JPH0828238A - Measuring method and device for engine oil consumption quantity - Google Patents

Abstract

PURPOSE:To provide such a method and a device for measuring engine oil consumption quantity that stabilizes SO3<2-> ion in a trap solution and remove interference caused by CO2, hydrocarbon, etc., in exhaust gas. CONSTITUTION:A device for measuring engine oil consumption quantity comprises a gas intake means 10 which samples exhaust gas and oxidizes S component contained therein, a gas exchange means 70 which dissolves SO2 straying in intake exhaust gas into a trap solution so as to change it into SO3 ion, and an SO2 detection means 90 which oxidizes SO3<2-> ion in the trap solution into SO4<2-> ion, mixes it with reaction solution, and measures chemical emission quantity. Therefore, stabilization process of SO3<2-> ion in the trap solution is added, PH of the trap solution is adjusted so as to eliminate negative interference caused by CO2 gas, insoluble carrier or organic solvent is continuously contacted with the trap solution in which SO3<2-> ion is solved, effects of organic substances such as hydrocarbon, etc., in exhaust gas are prevented, and dew condensation is prevented by keeping exhaust gas warm or diluted by inert gas.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a measuring method and apparatus for measuring engine oil consumption by continuously measuring the amount of SO ₂ contained in exhaust gas of an automobile.

[0002]

2. Description of the Related Art Conventionally, the engine oil consumption is calculated by adding a weight method for measuring the difference in weight of engine oil before and after operation, a capacity method for similarly measuring the volume of engine oil, and a radioisotoped component in engine oil. There is a radioisotope method for measuring radioactivity in exhaust gas. However, these methods have advantages and disadvantages, for example, the gravimetric method,
The capacity method has insufficient sensitivity, and the radioisotope method has a problem that it is a facility restriction.

Further, the sulfur content contained in the engine oil burns as the engine oil is consumed and S in the exhaust gas.
Known is an S-trace method or the like in which the emission of O ₂ is detected by FPD or NDIR. For example,
Among the S-trace methods, as an example of an apparatus using the flame photometric analysis method, there is an engine oil consumption measuring apparatus disclosed in Japanese Patent Laid-Open No. 63-198852. In this apparatus, sampling is performed from an engine exhaust pipe. The exhaust gas can be kept at a predetermined temperature by a heating conduit until just before the flame photometric detector, and the S component in the exhaust gas is prevented from being adsorbed on the inner wall of the pipe. While the O ₂ gas is being supplied by the combustion furnace provided in the above, the S component in the exhaust gas is oxidized to produce SO ₂ , and this SO ₂ component is detected by the flame photometric detector, and the detected SO ₂ component value It measures the consumption of engine oil. In addition, S
-In the trace method, commercially available S-free gasoline is used to ensure measurement accuracy.

The S-trace method is an excellent method which can be used for continuous analysis and has general versatility. However, there is a shortage in sensitivity with respect to reduction of engine oil consumption due to engine improvement in the future. it is conceivable that. Further, as a method for detecting SO ₂ gas, an infrared absorption analysis method and a solution conductivity method are known, but there are many interfering factors and the sensitivity is in the ppm order. In addition, S generated by SO ₂ dissolved in the aqueous solution
As a method for measuring O ₃ ²⁻ ion, there are an iodometry method, a colorimetric method, a maleimide method and the like, but there are still many problems such as the inability to measure sensitivity or continuous measurement and the strong influence of interfering substances.

On the other hand, a sulfite oxidase derived from chicken liver, which has an action of selectively oxidizing SO ₃ ²⁻ ions, is immobilized to form a bioreactor, and H ₂ O ₂ generated by the oxidation of SO ₃ ²⁻ ions is isoluminol. The method of reacting with peroxidase in the presence of peroxidase and detecting the chemiluminescence amount accompanying oxidative decomposition of isoluminol is capable of detecting ppb order as SO ₃ ²⁻ ion, and in combination with a flow injection analysis method, Continuous analysis is also possible. Therefore, based on the common principle with the S-trace method, the generated SO ₂ is dissolved in an aqueous solution to form SO ₃ ²⁻ ions, and then a combination of flow injection analysis and a sulfite oxidase bioreactor and chemiluminescence is used. A method for quantifying SO ₃ ²⁻ ions was invented. According to this method, standard SO ₂ gas can be continuously analyzed on the ppb order.

[0006]

However, as the first problem, the chicken liver-derived sulfite oxidase having the action of selectively oxidizing SO ₃ ²⁻ ions is immobilized to form a bioreactor. _{In the} method of reacting H ₂ O ₂ generated by the oxidation of ₃ ²⁻ ion with isoluminol in the presence of peroxidase, and detecting the chemiluminescence amount associated with the oxidative decomposition of isoluminol, the SO ₃ ²⁻ ion itself is in solution. It has the property of being easily oxidized by dissolved oxygen and oxygen-containing compounds, and also causes non-specific adsorption to the Teflon pipes and liquid pumps that make up the analyzer, glass beads used to immobilize sulfite oxidase, etc. However, there is an inconvenience that the SO ₂ concentration cannot be measured correctly.

As a second problem, the above-mentioned SO ₃
^A bioreactor is prepared by immobilizing sulfite oxidase derived from chicken liver, which has the effect of selectively oxidizing ^2- ions.
_{In a} method of reacting H ₂ O ₂ produced by the oxidation of ₃ ²⁻ ions in the coexistence of isoluminol and peroxidase, and detecting the chemiluminescence amount accompanying oxidative decomposition of isoluminol, CO ₂ gas contained in engine exhaust gas is detected. However, there is a disadvantage that any of the series of reaction steps described above has negative interference, and correct SO ₂ measurement cannot be performed.

Further, as a third problem, the above SO
₃ Sulfur oxidase derived from chicken liver, which has the effect of selectively oxidizing ^2- ions, is immobilized to form a bioreactor.
O ₃ ^{2 -} The H ₂ O ₂ produced by the oxidation of ion reacted with isoluminol and peroxidase coexistence of a method for detecting the amount of chemiluminescence caused by the oxidative decomposition of isoluminol, hydrocarbons and the like contained in engine exhaust gas It has been discovered that the organic substance of (1) interferes with the reaction of the above-mentioned series of reaction steps, exerts negative interference, and cannot perform correct SO ₂ measurement.

Finally, as a fourth problem, in the engine oil consumption measuring device disclosed in JP-A-63-198852, when the S component in the exhaust gas is oxidized in the combustion furnace. , O ₂ in exhaust gas after oxidation
Although O ₂ gas is supplied into the combustion furnace to generate SO ₂ while controlling the gas concentration to fall within a predetermined range, the exhaust gas contains various unburned components in addition to the S component. Therefore, it becomes an obstacle when detecting the SO ₂ component. on the other hand,
The sampled exhaust gas is kept at a predetermined temperature by a heating conduit until just before the flame photometric detector to prevent the S component in the exhaust gas from being adsorbed on the inner wall of the pipe. It is necessary to obtain a stable measurement result by taking a method to prevent the S component in the exhaust gas from being adsorbed on the inner wall of the pipe or absorbed by the condensed water even if the temperature is not kept at a predetermined temperature. There is.

The present invention has been made to solve the above-mentioned four problems of the method and apparatus for measuring engine oil consumption, in which SO ₂ gas in exhaust gas is brought into contact with a continuously flowing trap solution. Are dissolved to form SO ₃ ²⁻ ions, and the trap solution is passed through an immobilization reactor composed of sulfite oxidase to oxidize SO ₃ ²⁻ ions to SO ₄ ²⁻ ions and generate hydrogen peroxide. And a step of continuously reacting the trap solution with an aqueous solution of isoluminol and a peroxidase, and detecting the chemiluminescence amount associated with the oxidative decomposition of isoluminol by the hydrogen peroxide in the trap solution to continuously measure the SO ₂ amount. manner in the measurement method of the engine oil consumption and means for quantifying, stabilization of the sO ₃ ^2-ion and adsorption preventing The method of measuring the engine oil consumption which aimed, the method of measuring the engine oil consumption that eliminates interference by CO ₂ gas, the measuring method and the engine exhaust pipe of the engine oil consumption that prevents interference with an organic substance such as hydrocarbon exhaust In a sampling pipe system that takes in gas, burns S contained therein, and sends the exhaust gas to the SO ₂ component detection unit, prevents the S component in the exhaust gas from being adsorbed on the inner wall of the pipe or adsorbed by condensed water. Another object of the present invention is to provide a method and a device for measuring engine oil consumption, which completely oxidizes unburned components in exhaust gas and completes SO ₂ sampling.

[0011]

As a result of various investigations on the first problem, the inventors of the present invention have found that SO ₂ gas is dissolved in an aqueous solution to form SO ₃ ²⁻ ions, and immediately thereafter SO ₃
^The present invention has been completed by finding that the problem can be solved by adding and joining a stabilizing solution having an effect of stabilizing non-specific adsorption while stabilizing ^2- ions.

The method for measuring engine oil consumption according to claim 1 of the present invention is a method for measuring engine oil consumption by continuously measuring the amount of SO ₂ contained in engine exhaust gas, The SO ₂ gas in the exhaust gas is brought into contact with the continuously flowing trap solution to dissolve it
O ₃ ²⁻ ions, a step of oxidizing the SO ₃ ²⁻ ions into SO ₄ ²⁻ ions and generating hydrogen peroxide by passing the trap solution through a bioreactor consisting of sulfite oxidase, The amount of SO ₂ is continuously quantified by continuously reacting the trap solution with an aqueous solution of isoluminol and peroxidase and detecting the chemiluminescence amount accompanying the oxidative decomposition of isoluminol by the hydrogen peroxide in the trap solution. And a step of contacting SO ₂ gas in the exhaust gas with a continuously flowing trap solution to dissolve it into SO ₃ ²⁻ ions,
The gist is that the steps of stabilizing O ₃ ^2- ions and preventing adsorption are added.

According to a second aspect of the present invention, there is provided a method for measuring an engine oil consumption amount according to the first aspect, wherein the SO ₃ ^2-
It is summarized that the ion stabilization and adsorption prevention step is a step of joining a stabilizing solution having an SO ₃ ²⁻ ion stabilization and adsorption prevention effect with the trap solution in which the SO ₃ ²⁻ is dissolved. .

According to a third aspect of the present invention, there is provided a method for measuring an engine oil consumption amount according to the second aspect, wherein the SO ₃ ^2-
Compounds that have the effect of stabilizing ions and preventing adsorption,
The acid amide compound is an acid amide compound, and the ionic strength of the aqueous solution of the acid amide compound to be combined is 0.001 to 0.1, PH
Is in the range of 7-9.

According to a fourth aspect of the present invention, in the method for measuring engine oil consumption according to the third aspect, the acid amide compound is nicotinamide adenine dinucleotide (N
AD) and a linear or branched carboxylic acid amide compound having 2 to 4 carbon atoms.

The inventions of claims 1 to 4 will be described in detail below. The features of the inventions of claims 1 to 4 are that, after the contact between the sample gas and the trap solution, the aqueous solution containing the acid amide compound is merged from another pipe immediately after the SO ₂ gas becomes SO ₃ ^2- ₃ It is to prevent ^2- ions from being oxidized or adsorbed on piping.

Any acid amide compound may be used as long as it has the above-mentioned properties and does not affect the series of reactions after the step of passing through the bioreactor comprising sulfite oxidase. Preferably, it is a linear or branched carboxylic acid amide having 2 to 4 carbon atoms or nicotinamide adenine diadenine dinucleotide (NAD). Further, it is preferable that the pH of the aqueous solution of the acid amide compound is maintained at 7 to 9, and therefore, it is possible to add a salt having a PH buffering action. However, the ionic strength is 0.001
It is needless to say that ˜0.1 is preferable, and a salt thereof that does not affect the subsequent reaction is required.

As a result of intensive studies conducted by the present inventors in order to solve the second problem, as a result of contacting SO ₂ gas with an aqueous solution to capture gas components in water, CO ₂
Therefore, the inventors have found that SO _{2 in} exhaust gas can be measured with extremely high sensitivity without interference, and as a result, engine oil consumption can be measured with high sensitivity, and the present invention has been completed.

According to a fifth aspect of the present invention, the method for measuring engine oil consumption is SO ₂ contained in engine exhaust gas.
A method of measuring engine oil consumption by continuously measuring the amount, wherein SO ₂ gas in the exhaust gas is brought into contact with a continuously flowing trap solution to be dissolved to form SO ₃ ²⁻ ions. A step of oxidizing the SO ₃ ²⁻ ions into SO ₄ ²⁻ ions and generating hydrogen peroxide by passing the trap solution through a bioreactor consisting of sulfite oxidase, and the aqueous solution is an aqueous solution of isoluminol and peroxidase. Of the amount of engine oil consumed by continuously quantifying the SO ₂ amount by detecting the chemiluminescence amount accompanying the oxidative decomposition of isoluminol by the hydrogen peroxide in the trap solution. the measuring method, sO ₃ ² dissolved sO ₂ gas in the exhaust gas is contacted with continuously flowing trap solution ^- and summarized in that by adding the process of eliminating the interference by the CO ₂ gas in the step of the ion.

According to a sixth aspect of the present invention, in the method of measuring the engine oil consumption amount according to the fifth aspect of the invention, the step of eliminating the interference by the CO ₂ gas includes adding a buffer solution to the trap solution to remove the trap solution. The gist is that it is a step of adjusting PH to 3.5 to 4.5.

According to a seventh aspect of the present invention, in the method for measuring the amount of engine oil consumed according to the sixth aspect, the main component of the buffer solution is acetic acid, succinic acid, citric acid, dimethyl glutaric acid or glycine. That is the summary.

[0022] The present inventors have in a state where a third result of various studies with respect to problems, SO ₃ ^2-ions are dissolved in an aqueous solution state or SO ₂ gas SO ₂ gas, hydro The present invention has been completed by discovering that the organic substance such as carbon can be removed by adsorbing it to an insoluble carrier or an organic solvent to avoid interference with a series of subsequent reactions by the organic substance such as hydrocarbon.

The method for measuring engine oil consumption according to claim 8 of the present invention is a method for measuring engine oil consumption by continuously measuring the amount of SO ₂ contained in engine exhaust gas, The SO ₂ gas in the exhaust gas is brought into contact with the continuously flowing trap solution to dissolve it
A step of forming O ₃ ²⁻ ions, and a step of oxidizing the SO ₃ ²⁻ ions into SO ₄ ²⁻ ions and generating hydrogen peroxide by passing the trap solution through an immobilization reactor composed of sulfite oxidase. The SO ₂ amount is continuously quantified by continuously reacting the aqueous solution with an aqueous solution of isoluminol and peroxidase and detecting a chemiluminescence amount accompanying oxidative decomposition of isoluminol by the hydrogen peroxide in the trap solution. A method for measuring engine oil consumption comprising the steps of: contacting a SO ₂ gas in the exhaust gas with a continuously flowing trap solution or contacting the SO ₂ gas in the exhaust gas with a continuously flowing trap solution. It is a gist to add a step of preventing interference by an organic substance such as hydrocarbon after the above.

According to a ninth aspect of the present invention, in the engine oil consumption measuring method according to the eighth aspect of the invention, the step of preventing interference by the organic substance such as the hydrocarbon is adsorption to the organic substance such as the hydrocarbon. It is a step of passing the exhaust gas or the trap solution in which the SO ₃ ²⁻ ions are dissolved through a column packed with an insoluble carrier having the ability.

According to a tenth aspect of the present invention, in the method for measuring the engine oil consumption amount, the step of preventing interference by an organic substance such as the hydrocarbon in the eighth aspect is
After the step of contacting SO ₂ gas in the exhaust gas with a continuously flowing trap solution to dissolve it into SO ₃ ²⁻ ions, the SO ₃ ²⁻ ion is dissolved in the trap solution to be hydrophobic and to water. The gist of the invention is a step of continuously contacting an insoluble organic solvent to extract only the organic substance into the organic solvent.

The method for measuring engine oil consumption according to claim 11 of the present invention is the method according to claim 9, wherein the insoluble carrier is a monomethyl group, a tetramethyl group, an octyl group on the surface of the silica gel or the polymer gel itself, The gist is that it has an octadecyl group or a phenyl group.

According to a twelfth aspect of the present invention, in the method for measuring the engine oil consumption amount according to the tenth aspect of the invention, the hydrophobic and water-insoluble organic solvent is ethyl acetate, dichloromethane or dichloroethane. To do.

According to a thirteenth aspect of the present invention, in the engine oil consumption measuring device, the SO ₂ contained in the engine exhaust gas is included.
A device for measuring engine oil consumption by continuously measuring the amount of exhaust gas, which continuously takes in exhaust gas from an engine exhaust pipe, burns S in exhaust gas into SO ₂ and sends it to a gas exchange section. a gas intake section, sO ₂ dissolved by contacting sO ₂ in the exhaust gas from the continuously feeding trap solution the trap solution gas uptake section
SO ₃ By the passing and gas exchange unit to send the trap solution and SO ₃ ^2-ions SO ₂ detector, the bioreactor comprising the trap solution sulfite oxidase
Oxidation of ^{2 -} ions to SO ₄ ^2- ions and generation of hydrogen peroxide, and then the trap solution is continuously reacted with an aqueous solution of isoluminol and peroxidase to oxidatively decompose isoluminol by the hydrogen peroxide in the aqueous solution. By detecting the amount of chemiluminescence associated with
_An engine oil consumption measuring device comprising an SO ₂ detecting part for continuously quantifying _two amounts, the exhaust gas from the gas intake part or the trap solution from the gas exchanging part before reaching the next step. The gist is that a column packed with an insoluble carrier that is once passed through is attached to the column.

The material of the column is SO ₂ or SO ₃ ^2-
Any material that does not adsorb ions can be used, but glass or stainless steel is preferable, and the column diameter is preferably 2 to 10 mm and the length is 50 to 100 mm.
The particle size of the resin as the insoluble carrier used here is 2 to 100 so as not to affect the flow of gas or aqueous solution.
μm, and its pore diameter is preferably 10 to 1000 Å.

According to a fourteenth aspect of the present invention, in the engine oil consumption measuring device, the SO ₂ contained in the engine exhaust gas is included.
A device for continuously measuring the engine oil consumption by continuously measuring the amount, in which exhaust gas is continuously taken in from the engine exhaust pipe and S in the exhaust gas is burned to SO ₂ And a trap solution continuously fed to the trap solution, SO ₂ in the exhaust gas from the gas intake section is brought into contact with the trap solution to dissolve it, and SO _{2 is changed} to SO ₃ ²⁻ ion, and the trap solution is SO ₂ The gas exchange part to be sent to the detection part and the trap solution are passed through a bioreactor consisting of sulfite oxidase to oxidize SO ₃ ²⁻ ions to SO ₄ ²⁻ ions and generate hydrogen peroxide, and then the trap Oxidative decomposition of isoluminol by the hydrogen peroxide in the trap solution by continuously reacting the solution with an aqueous solution of isoluminol and peroxidase. In continuous measuring device of the engine oil consumption consisting of quantifying SO ₂ detector to the SO ₂ amount by detecting the amount of chemiluminescence with the SO
_{2 In} the flow path of the trap solution from the gas exchange section in the detection section, an organic solvent mixing means for mixing a hydrophobic, water-insoluble organic solvent, and separating the organic solvent from the mixture of the trap solution and the organic solvent The main point is to install a separator that operates.

As a result of various studies on the fourth problem, the inventors of the present invention have found that in the sampling pipe system for taking in exhaust gas from the engine exhaust pipe to the SO ₂ detecting means,
Exhaust gas can be kept at a predetermined temperature by attaching a heater and heat insulating material to the sampling pipe and each component that make up the sampling pipe, and the exhaust gas is diluted with a high-purity inert gas in the sampling pipe flow path. By doing so, it is possible to prevent the moisture in the exhaust gas from condensing on the inner wall of the sampling pipe system without maintaining it at a predetermined temperature, and selectively select heat-resistant particulate matter or S component inside the sampling pipe equipped with the combustion furnace. The present invention has been completed by finding that the unburned component in the exhaust gas is completely oxidized by filling the catalyst agent to be oxidized.

According to a fifteenth aspect of the present invention, in the method for measuring the engine oil consumption, SO ₂ contained in the engine exhaust gas is used.
A method for measuring engine oil consumption by continuously measuring the amount of exhaust gas, in which exhaust gas is continuously taken in from an engine exhaust pipe and S in exhaust gas is burned to SO ₂ and sent to a gas exchange section. In the gas uptake step, the trap solution is continuously supplied, and SO ₂ in the exhaust gas from the exhaust gas uptake portion is brought into contact with the trap solution to dissolve the SO ₂ into SO ₃ ²⁻ ion, and the trap solution is converted into S.
A gas exchange step of sending to the O ₂ detection part and passing the trap solution through a bioreactor consisting of sulfite oxidase oxidize SO ₃ ²⁻ ions to SO ₄ ²⁻ ions and generate hydrogen peroxide, and then The amount of SO ₂ is continuously quantified by continuously reacting the trap solution with an aqueous solution of isoluminol and peroxidase and detecting the chemiluminescence amount accompanying the oxidative decomposition of isoluminol by the hydrogen peroxide in the trap solution. In the method for measuring engine oil consumption, which comprises a SO ₂ detection step, the gist is that an SO ₂ sampling ensuring step is provided in the exhaust gas intake means.

According to a sixteenth aspect of the present invention, in the engine oil consumption measuring method according to the fifteenth aspect, the SO ₂
The gist of the sampling ensuring process is to heat and keep the sampling pipe for introducing the exhaust gas and its components heated.

According to a seventeenth aspect of the present invention, in the engine oil consumption measuring method according to the fifteenth aspect or the sixteenth aspect of the invention, the SO ₂ sampling ensuring step removes the exhaust gas when burning S in the exhaust gas. The gist is that the step is a step of bringing into contact with a sufficiently heated granular material or a catalyst agent for selectively oxidizing the S component.

An engine oil consumption measuring method according to an eighteenth aspect of the present invention is the method according to any one of the fifteenth to seventeenth aspects, wherein the SO ₂ sampling ensuring step burns S contained into SO ₂ . The gist of the present invention is to include an exhaust gas dilution step of diluting the exhaust gas after the step with an inert gas.

According to a nineteenth aspect of the present invention, in the engine oil consumption measuring device, the SO ₂ contained in the engine exhaust gas is included.
A device for measuring engine oil consumption by continuously measuring the amount of exhaust gas, which continuously takes in exhaust gas from an engine exhaust pipe, burns S in exhaust gas into SO ₂ and sends it to a gas exchange section. A gas intake part and a trap solution are continuously supplied, and SO ₂ in the exhaust gas from the exhaust gas intake part is brought into contact with and dissolved in the trap solution to form SO ₂ as SO ₃ ²⁻ ions and the trap solution is SO ₂
The gas exchange part to be sent to the detection part and the trap solution are passed through a bioreactor consisting of sulfite oxidase to oxidize SO ₃ ²⁻ ions to SO ₄ ²⁻ ions and generate hydrogen peroxide, and then the trap SO ₂ quantity is continuously quantified by continuously reacting the solution with an aqueous solution of isoluminol and peroxidase, and detecting chemiluminescence quantity accompanying oxidative decomposition of isoluminol by the hydrogen peroxide in the trap solution SO ₂ In the engine oil consumption measuring device including a detection unit, the summary is that the gas intake unit is provided with SO ₂ sampling securing means.

According to a twentieth aspect of the present invention, in the engine oil consumption measuring device according to the nineteenth aspect of the present invention, the SO ₂ sampling ensuring means replaces S in the exhaust gas with S.
The sampling pipe that takes in the exhaust gas after burning to O ₂ is branched, and most of the exhaust gas is exhausted from one of the sambling pipes through the pressure regulator, and part of the exhaust gas is exchanged from the other sampling pipe. In addition to the above, the gist is that the gas exchange part is equipped with a glass instrument including a spiral glass tube that dissolves SO ₂ in the exhaust gas into the trap solution while maintaining a high temperature.

[0038]

According to the first to fourth aspects of the present invention, there is provided a method for measuring engine oil consumption by continuously measuring the amount of SO ₂ contained in engine exhaust gas, wherein the exhaust gas SO _{2 in the} gas is contacted with a continuously flowing trap solution to dissolve it to form SO ₃ ²⁻ ions, and the trap solution is passed through a bioreactor composed of sulfite oxidase to produce SO ₃
A step of oxidizing ^{2 -} ions to SO ₄ ^2- ions and generating hydrogen peroxide; and a step of continuously reacting the trap solution with an aqueous solution of isoluminol and peroxidase to remove isoluminol from the hydrogen peroxide in the trap solution. In a method for measuring engine oil consumption, which comprises a means for continuously quantifying the amount of SO ₂ by detecting the amount of chemiluminescence accompanying oxidative decomposition, the exhaust gas and the trap solution contact each other, and SO ₂ in the exhaust gas is immediately after a sO ₃ ^2-ions, since is combined with an aqueous solution containing an acid amide from another pipe, attached through a weak interaction between the sO ₃ ^2-ions acid amide, sO ₃ ^2- It is possible to prevent destabilization due to oxidation of ions and non-specific adsorption. It is considered that even such a bound product does not hinder the oxidizing action of sulfite oxidase. Therefore, it has become possible to correctly measure the SO ₂ concentration in the exhaust gas that fluctuates due to fluctuations in engine oil consumption, especially on the low concentration side. In addition, the responsiveness to changes in the amount of light emission due to changes in the SO ₂ gas concentration during continuous measurement was improved.

According to the fifth to seventh aspects of the present invention, there is provided a method for measuring engine oil consumption by continuously measuring the amount of SO ₂ contained in engine exhaust gas, wherein the exhaust gas sO ₃ dissolved in contact with a trap solution flowing through the sO ₂ gas in the gas continuously ^2-
A step of the ion, SO ₃ by passing through a bioreactor comprising said aqueous sulfite oxidase ^2-
Oxidizing the ions to SO ₄ ²⁻ ions and generating hydrogen peroxide; and continuously oxidizing the trap solution with an aqueous solution of isoluminol and peroxidase to oxidatively decompose isoluminol by the hydrogen peroxide in the trap solution. In a method for measuring engine oil consumption, which comprises a means for continuously quantifying the amount of SO ₂ by detecting the amount of chemiluminescence associated with SO ₂ , SO _{2 in} exhaust gas is used as means for eliminating interference by CO ₂ gas. The pH of the trap solution that continuously flows in contact with the gas is 3.5 to
Since it is adjusted to 4.5, the chemiluminescence amount in the subsequent process can be made almost 100%, and SO ₂ gas in the engine exhaust gas is affected by CO ₂ gas contained in a large amount in the exhaust gas. It is possible to perform continuous measurement without any need, and as a result, highly sensitive continuous measurement of engine oil consumption can be performed.

In the inventions of claims 5 to 7, the pH of the aqueous solution in which the SO ₂ gas in the exhaust gas is dissolved is adjusted to 3.5 to 4.5.
This is because the solubility of O ₂ gas is lowered and the relative luminous intensity is lowered, and when PH exceeds 4.5, the interference effect by the dissolved CO ₂ gas is increased. Further, when the pH range of the aqueous solution is set to 3.5 to 4.0, the relative luminous intensity is further improved. Therefore, the pH range of the aqueous solution is preferably 3.5 to 4.0.

The method for measuring engine oil consumption according to claims 8 to 12 of the present invention is a method for measuring engine oil consumption by continuously measuring the amount of SO ₂ contained in engine exhaust gas. Therefore, a step of contacting SO ₂ gas in the exhaust gas with a continuously flowing trap solution to dissolve it to form SO ₃ ²⁻ ions, and passing the aqueous solution through a bioreactor made of sulfite oxidase A step of oxidizing ₃ ²⁻ ions to SO ₄ ²⁻ ions and generating hydrogen peroxide; and a step of continuously reacting the trap solution with an aqueous solution of isoluminol and peroxidase to produce isoluminol by the hydrogen peroxide in the trap solution. engine and means for continuously quantifying the sO ₂ amount by detecting the amount of chemiluminescence due to the oxidative decomposition of The measuring method yl consumption,
By passing an exhaust gas or a trap solution in which SO ₂ in the exhaust gas is dissolved through an insoluble carrier, or by allowing an organic solvent to act on the trap solution in which the exhaust gas is dissolved,
Since the organic substances such as hydrocarbons in the exhaust gas are adsorbed and removed, it is possible to prevent the negative interference on either or both of the bioreactor by the hydrocarbons or the chemiluminescent reaction by the isoluminol.

The engine oil consumption measuring device according to the thirteenth to fourteenth aspects of the present invention is a device for measuring the engine oil consumption by continuously measuring the amount of SO ₂ contained in the engine exhaust gas. Therefore, the exhaust gas is continuously taken in from the engine exhaust pipe and S in the exhaust gas is converted to S
A gas intake part that burns into O ₂ and sends it to the gas exchange part, and a trap solution are continuously supplied, and SO ₂ in the exhaust gas from the gas intake part is brought into contact with the trap solution to dissolve it and SO ₂ is dissolved in SO ₂ . Oxidizing SO ₃ ²⁻ ions to SO ₄ ²⁻ ions by passing the trap solution through a bioreactor consisting of sulfite oxidase as a ₃ ²⁻ ion and sending the trap solution to the SO ₂ detecting part. Together with hydrogen peroxide, and then the trap solution is continuously reacted with an aqueous solution of isoluminol and peroxidase to detect the chemiluminescence amount accompanying the oxidative decomposition of isoluminol by the hydrogen peroxide in the aqueous solution. the measuring device of the engine oil consumption consisting of sO ₂ detector to continuously quantify ₂ amount, or the gas uptake section The exhaust gas or the trap solution from the gas exchange section is once attached with a column filled with an insoluble carrier through which the trap solution from the gas exchange section in the detection section is passed. The organic solvent mixing means for mixing a hydrophobic, water-insoluble organic solvent, and a separator for separating the organic solvent from the mixture of the aqueous solution and the organic solvent are attached so that hydrocarbons in exhaust gas, etc. Since organic substances can be adsorbed and removed, it is possible to prevent negative interference with either or both of the bioreactor using hydrocarbon or the like and the chemiluminescent reaction using isoluminol.

The method for measuring engine oil consumption according to claims 15 to 18 of the present invention is a method for measuring engine oil consumption by continuously measuring the amount of SO ₂ contained in engine exhaust gas. Therefore, the exhaust gas is continuously taken in from the engine exhaust pipe and S in the exhaust gas is converted to S
An exhaust gas intake step of combusting into O ₂ and sending it to the gas exchange section, and a SO solution in the exhaust gas from the exhaust gas intake section for continuously supplying the trap solution to the trap solution.
The SO ₂ is dissolved by contacting ₂ and SO ₃ ^2-ions and gas exchange process to send the trap solution SO ₂ detector, SO ₃ ² by passing through a bioreactor comprising said trapping solution sulfite oxidase ^- to generate hydrogen peroxide with oxidizes the ions sO ₄ ^2-ions, then oxidative decomposition of isoluminol according to the hydrogen peroxide of said trap solution continuously reacting the trap solution and isoluminol and peroxidase solution the measuring method of the engine oil consumption consisting of sO ₂ detection step of continuously quantifying the sO ₂ amount by detecting the amount of chemiluminescence due to, in the exhaust gas uptake step,
Heating the sampling pipe that introduces exhaust gas to keep it warm,
When combusting S in the exhaust gas, the exhaust gas is brought into contact with a sufficiently heated granular material or a catalyst agent that selectively oxidizes the S component, or the exhaust gas after combusting the contained S into SO ₂ SO such as diluting with active gas
_{Since a} sampling securing process has been added, when sampling the exhaust gas, it is possible to prevent the S component in the exhaust gas from adsorbing on the inner wall of the sampling pipe system or being absorbed by dew condensation water, and unburned in the exhaust gas. When the components are completely oxidized and SO ₂ is produced and introduced into the SO ₂ component detection step, stable measurement results can be obtained.

The engine oil consumption measuring device according to claims 19 to 20 of the present invention is a device for measuring engine oil consumption by continuously measuring the amount of SO ₂ contained in engine exhaust gas. Therefore, the exhaust gas is continuously taken in from the engine exhaust pipe and S in the exhaust gas is converted to S
An exhaust gas intake section that burns into O ₂ and sends it to the gas exchange section, and a trap solution that continuously supplies SO _{2 in} the exhaust gas from the exhaust gas intake section to the trap solution
To dissolve SO ₂ into SO ₃ ²⁻ ions and to pass the trap solution to the SO ₂ detection section, and to pass the trap solution through a bioreactor consisting of sulfite oxidase to form SO ₃ ²⁻ ions. Is oxidized to SO ₄ ^2- ions and hydrogen peroxide is generated, and then the trap solution is continuously reacted with an aqueous solution of isoluminol and peroxidase to accompany the oxidative decomposition of isoluminol by the hydrogen peroxide in the trap solution. An engine oil consumption measuring device comprising an SO ₂ detector for continuously quantifying the amount of SO ₂ by detecting the amount of chemiluminescence, and sampling for incorporating exhaust gas after combustion of S in SO ₂ into SO _2. Divide the piping so that most of the exhaust gas is exhausted from one of the sambling pipes through the pressure regulator, and the other A part of the exhaust gas from the ring pipe is taken into the gas exchange part, and the gas exchange part is equipped with a glass instrument consisting of a spiral glass tube that dissolves SO ₂ in the exhaust gas into the trap solution, etc. Since the SO ₂ sampling securing means of is added, when sampling the exhaust gas, it is prevented that the S component in the exhaust gas is adsorbed on the inner wall of the sampling pipe system and is not absorbed by the dew condensation water. When the unburned components are completely oxidized and SO ₂ is produced and introduced into the SO ₂ component detection step, stable measurement results can be obtained.

[0045]

DESCRIPTION OF THE PREFERRED EMBODIMENTS A preferred embodiment of the present invention will be described with reference to the drawings while comparing it with a conventional example. Before that, an embodiment of the engine oil consumption measuring device according to claim 19 used in this embodiment will be described with reference to the schematic configuration diagram of FIG. This engine oil consumption measuring device continuously takes in exhaust gas from the engine exhaust pipe 14, and extracts S component in the exhaust gas as S component.
Gas intake unit 1 that burns O ₂ and sends it to the gas exchange unit 70
A gas exchange unit 70 sends dissolved as ions to SO ₂ detector 90, ^- 0, continuously trapped solution SO ₂ in the exhaust gas by supplying SO ₂ in the exhaust gas SO ₃ ² captured
Ions SO ₄ ^- SO ₃ ² by passing the bioreactor 92 of this trap solution sulfite oxidase
^After oxidizing ^2- ion and generating hydrogen peroxide, the aqueous solution is continuously reacted with an aqueous solution of isoluminol and peroxidase to detect the chemiluminescence amount accompanying the oxidative decomposition of isoluminol by hydrogen peroxide in the aqueous solution. SO ₂ detector 9 for continuously quantifying the amount of SO ₂ by
It consists of 0.

First, the structure of the gas intake portion 10 will be described. One end of the sampling pipe 12 is connected to the engine exhaust pipe 14 and reaches the filter box 18 via a three-way valve 16 for introducing air or standard gas. In the sambling pipe 12 between the three-way valve 16 and the filter box 18,
A first hot hose 20 composed of a flexible tube, a heater and a heat insulating material is attached to keep the exhaust gas taken into the sampling tube 12 at 130 ° C.

The filter of the filter box 18 is a glass fiber filter coated with Teflon. By passing the exhaust gas, fine particles in the exhaust gas are filtered to prevent damage to the components of the sampling pipe system. Like the hot hose, the filter box 18 uses the heater and the heat insulating material to remove exhaust gas passing therethrough.
Hold at 20 ° C.

An O ₂ gas supply pipe 22 is connected to the sampling pipe 12 coming out of the filter box 18, and a high-purity O ₂ gas set to a predetermined flow rate from an O ₂ gas cylinder 24 through a mass flow controller 26 passes through a solenoid valve 28. Supplied through. The exhaust gas supplied with oxygen gas is 120
Combustion components such as S in the exhaust gas passed through the combustion furnace 30 heated to 0 ° C. are oxidized.

A sectional view of the combustion furnace 30 is as shown in FIG. 2. The sampling tube 12a in the combustion furnace 30 is a transparent quartz tube, and the heat-resistant granular material 32 ( For example, SiC beads, quartz beads) or a catalyst agent 34 for selectively oxidizing the S component
(For example, Ni, Co, M on the surface of the base material of SiO ₂ , TiO ₂
n, Cr, etc.) to increase the contact area between the exhaust gas and the fully heated granular material 32 or the catalyst agent 34 to oxidize unburned components in the exhaust gas to generate SO ₂ . It has a structure that allows it.

Sampling tube 12a inside combustion furnace 30 and sampling tube 12 outside combustion furnace 30 (made of stainless steel)
A cylindrical ceramic pipe joint 38 attached to the opening hole 36 of the combustion furnace is used for the connection with the ceramic pipe joint 38, and the ceramic coating agent 40 is applied to the gaps between the ceramic pipe joint 38 and the sampling pipe 12a and the sampling pipe 12. Glued. The thermocouple 43 for monitoring the temperature inside the combustion furnace 30 is a platinum-platinum-rhodium alloy provided inside the sampling tube 12a and covered with a metal protective tube (for example, Inconel) that can be used in various severe corrosive environments at high temperatures. I was there. To replace the granular material 32 or the catalyst agent 34 filled in the sampling pipe 12a inside the combustion furnace 30, remove the pipe joint 42 used to connect the sampling pipes (made of stainless steel) outside the combustion furnace 30 to each other. The structure which can be easily performed by removing the cap 44 inserted in the inside of 12 is adopted.

The sampling pipe 12 exiting the combustion furnace 30 receives the exhaust gas introduced by the second hot hose 46 as 120
The temperature is maintained at 0 ° C. and the air supply pump 48 is connected. This air supply pump 48 is heat-resistant and introduces exhaust gas from the engine exhaust pipe 14 into the sampling pipe 12, or the three-way valve 1
A standard gas or the like from 6 is introduced into the sampling pipe 12, and these gases are sent to the gas exchange section 70.

A pressure regulator 50 and a fine meter 52, which is a flow meter, are attached to the sampling pipe 12 on the discharge side of the air supply pump 48, and by applying back pressure to the discharge side of the air supply pump 48, A certain amount of exhaust gas can be sampled even when the exhaust gas emission amount changes depending on the operating state. Also, the pressure regulator 5
The 0 and the sampling tube 12 between the fine meter 28, and the N ₂ gas supply pipe 54 is attached, N ₂ gas is supplied from the N ₂ gas cylinder 55.

The above structure is adopted because the molecular exchange membrane 72 of the next gas exchange section 70 to which the exhaust gas is supplied is made of Teflon molecular exchange membrane and cannot be heated above 80 ° C. due to its structure. From the exhaust gas intake port of the gas intake unit 10 to immediately after the air supply pump 48 or the pressure regulator 50, the S component in the exhaust gas is not adsorbed by the sampling pipe 12 and the inner wall of its constituent parts, or absorbed by the condensed water. As described above, the exhaust gas is kept at a predetermined temperature, and the exhaust gas is diluted with a high-purity inert gas (for example, N ₂ gas) in the flow passage in the subsequent stage of the air supply pump 48 or the pressure regulator 50. Reduces the water vapor concentration, prevents the exhaust gas from condensing on the sampling pipe 12 and other components of the gas intake part 10, and stabilizes the SO ₂ component even at 80 ° C. or less. It can be introduced into the exchange section 70.

Explaining the structure of the gas exchange section 70, the exhaust gas obtained by oxidizing the S component from the sampling tube 12 of the gas intake section 10 into SO ₂ gas is introduced into the molecular exchange membrane 72. On the other hand, from the trap solution tank 74 to the molecular exchange membrane 72 by the pump 76, the trap solution 7
5 is supplied. Therefore, SO ₂ in the exhaust gas supplied to the molecular exchange membrane 72 is dissolved in the trap solution to become SO ₃ ²⁻ ions, and this aqueous solution is sent to the SO ₂ detection unit 90. On the other hand, the exhaust gas after SO ₂ is dissolved in the aqueous solution is exhausted from the molecular exchange membrane 72.

The trap solution containing SO ₃ ²⁻ sent to the SO ₂ detection section 90 passes through the bioreactor 92 in which sulfite oxidase (derived from chicken liver) is fixed on glass beads, so that the SO ₃ ²⁻ Ions are oxidized to SO ₄ ²⁻ ions, and one molecule of H ₂ O ₂ is generated for one molecule of SO ₂ ²⁻ ions. A reaction solution 95 composed of a mixed solution of isoluminol and peroxidase is sent from the reaction solution tank 94 to the trap solution exiting the bioreactor 92 by a pump 96. The trap solution mixed with the reaction solution immediately passes through the chemiluminescence detector 98, but the isoluminol in the reaction solution reacts with H ₂ O ₂ in the trap solution to be oxidized, and the oxidant thereof is immediately decomposed. It produces chemiluminescence. By measuring this luminescence with the chemiluminescence detector 98, the S component contained in the exhaust gas can be quantified, and as a result, the engine oil consumption amount can be measured.

The reaction principle after the molecular exchange membrane is as follows. SO ₂ + H ₂ O → SO ₃ ^2- + 2H ⁺ (molecular exchange membrane) SO ₃ ^2- + H ₂ O + O ₂ → SO ₄ ^2- + H ₂ O ₂ (bioreactor) H ₂ O ₂ + isoluminol → isoluminol oxide → Luminescence + decomposition products

Next, examples of the inventions of claims 1 to 4 will be described in examples 1 to 3. (Example 1) A three-way valve 16 is manufactured by using the apparatus shown in FIG.
From this, a standard SO ₂ gas containing 5 ppb and 10 ppb of SO ₂ was continuously introduced for 10 minutes, the emission intensity was measured, and the relationship diagram between the obtained emission intensity and time is shown in FIG.

As is apparent from FIG. 3, although the SO ₂ gas concentration is switched by the cock operation within a time of 1 second, the change in the emission intensity accompanying it is stable from the rising of the signal. It took about 3 minutes. This tendency was also observed in returning to baseline when returning from 10 ppb to 0 ppb.

Therefore, as shown in FIG. 4, after the gas and the trap solution are brought into contact with each other by the molecular exchange membrane 72, the pump 7
8 from tank 79 to 10 ^-5 M NAD ⁺ , 0.0
The SO ₃ ²⁻ ion stabilizing solution 80 consisting of 1M phosphate buffer (PH8) was combined at a flow rate of 0.5 ml / min, the same experiment as above was performed, and the results are shown in FIG.

As is apparent from FIG. 5, the time from the rise of the signal to reaching the stable state was shortened to 10 seconds, and the return to the baseline when returning from 10 ppb to 0 ppb was also extremely good. . This effect is SO
It is considered that the adsorption of ₃ ²⁻ ions on the glass beads using the Teflon pipe or the enzyme reactor could be prevented by joining the NAD ⁺ solution.

Example 2 In Example 1, NAD ⁺
Under the condition that the solution does not join, the three-way valve 16
₂ was sequentially introduced with a standard SO ₂ gas containing 0 ppb to ₂₀ ppb, the emission intensity of each was measured, and the emission intensity and S
A relational diagram with the O ₂ content is shown in FIG. As shown in FIG. 6, in the SO ₂ low concentration region of 20 ppb or less, S
The relationship between the O ₂ concentration and the emission intensity was not a linear relationship, but a convex curve was shown below.

Then, as shown in FIG. 4, after the gas and the trap solution are brought into contact with each other by the molecular exchange membrane 42, a pump 78 is used.
The buffer solution 80 containing 10 ⁻⁴ M acetic acid amide and 0.01 M Tris-hydrochloric acid (PH 8.5) was added at 0.5 ml / mi.
The same experiment as above was performed, and the results are shown in FIG. 7.

As shown in FIG. 7, the relationship between the emission intensity and the SO ₂ concentration showed a good linear relationship. SO ₃ ^2-
Ions have a property of being easily oxidized to SO ₄ ²⁻ ions by dissolved oxygen or the like, and if they become SO ₄ ²⁻ , they will not react with the enzyme reactor. It is considered that what was subjected to the oxidizing action when the SO ₃ ²⁻ ion had a low concentration was prevented by the addition of the acid amide compound, and as a result, the linearity was improved.

Example 3 In the engine oil consumption measuring device shown in FIG. 4, the SO ₃ ²⁻ ion stabilizing solution 80 was used.
When using the 10 ^-4 M acetamide solution as, SO ₃
Optimum ionic strength and optimum pH of the ^2- ion stabilizing solution 48
In order to obtain P, the amount of light emission and the ion concentration when P is kept constant and the ionic strength is changed are kept constant.
The amount of light emission when H was changed was measured. Tris-HCl is used as the buffer component and 2
SO ₂ gas of 0 ppb was used. The amount of light emission was expressed in counts / minute, and the obtained results are shown in Table 1. As is clear from the results in Table 1, the strongest amount of light emission was obtained when the ionic strength was in the range of 0.001 to 01 and the PH was 7 to 9.

[0065]

[Table 1]

Next, the embodiments of claims 5 to 7 will be described.
The description will be made in Examples 4 to 7. (Example 4) Measurement of engine oil consumption shown in FIG.
In the device, from the three-way valve 16 to SO ₂0-100pp
Introduction of standard gas containing b at a rate of 2 liters / min
Then, while keeping the temperature at 120 ° C,
O after passing through the filter box 18.₂Gas supply pipe 20
Blow at a rate of 0.1 liter / min of pure oxygen gas
While watching, let it pass through the combustion furnace 22 heated to 1200 ° C.
By doing so, the S component in the gas was burned.

Next, for 1 liter of burnt gas,
9 liters of pure nitrogen gas was mixed from the N ₂ gas supply pipe 32, adjusted to 10 liters / min by the fine meter 52 and sent to the molecular exchange membrane 72. On the other hand, molecular exchange membrane 7
Into the inside of 2, the water is supplied from the trap solution tank 74 as a trap solution for trapping the gas component, and a water pump 76 is provided.
Then, the solution was sent at a flow rate of 1 liter / min, and SO ₂ in the gas was transferred to the trap solution through the molecular exchange membrane 72 to form SO ₃ ²⁻ ions.

When the trap solution containing the SO ₃ ²⁻ ions is passed through the bioreactor 92, the SO ₃ ²⁻ ions in the trap solution are oxidized to SO ₄ ²⁻ ions and at the same time the SO ₃ ²⁻ ions are oxidized. One molecule of H ₂ O ₂ was generated for each molecule. Subsequently, a reaction solution 95 composed of a mixed solution of isoluminol and peroxidase is sent to the trap solution by a pump 96 and mixed, and at the same time, the chemiluminescence detector 9
8 was passed. In this chemiluminescence detector 98, isoluminol in the reaction solution was oxidized by reacting with H ₂ O ₂ in the trap solution, and the oxidant was immediately decomposed and the chemiluminescence generated at that time was measured. Standard SO under these conditions
_The results of measuring _two gases are shown in FIG. As shown in FIG. 8, a good straight line was shown up to SO ₂ 100 ppb, and the minimum detection sensitivity was 5 ppb.

Next, examples of claims 5 to 7 of the present invention will be described below. (Embodiment 5) Using the measuring apparatus for engine oil consumption shown in FIG. 1, it was examined what effect the CO ₂ gas contained in the exhaust gas had on the measurement under the measurement conditions of the embodiment 4. The standard SO ₂ gas concentration to be introduced is 50 pp
fixed to b, mixed with CO ₂ gas in the range of 0 to 20%,
The luminescence amount of each was measured. The obtained results are shown in FIG. 9 as a relational diagram in which the vertical axis is the relative light emission amount% when the light emission amount is 100 when the CO ₂ gas mixture amount is 0%, and the horizontal axis is the mixed CO ₂ volume%. It was As is clear from FIG.
The amount of light emission decreased as the amount of CO ₂ gas mixed increased, and the amount of light emission decreased by about 30% at 15%, which is considered to be the CO ₂ concentration in the engine exhaust gas.

Example 6 Although water was used as the gas trap solution in Example 5, in this example, 0.01 was used.
An experiment similar to that of Example 5 was performed using M acetate buffer PH4, and the obtained results are similar to those of Example 5, with the vertical axis representing CO.
FIG. 10 shows a relationship diagram in which the relative amount of emitted light is 100 when the amount of emitted light when the mixed amount of _two gases is 0% is 100 and the mixed CO ₂ volume% is on the horizontal axis. As is clear from FIG.
Even when the CO ₂ concentration was 20%, the relative luminescence amount hardly decreased, and the absolute luminescence amount was not different from that when water was used as the trap solution.

(Example 7) The CO ₂ concentration of the introduced gas was fixed at 20%, the SO ₂ concentration was fixed at 50 ppb, and the pH of the gas trap solution was changed. Under the same measurement conditions as in Example 4, the emission intensity was changed. Was measured. 0.01 for PH adjustment
Citrate buffer was used. The results obtained are C on the vertical axis.
FIG. 11 shows a relative light emission amount% with the light emission amount as 100 when the O ₂ gas mixture amount is 0%, and the PH of the gas trap solution on the horizontal axis.

As is clear from FIG. 11, PH3.5-
At 4.5, a luminescence amount of almost 100% was obtained as the relative luminescence intensity, but at PH before and after that, the relative luminescence intensity drastically decreased. The cause of this is SO on the low PH side.
_This is because the solubility of the ₂ gas decreases, and it is considered that this is due to the buffering effect of the dissolved CO ₂ gas on the high PH side.
Further, as shown in FIG. 11, the emission intensity was particularly excellent in the PH range of 3.5 to 4.

Next, examples of the engine oil consumption measuring method and apparatus according to claims 8 to 14 will be described in Examples 8 to 10. (Embodiment 8) Using the measuring apparatus for engine oil consumption shown in FIG. 1, exhaust gas is introduced from the engine exhaust pipe 14 at a rate of 2 liters / min. S in exhaust gas of automobile gasoline engine
The emission intensity of the O ₂ content was continuously analyzed by a chemiluminescence detector 98. When performing this measurement, an engine fuel containing no S component was used, and all S components discharged into the exhaust gas were derived from engine oil. The engine operating conditions were 750 rpm and the torque was 0 kg · m. The results of the continuous analysis are shown in FIG.

As shown in FIG. 12, the SO in the exhaust gas is
_{2 Since the} concentration is constant, the obtained chart should be such that a constant emission intensity should be obtained while the exhaust gas is flowing, but the emission actually decreased gradually. As a cause of this, it was considered that unburned hydrocarbons contained in the exhaust gas negatively interfered with either or both of the bioreactor and the chemiluminescent reaction by isoluminol.

Therefore, as shown in FIG. 13, a column 56 (50 × 150 mm) filled with Amberlite XAD was installed between the fine meter 52 and the molecular exchange membrane 72, and the same experiment as in Example 8 was performed. As a result, the results shown in FIG. 14 were obtained. As a result, Amber Light X
It was confirmed by AD that the organic substances such as hydrocarbon contained in the exhaust gas were absorbed and removed, and the negative interference by these substances was eliminated.

(Example 9) In the engine oil consumption measuring device shown in FIG. 1, octadecyl group (C ₁₈ ) was added to the gel surface for the purpose of removing hydrophobic substances such as hydrocarbons in exhaust gas. As shown in FIG. 15, a column 56 filled with silica gel having a particle size of 5 μm and a pore size of 100 Å is
It was installed between the molecular exchange membrane 72 and the bioreactor 92. Using this apparatus, the emission intensity of the SO ₂ content in the exhaust gas of an automobile gasoline engine was continuously analyzed by a chemiluminescence detector 98 in the same manner as in Example 8. The obtained results are shown in FIG. As is clear from FIG. 16, it was found that the installation of the sludge column 56 for absorbing and removing organic substances such as hydrocarbon contained in the exhaust gas is effective in both the gas state and the aqueous solution state. .

(Embodiment 10) In the engine oil consumption measuring device shown in FIG. 1, as shown in FIG. 17, a water-insoluble organic solvent agent 58 is continuously added to the gas trap solution discharged from the molecular exchange membrane 72. Of the organic substance such as hydrocarbon contained in the gas trap solution is dissolved in the organic solvent agent, and then the aqueous solution and the organic solvent agent are separated by the separator 60, and the aqueous solution is subjected to the subsequent reaction. .

As a concrete example, an example is shown in which the operating conditions of the gasoline engine were measured at 2000 rpm and a torque of 5.0 kg · m. Ethyl acetate (1 m liter / min) was used as the organic solvent, the gas trap solution was merged at a flow rate of 1 m liter / min, and solvent extraction was performed in a 2 m line, and then a Teflon membrane (pore size 0.45 μm) was used.
FIG. 19 shows the result when the liquid was separated by the separator equipped with m) and only the aqueous solution was introduced into the subsequent reaction route. In addition, FIG. 18 shows the result without solvent extraction.

In the example of FIG. 18 in which the solvent extraction is not performed,
When the emission intensity of the exhaust gas was measured, the signal decreased rather than the background emission. This indicates that the substance that quenches chemiluminescence during operation is discharged into the exhaust gas and is transferred into the gas trap aqueous solution. On the other hand, the results shown in FIG. 19 were obtained by performing solvent extraction using ethyl acetate as shown in FIG. 17, which revealed that the chemiluminescence quenching was completely removed by ethyl acetate. did.

(Embodiment 11) An apparatus according to a nineteenth embodiment has already been described in paragraphs 0045 to 0056 based on FIG. The measuring methods of claims 15 to 18 are as described in the fourth embodiment. Therefore, an embodiment of claim 20 will be described here.

FIG. 20 shows an apparatus according to the twentieth aspect of the present invention. The structure of the gas intake unit 10 from the engine exhaust pipe 14 to the air supply pump 48 is exactly the same as that of the apparatus of the embodiment shown in FIG. In this embodiment, since it is necessary to introduce a much smaller amount of exhaust gas (0.01 liter / nin) than the discharge capacity (maximum 2 liter / min) of the air supply pump 48 into the gas exchange section 70, The sampling pipe 12 on the discharge side of the pump 48 is bifurcated, and the pressure regulator 50 is provided from one branch pipe sampling pipe 12b.
Most of the exhaust gas is exhausted via a, and a back pressure is applied to the other sampling pipe 12c on the discharge side of the air supply pump 48 by a pressure regulator 50b and a pressure gauge 62, and a heat-resistant mass flow meter 64 And a flow rate adjusting valve 66 to set a predetermined flow rate, while keeping the heat by the third hot hose 68,
The structure is such that a stable SO ₂ component can be introduced into the gas exchange section 70.

In this embodiment, the molecular exchange membrane 7 is used.
A glass instrument 82 having a spiral glass tube is used in place of 2, and the trap solution from the trap solution tank 74 is mixed with the high-temperature exhaust gas from the sampling tube 12c and allowed to flow down through the glass instrument 82. SO ₂ in the exhaust gas was dissolved in the trap solution. The structure of the SO ₂ detection unit 90 is exactly the same as that of the embodiment apparatus shown in FIG.

[0083]

In the invention of the method for measuring the engine oil consumption according to claims 1 to 4, the trap solution in which SO ₂ is dissolved has an ionic strength of 0.001 to 0.001.
0.1, pH was in the range of 7 to 9 because the addition of a stabilizing process of SO ₃ ²⁻ ions in the trap aqueous solution, such as merging with acid amide compounds, responsiveness to changes in the S content in the exhaust gas Was improved, the linearity of the emitted light amount corresponding to the change of the SO ₂ content was obtained, and the luminous intensity was increased.
In the invention of the method for measuring engine oil consumption according to claims 5 to 7, acetic acid, succinic acid,
A buffer solution containing citric acid, dimethyl glutaric acid, glycine, or the like is added to adjust the pH of the trap solution to 3.5 to 4.5.
The negative interference due to the CO ₂ gas in the SO ₂ gas detecting step can be eliminated, and the emission intensity in the SO ₂ detecting step can be improved. In the invention of the measuring method of engine oil consumption according to any one of claims 8 to 12, or the invention of the measuring apparatus for engine oil consumption according to any of claims 13 to 14, exhaust gas or SO _{3 is} contained in a column filled with an insoluble carrier. ^{Since a} hydrophobic and water-insoluble organic solvent was continuously contacted with the trap solution in which ^2- ions were dissolved or the SO ₃ ^2- ions were dissolved, the organic substances such as hydrocarbons were removed. In the SO ₂ detector, the influence of organic substances such as hydrocarbons in the exhaust gas could be prevented.
In the invention of the method for measuring the engine oil consumption according to any one of claims 15 to 18, or the invention of the measuring apparatus for the engine oil consumption according to any one of claims 19 to 20, the exhaust gas is introduced into the exhaust gas intake portion. Exhaust gas after combustion of S contained in SO ₂ by heating the sampling tube to keep it warm and bringing it into contact with a sufficiently heated granular material or a catalyst agent that selectively oxidizes S component when combusting S in the exhaust gas Since the exhaust gas was diluted with the inert gas, the S component in the exhaust gas can be completely oxidized together with other unburned substances, the water vapor concentration can be reduced, and the sampling pipe and other components of the gas intake section can be reduced. Further, it is possible to prevent the exhaust gas from being condensed and to introduce a stable SO ₂ component into the gas exchange section.

[Brief description of drawings]

FIG. 1 is a schematic configuration diagram of an engine oil consumption measuring device according to claim 19 of the present invention.

FIG. 2 is a detailed sectional view of a combustion furnace of the engine oil consumption measuring device of FIG.

FIG. 3 is a diagram showing the relationship between emission intensity and measurement time, showing the results of measurement of standard SO ₂ gas by a conventional method for measuring engine oil consumption.

FIG. 4 is a schematic configuration diagram of a measuring device used in the method for measuring engine oil consumption according to claims 1 to 4 of the present invention.

FIG. 5 is a relationship diagram between emission intensity and measurement time, which shows the result of measuring standard SO ₂ gas by the method for measuring engine oil consumption according to claims 1 to 4.

FIG. 6 shows the emission intensity and SO _{2 of} standard SO ₂ gas measured by a conventional method for measuring engine oil consumption.
It is a relationship diagram with content.

FIG. 7 is a relationship diagram between emission intensity and SO ₂ content, showing the results of measurement of standard SO ₂ gas by the method for measuring engine oil consumption according to claims 1 to 4.

FIG. 8 is a graph showing the relationship between emission intensity and SO ₂ content, showing the results of measurement of standard SO ₂ gas by the engine oil consumption measuring device according to claim 19 of the present invention.

FIG. 9 shows a standard SO ₂ gas mixed with CO ₂ gas,
FIG. ₂ is a relational diagram between emission intensity and CO ₂ content, which shows the result of measurement using the measuring device of FIG. 1.

FIG. 10 shows emission intensity and CO indicating a result of measurement of a gas obtained by mixing CO ₂ gas with standard SO ₂ gas using the method for measuring engine oil consumption according to claims 5 to 7 of the present invention. ₂ is a relationship diagram with ₂ content.

FIG. 11 shows the results of measuring the emission intensity under the same measurement conditions as in Example 4, with the CO ₂ concentration of the introduced gas fixed at 20% and the SO ₂ concentration fixed at 50 ppb, and the pH of the gas trap solution changed. FIG. 4 is a relationship diagram between relative emission intensity and PH indicating

FIG. 12 is a diagram showing the relationship between emission intensity and measurement time, which shows the result of measurement of automobile exhaust gas by a conventional method for measuring engine oil consumption.

FIG. 13 is a schematic configuration diagram of a measuring device used in the method for measuring engine oil consumption according to claim 8 to claim 12 of the present invention.

FIG. 14 is a relationship diagram between emission intensity and measurement time, which shows the result of measurement of automobile exhaust gas by the method for measuring engine oil consumption according to claim 8 to claim 12 of the present invention.

FIG. 15 is a schematic configuration diagram of a measuring device used in the method for measuring engine oil consumption according to claim 8 to claim 12 of the present invention.

FIG. 16 is a relationship diagram between emission intensity and measurement time showing the result of measurement of automobile exhaust gas by the method for measuring engine oil consumption according to claim 8 to claim 12 of the present invention using the device shown in FIG. 15. is there.

FIG. 17 is a line diagram showing a schematic configuration of a main part of an engine oil consumption measuring device according to claim 14 of the present invention.

FIG. 18 is a diagram showing the relationship between emission intensity and measurement time, which is the result of measuring automobile exhaust gas by a conventional method for measuring engine oil consumption.

FIG. 19 is a diagram showing the relationship between the emission intensity and the measurement time, which shows the result of measurement of automobile exhaust gas by the method for measuring engine oil consumption according to claim 8 to claim 12 of the present invention.

FIG. 20 is a schematic configuration diagram of an embodiment of an engine oil consumption measuring device according to claim 20 of the present invention.

[Explanation of symbols]

10 ... Gas intake part 12 ... Sampling pipe 14 ... Engine exhaust pipe 16 ... 3-way valve 18 ... Filter box 20. No. 1 hot hose 22 ... O ₂ gas supply pipe 30 ... Combustion furnace 32 ... Granular object 34 ... Catalytic agent 46 ... Second hot hose 48 ... Air supply pump 50 ... Pressure regulator 52 ... Fine meter 56 ... Column 58 ... Organic solvent 60 ... Separator 62. ··· Pressure gauge 64 ·· Mass flow meter 66 ·· Flow control valve 68 ·· Third hot hose 70 ·· Gas exchange unit 72 ·· Molecule Exchange membrane 75: Trap solution 80: Ion stabilizing solution 82 ... Glassware 90 ----- SO ₂ detector 92 ..... bioreactor 95 ----- reaction 98 ----- chemiluminescence detector

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Mika Nakayama, Nagakute-cho, Aichi-gun, Aichi Prefecture 1 No. 41 Yokochi, Toyota Central Research Institute Co., Ltd. (72) Inventor Osamu Asami Nagakute-cho, Aichi-gun, Aichi Prefecture 1 at 41 Chuo-dori, Toyota Central Research Institute Co., Ltd. (72) Inventor Yukio Yamada, Nagachite-cho, Aichi-gun, Aichi Prefecture, Nagatoji 1-41 Yokodoko Research Co., Ltd. (72) Inventor Hiroyuki Narita Aichi 1 in 41, Yokota, Nagakute-machi, Aichi-gun 1 in Toyota Central Research Laboratory, Inc. (72) Inventor, Kizo Hayakawa 1 in 41, Yokota, Nagakute-machi, Aichi-gun, Aichi-gun 1 in Toyota Central Research Institute (72) ) Inventor Toshiaki Tanaka 1 Toyota-cho, Toyota-shi, Aichi Toyota Motor Co., Ltd.

Claims (20)

[Claims] 1. A method for measuring engine oil consumption by continuously measuring the amount of SO ₂ contained in engine exhaust gas, wherein the trap solution continuously flows SO ₂ gas in the exhaust gas. Contact with and dissolve S
O ₃ ²⁻ ions, a step of oxidizing the SO ₃ ²⁻ ions into SO ₄ ²⁻ ions and generating hydrogen peroxide by passing the trap solution through a bioreactor consisting of sulfite oxidase, The amount of SO ₂ is continuously quantified by continuously reacting the trap solution with an aqueous solution of isoluminol and peroxidase and detecting the chemiluminescence amount accompanying the oxidative decomposition of isoluminol by the hydrogen peroxide in the trap solution. And a step of contacting SO ₂ gas in the exhaust gas with a continuously flowing trap solution to dissolve it into SO ₃ ²⁻ ions,
A method for measuring engine oil consumption, characterized in that a step of stabilizing O ₃ ^2- ions and a step of preventing adsorption are added. 2. The step of stabilizing and adsorbing SO ₃ ²⁻ ions, wherein the stabilizing solution having the effect of stabilizing SO ₃ ²⁻ ions and adsorbing SO ₃ ²⁻ ions is added to the trap solution in which the SO ₃ ²⁻ is dissolved. The method of measuring engine oil consumption according to claim 1, wherein the method is a step of merging. 3. The stabilizing solution having the effect of stabilizing SO ₃ ²⁻ ions and preventing adsorption is an aqueous solution of an acid amide compound, and the ionic strength of the aqueous solution is 0.001 to 0.001.
The method for measuring engine oil consumption according to claim 2, wherein 0.1 and PH are in the range of 7 to 9. 4. The acid amide compound is nicotinamide adenine dinucleotide (NAD) or having 2 to 4 carbon atoms.
The method for measuring engine oil consumption according to claim 3, wherein the acid amide compound is a linear or branched carboxylic acid. 5. A method for measuring engine oil consumption by continuously measuring the amount of SO ₂ contained in engine exhaust gas, the trap solution continuously flowing SO ₂ gas in the exhaust gas. Contact with and dissolve S
A step of forming O ₃ ²⁻ ions, a step of oxidizing the SO ₃ ²⁻ ions into SO ₄ ²⁻ ions and generating hydrogen peroxide by passing the trap solution through a bioreactor consisting of sulfite oxidase, A step of continuously quantifying the amount of SO ₂ by continuously reacting the aqueous solution with an aqueous solution of isoluminol and peroxidase, and detecting a chemiluminescence amount accompanying oxidative decomposition of isoluminol by the hydrogen peroxide in the trap solution. the measuring method of the engine oil consumption consisting of, to eliminate interference due to CO ₂ gas to the step of the said sO ₂ gas in the exhaust gas is contacted with a continuous flow trapped solution and dissolved sO ₃ ^2-ion A method for measuring engine oil consumption, characterized by adding steps. 6. The step of eliminating interference by the CO ₂ gas is a step of adding a buffer solution to the trap solution to adjust the pH of the trap solution to 3.5 to 4.5. Item 5. A method for measuring engine oil consumption according to Item 5. 7. The method according to claim 6, wherein the main component of the buffer solution is acetic acid, succinic acid, citric acid, dimethyl glutaric acid or glycine. 8. A method for measuring engine oil consumption by continuously measuring the amount of SO ₂ contained in engine exhaust gas, the trap solution continuously flowing SO ₂ gas in the exhaust gas. Contact with and dissolve S
A step of forming O ₃ ²⁻ ions, and a step of oxidizing the SO ₃ ²⁻ ions into SO ₄ ²⁻ ions and generating hydrogen peroxide by passing the trap solution through an immobilization reactor composed of sulfite oxidase. The SO ₂ amount is continuously quantified by continuously reacting the aqueous solution with an aqueous solution of isoluminol and a peroxidase and detecting a chemiluminescence amount accompanying oxidative decomposition of isoluminol by the hydrogen peroxide in the trap solution. In a method for measuring engine oil consumption comprising the steps of: contacting a SO ₂ gas in the exhaust gas with a continuously flowing trap solution or contacting the SO ₂ gas in the exhaust gas with a continuously flowing trap solution. After that, the engine is characterized by adding a process to prevent interference by organic substances such as hydrocarbons. Measurement method yl consumption. 9. The step of preventing interference by an organic substance such as hydrocarbon, the exhaust gas or the SO ₃ ²⁻ ion is applied to a column packed with an insoluble carrier having an adsorption ability for an organic substance such as hydrocarbon. The method for measuring engine oil consumption according to claim 8, wherein the method is a step of passing the dissolved trap solution. 10. The step of preventing interference by an organic substance such as hydrocarbon comprises a step of bringing SO ₂ gas in the exhaust gas into contact with a continuously flowing trap solution to dissolve it to form SO ₃ ²⁻ ions. And a step of subsequently contacting the trap solution in which the SO ₃ ²⁻ ions are dissolved with a hydrophobic water-insoluble organic solvent to extract only the organic substance into the organic solvent. Claim 8
Measuring method of engine oil consumption described in. 11. The insoluble carrier according to claim 9, which has a monomethyl group, a tetramethyl group, an octyl group, an octadecyl group or a phenyl group on the surface of the silica gel or the polymer gel itself or on the surface thereof. How to measure engine oil consumption. 12. The method for measuring engine oil consumption according to claim 10, wherein the hydrophobic and water-insoluble organic solvent is ethyl acetate, dichloromethane, or dichloroethane. 13. SO ₂ contained in engine exhaust gas
A device for measuring engine oil consumption by continuously measuring the amount of exhaust gas, which continuously takes in exhaust gas from an engine exhaust pipe and burns S in exhaust gas to SO ₂ and sends it to a gas exchange section. a gas intake section, said trap solution sO ₂ was sO ₂ dissolved by contacting sO ₂ in the exhaust gas from the continuously feeding trap solution the trap solution gas uptake section and sO ₃ ^2-ion
By passing the gas exchange section to the detection section and the trap solution through a bioreactor consisting of sulfite oxidase, SO ₃ ²⁻ ions are converted to SO ₄ ^2−.
It is oxidized to ions and hydrogen peroxide is generated, and then the trap solution is continuously reacted with an aqueous solution of isoluminol and peroxidase to detect chemiluminescence amount due to oxidative decomposition of isoluminol by the hydrogen peroxide in the aqueous solution. the trap solution from the in engine oil consumption measurement device comprising a sO ₂ detector to continuously quantify sO ₂ amount, the exhaust gas or the gas exchange unit from the gas intake section by the following An engine oil consumption measuring device equipped with a column filled with an insoluble carrier that is once passed through before the process. 14. SO ₂ contained in engine exhaust gas
A device for continuously measuring the engine oil consumption by continuously measuring the amount, in which exhaust gas is continuously taken in from the engine exhaust pipe and S in the exhaust gas is burned to SO ₂ for gas exchange section. And a trap solution continuously fed to the trap solution, SO ₂ in the exhaust gas from the gas intake section is brought into contact with and dissolved in the trap solution, and SO _{2 is changed} to SO ₃ ²⁻ ion, and the trap solution is SO ₂ By passing the gas exchange section to the detection section and the trap solution through a bioreactor consisting of sulfite oxidase, SO ₃ ²⁻ ions are converted to SO ₄ ^2−.
Oxidation to ions and generation of hydrogen peroxide, and then the trap solution is continuously reacted with an aqueous solution of isoluminol and peroxidase to detect chemiluminescence amount due to oxidative decomposition of isoluminol by the hydrogen peroxide in the trap solution. in continuous engine oil consumption measurement device comprising a sO ₂ detector to quantify the sO ₂ amount by, the flow path of the trap solution from the gas exchange unit in the sO ₂ detector, hydrophobic An apparatus for measuring engine oil consumption, comprising: an organic solvent mixing means for mixing an organic solvent insoluble in water, and a separator for separating the organic solvent from a mixture of the trap solution and the organic solvent. 15. SO ₂ contained in engine exhaust gas
A method for measuring engine oil consumption by continuously measuring the amount of exhaust gas, in which exhaust gas is continuously taken in from an engine exhaust pipe and S in exhaust gas is burned to SO ₂ and sent to a gas exchange section. In the gas uptake step, the trap solution is continuously supplied, and SO ₂ in the exhaust gas from the exhaust gas uptake portion is brought into contact with the trap solution to dissolve the SO ₂ into SO ₃ ²⁻ ions, and the trap solution is changed to SO 2. _{2 A} gas exchange step of sending to the detection section, and passing the trap solution through a bioreactor consisting of sulfite oxidase to convert SO ₃ ²⁻ ions to SO ₄ ²⁻
Oxidation to ions and generation of hydrogen peroxide, and then the trap solution is continuously reacted with an aqueous solution of isoluminol and peroxidase to detect chemiluminescence amount due to oxidative decomposition of isoluminol by the hydrogen peroxide in the trap solution. engine oil, wherein said at sO ₂ detection process and the measurement method of the engine oil consumption consisting of continuously quantify sO ₂ amount, to the exhaust gas capture means provided sO ₂ sampling securing step by How to measure consumption. 16. The SO ₂ sampling ensuring step comprises:
16. The step of heating and retaining the temperature of a sampling pipe for introducing exhaust gas and its constituent parts.
Measuring method of engine oil consumption described in. 17. The SO ₂ sampling securing step comprises:
The step of contacting the exhaust gas with a sufficiently heated granular material or a catalyst agent for selectively oxidizing the S component when combusting S in the exhaust gas, according to claim 15 or 16. How to measure the engine oil consumption described. 18. The SO ₂ sampling ensuring step comprises:
18. The engine oil consumption measurement according to claim 15, further comprising an exhaust gas dilution step of diluting the exhaust gas after burning the contained S into SO ₂ with an inert gas. Method. 19. SO ₂ contained in engine exhaust gas
A device for measuring engine oil consumption by continuously measuring the amount of exhaust gas, which continuously takes in exhaust gas from an engine exhaust pipe, burns S in exhaust gas into SO ₂ and sends it to a gas exchange section. a gas intake section, the sO ₂ is contacted Well dissolved sO ₂ in the exhaust gas from the continuously feeding trap solution the trap solution to the exhaust gas capture unit and sO ₃ ^2-ionic said trap solution sO ₂ By passing the gas exchange section to the detection section and the trap solution through a bioreactor consisting of sulfite oxidase, SO ₃ ²⁻ ions are converted to SO ₄ ^2−.
Oxidation to ions and generation of hydrogen peroxide, and then the trap solution is continuously reacted with an aqueous solution of isoluminol and peroxidase to detect chemiluminescence amount due to oxidative decomposition of isoluminol by the hydrogen peroxide in the trap solution. in continuous engine oil consumption measurement device comprising a quantifying sO ₂ detector to the sO ₂ amount by engine oil consumption, characterized in that a sO ₂ sampling securing means to the gas uptake section Quantity measuring device. 20. The SO ₂ sampling ensuring means,
The sampling pipe that takes in the exhaust gas after burning S in the exhaust gas to SO ₂ is branched, and most of the exhaust gas is exhausted from one of the sambling pipes via the pressure regulator, and the other of the sampling pipes A glass instrument comprising a spiral glass tube for dissolving SO ₂ in the exhaust gas into a trap solution while keeping a high temperature in the gas exchange section while incorporating a part of the glass into the gas exchange section. 19. The measuring device for engine oil consumption according to item 19.