JPH10170495A - Analyzing apparatus - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a simple and accurate analyzing apparatus which can evaluate quality of each kind of liquid produced, used or discharged at various factories, laboratories, etc., and can be utilized for process management. SOLUTION: The analyzing apparatus has an analysis path 1 in which a liquid S to be analyzed flows, mixing means 2a, 2b set at least at two points in the analysis path 1 for mixing a reagent A reacting with the liquid S to be analyzed, detecting means 4a, 4b set at the downstream of the corresponding mixing means for detecting a state of a produced liquid resulting from the mixing, and a judging means 8 for judging a state of the liquid S to be analyzed from the state of the produced liquid detected by the detecting means 4a, 4b.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an analyzer used for evaluating the quality of various liquids produced, used, or discharged in various factories and laboratories.

[0002]

2. Description of the Related Art In order to maintain and maintain the physical properties and the types and concentrations of dissolved substances in liquids produced, used, or discharged on a daily basis in various factories and laboratories, within a certain range. Analysis is being performed in the process. For example, a cleaning solution used in a semiconductor manufacturing factory or the like is analyzed for the acidity and the concentration of hydrogen peroxide, and a chemical solution is added based on the analysis result so that the concentration is always kept within a certain range. Conventionally, the chemical concentration of this cleaning solution is measured by manual sampling and titration analysis (acid-alkali neutralization titration) or by an electrochemical sensor. For example, when the chemical concentration decreases, a chemical concentration within an allowable range is obtained. Until then, control was performed by adding an acidic substance such as hydrochloric acid or an alkaline substance such as ammonia to the cleaning liquid. Conventionally, the concentration of hydrogen peroxide is measured by manual sampling and titration analysis (redox titration),
Alternatively, the absorbance of visible light, ultraviolet light, or near-infrared light is measured using an optical sensor, and the obtained analog electric signal is subjected to regression analysis calculation or the like.

For example, when acidic wastewater is discharged, a neutralizing agent (a basic aqueous solution) is used to maintain a certain neutral range.
Must be discharged after neutralization. For this purpose, a pH meter is inserted into the flow path of the wastewater to detect its liquidity, the obtained analog electric signal is digitally processed, and the required addition amount of the neutralizing agent is calculated and calculated. A flow control mechanism such as a solenoid valve was operated to control the amount of the neutralizing agent added.

[0004]

However, there are various problems in the conventional analytical method for evaluating the quality of a liquid using these various sensors. For example, in the control of the chemical concentration of the cleaning liquid and the neutralization control of the wastewater, it is necessary to frequently perform cleaning and verification of a pH meter and an electrochemical sensor for determining the chemical concentration and the pH of the wastewater, which is extremely complicated. there were.

[0005] In particular, as disclosed in Japanese Patent Application No. 4-272068, when measuring the concentration of hydrogen peroxide as a chemical solution concentration, the oxygen concentration obtained by decomposing hydrogen peroxide is electrochemically detected. When a sensor is used, the concentration of hydrogen peroxide must be calculated based on a small electric signal generated from the oxygen sensor. Therefore, cleaning of the sensor surface and verification of the sensor (the difference between the absolute concentration of hydrogen peroxide and the sensor output potential) are performed. ) Must be performed frequently, and maintenance is complicated in order to maintain the accuracy of the analyzer, which makes it difficult to use it during the process. Further, not only was the flow path of the liquid constituting the analyzer complicated, and miniaturization was difficult, but also complicated work was required for repairing and adjusting the device itself. Also, when using a sensor that optically detects the concentration of hydrogen peroxide, not only is it difficult to obtain sufficient sensitivity for process control, but also, for example, the absorbance of ultraviolet and near infrared rays is affected by dissolved components other than hydrogen peroxide. Therefore, it is necessary to perform a complicated regression analysis operation from preliminary measurement values of a multi-component aqueous solution, and the accuracy is insufficient for the purpose of obtaining the absolute value of the hydrogen peroxide concentration.

SUMMARY OF THE INVENTION The present invention has been made to solve the above problems, and has as its object to provide a simple and accurate analyzer used for evaluating and managing the quality of a liquid. It is in.

[0007]

An object of the present invention is to provide an analysis flow path through which a test liquid flows, and mixing means provided at at least two locations in the analysis flow path for mixing a reagent which reacts with the test liquid. Detecting means provided downstream of each mixing means for detecting the state of the product liquid generated by the mixing, and determining the state of the test liquid from the state of the product liquid detected by each of the detecting means The problem can be solved by providing an analyzer having a determination unit.

It is preferable that the above-mentioned analyzer has a module in which at least an analysis flow path, a mixing means, and a reagent flow path for supplying the reagent to each mixing means are integrally formed. This module is preferably formed of a three-layered laminate, in which at least an analysis channel, a mixing means, and a reagent channel are formed in an intermediate layer. Also, this module, downstream of each mixing means,
It is preferable that a light transmitting means capable of transmitting light across the analysis channel is provided.

The above-mentioned determination means binarizes each output signal provided from each detection means, and evaluates the quality of the test liquid based on each binarized output signal. Is preferred.

[0010]

Embodiments of the present invention will be described below with reference to the drawings. The analyzer of the present invention (hereinafter simply referred to as “analyzer”) can be used for analyzing various liquids and for process control. In this case, when analyzing or controlling the acidity and / or the concentration of hydrogen peroxide in the cleaning solution, Will be described.

(Embodiment 1) In FIG. 1, this analyzer is for controlling the acidity of a cleaning solution, and has an analysis channel 1 through which a test solution S flows, and two portions in the analysis channel 1. And mixing means 2a and 2b provided sequentially in the same direction, and detecting means 4a and 4b provided downstream of the respective mixing means. The detecting means 4a and 4b are electrically connected to the determining means 8.

The test liquid S flowing through the analysis channel 1 is an acidic cleaning liquid. A red aqueous solution containing a basic neutralizing agent (for example, sodium hydroxide) and a phenolphthalene indicator is supplied from the reagent supply path 3 to the mixing means 2a and 2b as a reagent that reacts with the test liquid S. The reagents Aa, Ab are introduced and branched via the reagent flow paths 3a, 3b, respectively.
It is supplied as. Reagent channels 3a, 3
b is provided with valve mechanisms 5a and 5b for adjusting the flow rates of the reagents Aa and Ab, respectively. Each of the detecting means 4a and 4b is an optical sensor, and is configured to detect the presence or absence of a red color of the product liquid generated by the above-described mixing in a binary manner and transmit the same to the determining means 8.

As shown in FIG. 2, the determining means 8 basically determines the acidity of the test liquid S (equivalent of dissolved acidic substance /
L) and reagents Aa, Ab to be supplied to the mixing means 2a, 2b
The stoichiometric excess / deficiency relationship with the basicity (equivalent of neutralizing agent / L) is compared in a binary manner with the discoloration point of the phenolphthalene indicator as a threshold value, and the above-mentioned excess The acidity of the test liquid S supplied to the analysis channel is determined by calculating from the shortage relationship and the supplied amounts of the reagents Aa and Ab.

That is, in FIG. 2, the detecting means 4a,
If both the binary signals from 4b are [colorless], the effluent W discharged from the effluent passage 1W which is the effluent side terminal of the analysis flow path 1 is acidic (+), that is, exceeds the set acidity control value. Is determined. This indicates that the supply amount of the reagent A is insufficient with respect to the acidity of the test liquid S. If the binary signals from the detection means 4a and 4b are both [red], the discharged liquid W is determined to be basic (-), that is, the control value of the set acidity is under. This indicates that the supply amount of the reagent A is excessive with respect to the acidity of the test liquid S. The signal from the detection means 4a is [colorless] and the other 4b is [colorless].
Is satisfied, the discharged liquid W is determined to be in the intermediate region (±). That is, if the signal from the detecting means 4b indicates [red] and the detecting means 4a indicates [colorless], the acidity of the test liquid S and the supply of the reagent A within the control range, that is, in the intermediate area within this range. This shows that the amount and the amount are almost equivalent. Table 1 shows the relationship (truth value) between the binary signals from the detection means 4a and 4b and the determination result.

[0015]

[Table 1]

In the analyzer of the above embodiment, the test solution S flows through the analysis channel 1, and the valve mechanisms 5a and 5b are opened to open the reagent A.
a and Ab are supplied to the respective mixing means 2a and 2b, and the opening degrees of the valve mechanisms 5a and 5b are adjusted so that the signal from the detection means 4a indicates [colorless] and the signal from the detection means 4b indicates [red]. If adjusted, the acidity (equivalent / time of the acidic substance / time of the acidic substance) of the test liquid S supplied to the analysis channel 1 is determined from the concentration and the flow rate (equivalent / time of the neutralizing agent) of the reagent A (Aa and Aa + Ab) in this state. ).

When this analyzer is used for controlling the concentration of the washing solution during the process, the supply amount of the reagent A is kept constant, the signal from the detecting means 4a indicates [colorless], and the signal from the detecting means 4b indicates The acidity of the cleaning solution may be adjusted so as to indicate [red].

The operation of the above analyzer will be described quantitatively. First, the test liquid S is allowed to flow through the analysis channel 1. At this time, the acidity (equivalent) of the test liquid S is MS mol / L, and the flow rate is VSL / min. Next, the reagents Aa and Ab colored red are respectively mixed from the reagent flow paths 3a and 3b by the mixing means 2.
a, 2b. At this time, the basicity (equivalent) of the reagent A is MA mol / L, and the supply flow rates of the reagents Aa and Ab are VA1 L / min and VA2L / min, respectively.

When the determination means determines that the discharged liquid W is in the intermediate region (±), the acidity MS of the test liquid S is expressed by the following equation (1).
Within the range. MAVA1 / VS≤MS≤MA (VA1 + VA2) / VS Equation 1 Therefore, if the basicity (equivalent) MA of the reagent A and the flow rate VS of the test liquid S are kept constant, the acidity of the test liquid S (washing liquid) is obtained. MS
Can be determined from the measured values of the supply flow rates VA1 to VA1 + VA2 of the reagent A.

Further, the supply flow rates VA1 and VA2 of the reagents Aa and Ab satisfying the formula 1 are maintained, and the signal from the detecting means 4b shows [red] and the signal from the detecting means 4a becomes "colorless". Test liquid S (washing liquid)
The acidity MS of the above indicates that the state is in an appropriate management state within an allowable range.

When the determination means determines that the discharged liquid W is acidic (+), the acidity MS of the test liquid S is expressed by the following equation (3). MS> MA (VA1 + VA2) / VS Equation 2 Here, since VA2 is a setting element of the allowable width of the intermediate region, if the allowable width of the intermediate region is not changed, the valve mechanism 5a is used.
Until the determination means determines that the discharged liquid W is neutral, that is, the signal from the detection means 4a is [colorless].
Until the signal from the detection means 4b indicates [red].
If the supply flow rate VA1 of the reagent Aa is increased, the increased amount of the reagent Aa at this time corresponds to the excess amount of the acidic substance in the washing solution.

When the determination means determines that the discharged liquid W is basic (-), the acidity MS of the test liquid S is expressed by the following equation (3). MS <MAVA1 / VS Equation 3 Here, if the allowable range of the neutral range is not changed, the valve mechanism 5
a until the determination means determines that the discharged liquid W is in the intermediate region, that is, until the signal from the detection means 4a indicates "colorless" and the signal from the detection means 4b indicates "red". If the supply flow rate VA1 of Aa is reduced, the amount of decrease in the reagent Aa at this time corresponds to the shortage of the acidic substance in the cleaning solution.

When the acidity of the washing solution is controlled using this analyzer, the amount of the reagent A required for neutralizing the test solution S does not always need to be obtained as a numerical value. Reagent A
It is not necessary to accurately determine the concentration of the neutralizing agent in advance. That is, a washing solution (standard solution) with an acidity that becomes a standard in advance
Is passed through the analysis flow path 1 at a constant flow rate, the allowable width of the neutralization zone is set by adjusting the opening of the valve mechanism 5b, that is, the flow rate of the reagent Ab, and then the opening of the valve mechanism 5a is adjusted. When increasing the flow rate of the reagent Aa, while the signals from the detection means 4a and 4b are both "colorless", the supply amount of the reagent A is still insufficient, so the increase in the flow rate of the reagent Aa is continued. The valve mechanism 5a when the signal from the detection means 4a is "colorless" and the signal from the detection means 4b is "red"
The opening of is slightly increased and fixed as the lower limit of the neutral region.

Conversely, after the concentration of the neutralizing agent in the reagent A is strictly determined, the flow rate VA1 of A1 is set by the valve 5a so that the equivalent point is set at the lower limit of the predetermined control range. Probably, there is a method of opening the valve 5b and setting VA2. Also,
Flow the cleaning liquid at the lower limit of the control value, gradually open the valve 5a,
A method may be used in which the valve 5b is set at a point where the discoloration starts, and the valve 5b is set at a point where the detection means 4b just starts coloring in a state in which the cleaning liquid having the concentration of the upper limit of the control value flows.

Next, the actual washing liquid is passed through the analysis channel 1 as the test liquid S, and if the signals from the detecting means 4a and 4b are both "colorless", the acidity is higher than the standard liquid.
For example, when the automatic control mechanism is activated to dilute the cleaning liquid with water, and when the signals from the detection means 4a and 4b both become [red], the acidity is lower than the standard liquid. By adding an acid to the cleaning liquid, the cleaning liquid can be maintained at an appropriate acidity in any case.

The case where the analyzer is used for controlling the acidity of the cleaning liquid has been described above, but the analyzer can also be applied to the concentration measurement and concentration control of other dissolved substances.
For example, the present invention can be applied to the case where the concentration of hydrogen peroxide in the cleaning liquid is controlled. In this case, the cleaning liquid containing hydrogen peroxide flows through the analysis flow path 1 as the test liquid S, and the reagent supply path 3 (3
For example, an aqueous solution of potassium permanganate is supplied as reagent A to a and 3b). Each of the detection means 4a and 4b is an optical sensor, and binary-detects the presence or absence of coloring of the product liquid generated by mixing the cleaning liquid and the aqueous solution of potassium permanganate, and transmits it to the determination means.

In this case, according to the truth values shown in Table 2, the determination means determines the content of hydrogen peroxide in the cleaning liquid as the flow rate of the aqueous solution of potassium permanganate A which is equivalent to the content.
Shown within certain tolerances.

[0028]

[Table 2]

Using the analyzer configured as described above, in the same manner as described for the case of acidity control, using a cleaning solution (standard solution) having a hydrogen peroxide concentration as a standard in advance, and setting an allowable range of an appropriate concentration. The opening of the valve mechanism 5b is set, and the opening of the valve mechanism 5a is set as the lower limit of the appropriate concentration. Next, the actual cleaning liquid is passed through the analysis channel 1 as the test liquid S, and when the signals from the detection means 4a and 4b both become "colorless", the concentration of hydrogen peroxide in the cleaning liquid is higher than the standard liquid. Then, for example, the automatic control mechanism is activated to dilute the cleaning liquid with water, and when the signals from the detection means 4a and 4b are both colored, the concentration is lower than the standard liquid. Then, by adding hydrogen peroxide to the cleaning liquid, the cleaning liquid can be maintained and controlled in an appropriate range of the hydrogen peroxide concentration in any case.

Conversely, after strictly determining the concentration of the neutralizing agent in the reagent A, the flow rate VA1 of A1 is set by the valve 5a so that the equivalent point is set at the lower limit of the predetermined control range. Probably, there is a method of opening the valve 5b and setting VA2.

(Embodiment 2) This embodiment shows an embodiment of an analyzer capable of simultaneously measuring the acidity and the hydrogen peroxide concentration of a cleaning solution containing an acid and hydrogen peroxide. As shown in FIG. 3, the analyzer includes an analysis flow path 1 through which a test liquid (washing liquid) S flows, and mixing means 2a, 2b, 2c, and 2d sequentially provided at four positions of the analysis flow path 1. And detection means 4a, 4b, 4 provided downstream of the respective mixing means.
c, 4d. Of these detection means, 4
Reference numerals a and 4b denote sensors capable of detecting the concentration of hydrogen peroxide in the cleaning liquid as an oxidation-reduction potential.
Sensors 4c and 4d which are capable of detecting the hydrogen ion concentration are connected to the judgment means 7a for judging the value, and are connected to the judgment means 7b for judging the hydrogen ion concentration in a binary manner.

Here, the test liquid S flowing through the analysis channel 1 is a cleaning liquid containing an acid and hydrogen peroxide. Further, the mixing means 2a,
2b includes reagents Aa and Ab that react with the test solution S,
An aqueous potassium permanganate solution is supplied from the reagent supply path 3 via the valve mechanisms 5a and 5b, respectively.
To c and 2d, an aqueous solution of a basic compound (for example, sodium hydroxide) is supplied as reagents Ba and Bb that react with the test liquid S from the reagent supply path 6 via the valve mechanisms 5c and 5d, respectively.

In this analyzer, when the washing solution S is passed through the analysis flow path 1 and the aqueous potassium permanganate solutions Aa and Ab are supplied to the mixing means 2a and 2b, the hydrogen peroxide and the potassium permanganate in the washing solution S are removed. React, the oxidation-reduction potential of the product liquid is detected by the detection means 4a and 4b, respectively, and the detection signal is sent to the hydrogen peroxide concentration determination means 7a.

The hydrogen peroxide concentration judging means 7a binarizes the signals from the detecting means 4a and 4b into an oxidizing side (+) and a reducing side (-) using a predetermined value of the oxidation-reduction potential as a threshold value. In comparison, according to the truth values in Table 3, the concentration of hydrogen peroxide in the cleaning solution S was set as the flow rate of the aqueous solution of potassium permanganate A when the equivalent range was reached, and the allowable range was set as the reagent Ab.
It is displayed as a flow rate.

Alternatively, when the difference between the measured signals from the detection means 4a and 4b is equal to or more than a predetermined value, that is, when the oxidation-reduction potential is, for example, 500 mV or more, it is possible to determine that it is in the intermediate region and within the management range. However, this method makes it difficult to determine whether it is over or under when it is not in the intermediate area.

[0036]

[Table 3]

In this analyzer, when the basic compound aqueous solutions Ba and Bb are supplied to the mixing means 2c and 2d in a state where the cleaning liquid S is circulated in the analysis flow path 1, the acidic substance in the cleaning liquid S and the supplied base are supplied. React with the active substance, the pH of the product liquid is detected by the detecting means 4c and 4d, respectively, and the detection signal is sent to the hydrogen ion concentration determining means 7b.

The hydrogen ion concentration determining means 7b binarizes the signals from the detecting means 4c and 4d into an acid side (-) and a base side (+) using, for example, pH = 7 as a threshold value and compares them. According to the value table, the acidity of the cleaning liquid S is displayed as the flow rate of the basic substance aqueous solution B when the neutralization range is reached, and the allowable range is displayed as the flow rate of Bb.

[0039]

[Table 4]

With the use of the analyzer of Example 2, the concentration of hydrogen peroxide and the acidity of the cleaning solution can be determined from the flow rate of the aqueous solution of potassium permanganate A or the flow rate of the aqueous solution of basic substance B, respectively. Instead, if the opening degree of the valve mechanism 5a, 5b, 5c, 5d is adjusted and fixed for the standard cleaning liquid, the result of determination based on Table 3 or Table 4 of the determination means 7a, 7b when the actual cleaning liquid flows is obtained. Accordingly, the concentration of hydrogen peroxide and the concentration of acidic substance in the cleaning solution can be controlled simultaneously.

An analyzer capable of simultaneously measuring the acidity and the hydrogen peroxide concentration of a cleaning solution containing an acidic substance and hydrogen peroxide includes:
Other than the format shown in the second embodiment, it is possible within the scope of the present invention. For example, an apparatus similar to that shown in the first embodiment is
A series is used, and the respective analysis channels 1 are merged at the upstream thereof. That is, the cleaning liquid as the test liquid S is set to an equal flow rate of 2
It is divided and distributed in each series, and an aqueous solution of a basic substance is used as the reagent A in one series, and the reagent B in the other series is used.
Using an aqueous solution of potassium permanganate, and using the same detection means and judgment means as those shown in Example 1, respectively, as the flow rate of the reagent A or the reagent B in the neutralization range or the equivalent range, respectively. The acidity and hydrogen peroxide concentration can be determined.

If the analyzers of the present invention described as Embodiments 1 and 2 are further generalized, a multi-component batch analyzer shown in FIG. 4 can be realized. In the collective analyzer shown in FIG. 4, the analysis flow path 1 that circulates the test liquid S containing the multicomponent to be measured has branch paths 1a, 1b,.
y, each branch flow path is provided at n places, and a mixing means 2 for mixing a reagent reacting with the component of the test liquid, and provided downstream of each mixing means, Detecting means 4 for detecting the state of the product liquid generated by the above. Each mixing means 2 has a reagent flow path 3
, A reagent is supplied which reacts with any component of the test liquid S to be measured, so that the state of the generated liquid can be detected by the detecting means 4.

In the first and second embodiments, two mixing means 2 are used to analyze one component to be analyzed. However, in the above-mentioned generalized analyzer, the mixing means used per component is The number is not limited to two, but may be one or three or more. If the number of the mixing means is one, the number of the detecting means 4 is also one. In this case, an appropriate allowable width cannot be set for the component. However, whether or not the component exceeds the threshold value is determined in a binary manner. be able to. If there are three or more mixing means per component, the component can be managed in multiple stages.

Further, the above-mentioned analyzing apparatus binarizes each output signal provided from each detecting means, and judges the quality of the test liquid based on each binarized output signal. If it has, for example, when analyzing using an ambiguous color reaction in which the discoloration changes in an analog manner, appropriateness / inappropriateness is clearly determined by the set threshold value, and management measures are properly instructed. become able to.

(Embodiment 3) This embodiment is an analyzer having the same mechanism as that shown in Embodiment 1, but a part thereof is modularized. Figure 5 shows this module.
And FIG. In FIG. 5, the module 10 is a laminate having a rectangular plate shape and includes three layers of an outer layer 11, an intermediate layer 12, and an outer layer 13. This module 10
Windows 110a and 110b made of a translucent member are formed at two places on the outer layer surfaces 11 and 13, respectively, so that light can be transmitted vertically through the module through the windows 110a and 110b. . A test liquid introduction pipe 1D and a reagent supply pipe 3D extend from one side surface of the intermediate layer 12, and a drainage pipe 1W extends from the other side surface. Reagent flow rate adjusting screws 108a and 108b are provided at two locations.

FIG. 6 shows the structure of the intermediate layer 12. Middle layer 1
2 is roughly four pieces of non-contacting blocks 12a, 1
2b, 12c, and 12d, and the gap between the blocks forms a liquid flow path. The analysis channel 1 extends through the intermediate layer 12 in the longitudinal direction from the test liquid introduction pipe 1D while expanding in diameter, and communicates with the drain pipe 1W. In the analysis flow path 1, a first mixing means 102a, a first measuring unit 101a, a second mixing means 102b, and a second measuring unit 101b are sequentially formed from the test liquid introduction pipe 1D side.

The first mixing means 102a and the second mixing means 102b are respectively provided with upstream mixing sections 103a, 103b.
b and downstream stirring units 105a and 105b. The mixing units 103a and 103b are spaces for mixing the test liquid S and the reagent A introduced from the reagent supply pipe 3D.
The agitating units 105a and 105b are made of, for example, a member having a helical split barrier (for example, a product name "Static Mixer") for generating a turbulent flow in the liquid and agitating the liquid.

First measuring section 101a and second measuring section 10
Reference numeral 1b denotes a portion of the analysis flow path 1 in which the windows 110a and 110b formed in the outer layers 11 and 13 of the module 10 are part of the wall surface, and the color of the liquid flowing through this portion is the window portion. It can be monitored from outside through 110a and 110b.

The reagent supply path 3 branches into reagent flow paths 3a and 3b, divides the reagent A introduced from the reagent supply pipe 3D into two parts, and passes through the branched paths to the mixing section 103.
a, 103b. Flow rate control valves 115a, 115b are mounted at the inlets of the reagent flow paths 3a, 3b, respectively. These flow rate control valves 115a, 115b are connected to reagent flow rate adjusting screws 108a, 108b, respectively, and the opening degree of the module 10 is controlled. It can be adjusted from outside. Also, the reagent flow rate adjusting screws 108a, 108
A pointer is engraved on b, and the degree of opening of the flow control valves 115a and 115b can be read on the scale by the scale provided on the side surface of the module.

The reagent flow paths 3a and 3b are respectively provided in the mixing section 1
03a, 103b, and check valves 107a, 107 which are movable in the front-rear direction of the flow.
The check valve b is installed, and the movable width in the downstream direction of the check valves 107a and 107b is limited by stoppers 116a and 116b, respectively, so that the liquid flow in the analysis flow path 1 is not obstructed.

The analyzer of the third embodiment uses the module 1
It is configured as follows using 0. Light sources 111a and 111b are provided in windows 110a and 110b formed in one of the outer layers (for example, outer layer 13) of module 10.
Attach. Light-receiving elements 112a and 112b are mounted on the corresponding windows of the other outer layer (11), respectively. These light-receiving elements 112a and 112b are provided with the same determination means (not shown) as shown in the first embodiment. Connect to The test liquid introduction pipe 1D is connected to a supply source of the test liquid S via a flow meter (or a quantitative pump), and the reagent supply pipe 3D is connected to a supply source of the reagent A via a flow meter (or a quantitative pump). Connecting.

A case where this analyzer is used for controlling the concentration of hydrogen chloride in the cleaning solution will be described below. The reagent A used is
It is an aqueous solution of sodium hydroxide of a certain concentration that is colored red and contains a phenolphthalene indicator. Further, the determination means determines the liquidity of the cleaning liquid according to the truth values shown in Table 5 below, and when the concentration (acidity) of hydrogen chloride in the cleaning liquid exceeds the allowable range and is large or small, respectively. The warning is issued.

[0053]

[Table 5]

First, the analyzer is corrected. Prepare a standard cleaning solution having an acidity in an appropriate range in advance, and use it in module 1
The test solution is introduced at a constant flow rate from the test solution introduction pipe 1D to the analysis flow path 1. Next, the flow rate control valves 115a and 115b are respectively opened appropriately by operating the reagent flow rate control screws 108a and 108b, and the reagent A at a constant flow rate is supplied from the reagent supply pipe 3D to the reagent flow paths 3a and 3b. Here, the opening of the flow control valve 115b is determined by the reagent A (A
The flow rate in b) is set so as to correspond to the allowable fluctuation range of the acidity of the cleaning liquid. Further, the opening degree of the flow control valve 115a is adjusted, and the determination means is fixed at a position where "lower limit of allowable range" is displayed. Thus, the correction of the analyzer is completed. This correction operation need not be repeated as long as the sodium hydroxide concentration of the reagent A and the supply pressure do not change.

When the liquid corresponding to the lower limit of the control value is flowed as a sample, the opening of the valve 115a is adjusted so as to be at the equivalent point, and the valve is set at the equivalent point when the liquid having the upper limit of the control value flows. A method of adjusting the opening of 115b is also possible.

In this state, the cleaning solution S actually used is continuously passed through the analysis flow path 1. If the acidity of the cleaning liquid S is within the allowable range, the determination means displays “within the allowable range”. During the flow,
If the acidity of the cleaning liquid fluctuates up and down beyond the allowable range, the determination means immediately sends an alarm of “excess acidity” or “insufficient acidity”.

When the alarm is issued, the cleaning liquid is diluted in the supply source until the judgment means displays "within the allowable range" in response to the display of "excess acidity" or "insufficient acidity". Alternatively, if hydrochloric acid is added, the cleaning solution can always be maintained and controlled within an appropriate range with respect to the acidity.

The modules that can be used in the analyzer of the present invention are not limited to the configurations and shapes shown in FIGS. For example, module 1 above
In No. 0, the liquid flow path was formed in the intermediate layer 12 of the rectangular plate-shaped laminate, but the liquid flow path may be formed by connecting a plastic pipe or the like. In the case of a three-layer laminated module, if the outer layers on both sides are formed of a transparent acrylic plate or the like, it is not necessary to separately provide a window.

The above windows 110a and 110b are provided in the module 10 when an optical sensor is used as the detecting means.
Since it is necessary to avoid mounting a light source and light receiving element with a complicated structure inside the sensor, when using a sensor that non-optically detects a change in the state of the liquid, remove the window and measure the sensor. What is necessary is just to mount | wear with the position of the part 101a, 102b. Furthermore, if sufficient stirring can be performed in the mixing units 103a and 103b, the stirring units 105a and 105b can be omitted or simplified.

[0060]

The analyzer according to the present invention comprises: an analysis channel through which a test solution flows; and mixing means provided at at least two locations in the analysis channel to mix a reagent that reacts with the test solution. Provided downstream of the mixing means, and having a detection means for detecting the state of the product liquid generated by the mixing, it is possible to perform a simple and accurate analysis,
It can be advantageously used for evaluating the quality of various liquids produced, used, or discharged in various factories and laboratories, and for process control.

If the above-mentioned analyzer has a module in which at least an analysis flow path, a mixing means, and a reagent flow path for supplying the reagent to each mixing means are integrally formed, a piping in the apparatus is provided. In addition to simplifying the apparatus, the size of the apparatus can be reduced, and by connecting a plurality of modules, analysis and management of individual components of the multi-component liquid can be performed simultaneously.

The analyzer has a decision means for binarizing each output signal provided from each detection means and evaluating the quality of the test liquid based on each binarized output signal. If there is, even if the detection information obtained by the detection means changes analogously or indistinctly, the appropriate / inappropriate boundary is clearly determined by the set threshold value, and management measures are properly performed. Be able to give instructions.

Even if the absolute value of the output of each detecting means (sensor) changes (shift or drift), the binarization allows the drift to a certain extent.

[Brief description of the drawings]

FIG. 1 is an organization diagram showing one embodiment of an analyzer of the present invention.

FIG. 2 is a flowchart showing a signal flow of a determination unit of the embodiment.

FIG. 3 is an organization diagram showing another embodiment of the analyzer of the present invention.

FIG. 4 is an organization diagram showing still another embodiment of the analyzer of the present invention.

FIG. 5 is a perspective view showing a module in an embodiment of the analyzer of the present invention.

FIG. 6 is a plan view showing a configuration of an intermediate layer of the module.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 ... Analysis flow path 1W ... Drainage path 2a, 2b ... Mixing means 3 ... Reagent supply path 3a, 3b ... Reagent flow path 4a, 4b ... Detection means 5a, 5b ... Valve mechanism 8 ... Judgment means S: Test liquid A, Aa, Ab: Reagent W: Discharge liquid

 ──────────────────────────────────────────────────の Continuation of the front page (72) Inventor Shiro Sawada 7-3-1, Hongo, Bunkyo-ku, Tokyo Inside the Faculty of Engineering and Science, the University of Tokyo

Claims (5)

[Claims] 1. An analysis flow path for flowing a test liquid, mixing means provided at at least two positions in the analysis flow path for mixing a reagent reacting with the test liquid, and a mixing means provided downstream of each mixing means. An analyzer having detection means for detecting the state of the product liquid generated by the mixing, and determination means for determining the state of the test liquid from the state of the product liquid detected by each of the detection means. 2. The analyzer according to claim 1, further comprising a module in which at least an analysis channel, a mixing unit, and a reagent channel for supplying the reagent to each mixing unit are integrally formed. 3. The analyzer according to claim 2, wherein the module comprises a three-layer laminate, and at least an analysis channel, a mixing unit, and a reagent channel are formed in an intermediate layer. 4. Downstream of each mixing means of the module,
3. The analyzer according to claim 2, further comprising a light transmitting means capable of transmitting light across the analysis channel. 5. The determination means binarizes each output signal provided from each detection means, and evaluates the quality of the test liquid based on each binarized output signal. The analyzer according to claim 1.