JPS58162852A - Analyzing apparatus of automatic titration - Google Patents

Abstract

PURPOSE:To operate a titration analyzing apparatus quickly, repeatedly and continuously and nearly unattendedly, by controlling sequentially the operations of a sampling mechanism, titration mechanism and analyzing mechanism. CONSTITUTION:A sampling burette 3, titration burettes 7, 8, an air pump 13, a discharge pump 14 and solenoid valves SV1-SV5, are operated for a prescribed time in a prescribed order by a controlling mechanism 15 and also, signals sent from a pH measuring electrode 11 and an oxidizing and reducing electric potential measuring electrode 12 provided in an analyzing cell 9 are received and then, the operations of the burettes 7, 8 are stopped at the time of arriving at a prescribed pH or electric potential. The, the titration quantity of a reagent is read. Moreover, this mechanism 15 is constituted so that the concentration of components to be measured in a sample is calculated from said read quantity and is displayed and recorded and also, an alarm is given at the time when the value becomes abnormal.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an automatic titration analyzer for automatically measuring the concentration of a liquid.

In general, chemical analysis is indispensable in the operational management of chemical reaction equipment, treatment equipment in which chemicals are added as treatment agents, and water quality management of industrial water and industrial wastewater. Conventionally, rapid chemical analysis has been carried out by experts in analytical techniques and improvements in analytical equipment.

Even so, there were problems in that measurement took time, individual errors were unavoidable, and when so-called repeated continuous analysis was performed, excessive labor was required on the part of the analyst.

In particular, for quality control and process control in the production process of chemical factories, it is extremely important to constantly produce highly accurate measurement values and feed this back into the production process. It had been waiting for a while.

The present invention provides an automatic titration analyzer that meets these demands, and includes a sampling mechanism for collecting a predetermined amount of sample, a reagent titration mechanism, and a system for receiving samples and reagents and titrating reagents. an analysis mechanism that converts a physical or chemical change in the sample into an electrical quantity and outputs it; and a sampling mechanism 1 that sequentially controls the operation of the sampling mechanism and the analysis mechanism, reads the titer of the reagent, and outputs the analysis result. It is characterized by being equipped with a control mechanism.

An embodiment of the present invention will be described with reference to the drawings.

This device is used to control the concentration of an etching solution for dissolving and removing a specific amount of copper from electrical circuit boards such as printed circuit boards.
This is an automatic titration analysis control device that automatically maintains the concentration of sulfuric acid and copper within a predetermined range, greatly streamlining the etching process.

That is, this device automatically titrates and analyzes the concentration of the etching solution through sequence control, and feeds back the analysis results to the etching solution concentration adjustment mechanism.
This makes it possible to easily and accurately manage the concentration of the etching solution.The automatic titration analysis mechanism is roughly divided into a sample sampling mechanism S, a reagent titration mechanism T0, an analysis mechanism A, and a control mechanism C. The etching solution concentration adjustment mechanism includes a hydrogen peroxide metering pump Ps and a sulfuric acid metering pump P! and etching liquid circulation pump P3
The discharge sides of the injection pumps P+ and Pt are connected to an etching device (not shown), and the discharge side of the circulation pump P3 is connected to the etching device via a copper sulfate crystallization and recovery device (not shown) via a pipe. has been contacted.

Therefore, the sampling mechanism S has the following main elements: a circulation pump for the sample for analysis; It is equipped with an overflow box (overflow cell) 2 and a sampling billet 3 which is a piston pump type metering pump (equipped with a check valve). SVa-8Vi is a solenoid valve. Said circulation pump1.
The overflow box 2 and the sample storage tank 4 constitute a sample circulation system.

The sample (etching solution) enters an overflow box 2 by a circulation pump 1 and is constantly refreshed.

The titration mechanism T has an alkaline reagent tank5. It is equipped with a potassium permanganate reagent tank 6 and a titration biulet 7.8 having a similar structure to the sampling biulet 5 for titrating these reagents to the sample in the analysis cell 9.

Next, 1 analysis mechanism A includes a container that receives the sample and the reagent, that is, the analysis cell 9, a solenoid valve that supplies a cleaning liquid for cleaning the inner wall thereof, and a dilution liquid for diluting the sample in the analysis cell 9. Sv1, and a liquid level controller (level switch) 10 for controlling the supply amount of cleaning liquid and diluting liquid to predetermined amounts.
and.

pH measuring electrode 11, redox potential measuring electrode 12 and 1 analysis cell? It is equipped with an air pump 13 (a soda lime pipe for removing carbon dioxide gas is connected to the discharge side) for stirring the content liquid, and a discharge pump 14 for the content liquid. Note that SV2. SV3 is a solenoid valve.

On the other hand, the control mechanism C (corresponding to the control section indicated by 15 in the figure) is equipped with a microcomputer, a display, and a converter.
+~SVs, sampling billet 5. m constant billet 7.8. Operating the air pump 15 and discharge pump 14 in a predetermined order for a predetermined time; 1. Opening and closing the solenoid valve SV+ in response to a signal from the novel suite 10; H measurement electrode 11. Upon receiving the signal from the redox potential measurement electrode 1z, when a predetermined pH or potential is reached, the operation of the titration biulet 7.8 is stopped, the end point of the titration is detected, and the titration amount of the reagent at the end point is determined by these titrations. Read from Billet 7.8 and calculate the hydrogen peroxide concentration or sulfuric acid concentration of the sample from this reading amount.

converting the difference between the set concentration and the measured concentration into time when the obtained concentration is lower than a preset concentration, and operating the injection pump P1 or P2 for that time; and a sample obtained in the same manner. When the copper concentration is higher than a preset concentration, the circulation pump P3 is operated to transfer the excess copper to the crystallization recovery device, separate and recover copper sulfate, and return the separated liquid to the etching device.

Displays the measured concentrations of hydrogen peroxide, sulfuric acid, and copper.

It is configured to perform functions such as recording and issuing an alarm when abnormal values are reached. Note that 16 is a supply pipe for washing water and dilution water.

This automatic titration analysis control apparatus having the above configuration performs a series of analysis operations and etching solution concentration adjustment operations in accordance with the output from the control mechanism C in the following order.

■Analysis operation (1) Preparation of sample - (I) Co-washing of analysis cell 9 by sample solenoid valve SV4
, SVs is opened and the sampling billet 6 is activated to inject a certain amount of sample into the analysis cell ν. Solenoid valve SVs
is opened and the air pump 13 is operated to agitate the sample for a certain period of time.

Next, the solenoid valve 8V2 is opened and the discharge pump 14 is operated for a certain period of time to discharge the sample. Repeat the above operation for the set number of times.

-(ill Open the washing electromagnetic valve SV+ of the analysis cell 9 and inject tap water to the washing level L1, then open the electromagnetic valve SVS to operate the air pump 16 and operate the tap water for a certain period of time.- Then, the above (:) Discharge tap water in the same manner as above.This operation is repeated a set number of times.

11iii) Injecting dilution water and sample into analysis cell 9 In the same manner as in (11), tap water is injected to the dilution level L2, and then a fixed amount of sample is injected in the same manner as in (1).

Next, the air pump 13 is operated for a certain period of time and the sample is stirred and mixed.

(2) Titration analysis - (1) Na, O) (or NB, tcOs) is used as a titration reagent for sulfuric acid concentration.

-(ill) Titration of total copper concentration Same as (1) above.Acidity and total steel analysis are performed when the sampling point is the same as in this example.

It can be carried out in one titration. After the titration of acidity or total steel is completed, the discharge pump 14 is operated for a certain period of time to discharge the liquid contained in the analysis cell 9.

- (Hit Titration of hydrogen peroxide concentration in advance (11)
- After co-washing the analysis cell 9 in the same manner as in (1), the sample dilution liquid is stored in the analysis cell 9 in accordance with the procedure in <11- (Ill, 01l). Titration is then carried out using KMno 4 as reagent. After the titration is completed, the discharge pump 14 is operated for a certain period of time to discharge the liquid contained in the analysis cell 9.

■ Etching solution concentration adjustment operation, sample concentration display, etc. (1) Read the titration of the analytical reagent at the end point of titration and calculate the sample concentration such as sulfuric acid concentration.

(2) When the obtained hydrogen peroxide concentration or sulfuric acid concentration is lower than the preset concentration, convert the difference between the set concentration and the measured concentration into time, and operate the injection pump P+ for that time.
Alternatively, in addition to replenishing sulfuric acid or hydrogen peroxide by operating P2, the measured concentration is displayed as described above.

Here, pH measuring electrode 11. To provide a supplementary explanation of the relationship between the oxidation-reduction potential measuring electrode 12, the control mechanism C, and the titration billet 7.8, changes in the physical properties of the sample due to the zero titration operation are momentarily outputted to the control mechanism C by each of the electrodes.
Detects the rate of change in the physical properties relative to the titration of the reagent, detects the end point of the titration based on this, stores the end point, and determines the magnitude of the change in the physical properties.

Adjust the reagent titration rate to small and small, respectively.
Furthermore, when a preset pH or redox potential is reached, the operation of the titration burette 7.8 is stopped.

The operations described above are performed repeatedly, but before.

The circulation pump P3 continues to operate until the subsequent titration analysis outputs an output indicating that the copper concentration is below the set concentration. In this way, the circulation pump Ps) performs an ON-OFF operation such that it is ON when the measured concentration ≦ the set temperature, and OFF when the measured concentration ≦ the set concentration (operation).

Although the automatic titration analyzer in the above embodiment was equipped with a concentration adjustment mechanism for the etching solution, this may be omitted.

As a modification of the above embodiment, the overflow from the sample storage tank 4 is made to flow into the overflow box 2, and the air pump 13 is replaced by a stirrer with stirring blades.0 Analysis cell 9 One in which the content liquid is discharged by its own weight and the discharge pump 14 is omitted, and one in which the discharge side of the discharge pump 14 is opened into the analysis cell 9 to wash the analysis cell 9 or stir the content liquid. , a cleaning liquid supply pipe for cleaning these liquid contact parts is connected to the sampling bilulet 31 and the titration bilulet 7.8; and the sampling mechanism S'.

A plurality of titration mechanisms T and analysis mechanisms A are arranged in parallel.

It is possible to use one in which the analysis operation is always performed in one of the analysis cells, and if the sample liquid has a high viscosity, a gear pump may be used instead of the sampling billet 3.

The device of the present invention can detect the physical properties or chemical properties of the sample (these include electromagnetic properties).

(Of course, it also includes optical properties, etc.) as long as it changes due to titration of the reagent.

Any conventionally known titration analysis method can be applied, and it can be used for operational management of chemical reaction equipment, arbitrary agents such as chemicals,
Management of supply of raw materials or auxiliary materials 1 Quality control of intermediate products or final products in various industrial fields, industrial water,
It can be extremely effectively used to streamline analysis operations in water quality management of industrial wastewater, etc.

As described above, according to the device of the present invention, it is possible to obtain highly accurate measurement values quickly and repeatedly and continuously almost unattended, and the device is equipped with the feedback control mechanism shown in the above-mentioned illustrated example. This has greatly streamlined the process control and quality control of the sample source (e.g. etching process), resulting in significant labor savings, simplified maintenance and management of the sample source device, and improved and stabilized product quality. be.

[Brief explanation of drawings]

The drawing is a flow sheet of one embodiment of the present invention. DESCRIPTION OF SYMBOLS 1... Circulation pump, 2... Overflow surface, 6... Sampling billet, 4... Sample storage tank, 5... Alkaline reagent tank, 6... Potassium permanganate reagent tank, 7,8...Titration billet, ν...Analysis cell. 10...Level switch, 11...pH measurement electrode. 12... Oxidation-reduction potential measuring electrode, 15... Air pump, 14... Discharge pump, 15... Control unit, 16...
...Supply pipe, L+...cleaning level, L2...dilution level. Pl, Ps... Injection pump, Ps... Circulation pump. 8V+~S'Vs...Solenoid valve. Procedural amendment April 21, 1986 Haruki Shimada, Commissioner of the Patent Office 1, Indication of the case 1981 Patent Application No. 4448
No. 6 No. 2, Title of the invention Automatic titration analyzer 3, Relationship to the case of the person making the amendment Patent applicant address (residence) 1-1 Ginza, Chuo-ku, Tokyo
No. 311, No. 6□ (8th title, Ebara Dendoyo Co., Ltd., I) 1) Kutabe 4, Agent's amendment t In the specification of the present application, the maple in the scope of claims is corrected as shown in the attached sheet. Z Correct “feedback” on page 6, line 4 and page 15, line 2 to “feedback”. 5. On page 13, line 6, "...ON, (operation) measured concentration" should be corrected to "...ONI operation), measured concentration." 4. Add the following sentence between lines 7 and 8 on page 14. [Note that a soda lime pipe for removing carbon dioxide gas is connected to the discharge side of the air pump 13, and this is for converting the air into a gas that is chemically inert to the liquid contained in the analysis cell 9.] Of course, inert gas such as horse gas can be used to remove carbon dioxide gas and replace the friendly air. Therefore, depending on type m of the content liquid, air may be directly supplied for stirring. ” 5 On page 14, line 16, “final product” is corrected to “final product.” Patent Application No. 1987-4486 Claims: 9. Automatic titration analyzer comprising a sampling mechanism, a titration mechanism, and an analysis mechanism controlled by a t1tllJ control mechanism, for analyzing a predetermined amount according to a signal from the control mechanism. a sampling mechanism that collects a sample and supplies it to the analysis mechanism; and a sampling mechanism that titrates a predetermined amount of a reagent for fractionation/splitting to the sample in the analysis mechanism based on signals from the control mechanism, and adjusts the titration amount at the end point of the titration. a titration mechanism that outputs to the control mechanism; an analysis mechanism that converts changes in the physical properties of the sample due to the titration operation into electrical quantities and outputs them to the control mechanism;
setting the sample collection amount and the titration amount of the reagent to predetermined amounts, reading the titration amount at the end point of the titration to calculate and output the measured concentration of the sample, and the sampling mechanism;
An automatic titration analyzer characterized in that it is equipped with a control mechanism that sequentially controls the operation of the titration peak and analysis mechanism from sampling to titration analysis to measurement and calculation and output of 111 degrees. 2. The #J control mechanism has an analysis result instruction function, recording function,
2. The device according to claim 1, which has at least one alarm function. 5. The apparatus according to claim 1 or 2, wherein the control mechanism sets the titration amount of the Shimaki reagent based on an electrical signal from the analysis mechanism. 4. The sampling mechanism includes an overflow connected to the sample circulation pump and its discharge side via a pipe line, and a metering pump for sucking and discharging a predetermined amount of the sample from the overflow. 4. The device according to claim 3, comprising: 5. The analysis mechanism includes a container that receives the sample and reagent, a round cleaning liquid supply mechanism that cleans the wetted parts of the container, a diluent supply mechanism that dilutes the sample, and a keyed cleaning liquid. and a round liquid level control-like tank for controlling the supply amount of the diluent to a predetermined amount, an electrode for measuring I)H, an electrode for determining the oxidation-reduction potential, and a stirring mechanism and a discharge mechanism for the multi-liquid in the container. 5. The apparatus of claim 4, comprising: & The apparatus according to item 1, wherein the titration mechanism includes a storage tank for the reagent and a range of the reagent. 7. The device according to claim 4 or 6, wherein the titration billet is a nine-piston pump equipped with a check valve. (a) The apparatus according to claim 1, wherein the metering pump and the titration billet are equipped with a circular cleaning liquid supply mechanism for subsequently cleaning the liquid section. 10. The device according to claim 9, further comprising a mechanism for removing carbon dioxide from the air on the discharge side. 1t. The apparatus according to claim 6, wherein the discharge mechanism provided in the analysis mechanism is a pump equipped with a solenoid valve on the suction side. that's all

Claims (1)

[Claims] 1. Sampling mechanism controlled by a control mechanism 1 An automatic titration analyzer equipped with a metering mechanism and an analysis mechanism,
a sampling mechanism that collects a predetermined amount of a sample for analysis according to a signal from the control mechanism and supplies it to the analysis mechanism; a titration mechanism that titrates a predetermined amount of an analytical reagent to a sample in the analysis mechanism based on a signal from the control mechanism, and outputs the titration amount at the end point of the titration to the control mechanism;
an analysis mechanism that converts changes in physical properties of the sample due to the titration operation into electrical quantities and outputs the electrical quantities to the control mechanism; The sample collection amount and the titration amount of the reagent are set to predetermined amounts, and the titration amount at the end point of the titration is read to calculate and output the measured concentration of the sample, and the sampling mechanism 9
An automatic titration analyzer characterized in that it is equipped with a control mechanism that sequentially controls the operations of the straining mechanism and the analysis mechanism in the order of sampling → titration analysis 4 calculation and output of measured concentration. 2. The apparatus according to claim 1, wherein the control mechanism has at least one of an analysis result indicating function, a recording function, and an alarm function. 6. The apparatus according to claim 1 or 2, wherein the titration amount is set based on an electric signal from the analysis mechanism. 4. The sampling mechanism is connected to the sample circulation pump and its discharge side. 54. The apparatus according to claim 3, comprising an overflow surface connected via a pipe line and a metering pump for sucking and discharging a predetermined amount of the sample from the overflow surface. The analysis mechanism includes a container that receives and receives the sample and reagent, a cleaning liquid supply mechanism for cleaning the liquid contact part of the container, a dilution liquid supply mechanism for diluting the sample, and the cleaning liquid and dilution liquid. A patent claim comprising: a liquid level control mechanism for controlling the supply amount by a predetermined pressure; 6. The apparatus according to claim 1, wherein the titration mechanism includes a storage tank for the reagent and a titration billet for the reagent. 7. Collecting the sample. The device according to claim 4 or 6, wherein the metering pump and the titration billet are piston pumps equipped with a check valve.8. 9. The device according to claim 7, which is equipped with a cleaning liquid supply mechanism for cleaning. 9. The stirring mechanism is an air supply pump, and a mechanism for removing carbon dioxide from the air is provided on the discharge side 10. The device according to claim 5, wherein the discharging mechanism provided in the analysis mechanism is a pump equipped with a solenoid valve on the suction side. Device.