JP2014232017A - Measurement apparatus for metal carbonyl in gas - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a metal carbonyl compound measurement apparatus capable of continuously monitoring a metal carbonyl compound.SOLUTION: The metal carbonyl compound measurement apparatus comprises: aspiration means 10 for aspirating an exhaust gas 11 which is a measured gas in a gas flue 12; a cooler 30 for cooling the aspirated exhaust gas 11 to a temperature equal to or lower than the temperature at which metal carbonyl is liquefied; a separator 32 for separating the liquefied metal carbonyl 31 from the exhaust gas 11, the separator 32 being provided in the cooler 30; a liquid cell 33 for collecting a specified quantity of the liquefied metal carbonyl 31 in the separator 32, the liquid cell 33 provided in the cooler 30; and infrared spectroscopic analysis means including an infrared-emitting part 34 and a light receiving part 35 which measure the metal carbonyl (liquid) 31 in the liquid cell 33.

Description

  The present invention relates to a measuring device for metal carbonyl contained in, for example, boiler fuel exhaust gas.

For example, combustor exhaust gas such as a boiler for power generation, coal gasification gas for coal gasification combined power generation (IGCC), and fuel gas for gas turbine combined cycle power generation (GTCC) such as blast furnace gas include metal carbonyl compounds. Since harmful substances such as (tetracarbonylnickel (Ni (CO) ₄ ) and pentacarbonyl iron (Fe (CO) ₅ ) are contained, measurement techniques thereof have been proposed (Patent Documents 1 and 2).

Japanese Patent Laid-Open No. 9-292337 JP 2001-305056 A

However, since the conventional method for measuring metal carbonyl is a batch process using an absorption bottle containing an absorption liquid that absorbs metal carbonyl, there are the following problems.
1) Of the metal carbonyl compounds, the main measurements are tetracarbonyl nickel Ni (CO) ₄ and pentacarbonyl iron Fe (CO) ₅ . Since only the sampling is performed at the site in the plant and the subsequent analysis in the analysis room is required, continuous monitoring at the site is not possible.
2) Besides the above-mentioned two kinds of metal carbonyls, there are, for example, Co ₂ (CO) ₈ , Mn ₂ (CO) ₁₀ , Cr (CO) ₆ , V (CO) ₆ and the like.

  Therefore, the appearance of a metal carbonyl compound measuring apparatus capable of continuously monitoring metal carbonyl compounds at the site in the plant is eagerly desired.

  In view of the above problems, an object of the present invention is to provide a metal carbonyl compound measuring apparatus capable of continuously monitoring a metal carbonyl compound.

  A first invention of the present invention for solving the above-described problems includes a suction means for sucking a gas to be measured in a gas flue, a cooler for cooling the sucked exhaust gas to a temperature below which the metal carbonyl is liquefied, A separator provided in the cooler for separating the liquefied metal carbonyl from the gas to be measured; a liquid cell provided in the cooler for collecting a predetermined amount of the liquid metal carbonyl in the separator; And an infrared spectroscopic analysis means for measuring metal carbonyl in the liquid cell.

  According to the first invention, the metal carbonyl compound can be liquefied and separated from the exhaust gas in a cooler, and the separated metal carbonyl can be measured in online and real-time by performing a liquid infrared absorption analysis. Therefore, continuous monitoring of metal carbonyl in the exhaust gas at the site is possible.

  According to a second aspect of the present invention, there is provided a suction means for sucking a gas to be measured in a gas flue, a cooler for cooling the sucked exhaust gas to a temperature lower than a temperature at which metal carbonyl is liquefied, and a liquefied metal provided in the cooler. A separator for separating carbonyl from the gas to be measured, a heater for heating the liquid metal carbonyl in the separator outside the cooler, a gas cell for collecting a predetermined amount of the heated gas component, And an infrared spectroscopic analyzing means for measuring metal carbonyl in the gas cell.

  According to the second invention, the metal carbonyl compound is liquefied and separated in the cooler from the exhaust gas, and the separated metal carbonyl is vaporized from the liquid state by the heater and analyzed in the gaseous infrared absorption, It is possible to measure on-line and in real time, and it is possible to continuously monitor metal carbonyl in the exhaust gas on site.

  According to the present invention, it is possible to measure a metal carbonyl compound on-line and in real time at the site of plant equipment, and continuous monitoring of metal carbonyl in exhaust gas at the site can be performed.

FIG. 1 is a schematic diagram of a metal carbonyl measuring apparatus according to the first embodiment. FIG. 2 is a schematic diagram of a metal carbonyl measuring apparatus according to the second embodiment.

  Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. In addition, this invention is not limited by this Example, Moreover, when there exists multiple Example, what comprises combining each Example is also included.

  FIG. 1 is a schematic diagram of a metal carbonyl measuring apparatus according to the first embodiment. As shown in FIG. 1, the metal carbonyl measuring device according to the present embodiment includes a gas suction means 10 for sucking an exhaust gas 11 that is a gas to be measured in a gas flue 12, and a metal carbonyl that absorbs the sucked exhaust gas 11. A cooler 30 that cools below the liquefying temperature; a separator 32 that is provided in the cooler 30 and separates the liquefied metal carbonyl 31 from the exhaust gas 11; and a cooler 30 that is provided in the cooler 30. A liquid cell 33 for collecting a predetermined amount of the liquid metal carbonyl 31, an infrared spectroscopic analysis means comprising an infrared light emitting part 34 and a light receiving part 35 for measuring the metal carbonyl (liquid) 31 in the liquid cell 33; Are provided.

The exhaust gas 11 is sucked by the suction pump P _{1, and the} gas suction amount is measured by the gas meter 37. The liquid cell 33 is connected to a suction pump P ₂ for sucking the metal carbonyl 31. A predetermined amount of the metal carbonyl (liquid) 31 is introduced into the liquid cell 33 to perform infrared emission analysis. Yes.

  Here, as the gas suction means 10, a gas sampling pipe 13 is provided in the flue 12 into which the exhaust gas 11 flows. This gas sampling tube 13 has a cylindrical filter paper 14 at the tip, and is made of a glass dust filter 15 surrounded by an aluminum protective outer cylinder, and is connected to the dust filter 15 and is made of glass with a glass tube positioned inside. The sampling tube body 16 is configured.

  In addition, one end side of the wake side of the gas sampling pipe 13 is connected to a drain bin 19 placed in the cooling tank 18 through a bellows-like pipe 17. In the cooling bath 18, the drain bin 19 is cooled to 0 ° C. by a throwing cooler. A calcium chloride tower 21 filled with calcium chloride 20 is connected to the drain bin 19. Both the drain bin 19 and the calcium chloride tower 21 are for removing water in the exhaust gas 11, and the water in the exhaust gas 11 is completely removed by passing through the calcium chloride tower 21.

  Next, a method for measuring nickel carbonyl using an apparatus having such a configuration will be described.

1. Preparation for collecting metal carbonyl As described above, the gas sampling tube 13 including the glass dust filter 15 having the cylindrical filter paper 14 at the tip and the glass sampling tube body 16 connected to the dust filter 15 is connected to the flue. 12 is arranged. Moreover, in order to remove the water | moisture content in the waste gas 11, while draining 19 is thrown in and it cools to 0 degreeC with a cooler, the calcium chloride tower 21 filled with the calcium chloride 20 is arrange | positioned, and this calcium chloride tower 21 is allowed to pass through. Water in the exhaust gas 11 is completely removed.

  Next, the cooler 30 in which the separator 32 is installed is disposed. This cooler is temperature-controlled at −20 ° C. or lower where the metal carbonyl is liquefied.

2. As a preparation before collection of metal carbonyl, the cooler 30 is cooled to −20 ° C. or lower (2 hours).
Next, the gas sampling tube 13 is carefully inserted into the flue 12 and fixed.
The bypass line (illustrated) that bypasses the cooler 30 is sufficiently evacuated, and the inside of the piping is replaced with the exhaust gas 11.

Thereafter, switching is performed so as to pass through the separator 32 in the cooler 30 from the bypass line. 50 L (liter) of exhaust gas 11 is sucked at a suction speed of 2 L / min. The suction is performed by the suction pump P ₁ and the amount of gas sucked by the gas meter 37 is obtained.

  In the gas passing through the cooler 30, the CO gas passes through without being liquefied. The metal carbonyl is liquefied and collected in liquid form in the separator 32. The collected metal carbonyl (liquid) 31 is used as a sample used for the subsequent analysis.

3. Measurement of Metal Carbonyl A predetermined amount of liquid metal carbonyl 31 as a sample is introduced into the liquid cell 33 by the suction pump P ₂ . Infrared light emitted from the light source of the infrared light emitting unit 34 is allowed to pass through the liquid cell 33, and the light passing through the liquid cell 33 is detected by the light receiving unit 35. By detecting and measuring the infrared absorption wavelength (λ: 4.7 μm) caused by carbonyl (CO), the total metal amount (μg) of the metal carbonyl is determined.

Since the gas suction amount (L) is known by the measurement of the gas meter 37, the metal carbonyl concentration (μg / m ³ ) can be converted.
In the infrared emission analysis, the total amount of both nickel carbonyl and iron carbonyl is obtained.

  Therefore, an infrared emission analysis chart corresponding to the composition ratio of nickel carbonyl and iron carbonyl is obtained in advance, and the composition ratio is determined by collating with the chart. From the determined composition ratio, the actual existence ratio is obtained by multiplying the conversion factors of both carbonyls.

  For example, when the ratio of both is 5: 5, when the total amount is Y μg, Y × 1.524 × 0.5 is the weight of nickel carbonyl, and Y × 1.399 × 0.5 is iron carbonyl. It becomes weight.

In addition to the above two types of metal carbonyl, there are Co ₂ (CO) ₈ , Mn ₂ (CO) ₁₀ , Cr (CO) ₆ and V (CO) ₆ , all of which decompose at 52 to 210 ° C. Therefore, the presence in the exhaust gas is extremely small, and the hazard is low. Therefore, it is important to confirm tetracarbonyl nickel Ni (CO) ₄ and pentacarbonyl iron Fe (CO) ₅ in the exhaust gas. It is important for the presence / absence judgment.

Therefore, according to the present embodiment, the measurement mainly focusing on tetracarbonyl nickel Ni (CO) ₄ and pentacarbonyl iron Fe (CO) ₅ among the metal carbonyl compounds is measured in real time online. However, it becomes possible at the site of plant equipment, and continuous monitoring of metal carbonyl in the exhaust gas at the site is possible.

  FIG. 2 is a schematic diagram of a metal carbonyl measuring apparatus according to the second embodiment. In addition, the same code | symbol is attached | subjected to the member which overlaps with the structure of the system which concerns on Example 1, and the description is abbreviate | omitted. As shown in FIG. 2, the metal carbonyl measuring apparatus according to the present embodiment includes a suction means 10 for sucking the exhaust gas 11 as the gas to be measured in the gas flue 12, and the metal carbonyl liquefies the sucked exhaust gas 11. A cooler 30 that cools below the temperature to be cooled, a separator 32 that is provided in the cooler 30 and separates the liquefied metal carbonyl 31 from the exhaust gas 11, and cools the liquid metal carbonyl 31 in the separator 32 A heater 41 that heats outside the vessel 30, a gas cell 43 that collects a predetermined amount of the gas component 42 of the heated metal carbonyl (gas body), and an infrared emission that measures the metal carbonyl in the gas cell 43. Infrared spectroscopic analysis means comprising a unit 34 and a light receiving unit 35.

  Since it is the same as Example 1 until metal carbonyl (liquid) 31 is collected, the subsequent measurement of metal carbonyl of Example 2 will be described.

  The liquid metal carbonyl 31 which is the collected sample in the separator 32 is introduced into the heater 41.

  The heater 41 is heated at a predetermined temperature (for example, 150 ° C.) in order to convert the liquid metal carbonyl 31 into a gaseous metal carbonyl.

A gas component 42 containing metal carbonyl (gaseous) vaporized by the heater 41 is introduced into the gas cell 43 by the suction pump P ₃ .

  Infrared light emitted from the light source of the infrared light emitting unit 34 is passed through the gas cell 43, and the light that has passed through the gas cell 43 is detected by the light receiving unit 35. By detecting and measuring the infrared absorption wavelength (λ: 4.7 μm) caused by carbonyl (CO), the total metal amount (μg) of the metal carbonyl is determined.

Since the gas suction amount (m ³ ) is known from the measurement by the gas meter 37, the metal carbonyl concentration (μg / m ³ ) can be converted.

10 suction means 11 exhaust gas 12 gas flue 30 cooler 31 metal carbonyl (liquid)
32 Separator 33 Liquid cell 34 Infrared light emitting part 35 Light receiving part 41 Heater 42 Gas component 43 Gas cell

Claims (2)

A suction means for sucking a gas to be measured in the gas flue;
A cooler that cools the sucked exhaust gas below the temperature at which the metal carbonyl liquefies,
A separator provided in the cooler for separating the liquefied metal carbonyl from the gas to be measured;
A liquid cell provided in the cooler and collecting a predetermined amount of liquid metal carbonyl in the separator;
Infrared spectroscopic analysis means for measuring metal carbonyl in the liquid cell, and a device for measuring metal carbonyl in gas. A suction means for sucking a gas to be measured in the gas flue;
A cooler that cools the sucked exhaust gas below the temperature at which the metal carbonyl liquefies,
A separator provided in the cooler for separating the liquefied metal carbonyl from the gas to be measured;
A heater for heating the liquid metal carbonyl in the separator outside the cooler;
A gas cell for collecting a predetermined amount of heated gas components;
Infrared spectroscopic analysis means for measuring metal carbonyl in the gas cell, and a device for measuring metal carbonyl in gas.

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