JPH0625759B2 - Continuous analyzer for carbonyl compounds in exhaust gas - Google Patents

Description

TECHNICAL FIELD The present invention relates to a carbonyl compound continuous analyzer in exhaust gas, and particularly to an exhaust gas suitable for transient analysis of an engine in the analysis of carbonyl compounds contained in the exhaust gas. It relates to a carbonyl compound continuous analyzer.

[Conventional technology]

In recent years, from the viewpoint of preventing air pollution, the necessity of suppressing carbonyl compounds (aldehydes and ketones) contained in exhaust gas has been discussed. Therefore, there is an increasing need to detect carbonyl compounds contained in exhaust gas.

One of the conventional examples for detecting this carbonyl compound is the one discussed in Toyota Technology VAOL.29 No.4 Reprinted Toyota Motor Corporation page 84-90. The method for detecting carbonyl compounds in this conventional example is a method for measuring various aldehyde components contained in automobile exhaust gas with high accuracy and in a short time. Specifically, aldehyde-2,4-dinitrophenylhydrazine derivatives can be detected at high speed. Reversed-phase partition separation is applied by applying liquid chromatography, and the high detection sensitivity of the ultraviolet spectrophotometer enables accurate aldehyde measurement with a small amount of exhaust gas sampling. In this conventional example, in order to measure various aldehyde components contained in automobile exhaust gas, a fixed amount of exhaust gas is sampled and
A so-called batch system is used in which 4-dinitrophenylhydrazine is reacted.

[Problems to be solved by the invention]

However, in the above-mentioned conventional example, various aldehydes contained in the exhaust gas of an automobile cannot be continuously measured. Therefore, the relationship between various states of the engine (during acceleration, deceleration, and constant speed operation) and the carbonyl compound in the exhaust gas discharged from the engine in that state cannot be sufficiently grasped. As a result, it becomes impossible to manage the amount of carbonyl compounds contained in the exhaust gas of various engines within the range of appropriate values.

In order to solve such a problem, it is an object of the present invention to provide a continuous analyzer for carbonyl compounds in exhaust gas, which is capable of continuously analyzing carbonyl compounds contained in engine exhaust gas.

[Means for solving problems]

In order to achieve the above object, the present invention, an exhaust gas supply pipe that penetrates the container upper part and continuously supplies exhaust gas from above,
Reagent solution supply pipe that continuously supplies a reagent solution in which a fluorescent reagent that selectively binds to a carbonyl compound contained in exhaust gas is dissolved from the bottom of the container to the inside, and the reagent solution from the reagent solution supply pipe is received from the bottom and stored And the tip of the exhaust gas supply pipe is submerged in the stored reagent solution.
, The reagent solution in the first funnel, and the reagent solution in which the product obtained by reacting the reagent solution with the carbonyl compound contained in the exhaust gas bubbled from the tip of the exhaust gas supply pipe is dissolved A second funnel for receiving the reagent solution overflowing from the first funnel, a gas discharge pipe for discharging the exhaust gas escaping upward after the bubbling to the outside of the container, and a second reagent solution for flowing the reagent solution flowing into the second funnel. A continuous carbonyl compound in exhaust gas, characterized by comprising a liquid discharge pipe for discharging from the bottom of the funnel to the outside of the container, and a fluorometer for continuously measuring fluorescence emitted from the reagent solution in the liquid discharge pipe. It is an analyzer.

[Action]

According to the above invention, the exhaust gas and the fluorescent reagent solution are continuously supplied to the first funnel, respectively, where the fluorescent reagent continuously binds to the carbonyl compound in the exhaust gas, and the produced product is the fluorescent reagent solution. After the binding, the gas component of the exhaust gas is discharged to the outside of the container through the gas discharge pipe, while the reacted reagent solution overflows from the first funnel and is discharged via the second funnel. Since the gas flows into the tube as rectification that is not disturbed by the gas component, the fluorescence emitted from the reacted reagent solution can be accurately and continuously analyzed by a fluorometer. As a result, the carbonyl compound in the exhaust gas can be continuously analyzed.

〔Example〕

Next, examples of the carbonyl compound continuous analyzer according to the present invention will be described.

FIG. 1 is a process diagram showing an analysis flow of the embodiment. In FIG. 1, the fluorescent reagent solution sending section 1 is connected to the carbonyl compound-fluorescent reagent reaction section 2. On the other hand, the exhaust gas supply unit 3 is also connected to the carbonyl compound-fluorescent reagent reaction unit 2. Carbonyl compound-fluorescent reagent reaction part 2
Is connected to the fluorescence detector unit 4.

Next, the operation will be described.

In the reagent solution sending part 1, a fluorescent reagent is dissolved in a solvent. The properties of the fluorescent reagent required here are to dissolve in a solvent and to selectively bond with a carbonyl compound in the exhaust gas. As such a reagent,
For example:

Such a fluorescent reagent selectively binds to the carbonyl compound in the exhaust gas. The reaction formula is shown in the following formula (1).

By continuously supplying the exhaust gas from the exhaust gas supply unit 3 to the carbonyl compound-fluorescent reagent reaction unit 2, the carbonyl compound in the exhaust gas and the fluorescent reagent are continuously contacted with each other to form a carbonyl compound-fluorescent reagent complex. Form. As the fluorescent reagent that selectively binds to such a carbonyl compound, various diazo-based fluorescent reagents can be used in addition to the above-mentioned fluorescent reagent. Since this fluorescent reagent is soluble in an aqueous solution, alcohol, acetonitrile, etc., in the reagent solution sending section 1, the fluorescent reagent is dissolved in these solvents and supplied to the fluorescent reagent-carbonyl compound reaction section 2.

Aldehydes such as formaldehyde, acetaldehyde, benzaldehyde, and acrolein are present in the carbonyl compound measured in the exhaust gas. Moreover, as the ketones, for example, acetone, methyl ethyl ketone, and the like exist. The carbonyl compound in the exhaust gas continuously contacts the fluorescent reagent to form a fluorescent reagent-carbonyl compound complex.

The carbonyl compound in the exhaust gas binds to the fluorescent reagent and dissolves in the reagent solution. Therefore, by sending this reagent solution from the carbonyl compound-fluorescent reagent reaction section 2 to the fluorescence detector section 4, fluorescence analysis can be performed. As the detector here, a fluorometer can be used, and by analyzing the difference in fluorescence between the fluorescent reagent and the carbonyl-fluorescent reagent complex, qualitative and quantitative determination of the carbonyl compound contained in the exhaust gas is possible. Becomes In the detector section 4, since the fluorescence analysis can be performed while the fluorescent reagent solution is continuously flowing, the carbonyl compound in the exhaust gas can be continuously analyzed.

Therefore, the transient analysis of the carbonyl compound in the exhaust gas can be continuously performed according to the load condition of the automobile engine.

FIG. 2 shows an embodiment of the carbonyl compound continuous analyzer according to the present invention. FIG. 2 is a vertical sectional view showing the embodiment.

In FIG. 2, the outer funnel 2 is provided inside the casing 20.
1 is provided. Inside the outer funnel 21, an inner funnel 22 is provided. This outer funnel 21
The casing 20 and the upper end are integrated to form the casing 20.
An exhaust gas discharge pipe 23 is connected to one end side of the. On the other hand, the outer funnel 21 is connected to the fluorescent reagent solution discharge pipe 24 at one end side of the lower end thereof. The discharge pipe 24 passes through the casing 20 and projects to the outside. A fluorescent reagent solution supply pipe 25 is connected to the lower end of the inner funnel 22. The supply pipe 25 has a structure protruding downward from the casing 20. On the other hand, an exhaust gas supply pipe 26 that passes through the casing 20 is provided inside the inner funnel 22. The fluorescent reagent solution discharge pipe 2
Fluorescence photometer 27 is connected to 4.

Next, the operation of this embodiment will be described. Exhaust gas is supplied into the inner funnel 22 by connecting the exhaust gas pipe of the automobile and the exhaust gas supply pipe 26. For the time being, a solution in which the fluorescent reagent is dissolved is supplied from the fluorescent reagent solution supply pipe 25. This solution reaches the inner funnel 22 and then overflows the inner funnel 22,
1, and then discharged from the fluorescent reagent solution discharge pipe 24. The exhaust gas supplied to the inner funnel 22 is bubbled into a solution in which the fluorescent reagent stored in the inner funnel 22 is dissolved. As a result, the carbonyl compound in the exhaust gas forms a complex with the fluorescent reagent, and the complex dissolves in the solution to pass through the outer funnel 21 and further into the exhaust pipe 25.
Emitted from. The exhaust gas supplied to the inner funnel 22 is exhausted from the exhaust gas exhaust pipe 23 to the outside of the system.

Since the fluorescence photometer 27 is provided in the middle of the exhaust pipe 24, the fluorescence emitted from the carbonyl compound-fluorescent reagent complex existing in the exhaust gas can be analyzed.

In this embodiment, although not shown, a pressure pump for replenishing the exhaust gas, a pressure pump for supplying the fluorescent reagent solution, a heating means for heating the exhaust gas, and a heating means for heating the fluorescent reagent solution are provided. You can also The pressurizing pump can contact the exhaust gas and the solution in which the fluorescent reagent is dissolved at a high flow rate, and the reaction temperature at the time of contact can be raised by the heating means. By doing so, the time resolution in the fluorescence analysis is improved, and the transient analysis of the carbonyl compound in the exhaust gas can be accurately performed according to the load state of the automobile engine.

FIG. 3 is a diagram showing the configuration of another analyzer for continuously analyzing carbonyl compounds in exhaust gas.

In FIG. 3, a reaction solution storage tank 3 for storing a reaction solution obtained by dissolving a fluorescent reagent that binds to a carbonyl compound in exhaust gas
0 and the liquid feed pump 31 are provided in the reaction liquid supply line 32. The reaction liquid supply line 32 is connected to the wavy reaction tube 33. A gas supply line 34 for supplying exhaust gas is provided at the other end of the reaction tube 33. On the side where the gas supply line 34 is provided, a reaction solution discharge line 35 that discharges a reaction solution containing a product formed by reacting the carbonyl compound in the exhaust gas with the fluorescent reagent is provided. A fluorescence photometer 27 is provided in the middle of the discharge line 35. On the other hand, an exhaust gas discharge line 36 for discharging exhaust gas is provided on the side where the reaction liquid supply line is provided. A pressure pump 37 is provided in the middle of the exhaust gas line 36.

Next, the operation of this embodiment will be described. Reaction liquid storage tank 3
In 0, a solution in which the fluorescent reagent is dissolved is stored. This solution is supplied into the reaction tube 33 by the operation of the liquid feed pump 31. On the other hand, the exhaust gas is supplied into the reaction tube 33 from the gas supply line 34. This reaction tube 3
In 3, a complex of the fluorescent reagent and the carbonyl reagent in the exhaust gas is formed. Since this reaction tube is wavy, it is possible to flow the exhaust gas and the solution in which the fluorescent reagent is dissolved in a countercurrent state, so that convection occurs in the reaction tube and the carbonyl compound and the fluorescent reagent complex are formed. The efficiency of formation is good.

FIG. 4 is a sectional configuration diagram of still another analyzer for continuously analyzing carbonyl compounds in exhaust gas.

In FIG. 4, an inner pipe 42 is provided inside the outer pipe 41. An ultrafiltration membrane 43 is provided on the outer peripheral surface of the inner tube. The reaction solution in which the fluorescent reagent is dissolved is
It passes through the inner pipe 42. On the other hand, the exhaust gas is supplied from the exhaust gas supply hole 44 of the outer pipe. The carbonyl component in the exhaust gas supplied between the outer tube and the inner tube forms a complex with the fluorescent reagent in the reaction solution and dissolves in the reaction solution. On the other hand, the insoluble gas component is discharged to the outside of the system via the exhaust gas discharge pipe 45.

〔The invention's effect〕

As described above, according to the carbonyl compound continuous analyzer in the exhaust gas according to the present invention, the fluorescent reagent in the fluorescent reagent solution and the carbonyl compound in the exhaust gas are selectively continuously bound, and the reacted fluorescent reagent Since the gas component of the exhaust gas is removed from the solution for rectification, the carbonyl compound in the exhaust gas can be accurately and continuously analyzed. As a result, the relationship between various states of the engine and the carbonyl compound in the exhaust gas discharged from the engine in that state can be sufficiently grasped, and the carbonyl compound contained in the exhaust gas is maintained within the appropriate range. Can be managed.

[Brief description of drawings]

FIG. 1 is a process diagram showing an analysis flow of an embodiment of the present invention,
FIG. 2 is a vertical cross-sectional configuration diagram showing an embodiment of the present invention, FIG. 3 is a vertical cross-sectional configuration diagram of another analyzer for continuously analyzing carbonyl compounds in exhaust gas, and FIG. 4 is carbonyl in exhaust gas. It is a block diagram which shows another analyzer which analyzes a compound continuously. 1 ... Reagent solution feeding part, 2 ... Reaction part, 3 ... Exhaust gas supply part, 4 ... Detector part, 20 ... Casing, 21 ... Outer funnel, 22 ... Inner funnel, 23 ... Exhaust Gas exhaust pipe 24 ... Fluorescent reagent solution exhaust pipe, 25 ... Fluorescent reagent solution supply pipe, 26 ... Exhaust gas supply pipe, 27 ... Fluorescence photometer.

Claims (1)

[Claims] 1. An exhaust gas supply pipe which penetrates an upper part of a container and continuously supplies an exhaust gas from above, and a reagent solution in which a fluorescent reagent which selectively binds to a carbonyl compound contained in the exhaust gas is dissolved, from inside the container to the inside thereof. And a reagent solution supply pipe continuously supplied to the bottom of the reagent solution supply pipe, the reagent solution from the reagent solution supply pipe is received from the bottom and stored therein, and the tip of the exhaust gas supply pipe is immersed in the stored reagent solution. The funnel, the reagent solution in the first funnel, and the carbonyl compound contained in the exhaust gas bubbled from the tip of the exhaust gas supply pipe in the reagent solution are dissolved to dissolve the product. A second funnel for receiving the reagent solution overflowing from the first funnel, a gas exhaust pipe for exhausting the exhaust gas that escapes upward after being bubbled out of the container, and the second funnel. A liquid discharge pipe for discharging the reagent solution flowing into the container from the second funnel bottom to the outside of the container, and a fluorometer for continuously measuring fluorescence emitted from the reagent solution in the liquid discharge pipe. A continuous analyzer for carbonyl compounds in exhaust gas, which is characterized in that