JPH01282450A - Analysis container - Google Patents

Abstract

PURPOSE:To enable accurate repeated analysis of multiple kinds of densities continuously with one container, by providing a check valve with a supply pipe set on the bottom of an analysis container. CONSTITUTION:A pipe 4 for supplying a reagent or the like and a detecting section 3 of a photo detector are disposed on the bottom of an analysis container. A check valve 43 is provided at the tip put within a container of the supply pipe 4 to block a liquid within the container 1 from reversing into a pipe. Then, a sample is supplied to the analysis container 1 from the supply pipe 4 by a specified value with a pump or the like and then, likewise, an indicator is supplied by a specified value. Then, a reaction is proceeded supplying a reagent by a small amount. Here, a blade 60 is driven to rotate and the photodetector 3 is turned ON beforehand. When the photo detector 3 detects the end of titration, the supply of the reagent is stopped. Then, the density of the sample is computed by a computing section to be displayed from an amount of the sample and an amount of the reagent required for titration.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to an analysis container, and more particularly, to a sample si
The present invention relates to an analysis container suitable for measuring the concentration of components therein by titration.

[Conventional technology]

Devices for measuring the concentration of components in liquids are needed in all industrial fields. Based on the results measured by the measuring device, the concentration of the liquid components is controlled to a constant level,
It is desirable to obtain stable, high-grade chemically processed products. For example, phosphate chemical conversion treatment is performed as a method to completely form a skin made of fine insoluble crystals of zinc phosphate, iron phosphate, etc. on the steel surface and use it as a base for painting to improve corrosion resistance and adhesion. It is well known that this is the case.

By the way, in the chemical conversion treatment mentioned above, it is of course necessary to control the concentration of the chemical liquid for quality control purposes, but automation is insufficient, manual analysis takes time, and response to analysis results tends to be delayed. The reality is that detailed management is not carried out. However, many automatic chemical analyzers have been proposed in the past. For example, automatic analyzers or analytical separation methods have been proposed in Japanese Patent Publication No. 55-21298 and Japanese Patent Publication No. 57-43864, and cells for measurement have been proposed in Japanese Patent Publication No. 59-52980. However, these proposed analytical devices have common drawbacks or problems. In other words, these analyzers insert a pair of electrodes into a cell containing the sample to determine the concentration of components in the sample.As a result of inserting the electrodes into the liquid, maintenance is required. This poses problems in terms of inspection and is disadvantageous in terms of cost.

Therefore, the present applicant proposed an automatic chemical analyzer that is easy to maintain and inspect and is low cost, in Japanese Patent Application No. 826,699/1982. This analyzer is composed of an analysis container, a plurality of pumps, a light detection device, and a controller. In particular, the means for detecting the end point of the reaction is a light emitting element and a light receiving element attached to the analysis container. It is composed of.

Therefore, when this automatic chemical analyzer is connected to the power supply and switched on, the
Liquid analysis can be automatically performed and the results displayed as follows. That is, a pump for supplying the sump is activated by a signal from the controller, and a predetermined amount of sample is supplied to the analysis container. At the same time or a little later, the controller issues a pump activation signal for the indicator, and a predetermined amount of indicator is supplied to the analysis container. At this time, the stirrer is also started.

The controller then issues a signal to activate the pump for reagent supply. Then, the reagent is continuously supplied to the analysis container in small amounts. At the same time, the controller activates the photodetector.

As the reagent supply progresses and the end point of the reaction is reached, the color of the sample changes and the photodetector over-reports a reaction end signal to the controller. Then, the controller calculates the component concentration of the sample from the sample amount and the supplied reagent amount. The results are then displayed on the display means. The above measurement operation is repeated at predetermined time intervals.

As described above, since the liquid is automatically analyzed and the results are displayed, the concentration of the liquid can be managed at low cost.Moreover, the detection means uses a commercially available light-emitting element and light receiver. Since the device can be applied, the intended purpose has been achieved.

By the way, it has since been discovered that there are points that should be improved in the above-mentioned automatic analyzer. In other words, since the sample or reagent is dripped from the supply tube into the analysis container proposed earlier, the tip of the supply tube needs to be squeezed into a nozzle shape in order to drain the liquid easily. The nozzle hole may become clogged by the deposits that dry and precipitate. If the nozzle hole is clogged, the next automatic analysis will not be possible. Therefore, to prevent drying, the tip of the supply tube is submerged in the liquid. It is conceivable to adopt a configuration in which the sample is submerged in water, but simply submerging the sample causes another problem in that part of the liquid in the supply pipe reacts with the sample in the analysis container, resulting in inaccurate analysis values.

In addition, sufficient consideration has not been given to cleaning the analytical vessels, so if you try to perform multiple measurements using multiple titrants, the trace amounts of remaining titrants may mix and distort the measurement results. Put it away. Furthermore, it has been found that there are points that need to be improved in terms of the compact structure of the analysis container and the structure and arrangement of the detection means.

[Purpose of the invention]

Therefore, the main object of the present invention is to provide an analysis container that allows multiple types of concentration analysis to be carried out repeatedly, continuously, and with high accuracy using one container. In addition, the purpose is to provide an analysis container equipped with an optical sensor that is inexpensive, easy to manufacture, and has excellent chemical resistance in place of conventional electrodes that are troublesome to maintain, but is not limited thereto. However, another object of the present invention is to provide an analysis container to which the automated analysis apparatus proposed in Japanese Patent Application No. 61-286699 can be applied.

[Structure of the invention]

In order to achieve the above-mentioned object, the present invention provides not only a drain port for discharging cleaning liquid and a titrated solution, but also a pipe for supplying a sample, an indicator, a reagent, etc., and a detection part of a light detection device in an analysis container. Provided at the bottom. A check valve is provided at the tip end of the supply pipe facing into the container to prevent the liquid in the container from flowing back into the pipe. Thus, the present invention is constructed as follows. That is, it is an analysis container into which a sample, an indicator, a reagent, etc. are supplied and titration analysis is performed, and the container has at least one blade for stirring the liquid inside and at least one blade to which a cleaning liquid is supplied. a drain port for discharging cleaning liquid and titrated solution, multiple chemical supply pipes for supplying samples, indicators, reagents, etc., and a light detection part of a light detection device for detecting the titration point. The drain port, the chemical supply pipe, and the light detection section are provided at the bottom of the analysis container, and the tip of the chemical supply pipe faces the inside of the container, and the tip of the chemical supply pipe faces the inside of the container. A backflow valve is provided to prevent liquid from flowing back into the pipe.

[Action/effect of the invention]

Since the present invention is constructed as described above, in its use, first a predetermined amount of a sample is supplied from a supply pipe to an analysis container using, for example, a pump, and then a predetermined amount of an indicator is similarly supplied. Then, the reaction is allowed to proceed while supplying a small amount of the reagent. At this time, the blades are rotated and the light detection device is also turned on. When the photodetector detects the end point of the titration, the reagent supply is stopped. The concentration of the sample is determined from the sample amount and the amount of reagent required for titration.
For example, the calculation is performed by a calculation unit such as that disclosed in Japanese Patent Application No. 61-286699, and necessary processing such as display and printing is performed.

When the titration is completed, the titrated liquid is discharged, water is injected into the container from the port, and the impeller base is rotated to clean the inside of the container. Drain the washing water from the main drain and wait until the next titration time. Of course, if the control device disclosed above is applied, the series of titration steps described above are all automatically performed.

According to the present invention, titration is performed as described above, and in particular, a supply pipe for supplying samples, reagents, etc. is provided at the bottom of the analysis container, and a reverse valve is provided. The tip will not be clogged with solutes that precipitate due to drying, and there will be no problem with the next titration.

Therefore, it is ideal as a container for automatic analyzers.

Further, since only the light detection part of the photodetection device is provided at the bottom of the container, the detection device will not be attacked by chemicals. This is because the detection part is preferably constructed of materials such as mirrors and lenses that are highly resistant to chemicals. Furthermore, since the main parts such as the supply pipe and the light detection section are arranged at the bottom of the analysis container, there is an advantage that the analysis container can be configured compactly.

〔Example〕

In implementing the present invention, a valve body may be formed at the tip of the drive shaft that drives the stirring blades, and the valve body may be used to open and close the drain port. An overflow port may also be provided. All of these will be explained in the following examples, but in this example, a preferred example will be described that is applied to an analysis container of an automatic analyzer.

Now, referring to FIG. 1, it can be understood at a glance that the analysis container according to the present embodiment includes various accessories to form the analysis container 1.

That is, the analysis container itself is formed into a cylindrical shape from chemical-resistant glass, porcelain, plastic, etc., and has a VC so that chemicals such as a sample, an indicator, and a reagent are supplied inside the container. A plurality of openings are formed at the bottom of the analysis container 1, the opening in the center is used as a drain port 2 for discharging the cleaning liquid or the titrated solution, and the other one is used as a light detection device (not shown). For example, the remaining openings arranged concentrically with respect to the drain port 2 can be used to attach a plurality of pipes 4.4 for supplying samples, indicators, reagents, etc.
......Mounting is provided through the hole. for example,
In controlling the concentration of the zinc phosphate chemical conversion treatment solution, at least the total acidity and oxidation promoter concentration are measured.・・・・・・
. . . are provided in numbers corresponding to the samples and their respective indicators and reagents, that is, five in total.

The drain port 2 is formed approximately at the center of the bottom, and a sleeve 20 is inserted thereinto to form the drain port.

The lower end of the sleeve 20 serves as a valve seat 21, and a pipe for discharging a solution is attached below. Valve seat 2
1 is opened and closed by a valve stem, which will be explained later. Further, the light detection section 3 will be similarly described later with reference to FIG. 2.

A plurality of medicine supplying vibrators 4.4, . . . are arranged concentrically with respect to the drain port 2. In the illustrated embodiment, nipples 40, 40, . . .
It consists of a cylindrical part 41.41 at its lower end,...
. . . has pipes or channels 42, 42. ...
......is designed to be installed in a watertight manner.

A pump (not shown) is connected to the tube, which is ultimately connected to a chemical container, such as a sample tank, an indicator bottle, a reagent bottle, etc. Therefore, when the pump is activated,
A predetermined amount of chemicals is supplied to the analysis container through these channels.

Check valves 43, 43, . . . are inserted into the portion of the nipple 40 facing into the analysis container 1. These backflow valves are designed to ensure that the liquid in the analysis container is at the nipple 40.40,
......i.e. vibrator or chave 42
, 42, . . . , and commercially available products are used. That is, as shown in FIG. 3, the entire body is made of an elastic material such as chemical-resistant propylene rubber, and the nipples 40, 40 . It consists of a flange part 44 that is inserted into the flange part 44, and a nozzle part 45 that is connected to this flange part and becomes narrower in a tapered shape. is included. therefore,
In the figure, the liquid pushes open the nozzle portion 45 and flows in the direction of the arrow, but when no fluid pressure is applied in the direction of the arrow, the notch 46 comes into close contact and prevents the liquid in the analysis container from flowing toward the nipple 40. do.

A port 5 for supplying washing water is formed in the side wall of the upper portion of the analysis container 1, and a socket 50 is inserted into this port in a watertight manner. An opening is also provided for overflowing a cleaning liquid, for example water, which overflows during cleaning of the analysis container.

In order to make the reaction more complete during titration or to enhance the cleaning effect, a stirring blade 60 is provided in the analysis container 1 near its bottom. The vane 60 is fixed to a valve rod 61 that coaxially extends inside the analysis container 1 . The lower end of this valve rod serves as a valve body 62, which opens and closes the drain port 2. Therefore, the valve body 62 has a narrow conical tip and is driven in the vertical direction.

The valve stem 61 extends upwardly from VcQ and connects to the motor 6 via a coupling means.
3 is combined. That is, a drive shaft 64 extends downward from the motor 63, and a joint 65 is fixed to this shaft with a pin 66. [The key 6 fixed to the upper end of the valve stem 61 with a pin 67 in the groove provided at the lower end of the joint 65
8 are slidingly connected. Therefore, the valve stem 61 is movable in the vertical direction, that is, in the axial direction, with respect to the drive shaft 64, and rotational force is transmitted thereto. Also, joint 6
5 and the upper end of the valve stem 61 is a coil spring 69.
is interposed, and the valve stem 61 is always urged downward.

A coil 70 and an electromagnetic core 71 are provided concentrically with the coil spring 69 in order to pull the valve stem 61 upward against the biasing force of the coil spring 69. coil 7
0 is disposed in a space between an upper housing 72 having a U-shaped cross section and a lower housing 74 having a flange portion 73, and the inside thereof is sealed with a cylinder 75 made of brass. A cylindrical electromagnet core 71 that is movable in the axial direction is provided inside the brass tube 75. This electromagnet core 7
1 has a locking portion 76 extending radially inward at its lower end. A key 68 is locked to this locking portion 76 via a thrust bearing 77. Therefore, when the key 68, that is, the valve stem 61 is pushed downward by the coil spring 69, the electromagnet core 71 is also pushed downward and moves, but when the coil is energized, the electromagnet core 71
9 and pull the valve stem 61t upward.

As mentioned above, the motor 63 is arranged above the analysis container 1, but in order to maintain a predetermined distance between them or to facilitate maintenance and inspection, the analysis container 1 and the motor 63 are A connecting pipe 80 is provided between them. That is,
The upper opening of the analysis container 1 is a single body 82 having seven flange 81.
It is set to be closed. The lid body 82 is Porto 83
．． The analysis container IK is attached at 83, . 7 langes 84 are similarly inserted into the upper part of the connecting pipe 80. Then, this 7 lange 84 is attached to the base B along with the lower housing 74)85.85. . . . The entire apparatus including the analysis container 1, the motor 63, etc. is supported by the base. In FIG. 1, reference numeral 86 indicates a motor mounting plate, and 87 indicates a motor shaft and a cover.

As shown in FIG. 2, the photodetecting section 3 of the photodetecting device has a generally cylindrical shape as a whole, and is inserted into the bottom wall T of the analysis container 1 through a seal S in a watertight manner. It looks like this. That is, the sensor cylinder part 30 has a cylindrical shape, and optical fibers 31 and 31 are supported inside by a cap 32 and a retainer 33. An annular 7 is provided approximately at the center of the outer circumference of the sensor cylinder portion 30.
Further above the flange 34 is a similar annular recess #13.
5 is formed. And 7 lunge 34 is analysis container l
An O-ring S is arranged in the concave groove 35 so as to be in contact with the lower surface of the bottom wall when the O-ring S is inserted into the bottom wall.

A lens seat 36 is attached to the upper end of the sensor cylinder section 30, and the lens L is attached to this seat in a watertight manner with a gasket 37. Further, as shown in the figure, the lens seat 36 has a U-shaped cross section, and a mirror M is fixed to a mirror seat 38 above the lens seat 36.

Light emitted from a photodetector (not shown) passes through an optical fiber 31 and is projected from a lens L toward a mirror M, and the light reflected by the mirror M is guided to the photodetector via another optical fiber 31. . Since the titration is thus detected by back-and-forth light, the accuracy is even higher. Further, since the lens seat 36 is formed in a U-shaped cross section, the reaction liquid effectively reaches the light path, allowing reliable detection of the titration end point.

Next, the operation of the above embodiment will be described. First, a pump is driven to supply, for example, a sample 10- to the analysis container 1 which has been thoroughly cleaned from the chemical supplying chevron 42 through the check valve 43. Then phenolphthalein k
0.3 m is similarly supplied by another chemical supplying channel 42. While driving the blade 60, caustic soda of known concentration is injected until phenolphthalein turns red. This red change is detected by the light detection section 3, and the titration is completed.

The concentration of the sample is calculated from the amount of caustic soda required for the titration, and then displayed or printed or otherwise processed as appropriate.

When the titration is completed, the coil 70 is energized. When applied to an automatic analyzer, it is automatically energized. Then, the electromagnet core 71 moves upward in the figure against the coil spring 69. Therefore, the valve stem 61 and hence the valve body 62
is separated from the valve seat 21, and the titrated solution is discharged to the outside. When the discharge is finished, the valve body 62 and valve seat 2 are removed from port 5.
The inside of analysis volume 1 is washed by injecting water at a flow rate slightly higher than that flowing through analysis volume 1 while rotating blades 60.

The overflowing water is discharged to the outside through another opening 5 similar to the port 5 provided in the side wall of the analysis volume 1. When the cleaning is completed, the water injection from the port 5 is stopped, the rotation of the blade 600 is stopped, and when the drainage is completed, the power to the coil 70 is cut off and the drain port 2 is closed.

Note that the indicator is not limited to phenolfretain; for example, in measuring the concentration of an oxidation promoter in a zinc phosphate chemical conversion treatment solution, 50% hydrogen chloride sulfuric acid can be used as an indicator and titrated with potassium permanganate. The above-mentioned analysis container can also be used in a manual analysis device or in the patent application No. 61-286699.
It is also clear that this method can also be applied to the automatic analyzer proposed in the above issue.

As an effect of the embodiment, for example, in the light detection unit 3, since only lenses and mirrors made of glass or the like are arranged in the analysis container 1, corrosion due to chemicals, water, etc. and reduction in electrical insulation are avoided. The effect is that there are no problems such as Furthermore, since the end point of titration is detected by reciprocating light, there is also the advantage that there is no false detection. Further, since the vane 60 is attached to the valve stem 61, the arrangement inside the analysis container can be made compact, and there are also four advantages such as titration can be performed with a small amount of sample.

[Brief explanation of the drawing]

The drawings show one embodiment of the present invention, in which FIG. 1 is a cross-sectional view of the whole, FIG. 2 is a cross-sectional view of a light detection section, and FIG. 3 is a perspective view of a check valve. DESCRIPTION OF SYMBOLS 1... Analysis container, 2... Drain port, 3... Light detection part, 4... Chemical supply pipe, 5... Washing water port, 4
3... Check valve, 60... Stirring blade.

Claims (1)

[Claims] An analysis container into which a sample, an indicator, a reagent, etc. are supplied for titration analysis, and the container has a blade for stirring the liquid inside and at least one port to which a cleaning liquid is supplied. , a drain port for discharging the cleaning liquid and the titrated solution, a plurality of chemical supply pipes for supplying samples, indicators, reagents, etc., and a light detection section of a light detection device for detecting the titration point. , the drain port, the chemical supply pipe, and the light detection section are provided at the bottom of the analysis container, and the tip of the chemical supply pipe faces the inside of the container, and the liquid in the container is exposed to that part. An analysis container characterized in that it is provided with a check valve that prevents the liquid from flowing back into the pipe.