JP3522223B2 - Automatic measuring device for powder adsorption of reagent - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an apparatus for automatically measuring the amount of adsorbed reagent on powder, and more particularly to an apparatus for automatically measuring the amount of adsorbed methylene blue on coal ash.

[0002]

A large amount of coal ash is discharged from a coal-fired power plant or the like. The discharged coal ash is reused for concrete, for example.

When coal ash is mixed with cement, an air entraining agent (surfactant) added to the cement to improve the workability of concrete is adsorbed by the unburned carbon content in the coal ash and the effect is reduced. Therefore, it is necessary to measure the unburned carbon content in the coal ash and adjust the addition amount of the air entraining agent.

The unburned carbon content in coal ash is measured using, for example, methylene blue (MB) as a reagent. MB is a kind of dye, and when the coal ash is suspended in the MB solution, the unburned carbon content in the coal ash adsorbs the MB and decolorizes it. Measure with a meter and use it as an index of unburned carbon content. This index is called the MB adsorption amount of coal ash.

Two types of test methods, the standard test method of Cement Association (Cement Association method) and the electric test method (electric method), are often used for measuring the amount of MB adsorbed. In the Cement Association method, 0 to 5 ml of a 25 mg / l MB solution was sampled, each 25 ml was made up to measure the absorbance at around 665 nm, and a relation line between the obtained absorbance and MB concentration was created to perform calibration. Let it be a line. When measuring the MB adsorption amount of coal ash, 25 ml of a 25 mg / l MB solution is added to 1 g of coal ash, shaken, and suction filtered. 25 ml of filtrate 5 ml
The absorbance is measured in the vicinity of the wavelength of 665 nm, the MB concentration is determined from the calibration curve, and the MB adsorption amount (mg / g) is calculated by the formula (1). d = (25-5x) / 40 (1) d: MB adsorption amount (mg / g) per 1 g of coal ash x: MB concentration of sample solution (mg / l) In addition, a sample with a significantly large MB adsorption amount is a sample Reduce the amount to be weighed appropriately. There is also a method by centrifugation in the Cement Association method.

In the electromotive method, 25 ml of 40 mg / l MB solution, 1.25, 2.5, 3.75, 5.0 ... 25 ml, each 25 ml was filtered and filtered.
A calibration curve is prepared by measuring the absorbance around 0 nm. When measuring the MB adsorption amount of coal ash, 40 g / g of coal ash
Add 25 ml of a mg / l MB solution, shake and filter. The absorbance of the filtrate in the vicinity of 560 nm is measured, the MB concentration is obtained from the calibration curve, and the MB adsorption amount is calculated by the formula (2). d = (40−x) / 40 (2) d · x: common with equation (1)

As described above, between the Cement Association method and the electric power generation method, when the calibration curve is prepared, the diluted MB solution is filtered by the electric power generation method but not filtered by the Cement Association method. There is a big difference in that the Cement Association uses suction filtration, and the Cement Association method measures the absorbance by filtering the sample solution and then diluting the sample solution five times, but the electric generation method measures the absorbance without diluting the filtrate. There is.

In general, the amount of MB adsorbed is measured by manual analysis, and it is difficult to obtain accurate analysis results because the measurement results are affected by individual differences. Therefore, an analyzer that automatically measures the MB adsorption amount is desired. Labor saving and improvement in measurement accuracy can be expected by automating the measurement of the MB adsorption amount.

Conventionally, as an apparatus for automatically measuring the MB adsorption amount, there is, for example, a methylene blue adsorption amount measuring apparatus disclosed in JP-A-11-94745. MB solution and pure water are stored in this device, and when the user installs a sample container containing coal ash, MB solution is added, stirred, filtered, and the absorbance is measured sequentially to automatically determine the MB adsorption amount. Measure. Moreover, zero point calibration is performed using pure water, and span calibration is performed using MB solution.

Since this apparatus is not equipped with a vacuum pump for performing suction filtration and is not equipped with means for adding pure water after filtering the sample solution, the measurement by the Cement Association method cannot be performed. . Moreover, since the span calibration is performed using the MB solution as a standard solution, there is only one calibration point for creating a calibration curve, and an accurate calibration curve cannot be created. In addition, the user has to sample the coal ash in a fixed amount to adjust the sample, and the washing of each part and the replacement of the filter paper are not automated, which is troublesome to use. In addition, it is difficult to measure online because there are many parts that depend on human power.

[0011]

SUMMARY OF THE INVENTION The problem to be solved by the present invention is to provide a powdery reagent capable of automatically measuring the MB adsorption amount of coal ash by both the Cement Association method and the electric power generation method. It is to provide an adsorption amount automatic measuring device.

[0012]

In order to solve the above problems, an apparatus for automatically measuring the amount of reagent adsorption of powder according to the present invention comprises a powder receiving part, a powder processing part, a filtering part, a filtrate processing part, a measuring part and a control part. Section.

The powder receiving unit is provided with a powder receiving container and a drive mechanism, receives powder input from the outside into the container, and transfers the powder to the powder processing unit. The powder processing unit is equipped with a sample container, a powder quantitative sampling device, a weigher, a reagent supply unit, a dilution water supply unit, and an agitator, and weighs a fixed amount of powder from the powder receiving container into the sample container and weighs it. Then, a reagent is added according to the weight of the powder and the mixture is stirred to form a measurement sample solution. When preparing a calibration curve, a reagent is placed in a sample container, diluted water is added, and the mixture is stirred to prepare a sample solution for calibration. The filtration section is equipped with a filter and a vacuum pump, and the sample solution is filtered to obtain a filtrate. If necessary, suction filtration can be performed with a vacuum pump.

The filtrate processing section is provided with a filtrate receiving container, a diluting container, a measuring liquid container, a diluting water supply device, a reagent supplying device, and an agitating device, receives the filtrate in the filtrate receiving container, and sends a part thereof to the measuring liquid container. When the filtrate needs to be diluted, a fixed amount is collected from the filtrate receiving container into a diluting container, diluted with diluting water, and a part thereof is sent to the measuring liquid container. Further, at the time of preparing the calibration curve, the reagent can be quantitatively sampled in the processing container, diluted, and then sent to the measurement liquid container.

The measuring section is equipped with a spectrophotometer, and the solution in the measuring liquid container is transferred to a cell and the absorbance is measured by the spectrophotometer. The control unit controls each unit according to an input from the outside, obtains the measurement result by the spectrophotometer, calculates the reagent adsorption amount of the powder, and outputs the result.

According to the apparatus for automatically measuring the amount of adsorbed reagent for powder according to the present invention, the reactivity can be measured by automatically mixing the powder and the coloring reagent, filtering and measuring the absorbance. Therefore, it is possible to eliminate an individual difference such as the skill level and obtain an accurate measurement result. The powdery reagent adsorption amount automatic measuring device of the present invention can be used for all tests in which the powdery and liquid coloring reagents are mixed and filtered to measure the absorbance. By incorporating the test procedure in the control unit, it is possible to test various procedures.

The powdery reagent adsorption amount automatic measuring apparatus of the present invention may further include a cleaning unit. The cleaning unit is provided with a cleaning liquid supply device and an air supply device, and the cleaning liquid is added to each part for cleaning, and the cleaning liquid is discharged and dried with air. Further, the filter section may be provided with an automatic filter paper changing device. The filter paper exchange device includes a filter paper supply device and a filter paper recovery device, supplies unused filter paper before filtration, and recovers used filter paper after filtration. Since the automatic reagent adsorption amount measuring apparatus for powder of the present embodiment automatically performs washing and replacement of the filter paper, the sample can be continuously measured without requiring human power. Therefore, it is useful for labor saving and can be used for online measurement and the like.

Further, in the apparatus for automatically measuring the amount of adsorbed reagent for powder according to the present invention, the powder receiving position is set in the powder receiving portion, and the sample collecting position, the stirring position, and the washing position are set in the powder processing portion. Equipped with a powder processing table that supports a container and a sample container and can be translated by a drive mechanism.The powder receiving container is selected at the powder receiving position and the sampling position, and the sample container is selected at the sampling position, the stirring position, and the cleaning position. You may make it possible to position it. It is advisable to move the powder processing table according to the work content and switch the powder receiving container and the sample container to positions corresponding to the work.

Further, the filtrate treatment section is provided with a filtrate container, a dilution container, a measurement liquid container, and a filtrate treatment table, and the filtrate treatment table supports the filtrate container, the dilution container, and the measurement liquid container, and can be translated by a driving device. Set the filtrate receiving position, the dilution position, the container cleaning position, and the measurement cell cleaning position, and drive the filtrate processing table to set the filtrate container, the dilution container, and the measurement solution container, respectively, to the filtrate receiving position, the dilution position, the container cleaning position, and the measurement. It may be arranged so that it can be located at the cell cleaning position. It is advisable to move the filtrate processing table according to the work content and switch the filtrate container, the dilution container, and the measurement liquid container to the positions according to the work.

According to the apparatus for automatically measuring the reagent adsorption amount of powder according to this aspect, the sequence control by the control unit is simplified,
The sequence allows measurement in various work procedures. Further, for example, it is possible to save space by arranging the sample container of the powder processing unit so as to move to the left and right with respect to the front of the apparatus and the containers of the filtrate processing unit so as to move back and forth.

In the apparatus for automatically measuring the amount of adsorbed reagent for powder according to the present invention, the reagent, the dilution water, the washing water, etc. may be supplied from the outside by a pipeline or the like, but the storage section is omitted because the piping is omitted. Preparation, reagents, dilution water, washing water, drainage from each part,
The discharged powder may be stored. The dilution water and the cleaning water may both be pure water and stored in the same tank. Further, dilute hydrochloric acid or the like may be separately stored as washing water used for the measuring liquid container or the cell of the spectrophotometer.

The apparatus for automatically measuring the amount of reagent adsorption of powder according to the present invention is further provided with a temperature adjusting section, and if the temperature of the stored reagent, the stirring section temperature and the room temperature in the apparatus are kept constant, the temperature change will result in a measurement result. The error given to can be reduced.

Further, the powder quantitative sampling device used in the powder sampling section may be capable of freely changing the sampling volume. For example, equipped with a sampling tube, extrusion rod and pulse motor,
The extruding rod may be built in the sampling tube, and the pulse motor may be arranged above the extruding rod. The sampling tube is driven up and down by a drive mechanism, and the push rod drives the sampling tube up and down by a pulse motor.

The volume of the powder taken into the sampling tube is increased or decreased by raising or lowering the set position of the extrusion rod when taking the powder. Since the position of the extrusion rod can be accurately controlled by the pulse motor, the volume of the powder taken into the sampling tube can be freely set. The automatic reagent adsorption amount measuring apparatus for powder according to the present embodiment can accurately collect a powder having a target weight, and thus a test result with less error can be obtained.

When the powder is sampled, the specific gravity of the powder is preliminarily assumed, and for example, the extruding rod is set at a position where about 1/2 of the object weight for sampling is sampled and the first sampling is performed. The weight of the collected powder is measured by a scale, and the position of the extrusion rod is corrected based on the volume and weight of the collected powder, and the second sampling is performed. In the second sampling, a powder having a weight corresponding to the difference between the target weight and the first sampling amount is sampled, and the powder having the target weight is sampled together with the first sampling. If the target weight is not reached in the second collection, the powder of the target weight may be collected by performing the third and subsequent collections.

Further, the automatic reagent adsorption amount measuring apparatus for powder of the present invention is convenient to use for measuring the methylene blue (MB) adsorption amount of coal ash, for example. In order to measure the MB adsorption amount of coal ash, the Cement Association standard test method (Cement Association method) and the electric power generation test method (electric power generation method) are generally used.
Therefore, it is advisable to incorporate a measurement program according to both methods into the control unit of the apparatus for automatically measuring the amount of reagent adsorption of powder according to the present invention so that it can be selected and used.

As described above, in both the Cement Association Method and the Electric Power Generation Method, a predetermined amount of MB solution was added to a certain amount of coal ash and mixed, and the mixture was filtered and the absorbance of the filtrate was measured to be determined in advance. This is a method of obtaining the MB adsorption amount in association with the calibration curve. There is a difference between the Cement Association method and the electromotive method in that the Cement Association method performs suction filtration and dilutes the filtrate to measure the absorbance, whereas the electrogenic method performs natural filtration and measures the filtrate as it is. . In addition, when the calibration curve is created, the MB solution is diluted by the electrophoretic method and then the absorbance is measured, but in the Cement Association method, the diluted MB solution is measured without filtering the absorbance.

Therefore, in the measurement program corresponding to the Cement Association Method, for example, a procedure of supplying the MB solution to the filtrate processing section and diluting it with a diluting water to a specified ratio, and diluting M
The procedure of delivering the solution B to the measurement unit and measuring the absorbance, the procedure of repeatedly obtaining the calibration curve while changing the dilution ratio and storing it in the control unit, and the procedure of receiving the coal ash sample in the powder receiving unit. , A procedure of preparing a sample solution by adding an MB solution to a coal ash sample at a prescribed ratio in a powder processing section and stirring, a procedure of delivering the sample solution to a filtering section and driving a vacuum pump to perform suction filtration, and a filtrate A procedure of delivering the filtrate to the treatment section and diluting it to a specified ratio by adding dilution water, a procedure of measuring the absorbance of the diluent in the measurement section, a procedure of obtaining the MB adsorption amount from the measurement result and the calibration curve in the control section, It is preferable to have a procedure for cleaning each part.

In addition, in the measurement program corresponding to the electric power generation method, for example, a procedure of supplying the MB solution to the powder processing unit and diluting it with a diluting water to a specified ratio, and delivering the diluted MB solution to the filtering unit. The procedure of filtering, the procedure of delivering the filtrate to the measuring section through the filtrate processing section and measuring the absorbance, the procedure of repeatedly obtaining the calibration curve while changing the dilution rate and storing it in the control section, and the powder receiving section A procedure for receiving a coal ash sample, a means for preparing a sample solution by adding the MB solution to the coal ash sample at a prescribed ratio in the powder processing section and stirring, and a procedure for delivering the sample solution to the filtering section and filtering it. It is advisable to provide a procedure for delivering the filtrate to the measurement section through the filtrate processing section and measuring the absorbance, a procedure for obtaining the MB adsorption amount from the measurement result and the calibration curve by the control section, and a procedure for cleaning each section.

When both the measuring program corresponding to the Cement Association method and the measuring program corresponding to the electric power generation method are provided, the MB reagent of coal ash can be adsorbed by either test method by the automatic reagent adsorption amount measuring apparatus for powder according to the present invention. The quantity can be calculated.

[0031]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described below in detail based on embodiments with reference to the drawings. FIG. 1 shows the first aspect of the present invention.
FIG. 2 is a configuration diagram of an apparatus for automatically measuring the amount of reagent adsorbed on powder in an example, and FIG. 2 is a process diagram thereof.

A powder feeding pipe 101 is provided above the powder receiving unit 1, and a powder receiving container 102 is provided below the powder feeding pipe 101. A shutter 103 is arranged near the powder receiving container 102. A powder storage tank 104 is arranged below the powder receiving unit 1, and a powder storage unit 2 is formed.

The powder sampling table 3 has a powder processing table 201.
A sample container 202 is provided with a flange supported on a hole provided in the sample container 202. In FIG. 2, a powder quantitative sampling device 203 is installed above the sample container 202 and a weighing machine 204 is installed below the sample container 202. There is. A driving mechanism (not shown) is connected to the powder processing table 201 and can be driven vertically and horizontally.
The powder quantitative sampling device 203 can be driven up and down. The powder receiving container 102 is provided at the end of the processing table 201.
Are connected.

The stirring unit 4 is arranged within the drive range of the powder processing table 201. The stirring unit 4 has a stirring position A and a cleaning position B. At the stirring position A, a stirrer 210 and a warmer 211 are arranged. The stirrer 210 can be driven up and down. In addition, from the reagent storage unit 5 to the reagent supply unit 6,
A pipe for supplying a reagent via the reagent switching unit 7 is arranged. The reagent storage unit 5 is provided with a reagent tank 601 and a warmer 602, the reagent supply unit 5 is provided with a reagent syringe 603, and the reagent switching unit 7 is provided with a reagent switching valve 6
04 is arranged. It should be noted that it is preferable to prepare a plurality of reagent tanks 601 that store reagents of different concentrations and replace and use them according to the measurement method.

Further, a pipe for supplying dilution water from the pure water storage unit 8 through the dilution water supply unit 9 and the dilution water switching unit 10 is arranged at the stirring position A. The pure water storage unit 8 is provided with a pure water tank 610, the dilution water supply unit 9 is provided with a dilution water syringe 611, and the dilution water switching unit 10 is provided with a dilution water switching valve 612. There is.

At the cleaning position B, a pipe for supplying cleaning water from the pure water storage section 8 through the cleaning water supply section 11 is arranged. The wash water supply unit 11 is provided with a wash water switching valve 620 and a pump (not shown). Further, at the cleaning position B, a pipe for supplying dry air from the dry heater 630 via the air switching valve 631 and supplying compressed air from the air set via the bubbling valve 650 is arranged. At the cleaning position B, the drainage is further stored in the drainage storage unit 13 via the drainage unit 12.
There is a pipe that discharges to. The drainage unit 12 is provided with a pump and a drainage collecting pipe 640, which are not shown,
The drainage storage unit 13 includes a drainage storage tank 641. Further, at the cleaning position B, a cleaning arm 220 is installed so as to be vertically movable. The cleaning arm 220 seals the sample container 202 when installed on the sample container 202. Further, each pipe is incorporated so that each pipe opens to the sample container 202 when the sample container 202 is sealed.

A filter section 15 is connected to the stirring section 4 via a solution collecting section 14. The solution collecting unit 14 is composed of a pump and a pipeline (not shown). The filter cylinder 301 is arranged immediately below the outlet of the pipeline to form the filter unit 15. A filter paper cassette holder 30 is provided at the center of the filter cylinder 301.
2 is inserted. A discharge pipe is provided at the lower end of the filter cylinder 301, and a pinch cock 303 is arranged. Also,
A pipe is connected to the lower side of the filtration cylinder 301, and a decompression pump 304 and an atmosphere release valve 305 are installed.
Further, a pipe for introducing air from a drying heater 630 and an air set and a pipe for introducing cleaning water from a pure water tank 610 are arranged in the pipes, and a bubbling valve 651 and a shutoff valve 652 are inserted in these pipes. .

A filter paper supply / recovery section 16 is arranged near the filter section 15. The filter paper supply / recovery section 16 includes a cassette supply unit 31 that stores an unused filter paper cassette 310.
1. A cassette collection unit 312 for accommodating a used filter paper cassette 310 is arranged.

A filtrate collecting section 17 and a diluting section 18 are provided below the filtering section 15. The filtrate collecting unit 17 and the diluting unit 18 have a drainage container 402, a filtrate container 403, and a diluting container 404 on a filtrate processing table 401 that can be driven left and right.
A measurement liquid container 405 is arranged. A drainage pipe is connected to the lower end of the drainage container 402, and the drainage pipe opens to the drainage storage tank 641. A stir bar 406 is loaded in the diluting container 404, and a magnetic stirrer 407 is attached under the table directly below the container.

In the diluting section 18, a filtrate receiving position C, a diluting position D, a container washing position E and a measuring cell washing position F are set. At the dilution position D, a pipe connected to the filtrate syringe 410 of the filtrate collection unit 17 and a pipe for supplying a reagent via the reagent switching valve 604 are arranged. Filtrate syringe 41
0 is further connected to a dilution water syringe 611 and a pure water tank 610 via a dilution water switching valve 612. At the container cleaning position E, a pipe from the cleaning water switching valve 620, a pipe from the air switching valve 631, a pipe to the drainage collecting pipe 640, and a cleaning arm 408 are arranged. Measurement cell cleaning position F
A dilute hydrochloric acid tank 411 via a dilute hydrochloric acid syringe 411.
There is a pipe to supply dilute hydrochloric acid from.

An absorbance measuring section 19 is provided downstream of the diluting section 18. The absorbance measuring unit 19 is equipped with a spectrophotometer 501 and a measuring syringe 502. Spectrophotometer 5
The cell of 01 is equipped with a pipe for introducing the measurement liquid from the measurement liquid container 405. A pipe to the drainage collecting pipe 640 is connected to the measuring syringe 502.

Further, a control unit 20 is provided in the apparatus, and each unit is controllably connected. The control unit 20 is a control device 70.
1, an operation calculation device 702, and a printer 703. The control device 701 sequentially drives and controls each unit. The operation calculation device 702 has a calculation function, an operation, and a display function, and performs various calculations and interfaces with an operator and the outside. In addition, a temperature control unit 21 is provided in the device to keep the room temperature constant.

It should be noted that the pipes opened in each container are equipped with arms that can be driven up and down, respectively, so that the pipes can be inserted into and pulled out from the container. Therefore,
Piping does not interfere when moving the container left and right.

The powder quantitative sampling device 203 used in the powder sampling unit 3 is equipped with a sampling tube, an extruding rod and a pulse motor, and the extruding rod is built in the sampling tube, and the pulse motor is provided above the extruding rod. Are arranged. The sampling tube is driven up and down by a drive mechanism, and the push rod is driven vertically in the sampling tube by a pulse motor.

The powder collecting container 1 is inserted into the powder receiving container 102 with the extruding rod being positioned at the back of the powder receiving container 1.
02, the fixed amount of powder is taken in and held in the sampling tube, and the extrusion rod is pushed up to the opening of the sampling tube on the sample container 202 and the powder is discharged to discharge the fixed amount of powder into the sample container 202.
To collect. The volume of the powder taken into the sampling tube is increased or decreased by raising or lowering the set position of the extrusion rod when taking the powder. Since the position of the extrusion rod can be accurately controlled by the pulse motor, the volume of the powder taken into the sampling tube can be freely set.

When the powder is sampled, the specific gravity of the powder is assumed in advance, and the extrusion rod is set at a position where about 1/2 of the target weight of the sample is sampled and the first sampling is performed. The weight of the collected powder is measured by the weighing machine 204, the position of the extrusion rod is corrected based on the volume and weight of the collected powder, and the powder receiving container 102
The second sampling is performed by slightly shifting the insertion position into the. In the second sampling, a powder having a weight corresponding to the difference between the target weight and the first sampling amount is sampled, and the powder having the target weight is sampled together with the first sampling. If the target weight is not reached in the second collection, the powder of the target weight may be collected by performing the third and subsequent collections.

The control section 20 incorporates a procedure for measuring the amount of methylene blue (MB) adsorbed in coal ash in accordance with the Cement Association Method and the Electric Power Generation Method, and each section operates under sequence control by the control section 20. 3 to 6 show the operation procedure of the apparatus for measuring the MB adsorption amount of coal ash with the powder reagent adsorption amount automatic measuring apparatus of the present embodiment.

At the start of operation (S1), the control unit 20 is in the state of measuring method input S2. In the measurement method input S2, either the cement association method or the electric power generation method input from the outside is stored, and the operation mode input S3 is performed. In the operation mode input S3, either a measurement mode in which coal ash is charged to measure the MB adsorption amount or a calibration curve mode in which a calibration curve is created is input.

When the calibration curve mode is input, the control unit 20 shifts to the calibration condition input S4. In the calibration condition input S4,
Enter the number of calibration points for obtaining the calibration curve and the amount of MB standard solution at each point. The measurement can be started when the amount of the MB standard solution having the set calibration point is input. The number of calibration points and the amount of MB standard solution may be input from an input device, or may be input from a storage device in which data is recorded.

If the Cement Association method is selected in the measurement method input S1, first a predetermined MB standard solution is supplied to the diluting section 18 (S6), and then a specified amount of dilution water is supplied and stirred to obtain a predetermined concentration. Of the MB solution is prepared (S7), the absorbance is measured by the absorbance measuring unit 19 (S8), and each part is washed (S).
8.5).

Specifically, the filtrate processing table 401 is driven to set the dilution container 404 to the dilution position D, and the amount of MB set in the calibration condition input S4 from the reagent tank 601 is set.
The standard solution is sucked up by the reagent syringe 603 of the reagent supply unit 6 and discharged to the dilution container 404 via the reagent switching valve 604.

Pure water in an amount necessary for diluting to a specified concentration from the pure water tank 610 is sucked up into the diluting water syringe 611, the pure water switching valve 612 is set toward the diluting section 18, and the diluting container 404 is passed through the filtrate syringe 410. To discharge. The stirrer 406 is rotated by the magnetic stirrer 407 and stirred. The MB standard solution diluted with the filtrate syringe 410 is quantitatively sampled, the measurement solution container 405 is moved to the dilution position, the diluted MB standard solution is discharged to the measurement solution container 405, and diluted by the measurement syringe 502 into the cell of the spectrophotometer 501. MB
A standard solution is introduced and the absorbance is measured.

After the measurement, the measurement result is transmitted to the control unit 20,
The measurement liquid container 405 is moved to the measurement cell washing position F, and diluted hydrochloric acid is supplied from the diluted hydrochloric acid tank 412 through the measurement liquid container 405 and the spectrophotometer 501 to the drainage collecting pipe 640 by the diluted hydrochloric acid syringe 411 and the measurement syringe 502 to wash each part. Further, the diluting container 404 is moved to the container washing position E, the diluting container 404 is sealed by the washing arm 408, pure water is supplied from the pure water storage unit 610 through the washing water switching valve 620, and the drainage is discharged to discharge the container. Clean the inside. The drainage is discharged to the drainage tank 641 through the drainage collecting pipe 640.
The supply of pure water is stopped, dry air is introduced from the dry heater 630 to dry the dilution container 404, and the cleaning is completed.

After the measurement of the absorbance and the washing of each part are completed, it is confirmed whether all the calibration points corresponding to the MB standard solution amount set in the calibration condition input S4 have been obtained (S9). Returning to the standard solution supply S6, the calibration point is measured again. If the measurement of the calibration point is completed, the control unit 20 creates a calibration curve (S10), rewrites and saves the calibration curve file of the Cement Association method, and displays the calibration curve as necessary (S11, S12). The preparation of the calibration curve is completed (S13), and the process returns to the measurement mode selection S2.

On the other hand, if the electrification method is selected in the measurement method input S2, the MB standard solution is first supplied to the stirring section 4 (S1
4) Further, the diluent is supplied and stirred (S15), filtration is performed by the filtration unit 15 (S16), the absorbance of the filtrate is measured by the absorbance measurement unit 19 (S8), and each part is washed (S8.
5).

Specifically, the powder processing table 201 is driven to move the sample container 202 to the stirring position A, and a preset amount of MB standard solution and dilution water are supplied from the reagent syringe 603 and the dilution water syringe 611. Then, the stirrer 210 is lowered to stir the diluted MB standard solution. When the MB standard solution and the dilution water are sufficiently mixed, the diluted MB standard solution is sent to the filter cylinder 301 by a pump (not shown), the pinch cock is closed, and the atmosphere opening valve 305 is opened to perform natural filtration. An unused filter paper cassette 310 is set in the filter paper cassette holder 302 from the cassette supply unit 311.

After filtration, the filtrate container 403 is moved to the filtrate receiving position C.
Then, the pinch cock 303 is opened and the filtrate stored in the filter cylinder 301 is discharged to the filtrate container 403. Filtrate container 4
03 is moved to the dilution position D, a prescribed amount of filtrate is collected by the filtrate syringe 410, the measurement liquid container 405 is moved to the dilution position D, the filtrate is discharged to the measurement liquid container 405, and the measurement liquid container 502 is used. The filtrate in 405 is transferred to the cell of the spectrophotometer 501, and the absorbance of the filtrate is measured.

After the measurement, the measurement result is transmitted to the control unit 20,
The measurement liquid container 405, the spectrophotometer 501, the diluting container 404, and the like are washed as in the case of the Cement Association Method. At the same time, the sample container 202 is moved to the cleaning position B, and the cleaning arm 22
It is hermetically sealed at 0, and the cleaning water is supplied and the air is supplied from the air set through the bubbling valve 650 to perform the bubbling cleaning. After sufficient cleaning, drainage is drained and dry air is introduced to dry the product to complete the cleaning.

After the measurement of the absorbance S8 and the washing of each part are completed, it is confirmed whether all the calibration points corresponding to the MB standard solution amount set in the calibration condition input S4 have been obtained (S9).
If not obtained, the process returns to the MB standard solution supply S14 and the calibration point is measured again. If the measurement of the calibration points has been completed, the control unit 20 creates a calibration curve (S10), rewrites and saves the calibration curve file of the electromotive method, and displays the calibration curve as necessary (S11 / S12). The preparation of the calibration curve is completed (S13), and the process returns to the measurement mode selection S2.

When the measurement mode is selected with the control unit 20 in the operation mode input S2 after the preparation of the calibration curve is completed, the measurement is started (S17) and the coal ash is put into the powder receiving unit 1. (S18). Coal ash is quantitatively collected by the powder sampling unit 3 (S19), the MB standard solution is added by the stirring unit 4, stirred and left still (S20 to S22), and at the same time, the filter paper supply / recovery unit 1
In step 6, the filter paper is set in the filter unit 15 (S23), the sample solution is delivered to the filter unit 15 and filtered (S24).

After the filtration, the filter paper is recovered by the filter paper supply / recovery section 16 (S25), and the stirring section 4 is washed (S26). Also,
The filtrate is sent to the filtrate sampling unit 17 (S27), the zero point calibration of the spectrophotometer 501 is simultaneously performed (S28), and the absorbance of the filtrate is measured by the absorbance measuring unit 19 (S29). If the Cement Association method is selected in the measurement method input S1, the filtrate is diluted to a specified magnification before the measurement (S30).

After the measurement, a calibration curve corresponding to the measurement method selected by the measurement method input S2 is read from the calibration curve stored in the control unit 20 (S31 / S32), and the MB adsorption amount of coal ash is determined from the absorbance and the calibration curve. Is calculated and output (S33). At the same time, the diluting unit 18 and the filtering unit 15 are washed (S34 / S3
5), measurement is completed (S36).

Specifically, when the measurement mode is selected as a trigger to start the measurement, coal ash is charged from the powder charging pipe 101 and received by the powder receiving container 102. The coal ash that could not be received in the powder receiving container 102 is the powder storage tank 1
It is designed to fall to 04. Although the selection of the measurement mode is used as a trigger, the trigger may manually instruct the start of measurement, or the measurement start signal may be input online.

The shutter 103 is opened, and the powder processing table 201 moves the powder receiving container 102 containing the coal ash to a position right below the powder quantitative sampling device 203. A predetermined amount of coal ash is taken into the powder quantitative sampling device 203, and the sample container 20
2 is moved to directly below the powder quantitative sampling device 203 to discharge coal ash. Lower the powder processing table 201 to the sample container 2
02 is placed on the weighing machine 204, and the weight of the collected coal ash is measured. If the amount of coal ash collected is small, the collection of coal ash is repeated again.

After collection, the powder receiving container 102 is moved above the powder storage tank 104, and the powder receiving container 1 is driven by the driving device.
02 to reverse the coal ash in the container to the powder storage tank 104
To discharge. The powder is charged and discharged by closing the shutter 103 so that unnecessary coal ash does not enter the apparatus chamber. Further, a dustproof fan may be further provided above the powder storage tank 104 to prevent unnecessary coal ash from entering the apparatus chamber when handling the coal ash.

The sample container 202 is moved to the stirring position A, and the MB standard solution in an amount corresponding to the weight of the collected coal ash is charged by the reagent syringe 603. While the temperature is kept warm by the warmer 211, the stirrer 210 is inserted, and the mixture is sufficiently stirred and left to stand.

Filter paper cassette holder 302 of filter cylinder 301
Then, an unused filter paper cassette 310 is set from the cassette supply unit 311. It should be noted that the filter paper is attached to the filter paper cassette 310 in advance and loaded in the cassette supply unit 311.

After setting the filter paper cassette 310, the pinch cock 303 is closed for co-washing, and a small amount of the sample solution in the sample container 202 is flown into the filter cylinder 301. Next, the filtrate treatment table 401 is driven to move the drainage container 402 to the filtrate receiving position 410, open the pinch cock 303, and drain the liquid.

After the co-washing, the pinch cock 303 is closed and the sample solution in the sample container 202 is continuously flowed and filtered.
At this time, if the Cement Association Act is selected, the atmosphere opening valve 305, the bubbling valve 651, and the closing valve 652 are closed,
The vacuum pump 304 is operated to perform suction filtration. If the electric power generation method is selected, the atmosphere opening valve 305 is opened to perform natural filtration.

After the filtration, the used filter paper cassette 310 is recovered in the cassette recovery unit 312. At the same time, the sample container 202 is moved to the cleaning position B, sealed by the cleaning arm 220, and the cleaning water is supplied and the air is supplied from the air set through the bubbling valve 650 to perform the bubbling cleaning.
After sufficient cleaning, drainage is drained and dry air is introduced to dry the product to complete the cleaning.

The filtrate container 403 is moved to the filtrate receiving position C, the atmosphere opening valve 305 and the pinch cock 303 are opened, and the filtrate is transferred to the filtrate container 403. Next, the measuring liquid container 405
Is moved to the dilution position D, pure water is injected from the dilution water syringe 611, and the spectrophotometer 501 is measured by the measurement syringe 502.
Suction pure water to zero point calibration.

The filtrate container 403 containing the filtrate is moved to the dilution position D. If the electrification method is selected in the measurement method selection S2, a fixed amount of the filtrate is sucked by the filtrate syringe 410, the measurement liquid container 405 is moved to the dilution position D, the filtrate is discharged, and the measurement syringe 502 is operated. The filtrate is sent to the spectrophotometer 501, and the absorbance of the filtrate is measured.

If the cement association method is selected in the measurement method selection S2, a fixed amount of filtrate is sucked from the filtrate container 403 at the dilution position D with the filtrate syringe 410, and the dilution container 404 is moved to the dilution position D. The filtrate is discharged from the filtrate syringe 410 to the dilution container 404. Then, pure water corresponding to the amount of the filtrate is supplied from a pure water syringe 611 to dilute the filtrate at a specified ratio. Magnet stirrer 407 to stir bar 4
Rotate 06 and stir well. The diluted filtrate is sucked into the filtrate syringe 410. Set the measurement solution container 405 to the dilution position D
The filtrate is discharged to the measurement solution container 405, sucked by the measurement syringe 502, transferred to the cell of the spectrophotometer 501, and the absorbance of the filtrate is measured.

After measuring the absorbance, the measurement result is displayed on the control device 70.
Send to 1. Data is sent from the control device 701 to the operation calculation device 702, and the operation calculation device 702 receives the measurement method input S.
The calibration curve corresponding to the measurement method selected in 2 is read out, and the MB adsorption amount of coal ash is calculated from the measured absorbance and the calibration curve,
It is displayed on the screen and is output by the printer 703.

At the same time, a filtrate container 403 and a dilution container 404
Are sequentially moved to the container cleaning position E, and the cleaning arm 408 is lowered to perform cleaning. In addition, the measurement liquid container 405 is moved to the measurement cell cleaning position F, and diluted hydrochloric acid is supplied from the diluted hydrochloric acid tank 412 by the diluted hydrochloric acid syringe 411.
2 to draw in dilute hydrochloric acid for circulation, and
5. Wash the spectrophotometer 501 and the measuring syringe 502. The washing liquid and dilute hydrochloric acid that have washed the filtrate container 403 and the diluting container 404 pass through the drainage collecting pipe 640 and the drainage storage unit 64.
Discharge to 1.

Subsequently, the filter cylinder 301 is washed. The pinch cock 303 is closed, the stop valve 652 is opened, and pure water is supplied from the pure water storage unit by a pump (not shown). The stop valve 652 is closed, and air is intermittently blown from the bubbling valve 651 to perform bubbling cleaning. The drainage container 402 is moved to the filtrate receiving position C, the pinch cock 303 and the atmosphere opening valve 305 are opened to discharge the drainage liquid to the drainage container 402, and dry air is introduced from the drying heater 630 to dry the inside. The measurement is finished when the output of the measurement result and the cleaning of each part are finished.

If the unburned carbon content in the coal ash is too small and the filtrate is thick and the absorbance is at or above the maximum preset value, the dilution ratio is increased and the filtrate in the filtrate container is diluted again for measurement. If the unburned carbon content is excessive and the filtrate is thin and the absorbance is below the minimum specified value, reduce the coal ash and resample to measure. If it is estimated from the beginning that the unburned content is too large or too small, the dilution rate and the amount of coal ash collected should be adjusted in advance.

As described above, according to the automatic reagent adsorption amount measuring apparatus for powder of the present embodiment, the MB adsorption amount of coal ash can be automatically measured by both the cement association method and the electric power generation method. You can Since the replacement of the filter paper and the cleaning of each part are also automatically performed, it is possible to continuously measure a plurality of samples online.

The ratio of MB standard solution to coal ash, the dilution ratio, the amount of MB standard solution at each calibration point, and the like may be appropriately defined with reference to the standard test method of the Cement Association Method or the Electric Power Generation Method. Further, the cleaning of each part, the replacement of the filter paper, etc. are not limited to the procedure of this embodiment, and may be appropriately performed when the device is not performing the measurement operation. In this embodiment, the control unit 20 controls each unit and sequentially performs each procedure, but each device or process may be individually operated for maintenance or the like.

Table 1 shows an example of the test results of measuring the MB adsorption amount of coal ash by the reagent reagent adsorption amount automatic measuring device of the present example.

[Table 1] 7 and 8 show the calibration curves prepared according to the Cement Association Method and the Electron Electrification Method by the reagent reagent adsorption amount automatic measuring apparatus of the present example.

In the apparatus of this embodiment, the control unit 20 is provided with M of coal ash.
Although the procedure for measuring the amount of adsorbed B was incorporated and used, by incorporating another procedure in the controller 20, it can be used for various measurements using other powders and reagents.

[0082]

As described above, according to the automatic reagent adsorption amount measuring apparatus for powders of the present invention, the MB adsorption amount of coal ash can be automatically measured by either of the Cement Association Method and the Electric Power Generation Method. . In the automatic reagent adsorption amount measuring device for powder according to the present invention, since human power is not involved in the measurement, the measurement result does not have an error due to individual differences. In addition, it can be used for online measurement because continuous automatic measurement can be performed.

[Brief description of drawings]

FIG. 1 is a structural diagram of an apparatus for automatically measuring an amount of reagent adsorption of a powder according to an embodiment of the present invention.

FIG. 2 is a process diagram of an apparatus for automatically measuring the amount of reagent adsorption of powder according to an embodiment of the present invention.

FIG. 3 is a first part of a flowchart showing an operation procedure of the automatic reagent adsorption amount measuring device for powder according to one embodiment of the present invention.

FIG. 4 is a second part of the flowchart showing the operation procedure of the automatic reagent adsorption amount measuring device for powder according to the embodiment of the present invention.

FIG. 5 is a third part of the flowchart showing the operating procedure of the automatic reagent adsorption amount measuring device for powder according to the embodiment of the present invention.

FIG. 6 is a fourth part of the flowchart showing the operation procedure of the automatic reagent adsorption amount measuring device for powder according to the embodiment of the present invention.

FIG. 7 is an example of a calibration curve prepared according to the Cement Association Method by an apparatus for automatically measuring the amount of reagent adsorbed on powder in one example of the present invention.

FIG. 8 is an example of a calibration curve prepared according to the electro-electrometry method by the apparatus for automatically measuring the amount of reagent adsorbed on powder in one example of the present invention.

[Explanation of symbols]

101 powder feeding pipe 102 powder receiving container 103 shutter 104 powder storage tank 201 powder processing table 202 sample container 203 Powder quantitative sampling device 204 Weighing machine 210 stirrer 211 warmer 220 washing arm 301 Filter tube 302 cassette holder 303 Pinch cock 304 Decompression pump 310 filter paper cassette 311 cassette supply unit 312 cassette collection unit 401 Filtrate processing table 402 drain container 403 Filtrate container 404 dilution container 405 Measuring liquid container 406 Star bar 407 Magnet Stirrer 408 Washing arm 410 Filtrate syringe 411 dilute hydrochloric acid syringe 412 dilute hydrochloric acid tank 501 spectrophotometer 502 Measuring syringe 601 Reagent tank 602 Incubator 603 Reagent syringe 610 Pure water tank 611 dilution water syringe 630 Drying heater 640 drainage pipe 641 drainage tank 701 control device 702 Operation computing device 703 Printer A stirring position B Cleaning position C Filtrate receiving position D dilution position E Container cleaning position F Measurement cell cleaning position

─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Tetsuhiro Kinoshita 2-11-1 Minamisuna, Koto-ku, Tokyo Kawasaki Heavy Industries, Ltd. Tokyo Design Office (72) Akira Yamashita 2-11-1 Minamisuna, Koto-ku, Tokyo No. Kawasaki Heavy Industries, Ltd. Tokyo Design Office (56) References JP-A-11-94745 (JP, A) JP-A-9-49845 (JP, A) JP-A-7-244051 (JP, A) JP-A-7-244051 (JP, A) 10-78381 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) G01N 21/75-21/83 G01N 21/00-21/61 PATOLIS

Claims (11)

(57) [Claims] 1. An apparatus for automatically measuring a reagent adsorption amount of powder, comprising a powder receiving section, a powder processing section, a filtering section, a filtrate processing section, a measuring section and a control section. The receiving part is provided with a powder receiving container, and the powder receiving container receives powder input from the outside, and the powder processing part has a sample container, a powder quantitative sampling device, a weighing machine, and a first reagent. A powder supply device, a first dilution water supply device, and a first stirring device are provided, and the powder contained in the powder receiving container is quantitatively sampled in the sample container by the powder quantitative sampling device to obtain the amount of the collected powder. Accordingly, the reagent is added from the first reagent supply device to the sample container to stir with the first stirring device to prepare a sample solution, or the sample container receives the reagent from the first reagent supply unit. Sample water is prepared by adding dilution water from the first dilution water supply device and stirring with the first stirring device. A shall, said filtration unit e Bei a filter, either natural filtering said sample solution, or,
Further, a vacuum pump is provided for suction filtration, and the filtrate treatment section is provided with a filtrate container, a second dilution water supply device, a second reagent supply device, and a second stirring device, and the filtrate obtained in the filtration section is selected. The measurement solution is received in the filtrate container, the filtrate is received in the filtrate container and diluted with diluted water to prepare a measurement solution, or the reagent is received in the filtrate container and diluted with diluted water and stirred. To prepare a measurement solution, the measurement unit is equipped with a spectrophotometer, which is to measure the absorbance of the measurement solution, the control unit controls each component to measure the measurement result of the measurement unit. An apparatus for automatically measuring the amount of reagent adsorbed on a powder, which calculates the amount of reagent adsorbed on the powder based on the above and outputs the result. 2. An apparatus for automatically measuring the amount of reagent adsorbed on a powder is provided with a cleaning section, and the cleaning section comprises the powder processing section, the filtering section, and the filtrate processing.
2. The automatic reagent adsorption amount measuring device for powder according to claim 1 , wherein each of the measuring unit and the measuring unit is washed with a washing liquid and dried. 3. A powder receiving position is set in the powder receiving unit, and a sampling position, a first stirring position, and a first cleaning position are set in the powder processing unit, and the powder is placed in the sampling position. The quantitative sampling device and the weighing machine are disposed, and the first stirring position is provided with the supply end of the first reagent supply device, the supply end of the first dilution water supply device, and the first stirring device. A first cleaning device is arranged at a cleaning position, and a powder processing table that supports the powder receiving container and the sample container and is translatable by a drive mechanism is provided, and the powder receiving container receives the powder receiving table. 3. The reagent for powder according to claim 2, wherein the sample container can be selectively positioned between the position and the sample collecting position, the sample collecting position, the first stirring position and the first cleaning position. Adsorption amount automatic measuring device. 4. The control unit drives the powder processing table to position the powder receiving container at the powder receiving position to receive powder input from the outside, and the powder receiving container The powder in the powder receiving container is taken into the powder sampling device by moving to the sample collecting position, the sample container is moved to the sample collecting position and discharged, and the sample container is subjected to the first stirring. A procedure of moving to a position and adding the reagent by the first reagent supply device and stirring by the first stirrer to prepare a sample solution; and positioning the sample container at the first stirring position, The reagent is added by
One of the procedures for preparing the sample solution by adding the dilution water by the dilution water supply device and stirring by the first stirring device is further selected, and after the sample solution is delivered to the filtration unit, the sample container 5. The automatic reagent adsorption amount measuring device for powder according to claim 3, wherein the sample container is moved to the first cleaning unit to clean the sample container. 5. A drive unit comprising a dilution container, a measurement liquid container, and a filtrate treatment table in the filtrate treatment unit, the filtrate treatment table supporting the filtrate container, the dilution container, and the measurement liquid container. The filtrate receiving position, the diluting position, the second washing position, and the third washing position are set, the filter is located above the filtrate receiving position, and the filtrate is placed at the diluting position. 2 The supply end of the diluting water supply device, the supply end of the second reagent supply device, and the filtrate sampling device, the second cleaning device at the second cleaning position, and the third cleaning device at the third cleaning position are provided. Driving the filtrate processing table to move the filtrate container, the dilution container, and the measurement liquid container to the filtrate receiving position, the diluting position, the second cleaning position, and the third cleaning position, respectively.
The automatic reagent adsorption amount measuring device for powder according to any one of claims 2 to 4, which can be located at a washing position. 6. The filtrate collection device, wherein the controller drives the filtrate processing table to position the filtrate container at the filtrate receiving position to receive the filtrate, and moves the filtrate container to the diluting position to obtain the filtrate collecting device. By collecting the filtrate, moving the measurement solution container to the diluting position and discharging it to obtain a measurement solution, and positioning the filtrate container at the filtrate receiving position to receive the filtrate, The filtrate is moved to the diluting position and the filtrate is collected by the filtrate collecting device, the diluting container is moved to the diluting position and discharged, the diluting water is supplied from the second diluting water supply device, and the second stirring is performed. A step of stirring with an apparatus, moving the dilution container to the dilution position and collecting the filtrate diluted with the filtrate collecting apparatus, moving the measurement solution container to the dilution position and discharging it to obtain a measurement solution; The diluting container is located at the diluting position and the second The reagent is supplied from a reagent supply device, the dilution water is supplied from the second dilution water supply device, and the second dilution water is supplied from the second dilution water supply device.
The procedure is to select one of the procedures of stirring with a stirrer to obtain a diluted reagent, collecting the diluted reagent with the filtrate sampling device, moving the measuring solution container to the diluting position and discharging it to obtain a measuring solution. Then, after measuring the absorbance, the measurement liquid container is positioned at the third cleaning position and cleaned by the third cleaning device, and the filtrate container is positioned at the second cleaning position and the second cleaning device. 6. The automatic reagent adsorption amount measuring device for powder according to claim 5 , wherein the diluting container is positioned at the second washing position and washed by the second washing device. 7. The automatic reagent adsorption amount of powder according to claim 1, wherein the filter section is provided with a filter paper exchanging device, and the filter paper exchanging device replaces the filter paper. measuring device. 8. The automatic reagent adsorption amount measuring apparatus for powders is provided with a temperature adjusting section, and the reagent temperature, the stirring section temperature and the room temperature in the apparatus are kept constant. Automatic measuring device for reagent adsorption of powder. 9. The automatic reagent adsorption amount measuring device for powder is provided with a storage unit, and the storage unit is provided with a tank for storing the reagent, the dilution water, the cleaning liquid, the drainage liquid, and the discharged powder. The automatic reagent adsorption amount measuring device for powder according to any one of claims 1 to 8. 10. The powder quantitative sampling device is capable of changing a capacity for taking in powder, and a quantity of powder smaller than a target collection quantity is collected in the sample container in the first sampling and collected in the first sampling. The volume of the powder to be sampled is determined based on the weight of the powder obtained, the sample is sampled a second time and added to the sample container, and the powder having the target weight is sampled by sampling twice. Item 10. An apparatus for automatically measuring the reagent adsorption amount of powder according to any one of Items 1 to 9. 11. The powder is coal ash, the reagent is an aqueous solution of methylene blue, and the control unit is provided with a measurement procedure according to the Cement Association Standard Test Method and a measurement procedure according to the Electrification Test Method. Claim 1 to 1 characterized by
0. A device for automatically measuring the amount of a reagent adsorbed on a powder according to 0.