JPS58127152A - Continuous batch type total iron analyzing meter - Google Patents

Abstract

PURPOSE:To provide a continuous batch type total iron analyzing meter which normally provides an accurate result, by a method wherein an electromagnetic valve is sequence-controlled to automate a continuous analysis including a sample collecting, discharging, and cleansing. CONSTITUTION:A sample water SW is collected in a manner to prevent preciptation and adhesion of suspension iron in a line through the flow of the sample water SW via 3-way switching valves SV1 and SV2 of an electtromagnetic valve being sequence-controlled and a discharge pipe 52. A self-operated discharge valve SV3 of said electromagnetic valve is then closed, self-operated bypass, overflow, and vent valves SV4-SV6 are opened, and the valve SV2 is switched to feed the sample water SW to sample weighing tank 56. After the tank 56 is washed, the valve SV4 is closed, and the valve V2 is switched to the discharge pipe 52 to perform a weighing of the sample water. Similarly, a sample heating, a reaction, a colorimetry analyzing measurement, an acid liquid washing of a first sample system, a pure water cleaning, a forced discharge of residual liquid by clean air, a similar processing against a second sample, a warming up of a total analyzing meter by the flow of pure water, and calibration of an analyzing meter are automatically conducted in order named.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a continuous batch type total iron analyzer, and more particularly to an improved continuous batch type total iron analyzer for always accurately performing colorimetric determination of trace amounts of iron in feed water and condensate water of thermal and nuclear power plants. This article concerns a total iron analyzer.

The iron concentration in the feed water and afterwater of thermal and nuclear power plants must be controlled to below /Oppb for drum-type plants and Jppb or less for once-through plants.

Conventionally, as a measuring device for such extremely low concentrations, an analyzer that uses T, P, T, Z, and reagents shown in Figure 1 to generate a blue-purple ferrous complex compound for colorimetric analysis has been known. There is.

According to this analyzer, a fixed amount of sample water of constant head cypress 10 or more is measured with a sample meter jjk phase/co, hydrochloric acid/Hiroshi is added to this sample water, and suspended iron in the sample water is added with a heating tank/j. Dissolves warmly. For heating, hot water from 20 is circulated in a circulating constant temperature bath heated by heater/J' and heated by Bonguco to heat heating bath/6. The heated and dissolved sample water is cooled with a 24-ton cooler and transferred to the reaction tank 21. Next, 2 g of a reducing agent (hydroxylamine hydrochloride solution).

- Adjustment agent (ammonium acetate buffer,) 30, color former (
T, P, T, Z, i.e. -2≠, 6φ tripyrisyl S triazine) 3.2 was added and mixed and stirred with the stirrer 3≠, and the colored sample water was transferred to the absorption cell 3r of the colorimeter 36 and colorimetrically measured. analyse. Cooling water over 70-Narao to the analyzer
A continuous batch type total iron analyzer is assembled by connecting these six tanks and equipment with piping.

However, when conventional analyzers continuously analyze water with an iron concentration of %'PPb or less in a continuous batch manner, various problems occur due to analytical inaccuracies. As a result of studies by the present inventors regarding the causes of analytical inaccuracies, the following problems were discovered.

(1) The iron concentration of the sample water in the sample collection tube and the sample water collected in sample measuring tank/2 may differ.

The reason for this is that when sample water is collected in the sample measuring tank 12, the sample water accumulates in the piping of the constant head cypress 10 and the large mouth valve of the sample measuring tank 12, causing suspended iron to adhere and settle in the piping. Since the sample water is introduced from the bottom of the sample measuring tank, if suspended iron with a large particle size is present during introduction, it will settle in the sample measuring phase/2, and the total iron I# in the actual sample water will be reduced. :
Sample water may be collected at different times.

(2) If the heating tank/6 is heated and dissolved using hot water from the circulation constant temperature tank 20, the #r release time will be long, and depending on the type of suspended iron, it may not be completely dissolved.

(3) During continuous measurements, iron and other impurities in the sample water adhere to and settle on component equipment and piping, which causes indicator drift, and also causes history phenomena due to a small amount of remaining test liquid from the previous test. .

SUMMARY OF THE INVENTION It is therefore a general object of the present invention to provide a continuous batch type total iron analyzer which eliminates the above-mentioned drawbacks and consistently provides accurate total iron analysis results.

Another object of the present invention is to provide a continuous batch type total iron analyzer that can be easily and safely operated and managed in a factory.

In order to achieve this objective, in the present invention, a bypass pipe is provided in the inlet pipe and the discharge pipe of the sample measuring tank for discharging the water accumulated in the pipe, and a condenser gold film is formed on the upper part of the heating tank until the sample water boils and refluxes. The heating tank was heated electrically, and the analyzer was equipped with a cleaning function and a function to forcefully discharge a small amount of residual liquid. That is, a pure water meter cap connected to the pure water supply pipe is installed above the condenser, and an acid liquid tank for cleaning and an inert scum and clean air supply device are installed.
A first sample system has an analyzer connected to a sample measuring tank, a heating tank, a cooler, and their auxiliary equipment through valves, and a second sample system has a reaction tank and these auxiliary equipment connected through valves through piping. The system was constructed such that the first sample system and the co-sample system could be washed independently. Furthermore, a calibration liquid 411 is provided to enable the analyzer to be calibrated.

That is, the continuous batch type total iron analyzer according to the present invention,
A fixed amount of sample water is measured in a total sample measuring tank via a constant head phase, and a 24-chloride glycolic acid solution is added to the sample water in a heating tank and heated to dissolve suspended iron and ferrous iron. After the ions are reduced to ferrous ions, they are introduced into a reaction tank via a cooler, and after adjusting the pH to 1J by adding ammonium acetate buffer, the sample water is measured by adding T, P, T, Z, and reagents to develop color. In conventional all-iron analyzers that introduce light into a tank and measure absorbance, bypass pipes are installed in the inlet and outlet pipes installed above and below the sample measuring tank to drain water accumulated in the pipes, and a heater and condensate are placed in the heating tank. After heating the sample water is transferred to the reaction tank via a cooler, a certain amount of pure water is transferred from the pure water measuring tank to the heating tank via a condenser. , flow it through a cooler, completely transfer the remaining sample water to the reaction tank, and install a cleaning acid liquid tank and an inert gas or clean air supply device outside the analyzer system, and connect the analyzer to the sample measuring tank and heating tank. , a cooler, and these accessories R are connected via valves to form a first sample system, and further a reaction tank, a measurement tank, and these accessories R are connected via valves. g! A second sample system is constructed by connecting the piping through a valve, and each of the first sample system and second sample system is independently supplied with a cleaning acid solution, pure water, inert gas, or clean air. It is possible to clean the pipes and forcibly discharge the cleaning solution, and to clean the second sample system during operation of the first sample system of the analyzer, or the first sample system during operation of the second sample system after cleaning with a cleaning acid solution. It is possible to wash with water and then forcefully discharge the remaining liquid from the analyzer using inert gas or clean air, and when the plant is stopped or when measurement is not necessary, it can be cleaned by simply passing pure water through it. In addition, it is possible to warm up the sample water with pure water at the time of starting the plant before sample water can be collected, and to immediately take measurements by switching the system when necessary. .

Therefore, for convenience in understanding the structure, percentage characteristics, and embodiments of the present invention, the structure of the present invention is expressed in the form of a flowchart as follows.

Next, preferred embodiments of the continuous batch type total iron analyzer according to the present invention will be described in detail with reference to the accompanying drawings.

In FIG. 2, a sample water supply system is provided at the top of the analyzer.

In the sample water supply system, the sample water SW passes through the sample water supply pipe jO, the three-way automatic switching valve SV/, and the three-way switching automatic valve SV,! The discharge pipe that connects to! The circuit that is discharged from this is a constant head yuzu! It is connected to Hiro and the sample water supply pressure is adjusted. The sample water supply system is connected to the sample measuring system via a three-way automatic valve SVJ.

The sample measuring system consists of 4 test tanks and 1 tank! From now on, the discharge pipe sr provided at the bottom of the sample measuring tank is connected to the sample heating, dissolving and cooling system via an automatic discharge valve SVj. A bypass pipe 6Q is connected to the discharge pipe j, and the sample water in the sample measurement 4iyj4 and the discharge pipe sr is discharged via an automatic bypass valve SVg. Overflow pipes A and 2 are provided in the middle of the sample needle km, and sample water is discharged through an automatic overflow valve SVj to measure a certain amount of sample water. A vent pipe 64t is connected to the upper part of the sample measuring tank, and the tank is exhausted through an automatic vent valve sva'l. 1 and a calibration liquid tank 2 are connected to the upper part of the sample measuring column via an automatic valve SV7.

The sample heating melting and cooling system includes a sample heating tank tg, a cooler 70.
It is composed of 7 condensers as the main components, and the discharge pipe at the bottom of sample heating
The cooler 70 is connected to the sample reaction system via an automatic outlet valve SV. The upper part of the heating tank is connected to the condenser 7.2, and the upper part of the condenser 72 is connected to the pure water metering scale 7≠ via an automatic valve 5V10, and to the vent pipe 7 O via an automatic vent valve SV//. Connecting.

A thioglycolic acid solution tank 7r is connected to the upper part of the heating tank t via a metering pump P1. A Hime H1 temperature detector/temperature regulator TE is attached to the heating tank 6♂. The cooler and condenser are cooled by cooling water CW.

The sample reaction system consists of a reaction tank rO9, and an acetic acid ammonia solution tank lr, 2ic,
Metering pump P, i through one' (T, P, 'f', Z
.

The solution tank r≠ is connected to a vent pipe via an automatic vent valve SV/2f. A stirrer AG is attached to the reaction tank.

The discharge pipe connected to the lower part of the reaction tank is connected to the sample measurement system via an automatic discharge valve 5V13.

The sample measurement system consists of measurement tank ♂O and 6.Measurement tank and 6 are equipped with absorption cell lr♂, and the sample developed in reaction tank ♂O is transferred to the lower part of absorption cell ♂ through automatic valve SV/3. P is introduced from the upper part and discharged from the discharge pipe O via the automatic discharge valve SV/≠.

The analyzer is equipped with an automatic cleaning mechanism, that is, a pure water supply pipe is installed at the top of the analyzer in parallel to the sample water supply pipe. , 2. A clean air PA or inert gas INAC supply pipe tag is installed in the middle of the analyzer, and an acid solution tank 2 for cleaning is installed at the bottom of the analyzer, and the first sample system (sample measuring system, sample heating system), The second sample system (sample reaction system and sample measurement system) are connected to each other via valves to allow for independent cleaning and forcible discharge of the cleaning liquid.

1st sample system cleaning acid solution tank t, metering pump P4, automatic valve SV/J
- The acid cleaning circuit connected to the upstream side of the outlet valve SV of the cooler 70 and the pure water supply pipe octopus share piping with the downstream side of the automatic valve Sv/j via the automatic valve SV#; This forms the main stream of the pure water cleaning circuit, and also includes a subcircuit connected to the upper part of the pure water measuring tank 7 from a branch pipe on the pure water supply pipe via an automatic valve SV/7. A discharge pipe r is connected to the downstream part of the automatic valve SV# and the upstream part of the cooling pipe connection part via a discharge valve SV/. Clean air PA or inert gas I
NAG supply pipe tag is connected to vent valve SV+ via automatic valve/re
It is connected to the upstream vent pipe 6 to form a first sample system circuit for forcibly discharging cleaning residual liquid using clean air PA or inert gas INAG.

A branch pipe connected to the upstream part of the automatic valve SV/J- downstream of the No. 1 co-sample system metering pump P4 forms a common pipe with the downstream part of the discharge valve SV/J via the automatic valve SV, 20, SV, 2/. A branch pipe is connected to the measuring tank, and a branch pipe is connected from the downstream side of the automatic outlet valve SV to form a discharge pipe via the automatic discharge valve SVj2. Connect the discharge pipe through. The pure water supply pipe octopus is connected to the downstream part of the automatic valve 8V20 via the automatic valve SV Kohiro to constitute a pure water cleaning circuit. Clean air PA or inert gas INA
G supply pipe? ≠ is connected to the branch pipe downstream of automatic valve SV, lt, one is connected to the upstream part of automatic discharge valve SV, 2.2, and the other is connected to the vent pipe ioo installed at the upper part of the discharge pipe of the measuring tank. A vent valve 8V, 2 is connected to the upstream portion to constitute a forced discharge circuit for cleaning residual liquid using clean air PA or inert gas INAG.

Cleaning circuit for all analyzers with pure water In order to flow pure water into all analyzers while analysis operations are stopped, the pure water supply pipe is connected to the automatic valve SV Cocoa via the three-way switching automatic valve SV.
/ to configure.

Next, the procedure for operating the analyzer will be explained.

-76-111 (1) Sample water collection SV/, SV, 2, discharge 1f! 2, water is flushed with water to prevent suspended iron from settling in the piping, to prevent buildup, and to ensure that the collected sample is always the standard sample water at the time of collection.

(2) Close sample water measurement SVj, SVF, SVj, 5VQ-open, SV
2 and introduce the sample water into the sample measuring tank jB. After washing the sample measuring tank with an appropriate amount of sample water, SV + fully closed, S
Confirm that the sample water overflows from VJ'', then SV, 2.
The discharge pipe! - Switch to -.

(3) Close the sample heating svr, open the SV//, and open the 5v3t- to introduce the sample water into the heating tank tr. A predetermined amount of the thioglycol solution is added by the metering pump P, and the heater H is energized to heat it and the condenser 72 is cooled by CW. The tumor is refluxed for a predetermined period of time.

(4) Reaction 77- Cooling 1KcWe through L, close SVI3, open SVI2,
Next, the SV and svP are opened to introduce the heated sample into the reaction tank. Furthermore, SV/7 is fully opened to introduce pure water to the pure water meter fk Hinoki 7-hiro and measure a certain amount. Open 5V10 and connect 7 condensers,
Next is heating tank 6? , a small amount of sample water remaining on the cooler 70 is introduced into the reaction tank. After adjusting the pH by saturating a predetermined amount of ammonium acetate solution using metering pump P2Vc, add a predetermined amount of T, P, T, Z, and solutions using metering pump P3, and react for a predetermined time using stirrer AG. let

(5) Open colorimetric measurement SV/+ and next tlc SVI2, SVI3
.

Open the SV and 2J, introduce the coloring sample into the measurement cell, and perform colorimetric analysis.

(6) During the operation of the second sample system with the acid solution cleaning SV of the first sample system closed, SVj
I, 5V10, SV//, SV! 1 closed, sv
, r, SV3. svt, 5vit is opened and the p-acid liquid is supplied to the cooler 70 by the metering pump P4.

After cleaning in the order of heating, sample measurement, and tj, the sample is discharged from the SVj. Next, open SVjj and SVjI and select the first
Drain the acid solution from the sample system.

(7) Clean the first sample system with pure water SVjj in the same manner as the acid solution cleaning to the cooler 70,
Heating tank t♂, sample measuring tank! After washing the first sample thread, fully open the SV/door to drain the pure water inside the first sample thread.

(8) Forced discharge of cleaning residual liquid by clean air PA in the first sample system Close sv, g and open SVjP and supply clean air PA to SV/J
The remaining cleaning water is forcibly discharged through the SVj.

Open the SVz and drain the snow.

In this way, the preparation for receiving the sample measurement in item (g) is completed.

(9) Acid solution cleaning of the second sample system SV/, 2,5Vtz3. SV, z+, sVF&'tl
rljiSV, 2/, SVI44. SVI3.5V2
2.5V20 is opened and the p acid solution is introduced into the measuring tank, r4, by the metering pump P4 to clean the measuring tank ♂2. After the cleaning of the measurement tank ♂t is completed, the SV/4t is closed, and then introduced into the reaction phase 10 for cleaning. Stop metering pump P4, close svxo,
SVju, SV/4'.

5Vjj, SV fully open and drain the acid solution in the second sample system.

(10) Purified water cleaning of the second co-sample system 5V20 Acid solution cleaning cost 5KSV2≠ 5KSV2≠ Pure water is led to the second sample system, and pure water cleaning is performed in the same manner as the acid solution cleaning.

(11) Forced discharge of cleaning residual liquid by clean air PA in the co-sample system SV/, 2 , SV,! , 2.5V21sf closed, SV
, lt is opened, clean air PA is introduced from the upper part of the reaction tank and the upper part of the measurement tank, and the remaining cleaning liquid can be forcibly discharged by exhausting from SV/≠, SVj3.

In this way, the acceptance of the reaction of the (Hiroj term) and the colorimetric measurement of the (52nd term) is completed.

(12) Warming up all analyzers by running pure water SV, 2 is the sample measuring tank! On the other side, SVj.

SVI, 8VP, SVI3, SV/! Open SV
Switch / to SV cocoa which leads to pure water, SV, 27 fully open, pure water with sample needle amount hinoki jt, heating tank 2g, cooler 70.
Sv/4L is discharged from the reaction tank 01 through the measuring tube 6 and maintained in a warm-up state.

(16) Calibration of the analyzer Add a calibration solution of known concentration to the predetermined lid meter ik@j4 via the calibration liquid tank t6 and F) SV7, and then perform the above analysis operations to calibrate the analyzer. can.

As described above, the analyzer according to the present invention uses a solenoid valve as a valve, and by setting a predetermined sequence and controlling the solenoid valve in a predetermined manner, analysis and cleaning as well as forced discharge of cleaning residual liquid are performed in a fully automatic manner. be able to.

According to the continuous batch type total iron analyzer according to the present invention, the causes of inaccurate analysis results that tend to occur with conventional analyzers are eliminated, and accurate analysis values can always be provided.

Although the preferred embodiments of the present invention have been described above, it goes without saying that various improvements and changes can be made without departing from the spirit of the present invention.

[Brief explanation of drawings]

FIG. 1 is a system diagram of a conventional total iron analyzer, and FIG. 2 is a system diagram of a continuous batch type total iron analyzer according to the present invention. /4'...Hydrochloric acid/l...Heating tank/l.
...Heater, 20...Circulation constant temperature bath, 2 pieces...Pump 2≠...Cooler 2t...Reaction tank cor...Reducing agent 30-...p) Ipi
Agent 3.2 , T, P, T, Z, Liquid 3≠... Stirrer 3t... Colorimeter so... Sample water supply pipe 3.2... Discharge pipe jr... Discharge tube t
o... Bypass pipe g! ...over 70 tube z4t...
・Vent pipe AJ...Calibration liquid tank tg...Sample heating tank 70...Cooler 7...Condenser 7
G...Pure water measuring tank 7t...Vent pipe lrt.
...Measurement tank J'♂...Absorption Celta O...
Discharge pipe Octopus...Pure water supply pipe r...Discharge pipe 100...Vent pipe AG...Agitator CW...Cooling water H...Heater
INAG...Inert gas P, , P2. P3. P4
... Metering pump PA ... Clean air SV/, 5V-2 ... Three-way automatic valve SVj ...
Domestic output automatic valve SV≠...Bypass automatic valve SVj...Over 70 automatic valve SVa...Vent automatic valve SV7...Automatic valve s
vr...Automatic discharge valve SVri...Kawaguchi automatic valve 5v10...Automatic valve SV//, SV/co...Automatic vent valve SV/3...
Automatic discharge valve SV/≠・・・Automatic discharge valve SV2.2
, 5V2J-... Automatic discharge valve SV Coro... Automatic vent valve SW... Sample water TE... Temperature detector and temperature regulator Patent applicant Kyushu Electric Power Co., Inc. FIG, 1

Claims (1)

[Scope of Claims] (1) Sample water is weighed in a sample measuring tank through a constant head tank, and the fixed amount of sample water is led to a heating tank, and a thioglycolic acid solution is added thereto and heated to remove suspended iron. After completely dissolving and reducing ferric ions to ferrous ions, the mixture is introduced into a reaction tank via a cooler, and ammonium acetate buffer is added. In an all-iron analyzer that introduces colored sample water into a measuring tank and measures its absorbance, a bypass pipe for discharging water accumulated in the pipes is installed in each of the sample water inlet pipe and discharge pipe installed above and below the sample measuring tank. A continuous batch type characterized in that a heating tank is provided with a heater and a condenser to enable boiling and reflux of sample water, and the condenser is connected to a pure water measuring tank and communicated with a pure water supply pipe. Total iron analyzer. (2) Sample water is sampled through a constant head wheel.
/-〇Measure the sample water using a measuring cypress with a lid, and then introduce the specified amount of sample water into a heating tank and add a thioglycolic acid solution and heat to dissolve suspended iron and convert ferric ions to ferrous iron. After being reduced to ions, the sample water is introduced into a reaction tank via a cooler, and after one adjustment by adding ammonium acetate buffer, the sample water is colored by adding T, P, T, Z, and reagents, and the sample water is introduced into a measurement tank to measure the absorbance. In the total iron analyzer to be measured, bypass pipes for discharging water accumulated in the pipes are provided in each of the sample water introduction pipe and discharge pipe provided above and below the sample measuring tank, and a heater and a condenser are provided in the heating tank. The sample water can be boiled and refluxed, and the condenser is connected to a pure water needle and connected to a pure water supply pipe, and an acid solution for cleaning and an inert gas or clean air are supplied outside the analyzer system. A first sample system is constructed by connecting a sample measuring tank, a heating tank, a cooler, and these auxiliary devices via valves, and also connects a reaction tank, a measuring tank, and these auxiliary devices via valves. Connect the piping to configure the first sample system, and connect the first sample system and the first sample system! - A continuous batch type total iron analyzer characterized in that the sample system is individually cleaned using an acid solution, pure water, an inert gas, or clean air, and the cleaning liquid is forcibly discharged. (3) The patent of Zhao Qiu, which is characterized in that a certain amount of pure water is supplied to a heating tank and a cooler through a pure water measuring tank and a condenser, and the remaining sample water is completely transferred to a reaction tank. Total iron analyzer as described in Scope 2. (4) By configuring the valve with a solenoid valve and automatically operating the valve by setting a sequence, the p1 first sample system can be operated, and in parallel, the second co-sample system can be cleaned with acid solution and purified water.
Forced discharge of cleaning residual liquid using clean air or inert gas, operation of the λ sample system, and parallel cleaning of the first sample system with acid solution, pure water cleaning, and cleaning residual liquid using clean air or inert gas. 2. The total iron analyzer according to claim 2, characterized in that the entire operation consisting of forced discharge of the liquid is carried out fully automatically. (5) A total iron analyzer according to claims 1 and 2, characterized in that the analyzer is kept clean by flowing pure water into the analyzer while the analysis operation is stopped.