TW201838710A - Diluent manufacturing device and diluent manufacturing method - Google Patents

Abstract

The diluent production apparatus 10 includes a first pipe 11 to supply a first liquid, a first tank 12a to store a second liquid, a second pipe 13 to connect the first tank 12a to the first pipe 11, and a pressure regulator 18, The pressure in the first tank 12a is adjusted, and the second liquid in the first tank 12a is pressure-fed through the second pipe 13 and supplied to the first pipe 11; the control unit 20, according to the first flow through the first pipe 11, The flow rate of the liquid or the diluent and the measured value of the concentration of the diluent are adjusted by adding the second liquid to the first liquid by the pressure adjustment unit 18 so that the concentration of the diluent becomes a predetermined concentration; the second tank 12b, It is connected in series to the first tank 12a, and temporarily stores a second liquid to be replenished to the first tank 12a.

Description

Diluent manufacturing device and method

The present invention relates to a diluent production apparatus and a diluent production method.

In the past, in the manufacturing process of semiconductor devices and liquid crystal devices, as for the cleaning liquid for cleaning electronic components such as semiconductor wafers and glass substrates, ultrapure water has been used to remove impurities to a high degree. It is known that in the cleaning using such ultrapure water, since ultrapure water having a high resistivity value is used, static electricity is easily generated during cleaning, which may cause electrostatic damage to the insulating film and reattachment of particles. Therefore, in recent years, in order to adjust the resistivity value (conductivity) to a predetermined range and suppress the generation of static electricity, a chemical solution such as ammonia or carbonated water is added to the ultrapure water to adjust the concentration to a predetermined concentration. Of diluent.

As a manufacturing apparatus for such a diluent, Patent Document 1 describes a manufacturing apparatus including a first pipe for supplying ultrapure water, a tank for storing a chemical solution, a second pipe for connecting the tank to the first pipe, and an adjustment. A pressure regulator for the pressure in the tank; the manufacturing device hydraulically sends the medicine in the tank through the second pipe through the pressure regulator and adds it to the ultrapure water in the first pipe to manufacture a diluent. According to this manufacturing apparatus, by appropriately controlling the pressure in the tank based on the measured value of the flow rate of ultrapure water or diluent and the concentration of the diluent, the amount of medicinal solution can be adjusted with high precision. As a result, the production can be adjusted to a predetermined level. Concentration of diluent. [Prior Art Literature] [Patent Literature]

[Patent Document 1] International Publication No. 2016/042933

[Problems to be Solved by the Invention] As for a manufacturing apparatus for a diluent, when the manufactured diluent is used for cleaning electronic components such as semiconductor wafers and glass substrates, continuous and stable manufacturing is required to have been adjusted to a predetermined concentration. The diluted solution is supplied to the use end. However, in the manufacturing apparatus described in Patent Document 1, when the medicinal solution in the tank is used up, it is necessary to stop the operation of the apparatus, release the pressure in the tank and replenish the medicinal solution, or replace it with another tank filled with the medicinal solution. In this case, it takes time to stabilize the concentration of the manufactured diluent after the device is turned on again. From the viewpoint of continuous operation of the device, some people have also considered that, until the medicine liquid in the tank is used up, the same liquid is replenished while the medicine liquid is continuously supplied from the tank. However, in the case of such a supplementary method, the supply of the chemical liquid from the tank is performed by controlling the inside of the tank to a pressurized state using a gas for pressurization. The concentration becomes unstable.

Therefore, an object of the present invention is to provide a diluent manufacturing apparatus and a diluent manufacturing method capable of continuously and stably manufacturing a diluent adjusted to a predetermined concentration. [Means for solving problems]

In order to achieve the above-mentioned object, the diluent production device of the present invention is to add a second liquid to the first liquid to produce a diluent of the second liquid and supply the diluent to the use end; The first liquid is supplied; the first tank stores the second liquid; the second piping connects the first tank to the first piping; the pressure adjusting section adjusts the pressure in the first tank and connects the second in the first tank. The liquid is pressure-fed through the second pipe and supplied to the first pipe; the control unit adjusts the position of the pressure adjusting unit based on the measured value of the flow rate of the first liquid or the diluent flowing through the first pipe and the concentration of the diluent. The amount of the two liquids added to the first liquid is such that the concentration of the diluent becomes a predetermined concentration. Further, the diluent manufacturing device of the present invention has a second tank connected in series with the first tank in one aspect, and temporarily stores a second tank of the second liquid to be replenished in the first tank, and has a second tank in the other aspect. The first tanks are connected in parallel and store the second tank to be supplied to the first pipe instead of the second liquid of the first tank.

In addition, the diluent manufacturing method of the present invention comprises adding a second liquid to the first liquid to produce a diluent of the second liquid and supplying the diluent to the use end; and including the following steps: supplying the first liquid To the first piping; the supply of the second liquid to the first piping is to adjust the pressure in the first tank storing the second liquid, and to pressure-feed the second liquid in the first tank by feeding the first tank and the first piping The second pipe connected and supplied to the first pipe includes measuring the flow rate and concentration of the first liquid or diluent flowing through the first pipe, and adjusting the concentration of the second liquid to the first liquid based on the measured value. The amount is added so that the concentration of the diluent becomes a predetermined concentration. Further, the diluent manufacturing method of the present invention includes, in one aspect thereof, the following steps: temporarily storing the second liquid in a second tank connected in series with the first tank; according to the liquid level in the first tank, storing in the The second liquid in the second tank is replenished to the first tank. In another aspect, the following steps are included: storing the second liquid in the second tank connected in parallel with the first tank; and supplying the second liquid from the second tank instead of the first tank according to the liquid level in the first tank To the first piping.

In such a diluent production device and diluent production method, by using two tanks, the second liquid can be replenished from the other tank to the tank before one tank is used up, or it can be switched to the other tank to supply the second tank. liquid. Thereby, the operation | movement of an apparatus does not need to be stopped, etc., and the operation | movement of a device is stopped, and manufacture of a diluent can be performed continuously and stably. [Effect of the invention]

As described above, according to the present invention, a diluent adjusted to a predetermined concentration can be continuously and stably produced.

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

(First Embodiment) FIG. 1 is a schematic configuration diagram of a diluent manufacturing apparatus according to a first embodiment of the present invention. In addition, the structure shown in the figure is only an example, and of course, it can be appropriately changed according to the purpose, use, and required performance of the device, such as adding a valve, a filter, and the like.

The diluent production apparatus 10 includes: a first pipe 11 for supplying a first liquid; two tanks 12a and 12b for storing a second liquid; and two tanks 12a and 12b connected to the first pipe 11 and connected in parallel with each other.支 第二 管管 13。 The second pipe 13. The second liquid is a chemical liquid to be diluted, and the first liquid is a diluting medium for diluting the second liquid. Therefore, the diluent manufacturing device 10 is to add a second liquid to the first liquid flowing through the first pipe 11 through the second pipe 13 to produce a diluent of the second liquid, and pass the prepared diluent through the first The 1 pipe 11 is supplied to the use end 1.

There is no particular limitation on the type of the first liquid, and ultrapure water, pure water, water obtained by dissolving electrolytes and gases, and alcohols such as isopropyl alcohol can be used in accordance with the application. As for the second liquid, the type is not particularly limited as long as it is used for the purpose of being diluted, and it is possible to use water obtained by dissolving electrolytes and gases such as carbonated water and hydrogen-rich water in accordance with the application; isopropyl alcohol And other alcohols. When the manufactured diluent is used for cleaning semiconductor wafers, it is preferable to use ultrapure water as the first liquid and ammonia solution as the second liquid. Alternatively, a tetramethylammonium hydroxide (TMAH) aqueous solution may be appropriately used as the second liquid. In addition, the ultra-pure water referred to here refers to treated water obtained by removing ionic and non-ionic substances from the water to be treated (raw water) by using an ultra-pure water production device, and specifically, the resistivity value is 18 MΩ ･ cm or more of treated water.

The two grooves 12a and 12b are connected in parallel with each other. That is, the two grooves 12a and 12b are connected in series with the plurality of second pipes 13 through the valves 14a and 14b, respectively, on the outlet side thereof. Valves 13a are provided on the inlet sides of the plurality of second pipes 13 respectively. A filter F1 is provided between the two valves 14a and 14b and the plurality of valves 13a. In addition, a three-way valve may be provided at the outlet side of the two grooves 12a and 12b instead of the two valves 14a and 14b. The two tanks 12a and 12b are connected to a chemical liquid supply line (liquid supply means) 16 for supplying a second liquid to each of the tanks 12a and 12b via valves 15a and 15b, respectively. Filters F2 and F3 are respectively provided between the valve 15a and the groove 12a, and between the valve 15b and the groove 12b. A valve 16a is provided in the chemical liquid supply line 16. Further, atmospheric valves 17a and 17b are respectively provided in the two grooves 12a and 12b. In addition, a three-way valve may be provided on the inlet side of the two grooves 12a and 12b instead of the two valves 15a and 15b.

Further, the diluent production apparatus 10 includes a pressure adjustment section 18 for adjusting the pressure in the tanks 12a and 12b as a pressure feed unit for feeding the second liquid in the tanks 12a and 12b through the second pipe 13 and supplying the second liquid to the first pipe 11. means. The pressure adjustment unit 18 is composed of a tank pressurization gas supply line 18a that supplies the tank pressurization gas into the tanks 12a and 12b, and an air intake and exhaust mechanism 18b provided in the tank pressurization gas supply line 18a. The intake / exhaust mechanism 18b includes an intake valve 18c and an exhaust valve 18d. By opening and closing these valves, it is possible to pressurize or decompress the inside of the grooves 12a, 12b. In addition, the intake / exhaust mechanism 18b is not limited to the configuration shown in the figure, that is, it is not limited to a configuration in which the intake pressure increasing mechanism (intake valve 18c) and the exhaust pressure reducing mechanism (exhaust valve 18d) are individually configured, for example An intake pressure increasing mechanism such as an electric pneumatic regulator and an exhaust pressure reducing mechanism may be integrated. The tank pressurizing gas supply line 18a is connected to one of the tanks (first tank) 12a via a valve 19a, and is connected to the other tank (second tank) 12b via a valve 19b. A pressure gauge 19c for measuring the supply pressure of the tank pressurizing gas is provided in the tank pressurizing gas supply line 18a. There is no particular limitation on the type of tank pressurizing gas, and it is preferable to use nitrogen, which is a passive gas, which can be used relatively easily. However, when the diluent produced is used for washing and cleaning of the object to be oxidized, the use of oxygen and air should be avoided in terms of the tank pressurizing gas. Therefore, even when an inert gas such as nitrogen is used, it may be affected by the oxygen contained in the form of impurities, so its purity needs to be fully considered.

In the present embodiment, during normal operation for producing a diluent, the second liquid is alternately supplied to the first pipe 11 from the two tanks 12a and 12b. That is, the first supply mode for supplying the second liquid from the first tank 12a to the first piping 11 and the second supply mode for supplying the second liquid from the second tank 12b to the first piping 11 are based on the respective tanks 12a, The liquid level in 12b is appropriately switched. For example, in the first supply mode, if the liquid level in the first tank 12a is lower than the predetermined lower limit liquid level, the supply of the second liquid from the first tank 12a is stopped, and the supply of the second liquid from the second tank 12b is stopped. This switching operation will be described later.

In this embodiment, the supply of the second liquid system to the first pipe 11 is performed by one of the plurality of second pipes 13. However, in order to achieve a wide range of supply of the second liquid, the plurality of second pipes 13 have an inner diameter. And at least one of the lengths is configured to be different from each other. That is, the plurality of second pipes 13 are configured so that at least one of the inner diameter and the length are different from each other, so that the second liquid can be passed at different flow rates even if the pressures in the respective grooves 12a, 12b are fixed. The configuration of these second pipes 13 is also described later.

Further, the diluent production apparatus 10 includes a control unit 20 that controls various operation operations of the diluent production apparatus 10. In particular, the control unit 20 can adjust the measurement result of the pressure adjusting unit 18 based on at least the measurement results of the flow rate measuring means 21 for measuring the flow rate of the first liquid flowing through the first pipe 11 and the concentration measuring means 22 for measuring the concentration of the diluent. The amount of the two liquids added to the first liquid is such that the concentration of the diluent becomes a predetermined concentration. Hereinafter, the method for adjusting the amount of the second liquid added by the control unit 20 will be described. However, before this, the Hagen-Poiseuille rule, which is the basis for adjusting the amount of the liquid, will be briefly explained. .

Hagen Baiyi ’s solicitation rule is a rule about the head loss of laminar flow in a circular pipeline. If the inner diameter of the tube is defined as D [m], the length of the tube is L [m], and the pressure gradient at both ends of the tube ΔP [Pa], the viscosity coefficient of the liquid is μ [Pa ･ s], and the flow rate of the liquid flowing through the tube is Q [m ³ / s], then it is expressed by the following relationship: Q = (π × D ⁴ × ΔP ) / (128 × μ × L). That is, according to Hagen's principle, the flow rate Q of the liquid flowing through the circular tube is proportional to the fourth power of the internal diameter D of the circular tube and the pressure gradient ΔP at both ends, which is proportional to the length L of the circular tube and the liquid The viscosity coefficient μ is inversely proportional.

In the diluent production apparatus of this embodiment, the Hagen-Bailey solicitation rule is applied to the supply of the second liquid through each second pipe. The length L and the inner diameter D of each second pipe are fixed values, and if the type of the second liquid is determined, the viscosity coefficient μ is also a fixed value. Therefore, by controlling the pressure in the tank corresponding to the pressure gradient ΔP between the ends of each second pipe, the flow rate Q in each second pipe can be controlled proportionally.

Next, a method for adjusting the amount of the second liquid added by the control unit 20 when the second liquid to the first liquid is added from the first tank 12a will be described.

First, a target value of the concentration of the manufactured diluent is set, and the added amount of the second liquid is calculated for the set target concentration. Specifically, the flow rate of the first liquid is measured by the flow rate measuring means 21, and the target addition amount of the second liquid to achieve the target concentration is calculated. Then, with respect to the calculated target addition amount, one second piping 13 to be used is determined among the plurality of second pipings 13, and for the determined second piping 13, the first one for achieving the target addition amount (flow rate) is calculated. Target value of the pressure in the groove 12a. Then, after the valve 13a of the second pipe 13 to be used is opened, the pressure in the first tank 12a is adjusted to the calculated target pressure by the pressure adjustment unit 18, and thereby the second liquid is removed from the first liquid at a predetermined addition amount. The tank 12 a is added to the first liquid in the first pipe 11 through the second pipe 13.

At this time, according to the Hagen-Bailey principle, the flow rate Q of the second liquid flowing through the second pipe 13 is proportional to the pressure gradient ΔP at both ends of the second pipe 13. Therefore, for example, when the flow rate of the first liquid changes, the pressure in the first tank 12a is changed so that the pressure gradient ΔP is proportional to a certain proportional constant with respect to the change. For example, when the flow rate of the first liquid is doubled, the pressure gradient ΔP is doubled, while the flow rate of the second liquid is doubled, and when the flow rate of the first liquid is 1/2, the pressure gradient ΔP is 1 / 2, and the flow rate of the second liquid becomes 1/2. With such an adjustment method, as a result, the proportional relationship between the flow rate of the first liquid and the flow rate of the second liquid can be maintained, and even when the flow rate of the first liquid changes, a dilute solution with a stable concentration can be obtained.

However, due to volatilization and decomposition of the second liquid in the first tank 12a, the concentration of the second liquid itself may not be constant. At this time, the concentration of the manufactured diluent may gradually deviate from the concentration range even if it has been adjusted within a predetermined concentration range including the target concentration. Therefore, in this embodiment, the concentration of the diluent is measured by the concentration measuring means 22. If the measured concentration of the diluent deviates from a predetermined concentration range, the above-mentioned proportionality constant is corrected so that the concentration of the diluent falls back to a predetermined value. Within the concentration range. With this feedback control, even when the operation of the device is just started or the target value of the concentration of the diluent is changed, the proportionality constant can be automatically changed to the most suitable value. As a result, a diluent adjusted to a predetermined concentration can be stably produced.

The flow rate measuring means 21 is not particularly limited in its configuration. For example, a Karman vortex flow meter or an ultrasonic flow meter can be used. The flow rate measuring means 21 may be provided at a position where the flow rate change of the first liquid flowing through the first pipe 11 can be monitored, and the installation position is not particularly limited. In the illustrated embodiment, the flow rate measuring means 21 is provided on the upstream side of the first pipe 11 from the connection portion with the plurality of second pipes 13, and may be provided further downstream than the connection portion. Position to measure the flow rate of the diluent flowing through the first pipe 11. The reason is that the supply amount (flow rate) of the second liquid is much smaller than the flow rate of the first liquid, and the flow rate of the diluent can be regarded as the flow rate of the first liquid.

The concentration measuring means 22 is not limited as long as it can measure the concentration of the diluent in the form of an electrochemical constant. For example, a conductivity meter, a pH meter, a resistivity meter, or an ORP meter can be used. (Redox potentiometer), or ion electrode meter. When the manufactured diluent is used for the purpose of antistatic and antistatic elimination and used for washing and cleaning the object to be treated, it is preferable to use a conductivity meter and a resistivity meter as the concentration measuring means 22. The concentration measuring means 22 is installed on the lower side of the first pipe 11 than the connection portion with the plurality of second pipes 13 as shown in the figure. The concentration measuring means 22 may be directly installed on the first pipe 11 or It is installed beside the first piping 11 and placed in parallel.

It can also be understood from Hagen Baiyi's solicitation rule that the accuracy of the supply amount (flow rate Q) of the second liquid is greatly affected by the pressure gradient ΔP at both ends of the second pipe 13. Therefore, when the pressure of the connection portion between the first piping 11 and the second piping 13 changes greatly, it becomes difficult to stably produce the diluent adjusted to a predetermined concentration. In order to monitor the pressure fluctuation in the connection portion, a pressure measuring means 23 for measuring the pressure in the first pipe 11 is provided as shown in the figure. Therefore, the control unit 20 can calculate a target value of the pressure in the first tank 12a so that the concentration of the diluent becomes the target concentration based on the measurement results of the flow rate measurement means 21, the concentration measurement means 22, and the pressure measurement means 23. Adjustment of the added amount of the second liquid. The configuration of the pressure measuring means 23 is not particularly limited. In the embodiment shown in the figure, the position of the pressure measuring means 23 is also more upstream than the connection portion with the plurality of second pipes 13. The pressure in the pipe of the connecting portion may be located on the downstream side of the connecting portion.

As repeatedly described so far, the flow rate Q of the second liquid flowing through the second pipe 13 is proportional to the pressure gradient ΔP at both ends of the second pipe 13. Therefore, if the pressure gradient ΔP can be greatly changed, a wide range of supply amount (flow rate) of the second liquid can be realized, and it can correspond to a wide concentration range. However, since there is an upper limit to the pressure applied to each of the grooves 12a and 12b in practice, it is difficult to change the pressure gradient ΔP greatly, and the adjustment range of the amount of the second liquid is also limited.

On the other hand, according to Hagen's law, the flow rate Q of the second liquid is also proportional to the inner diameter D (fourth power) of the second pipe 13 and inversely proportional to its length L. Focusing on this point, in order to achieve a wide range of supply amount (flow rate) of the second liquid in the present embodiment, the plurality of second pipes 13 are configured so that at least one of the inner diameter and the length are different from each other. That is, the plurality of second pipes 13 are different from each other by at least one of an inner diameter and a length, and are configured to allow the second liquid to pass through at different flow rates even when the pressure in the respective grooves 12a, 12b is constant. . Thereby, the adjustment range of the addition amount of a 2nd liquid can be widened as a whole apparatus, and the dilution liquid of a wide concentration range can be manufactured.

The inner diameter of each second pipe 13 is not limited to a specific size, but in order to more precisely control the concentration of the diluent produced, the inner diameter of each second pipe 13 should be more than 0.1 mm and less than 4 mm, and more than 0.2 mm. It is more preferable to be 0.5 mm or less. The reason is that the flow of the second liquid in the second pipe 13 easily becomes a laminar flow (regular and orderly flow). That is, because the flow in the tube is turbulent (irregular flow), the Hagen Baiyi principle is not valid, and it is difficult to proportionally control the flow through the second pipe by the pressure gradient ΔP between the two ends of the second pipe. Flow rate Q of the second liquid in the piping. In other words, in order to maintain a good proportional relationship between the flow rate Q and the pressure gradient ΔP, for each of the second pipes 13, the flow of the second liquid flowing through the pipe should be a laminar flow. For details of the ideal range of the inner diameter, refer to Patent Document 1.

In addition, the length of each second pipe 13 is not limited to a specific size, but if the length is too short, the flow rate in the pipe is easily affected, and it becomes difficult to control the flow rate of the liquid in proportion to the pressure gradient at both ends of the pipe. In addition, if the length is too long, installation of the piping becomes difficult, and the contact area between the piping and the liquid becomes large, which may increase the contamination of the liquid in the piping. Therefore, the length of each second pipe 13 is preferably in the range of 0.01 m to 100 m, and more preferably in the range of 0.1 m to 10 m.

Furthermore, if the second pipe 13 has an inner diameter of 0.1 mm or less and a length of more than 100 m, the resistance of the second liquid flowing through the second pipe 13 is likely to increase even though it depends on the combination, that is, in the tank. The pressure easily becomes high pressure. Therefore, in view of such an inner diameter and length, it is difficult to select components (piping, valves, etc.) constituting the device from the viewpoint of pressure resistance, which is not preferable. In addition, if the second pipe 13 has an inner diameter of more than 4 mm and a length of less than 0.01 m, it depends on the combination, but the resistance of the second liquid when flowing through the second pipe 13 tends to be small, that is, the second pipe 13 The flow rate of the liquid is easily changed by slight changes in the pressure in the tank. Therefore, such an inner diameter and length will make the pressure control in the groove difficult and unsatisfactory.

The material and shape of the second pipe 13 are not particularly limited, and a flexible pipe made of resin can be used as appropriate. Examples of such resins include fluororesins such as PFA and ETFE, polyethylene-based resins, and polypropylene-based resins. Fluorinated resins which are not easily eluted when the diluent produced is used for washing and cleaning of semiconductor wafers are particularly preferred. In addition, when the second liquid is a volatile liquid, in order to suppress fluctuations in the concentration of the liquid caused by the liquid in the tube diffusing and diffusing to the outside, it is preferable to use the one having a low air permeability as the second pipe 13. In this case, as described above, depending on the use of the diluent to be manufactured, the oxygen contained in the diluent may have an adverse effect. Therefore, it is possible to suppress the diffusion of oxygen in the air from the outside of the second pipe 13 to the inside It is also preferable to suppress the increase of the dissolved oxygen concentration in the second liquid.

The method of connecting the second pipe 13 to the first pipe 11 is not particularly limited as long as the first liquid and the second liquid are appropriately mixed. For example, it is preferable to connect the first pipe 11 to the first pipe 11 so that the front end of the second pipe 13 is located at the center of the first pipe 11, so that the first liquid and the second liquid can be efficiently mixed. In addition, regarding the plurality of second pipes 13, considering the simple structure and the fact that there is less fluid accumulation, they should be connected to the first pipes 11 individually.

In the example shown in the figure, four second pipes 13 are provided, but the number of the second pipes 13 is not limited to four. The concentration range of the diluent can be appropriately changed to, for example, two, three, or five or more. Correspondingly, the combination of the inner diameter and the length is not limited to a specific combination, and can be appropriately changed. As for the combination of the inner diameter and the length, a combination that differs only by any one of them may be considered. At this time, since the pressure applied to each of the tanks 12a and 12b has an upper limit as described above, considering the viewpoint of further widening the adjustment range of the amount of the second liquid added, it is desirable to combine the inner diameters which are different from each other. It can also be known from the following circumstances that the combination of internal diameters that are different from each other: According to the Hagen Baiyi solicitation rule, for the flow rate Q of the second liquid flowing through the second pipe 13, the length L is affected by a power of 1, and the internal diameter D It is affected by 4th power. In addition, in this embodiment, the supply of the second liquid system to the first pipe 11 is performed through one of the plurality of second pipes 13. However, depending on the required concentration range of the diluent, the plurality of second pipes 13 may be used. Two or more of the second pipes 13 are performed.

As described above, in the present embodiment, during the normal operation of producing the diluent, the first supply mode of supplying the second liquid from the first tank 12a to the first pipe 11 and the supply of the second liquid from the second tank 12b to Switching of the second supply mode of the first piping 11. Thereby, it is not necessary to replace the tank, etc., and it is not necessary to stop the operation of the device, so the production of the diluent can be performed continuously and stably. Hereinafter, a case where the first supply mode is switched to the second supply mode will be described as an example, and the switching operation will be described.

In the first supply mode, the valve 19a connecting the tank pressurizing gas supply line 18a and the first tank 12a is opened, and the tank pressurizing gas (for example, nitrogen) is introduced to the first through the tank pressurizing gas supply line 18a. 1 槽 12a. Then, the measurement value (the pressure in the first tank 12a) measured by the pressure gauge 19c is adjusted to the target pressure by the intake / exhaust mechanism 18b. In this way, the second liquid in the first tank 12a passes through the designated second pipe 13 and is added to the first liquid in the first pipe 11 at a predetermined amount. In addition, at this time, the following valves are all closed, that is, the valve 19b connecting the tank pressure gas supply line 18a and the second tank 12b, the valve 16a of the chemical liquid supply line 16, the chemical liquid supply line 16 and the first tank The valve 15a between 12a, the valve 15b between the chemical liquid supply line 16 and the second tank 12b, the air valve 17a of the first tank 12a, and the air valve 17b of the second tank 12b are all closed. The second tank 12b is in a standby state in which a small amount of the second liquid is stored.

By supplying the second liquid from the first tank 12a to the first piping 11, when the liquid level in the first tank 12a is lower than the predetermined lower limit level, the valve 16a of the chemical liquid supply line 16 is opened, and the second tank is opened. Atmospheric valve 17b of 12b. Then, the valve 15 b between the chemical liquid supply line 16 and the second tank 12 b is opened, and the second liquid is supplied to the second tank 12 b through the chemical liquid supply line 16 and stored. Then, when the liquid level in the second tank 12b reaches a predetermined upper limit level, the valve 16a of the chemical liquid supply line 16, the atmospheric valve 17b of the second tank 12b, and the space between the chemical liquid supply line 16 and the second tank 12b are closed. Valve 15b. Thereafter, the valve 19b connecting the tank pressurizing gas supply line 18a and the second tank 12b is opened, and the tank pressurizing gas is introduced into the second tank 12b through the tank pressurizing gas supply line 18a. At this time, the measured value measured by the pressure gauge 19c is adjusted to the target pressure by the intake / exhaust mechanism 18b. That is, in a state where the pressure in the first groove 12a is maintained at the adjusted target pressure, the pressure in the second groove 12b is also adjusted to the target pressure. When the pressure in the second tank 12b reaches the target pressure, the valve 14b connecting the second tank 12b and the second pipe 13 is opened, and then the valve 14a connecting the first tank 12a and the second pipe 13 is closed. This completes the switching from the first supply mode in which the second liquid is supplied from the first tank 12a to the second supply mode in which the second liquid is supplied from the second tank 12b. After that, the valve 19a connecting the tank supply gas supply line 18a and the first tank 12a is closed, and the first tank 12a is in a standby state until the second liquid is replenished for the first supply mode.

In this switching operation, as described above, the supply of the second liquid system from the second tank 12b is performed after the pressure in the second tank 12b is adjusted to match the pressure in the first tank 12a. Thereby, even when the first supply mode is switched to the second supply mode, the second liquid in the second tank 12b can be added to the first liquid in the first pipe 11 at a predetermined addition amount. As a result, it is possible to suppress the fluctuation of the added amount of the second liquid as much as possible when the mode is switched. Therefore, it is possible to suppress the fluctuation of the concentration of the produced diluent as much as possible.

In the above example, when the second tank 12b is in a standby state, the atmospheric valve 17b is closed. This is to prevent oxygen from entering the second tank 12b, and to prevent the oxygen from dissolving into the second liquid when the second liquid is added to the second tank 12b afterwards. However, when the second liquid in which the oxygen is dissolved in the second tank 12b is not a problem, the atmospheric valve 17b may not be in the closed state. In addition, when the second liquid is replenished to the second tank 12b and the gas component in the tank is replenished to the extent that the atmosphere in the tank is discharged from the atmospheric valve 17b, it is possible to reduce the dissolution of oxygen into the second tank. In liquid, the atmospheric valve 17b can be in any state of being opened and closed.

In the above example, the second liquid system is supplemented to the second tank 12b just before the end of the first supply mode. However, the timing of the replenishment is not limited to this. For example, the second liquid may be replenished at any timing in the first supply mode, such as immediately after switching to the first supply mode. At this time, when the second liquid is a volatile liquid, in order to suppress the volatilization of the second liquid, it is desirable to keep the atmospheric valve 17b closed after the second liquid is replenished.

In addition, in the first supply mode, if the second liquid is supplied until the first tank 12a is used up, there will be a volume of tank pressurization gas in the second pipe. When switching to the next first supply mode, the gas It is supplied to the first pipe, and the concentration of the manufactured diluent may vary. Therefore, switching from the first supply mode to the second supply mode should be started before the first tank 12a is used up as described above.

In the diluent production device 10 of this embodiment, when the use end 1 does not require a diluent, such as during normal operation, it may be switched to a temporary stop of supplying the first liquid to the first pipe 11 and a temporary suspension of the production of the diluent. Standby mode. At this time, for example, when switching from the first supply mode to the standby mode, it is considered that the pressure in the first tank 12a, which has been adjusted to the target pressure, should be restored to atmospheric pressure in consideration of the safety surface. However, such decompression to atmospheric pressure is actually not good from the following viewpoints.

That is, when the pressure in the first tank 12 a is reduced to return to atmospheric pressure, gas components dissolved in the second liquid under high pressure will generate bubbles, and the bubbles will remain in the second pipe 13. Therefore, even if the first tank 12a is pressurized again after the normal operation is restarted, the second liquid is not added, and the first tank 12a is in an excessively pressurized state. After that, the air bubbles escape from the second pipe 13 and the second liquid can be added to the first liquid again. However, since the second liquid is added sharply at this time, the addition amount cannot be adjusted well until the concentration of the diluted liquid produced It takes time to become stable. The effect caused by such bubbles is the first discovery by the inventors of this case.

Therefore, in the diluent production apparatus 10 according to this embodiment, even if, for example, the first supply mode is switched to the standby mode, the pressure in the first tank 12a should be adjusted and maintained at a pressure higher than the atmospheric pressure. Thereby, the generation of bubbles in the gas component dissolved in the second liquid can be suppressed. As a result, the amount of the second liquid can be adjusted well after the first supply mode is turned on again. Furthermore, especially when the second liquid is a volatile liquid, in order to suppress the volatilization of the second liquid and suppress the concentration fluctuation, the pressure in the first tank 12a in the standby mode should be higher than the atmospheric pressure and higher than the second pressure. The liquid has a higher saturated vapor pressure. However, depending on the combination of the second liquid and the tank pressurizing gas, the tank pressurizing gas may be dissolved in the second liquid during normal operation. Therefore, in such a case, it is desirable to determine the pressure in the first tank 12a in the standby mode in consideration of the solubility of the tank pressurizing gas for the second liquid in addition to the saturated vapor pressure of the second liquid. On the other hand, considering normal operation, it can be re-opened quickly after a good addition amount adjustment, so even in the standby mode, the pressure in the first tank 12a can be maintained in the same state as the first supply mode has been adjusted to the target pressure . Such adjustment is particularly suitable when the second liquid is water obtained by dissolving an electrolyte or a gas, such as carbonated water or hydrogen-rich water.

(Second Embodiment) Fig. 2 is a schematic configuration diagram of a diluent manufacturing apparatus according to a second embodiment of the present invention. Hereinafter, the same configurations as those in the first embodiment are denoted by the same reference numerals in the drawings, and descriptions thereof will be omitted, and only configurations different from the first embodiment will be described.

This embodiment is different from the first embodiment in that the function of the second groove 12b is changed. Specifically, the second tank 12b is not connected in parallel with the first tank 12a, but is connected in series with the first tank 12a via a connection line 31. More specifically, the second tank 12b is connected to the first tank 12a so that the second liquid in the second tank 12b is supplied to the first tank 12a by head pressure. In response to the above, the valves 14a, 14b, 15a, and 15b of the first embodiment are omitted, and the plurality of second pipes 13 are provided only between the first tank 12a and the first pipe 11, and the chemical liquid supply line 16 is only connected to the second tank 12b. connection. The pressure gauge 19c is provided in the first tank 12a, and a valve 31a and a check valve (not shown) are provided in the connection line 31.

Therefore, in the present embodiment, the second tank 12b functions as a temporary storage tank for temporarily storing the second liquid to be replenished to the first tank 12a. That is, during the normal operation of manufacturing the diluent, the second liquid is appropriately replenished from the second tank 12b to the first tank 12a according to the liquid level of the first tank 12a. As a result, the second tank can be continuously supplied from the first tank 12a. The liquid goes to the first pipe 11. Thereby, the production of the diluent can be performed continuously and stably, without the need for replacing the tank, and without stopping the operation of the device. This supplementary operation will be described below.

During normal operation, the tank pressurizing gas (for example, nitrogen) is introduced into the first tank 12a through the tank pressurizing gas supply line 18a, and the measured value measured by the pressure gauge 19c (the first tank The pressure in 12a) is adjusted to the target pressure. In this way, the second liquid in the first tank 12 a passes through the designated second pipe 13 at a predetermined addition amount and is added to the first liquid in the first pipe 11. In addition, at this time, the following valves are all closed, that is, the valve 19b connecting the tank pressurizing gas supply line 18a and the second tank 12b, the valve 16a of the chemical liquid supply line 16, the atmospheric valve 17b of the second tank 12b, And the valve 31a of the connection line 31 is in a closed state. However, the state of the atmospheric valve 17b of the second tank 12b at this time is not limited to the closed state as in the first embodiment, and may be an opened state as necessary.

By supplying the second liquid from the first tank 12a to the first piping 11, when the liquid level in the first tank 12a is lower than the predetermined lower limit liquid level, the atmospheric valve 17b of the second tank 12b is opened. Then, the valve 16 a of the chemical liquid supply line 16 is opened, and the second liquid is supplied to the second tank 12 b through the chemical liquid supply line 16 and stored. Then, when the liquid level in the second tank 12b reaches a predetermined upper limit liquid level, the valve 16a of the chemical liquid supply line 16 is closed, and the atmospheric valve 17b of the second tank 12b is closed. Thereafter, the valve 19b connecting the tank pressurizing gas supply line 18a and the second tank 12b is opened, and the tank pressurizing gas is introduced into the second tank 12b through the tank pressurizing gas supply line 18a. At this time, the measured value measured by the pressure gauge 19c is adjusted to the target pressure by the intake / exhaust mechanism 18b. That is, in a state where the pressure in the first groove 12a is maintained at the adjusted target pressure, the pressure in the second groove 12b is also adjusted to the target pressure. When the pressure in the second tank 12b reaches the target pressure, the valve 31a of the connection line 31 is opened, and the second liquid is transferred from the second tank 12b to the first tank 12a by the head pressure. When the transfer of the second liquid is completed, the valve 31a of the connection line 31 is closed, and the second tank 12b is in a standby state until the next replenishment operation.

In this replenishing operation, as described above, the second liquid is transferred from the second tank 12b to the first tank 12a, and the pressure in the second tank 12b is adjusted to match the pressure in the first tank 12a. Thereby, when the second liquid is transferred from the second tank 12b to the first tank 12a by the head pressure, the pressure fluctuation of the first tank 12a can be suppressed as much as possible, and the concentration fluctuation of the manufactured diluent can be suppressed as much as possible. . In addition, in order for the second liquid to be reliably transferred to the first tank 12a by the head pressure, the bottom surface of the second tank 12b should be higher than the top surface of the first tank 12a.

In the above example, the second liquid is stored in the second tank 12b at the time when the liquid level in the first tank 12a is lower than the predetermined lower limit liquid level, but it is not limited to this timing and may be performed at any timing. At this time, when the second liquid is a volatile liquid, in order to suppress the volatilization of the second liquid, it is particularly preferable that the atmospheric valve 17b is kept closed after the second liquid is replenished. Similarly, the transfer of the second liquid from the second tank 12b to the first tank 12a may be performed at any timing after the second liquid is stored in the second tank 12b. However, when the second liquid is supplied until the first tank 12a is used up, a volume of tank pressurizing gas will be stored in the second pipe, and the gas will be supplied to the first pipe, and the concentration of the manufactured diluent may vary. Therefore, in order to continuously supply the second liquid from the first tank 12a, it is desirable to start conveying the second liquid from the second tank 12b to the first tank 12a at least at the above-mentioned timing, that is, before the first tank 12a is used up. [Example]

Next, an example corresponding to the second embodiment will be described with reference to the flowchart shown in FIG. 3. In the flowchart of FIG. 3, the same reference numerals as those shown in FIG. 2 indicate the same configuration as the second embodiment.

(Example 1) In this example, a dilute aqueous solution was produced using the diluent production apparatus 10 having the configuration shown in FIG. 3 as a diluent, and the conductivity of the dilute aqueous ammonia was measured.

The second piping 13 uses five ETFE pipes A to E (pipes A and B: article number "7009" and pipes C to E: article number "7010") having different inner diameters and lengths. By Flom). The inner diameter and length of each of the tubes A to E are as follows. Tube A inner diameter: 0.2mm, length: 3m Tube B inner diameter: 0.2mm, length: 1m Tube C inner diameter: 0.3mm, length: 1m Tube D inner diameter: 0.3mm, length: 0.5m Tube E inner diameter: 0.3mm, length: 0.3m

The first piping 11, the first tank 12a, and the second tank 12b are each made of PFA.

Ultrapure water with a resistivity value of 18 MΩ ･ cm or more and a total organic carbon (TOC) of 1.0 ppb or less was used as the first liquid, and water was passed through the first pipe 11 at a flow rate of 40 L / min and a water pressure of 0.35 MPa. 29% by weight of ammonia water (for the electronics industry, manufactured by Kanto Chemical Co., Ltd.) was used as the second liquid, and nitrogen was used as the tank pressurizing gas introduced into the first tank 12a.

For each of the tubes A to E, a conductivity meter (product number "M300", manufactured by METTLER TOLEDO) was used to measure the pressure when the pressure in the first tank 12a was changed and the amount of ammonia added to the ultrapure water was changed. Electrical conductivity of dilute ammonia. FIG. 4 is a graph showing the measurement results at this time. The horizontal axis represents the amount of ammonia water added to the ultrapure water, and the vertical axis represents the conductivity of the obtained diluent (dilute ammonia).

Ammonia water is a weak base. In a low-concentration region, the change in conductivity with respect to the amount of addition is large, but in a high-concentration region, the change in conductivity with respect to the amount of addition becomes slow. Therefore, the minimum amount of ammonia added in tube A and the conductivity of the diluted solution at this time are 0.015 mL / min and 1.2 μS / cm, respectively. In contrast, the maximum amount of ammonia added in tube E and the conductivity of the diluted solution at this time The rates were 8.18 mL / min and 62.1 μS / cm, respectively. That is, in order to increase the conductivity of the diluted solution from 1.2 μS / cm (tube A) to 62.1 μS / cm (tube E) by about 50 times, it is necessary to increase the amount of ammonia water from 0.015 mL / min (tube A) to 8.18. mL / min (tube E) changed about 545 times. It can also be seen from the graph in FIG. 4 that by using 5 pipes having at least one of an inner diameter and a different length, it is possible to correspond to such an adjustment range of the addition amount of ammonia water, and it has been confirmed that a wide range of dilute concentrations can be continuously produced. ammonia.

(Example 2) In this example, a diluent manufacturing apparatus 10 having the structure shown in FIG. 3 was used, and ultrapure water as the first liquid was passed into the first pipe 11 at a water pressure of 0.16 MPa. The dilute ammonia was produced under the same conditions as in Example 1. Then, the supply of the first liquid is temporarily stopped, that is, the production of the dilution liquid is temporarily stopped, and the conductivity of the diluted ammonia water before and after it is measured. In addition, the temperature of the ultrapure water and ammonia water was adjusted to 23 ° C., and the target value of the conductivity of the diluent was set to 40 μS / cm. The measurement results at this time (the flow rate of the first liquid, the pressure in the first tank, and the time change of the conductivity of the dilute ammonia water) are shown in FIG. 5A. In addition, FIG. 5B also shows a measurement result in a case where the pressure in the first tank 12a returns to atmospheric pressure when the supply of the first liquid is temporarily stopped, as a comparative example.

In this embodiment, as shown in FIG. 5A, it can be confirmed that even after the supply of the first liquid is turned on again (after the normal operation is turned back on), the conductivity of the diluent can be adjusted well. On the other hand, in the comparative example, as shown in FIG. 5B, when the supply of the first liquid is temporarily stopped, the pressure in the first tank 12a returns to atmospheric pressure, although the pressure in the first tank 12a is restored after the normal operation is resumed. Higher than before, the conductivity of the diluent cannot be adjusted well. The reason is considered to be that when the supply of the first liquid is temporarily stopped in this embodiment, the pressure in the first tank 12a is maintained at a pressure higher than the atmospheric pressure, so that generation of bubbles can be suppressed.

1‧‧‧ end of use

10‧‧‧Diluent manufacturing equipment

11‧‧‧The first piping

12a‧‧‧Slot 1

12b‧‧‧Slot 2

13‧‧‧ 2nd piping

13a‧‧‧ Valve

14a, 14b‧‧‧ Valve

15a, 15b‧‧‧ valve

16‧‧‧ chemical liquid supply line (liquid supply means)

16a‧‧‧valve

17a, 17b‧‧‧Air valve

18‧‧‧Pressure adjustment department

18a‧‧‧ Tank pressure gas supply line

18b‧‧‧Intake and exhaust mechanism

18c‧‧‧Air inlet valve

18d‧‧‧Exhaust valve

19a, 19b‧‧‧ valve

19c‧‧‧Pressure gauge

20‧‧‧Control Department

21‧‧‧Flow measurement method

22‧‧‧Concentration measuring means

23‧‧‧Pressure measurement method

31‧‧‧connection pipeline

31a‧‧‧valve

F2, F3‧‧‧ filters

FIG. 1 is a schematic configuration diagram of a diluent manufacturing apparatus according to a first embodiment of the present invention. FIG. 2 is a schematic configuration diagram of a diluent manufacturing apparatus according to a second embodiment of the present invention. 3 is a flowchart of a diluent manufacturing apparatus according to an embodiment of the present invention. [Fig. 4] A graph obtained by plotting the conductivity of the diluted ammonia water with respect to the amount of ammonia water added in Example 1. [Fig. 5A is a graph showing a time change of the flow rate of the first liquid, the pressure in the first tank, and the conductivity of the dilute ammonia water in Example 2; [Fig. 5B] A graph showing the time change of the flow rate of the first liquid, the pressure in the first tank, and the conductivity of the dilute ammonia water in the comparative example.

Claims (13)

A diluent manufacturing device is provided by adding a second liquid to a first liquid to produce a diluent of the second liquid and supplying the diluent to a use end; the first pipe is configured to supply the first liquid; The first tank stores the second liquid; the second piping connects the first tank to the first piping; the pressure adjustment section adjusts the pressure in the first tank and the first tank in the first tank 2 The liquid is pressure-fed through the second pipe and supplied to the first pipe; the control unit adjusts based on the measured value of the flow rate of the first liquid or the diluent flowing through the first pipe and the concentration of the diluent Using the amount of the second liquid added to the first liquid by the pressure adjustment section so that the concentration of the diluent becomes a predetermined concentration; and a second tank connected in series with the first tank and temporarily stored for replenishment To the second liquid in the first tank. A diluent manufacturing device is provided by adding a second liquid to a first liquid to produce a diluent of the second liquid and supplying the diluent to a use end; the first pipe is configured to supply the first liquid; The first tank stores the second liquid; the second piping connects the first tank to the first piping; the pressure adjustment section adjusts the pressure in the first tank and the first tank in the first tank 2 liquid is pressure-fed through the second pipe and supplied to the first pipe; the control unit is based on the measured value of the flow rate of the first liquid or the diluent flowing through the first pipe and the concentration of the diluent, Adjusting the addition amount of the second liquid to the first liquid by the pressure adjustment part so that the concentration of the diluent becomes a predetermined concentration; and a second tank, connected in parallel with the first tank, and storing to be supplied To the first pipe instead of the second liquid in the first tank. For example, the diluent manufacturing device of the first scope of the patent application, wherein the pressure adjusting section can adjust the pressure in the second tank; when the liquid level in the first tank is lower than a predetermined lower limit liquid level, the control section The pressure adjustment unit adjusts the pressure in the second tank to be consistent with the pressure in the first tank, and then replenishes the second liquid from the second tank to the first tank. For example, the dilution liquid manufacturing device according to item 1 or 3 of the scope of patent application, wherein the first tank is connected to the second tank so that the second liquid in the second tank is supplied to the first tank by head pressure. 1 slot. For example, the diluent manufacturing device of the second scope of the patent application, wherein the pressure adjusting section can adjust the pressure in the second tank, and when the liquid level in the first tank is lower than a predetermined lower limit liquid level, the control section The pressure adjustment unit is used to adjust the pressure in the second tank to be the same as the pressure in the first tank, and then the second liquid is supplied from the first tank to the first pipe and switched to the second pipe. The tank supplies the second liquid to the first pipe. For example, the dilution liquid manufacturing device according to any one of claims 1, 2, 3, or 5 has a plurality of the second pipes, and at least one of the inner diameter and the length of the plurality of the second pipes is different from each other. For example, the dilution liquid manufacturing device according to item 6 of the patent application, wherein each of the plurality of second pipes is connected to the first pipe. For example, the dilution liquid manufacturing device according to any one of claims 1, 2, 3, or 5, wherein the first liquid is ultrapure water, and the second liquid is an ammonia aqueous solution or a tetramethylammonium hydroxide aqueous solution. For example, if the supply of the first liquid to the first piping is stopped and the production of the diluent is stopped, the control unit may be a diluent production device according to any one of claims 1, 2, 3 or 5. The pressure in the first tank is adjusted so that the pressure in the first tank is maintained at a pressure higher than atmospheric pressure. For example, the diluent manufacturing device of the ninth scope of the patent application, wherein the control unit adjusts the pressure in the first tank so that the pressure in the first tank is maintained at a pressure higher than the saturated vapor pressure of the second liquid. . For example, the diluent manufacturing apparatus of the ninth scope of the patent application, wherein the control unit adjusts the pressure in the first tank so that the pressure in the first tank is maintained at the pressure adjusted before the production of the diluent is stopped. . A method for manufacturing a diluent is to add a second liquid to the first liquid to produce a diluent of the second liquid and supply the diluent to the use end. The method includes the following steps: supplying the first liquid to the first liquid; 1 piping; supplying the second liquid to the first piping is to adjust the pressure in the first tank storing the second liquid, and to pressure feed the second liquid in the first tank through the first tank and A second pipe connected to the first pipe and supplied to the first pipe; including measuring the flow rate of the first liquid or the diluent flowing through the first pipe and the concentration of the diluent, and according to the measurement Adjust the amount of the second liquid added to the first liquid so that the concentration of the diluent becomes a predetermined concentration; temporarily store the second liquid in a second tank connected in series with the first tank; The liquid level in the 1 tank fills the 2nd liquid stored in the 2nd tank to the 1st tank. A method for manufacturing a diluent is to add a second liquid to the first liquid to produce a diluent of the second liquid and supply the diluent to the use end. The method includes the following steps: supplying the first liquid to the first liquid; 1 piping; the supply of the second liquid to the first piping is to adjust the pressure in the first tank storing the second liquid, and the second piping connecting the first tank to the first piping The second liquid in the first tank is pressure-fed and supplied to the first pipe; including measuring the flow rate of the first liquid or the diluent flowing through the first pipe and the concentration of the diluent, and according to the The measured value adjusts the addition amount of the second liquid to the first liquid so that the concentration of the diluent becomes a predetermined concentration; the second liquid is stored in a second tank connected in parallel with the first tank; The liquid level in 1 tank supplies the second liquid to the first pipe from the second tank instead of the first tank.