WO2005089919A1

WO2005089919A1 - Apparatus for producing water containing nitrogen dissolved therein

Info

Publication number: WO2005089919A1
Application number: PCT/JP2005/005468
Authority: WO
Inventors: Hiroshi Kurobe; Hiroshi Morita
Original assignee: Kurita Water Industries Ltd.
Priority date: 2004-03-24
Filing date: 2005-03-17
Publication date: 2005-09-29
Also published as: TW200536600A; JP2005270793A; JP4470101B2

Abstract

An apparatus for producing the water containing nitrogen dissolved therein, characterized in that it comprises (A) a membrane type gas dissolution device having a water chamber and a gas chamber being partitioned by a gas-permeable membrane, (B) a deoxygenated water supply pipe for supplying deoxygenated water to said water chamber, (C) a gas dissolving water discharge pipe for discharging a gas dissolving water from said water chamber, (D) a nitrogen supply pipe for supplying nitrogen to said gas chamber, (E) a nitrogen feed adjusting means for adjusting a nitrogen feed to said gas chamber and (F) a pressure gage for measuring the pressure of said gas chamber, wherein the nitrogen feed is adjusted by the nitrogen feed adjusting means, based on the values measured by said pressure gage, and the pressure of said gas chamber is maintained at a predetermined value. The above apparatus allows the production of the water having a concentration of dissolved nitrogen which is controlled with good accuracy by a simple and easy manner.

Description

Specification

Technical field

The present invention relates to difficulties in producing nitrogen-dissolved water. More specifically, the present invention relates to an apparatus for producing nitrogen-dissolved water that can easily and accurately produce water whose nitrogen concentration is controlled.

Disgusting background

It is extremely important to remove foreign matter such as fine particles from the surface of electronic materials such as silicon for body, glass for liquid crystal, and photomask for securing the quality and yield of products. It has been found that good results can be obtained by using »zk, which dissolves gas, which disputes electronic materials and ultrasonic waves. In general, the higher the concentration of the free gas, the better, but the i inclusion will generate ii air bubbles, which will hinder the propagation of ultrasonic waves and adhere to the surface of the object to be cleaned, causing uneven cleaning. Or become. ¾Using a nozzle with a built-in plate creates a gas pool inside the nozzle, which not only prevents ultrasonic waves from reaching the water, but also causes damage to the ultrasonic wave generator! 5. For this reason, it has become necessary to obtain high-concentration gas and dissolved water within a range that does not result in gas concentration s supersaturation.

Use water with dissolved hydrogen to remove the mattress! Ultrasonics are the most effective, but because of the ease of gas handling, nitrogen-dissolved hydropower, which dissolves nitrogen, has been increasingly used. Means for dissolving nitrogen in the super yarn fcK include nitrogen coupling in a water tank. Although this method is very simple, it is difficult to maintain the concentration of free nitrogen with high accuracy. In addition, there is a simple gas dissolution method using a gas module of 141 mm. Using the gas module, it is relatively easy to obtain nitrogen-dissolved water with a high nitrogen concentration, but the nitrogen concentration is not constant and the nitrogen-dissolved water is not supersaturated. It was difficult to produce it stably.

In response to this, super-surgery and nitrogen are supplied to the gas dissolving device, and the free nitrogen concentration of the resulting nitrogen-dissolved water is measured with a nitrogen concentration meter, and the supplied nitrogen amount is controlled in comparison with the target nitrogen concentration. The method is known. However, in the measurement using a conventional nitrogen concentration meter, it is troublesome to set the operating conditions such as the supply of purge gas and the adjustment of the flow rate of the pot water, and the fl It is troublesome and troublesome to work s because of branching and i¾g.

After completely removing the gas in the raw material by degassing, a gas module is used to supply the required amount of specific gas and dissolve it, thereby dissolving the gas at a predetermined concentration in the raw ice. Can be produced without generating bubbles. FIG. 3 is a process flow diagram of an example of a conventional apparatus for producing nitrogen-dissolved water. The Slfck sent from the ultrapure water tank 25 by the pump 26 is subjected to the removal of the free gas by the gasifier 27 and the nitrogen gas S is dissolved by a predetermined amount in the membrane gas dissolver 28. Degree of nitrogen dissolved hydraulic power S manufactured.

The super-R used in the dispute over electronic materials is degassed for the purpose of degassing and decarbonation, and after the free gas is removed, the upper space is kept in a nitrogen atmosphere. There are many ^. In such a case, since the nitrogen power of the other is dissolved, the complete removal of free nitrogen by degassing and then supplying and dissolving the required amount of nitrogen requires many steps and waste. Many ,. For this reason, there has been a demand for a means capable of easily and accurately producing water having a controlled nitrogen concentration.

An object of the present invention is to provide a method for producing nitrogen-dissolved water, which is capable of producing water in which the concentration of free nitrogen is controlled with ease and accuracy. Disclosure of the invention

The present inventors have conducted intensive studies to solve the above-mentioned problem. As a result, the original ice was supplied to the water chamber of the membrane-type gas dissolution apparatus, and the pressure of the gas chamber was measured to obtain a nitrogen conversion of 7_K. By automatically calculating the difference from the set value corresponding to the agricultural level and controlling the amount of nitrogen supplied to the air chamber so as to maintain the air chamber pressure force s set value, the nitrogen concentration is constant It has been found that the nitrogen-dissolved water can be produced stably, and based on this finding, the present invention has been accomplished.

That is, the present invention

(1) (Α) gas A membrane gas dissolving apparatus having a water chamber and an air chamber partitioned by gas, (Β) a deoxygenated water supply pipe for supplying deoxygenated water to the water chamber, (C) a gas-dissolved water discharge pipe for discharging gas-dissolved water from the water chamber; (D) a nitrogen supply pipe for supplying nitrogen to the gas chamber; and (E) a nitrogen supply to the gas chamber. And (F) a pressure gauge for measuring the pressure of the air chamber, wherein the nitrogen supply amount is adjusted by the nitrogen supply amount adjusting means based on the measured value of the pressure gauge. Difficulty in producing nitrogen-dissolved water, wherein the pressure of the air chamber is adjusted to a set value; and (2) The separation and separation of the dissolved water according to (1), wherein

To Brief Description of Drawings

FIG. 1 is a process flow diagram of one embodiment of the apparatus for producing nitrogen-dissolved water of the present invention, FIG. 2 is another explanatory diagram of the apparatus for producing a nitrogen melt angle Zk of the present invention, FIG. ig. 3 is an example of a conventional method for producing nitrogen-dissolved water. In the figure, reference numeral 1 denotes a ® zk tank, 2 denotes a pump, 3 denotes a desalination zk supply pipe, 4 denotes an S test gas dissolving apparatus, 5 denotes a nitrogen supply pipe, 6 denotes a pressure gauge, 7 denotes a gas dissolved water discharge pipe, and 8 denotes a gas dissolving pipe. Controller, 9 is a valve, 10 is a gas discharge pipe, 11 is a valve, 12 is a pump, 13 is a hollow fiber gas dissolving device, 14 is a hollow fiber membrane, 15 is a gas supply chamber, 16 is a gas discharge chamber, 17 is a partition plate, 18 is a tt0 plate, 19 is a nitrogen source, 20 is a flow valve, 21 is a nitrogen supply, 22 is a gas outlet pipe, 23 is a pressure gauge, 24 is a controller, and 25 is a super ¾R A tank, 26 is a pump, 27½M ^, and 28 is a membrane gas dissolving device. Best mode for carrying out the invention

The separation and production of nitrogen-dissolved water according to the present invention includes: (A) a membrane-type gas dissolution apparatus including a water chamber and an air chamber partitioned by a gas control unit; and (B) a deoxygenated water in the water chamber. (C) a gas-dissolved water discharge pipe for discharging gas-dissolved water from the water chamber; (D) a nitrogen supply pipe for supplying nitrogen to the gas chamber; And (F) a pressure gauge for measuring the pressure in the air chamber, wherein the nitrogen supply adjusting means based on the measured value of the soda meter. The nitrogen supply is further adjusted to maintain the pressure in the air chamber at the set value.

FIG. 1 is a diagram of one example of the separation and production of nitrogen-dissolved water of the present invention. In the device of the book! ^, The super MzK tank 1 is super depowered. By deoxidizing the superfiber fck, it is possible to prevent oxidation of the surface of the subject to be oxidized and also to prevent live bacteria in the zR. During the deoxygenation treatment, silicon dioxide, which ionizes in water and increases electrical conductivity, is also removed. The space above the ultra-tank tank that ff? ^ Deoxygenates the air is filled with nitrogen. Therefore, the amount of nitrogen that is present in the super ¾ * is dissolved by the amount of @s, but the nitrogen power over the concentration of 辦 is hardly dissolved. The nitrogen concentration of ^ fek in the tank varies depending on the location in the tank, and β also depends on the time in the tank at an ultra-high temperature of ¾K. Most ^ are not controlled. The S fek in the ultrapure water tank is sent by a pump 2 through a deoxygenated water supply pipe 3 to a membrane gas dissolving apparatus 4 having a water chamber and an air chamber partitioned by a gaseous membrane. The gas supply apparatus is provided with a nitrogen supply pipe 5 for supplying nitrogen to the gas chamber and a pressure gauge 6 for measuring the pressure of the gas chamber. In the gas-capacity system, the gas is dissolved in nitrogen gas with a power of 3 seconds, and the nitrogen-dissolved water is discharged from the gas-dissolved water discharge pipe 7. The measured value of the pressure gauge is sent to the controller 8 as a signal, the difference from the set value is automatically calculated during leisure, a signal is sent to the valve 9, and the nitrogen supply amount is determined by the opening of the norp. The pressure force of S is maintained at the set value. That is, the controller 8 and the valve 9 serve as nitrogen supply adjusting means.

If the gas chamber of the membrane gas dissolver is filled with nitrogen and the pressure is 0 kPa (gage pressure), which is the standard size, the concentration of free nitrogen in the nitrogen-dissolved water becomes saturated. For example, when the temperature is 20 ° C. and the temperature is large E10 1.3 kPa, nitrogen-dissolved water in which nitrogen HOmgZL is dissolved is obtained. If the air chamber is completely evacuated to a pressure of 101.3 kPa (gauge pressure), the nitrogen concentration of water discharged from the water chamber will be 0 mg / L. Assuming that the saturation solubility of nitrogen in water at t ° C is _t mg gL, the pressure in the gas chamber of the gas dissolving unit is X times the gauge pressure of 110 1 · 3 kPa (0 ≤ x ≤ 1) and the time, dissolved nitrogen concentration of nitrogen dissolved water discharged from the gas dissolved water discharge pipe becomes _{a t (l _ x) mg} / L. By utilizing this relationship, by supplying nitrogen so that the pressure of the air chamber becomes a set value, it is possible to produce a nitrogen melt angle ¾k having a predetermined nitrogen concentration. The pressure in the air chamber of the membrane gas dissolving device is measured at the farthest position from the connection point where nitrogen is supplied.

According to the apparatus of the present invention, by reducing the pressure of the gas chamber of the H test gas dissolving apparatus filled with nitrogen to a set value, the nitrogen concentration of the supplied deoxygenated water; However, it is possible to stably produce nitrogen-dissolved water having a predetermined free nitrogen concentration. In the case of a male who performs degassing before the nitrogen dissolution process, which is a conventional sickle, the necessary amount of nitrogen is dissolved after the nitrogen that has been dissolved in the raw water is easily removed. In the deoxygenated superfluous gas, only nitrogen is dissolved as a free gas, so by using this gas without removing it, it is possible to reduce the difficulty of producing nitrogen-dissolved water and save nitrogen. Can be used.

In the production of the nitrogen-dissolved water of the present invention, (G) a gas discharge pipe for discharging gas from the air chamber can be provided. In the embodiment shown in Fig. 1, a gas discharge pipe 10 power S is provided in the gas chamber of the gas dissolving apparatus, and a knurl 11 and a pump 12 power S are provided in the gas discharge pipe. ing. When starting operation of the device of the present invention, the gas discharge pipe feeds nitrogen into the air chamber to release the internal air. When replacing with nitrogen, air can be used to exhaust the mixed gas. In addition, the nitrogen concentration of the produced nitrogen dissolved water is lower than the nitrogen concentration of nitrogen supplied from the m tank. Can be used. In the apparatus of the present invention, the pressure of the gas chamber of the membrane gas dissolving apparatus is lower than that of nitrogen, which is supplied from the ultra-fck tank. As you manufacture, it rises. At this time, the measured value of the pressure gauge 6 is sent to the controller 8 as a signal, the difference from the set value is automatically calculated in the controller, and the signal is sent to the valve 11 to open the valve, thereby reducing the nitrogen emission. Is adjusted to maintain the pressure s set in the air chamber. The downstream side of the valve 11 is kept at a large ffi or less by the pump 12.

In order to produce nitrogen-dissolved water having a constant free nitrogen concentration by the apparatus of the present invention, it is only necessary to add a pressure gauge for measuring the pressure of the air chamber of the membrane gas dissolution apparatus to the air chamber. Since it is ^ 1 "in the air chamber, there is no need for measurement using ^, and there is no need for a branch pipe for sampling the test water, and it can be simply placed as a nitrogen-dissolved water S¾t¾. Furthermore, since only pressure is measured, complicated operations such as a densitometer are required, and wastewater is not generated.In the present invention, based on the deoxygenated super ¾ *, Gases other than nitrogen are not dissolved, and the pressure measured by the pressure gauge immediately corresponds to the dissolved nitrogen concentration of the nitrogen-dissolved water, and the nitrogen concentration of the nitrogen-dissolved water can be accurately controlled. The nitrogen supplied to the gas chamber of the membrane type gas dissolver is usually In other words, the measured pressure value corresponds to the concentration of nitrogen.In other words, using 100 kN of deoxygenated raw water, 100% of fiber is used as the nitrogen to be supplied. By measuring the pressure in the air chamber to use the water, it is possible to produce nitrogen-dissolved water with a predetermined ^^ nitrogen concentration.

In the apparatus of the present invention, the ^ concentration of the desorbed ^ fok used as raw water is 10

The force S is preferably 0 μg / L or less. If the concentration of nitrogen is less than 100 μg ZL, the oxygen concentration has substantially no effect on measuring the pressure corresponding to the dissolved nitrogen concentration. As long as the concentration of free syrup supplied from the ultra-fek manufacturing process is 100 μg / L or less, it can be used as it is as the original ice of nitrogen-dissolved water. When the oxygen concentration is high and the age is high, degassing can be performed to remove mm.

In the apparatus of the present invention, when the ifeK supplied to the B gas dissolving apparatus and the fck production ax are purged with nitrogen in the super-fiber fcK tank in the course of the supply, the nitrogen is dried up. k is supplied to the gas dissolving device, but in the device of the present invention, the previously dissolved nitrogen is Well, it is used as nitrogen, and the shortage of nitrogen is replenished.

There is no particular limitation on the material of the gas used in the apparatus of the present invention. Examples thereof include xanthop block copolymers, polyurenophenols, polydimethylsiloxanes, polysulfone block copolymers, polytetraphenylol ethylene, and polyimides. The apparatus of the present invention dissolves nitrogen, which is not corrosive, etc., so that a polyolefin-based gas such as polypropylene or poly (4-methylpentene-1) can be suitably used. The type of gas used in the apparatus of the present invention is not particularly limited, and examples thereof include a flat membrane, a tube type, a snail, a hollow fiber, a monolith type, a tank immersion type, and a rotating circular type.

In the apparatus of the present invention, the supply of deoxygenated water and nitrogen to the membrane type gas conversion apparatus is preferably performed in the countercurrent flow ^ :. That is, is supplied to one end of the water chamber of the membrane type gas dissolving apparatus in the length direction of the membrane, and nitrogen-dissolved water is discharged from the other end, whereas nitrogen is supplied from the nitrogen-dissolved water discharge side of the gas chamber. And it is preferable to discharge from the supply side of more than ²超 κ. By counterflowing the super ifeK and nitrogen, good gas dissolution efficiency can be obtained.

FIG. 2 is an explanatory view of another key of the storage of the nitrogen-dissolved water of Honkiaki. In the present I ^, a hollow fiber membrane gas dissolving apparatus 13 force S was used as a membrane gas dissolving apparatus, and nitrogen was co-supplied inside the hollow fiber membrane 14, and ultra-fek was applied outside the hollow fiber membrane. Power S supplied. A gas supply chamber 15 is provided at one end of the membrane-type gas dissolving apparatus, and a gas outlet chamber 16 is provided at the other end via partition plates 17 and 18.Hollow fibers are supplied through the partition plate to supply gas. Open to the discharge chamber. A nitrogen supply pipe 21 is connected to the gas supply chamber via a nitrogen source 19 through a flow control valve 20. Further, a gas discharge pipe 22 is connected to the gas discharge chamber. The pressure in the gas discharge chamber is measured by the pressure gauge 23, and the measured value of the pressure gauge is sent to the control unit 24 as a signal, and the difference from the set value is automatically calculated by the controller. The nitrogen discharge is adjusted by the opening of the valve, and the pressure inside the hollow fiber membrane is maintained at the set value.

In the apparatus of the present invention, there is no particular limitation on the pressure gauge installed in the air chamber of the membrane gas dissolving apparatus. For example, a pressure gauge for liquids such as a U-tube type, a single-tube type, a mounting type, and a Pourdon tube Type, bellows type

, Such as diaphragm type elastic body: ^ X is force balance; ^: pressure gauge, single bell type, Nelt type etc. ¾ϋ

^: You can fist the pressure gauge.

In the apparatus of the present invention, the means for adjusting the amount of nitrogen supply is not particularly limited. Thus, the nitrogen supply can be adjusted so that the measured value of the pressure becomes a set value corresponding to the predetermined free nitrogen concentration. When adjusting the nitrogen supply automatically, the measured value of the pressure is input to the calculating device, the calculated value is compared with the set value of the pressure, and a signal corresponding to the difference is sent to the male means for supplying the nitrogen. 4 can be adjusted. Examples of the means for analyzing the amount of nitrogen supply include a flow-resistant valve provided in a nitrogen supply pipe or a nitrogen discharge pipe. By manual, the opening of the valve can be manually adjusted. Example

Hereinafter, the present invention will be described in more detail by way of examples. However, the present invention is not limited to these examples.

Example 1

20 using the apparatus shown in FIG. In C, a nitrogen-dissolved water having a nitrogen concentration of 12 mg ZL was produced. The gas dissolving device is a membrane module with a polypropylene hollow fiber and an outer dimension of 12 Omm in diameter and 835 mm in length.

From the super-fek tank 1, super-nitrogen concentration of 7.6 mg, L is pumped into the water chamber of the membrane gas dissolver 4 by the pump 2, and the pressure in the gas chamber of the gas dissolver is reduced to 37 k. The supply of nitrogen was controlled by a pressure gauge 6 and a knurl 9 so that the pressure became Pa (gauge pressure). The supply amount of nitrogen was 7 OmL (standard condition), and the nitrogen concentration of the nitrogen-dissolved water flowing out of the membrane dissolving apparatus was 12.2 mg / L. The 70 mL of nitrogen supplied to the membrane gas dissolver (standard state) Z content was equal to the increase in the nitrogen concentration of 20 LZ for the super-vein, 4.4 mgZL. It was found that the nitrogen supplied to the country was consumed to increase the superficial nitrogen concentration. Example 2

In the same manner as in Example 1, nitrogen-dissolved water having a nitrogen concentration of 15 mg, L was produced.

The same operation as in Example 1 was carried out except that the nitrogen supply was controlled by the pressure gauge 6 and the panoleb 9 so that the pressure in the gas chamber of the membrane gas dissolving apparatus became 121 kPa (gauge pressure). I went. The supply of nitrogen was 118 mL (standard condition) of Z minutes, and the nitrogen concentration of the nitrogen-dissolved water flowing out of the membrane-type gas dissolution apparatus was 15. OmgZL. The 118 mL of nitrogen supplied to the membrane gas dissolver (standard condition), the Z content, was equal to the increase of free nitrogen concentration of super 20 L / min, 7.4 mg ZL. It has been found that the nitrogen supplied is ultra-ffok? »Spent on increasing the nitrogen concentration. As can be seen from the results of Difficult Example 1 and Difficult Example 2, set the temperature of the membrane melting device at 20 ° C. By controlling the pressure of the air chamber to be 0.37 times or 0.21 times the pressure of 110.13 kPa (gauge pressure), and supplying nitrogen to the air chamber, The nitrogen concentration is 10.9 O mg / L, 0.63 times or 0.79 times of O mg / L. Nitrogen dissolving hydraulic power S is obtained. even if the赫窒iodine concentration force ^s noodles, nitrogen by a Kyoito ^ Rukoto the air chamber of the control to membrane-type gas dissolving apparatus to be pressure mosquito镦定value of membrane type gas dissolving apparatus, predetermined ^ nitrogen Nitrogen-condensed water with elemental concentration can be produced.

By using the nitrogen-dissolved water production apparatus of the present invention, the nitrogen force is dissolved and the superfiber fek is used as raw water to dissolve the insufficient nitrogen for a predetermined concentration of nitrogen, and to reduce the nitrogen concentration. In the process, it is possible to easily and accurately produce nitrogen-dissolved water whose nitrogen concentration is controlled.

Claims

- 'The scope of the claims

1. (A) Membrane gas dissolving device with water chamber and air chamber partitioned by Gas Luo Yumo, (B) Deoxygenated water supply to supply deoxygenated water to the wording room A pipe, (C) a gas-dissolved water discharge pipe for discharging gas-dissolved water from the water chamber, (D) a nitrogen supply pipe for supplying nitrogen to the gas chamber, and (E) a nitrogen supply amount to the gas chamber. And (F) a pressure gauge for measuring the pressure in the air chamber, based on the measured value of the pressure gauge! The nitrogen supply is adjusted by the nitrogen supply adjusting means, and the pressure of the air chamber is adjusted to a set value.

2. The method according to claim 1, wherein the water is a super yarn.