissolved water manufacturing device (hereinafter simply referred to as a manufacturing device) 10, and a cleaning means 40 connected to the secondary side of the manufacturing device 10. And have.

  As the ultrapure water production apparatus 12, an existing apparatus can be used. For example, an apparatus composed of a pretreatment system, a primary pure water system, and a subsystem can be used. The pretreatment system can include, for example, coagulation sedimentation, sand filtration, activated carbon filtration, or a combination thereof. Examples of the primary pure water system may include a combination of an RO membrane, a two-bed / three-column ion exchanger, a mixed bed ion exchanger, a precision filter, and the like. Examples of the subsystem include a combination of an ultraviolet oxidation device, a cartridge polisher (CP), and an ultrafiltration device.

  The production apparatus 10 includes a hydrogen dissolving unit 14, a catalyst reaction unit 16, a hydrogen supply unit 18, a dissolved hydrogen concentration meter 20, and a control unit 22. The hydrogen dissolving part 14 is connected to the secondary side of the ultrapure water production apparatus 12, and the catalyst reaction means 16 is connected to the secondary side of the hydrogen dissolving part 14. The secondary side of the catalyst reaction means 16 is connected to the cleaning means 40 by a pipe 42. A hydrogen supply unit 18 is connected to the hydrogen dissolving unit 14, and the hydrogen dissolving unit 14 and the hydrogen supply unit 18 constitute a hydrogen addition unit. A branch pipe 21 is provided in the pipe 42, the branch pipe 21 is connected to the dissolved hydrogen concentration meter 20, and the dissolved hydrogen concentration meter 20 is connected to the hydrogen supply unit 18 via the control means 22. And the manufacturing apparatus 10 does not have a degassing means.

  The degassing means is means for positively removing gas components such as oxygen and nitrogen in the water to be treated, and examples thereof include one that performs vacuum degassing through a gas permeable membrane.

  The hydrogen dissolving unit 14 is for dissolving and adding hydrogen to the water to be treated (ultra pure water) supplied from the ultra pure water production apparatus 12. The hydrogen dissolving part 14 can select what can make the water to be treated have an arbitrary dissolved hydrogen concentration, for example, a membrane dissolving apparatus for dissolving hydrogen gas in water through a gas permeable membrane, bubbling hydrogen gas in water And a device for dissolving hydrogen gas in water through an ejector, a device for supplying hydrogen gas to the upstream side of the pump, and dissolving by stirring in the pump. Among these, a membrane dissolving apparatus is preferably used. As the membrane dissolving apparatus, a device using a gas permeable membrane of a hollow fiber membrane is preferable, and a device in which a number of the hollow fiber membranes are installed and modularized is particularly preferable. This is because such a membrane dissolving apparatus can efficiently dissolve hydrogen into the water to be treated.

  The hydrogen supply unit 18 may be any unit that can supply hydrogen to the hydrogen dissolving unit 14, and examples thereof include a water electrolysis device and a hydrogen gas cylinder. When a water electrolyzer is used, ultrapure water is supplied to the electrolyzer, and the ultrapure water is electrolyzed in the electrode device, and high purity hydrogen gas can be generated in the cathode chamber of the electrolyzer.

  The catalytic reaction means 16 has a reaction layer filled with a platinum group metal catalyst. The shape of the platinum group metal catalyst filled in the reaction layer is not particularly limited, and examples thereof include powder shapes, granular shapes, and pellet shapes.

  A known technique can be used as the platinum group metal catalyst. For example, a material in which a metal such as palladium (Pd) or platinum is supported on a carrier such as an ion exchange resin, alumina, activated carbon, or zeolite can be used. Among these, it is preferable to use a catalyst having metal Pd supported on a carrier. As the carrier, an anion exchange resin is preferably used.

  The dissolved hydrogen concentration meter 20 only needs to be able to measure the dissolved hydrogen concentration in water on the secondary side of the catalyst reaction means 16, and can measure the dissolved hydrogen concentration over time, and record and display the measured value. Is preferred.

  The control means 22 can adjust the hydrogen supply amount and concentration from the hydrogen supply unit 18 to the hydrogen dissolution unit 14 in response to the value of the dissolved hydrogen concentration measured by the dissolved hydrogen concentration meter 20. For example, a desired dissolved hydrogen concentration of hydrogen-dissolved water is set in advance, and a measured value of the dissolved hydrogen concentration is fed back from the dissolved hydrogen concentration meter 20 to the control means 22 as an electrical signal, and the set value and measured value of the dissolved hydrogen concentration are Depending on the difference, one that adjusts the opening of the valve of the hydrogen cylinder or the voltage of the electrolyzer can be mentioned. Further, for example, based on the value measured by the dissolved hydrogen concentration meter 20, the opening of the valve of the hydrogen cylinder may be adjusted manually, or the voltage of the electrolyzer may be adjusted.

The cleaning means 40 is for cleaning and rinsing (hereinafter sometimes referred to as “cleaning” as a whole) of electronic parts and the like to be cleaned. The cleaning method of the cleaning means 40 can be selected according to the type of object to be cleaned and the purpose of cleaning. For example, a cleaning liquid or a rinsing liquid using hydrogen-dissolved water manufactured by the manufacturing apparatus 10 (hereinafter generally referred to as a cleaning liquid). ) Washing by immersing the object to be cleaned in batch cleaning, circulating cleaning in contact with the object to be cleaned while circulating the cleaning liquid, supplying the cleaning liquid to the bottom of the cleaning tank, and cleaning while overflowing Examples include flow cleaning, a method of cleaning the object to be cleaned by spraying the cleaning liquid in a shower, a method of cleaning the object to be cleaned rotated at high speed and the like.
Here, the electronic component is, for example, a semiconductor substrate such as a silicon substrate or a semiconductor wafer, a substrate material such as a glass substrate for liquid crystal, a memory element, a CPU, a sensor element, a solar cell, or an electronic contact such as an electrical contact made of copper or silver. It means a finished product of a part or a semi-finished product thereof, and the electronic device manufacturing equipment means a quartz reaction tube, a cleaning tank, a substrate carrier, and the like.

  A method for producing hydrogen-dissolved water according to this embodiment will be described. In the method for producing hydrogen-dissolved water in the first embodiment, hydrogen is added (hydrogen addition step) without degassing the ultrapure water (treated water) supplied from the ultrapure water production apparatus 12. In the presence of a platinum group metal catalyst, hydrogen peroxide and oxygen are removed (catalytic reaction step). Note that “without degassing” means that a treatment for positively removing a gas component such as oxygen from the water to be treated is not performed.

  First, raw water A is supplied to the ultrapure water production apparatus 12 to produce ultrapure water. An arbitrary amount of hydrogen gas is supplied from the hydrogen supply unit 18 to the hydrogen dissolving unit 14. The ultrapure water produced by the ultrapure water production apparatus 12 is supplied to the hydrogen dissolving part 14 without degassing, and in addition to the dissolved hydrogen concentration of the target hydrogen dissolved water, the amount of hydrogen consumed by the catalytic reaction means 16 is determined. Dissolve in the water to be treated (hydrogenation step). Water to be treated having an arbitrary dissolved hydrogen concentration is supplied to the catalyst reaction means 16 and passed through the reaction layer of the catalyst reaction means 16. In the reaction layer, the water to be treated flows while being in contact with the platinum group metal catalyst filled in the reaction layer. During this time, the hydrogen peroxide in the water to be treated causes water to react in the presence of the platinum group metal catalyst, as shown in the following formulas (1) to (2), or in the following formula (3). Is generated.

_{2H 2 O 2 → 2H 2 O} + O 2 ··· (1)
O ₂ + 2H ₂ → 2H ₂ O (2)

H ₂ O ₂ + H ₂ → 2H ₂ O (3)

  On the other hand, oxygen and hydrogen in the water to be treated cause a reaction represented by the following formula (4) in the presence of a platinum group metal catalyst to produce water (the catalytic reaction step).

2H ₂ + O ₂ → 2H ₂ O (4)

  Thus, the hydrogen-dissolved water from which hydrogen peroxide and oxygen are removed is supplied from the catalyst reaction means 16 to the cleaning means 40. In the dissolved hydrogen concentration meter 20, part of the hydrogen dissolved water supplied from the catalyst reaction means 16 to the cleaning means 40 is drawn into the branch pipe 21 and the dissolved hydrogen concentration is measured. The measured value of the dissolved hydrogen concentration is sent to the control means 22. In the control means 22, hydrogen dissolution from the hydrogen supply unit 18 is performed based on a concentration difference between a preset target value of the dissolved hydrogen concentration of the hydrogen-dissolved water and a measured value of the dissolved hydrogen concentration obtained by the dissolved hydrogen concentration meter 20. The supply amount of hydrogen gas to the unit 14 is controlled. Thus, the dissolved hydrogen concentration of the hydrogen-dissolved water supplied from the catalyst reaction means 16 to the cleaning means 40 is adjusted to an arbitrary range. The hydrogen-dissolved water is used as a cleaning liquid for electronic parts and the like by the cleaning means 40.

  The raw water A is not particularly limited, and industrial water, clean water, well water, river water, lake water, and the like can be used.

The water to be treated contains hydrogen peroxide and oxygen.
As the water to be treated, the ultrapure water obtained by the ultrapure water production apparatus 12 is obtained by removing impurities such as fine particles, colloidal substances, organic substances, metal ions and anions as much as possible. The quality of the ultrapure water is, for example, resistivity: 18 MΩ · cm or more, TOC: 10 μg-C / L or less, number of fine particles (particle size of 0.05 μm or more): 10 / mL or less, viable count: 10 Pieces / L or less, silica: 1 μg-SiO / L or less, sodium: 0.01 μg-Na / L or less, iron: 0.01 μg-Fe / L or less, copper: 0.01 μg-Cu / L or less, chloride ion : 0.01 μg-Cl / L or less, hydrogen ion concentration: pH 7, and oxidation-reduction potential: +50 mV (vs NHE) are preferable. Here, in the case of water containing no impurities at all, the theoretical value of resistivity at 25 ° C. is 18.2 MΩ · cm. The water quality of ultrapure water approaches 18.2 MΩ · cm, and the higher the water quality, the better the water quality.

When the dissolved oxygen concentration in the ultrapure water is 10 ppb or more at the inlet of the hydrogen dissolving device 14, the effect of the present invention is easily exerted, and when it is 50 ppb or more, it is more easily exhibited. The effects of the invention are particularly prominent. For example, if oxygen in ultrapure water is to be removed using a degassing device, the scale and running cost of the degassing device increase as the dissolved oxygen concentration in the ultrapure water increases.
When the hydrogen peroxide concentration in the ultrapure water is 5 ppb or more at the inlet of the hydrogen dissolving device 14, the effect of the present invention is easily exhibited, and when it is 10 ppb or more, the effect of the present invention is particularly noticeable.

  The dissolved hydrogen concentration of the hydrogen-dissolved water supplied from the production apparatus 10 to the cleaning means 40 can be determined according to the use of the hydrogen-dissolved water, and is preferably 50 ppb or more at 1013 hPa, for example, 800 to 1600 ppb It is preferable that This is because when the dissolved hydrogen concentration is 50 ppb or more, the redox potential of the hydrogen-dissolved water becomes a sufficient reduction potential, and when the hydrogen-dissolved water is used as a cleaning liquid, fine particles on the surface of the object to be cleaned can be efficiently removed. .

  The hydrogen dissolving part 14 dissolves the amount of hydrogen consumed by the catalytic reaction means 16 in the water to be treated in addition to the dissolved hydrogen concentration of the target hydrogen dissolving water. The amount of hydrogen gas dissolved in the water to be treated in the hydrogen dissolving section 14 is determined by the dissolved hydrogen concentration required for the hydrogen dissolved water supplied from the catalyst reaction means 16 to the washing means 40 and the amount of hydrogen consumed by the catalyst reaction means 16. Can be determined according to For example, when the dissolved hydrogen concentration of the hydrogen-dissolved water is 50 ppb, the dissolved hydrogen concentration is adjusted by adding the amount of hydrogen consumed by the catalytic reaction means 16 in addition to the amount of hydrogen corresponding to 50 ppb.

  Since the hydrogen addition step dissolves hydrogen without degassing, the dissolved gas concentration in the water to be treated is high, and the desired dissolved hydrogen concentration may not be reached below atmospheric pressure. For example, a tank that stores primary pure water is purged with nitrogen gas to prevent dissolution of oxygen in the atmosphere. For this reason, high concentration of nitrogen may be dissolved in the obtained ultrapure water. Therefore, the hydrogen addition step can determine the hydrogen dissolution pressure (hydrogen gas pressure) in consideration of the dissolved gas concentration of the water to be treated and the target dissolved hydrogen concentration, for example, higher than atmospheric pressure. By carrying out under pressure, the dissolved hydrogen concentration can be increased.

  In the catalytic reaction means 16, a catalytic reaction step is performed. The residence time of the water to be treated in the reaction layer of the catalyst reaction means 16 takes into consideration the catalyst conditions such as the type of catalyst, the amount of the catalyst supported, the dissolved oxygen concentration and hydrogen peroxide concentration in the water to be treated, and the quality of the hydrogen-dissolved water. Can be determined. Moreover, although the temperature of the to-be-processed water in a catalyst reaction process is not specifically limited, It is preferable to determine in the range of 10-50 degreeC. This is because the catalytic reaction can be performed efficiently within the above temperature range. In addition, when using an anion exchange resin as a single-piece | unit, it is set to 60 degrees C or less from a heat resistant viewpoint of an anion exchange resin.

  The hydrogen-dissolved water supplied to the cleaning means 40 may be used as it is for cleaning or rinsing electronic parts or the like, or may be used for cleaning or rinsing after pH adjustment. The pH can be adjusted by adding various acids and alkalis. Examples of the acid to be added include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and hydrofluoric acid. Examples of the alkali include aqueous ammonia and hydroxylation. Sodium, potassium hydroxide, TMAH (tetramethylammonium hydroxide), choline, etc. are mentioned. These can be selected in consideration of the purpose of cleaning and the type of object to be cleaned.

  As described above, by adding hydrogen consumed in the catalytic reaction process to the water to be treated in advance, hydrogen peroxide generated and dissolved by ultraviolet irradiation in the pure water production process without degassing the water to be treated and It is possible to remove dissolved oxygen from the water to be treated and to obtain hydrogen-dissolved water having a desired dissolved hydrogen concentration. As a result, the apparatus for producing hydrogen-dissolved water does not require a degassing means, and the production apparatus can be made compact and the equipment investment and running cost can be reduced. In addition, by measuring the dissolved hydrogen concentration in the hydrogen-dissolved water after the catalytic reaction step and controlling the dissolved hydrogen concentration in the hydrogen addition step, the hydrogen-dissolved water having an appropriate dissolved hydrogen concentration is supplied to the cleaning means. Can do. Furthermore, by performing the hydrogenation step under a pressure exceeding atmospheric pressure, the hydrogen-dissolved water can be adjusted to a desired dissolved hydrogen concentration even when the dissolved gas concentration in the water to be treated is high.

(Second embodiment)
A second embodiment of the present invention will be described with reference to FIG. FIG. 2 is a schematic view of a cleaning device 50 according to the second embodiment of the present invention. As shown in FIG. 2, the cleaning apparatus 50 includes an ultrapure water manufacturing apparatus 12, a manufacturing apparatus 60, and a cleaning unit 40 connected to the secondary side of the manufacturing apparatus 60.

  The production apparatus 60 includes a hydrogen dissolving unit 14, a catalyst reaction unit 16, a hydrogen supply unit 18, a dissolved hydrogen concentration meter 20, a control unit 22, a branch pipe 30, and a pump 32. The catalytic reaction means 16 is connected to the secondary side of the ultrapure water production apparatus 12, and the hydrogen dissolving part 14 is connected to the secondary side of the catalytic reaction means 16. The secondary side of the hydrogen dissolving part 14 is connected to the cleaning means 40 by a pipe 44. A hydrogen supply unit 18 is connected to the hydrogen dissolving unit 14, and the hydrogen dissolving unit 14 and the hydrogen supply unit 18 constitute a second hydrogen addition unit. A branch pipe 21 is provided in the pipe 44, and the branch pipe 21 is connected to the dissolved hydrogen concentration meter 20. The dissolved hydrogen concentration meter 20 is connected to the hydrogen supply unit 18 via the control means 22. The pipe 44 is provided with a branch pipe 30 including a pump 32, and the branch pipe 30 is connected to the primary side of the catalyst reaction means 16. And the manufacturing apparatus 60 does not have a degassing means.

  The branch pipe 30 and the pump 32 supply the hydrogen-dissolved water obtained in the hydrogen-dissolving unit 14 to the primary side of the catalytic reaction means 16 and first add hydrogen consumed in the catalytic reaction process in advance. Is configured.

  A method for producing hydrogen-dissolved water according to this embodiment will be described. In the method for producing hydrogen-dissolved water according to the second embodiment, hydrogen-dissolved water in which hydrogen is dissolved in the treated water by the branch pipe 30 in the ultrapure water (treated water) obtained by the ultrapure water production apparatus 12. After the addition of hydrogen (hydrogen addition step), the catalyst reaction means 16 removes hydrogen peroxide and oxygen in the presence of the platinum group metal catalyst (catalysis reaction step), and then the hydrogen dissolution unit 14 further dissolves hydrogen. (Secondary hydrogenation step).

When the dissolved oxygen concentration in the ultrapure water is 10 ppb or more at the inlet of the catalytic reaction means 16, the effect of the present invention is easily exhibited, and when it is 50 ppb or more, it is more easily exhibited. The effects of the invention are particularly prominent. For example, if oxygen in ultrapure water is to be removed using a degassing device, the scale and running cost of the degassing device increase as the dissolved oxygen concentration in the ultrapure water increases.
When the concentration of hydrogen peroxide in the ultrapure water is 5 ppb or more at the inlet of the catalyst reaction means 16, the effect of the present invention is easily exhibited, and when it is 10 ppb or more, the effect of the present invention is particularly remarkable.

  The hydrogen addition step is a step of adding hydrogen-dissolved water to the water to be treated and adding hydrogen consumed in the catalytic reaction step to the water to be treated. The amount of hydrogen-dissolved water added to the water to be treated in the hydrogenation step can be determined according to the dissolved hydrogen concentration of the hydrogen-dissolved water and the concentrations of hydrogen peroxide and oxygen in the water to be treated. Specifically, the dissolved hydrogen concentration is set to an amount of hydrogen that is in excess of the amount of hydrogen consumed when removing hydrogen peroxide and oxygen in the water to be treated in the catalytic reaction step.

  In the catalytic reaction step, water derived from the hydrogen-dissolved water added in the hydrogen addition step is reacted with hydrogen peroxide or oxygen to generate water. By this reaction, hydrogen peroxide and oxygen are removed, and hydrogen added in the hydrogenation step is consumed.

  The secondary hydrogenation step is a step of obtaining hydrogen-dissolved water having an arbitrary dissolved hydrogen concentration by dissolving hydrogen in the water to be treated in which hydrogen has been consumed in the catalytic reaction step. The amount of hydrogen gas dissolved in the water to be treated in the secondary hydrogenation step can be determined in consideration of the hydrogen concentration remaining in the catalyst reaction means 16 and the desired dissolved hydrogen concentration of the hydrogen-dissolved water. In the secondary hydrogen addition step, the dissolved hydrogen concentration can be increased by performing the hydrogen gas pressure at a pressure higher than atmospheric pressure.

  As described above, the concentration of dissolved hydrogen in the resulting hydrogen-dissolved water can be more accurately adjusted by performing the secondary hydrogenation step after the catalytic reaction step.

The present invention is not limited to the embodiment described above.
In the second embodiment, the pipe 30 and the pump 32 constitute the first hydrogen addition means. However, a hydrogen dissolving part is newly provided on the primary side of the catalyst reaction means 16 to add hydrogen to the water to be treated. May be.

  In the first and second embodiments, a cleaning means is connected as a use point to the hydrogen dissolving apparatus, but the use point of the hydrogen dissolved water is not limited to this, for example, extracted water for beverage production, diluted water Alternatively, it can be used as boiler water or cooling water for various devices.

  Impurity removing means may be provided on the secondary side of the catalytic reaction means in the first embodiment, and on the secondary side of the hydrogen dissolving part in the second embodiment. The impurity removing means can remove fine particles generated due to deterioration of the support of the platinum group metal catalyst, amines, etc., and can reliably maintain the purity required for ultrapure water. Examples of the impurity removing means include an ion exchange device for removing ion components, an ultrafiltration device for removing fine particles, and a membrane treatment device such as an RO membrane device. Further, an ion adsorption film device can be used as the impurity removing means. Since the membrane itself has an ion exchange function, the ion adsorption membrane device can simultaneously remove the ion component and the fine particles as impurities.

It is a schematic diagram which shows the washing | cleaning apparatus for the electronic components concerning 1st embodiment of this invention, or the manufacture instrument of an electronic component. It is a schematic diagram which shows the washing | cleaning apparatus for the electronic components concerning 2nd embodiment of this invention, or the manufacture tool of an electronic component.

Explanation of symbols

8, 50 Cleaning device for electronic component or electronic component manufacturing instrument 10, 60 Hydrogen dissolved water manufacturing device 12 Ultrapure water manufacturing device 14 Hydrogen dissolving unit 16 Catalytic reaction means 18 Hydrogen supply unit 20 Dissolved hydrogen concentration meter 22 Control unit 30 Branch piping 32 Pump 40 Cleaning means

Claims (8)

Hydrogen peroxide and oxygen are produced from water to be treated containing hydrogen peroxide and oxygen by using the reaction of generating water from hydrogen peroxide and the reaction of generating water from oxygen and hydrogen in the presence of a platinum group metal catalyst. In the method for producing hydrogen-dissolved water having a catalytic reaction step to be removed,
A method for producing hydrogen-dissolved water, comprising: a hydrogen addition step in which hydrogen consumed in the catalytic reaction step is added in advance to the water to be treated without degassing the water to be treated.   The dissolved hydrogen concentration of hydrogen-dissolved water is measured after the hydrogenation step and the catalytic reaction step, and the amount of hydrogen added in the hydrogenation step is controlled by feeding back the measured value. 2. The method for producing hydrogen-dissolved water according to 1.   The method for producing hydrogen-dissolved water according to claim 1 or 2, further comprising a secondary hydrogen addition step of adding hydrogen to the water to be treated after the catalytic reaction step.   The method for producing hydrogen-dissolved water according to claim 3, wherein in the hydrogenation step, the hydrogen-dissolved water obtained in the secondary hydrogenation step is added to the water to be treated.   The method for producing hydrogen-dissolved water according to any one of claims 1 to 3, wherein in the hydrogen addition step, hydrogen is added to the water to be treated under a pressure condition higher than atmospheric pressure.   The method for producing hydrogen-dissolved water according to claim 3 or 4, wherein in the secondary hydrogen addition step, hydrogen is added to the water to be treated under a pressure condition higher than atmospheric pressure. Hydrogen addition means for adding hydrogen to the water to be treated without degassing the water to be treated containing hydrogen peroxide and oxygen;
A reaction layer filled with a platinum group metal catalyst, water to be treated to which hydrogen has been added by the hydrogenation means is passed through the reaction layer, and water from hydrogen peroxide in the presence of the platinum group metal catalyst. Catalytic reaction means for removing hydrogen peroxide and oxygen from water to be treated using a reaction for generating water and a reaction for generating water from oxygen and hydrogen;
An apparatus for producing hydrogen-dissolved water. Hydrogen addition means for adding hydrogen to the water to be treated without degassing the water to be treated containing hydrogen peroxide and oxygen;
A reaction layer filled with a platinum group metal catalyst, water to be treated to which hydrogen has been added by the hydrogenation means is passed through the reaction layer, and water from hydrogen peroxide in the presence of the platinum group metal catalyst. Catalytic reaction means for removing hydrogen peroxide and oxygen from water to be treated using a reaction for generating water and a reaction for generating water from oxygen and hydrogen;
In the catalytic reaction means, cleaning means for cleaning the electronic component or the electronic device manufacturing apparatus with hydrogen-dissolved water from which hydrogen peroxide and oxygen have been removed,
A cleaning device for electronic parts or electronic parts manufacturing instruments having

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