JP5210854B2 - Mercury analyzer and mercury analysis method - Google Patents

Description

  The present invention relates to a mercury analyzer by a reduction vaporization method and a mercury analysis method.

  Conventionally, mercury analysis by reductive vaporization has been widely used in environmental analysis and quality control analysis for many years. In the analysis of river water and the like, an atomic absorption mercury analyzer using the reductive vaporization method shown in FIG. 10 of Patent Document 1 is used, and air is applied to a solution sample placed in a reduction container together with a reagent such as a reducing agent. The sample solution is bubbled by the bubbler by the air sent from the pump, and the mercury oxide present in the sample is reduced by the reducing agent to become vaporized mercury, which is introduced into the absorption cell and measured. Between the air pump and the reduction vessel shown in FIG. 10, there is a mercury removal unit, which removes mercury from the air sent from the air pump by a mercury removal agent filled inside, and is clean without mercury. Air is supplied.

  There is an apparatus as shown in FIG. 5 as an atomic fluorescence type mercury analyzer different from the atomic absorption type by the reductive vaporization method. The mercury analyzer 100 includes a reduction vessel 21 for reducing and vaporizing mercury in the solution sample S, a bubbler 3 for bubbling the solution sample S in the reduction vessel 21, and mercury removed from the bubbler 3 by a mercury removal filter 43. Carrier gas control means 4 for flowing clean carrier gas G, mercury collecting tube 6 for collecting mercury in solution sample S reduced and vaporized in reducing vessel 21, and mercury collecting tube for collecting mercury 6 controls the vaporizing device 7 for vaporizing mercury by heating 6, the mercury measuring device 5 for measuring the mercury vaporized by the heating vaporizing device 7, the carrier gas control means 4, the heating vaporizing device 7 and the mercury measuring device 5. And a control device 102.

After the stannous chloride solution 25 and the sulfuric acid 26 are added to the solution sample S in the reduction vessel 21 by the pumps P1 and P2, respectively, the argon gas G, which is the carrier gas G supplied from the argon cylinder 41, is added by the mass flow controller 4. The flow rate is controlled, and the solution sample S is bubbled with clean argon gas G (long broken line) from which mercury is removed by the mercury removal filter 43, and the mercury in the solution sample S is reduced and vaporized. The vaporized mercury is collected by a collecting agent in the mercury collecting tube 6 through a mist catcher 8 that captures mist such as sulfuric acid. The mercury analyzer 100 equipped with the atomic fluorescence mercury measuring instrument 5 has a markedly reduced sensitivity when measured with a carrier gas G containing oxygen and moisture in the air. The mercury collecting pipe 6 other than the reduction vessel 21 with the clean argon gas G from which mercury has been removed, the flow cell (not shown) in the mercury measuring instrument 5, and the flow path connected to them are shown by short broken lines. Then, the mercury collection tube 6 is heated by the heating vaporizer 7 to vaporize the mercury in the mercury amalgam state in the mercury collection tube 6 and sent to the mercury measuring device 5 for measurement.
JP2008-102068

In the atomic absorption method and atomic fluorescence method mercury analyzers described above, when the solution sample is reduced and vaporized in the reduction vessel, the cap of the reduction vessel is sealed with a cap, and the solution sample is stirred with the carrier gas bubbles coming out of the bubbler. The mercury in the sample is sent to the flow cell or collection tube by the carrier gas. However, the atomic absorption mercury analyzer does not purge the flow path of the absorption cell or the reduction vessel with clean air, and the atomic fluorescence mercury analyzer does not purge the purge line indicated by the short broken line. At the time of purging, the inside of the reduction container is not purged. Therefore, the air in the measurement environment remains as it is in the reduction container, and the mercury in the air in the reduction container is also measured together. For example, if the mercury concentration in the air in a measurement environment such as a measurement chamber that is an atmospheric atmosphere is about 20 ng / m ³ , and the amount of air in the reduction vessel is 20 mL, the mercury amount is 0.4 pg, which is in the order of pg. It was a value that could not be ignored when measuring, and the accuracy of trace analysis of mercury was reduced. In particular, the atomic fluorescence mercury analyzer is highly sensitive, so the influence is great. In addition, an atomic absorption mercury analyzer is problematic, although it has little effect.

  The present invention has been made in view of the above-described conventional problems, and improves the accuracy of mercury analysis by discharging air in a measurement environment remaining in a reduction container before reducing and vaporizing mercury in a solution sample. With the goal.

  In order to achieve the above object, a mercury analyzer according to the first configuration of the present invention includes a reduction container for reducing and vaporizing mercury in a solution sample, and a cap for holding a bubbler for bubbling the solution sample in the reduction container. A cap driving means for driving the cap up and down, a mercury measuring device for measuring mercury in the solution sample reduced and vaporized in the reducing vessel, and a supply amount of carrier gas to be supplied to the bubbler and the mercury measuring device. The carrier gas control means for controlling, and the bubbler is disposed at a position close to the liquid surface of the solution sample in the reduction container by controlling the cap driving means before reducing and vaporizing the solution sample in the reduction container And after purging the inside of the reduction vessel by flowing a carrier gas from the carrier gas control means to the bubbler, the mercury meter measures the water in the solution sample. And a control device for quantifying.

  According to the mercury analyzer of the first configuration of the present invention, before the solution sample in the reduction vessel is reduced and vaporized, a bubbler is disposed on the liquid surface of the solution sample in the reduction vessel, and the bubbler is a clean carrier. The accuracy of mercury analysis can be improved by flowing gas to purge the inside of the reduction container and exhausting the air in the measurement environment remaining in the reduction container.

  A mercury analyzer according to a second configuration of the present invention includes a reduction container for reducing and vaporizing mercury in a solution sample, a cap for holding a bubbler for bubbling the solution sample in the reduction container, and driving the cap up and down. Cap driving means, a mercury collecting tube for collecting mercury in the solution sample reduced and vaporized in the reducing vessel, and heating vaporization for heating the mercury collecting tube for collecting mercury to vaporize mercury An apparatus, a mercury measuring device for measuring mercury vaporized and heated by the heating and vaporizing device, a carrier gas control means for controlling a supply amount of a carrier gas flowing to the bubbler and the mercury measuring device, and a solution in the reducing vessel Before reducing and vaporizing the sample, the cap driving means is controlled so that the bubbler is disposed at a position close to the liquid surface of the solution sample in the reduction vessel, and the carrier is moved to the carrier. After purging the reduction vessel by flowing a carrier gas from the gas control means, and a control device for quantifying the mercury in the solution sample by the mercury measuring instrument.

  The mercury analyzer according to the second configuration of the present invention is obtained by adding a mercury collecting tube and a heating vaporizer to the mercury analyzer according to the first configuration, and is similar to the mercury analyzer according to the first configuration. There is an effect.

  In the mercury analyzer according to the second configuration of the present invention, the mercury analyzer includes a gas switching valve that switches between a reduction flow path for flowing the carrier gas from the carrier gas control means to the bubbler and a bypass flow path for bypassing the bubbler, The reduction channel has a mist catcher that collects the moisture of the carrier gas on the downstream side of the bubbler, and the bypass channel has the mercury collecting tube on the downstream side of the gas switching valve. It is preferable that the reduction channel and the bypass channel are connected on the upstream side of the mercury collecting pipe, which is the downstream side of the catcher. With this configuration, since the carrier gas does not pass through the mist catcher during the purge of the bypass flow path, moisture in the mist catcher is not mixed into the carrier gas such as argon gas or air, and more accurate mercury analysis can be performed. it can.

  In the mercury analyzer of the present invention, the mercury measuring device is preferably an atomic fluorescence method. With this configuration, mercury analysis can be performed with higher sensitivity than an atomic absorption mercury analyzer.

  According to the first mercury analysis method of the present invention, a reduction vessel for reducing and vaporizing mercury in a solution sample, a cap for holding a bubbler for bubbling the solution sample in the reduction vessel, and reduction vaporization in the reduction vessel A mercury measuring device for measuring mercury in a solution sample, and a carrier gas control means for controlling a supply amount of a carrier gas flowing through the bubbler and the mercury measuring device are prepared, and the solution sample in the reducing vessel is reduced and vaporized. Before, the bubbler is disposed at a position close to the liquid surface of the solution sample in the reduction container, and the inside of the reduction container is purged by flowing a carrier gas from the carrier gas control means to the bubbler. Quantify the mercury in the sample.

  According to the first mercury analysis method of the present invention, the same effects as those of the mercury analyzer according to the first configuration are achieved.

  According to the second mercury analysis method of the present invention, a reduction vessel for reducing and vaporizing mercury in a solution sample, a cap for holding a bubbler for bubbling the solution sample in the reduction vessel, and reduction vaporization in the reduction vessel A mercury collecting tube for collecting mercury in a solution sample, a heating vaporizer for heating the mercury collecting tube in which mercury is collected to vaporize mercury, and mercury vaporized by heating with the heating vaporizer Preparing a mercury measuring device and a carrier gas control means for controlling a supply amount of a carrier gas flowing through the bubbler and the mercury measuring device, and reducing the solution sample in the reducing vessel before reducing and vaporizing The bubbler is disposed at a position close to the liquid surface of the solution sample in the container, and after purging the inside of the reduction container by flowing a carrier gas from the carrier gas control means to the bubbler, To quantify the mercury.

  According to the second mercury analysis method of the present invention, the same effect as that of the mercury analyzer according to the second configuration can be obtained.

  In the method of the present invention, the mercury measuring device is preferably an atomic fluorescence method. With this configuration, mercury analysis can be performed with higher sensitivity than using an atomic absorption mercury measuring instrument.

  Hereinafter, a mercury analyzer according to the first embodiment of the present invention will be described. The mercury analyzer 1 quantifies the mercury content in the solution sample S. As shown in FIG. 1, the mercury analyzer 1 includes a reduction container 21 for reducing and vaporizing mercury in a solution sample S, a cap 22 for holding a bubbler 3 for bubbling the solution sample S in the reduction container 21, and a cap 22. The cap driving means 23 for driving the plate up and down, the reagent injection unit 20 for injecting a reagent for reducing mercury in the solution sample S into the reduction container 21, and the clean carrier from which mercury is removed by the mercury removal filter 43 in the bubbler 3 Carrier gas control means 4 for controlling the amount of supply of argon gas G as gas G, a reduction flow path 82 through which the carrier gas G from the carrier gas control means 4 flows to the bubbler 3, and a bypass flow path 83 for bypassing the bubbler 3. A gas switching valve V for switching to and an atomic fluorescence mercury measuring instrument 5 for measuring mercury in the solution sample S reduced and vaporized in the reduction vessel 21; Before reducing and vaporizing the solution sample S in the reduction vessel 21, the cap driving means 23 is controlled to place the bubbler 3 at a position close to the liquid surface of the solution sample S in the reduction vessel 21, and the bubbler 3 has a carrier. A control device 2 is provided that allows the mercury in the solution sample S to be quantified by the mercury measuring device 5 after flowing the carrier gas G from the gas control means 4 to purge the inside of the reduction vessel 21. Mercury measured by the mercury measuring instrument 5 is adsorbed and removed by a filter means 9 such as an activated carbon filter provided on the downstream side of the mercury measuring instrument 5.

  The reduction container 21 has, for example, a 18 mL (milliliter) capacity test tube shape, and the cap 22 holds a bubbler 3 for bubbling the solution sample S in the reduction container 21 and an injection tube for injecting the reagent. The upper part of 21 is sealed from above. A plurality of reduction containers 21 are placed on a sample stage (not shown), and the solution samples S in the plurality of reduction containers 21 are sequentially measured and before the solution samples S are reduced and vaporized. In order to purge with clean argon gas G, the cap driving means 23 is controlled by the control device 2 and the cap 22 is driven and controlled in the vertical direction.

  The carrier gas control means 4 includes, for example, a mass flow controller 4 that controls the supply amount of the argon gas G supplied from an argon cylinder 41 that is a supply source of the argon gas G. The reagent injection unit 20 includes pumps P1 and P2 that send the reagents, that is, the stannous chloride solution 25 and the sulfuric acid 26, which are reducing agents, into the reduction vessel 21 through the injection tube. The carrier gas control means 4 and the pumps P1 and P2 are controlled by the control device 2.

  The reduction channel 82 passes through the gas switching valve V, the mercury removal filter 43, the bubbler 3, the reduction vessel 21, the mist catcher 8 that collects the moisture of the carrier gas G, and the mercury measuring device 5 in order from the upstream side. 5 is connected to the reduction flow path 82 on the downstream side of the mist catcher 8. The bypass flow path 83 that bypasses the bubbler 3 passes through the gas switching valve V, the mercury removal filter 45, and the mercury measuring device 5 in order from the upstream side, and is reduced upstream of the mercury measuring device 5 and downstream of the mercury removing filter 45. The flow path 82 is connected. The opening and closing of the gas switching valve V is controlled by the control device 2. For the mercury removal filters 43 and 45, as a filler for collecting mercury, for example, a granular material such as gold or silver which reacts with metallic mercury to produce amalgam or a woolen fine wire, or gold on the surface of the porous carrier. A material coated with silver or the like is used.

  Next, operation | movement of the mercury analyzer 1 of this embodiment is demonstrated. In the atomic fluorescence mercury measuring instrument 5, when the measurement is performed in a state where air, moisture or the like is mixed in the flow path, the sensitivity is remarkably lowered, and therefore a clean argon gas G is used. Therefore, the reduction flow path 82 is closed and the bypass flow path 83 is opened by the gas switching valve V controlled by the control device 2 before the measurement is started, for example, the flow rate is 0.2 L / min. A flow path such as a flow cell (not shown) in the mercury measuring instrument 5 is purged with, for example, 10 liters of clean argon gas G for 10 seconds.

  Next, as shown in FIG. 2, the cap 22 is lifted upward by the cap driving means 23 controlled by the control device 2, and the tip of the bubbler 3 is on the liquid surface of the 5 mL solution sample S in the reduction container 21, for example, In the state where the bypass flow path 83 is closed by the gas switching valve V and the reduction flow path 82 is opened, for example, the flow rate is 0.2 L / min. Then, the clean argon gas G controlled by the mass flow controller 4 is flowed to purge the inside of the reduction vessel 21 for 10 seconds, for example, and then the purge is finished.

  Next, as shown in FIG. 1, the cap 22 is lowered downward by the cap driving means 23, and the upper portion of the reduction container 21 is sealed from above by the cap 22 while the tip of the bubbler 3 enters the solution sample S. . In this state, 0.5 mL of the stannous chloride solution 25 and 0.3 mL of the sulfuric acid solution 26 are respectively injected into the solution sample S in the reduction vessel 21 by the pump P1 and the pump P2 controlled by the controller 2. The flow rate from the means 4 is 0.2 L / min. Of argon gas G is caused to flow through the bubbler 3, and the solution sample S is bubbled by the bubbler 3. By this bubbling, the mercury in the solution sample S is vaporized by a reduction reaction with the stannous chloride solution 25 into which the mercury has been injected, and the vaporized mercury passes through a reduction channel 82 having a mist catcher 8 that captures mist such as sulfuric acid. The mercury is sent to the mercury measuring instrument 5 and measured by the mercury measuring instrument 5 to quantify the mercury in the solution sample S. The above series of operations is automatically controlled by the control device 2.

  Thus, according to the mercury analyzer 1 of the present invention, before the solution sample S in the reduction container 2 is reduced and vaporized, the bubbler 3 is disposed on the liquid surface of the solution sample S in the reduction container 21, A clean carrier gas G is allowed to flow through the bubbler 3 to purge the inside of the reduction container 21, and the air in the measurement environment remaining in the reduction container 21 can be discharged and measured.

  The mercury analysis method for purging the inside of the reducing vessel 21 before reducing and vaporizing the solution sample S in the reducing vessel 21 may be performed automatically as described above or manually.

  A mercury analyzer according to a second embodiment of the present invention will be described. As shown in FIG. 3, the reduction container 21, the cap 22, the bubbler 3, the cap driving means 23, the mercury removal filter 43, the carrier gas control means 4, the reagent injection unit 20, the mercury measuring instrument 5, and the filter of the mercury analyzer 10. The means 9 has the same configuration as that of the first embodiment, and the gas switching is performed so that the carrier gas G from the carrier gas control means 4 is switched to the reduction flow path 84 through which the bubbler 3 flows and the bypass flow path 85 that bypasses the bubbler 3. Heating for heating the valve V, the mercury collecting tube 6 for collecting mercury in the solution sample S reduced and vaporized in the reducing vessel 21, and the mercury collecting tube 6 for collecting mercury to vaporize mercury. Before the reductive vaporization of the solution sample S in the reduction vessel 21, the cap driving means 2, the vaporizer 7, the atomic fluorescence type mercury measuring device 5 for measuring the mercury vaporized by the heating vaporizer 7. The bubbler 3 is arranged at a position close to the liquid surface of the solution sample S in the reduction container 21 and the inside of the reduction container 21 is purged by flowing the carrier gas G from the carrier gas control means 4 to the bubbler 3. And a control device 12 for quantifying mercury in the solution sample S by the mercury measuring device 5.

  The reduction flow path 84 passes through the gas switching valve V, the mercury removal filter 43, the bubbler 3, the reduction vessel 21, the mist catcher 8, the mercury collection pipe 6, and the mercury measuring instrument 5 in order from the upstream side, On the upstream side, it is connected to the bypass flow path 85 on the downstream side of the mist catcher 8. The bypass flow path 85 passes through the gas switching valve V, the mercury removal filter 45, the mercury collection pipe 6, and the mercury measuring device 5 in order from the upstream side, and is upstream of the mercury collection pipe 6 and downstream of the mercury removal filter 45. And connected to the reduction flow path 84.

  As a filler for collecting mercury, the mercury collecting tube 6 is a porous material whose surface is coated with a granular material such as gold or silver, wool-like fine wire, gold or silver, etc., which reacts with metallic mercury to produce amalgam. A carrier or sea sand is used. The heating vaporizer 7 accommodates a mercury collection tube 6 that collects mercury in a heating furnace, and heats the mercury collection tube 6 to vaporize the collected mercury.

  The mercury analyzer 10 according to the second embodiment operates in the same manner as in the first embodiment, but is measured after the mercury in the reduced vaporized sample solution S is collected in the mercury collecting tube 6. The point is different. Since the mercury measuring instrument 5 is of the atomic fluorescence method as in the first embodiment, the reduction flow path 84 is closed by the gas switching valve V before the measurement is started, the bypass flow path 85 is opened, and the mercury collecting pipe 6, A flow path such as a flow cell (not shown) in the mercury measuring instrument 5 is purged by the argon gas G.

  Next, similarly to the operation shown in FIG. 2 of the first embodiment, the cap driving means 23 is controlled by the control device 12 to lift the cap 22 upward, and the tip of the bubbler 3 is on the liquid surface of the solution sample S. For example, clean argon gas G is flowed and reduced in a state where the bypass flow path 85 is closed by the gas switching valve V held by 2 to 3 mm and controlled by the control device 12 and the reduction flow path 84 is opened. The inside of the container 21 is purged.

  Next, as shown in FIG. 3, the cap 22 is lowered downward by the cap driving means 23, and the upper portion of the reduction container 21 is sealed from above by the cap 22 while the tip of the bubbler 3 enters the solution sample S. . In the same manner as in the first embodiment, mercury in the solution sample S is reduced and vaporized, and the mercury vaporized by bubbling passes through the mist catcher 8 and enters the mercury collecting tube 6 to collect mercury. At this time, the mercury collecting tube 6 is heated to 150 to 200 ° by the heating and vaporizing device 7 controlled by the control device 12 so as not to collect any gas other than the reduced vaporized mercury.

  Next, the reduction flow path 84 is closed by the gas switching valve V, the bypass flow path 85 is opened, and the flow rate is, for example, 0.2 L / min. A flow path such as a flow cell (not shown) in the mercury measuring device 5 is purged by the clean argon gas G for 10 seconds, for example.

  Next, in a state where the gas switching valve V opens the bypass flow path 85 and closes the reduction flow path 84, the mercury collecting pipe 6 in the heating furnace of the heating vaporizer 7 is heated to 600 to 800 ° C. The heated and vaporized mercury is converted into argon gas G by the carrier gas control means 4 controlled by the control device 12, for example, at a flow rate of 0.07 L / min. The mercury in the solution sample S is quantified by introducing the mercury into the mercury measuring device 5 by adjusting the flow rate so that The above series of operations is automatically controlled by the control device 12.

  Thus, according to the mercury analyzer 10, the same effect as the mercury analyzer 1 of the first embodiment can be obtained.

  Prior to reducing and vaporizing the solution sample S in the reducing vessel 21, after purging the reducing vessel 21, the mercury that has been reduced and vaporized is collected in a mercury collecting tube and heated and vaporized. It may be done automatically or manually.

An experiment was conducted on the relationship between the time for purging the inside of the reduction vessel 21 with the argon gas G and the amount of mercury remaining in the reduction vessel 21 using the mercury analyzer of the second embodiment. In this experiment, only the air in the measurement environment is put in the reduction vessel 21, and the inside of the reduction vessel 21 is purged by flowing a clean argon gas G from which mercury is removed for a predetermined time, and then mercury is collected. Mercury in the air remaining in the reduction vessel 21 was collected in the tube 6 and quantified by heating and vaporizing with the heating vaporizer 7. The purge times are 0, 2, 4, 6, 8, 10, and 12 seconds, respectively. A plot of the purge time on the horizontal axis and the quantitative value of mercury corresponding to each purge time on the vertical axis is shown in FIG. Shown in

  From this result, the flow rate of the purge gas argon gas G is 0.2 L / min. It can be seen that the 18 mL capacity reducing vessel 21 is sufficiently replaced with argon gas G in 10 seconds. In the 18 mL capacity reducing container 21, about 0.4 pg which is the amount of mercury in the air under the environmental measurement when the purge gas is not flowed by the purge for 10 seconds is discharged from the reducing container 21. When analyzing a very small amount of mercury, it is possible to eliminate measurement variations due to variations in the mercury concentration in the air in the measurement environment by inserting a clean argon gas replacement step. Moreover, the blank value of the measurement can be lowered.

Using the mercury analyzer 10 of the second embodiment and the conventional mercury analyzer 100 shown in FIG. 5, the time for purging the bypass passage 85 and the bypass passage 88 with the argon gas G and the mercury measuring device 5 at the time of measurement. Experiments were conducted on the relationship with signal strength. The reduction flow path 87 of the conventional mercury analyzer 100 includes a gas switching valve V, a mercury removal filter 43, a bubbler 3, a reduction vessel 21, a mist catcher 8, a mercury collecting pipe 6, and a mercury measuring device 5 in order from the upstream side. As shown in FIG. 2, the gas flow control valve V, the mercury removal filter 45, the mist catcher 8, the mercury catcher 8 are sequentially connected from the upstream side to the bypass flow path 88 on the downstream side of the bubbler 3 and on the upstream side of the mist catcher 8. It passes through the collecting pipe 6 and the mercury measuring device 5, and is connected to the reduction channel 87 upstream of the mist catcher 8 and downstream of the mercury removal filter 45. As described above, in the mercury analyzer 10 (FIG. 3), the carrier gas G does not pass through the mist catcher 8 when the carrier gas G flows in the bypass flow path 85, but in the mercury analysis apparatus 100 (FIG. 5), the carrier gas flows in the bypass flow path 88. When G flows, it passes through the mist catcher 8.

  In this experiment, the same amount of mercury is collected in the respective mercury collecting tubes 6 of the mercury analyzers 10 and 100 and heated by the heating vaporizer 7, and the flow rates of the bypass passage 85 and the bypass passage 88 are increased. 0.2 L / min. The signal intensity of each mercury measuring device 5 was measured while purging with argon gas G. A plot diagram in which the signal intensity of the mercury analyzer 10 of the present invention is represented by a square mark and the signal intensity of the conventional mercury analyzer 100 is represented by a rhombus mark, with the purge time as the horizontal axis and the signal intensity as the vertical axis. It is shown in FIG.

  From this result, the signal intensity of the mercury analyzer 10 of the present invention is stable with almost no change, but the intensity of the conventional mercury analyzer 100 is low immediately after measurement, and the intensity is stable after 10 seconds or more. It has become. In the conventional apparatus, the carrier gas G flows through the bypass flow path 88 during measurement and passes through the mist catcher 8, so that moisture collected by the mist catcher 8 is carried by the carrier gas G and adheres to the flow path piping. The measurement sensitivity decreases due to the moisture. On the other hand, in the mercury analyzer of the present invention, the carrier gas G is connected to the mercury collecting pipe 6 without passing through the mist catcher 8 at the time of measurement. Can stabilize the signal intensity. This means that the purge time by the carrier gas G before the start of measurement and after being collected in the mercury collection tube 6 can be shortened, whereby the total analysis time can be shortened and mercury analysis can be performed efficiently.

  In the first and second embodiments, the atomic fluorescence type mercury measuring device 5 has been described. However, in the present invention, the atomic absorption type mercury measuring device 5 may be used. In the case of a mercury analyzer equipped with an atomic absorption mercury measuring instrument, the amount of mercury in the air under environmental measurement is reduced by purging the inside of the reduction vessel 21 with clean air from which mercury has been removed. It is discharged from the inside.

It is the schematic of the mercury analyzer of 1st Embodiment of this invention. It is the schematic at the time of the purge of the mercury analyzer. It is the schematic of the mercury analyzer of 2nd Embodiment of this invention. It is a plot figure which shows the relationship between purge time and the amount of mercury which remains in a reduction | restoration container. It is the schematic of the conventional mercury analyzer. It is a plot figure which shows the relationship between purge time and signal strength.

Explanation of symbols

1 10 100 Mercury analyzer 2 12 102 Control device 3 Bubbler 4 Carrier gas control means 5 Mercury meter 6 Mercury collection tube 7 Heating vaporizer 8 Mist catcher 21 Reduction container 22 Cap 23 Cap drive means 82 84 87 Reduction flow path 83 85 88 Bypass channel G Carrier gas S Sample V Gas switching valve

Claims (7)

A reduction vessel for reducing and vaporizing mercury in the solution sample;
A cap for holding a bubbler for bubbling the solution sample in the reducing vessel;
Cap driving means for driving the cap up and down;
A mercury measuring device for measuring mercury in the solution sample reduced and vaporized in the reducing vessel;
A carrier gas control means for controlling a supply amount of a carrier gas flowing to the bubbler and the mercury measuring device;
Before reducing and vaporizing the solution sample in the reduction container, the cap driving means is controlled to place the bubbler at a position close to the liquid surface of the solution sample in the reduction container, and the carrier gas is placed in the bubbler. A mercury analyzer comprising: a control device for quantifying mercury in a solution sample by the mercury measuring device after flowing the carrier gas from the control means and purging the inside of the reduction container. A reduction vessel for reducing and vaporizing mercury in the solution sample;
A cap for holding a bubbler for bubbling the solution sample in the reducing vessel;
Cap driving means for driving the cap up and down;
A mercury collecting tube for collecting mercury in the solution sample reduced and vaporized in the reducing vessel;
A heating and vaporizing apparatus for vaporizing mercury by heating the mercury collecting tube in which mercury is collected;
A mercury measuring device for measuring mercury heated and vaporized by the heating vaporizer;
A carrier gas control means for controlling a supply amount of a carrier gas flowing to the bubbler and the mercury measuring device;
Before reducing and vaporizing the solution sample in the reduction container, the cap driving means is controlled to place the bubbler at a position close to the liquid surface of the solution sample in the reduction container, and the carrier gas is placed in the bubbler. A mercury analyzer comprising: a control device for quantifying mercury in a solution sample by the mercury measuring device after flowing the carrier gas from the control means and purging the inside of the reduction container. The gas switching valve according to claim 2, further comprising a switching channel for switching between a reduction channel for flowing the carrier gas from the carrier gas control means to the bubbler and a bypass channel for bypassing the bubbler,
The reduction flow path has a mist catcher that collects the moisture of the carrier gas on the downstream side of the bubbler,
The bypass flow path has the mercury collection pipe on the downstream side of the gas switching valve, and on the upstream side of the mercury collection pipe, which is the downstream side of the mist catcher, the reduction flow path and the bypass Mercury analyzer connected to the flow path. In any one of Claims 1-3,
A mercury analyzer in which the mercury measuring instrument is an atomic fluorescence method. A reduction vessel for reducing and vaporizing mercury in the solution sample;
A cap for holding a bubbler for bubbling the solution sample in the reducing vessel;
A mercury measuring device for measuring mercury in the solution sample reduced and vaporized in the reducing vessel;
A carrier gas control means for controlling a supply amount of a carrier gas flowing to the bubbler and the mercury measuring device;
Prepare
Before reducing and vaporizing the solution sample in the reduction vessel, the bubbler is disposed at a position close to the liquid surface of the solution sample in the reduction vessel, and carrier gas is caused to flow from the carrier gas control means to the bubbler. A mercury analysis method for quantitatively determining mercury in a solution sample after purging the inside of the reduction vessel. A reduction vessel for reducing and vaporizing mercury in the solution sample;
A cap for holding a bubbler for bubbling the solution sample in the reducing vessel;
A mercury collecting tube for collecting mercury in the solution sample reduced and vaporized in the reducing vessel;
A heating and vaporizing apparatus for vaporizing mercury by heating the mercury collecting tube in which mercury is collected;
A mercury measuring device for measuring mercury heated and vaporized by the heating vaporizer;
A carrier gas control means for controlling a supply amount of a carrier gas flowing to the bubbler and the mercury measuring device;
Prepare
Before reducing and vaporizing the solution sample in the reduction vessel, the bubbler is disposed at a position close to the liquid surface of the solution sample in the reduction vessel, and carrier gas is caused to flow from the carrier gas control means to the bubbler. A mercury analysis method for quantitatively determining mercury in a solution sample after purging the inside of the reduction vessel.   7. The mercury analysis method according to claim 5, wherein the mercury measuring instrument is an atomic fluorescence method.

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