JP3328447B2 - Metal sample continuous electrolyzer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a metal sample continuous electrolysis apparatus for preparing a sample solution in atomic absorption spectrometry, spectrophotometry, plasma emission analysis, and other analysis methods.

[0002]

2. Description of the Related Art In the process of producing a metal, the rapid measurement of the chemical composition of the molten metal during the refining process, and control of the refining or adjustment of the composition determines the physical or chemical properties of the metal. That is very important. Conventionally,
There are various methods for quickly measuring chemical components in metals, and many of them are used, but most of them are physical analysis methods and have problems in analysis accuracy.

On the other hand, chemical analysis such as plasma emission analysis generally has high analytical accuracy and is widely used in research laboratories. However, it is difficult to use for analyzing the chemical components of the molten metal during the refining process due to its poor speed. The reason for the lack of rapidity is that it takes a long time to prepare a sample solution for the chemical analysis. That is, in order to prepare the sample solution, grinding powder is obtained from a metal specimen (target base material) by a drill or the like, 1 g of the sample is accurately weighed, the weighed sample is transferred to a beaker, and the acid for dissolution ( Hydrochloric acid, nitric acid, sulfuric acid, perchloric acid, etc.)
It is necessary to go through each of the steps of adding ml, heating to completely dissolve the sample, cooling the lysate after complete lysis, and transferring the lysate to a 100 ml volumetric flask and diluting it to 100 ml with pure water. It takes a long time of about 20 minutes. At steelmaking plants, thousands of samples are analyzed a day, and reducing the sample preparation time is an important issue.

In order to greatly speed up the process of disassembling such a metal sample to prepare a sample solution and to save labor, the surface of a block-shaped cast sample is electrolyzed to obtain a sample solution and to directly and continuously perform the process. Japanese Patent Application Laid-Open No. Sho 6
It is disclosed in JP-A-3-151853.

[0005]

According to the apparatus for chemical analysis disclosed in the above publication, it is possible to prepare a sample solution in a short time of several minutes per sample, which is compared with the time required for the conventional chemical analysis method. As a result, it is possible to greatly reduce it to about 1/10.

However, the above-described apparatus has a disadvantage that gas generated by electrolysis stays in the electrolysis chamber of the electrolysis cell, and the staying gas insulates between the metal sample and the counter electrode, so that electrolysis cannot be performed.

An object of the present invention is to solve the above problems,
It is an object of the present invention to provide a metal sample continuous electrolysis apparatus that enables stable electrolysis.

[0008]

According to a first aspect of the present invention, there is provided a continuous electrolysis apparatus for a metal sample having a cell body provided with an electrolyte inlet and an electrolyte outlet, and a columnar counter electrode penetrating the cell body. An electrolytic chamber is formed between the block-shaped metal sample supported on the sample support of the cell body and the top surface of the counter electrode,
In a metal sample continuous electrolyzer, a voltage is applied between a metal sample and a counter electrode while the electrolyte is being supplied from the electrolyte inlet to the electrolysis chamber to electrolyze the metal sample, and a sample solution is continuously obtained from the electrolyte outlet. The counter electrode vertically penetrates the cell main body, and an inlet-side flow path communicating with the electrolyte inlet is formed between the cell main body and the peripheral surface of the counter electrode and opens to the electrolytic chamber.

The cell body is made of a non-conductive material such as fluororesin, and the counter electrode is made of graphite or the like.

[0010] In order to form an inlet flow path between the cell body and the counter electrode peripheral surface, a groove is provided which extends perpendicularly to the surface of the cell body in contact with the counter electrode peripheral surface or the counter electrode peripheral surface and reaches the electrolytic chamber. In order to form the outlet-side channel, a groove may be provided on the cell body or the peripheral surface of the counter electrode as in the case of the inlet-side channel, or a channel that directly connects the electrolytic chamber and the electrolyte outlet may be provided.

According to a second aspect of the present invention, there is provided a continuous metal sample electrolysis apparatus having a cell body provided with an electrolyte inlet and an electrolyte outlet, and a columnar counter electrode penetrating the cell body. An electrolysis chamber is formed between the block-shaped metal sample supported on the tip of the counter electrode and an electrolytic solution is supplied to the electrolysis chamber from the electrolyte inlet while applying a voltage between the metal sample and the counter electrode. In a metal sample continuous electrolysis apparatus for electrolyzing a metal sample and continuously obtaining a sample solution from an electrolyte outlet, a counter electrode extends horizontally through the cell body, and a sample support surface of the sample support section is vertical. The inlet channel connecting the electrolyte inlet and the electrolytic chamber is connected to the bottom of the electrolytic chamber, and the outlet channel connecting the electrolytic chamber and the electrolyte outlet is connected to the top of the electrolytic chamber. A sample pressing device for pressing the sample supporting portion;

The materials of the cell body and the counter electrode are the same as those of the first invention.

The sample pressing device uses a pneumatic cylinder, a hydraulic cylinder, or an electric linear actuator as a drive source, and presses the metal sample to the sample support portion of the cell body via the sample holder.

In the metal sample continuous electrolyzer according to the first and second aspects of the present invention, an analyzer that uses a sample solution as an analysis sample is connected to an outlet channel of the electrolysis chamber.

[0015]

In the first aspect of the present invention, an electrolytic chamber is formed from the metal sample, the cell body, and the top of the counter electrode by placing the block-shaped metal sample on the sample support at the top of the cell body. Here, while continuously flowing the electrolytic solution from the electrolytic solution inlet through the electrolytic chamber through the inlet-side channel, and the electrolytic solution to the electrolytic solution outlet through the outlet-side channel, a voltage is applied between the metal sample and the counter electrode. Electrolysis is performed by applying voltage.

In the inlet flow path, the electrolytic solution is supplied to the electrolytic chamber while maintaining contact with the counter electrode. Therefore, the counter electrode is not insulated by gas bubbles generated by the electrolysis. Further, since the entrance flow path is formed along the counter electrode, the entrance flow path is perpendicular to the metal sample surface. Therefore, the electrolytic solution flows into the electrolytic chamber so as to be sprayed at right angles to the metal sample surface. By spraying the electrolytic solution at right angles to the surface of the metal sample, gas bubbles generated by electrolysis from the metal sample are eliminated, and the metal sample is prevented from being insulated.

In the second invention, an electrolytic chamber is formed from the metal sample, the cell body, and the counter electrode by pressing the block-shaped metal sample against the vertical sample support surface. Here, while continuously flowing the electrolytic solution from the electrolytic solution inlet through the electrolytic chamber through the inlet-side channel, and the electrolytic solution to the electrolytic solution outlet through the outlet-side channel, a voltage is applied between the metal sample and the counter electrode. Electrolysis is performed by applying voltage.

The gas bubbles generated in the electrolytic chamber are:
It rises in the electrolytic chamber and is continuously discharged to the outside of the electrolytic chamber from an electrolytic solution outlet provided at the top of the electrolytic chamber.

Further, since there is provided a sample pressing device for pressing the metal sample against the sample supporting portion, even if the sample supporting surface is vertical, the electrolyte does not leak from the electrolytic chamber.

[0020]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the present invention will be described with reference to the drawings.

FIG. 1 and FIG. 2 show an example of the continuous electrolysis apparatus for metal samples according to the first invention. The metal sample decomposition apparatus of this embodiment is used when a metal sample is electrolyzed to prepare a sample solution.

The continuous electrolysis apparatus for a metal sample mainly comprises a cell body 1 and a counter electrode 10.

The cell body 1 is made of fluorinated ethylene resin, and has a counter electrode 10 as a graphite electrode in the center thereof.
Penetrates vertically. The metal sample 18 is connected to the sample support portion 16 of the cell body 1 via the annular gasket 15 made of fluororubber.
, An electrolytic chamber 17 is formed.

An electrolyte inlet 4 and an electrolyte outlet 5 are provided on the side of the cell body 1. Cell body 1 and counter electrode 1
Between 0, an inlet channel 12 and an outlet channel 13 are provided. The upper end of the inlet channel 12 is open to the electrolytic chamber 17, and the other end is connected to the electrolyte inlet 4. The upper end of the outlet channel 13 is open to the electrolytic chamber 17, and the other end is connected to the electrolyte outlet 5. The electrolytic solution outlet 5 is connected to an atomic absorption analyzer, a spectrophotometer, a plasma emission analyzer, and other analyzers.

FIG. 3 shows an example in which the metal sample continuous electrolysis apparatus configured as described above is connected to a plasma emission analyzer.

The electrolyte inlet 4 is connected to an electrolyte tank 21 via a constant flow pump 22. The electrolyte outlet 5 is connected to a plasma emission analyzer 36 via a filter 30, a gas-liquid separation tube 32, and an analyzer sample introduction tube 34. A waste liquid container 38 is provided in the gas-liquid separation tube 32.
Is connected.

Here, a method of preparing a sample solution and analyzing the sample solution using the plasma emission analyzer configured as described above will be described.

The molten steel collected in the steel making process is cast into a short columnar shape (diameter 30 mm, height 10 to 50 mm), and one surface is polished to obtain a steel sample 18. The steel sample 18 is placed on the sample support 1 with the polished surface down via the annular gasket 15 of the cell body 1.
6 and the electrode connector 25 on the steel sample 18 and the counter electrode 10.
And 26 are brought into contact. The steel sample 18 and the counter electrode 10 are connected to a constant potential / constant current electrolytic device 28 via electrode connectors 25 and 26. Next, an electrolytic solution (HCl) is supplied from the electrolytic solution tank 21 to the electrolytic solution inlet 4 of the cell body 1 at a constant flow rate (5 ml / min) by the constant flow rate pump 22. The electrolytic solution flows in the electrolytic chamber 17 so as to be sprayed on the steel sample surface while maintaining contact with the counter electrode 10 in the inlet flow path 12, and is discharged from the electrolytic solution outlet 5 through the outlet flow path 12. You. Here, while supplying the electrolytic solution, while controlling the voltage applied to the steel sample 18 and the counter electrode 10 from the constant potential / constant current electrolytic device 28, a constant current (1.5
By flowing A), the steel sample 18 is continuously electrolyzed, and a sample solution containing the chemical components in the steel is quickly obtained.
The flow rate of the electrolyte, the composition of the electrolyte, the electrolytic voltage and the current can be appropriately selected according to the sample, the analyzer, and the purpose of analysis.

The sample solution obtained from the electrolyte outlet 5 is
It is filtered by the filter 30 and flows into the gas-liquid separation tube 32. The sample solution that constantly replaces the inside of the gas-liquid separation tube 32 is continuously supplied to the plasma emission analyzer 36 via the analyzer introduction tube 34, and each component element is analyzed.

It takes about 2 minutes from the start of electrolysis until the analysis result is obtained. Electrolysis was not disabled due to gas bubbles generated in the electrolysis chamber.

In the above embodiment, the metal sample 18
A sample pressing device for pressing the sample against the annular gasket 15 of the cell body 1 may be provided. Further, in order to increase the electrolysis speed, a heating device such as a heating lamp for heating the metal sample 18 may be provided. As an analyzer, an atomic absorption analyzer or another analyzer can be applied instead of the plasma emission analyzer.

FIG. 4 shows an example of a continuous metal sample electrolysis apparatus according to the second invention. The metal sample decomposition apparatus of this embodiment electrolyzes a steel sample to prepare a sample solution.

The continuous metal sample electrolysis apparatus mainly comprises a cell body 1, a counter electrode 10, and a sample pressing device 41.

The cell body 1 is made of fluorinated ethylene resin, and has a counter electrode 10 which is a graphite electrode in the center thereof.
Penetrates horizontally. The electrolysis chamber 17 is formed by disposing the metal sample 18 on the sample support 16 via the annular gasket 15 of the cell body 1.

An electrolytic solution inlet 4 is provided on the lower surface of the cell body 1, and the electrolytic solution inlet 4 communicates with the bottom of the electrolytic chamber 17 via an inlet channel 12. The cell body 1
An electrolyte outlet 5 is provided on the upper surface of the electrolyte chamber, and the electrolyte outlet 5 communicates with the top of the electrolytic chamber 17 through the outlet channel 13.

The sample pressing device 41 comprises a sample holder 42 and a pneumatic cylinder 43. When performing the electrolysis, the pneumatic cylinder 43 is driven, and the metal sample 18 is moved through the sample holder 42 to the annular gasket 15 of the cell body 1.
And the electrolytic chamber 17 is sealed.

The structure and method for preparing a sample solution using the metal sample continuous electrolysis apparatus having the above-described structure are the same as those of the metal sample continuous electrolysis apparatus according to the first invention described with reference to FIG. It is almost the same as the case.

[0038]

According to the present invention, the electrolysis of a metal sample can be carried out quickly, and the analysis time of the metal sample can be greatly reduced. In addition, since electrolysis is not disabled due to gas bubbles generated in the electrolysis chamber, stable electrolysis and analysis can be performed, and strict electrolysis conditions can be applied.

[Brief description of the drawings]

FIG. 1 is a longitudinal sectional view of one embodiment of a continuous metal sample electrolysis apparatus according to the first invention.

FIG. 2 is a plan view of one embodiment of the continuous metal sample electrolysis apparatus according to the first invention.

FIG. 3 is a device configuration diagram showing an example of a metal sample analyzer into which the metal sample continuous electrolysis device shown in FIG. 1 is incorporated.

FIG. 4 is a longitudinal sectional view of one embodiment of a continuous metal sample electrolysis apparatus according to the second invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Cell main body 4 Electrolyte inflow port 5 Electrolyte discharge port 10 Counter electrode 12 Inlet side channel 13 Outlet side channel 15 Annular gasket 16 Sample support part 17 Electrolysis chamber 18 Sample 21 Electrolyte tank 22 Constant flow pump 25 Electrode connector 26 Electrode connector 28 Constant potential / constant current electrolysis device 30 Filter 32 Gas-liquid separation tube 34 Analyzer sample introduction tube 36 Plasma emission analyzer 41 Sample pressing device 42 Sample holder 43 Pneumatic cylinder

──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Ken Uemura 1 Fujimachi, Hirohata-ku, Himeji-shi, Hyogo Nippon Steel Corporation Hirohata Works (72) Inventor Masahiro Midorikawa 3-15 Izumicho, Sakado-shi, Saitama -10 (56) References JP-A-63-151813 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) G01N 33/20 G01N 1/28 G01N 27/26

Claims (2)

(57) [Claims] 1. A cell body provided with an electrolyte inlet and an electrolyte outlet, a column-shaped counter electrode penetrating the cell body, and a block-shaped metal sample supported on a sample support portion of the cell body and a top of the counter electrode. An electrolysis chamber is formed between the metal sample and the counter electrode, and while supplying the electrolysis solution from the electrolysis solution inlet to the electrolysis chamber, a voltage is applied between the metal sample and the counter electrode to electrolyze the metal sample. In a metal sample continuous electrolysis apparatus that obtains a sample solution from an outlet, a counter electrode vertically penetrates the cell body, and an inlet channel communicating with the electrolyte inlet is formed between the cell body and the counter electrode peripheral surface. And a metal sample continuous electrolysis apparatus characterized by being open to an electrolysis chamber. 2. A cell body provided with an electrolyte inlet and an electrolyte outlet, a column-shaped counter electrode penetrating the cell body, and a block-shaped metal sample supported by a sample support of the cell body and a tip of the counter electrode. An electrolysis chamber is formed between the metal sample and the counter electrode, and while supplying the electrolysis solution from the electrolysis solution inlet to the electrolysis chamber, a voltage is applied between the metal sample and the counter electrode to electrolyze the metal sample. In the metal sample continuous electrolysis apparatus for obtaining a sample solution from the outlet, the counter electrode extends horizontally through the cell body, the sample support surface of the sample support unit is vertical, and connects the electrolyte inlet and the electrolytic chamber. An inlet channel is connected to the bottom of the electrolytic chamber, an outlet channel connecting the electrolytic chamber and the electrolyte outlet is connected to the top of the electrolytic chamber, and a sample pressing device for pressing a metal sample against the sample support is provided. A continuous electrolysis device for metal samples, comprising: