JP5189193B2 - Operation method of ultrapure water production system - Google Patents

Description

  The present invention relates to an operation method of an ultrapure water production system in which the concentration of TOC existing in ultrapure water piping before initial water flow is reduced.

  For example, in a semiconductor integrated circuit manufacturing system, ultrapure water used for cleaning silicon wafers has a specific resistance at a water temperature of 25 ° C. of 18.2 MΩ · cm or more, and an ionic compound (cation, anion, metal). ), TOC (Total Organic Carbon), residual fine particles, bacteria content, etc. are required to have high water quality of 1 ppb.

  Further, in recent years, dissolved oxygen (DO) causes oxidation of the silicon wafer surface, so that ultrapure water having a dissolved oxygen concentration reduced to about 3 ppb has been required. .

  For this reason, in addition to conventional devices such as conventional filters, reverse osmosis membrane devices and ion exchange devices, oxygen permeable membrane devices and the like have been used for the production of ultrapure water.

JP 2004-50048 A

  By the way, in the ultrapure water production system, it is desirable to be able to produce ultrapure water with a predetermined water quality within the shortest possible period after the construction of the piping is completed and the initial water flow is started. There is a problem that the higher the water quality standard required for ultrapure water, the longer the initial water flow time until ultrapure water with a predetermined water quality is obtained.

  In other words, even if an ultrapure water production system is designed to produce ultrapure water with a predetermined water quality, ultrapure water with a predetermined water quality is not produced as soon as plumbing is performed and water is passed. Rather, after the start of water flow after construction, the water quality gradually increases as water continues to flow for a long time, and finally ultrapure water with a predetermined water quality can be obtained.

  As described above, since the ultrapure water produced until a predetermined water quality cannot be used, there is a problem that a large amount of water is wasted if the initial water flow time required for the predetermined water quality is increased. It was. In addition, there is a problem that the period until the start of operation of the ultrapure water production system is increased by the time required for the initial water flow.

  The present inventor conducted research on such conventional difficulties, and as a result, the state of the atmosphere in the pipe before the initial water flow greatly affects the initial water flow time until the water quality after the water flow reaches the design value. I got the knowledge to give.

  The present invention has been made in view of such a situation. The present invention reduces the TOC concentration in the pipe before the initial water flow, shortens the initial water flow time required until the water quality after the water reaches the design value and a predetermined water quality can be obtained, An object of the present invention is to provide an operation method of an ultrapure water production system capable of reducing the initial water flow rate.

  In this specification, after the construction of the ultrapure water production system, the water flow that is performed until the water quality after the water flow reaches the design value and ultrapure water of a predetermined water quality is obtained is referred to as initial water flow. .

  According to another aspect of the present invention, there is provided a method for operating an ultrapure water production system in which at least 4 hours of dust removal and dehumidification is performed in a pipe that has already been constructed before initial passing through an ultrapure water pipe having a connection part of the ultrapure water production system. It is characterized by passing water after aeration of gas.

  According to one aspect of the present invention, the organic matter contained in the adhesive or the like is converted into ultrapure water by a relatively simple method in which the dehumidified and dehumidified gas is passed through the installed pipe for at least 4 hours. Dissolution can be prevented. Therefore, the operating method of the ultrapure water manufacturing system which can reduce TOC in a short period can be provided.

  Furthermore, by venting at a pressure higher than the outside air pressure, it is possible to prevent fine particles in the external atmosphere from entering the pipe, so the initial water flow time until the number of remaining fine particles reaches a predetermined value is greatly increased. It can be shortened.

The graph which showed the relationship between the initial water flow time and dissolved oxygen concentration about the reference example 1 and the reference comparative example 1. FIG. 6 is a graph showing the relationship between the initial water passage time and the number of remaining fine particles for Reference Example 2 and Reference Comparative Example 2. The graph which showed the relationship between the initial water flow time and TOC density | concentration about Example 1 and Comparative Example 1. FIG.

  Next, the form for implementing this invention is demonstrated.

  In the present invention, in order to prevent contamination by air existing in the pipe before the initial water flow, clean gas is passed through the pipe and the air in the pipe is replaced with clean gas.

  As the aerated clean gas, a clean inert gas is used to reduce dissolved oxygen. Nitrogen gas, helium gas, argon gas, etc. can be used as the clean inert gas, but nitrogen gas is preferred from the economical aspect. In particular, high-purity nitrogen gas containing almost no oxygen is preferable. As the high purity nitrogen gas, an easily available gas widely used in an ultrapure water production system can be used.

  Ventilation is performed so that the air in the pipe can be replaced with clean gas. For example, one end of the pipe is opened, clean gas is supplied from the other end, and the air in the pipe is discharged to the outside. Ventilation may be started after the completion of piping construction, but the ventilation is started almost simultaneously with the start of construction of the pipe. This is preferable in that the startup time after construction can be further shortened. That is, it is preferable to connect the pipes sequentially to the other end while venting from one end of the pipe. In any case, after completion of the piping work, the clean gas is always circulated in the pipe, the air in the pipe is discharged to the outside, and the clean gas is replaced.

  The pipe to be ventilated is a continuous pipe that will transfer ultrapure water after the construction of the ultrapure water production system is completed, that is, an ultrapure water transfer pipe. A pipe through which primary deionized water before degassing is sent may be included, but at least pipes of a route for transferring secondary deionized water after degassing, so-called ultrapure water, to a use point are included. Of course, ultrapure water transfer pipes after completion of construction will be included, but even pipes that are under construction should be included in the pipes that are subject to ventilation for those parts that have been connected and completed. Can do. By continuously ventilating the pipe in the finished construction and replacing the air in the finished pipe with a clean gas, the atmosphere in the finished pipe is the same as the cleanliness at the time of delivery to the construction site. It is kept equal or cleaner.

  A plurality of bent portions, valves, and branches may exist in the middle of the ultrapure water transfer pipe. A structure having a loop portion may be used. A structure in which the entire pipe is looped may be used. It is preferable to have a piping structure that does not create a place where ventilation is not possible (dead point). However, even if a dead point occurs, the piping structure should be able to ventilate the main part of the piping and discharge the air in the piping to the outside. That's fine. By exhausting the air inside the pipe to the outside and always ventilating the inside of the pipe, the atmosphere inside the pipe is kept clean.

  There is no restriction | limiting in particular as a material of piping made into object, For example, resin-made piping, such as a hard vinyl chloride resin (PVC), a polyvinylidene fluoride (PVDF), a polypropylene (PP), a high density polyethylene (HDPE), is used. be able to. These are materials generally used as ultrapure water transfer piping. Metal pipes are not generally used as ultrapure water transfer pipes in order to avoid mixing metal oxides.

  In the present invention, it is preferable to ventilate the clean gas at a pressure equal to or higher than the external pressure, but it is not necessary to have a high pressure. This is because if the air is vented at a pressure equal to or higher than the external air pressure, the inside of the pipe becomes a positive pressure compared to the external atmosphere even if the pressure is not particularly high, so that impurities such as dust in the external atmosphere can be prevented even during pipe connection work. In the present invention, the temperature of the supplied clean gas is not particularly limited. A normal temperature (eg 25 ° C.) is sufficient. Further, the flow rate and flow rate of ventilation are not particularly limited.

  It is sufficient if the air in the piping is replaced with clean gas. If the air in the pipe is replaced with a clean gas, the TOC is reduced because the solvent gas that fills the pipe is discharged outside the pipe when the adhesive is used. If the air in the pipe is replaced with a clean inert gas, the oxygen contained in the air in the pipe is discharged outside the pipe, so that the dissolved oxygen concentration is also reduced.

  The aeration period is at least a period from the completion of pipe construction to immediately before the initial water flow, and preferably the entire period from the start of pipe construction to immediately before the initial water flow. The length of the period from the completion of the construction of the pipe to just before the initial water flow is not particularly limited, but it is preferable to ventilate at least the time until the air in the pipe is replaced with the clean gas. Even if the air in the pipe is not completely replaced, the effect of the present invention can be obtained if the air is replaced to some extent.

  Whether or not it has been replaced can be known by examining the gas flowing out at the pipe outlet, etc., but for the sake of simplicity, prepare a clean gas with an appropriate volume according to the volume of the entire pipe. You may make it complete | finish ventilation | gas_flowing at the time of having disappeared. The amount of clean gas to be supplied depends on the volume and flow rate of the entire pipe, but is, for example, about 300 to 1000 liters per hour, and not a large amount.

  The ventilation time required until the air in the pipe is replaced with the clean gas depends on the flow rate of the clean gas (the flow rate of the clean gas supplied per unit time), the length and the inner diameter of the pipe, and the like. As described above, the flow rate is not limited, but by increasing the flow rate, it is possible to shorten the ventilation time performed after the completion of piping construction. In the case where the air is continuously ventilated during the piping construction, the replacement is almost completed when the piping construction is completed, so that the ventilation time performed after the piping construction is completed can be further shortened.

  In the case of a piping member made of a material such as PVC, it is usual to connect the piping using an adhesive. When using an adhesive, it is necessary to dry the applied adhesive and volatilize the organic solvent. This is to reduce the TOC by exhausting the organic solvent gas generated frequently when the organic solvent of the adhesive is volatilized out of the pipe. If the pipe is closed before the adhesive is completely dried, the solvent gas is generated even after the pipe is closed, so the pipe is filled with the solvent gas, and the TOC in the water increases significantly during the initial water flow. It becomes.

  Thus, when using an adhesive for pipe connection, it is preferable to continuously vent clean gas, for example, all day and night, in order to ensure the time required for drying the adhesive and evaporating the organic solvent. Considering that the time required to solidify the adhesive and increase the adhesive strength is usually about 4 hours, it is preferable to ventilate the inside of the pipe with a clean gas for at least about 4 hours. In addition, when no adhesive is used, for example, when heat welding is performed, the TOC in water increases with the organic matter remaining in the pipe by ventilating the pipe with a clean gas for at least about 4 hours. The effect which prevents is obtained.

  When the purpose is to reduce the TOC, it is not necessary to vent an inert gas not containing oxygen, and it is only necessary to vent a dehumidifying and dehumidifying gas containing oxygen. For example, it is possible to achieve an early reduction in the TOC concentration by ventilating dehumidified and dehumidified air (clean dry air) having an external atmospheric pressure dew point temperature of about −30 ° C. to −60 ° C. Of course, you may ventilate clean inert gas, such as high purity nitrogen gas. In that case, it is possible to achieve both the reduction of dissolved oxygen and the early reduction of the TOC concentration. Furthermore, by ventilating the pipe at a pressure higher than the external atmospheric pressure, it is possible to prevent mixing of fine particles such as dust in the external atmosphere. That is, by blowing clean inert gas into the pipe at a pressure higher than the external atmospheric pressure, three effects of early reduction of dissolved oxygen concentration, early reduction of TOC concentration, and early reduction of residual fine particles can be obtained simultaneously. It is done.

  In order to keep the atmosphere in the piping clean, even if the replacement of the air in the piping is completed or the drying of the adhesive is completed, the clean gas is continuously used until the initial water flow starts. It is preferable to ventilate. This is because if there is a period during which the ventilation is stopped halfway between the start of water flow and the start of water flow, the cleanliness of the atmosphere in the pipe may be reduced.

  In the case of ventilation even during the construction period from the start of pipe construction, the ventilation period is a period obtained by adding a period from the start of construction to the completion of construction and a period from the completion of construction to the start of initial water flow. For example, if the period from the start of construction to the completion of construction is 1 day and the period from the completion of construction to the start of initial water flow is 1 day, it will be 2 days, and from the start of construction to the completion of construction will be 60 days from the completion of construction to the start of initial water flow. If it is 3 days, it will ventilate continuously for 63 days.

  In addition, it is normal to ventilate in piping for piping inspection before the start of initial water flow after construction. The ventilation in this pipe inspection is different from the ventilation in the present invention in that it is an airtight test that is performed at a high pressure by closing the pipe in the test target section with a valve, a flange or the like in order to check whether there is a leak in the pipe. . Since ventilation in the present invention is for ventilation purposes, the piping is not closed when venting according to the present invention. During the period of the hermetic test, the end of the pipe cannot be opened to vent the air, so that it is excluded from the venting period of the present invention.

  As described above, in the present invention, since at least one end of the pipe is opened and a clean inert gas is passed through the pipe, the air in the pipe is replaced with a clean inert gas, so dissolved oxygen The concentration can be lowered.

  By ventilating clean gas in the pipe at a pressure higher than the external pressure, the inside of the pipe becomes a positive pressure compared to the outside, so even if it is a pipe made of resin such as vinyl chloride resin or polyvinylidene fluoride, Impurities such as dust in the external atmosphere can be prevented from being mixed. This is because resin piping tends to generate static electricity and easily absorb impurities, but impurities are not mixed and adsorbed in the piping by making the inside of the piping positive pressure compared to the outside. Therefore, the cleanliness of the inner surface of the pipe can be maintained at a cleanliness level equal to or lower than when it was first brought into the construction site, and the number of fine particles remaining after the initial water flow can be reduced in a short time. it can.

  By blowing clean gas through the pipe after construction for at least 4 hours before the initial water flow, drying of the adhesive and volatilization of the organic solvent are promoted, and the TOC value can be reduced early.

  In the case of ventilating dehumidified and dehumidified air containing oxygen as a clean gas to be ventilated, the effect of lowering dissolved oxygen concentration cannot be expected because oxygen is contained, but drying of the adhesive and volatilization of the organic solvent are promoted, and TOC The effect of reducing is obtained.

  Next, reference examples, reference comparative examples, examples and comparative examples will be described.

(Reference Example 1)
In Reference Example 1 and Reference Comparative Example 1, a pipe having a predetermined shape is formed by connecting by hot welding in the field using a clean pipe member for ultrapure water made of polyvinylidene fluoride (PVDF) having an inner diameter of 40 mm. This is an example in which ultrapure water was initially passed through the constructed pipe and the dissolved oxygen concentration in the water was measured. The ultrapure water supplied for the initial water flow is one having an oxygen removal treatment and a dissolved oxygen concentration of about 1 to 5 ppb.

  This pipe has a total length of about 300 meters and is a loop as a whole. Of these, the measurement section is 30 meters. In addition to the straight pipe portion, there are 40 bent portions, 4 branches, and 7 valves in the measurement execution section. This piping member is available as a piping member for ultrapure water. The piping inside is cleaned in advance, filled with nitrogen gas, and sealed at both ends with caps etc. It has been brought in.

Reference Example 1 is an example in which a clean inert gas was ventilated in a pipe to replace the air in the pipe with an inert gas, and then the water was passed through for the initial water flow. Specifically, during the construction period of this pipe, one end of the pipe is opened and the pipe members are sequentially joined by thermal welding, while continuously supplying high purity (99.999%) nitrogen gas from the other end. Then, nitrogen gas was circulated in the pipe, and the air in the pipe was replaced with nitrogen gas. After the connection of all the pipes was completed (after the completion of construction), nitrogen gas was further passed through the pipes. As soon as the air in the pipe was replaced with nitrogen gas, the open end was closed to form a loop pipe, and water was passed through the loop pipe at a flow rate of 4 m ³ / h. About the ultrapure water which distribute | circulates the area about 30 m in length in the said piping, the dissolved oxygen concentration in water was measured. A dissolved oxygen (DO) analyzer [MOCA-3600] manufactured by Orbis Fair was used to measure the dissolved oxygen concentration.

  Reference Comparative Example 1 has the same conditions as Reference Example 1 except that clean inert gas was not ventilated in the piping during and after the construction period.

  FIG. 1 is a graph showing the relationship between the initial water flow time and the dissolved oxygen concentration in Reference Example 1 and Reference Comparative Example 1. The vertical axis represents the dissolved oxygen concentration in water (unit: ppb), and the horizontal axis represents the initial water flow time (unit: hours).

  As shown in the figure, in Reference Example 1, compared to Reference Comparative Example 1, the initial water flow time until the dissolved oxygen concentration was reduced significantly decreased. Specifically, in Reference Example 1, the dissolved oxygen concentration decreased to 5 ppb after 4 hours from the start of the initial water flow and decreased to the same level as the dissolved oxygen concentration of the supplied water. It decreased to 3.2 ppb after 6 hours, 2.5 ppb after 9 hours, 2.2 ppb after 12 hours, about 1.8 ppb after 18 hours, and about 1.5 ppb after 24 hours.

  On the other hand, in Reference Comparative Example 1, it finally decreased to 10 ppb after 12 hours, became about 5.8 ppb after 18 hours, and remained about 4.5 ppb even after 24 hours. That is, it took about 20 hours to recover to 5 ppb, which is the dissolved oxygen concentration of the supplied water, and even after 24 hours, it was far from 3 ppb.

  As described above, even when the construction is performed using a piping member in which the inside of the piping is cleaned and the air in the piping is replaced with nitrogen gas, the nitrogen gas is vented into the installed piping, When nitrogen is replaced with nitrogen gas, the initial water flow time required to reduce the dissolved oxygen concentration to a predetermined value can be greatly shortened compared to the case where it is not replaced. It was possible to reduce.

  Although omitted in FIG. 1, in order to further reduce the dissolved oxygen concentration, it is necessary to conduct the initial water for a longer time, which is required when the installed pipe is replaced with an inert gas and when it is not replaced. The difference in the initial water flow time appears as a more significant difference.

  The reason why such a significant difference has occurred is considered to be as follows. That is, when nitrogen gas is not vented, oxygen in the external atmosphere flows into the pipe when the pipe member cap is opened and connected to the pipe and before the start of water flow. In this case, the oxygen in the pipe is considerably increased. On the other hand, when nitrogen gas is passed, the oxygen in the pipe is not increased because the air in the pipe is replaced with nitrogen gas. .

  When construction is performed using a piping member in which the air in the pipe is not replaced with nitrogen gas in advance, this difference in dissolved oxygen concentration becomes even more significant. That is, when the initial water flow is started in a state where oxygen is normally present in the pipe, the dissolved oxygen concentration in the water immediately after the start of water flow is almost saturated (about 8 ppm), while the construction has been completed. This is because when nitrogen gas is passed through the pipe and the air in the pipe is replaced with nitrogen gas, the dissolved oxygen concentration in the water immediately after the start of water flow hardly increases compared to the supplied water.

(Reference Example 2)
Reference Example 2 is an example in which the number of remaining fine particles was measured. As a measuring instrument, a fine particle count meter [UDI-50] manufactured by PMS, USA was used. It is the same as Reference Example 1 except that instead of measuring the dissolved oxygen concentration, the number of fine particles is measured.

  Reference Comparative Example 2 is the same as Reference Example 2 except that clean gas was not ventilated at all during and after the construction period.

  FIG. 2 is a graph showing the relationship between the number of fine particles of 0.05 μm or more existing in water and the initial water passage time in Reference Example 2 and Reference Comparative Example 2. The vertical axis represents the number of fine particles of 0.05 μm or more (particles / mL), and the horizontal axis represents time.

  As shown in the figure, in Reference Example 2, the number becomes 4 12 hours after the start of the initial water flow, decreases to 2 after 18 hours, 1.6 after 24 hours, and 1 after 48 hours. 2. Decreased to 1 after 96 hours.

  On the other hand, in Reference Comparative Example 2, there are 5 or more even after 24 hours, 4 after 36 hours, 2 after 72 hours, and about 1.6 remaining after 96 hours. It did not become less than pieces. In Reference Comparative Example 2, it took 3 times as long as that of Reference Example 1 to decrease to 4, and 4 times that of Reference Example 1 to decrease to 2.

  Thus, after the start of the initial water flow, the number of fine particles of 0.05 μm or more can be reduced in Reference Example 2 in a very short time compared to Reference Comparative Example 2, and at a predetermined value after 4 days. The number could be reduced to one.

  In other words, by passing high-purity nitrogen gas through the pipe and replacing the pipe with nitrogen gas, the time required to reduce the dissolved oxygen concentration in the water to a value within the specified range is shortened. In addition, the time required to reduce the number of fine particles of 0.05 μm or more to a predetermined value could be shortened. As a result, it was possible to reduce the initial water flow time and the initial water flow amount as compared with Reference Comparative Example 2.

Example 1
Example 1 is an example using piping for ultrapure water made of vinyl chloride resin (PVC), so-called clean PVC piping. The inner diameter, length, shape, etc. of the piping are the same as in Reference Example 1. Aeration was performed continuously from the start of construction, and construction was performed while connecting pipes sequentially using an adhesive. Even after the completion of the construction, it was ventilated for 4 hours or more. The gas vented into the pipe is a dust removal / dehumidification gas, specifically, a dust removal / dehumidification air (clean dry air) having an external atmospheric pressure dew point temperature of about minus 30 ° C. Immediately after the end of aeration, the open end was closed to make a pipe with a loop, and initial water flow was started at 4 m ³ / h. After a predetermined time, the remaining TOC concentration was measured for ultrapure water in a section of about 30 m in the pipe. The measuring instrument used is a TOC analyzer [A-1000XP] manufactured by Anatel, USA.

  Comparative Example 1 has the same conditions as Example 1 except that clean gas was not passed through the piping.

  FIG. 3 is a graph showing the relationship between the TOC concentration and the initial water passage time in the case of Example 1 and Comparative Example 1. The vertical axis represents the TOC concentration (unit: ppb), and the horizontal axis represents the initial water passage time (unit: time).

  As shown in FIG. 3, in Example 1, the TOC concentration became 8 ppb 24 hours after the start of the initial water flow, decreased to 5.7 ppb after 36 hours, 4 ppb after 48 hours, and 2 after 72 hours. .8 ppb and decreased to 2.1 ppb after 96 hours.

  In contrast, in Comparative Example 1, the TOC concentration immediately after the start of the initial water flow is very high, 10 ppb even after 48 hours, and corresponds to about 2.5 times the TOC concentration in Example 1 even after 96 hours. It was 5.3 ppb.

  In this way, from the start of pipe construction to the start of initial water flow through completion of construction, at least 4 hours after applying the adhesive to the last connection part of the pipe, the dehumidifying and dehumidifying gas continuously enters the pipe from one end of the pipe. When the air is ventilated (Example 1), the TOC concentration contained in the water in the pipe after the initial water passage is reduced in a short period of half or less compared to the case where the air is not ventilated (Comparative Example 1). I was able to. As a result, the initial water flow time and the initial water flow amount were significantly reduced as compared with Comparative Example 1.

  Although omitted in FIG. 3, when further reducing the TOC, it is necessary to conduct the initial water flow for a longer time. The difference in the initial water flow time required when the inside of the installed pipe is ventilated and when it is not ventilated is as follows: Even more noticeable. For example, when the TOC is reduced to about 0.7 ppb, the difference between the initial water passage times is about several days to several tens of days.

Claims (3)

In the initial water flow to the ultrapure water pipe having the connection of the ultrapure water production system,
A method of operating an ultrapure water production system, wherein the dehumidified and dehumidified gas is aerated for at least 4 hours in the installed pipe, and then the water is passed.   The operation method of the ultrapure water production system according to claim 1, wherein the aeration is performed at a pressure higher than an external pressure.   The method of operating an ultrapure water production system according to claim 1 or 2, wherein the ventilation is continuously performed from the start of pipe construction.

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