JP2007139568A - Uv chamber and toc monitor device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a TOC monitor device capable of controlling the flow of a sample (water) being a measuring target according to a first-in first-out system to continuously measure and monitor a stable and accurate TOC value inexpensively and capable of achieving the safety of water. <P>SOLUTION: In a UV chamber having a reaction pipe device constituted so as to irradiate with ultraviolet rays the sample in a flow channel through which the sample flows in a longitudinal direction, the reaction pipe device is equipped with an ultraviolet irradiation member for irradiating the sample with ultraviolet rays so as to have the irradiation angle crossing the longitudinal direction at a right angle and the cylindrical cover block member arranged to the outside of the ultraviolet irradiation member so as to cover the flow channel and constituted as a solid structure. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a water quality analyzer, and more particularly, to a UV chamber and a TOC (Total Organic Carbon) monitoring device that incorporates a reaction tube device that reacts in a sample to quantitatively analyze the total organic carbon content.

  Regarding this type of UV chamber and TOC monitoring device, “water quality analysis device and water quality analysis method” was disclosed in Japanese Patent Application Laid-Open No. 2004-177164 (Patent Document 1) by the applicant of the present invention (Techno Morioka Co., Ltd.) in 2002. An application is filed on November 25 and discloses a method for quantitative analysis of the total organic carbon (hereinafter referred to as TOC) contained in a sample.

  According to “Water quality analysis device and water quality analysis method” of Patent Document 1, in a reaction tube device in a UV chamber, an organic matter is oxidized by irradiating a sample, for example, an organic matter contained in the sample water with ultraviolet light. The wet ultraviolet oxidation method that can quantitatively analyze the amount of carbon contained in water based on the difference in the electrical conductivity of water before and after irradiation with ultraviolet light is used. And as one of the indexes representing the cleanliness of water, there is the total organic carbon (TOC) value (expressed in μg / l or ppb (parts / per / billion)) which is the amount of carbon in organic matter in water. . In particular, in semiconductor cleaning in which it is important to use water containing almost no impurities, a TOC value of 0.20 μg / l or less may be required. A TOC monitoring device using an ultraviolet oxidation method is widely used. The TOC monitoring device using the wet UV oxidation method measures the conductivity of the sample water to be measured with a conductivity sensor, and then irradiates the sample water with ultraviolet light to oxidize organic substances contained in the sample water. And measure the conductivity again. The TOC monitoring device calculates the TOC value of the sample water based on the difference in the conductivity of the sample water before and after being irradiated with ultraviolet rays.

  The above-described TOC monitoring device is installed in a cleaning process for cleaning semiconductors, and monitors the cleanliness of water used for cleaning in real time. In a semiconductor cleaning process, it is important to manage water quality by performing in-line real-time measurement for monitoring the cleanliness of water containing organic substances such as organic solvents in real time, and always use water with good cleanliness. In addition to the semiconductor cleaning process described above, the TOC monitoring device is used to measure the cleanliness of water used in manufacturing processes that require water with good cleanliness or pharmaceutical processes that handle various organic substances. Are also used.

  Referring to FIGS. 3 and 4, the structure of the reaction tube device in the UV chamber in the TOC monitoring device of the related invention has a quartz helical hollow glass tube.

  In this case, the synthetic quartz tube is formed into a helical shape and irradiated with ultraviolet rays from an ultraviolet irradiation member (UV lamp) disposed inside the helically extending sample channel.

JP 2004-177164 A

  However, in the above-described conventional examples and related inventions, the flow of the sample in the flow path is poor, the first-in first-out is incomplete, and there is a measurement error that occurs due to flow rate fluctuations due to changes in the measurement environment.

  In addition, the sample water flowing from the sample IN to the sample OUT has a radial incident angle, and the ultraviolet reflection efficiency is not good, and a manufacturing technique for forming the thickness of the synthetic quartz tube substantially constant is difficult.

  Therefore, the technical problem of the present invention is to provide a UV chamber and a TOC monitoring device that have a first-in first-out function that improves the distribution of the sample to be measured, can measure and monitor a stable and accurate TOC value, and are inexpensive to manufacture. Is to provide.

  The present invention that achieves the above-described object is a UV chamber having a reaction tube device that performs processing by irradiating the sample in a flow path in which the sample flows in the longitudinal direction with ultraviolet rays, and the reaction tube device includes: An ultraviolet irradiation member that irradiates the ultraviolet rays so as to have an irradiation angle orthogonal to the longitudinal direction, and a cylindrical coating block that is disposed outside the ultraviolet irradiation member so as to cover and form the flow path and is solid And a member.

  The ultraviolet irradiation member of the UV chamber according to the present invention irradiates the sample at an irradiation angle that is directly orthogonal. As a result, the sample covered with the cylindrical covering block member can be directly and efficiently irradiated with ultraviolet rays. Therefore, a TOV monitoring apparatus having such a UV chamber of the present invention can be obtained.

  According to the present invention, the sample sample (water) to be measured is inclined convection, and the first-in first-out flow can be controlled. As a result, it is possible to provide a UV chamber and a TOC monitoring device capable of continuously measuring and monitoring an inexpensive, stable and accurate TOC value and ensuring the safety of water.

  Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. The configuration of the TOC monitoring device 1 that detects the amount of carbon contained in the sample water to be measured will be described.

  1, 2, 5, and 6, the UV chamber 12 included in the TOC monitoring device 1 that detects the amount of carbon contained in the water (sample) 10 includes a reaction tube device 12 </ b> A, And a hippo covering. The reaction tube device 12A is configured to irradiate ultraviolet rays (ultraviolet rays: UV) onto the sample water 10 to be measured, in the direction perpendicular to the longitudinal direction, that is, the irradiation light 11-1a having an irradiation angle of 90 degrees (UV). Lamp) 11-1, an ultraviolet ray transmitting member (quartz glass tube) 11-2 that receives, transmits, and transmits the irradiated ultraviolet light 11-1a to the water 10 as a transmitted ultraviolet ray, and receives the water 10 in a tilted convection manner to make first-in first-out. A first-in first-out promotion gap 11-3A for promoting processing includes a formed cylindrical covering block member (resin) 11-3. The cylindrical covering block member (resin) 11-3 is an ultraviolet transmissive member (synthetic quartz glass tube) that accommodates the ultraviolet irradiation member (UV lamp) 11-1 by cutting from a solid cylindrical resin with an NC machine tool. ) The outer periphery of 11-2 is tightly fitted, and the O-rings 14-1 and 14-2 are inserted so as to fit in, and an insoluble resin such as a pure PTE (poly-tetra-fluoro-ethylene) material, Made of PFA (Perfluoroalkoxy copolymer) (trade name S-PFA) material.

  As shown in FIG. 6, the first-in first-out acceleration gap 11-3A-1 has an interference fitting portion (helical contact portion) 11-3a with a helical gap formed of a helical surface through which the sample water 10 is circulated while inclining convection. . Therefore, the reaction tube device 12A-1 has an effect that the first-in first-out process of the ultraviolet irradiation-treated water (sample) 10 from the inlet of the connecting portion 14a to the outlet of the connecting portion 14b is promoted by the reaction tube device 12A. As a result, the total organic carbon content of the sample water (sample) 10 is accurately measured and monitored.

  To reiterate, the first-in first-out acceleration gap 11-3A of the reaction tube device 12A in the UV chamber 12 forms a flow path for the sample water 10, and is an interference fit with the ultraviolet transmitting member 11-2 (quartz glass). Part (helical contact part) 11-3a and sealed. Note that only both ends of the ultraviolet lamp 11-1 protrude from both ends of the chamber 12.

  The ultraviolet lamp 11 is used in a wet ultraviolet oxidation method, and may be any lamp that generates ultraviolet light having a wavelength sufficient to oxidize an organic substance contained in sample water, and is not limited to ultraviolet light.

  Furthermore, the ultraviolet transmissive member 11-2 is formed of a synthetic quartz glass material that transmits ultraviolet rays from the ultraviolet lamp 11-1. The organic matter contained in the sample water 10 is oxidized by irradiation with ultraviolet rays while flowing through the reaction tube device 12A, and is sent to the conductivity sensor 30.

  FIG. 7 is a diagram of a reaction tube device 12A-1a in another modification of FIG. The reaction tube device 12-1a has a cylindrical covering transmission member (quartz glass) 13 so as to keep a predetermined separation distance around the ultraviolet irradiation member (UV lamp) 11, and the bottomed groove 13A has a longitudinal direction. It is formed as an inclined interval that spirals with a predetermined acute angle θ with respect to the discharge direction. As a result, the bottomed groove 13A of the cylindrical covering transmission member (quartz glass tube) 13 acts as a first-in first-out promotion gap that is spaced apart from the UV lamp 11 by a larger distance than the predetermined spacing interval. As a result, the water 10 causes inclined convection and is first-in first-out.

  The UV chamber 12 may not require an aluminum cover in order to reduce the use environment and the weight of the entire apparatus. The UV chamber 12 is the same as the reaction tube device 12A.

(First embodiment)
In the first embodiment according to FIGS. 5 and 9, the TOC monitoring apparatus 1 measures the intake part 45 for taking sample water, the discharge part 46 for discharging sample water containing bubbles, and the amount of carbon. A drainage part 48 for discharging the sample water is provided.

  A constant flow manifold 50 comprising a plurality of orifices as pressure limiting means for keeping the pressure of the sample water substantially constant is attached to the discharge portion 46, and the orifice discharges the sample water 10 containing bubbles. This restricts the pressure of the sample water 10 flowing through the flow path from rapidly decreasing.

  The TOC monitoring device 1 in FIG. 5 employs the constant flow valve 1 of 49-1, and the constant flow valve 2 of 49-2, and either one can perform low flow control. In the case of high-purity sample water, it is arranged at 49-2 on the drain side. When there are many pressure fluctuations, it arranges in 49-1 of the rewater side. And it is necessary to provide the conductivity sensors 30-1 and 30-2 as carbon amount detection means for detecting the amount of carbon contained in the sample water. Moreover, the TOC monitoring apparatus 1 includes control means (not shown) for controlling the flow rate / flow velocity of sample water.

  The water intake unit 45 is connected to an external pipe that supplies sample water to the TOC monitoring device 1. The pressure of the sample water 10 taken is varied using a multistage rotary tube pump 70 disposed on the downstream side of the UV chamber 12.

  Referring to FIGS. 5, 9, and 12, for example, sample water 10 is sampled at a flow rate of 10 ml / min, and zero point measurement, isopropyl alcohol organic substance injection, and UV irradiation on / off are performed to turn sample water 10 on. The amount of carbon is continuously measured from the change in conductivity. At this time, compared with the conventional model of the related invention, according to the present invention, since the sample water 10 having a constant flow rate in which the first-in first-out is promoted can be continuously flowed, the cleanliness of the sample water can be constantly managed.

(Second Embodiment)
8 and 10, in the TOC monitoring apparatus 1, the conductivity sensor 30 is a single signal processing means 40 having the control unit 101 and the like, and the display unit 100 for displaying the signal processing result. .

  The signal processing unit 40 includes a storage unit 102 that stores the signal processing result, a sensor unit 103 as a flow meter that measures the flow rate of the sample water, and a flow rate that measures the flow rate of the sample water from the sensor unit 103. The measurement unit 104 includes a conductivity measurement unit 105 that measures conductivity from the conductivity sensor 30.

  The flow velocity measuring unit 104 measures the flow velocity of the sample water 10 flowing in the TOC monitoring device 1 with the sensor unit 103 of the flow meter, and controls the sample water 10 to be promoted in first-in first-out using the data relating to the flow velocity. It is also possible.

  Referring to FIG. 10, when measuring and monitoring the TOC value of the TOC monitoring device 1 of the present invention, the TOC value is calculated based on the conductivity of the sample water 10 to be measured. First, in the purge operation before the measurement after the power supply 60 is turned on, the UV irradiation driving means 80 performs ultraviolet irradiation so as to turn on the tube pump 70 and increase the flow velocity. The control unit 102 causes the vibration motor 107, the tube pump 70, and the UV irradiation driving unit 80 to operate in a predetermined procedure, and repeatedly performs a zero calibration operation of data of various measurement values at regular time intervals (periodic). As a result of such control, only one conductivity sensor 30 needs to be arranged on the downstream side of the UV chamber 12. Then, the vibration motor 107 is driven in order to eliminate measurement obstruction factors such as bubbles generated in the reaction tube device 12A. In order to reduce the periodic calibration, it is necessary to provide two conductivity sensors.

  The control unit 101 processes data obtained from the storage unit 102, the sensor unit 103, and the flow velocity measurement unit 104, and acquires data from the storage unit 102, the sensor unit 103, and the flow velocity measurement unit 104 at a predetermined operation timing. . Further, the storage unit 102 stores data related to the conductivity of the sample water 10 to be measured at a required operation timing. In addition, the control unit 101 calculates the TOC value of the sample water to be measured based on data obtained from the storage unit 102, the sensor unit 103, and the flow velocity measurement unit 104.

  The storage unit 102 stores data related to the conductivity of the sample water 10 to be measured. For example, based on the data relating to the conductivity that is once stored in the storage unit 102 and read out again by the control unit 101 and the data relating to the conductivity newly acquired from the sensor unit 103 by the control unit 102, the control unit 101. The TOC value can be calculated.

  By the way, in the reaction tube device 12A in the UV chamber 12 of FIG. 8, a vibration motor 107 is attached to a desired position in the longitudinal direction around the ultraviolet irradiation processing member 12A-1 of FIG. The vibration motor 107 is a vibration member (swing member) made of a piezoelectric element or the like disposed along the periphery of the reaction tube device 12A-1 in FIG.

(Third embodiment)
Referring to FIGS. 8 and 11, the sensor unit 103 of the UV chamber 12 is a Peltier for cooling the water 10 that has been heated to high temperature by ultraviolet rays instead of a flow meter when the flow rate measurement unit 104 does not require flow rate control. An element may be provided. In a use environment such as medical use or clean room, it is necessary to use sample water 10 which is cooled and free of bubbles. Temperature-controlled and stably measured as a conductivity signal from the conductivity sensor 30, data related to conductivity is sent to the control unit 101.

  As described above, in the first to third embodiments, according to the TOC monitoring apparatus, it is possible to keep the sample water (sample) 10 that is first-in-first-out and contains almost no bubbles. Therefore, the TOC value can be measured and monitored with high accuracy. Furthermore, it is possible to accurately measure and monitor the TOC value of the sample water 10 to be measured in a flowing state in real time. That is, in order to manage the cleanliness of the water 10 used in the flowing state, a measurement value of the TOC value suitable for the display is displayed on the display unit 100 and monitored by the user.

  As described above, according to the UV chamber and the TOC monitoring device of the present invention, the first-in first-out of the sample water flowing in the reaction tube device can be maintained, and the sample water without bubbles is continuously flowed into the sample water. The concentration of impurities such as contained organic substances can be measured and monitored accurately and continuously in real time. Therefore, the present invention can be applied to semiconductor manufacturing apparatuses, pharmaceutical manufacturing apparatuses, and the like.

It is a front view of the reaction tube apparatus in the UV chamber in the TOC monitoring apparatus of this invention. It is a side view of the reaction tube apparatus of FIG. It is a front view of the reaction tube apparatus concerning related invention. FIG. 4 is a side view of FIG. 3. It is a figure which shows the internal structure of the TOC monitoring apparatus in 1st Embodiment of this invention. It is sectional drawing of the principal part of a reaction tube apparatus in the state without the cover of the UV chamber in the TOC monitoring apparatus of this invention. It is sectional drawing of the modification of the reaction tube apparatus of FIG. It is a block diagram which shows the data processing structure of the TOC monitoring apparatus in 2nd Embodiment of this invention. It is a timing chart for demonstrating the data processing result in 1st Embodiment of this invention. It is a timing chart for demonstrating the data processing result in 2nd Embodiment of this invention. It is a timing chart for demonstrating the data processing result in 3rd Embodiment of this invention. It is a figure which shows the comparison with the evaluation test result of related invention by the evaluation test result which concerns on the change of the electrical conductivity of the sample water by the electrical conductivity measurement part of the TOC monitoring apparatus in 1st Embodiment of this invention. It is a figure which shows the voltage flow volume at the time of driving the tube pump of the TOC monitoring apparatus in FIG.5 and FIG.8. It is a figure showing the cooling effect of the Peltier device (sensor part) of the TOC monitoring apparatus of FIG. It is a figure which shows the evaluation test result showing the voltage rotation speed at the time of driving the vibration motor of FIG.

Explanation of symbols

10 Sample (sample water)
11 Ultraviolet irradiation member (ultraviolet (UV) lamp)
11-1 Ultraviolet irradiation member (ultraviolet lamp)
11-1a UV light 11-2 UV transmitting member (quartz glass tube)
11-3 Tubular covering block member (resin)
11-3a Spiral contact part (襞)
11-3A First-in-first-out acceleration gap 11-3A-1 First-in first-out acceleration gap 12 UV chamber 12-1 Ultraviolet irradiation means 12A Reaction tube device 12A-1 Reaction tube device 12A-1a Reaction tube device 13 Quartz glass tube)
13A First-in first-out acceleration gap (bottom groove, inclined gap)
14a Inlet means 14b Outlet means section 30 Conductivity sensors 30-1, 30-2 Conductivity sensor 40 Signal processing means 45 Water intake section 46 Air mixed water discharge section 48 Drain section 49-1, 49-2 Constant flow valve 50 Constant flow rate Manifold 60 Power supply 70 Tube pump 80 UV irradiation drive means 100 Display unit 101 Control unit 102 Storage unit 103 Sensor unit 104 Flow rate measurement unit 105 Conductivity measurement unit 106 Carbon content measurement unit 107 Vibration motor

Claims (9)

A UV chamber having a reaction tube device that performs processing by irradiating the sample with ultraviolet rays in a flow path in which the sample flows in a longitudinal direction;
The reaction tube device comprises:
An ultraviolet irradiation member that irradiates the ultraviolet rays so as to have an irradiation angle orthogonal to the longitudinal direction;
A cylindrical covering block member which is disposed outside the ultraviolet irradiation member so as to cover the flow path and is solidly configured;
A UV chamber characterized by comprising: The UV chamber of claim 1,
The ultraviolet irradiation member is
A substantially cylindrical UV lamp disposed in the approximate center of the chamber block;
A quartz glass tube disposed around the UV lamp;
With
In the cylindrical covering block member,
The UV chamber, wherein the channel is a spiral channel spirally wound around an outer periphery of the quartz glass tube and has a substantially semicircular cross section. The UV chamber of claim 2,
The UV chamber, wherein the spiral flow path is formed with a helical contact portion that is in close contact with the outer periphery of the quartz glass tube at a predetermined interval as an interference fit. The UV chamber according to claim 2,
In the cylindrical covering block member,
An inlet as a pipe joint for receiving the sample is formed at the bottom, an outlet as a drain pipe is formed at the top, and an O-ring is disposed in the vicinity of each of the inlet and the outlet. Chamber. The UV chamber of claim 2,
The cylindrical covering block member is
A UV chamber formed of an insoluble resin material that does not dissolve in the sample. The UV chamber according to claim 4,
The reaction tube device comprises:
A UV chamber, further comprising an oscillating member that oscillates the sample in the spiral flow path to prevent bubble retention as a measurement inhibiting factor. In the TOC monitoring apparatus having the UV chamber according to claim 6,
A TOC monitoring apparatus, further comprising a tube pump connected and arranged on the downstream side of the UV chamber for changing the flow rate of the sample from a high flow rate drainage state to a predetermined state with a substantially constant low flow rate. In the TOC monitoring device according to claim 7,
A Peltier element for adjusting the temperature of the sample to a predetermined temperature is arranged as a sensor unit,
A conductivity sensor for sensing the conductivity of the sample;
A conductivity measurement unit for generating a conductivity measurement value from the conductivity sensor;
A flow rate measurement unit that generates a flow rate measurement value of the sample in the predetermined state at the predetermined temperature;
Signal processing means for processing data of the conductivity measurement value and the flow velocity measurement value;
A TOC monitoring device further comprising: The monitoring device according to claim 8, wherein
Ultraviolet irradiation drive means for driving the ultraviolet irradiation member to respond to the operation timing of the tube pump and the swinging member;
A controller for repeatedly performing a zero calibration operation of the data at regular time intervals;
A TOC monitoring device characterized by comprising: