JPH1123545A - Removal/concentration method of carbon monoxide and analysis device of trace carbon monoxide - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a removal/concentration method of carbon monoxide capable of concentrating carbon monoxide in a reusable form in addition to perform removal and concentration at low cost, and provide an analysis device of trace carbon monoxide capable of measuring carbon monoxide of low concentration. SOLUTION: This method is to remove or concentrate carbon monoxide utilizing characteristic of hemoglobin selectively and chemically bonding with carbon monoxide, and in a view from the liquid side or the gas side containing carbon monoxide, carbon monoxide is removed, in a view from the hemoglobin side chemically bonded with carbon monoxide, carbon monoxide is concentrated. When carbon monoxide is contacted with hemoglobin (a), oxygen bonded with hemoglobin is substituted by carbon monoxide so as to chemically bond with hemoglobin (b), and hence removal and concentration of carbon monoxide is performed. By chemically reacting hemoglobin chemically bonded with the carbon monoxide, concentrated carbon monoxide can be taken out of the hemoglobin (c).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for removing carbon monoxide contained in gases and liquids, a method for increasing the concentration of carbon monoxide contained in gases and liquids, and a method for concentrating the same. The present invention relates to a trace carbon monoxide analyzer that concentrates and measures a trace amount of carbon monoxide by a concentration method.

[0002] The removal of carbon monoxide according to the present invention can be applied to the removal of carbon monoxide contained in exhaust gas generated by combustion. It can be applied to carbon recycling.

[0003] The concentration measurement of trace amounts of carbon monoxide is performed by measuring indoor environmental pollution due to exhaust gas generated by the combustion of city gas, propane gas, petroleum stoves, etc., air pollution surveys, and metallurgical products such as steel plants and chemical plants. It can be applied to the analysis of carbon monoxide generated by smelting and chemical reactions.

[0004]

2. Description of the Related Art Conventionally, carbon monoxide is removed by exhausting gas containing carbon monoxide by converting it to ozone or carbon dioxide by combustion or catalysis, or by concentration by adsorption or lowering the temperature. I have.

[0005] As a method of analyzing carbon monoxide, JI
As shown in SK0098, a gas chromatographic method, a gas detection method using a detection tube type gas measuring instrument, a pen pal analysis method using a pen pal analysis apparatus, an infrared absorption method using an infrared gas analyzer, and a potentiostatic electrolysis analyzer were used. The potentiostatic electrolysis method used is known.

[0006]

Conventionally, the methods for removing and concentrating carbon monoxide have a problem that the cost is high, and the carbon monoxide that has been removed and concentrated is obtained in the form of ozone or carbon dioxide. Another problem is that it is difficult to reuse carbon monoxide.

[0007] The toxicity of carbon monoxide can be determined, for example, by referring to standards in buildings (Enforcement Ordinance on Ensuring Sanitary Environment in Buildings, Order No. 304) and Office Sanitary Standard Regulations (Ministry of Labor Order No. 43). ) Indicates that the CO concentration is 10 pp
m or less, the allowable concentration in the working environment is specified as 50 ppm.

In the above-described measurement, it is necessary to measure a reference concentration in an environment serving as a background. In general, since carbon monoxide is not contained in the atmosphere, measurement of a trace concentration is required to measure the background concentration.

In a conventional method for analyzing carbon monoxide, the concentration range that can be measured, for example, by gas chromatography or infrared absorption is 0.1 ppm or more, and it is difficult to measure the concentration of carbon monoxide below this concentration. Therefore, the background concentration of carbon monoxide cannot be determined, and the concentration of generated carbon monoxide cannot be measured accurately.

Therefore, the present invention solves the problems of the conventional methods for removing and enriching carbon monoxide, and enables the removal and enrichment at a low cost and the enrichment of carbon monoxide in a reusable form. It is an object of the present invention to provide a method for removing and concentrating carbon monoxide capable of performing the above-mentioned method, and to provide a trace carbon monoxide analyzer capable of measuring a low concentration of carbon monoxide.

[0011]

SUMMARY OF THE INVENTION The present invention utilizes the property of hemoglobin to selectively bind carbon monoxide.
It removes or concentrates carbon monoxide.It removes carbon monoxide when viewed from the liquid or gas side containing carbon monoxide, and when viewed from the hemoglobin side where carbon monoxide is chemically bonded. Carbon concentration is performed.

FIG. 1 is a schematic diagram for explaining a method for removing and concentrating carbon monoxide according to the present invention.

[0013] Hemoglobin has the property of selectively chemically binding carbon monoxide. Then, when carbon monoxide is brought into contact with hemoglobin (FIG. 1 (a)), oxygen bonded to hemoglobin replaces carbon monoxide and chemically bonds to hemoglobin (FIG. 1 (b)), and Removal and concentration are performed. By chemically reacting the hemoglobin chemically bonded to the carbon monoxide, concentrated carbon monoxide can be extracted from the hemoglobin (FIG. 1 (c)).

In a first method of removing and concentrating carbon monoxide according to the present invention, a gas or liquid containing carbon monoxide is brought into contact with a hemoglobin solution through a thin film, and carbon monoxide in the gas or liquid is converted into the hemoglobin solution. And selectively chemically binds carbon monoxide to hemoglobin. As a result, carbon monoxide in the gas or liquid is removed, and the carbon monoxide is concentrated in the hemoglobin solution.

As the thin film, a gas-liquid separation membrane made of a silicon membrane, a Teflon membrane, or a polyethylene membrane called a membrane filter that allows only the gas component to pass from the gas or liquid side to the hemoglobin solution side can be used.

According to the first method of removing and concentrating carbon monoxide of the present invention, when a gas or liquid containing carbon monoxide is brought into contact with a hemoglobin solution through a thin film, the gas or liquid containing carbon monoxide passes through the thin film. The gas component passes to the hemoglobin solution side. Carbon monoxide in the hemoglobin solution selectively chemically bonds to hemoglobin. As a result, the carbon monoxide chemically bonded to hemoglobin does not return to the gas or liquid side, and the carbon monoxide is removed. Also,
The carbon monoxide on the hemoglobin solution side is in a concentrated state.

The second method of removing and concentrating carbon monoxide according to the present invention comprises contacting a gas containing carbon monoxide with fine powder coated with hemoglobin, and selecting carbon monoxide in the gas as hemoglobin. Are chemically bonded. As a result, the carbon monoxide in the gas is removed, and the carbon monoxide is concentrated in the hemoglobin solution.

The fine powder can be composed of silica or polyethylene fine particles, and hemoglobin can be applied by coating the fine powder with a hemoglobin solution.

According to the second method for removing and concentrating carbon monoxide of the present invention, when a gas containing carbon monoxide is passed through a fine powder coated with hemoglobin and brought into contact with moglobin, the monoxide in the gas is removed. Carbon selectively chemically bonds to hemoglobin. As a result, carbon monoxide chemically bonded to hemoglobin does not return to the gas side, and carbon monoxide is removed. Further, the carbon monoxide on the hemoglobin side applied to the fine powder is in a concentrated state.

[0020] The trace amount of carbon monoxide analyzer of the present invention comprises: carbon monoxide collecting means for storing fine powder coated with hemoglobin; introduction means for introducing a chemical reaction solution into the collecting means;
Equipped with an analytical measuring means for analyzing at least carbon monoxide,
Carbon monoxide is extracted from hemoglobin by a chemical reaction and analyzed and measured by an analytical measuring means.

The carbon monoxide collecting means can be constituted by a container containing fine powder coated with hemoglobin, and by passing a gas containing carbon monoxide through this container, the hemoglobin coated on the fine particles can be collected. Chemical bonding of carbon monoxide.

The introducing means is for introducing a chemical reaction liquid such as an acid into the collecting means, and is for separating the chemically bonded carbon monoxide from the hemoglobin by a chemical reaction and extracting it as a gas.

As the analysis / measurement means, an analysis / measurement device such as a gas chromatograph can be used, and thereby, the extracted carbon monoxide is analyzed.

FIG. 2 is a schematic diagram of a trace carbon monoxide analyzer of the present invention. In FIG. 2, the trace carbon monoxide analyzer 1 includes a carbon monoxide trapping unit 2, a pretreatment unit 3, and an analysis and measurement unit 4. The carbon monoxide trapping unit 2 concentrates and collects carbon monoxide. Then, the carbon monoxide is taken out by introducing the chemical reaction liquid into the carbon monoxide collecting means provided in the pretreatment device 3, and the carbon monoxide is taken out and measured by the analytical measuring means 4.

According to the trace amount of carbon monoxide analyzer of the present invention, the gas containing carbon monoxide is passed through the carbon monoxide collecting means, the fine powder is brought into contact with carbon monoxide, and the applied hemoglobin is chemically converted into carbon monoxide. Combine and collect. The carbon monoxide trapping means for trapping carbon monoxide is installed in a trace carbon monoxide analyzer, and a chemical reaction solution such as an acid is introduced into hemoglobin in the carbon monoxide trapping means. By the chemical reaction between the chemical reaction solution and hemoglobin, carbon monoxide chemically bonded to hemoglobin is separated and taken out as a gas. The extracted carbon monoxide is concentrated to a concentration that can be analyzed by the analytical measuring means, and the carbon monoxide measurement by the analytical measuring means becomes possible.

[0026]

Embodiments of the present invention will be described below in detail with reference to the drawings. First, the method for removing and concentrating carbon monoxide of the present invention will be described with reference to FIGS. FIGS. 3 and 4 are schematic block diagrams for explaining the removal and concentration of carbon monoxide of the present invention. FIG. 3 shows the configuration when a gas or liquid containing carbon monoxide is caused to flow. Is a configuration in the case where a gas or liquid containing carbon monoxide is not allowed to flow.

In the configuration shown in FIG. 3, a hemoglobin solution is accommodated in a container 11, and a hollow membrane tube 12 made of a gas-liquid separation membrane such as silicon, Teflon or polyethylene is passed through the inside of the container 11. Let it through. This tube 1
A gas or liquid containing carbon monoxide passes through 2, and the hemoglobin solution in the container 11 is circulated through a pellester pump 13 and a pipe 14.

A gas or liquid containing carbon monoxide is placed in a tube 1
When passed through 2, the gaseous components in tube 12 pass through the pores of tube 12 and into the hemoglobin solution. Carbon monoxide in the gaseous component selectively bonds to hemoglobin. Tube 12
By continuously flowing gas or liquid into the inside, carbon monoxide is taken into the hemoglobin solution side, and carbon monoxide is removed from the gas or liquid after passing through the container. On the other hand, in the hemoglobin solution, carbon monoxide is accumulated and concentrated with the supply of gas or liquid. By circulating the hemoglobin solution in the container 11, the total amount of carbon monoxide chemically bonded to hemoglobin can be increased.

In the configuration shown in FIG. 4, a gas or a liquid containing carbon monoxide is stored in a container 15, and the same hollow tube 12 is passed through the inside of the container 15 as described above. The pipe 12 forms a circulation path via a Pelletian pump 13 and a pipe 14. A hemoglobin solution circulates through this tube 12.

The gas in the solution 15 or the gas component in the liquid passes through the pores of the tube 12 and reaches the hemoglobin solution. Carbon monoxide in the gaseous component selectively bonds to hemoglobin. By circulating the hemoglobin solution, carbon monoxide is taken into the hemoglobin solution side,
Carbon monoxide is removed from the gas or liquid in the container. On the other hand, carbon monoxide is accumulated in the hemoglobin solution, and concentration is performed.

FIG. 5 is a chemical formula for explaining the chemical bond between hemoglobin and carbon monoxide and the removal of carbon monoxide from hemoglobin by a chemical reaction.

In FIG. 5, when carbon monoxide is supplied to hemoglobin, carbon monoxide replaces oxygen (A in FIG. 5 (a)) bonded to divalent iron of hemoglobin and chemically bonds. . Oxygen gas is released by this chemical bond. Thereby, removal and concentration of carbon monoxide are performed.

Next, when hydrochloric acid, sulfuric acid, or the like is added to the hemoglobin chemically bound to carbon monoxide, a chemical reaction occurs to release carbon monoxide. At this time, iron in moglobin becomes trivalent. Thereby, the concentrated carbon monoxide can be taken out.

Next, an embodiment of carbon monoxide concentration will be described.
In this embodiment, a glass tube having a diameter of 8 mm and a length of 10 cm is attached to a container 11 and a silicon tube 12 having a thickness of 80 μm, an inner diameter of 180 μm, and an outer diameter of 340 μm is attached to the configuration shown in FIG. Then, 25 ml of a diluted solution of blood was added to the inside of the vessel twice with distilled water, and a total volume of 25 ml was circulated at a flow rate of 1 ml / min. Calculate with a gas chromatograph under the condition of flowing through. FIG. 6 shows the measurement results under the above conditions, and the concentration of carbon monoxide can be confirmed.

Next, an apparatus for measuring a trace amount of carbon monoxide according to the present invention will be described with reference to FIGS. FIGS. 7 to 9 are diagrams for explaining a carbon monoxide trapping unit used in a trace carbon monoxide measuring device. Reference numeral 21 in FIG. 7 denotes fine particles for applying hemoglobin, which can be formed by, for example, glass beads of 100 to 120 mesh. Hemoglobin is applied to the fine particles. The application of hemoglobin can be performed, for example, by mixing fine particles with blood at 20% of the weight of the fine particles.

As shown in FIG. 8, the carbon monoxide concentrating tube 20 can be formed of a Pyrex tube 23 having an inner diameter of 3 mm and a length of 5 cm, and accommodates fine particles 21 coated with internal hemoglobin. The carbon monoxide concentration tube 20 has a portable structure, and covers 24 can be attached to both open ends of the tube. When the device is carried, the cover 24 is attached to prevent the carbon monoxide from binding.

FIG. 9 shows a use state of the carbon monoxide concentrating tube. The cover 24 is removed, a sample gas is supplied from one open end of the tube, and discharged from one open end of the tube. The carbon monoxide contained in the supply gas chemically bonds with hemoglobin applied to the fine particles 21 while passing through the Pyrex tube 23.

Thus, carbon monoxide can be removed from the gas released from the carbon monoxide concentration tube, and carbon monoxide can be concentrated and accumulated in hemoglobin in the carbon monoxide concentration tube.

FIG. 10 is a schematic block diagram for explaining the apparatus for measuring a trace amount of carbon monoxide of the present invention. FIG.
, The measuring device 1 for trace carbon monoxide includes a pretreatment device 3 and an analysis / measurement means 4, and the pretreatment device 3 is provided with a carbon monoxide concentration tube 20. The pretreatment device 3 is a device for taking out carbon monoxide trapped in the carbon monoxide concentrating tube 20 in the form of a gas, and the analysis / measurement means 4 is a device for performing analytical measurement of the taken out carbon monoxide.

The pre-processing device 3 takes in nitrogen gas 6
A cock 31, a gas-liquid separator 32 for separating gas and liquid, a reaction liquid inlet 33 for introducing a chemical reaction liquid into the carbon monoxide concentrating tube 20, and a water removing device 34 for removing liquid contained in the gas. And In addition, the analysis and measurement means 4
Are a sample inlet 41 for introducing a standard sample, and a column 42
, A small reaction furnace 43 and a detector 44.

The six-way cock 31 is a valve for selectively supplying nitrogen gas for cleaning and carrier gas, and an acid solution such as hydrochloric acid or sulfuric acid is injected into the reaction solution inlet 33 by a syringe or the like. The removing device 34 removes water using calcium hydroxide or the like. As the carbon monoxide concentration tube 20, the carbon monoxide concentration tube shown in FIGS. 7 to 9 can be used.

The column 42 can use a molecular tube of 2.0 mx 3 mmφ, and the small reactor 43 performs a reduction reaction of carbon monoxide to CH ₄ by hydrogen supplied using a Ni catalyst. The detector 44 measures CH ₄ obtained by reduction using the FID, and thereby performs an analytical measurement of carbon monoxide.

Next, the operation of the apparatus for measuring trace amounts of carbon monoxide of the present invention will be described with reference to FIGS. Note that FIG.
Shows a process for removing air and impurities in the tube, and FIG. 12 shows a process for separating and measuring concentrated carbon monoxide.

In FIG. 11, nitrogen gas is supplied from ports A and F with the six-way cock 31 positioned at the solid line. The nitrogen gas supplied from the port F is discharged through the port C, the gas-liquid separator 32, the reaction liquid inlet 33, the carbon monoxide concentrating tube 20, and the ports D and E to drive out air and impurities in the tube. .

The nitrogen gas supplied from the port A of the six-way cock 31 is sent to the analysis / measurement means 4 through the water removing device 34. At this stage, the gas sent to the analysis and measurement means 4 is a carrier gas of nitrogen gas. At this time, by introducing a standard sample from the sample inlet 41 and performing analysis, a base for measurement can be obtained.

Next, in FIG. 12, the supply of nitrogen gas from the port F is stopped, and for example,
Inject 5 ml of 2N HCl reaction. After 1-2 minutes, the 6-way cock 31 is switched to the position indicated by the solid line. Port A
The nitrogen gas supplied from is supplied to the gas-liquid separator 32 through the port D and the reaction solution and the gas in the carbon monoxide concentrating tube 20. The gas-liquid separator 32 removes the reaction liquid and sends the gas to the water removing device 34. The moisture removing device 34 removes moisture that has not been completely removed by the gas-liquid separator 32 and sends the gas component to the analysis and measurement means 4.

In the analysis and measurement means 4, carbon monoxide contained in the sent gas is separated from other components in the column 42. The separated carbon monoxide is reduced to CH ₄ by hydrogen in a small reactor 43 using a Ni catalyst. The reduced CH ₄ is detected by the detector 44 of the FID, thereby performing an analytical measurement of carbon monoxide.

FIG. 13 shows a measurement example of the trace carbon monoxide analyzer of the present invention.
Using 100 ml of a 1 ppm concentration sample, the column temperature was 60
° C, flow rate of carrier gas (nitrogen gas) 40 ml / mi
n, Examples of measurement results when the flow rate of hydrogen gas for reduction was 50 ml / min.

According to the measurement example shown in FIG.
Carbon monoxide concentrated to ppm is measured.

According to the embodiment of the present invention, hemoglobin can be easily obtained because it is contained in a large amount in animal blood.

Further, according to the embodiment of the present invention, stable storage becomes possible in a state where carbon monoxide is chemically bonded to hemoglobin.

According to the embodiment of the present invention, it is possible to measure a low concentration, which has conventionally been impossible.

Further, according to the embodiment of the present invention, the influence of the interference component can be reduced, and accurate measurement can be performed.

[0054]

As described above, according to the present invention,
It is possible to provide a method for removing and concentrating carbon monoxide, which can perform removal and concentration at low cost and can perform concentration of carbon monoxide in a reusable form,
Further, it is possible to provide a trace carbon monoxide analyzer capable of measuring low concentration of carbon monoxide.

[Brief description of the drawings]

FIG. 1 is a schematic diagram for explaining a method for removing and concentrating carbon monoxide of the present invention.

FIG. 2 is a schematic view of a trace carbon monoxide analyzer of the present invention.

FIG. 3 is a schematic block diagram illustrating the removal and concentration of carbon monoxide according to the present invention.

FIG. 4 is a schematic block diagram for explaining the removal and concentration of carbon monoxide according to the present invention.

FIG. 5 is a chemical formula for explaining a chemical bond between hemoglobin and carbon monoxide, and extraction of carbon monoxide from hemoglobin by a chemical reaction.

FIG. 6 shows measurement results of an example of carbon monoxide concentration.

FIG. 7 is a diagram for explaining a carbon monoxide trapping means used in a trace carbon monoxide measuring device.

FIG. 8 is a view for explaining a carbon monoxide trapping means used for a trace carbon monoxide measuring device.

FIG. 9 is a diagram for explaining a carbon monoxide trapping unit used for a trace carbon monoxide measuring device.

FIG. 10 is a schematic configuration block diagram for explaining the trace carbon monoxide measuring device of the present invention.

FIG. 11 is a diagram for explaining the operation of the trace carbon monoxide measuring device of the present invention.

FIG. 12 is a diagram for explaining the operation of the trace carbon monoxide measuring device of the present invention.

FIG. 13 is a measurement example of the trace carbon monoxide analyzer of the present invention.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 ... Trace carbon monoxide analyzer, 2 ... Carbon monoxide collection means, 3 ... Pretreatment apparatus, 4 ... Analytical measurement means, 11, 15 ...
Container, 12 ... 14 ... Tube, 13 ... Pelester pump, 20
... carbon monoxide concentrating tube, 21 ... fine particles, 22 ... hemoglobin, 23 ... pyrex tube, 24 ... cover 1 ..., 31 ...
6-way cock, 32 ... gas-liquid separator, 33 ... reaction liquid inlet, 34 ... moisture removal device, 41 ... sample inlet, 42 ... column, 43 ... small reactor, 44 ... detector.

Claims (3)

[Claims] 1. A gas or liquid containing carbon monoxide is brought into contact with a hemoglobin solution via a thin film, carbon monoxide in the gas or liquid is transferred to the hemoglobin solution, and carbon monoxide is selectively chemically bonded to hemoglobin. A method for removing and concentrating carbon monoxide. 2. Removal and concentration of carbon monoxide, wherein a gas containing carbon monoxide is brought into contact with fine powder coated with hemoglobin to selectively chemically bond carbon monoxide in the gas to hemoglobin. Method. 3. A system comprising: carbon monoxide collecting means for containing fine powder coated with hemoglobin; introduction means for introducing a chemical reaction solution into the collecting means; and analysis measuring means for analyzing at least carbon monoxide. A trace amount of carbon monoxide, wherein carbon monoxide is taken out of hemoglobin by the chemical reaction and analyzed and measured by an analytical measuring means.