JP2007017317A - Gas sensor, gas concentration measuring instrument using it and method of measuring concentration of nitrogen oxide - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a gas sensor capable of measuring the accurate concentration of nitrogen oxide without being affected by an interference gas. <P>SOLUTION: In the gas sensor 1, a counter electrode 5, a comparing electrode 6 and the acting electrode 7 mainly comprising carbon and arranged on a filter film 4b are immersed in an electrolyte 12, a sample gas is brought into contact with the filter film 4b provided to the back position of the acting electrode 7 to permeate the nitrogen oxide contained in the sample gas in the thickness direction of the filter film 4b, the potential of the acting electrode 7 to the comparing electrode 6 is set to the potential causing the oxidation reaction of nitrogen monoxide due to the acting electrode 7 or the potential causing the reducing reaction of nitrogen dioxide. Since the effect of the interference gas is small when the oxidation or reduction current flowing to the acting electrode is measured, the concentration of the nitrogen monoxide gas can be calculated from the oxidation current and the concentration of nitrogen dioxide can be calculated from the reduction current. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

The present invention relates to a constant potential electrolytic gas sensor and an apparatus and method for measuring the concentration of nitrogen oxides such as nitrogen monoxide and nitrogen dioxide gas using the same, and more particularly, combustion of exhaust gas from combustion equipment or automobile exhaust gas. Without being substantially affected by the interference of carbon monoxide and hydrogen present in the exhaust gas at a high concentration, without being affected by the interference of coexisting SO ₂ and H ₂ S, and further exposed to these gases. The present invention relates to an apparatus and method capable of selectively and stably measuring only the concentration of nitrogen oxides without changing the sensitivity due to being applied.

  The nitrogen oxide gas concentration contained in the combustion exhaust gas needs to be measured from the viewpoint of controlling the combustion state or preventing air pollution, and is conventionally measured by a chemiluminescence method or an infrared analyzer. However, since these analyzers are large and expensive, a small and inexpensive measuring device that can be easily measured is desired.

  As a sensor used in such a simple measuring instrument, a constant potential electrolytic sensor utilizing an electrolytic current, a solid electrolyte sensor utilizing an equilibrium potential, a semiconductor sensor utilizing an adsorption reaction, and the like are known.

Among these, the potentiostatic sensor has characteristics such as a signal proportional to the gas concentration, relatively excellent selectivity, and low power consumption. Carbon monoxide (CO) and hydrogen sulfide (H ₂₎ It is popular for S). It is also known that measurement can be performed for nitric oxide (NO) and nitrogen dioxide (NO ₂ ) by using gold as an electrode material and setting each electrode to an appropriate potential.

  Conventional nitrogen oxide sensors have used gold as the working electrode. This is to suppress interference and influence of coexisting carbon monoxide. In fact, when used as a working electrode, the sensitivity of carbon monoxide is about 1/1000 of that of nitric oxide or nitrogen dioxide, so the effect can be virtually ignored when measuring in normal air. Met.

  However, when trying to measure the nitrogen oxide gas concentration in the combustion exhaust gas, depending on the conditions, the concentration of carbon monoxide may reach as much as 10 vol%. Since an output equivalent to about 100 ppm was shown in terms of conversion, accurate measurement could not be performed. In fact, the condition for generating a high concentration of carbon monoxide is an incomplete combustion state, and the nitrogen oxide concentration at that time is low, which is a particular problem.

In addition, in the case of exhaust gas from a combustion apparatus using light oil or heavy oil as fuel, sulfur dioxide (SO ₂ ) or hydrogen sulfide (H ₂ S) is contained in the exhaust gas, but gold was used for the working electrode as in the past. Sensors have a large amount of interference and influence, and the sensitivity to nitrogen oxides changes when exposed to these gases, so measurement is performed after removing the interference gas using a remover. There was a need to do.
A NEW ELECTROCHEMICAL ANALYZER FOR NITRIC OXIDE AND NITROGEN DIOXIDE, JMSedlak and KFBlurton, Talanta, 1976, 23, 811-814 JP-A-2005-83956 JP 2001-289816 A

  It is an object of the present invention to provide a gas sensor and a measurement device that can selectively and stably measure a nitrogen oxide concentration in the presence of a high concentration gas or in the presence of a high concentration gas.

In order to solve the above problems, a first sensor of the present invention includes an electrolytic solution housed in a container body, a working electrode whose surface is in contact with the electrolytic solution, and into which the electrolytic solution can penetrate, and the working A measurement target gas included in a sample gas in contact with the filter membrane has a filter membrane that is in contact with the back surface of the electrode and allows gas to permeate, a counter electrode that is in contact with the electrolyte solution, and a reference electrode, respectively. A gas sensor configured to pass through a membrane, cause a chemical reaction by the working electrode, and cause a current to flow through the working electrode, wherein the working electrode is a gas sensor mainly composed of carbon.
The first sensor is a gas sensor in which the electrolytic solution is acidic.
The first measuring device of the present invention having the first sensor includes an ammeter connected to the working electrode, and the potential of the working electrode with respect to the comparison electrode. Nitric oxide is oxidized by the working electrode. It is a gas concentration measuring device having a circuit for setting a potential to be reacted and a display device for displaying the nitric oxide concentration obtained from the measured value of the ammeter.

The first measuring device of the present invention is a gas concentration measuring device in which the potential of the working electrode with respect to the reference electrode is set to a potential of +100 mV or more and +600 mV or less.
Further, the second measuring apparatus of the present invention causes the working potential of the working electrode with respect to the first electrode, an ammeter connected to the working electrode, and the comparison electrode to cause nitrogen dioxide to undergo a reduction reaction at the working electrode. It is a gas concentration measuring device having a circuit for setting a potential and a display device for displaying the nitrogen dioxide concentration obtained from the measured value of the ammeter.
The second measuring apparatus of the present invention is a gas concentration measuring apparatus in which the potential of the working electrode with respect to the reference electrode is set to a potential of −500 mV to −100 mV.

The third sensor of the present invention includes an electrolyte contained in a container body, first and second working electrodes whose surfaces are in contact with the electrolyte and are capable of penetrating the electrolyte, and the first Measurements included in the sample gas in contact with the filter membrane, having a filter membrane in contact with the back surface of the first and second working electrodes and allowing gas to permeate, a counter electrode in contact with the electrolytic solution, and a reference electrode A gas sensor configured such that a target gas permeates the filter membrane, a chemical reaction is generated by the first and second working electrodes, and currents flow through the first and second working electrodes, respectively. The first and second working electrodes are gas sensors mainly composed of carbon.
The third sensor of the present invention is a gas sensor in which the electrolyte is acidic.
The third measuring device of the present invention includes the third sensor, the first and second ammeters respectively connected to the first and second working electrodes, and the first action on the comparison electrode. The potential of the electrode is set to a potential at which nitric oxide is oxidized by the first working electrode, the potential of the second working electrode with respect to the comparison electrode is reduced, and the nitrogen dioxide is reduced by the second working electrode. A circuit for setting the potential to be applied, a nitric oxide concentration obtained from the measurement value of the first ammeter, and a display device for displaying the nitrogen dioxide concentration obtained from the measurement value of the second ammeter. It is a gas concentration measuring device.

In the third measuring apparatus of the present invention, the potential of the first working electrode with respect to the comparison electrode is set to a potential of +100 mV or more and +600 mV or less, and the potential of the second working electrode with respect to the comparison electrode is −500 mV. This is a gas concentration measuring device set to a potential of −100 mV or less.
The third measuring device of the present invention is a gas concentration measuring device for correcting the measured value of the first ammeter with the measured value of the second ammeter to obtain the nitric oxide concentration.

Further, the first measuring method of the present invention comprises contacting a counter electrode, a comparative electrode, and a working electrode mainly composed of carbon and disposed on a filter membrane with an electrolyte solution, and supplying a sample gas to the working electrode back surface position. The nitric oxide contained in the sample gas is transmitted in the thickness direction of the filter membrane, the potential of the counter electrode is controlled, and the potential of the working electrode with respect to the comparison electrode is set to the working electrode. And measuring the oxidation current flowing through the working electrode, and determining the concentration of nitrogen monoxide from the oxidation current.
The first measuring method is a measuring method of the nitrogen oxide concentration in which the potential of the working electrode with respect to the reference electrode is set to a potential of +100 mV or more and +600 mV or less.

Further, the second measuring method of the present invention is such that the counter electrode, the reference electrode, and the working electrode mainly composed of carbon and disposed on the filter membrane are brought into contact with the electrolytic solution, and the sample gas is placed on the back surface position of the working electrode. The nitrogen gas contained in the sample gas is transmitted in the thickness direction of the filter film, the potential of the counter electrode is controlled, and the potential of the working electrode with respect to the comparison electrode is adjusted by the working electrode. This is a method for measuring the nitrogen oxide concentration by setting the potential at which a reduction reaction of nitrogen dioxide occurs, measuring the oxidation current flowing through the working electrode, and determining the concentration of the nitrogen dioxide from the oxidation current.
The second measuring method is a measuring method of the nitrogen oxide concentration in which the potential of the working electrode with respect to the reference electrode is set to a potential of −500 mV to −100 mV.

Further, the third measurement method of the present invention is to bring the counter electrode, the reference electrode, and the first and second working electrodes, each of which is mainly composed of carbon and disposed on the filter membrane, into contact with the electrolytic solution, By controlling the potential of the counter electrode, the potential of the first working electrode with respect to the reference electrode is set to a potential at which oxidation reaction of nitric oxide occurs at the first working electrode, and the second potential with respect to the reference electrode is set. The potential of the working electrode is set to a potential at which a reduction reaction of nitrogen dioxide occurs at the second working electrode, the sample gas is brought into contact with the filter membrane, and the nitrogen monoxide and nitrogen dioxide contained in the sample gas are Nitrogen that is transmitted in the thickness direction of the filter membrane and determines the concentration of nitrogen monoxide and the concentration of nitrogen dioxide in the sample from the oxidation current flowing through the first working electrode and the reduction current flowing through the second working electrode Measuring method of oxide concentration A.
In the third measurement method, the potential of the first working electrode with respect to the comparison electrode is set to a potential of +100 mV or more and +600 mV or less, and the potential of the second working electrode with respect to the comparison electrode is set to −500 mV or more and −100 mV or less. It is the measuring method of the nitrogen oxide concentration set to the electric potential.
The third measurement method is a nitrogen oxide concentration measurement method in which the nitrogen monoxide concentration is corrected using the measurement value of the reduction current.

The present invention is configured as described above. When oxygen is supplied to the electrolyte and a predetermined voltage is applied to each electrode, an oxidation reaction or a reduction reaction is performed at the working electrode or the first and second working electrodes. And an oxidation current or a reduction current flows through the working electrode.
If the value of the oxidation or reduction current flowing through the working electrode is previously associated with the concentration of nitric oxide and the concentration of nitrogen dioxide, when the actual measurement target gas is measured, the oxidation current value is converted to the nitric oxide concentration. The reduction current can be converted to a nitrogen dioxide concentration. The oxidation current value can also be corrected from the reduction current value.
The working electrode is an electrode having carbon as a main component and having a thickness that allows measurement object gas to pass through in the thickness direction. When the working electrode is made of carbon, according to experiments, the reaction rate of oxidation or reduction reaction of nitrogen monoxide and nitrogen dioxide is high, and the reaction rate of interference gases such as hydrogen, hydrogen sulfide, and carbon monoxide is low. As a result, even if an interference gas is present, a large current value can be obtained by the oxidation or reduction reaction of nitric oxide or nitrogen dioxide, so that the influence of the reaction current of the interference gas can be substantially ignored. .
The current may be directly measured, or may be converted into a current by measuring a voltage flowing through a resistor.
A property of allowing gas to permeate the filter membrane is required, and a porous membrane is generally used.

A nitrogen oxide gas sensor that is not affected by interference gases such as carbon monoxide, hydrogen, hydrogen sulfide, and sulfur dioxide, and a measuring device and a measuring method using the same are obtained.
In the case of one working electrode, both the nitric oxide concentration and the nitrogen dioxide concentration can be determined by changing the potential of the working electrode.

  On the other hand, when the first and second working electrodes are provided in common with the counter electrode and the reference electrode and brought into contact with the same electrolyte solution, the first and second working electrodes can be set to different potentials. On the other hand, a reduction reaction can occur.

  When the oxidation current and the reduction current flowing through the first and second working electrodes are measured, the measured value of the oxidation current is corrected using the nitrogen dioxide concentration obtained from the reduction current, and the influence of nitrogen dioxide is removed. Accurate nitric oxide concentration.

  Reference numeral 1 in FIG. 1 denotes a gas sensor according to a first example of the present invention, which has a cylindrical container body 3 having openings at both ends.

  Each opening is closed by gas permeable porous filter membranes 4a and 4b, respectively. The filter membrane 4a located at one opening has a counter electrode (on the inner surface of the container body 3). CE) 5 and the reference electrode (RE) 6 are arranged in close contact with each other, and the filter film 4b located in the other opening is similarly provided with a working electrode (WE) 7 on the inner surface of the container body 3. Are closely arranged.

  The comparison electrode 6 and the counter electrode 5 are made of a corrosion-resistant film-like electrode, for example, a film-like platinum (including platinum black) electrode. The powder can be directly pressed on the filter film 4a, or can be formed on the filter film 4a by vacuum deposition, sputtering, ion plating, or electroless plating. Other noble metals can be used instead of platinum.

  The working electrode 7 is a film-like electrode containing carbon as a main component. For example, a graphite powder is directly pressed on the filter film 4b, or bonded with an appropriate binder such as a powder of tetrafluoroethylene resin. It can be formed by applying on the filter film 4b. Moreover, it can also form by methods, such as vacuum evaporation, sputtering, and ion plating, and can also form by the method of electroless plating. Instead of graphite, carbon fine powder called carbon black may be used.

  In the case of platinum or platinum black electrodes, platinum or platinum black powder is used alone or mixed with a binder such as tetrafluoroethylene resin powder and dispersed in an appropriate solvent, and the porous filter membrane 4a is used as filter paper. The electrode can be formed by adhering directly onto the porous filter membrane 4a by vacuum filtration (or transferring the film obtained by vacuum filtration onto the porous filter membrane 4a) and pressing it.

  The same applies to an electrode mainly composed of carbon such as graphite. Carbon powder such as graphite alone or mixed with a binder such as tetrafluoroethylene resin powder is dispersed in an appropriate solvent, and porous. Using the filter membrane 4b as filter paper, the electrode can be formed by adhering directly on the porous filter membrane 4b by vacuum filtration (or transferring the film obtained by vacuum filtration onto the porous filter membrane 4b) and pressing it. it can.

  As will be described later, in order to generate an oxidation or reduction reaction at the interface between the working electrode 7 and the filter membrane 4b, the filter membrane 4b needs to be breathable, and water penetrates into the working electrode 7 in the thickness direction. The nature to do is necessary. Because of these properties, for example, a film of tetrafluoroethylene resin (PTFE) can be used as the filter films 4a and 4b.

As the electrolytic solution, an aqueous acid solution such as sulfuric acid or phosphoric acid, that is, an acidic aqueous solution can be used. Nitric acid and hydrochloric acid are also acidic aqueous solutions and can be used, but are not desirable because they are volatile.
On the other hand, a basic electrolyte is not desirable because it reacts with carbon dioxide in the air.

  In the case of an aqueous solution of neutral salt such as lithium chloride or calcium chloride, it can be used for measurement of nitrogen dioxide as described later, but it is not suitable for measurement because the current generated by the reaction is small for nitric oxide. It is.

  Next, packings 8 a and 8 b made of ring-shaped rubber are disposed between the filter membranes 4 a and 4 b and the end of the container body 3 or between the electrodes 5 to 7 and the end of the container body 3. ing.

  Packing 9a, 9b made of ring-shaped rubber is also disposed on the opposite surface of the filter membranes 4a, 4b, and the side plates 10a, 10b are pressed against the surfaces, and the side plates 10a, 10b Is applied to the container body 3 with screws 17.

  An electrolytic solution 12 is sealed in the container body 3 in advance. The filter films 4a and 4b on which the electrodes 5 to 7 are formed are pressed against the container body 3 so that the electrolyte solution 12 does not leak out.

  An air hole 15 penetrating in the thickness direction is formed in the side plate 10a that presses the filter film 4a on which the counter electrode 5 and the comparison electrode 6 are arranged.

  Part of the filter membrane 4 a is not formed with the counter electrode 5 and the comparison electrode 6, and is in contact with the electrolytic solution 12, and the back surface of the portion in contact with the electrolytic solution 12 is exposed at the bottom of the air hole 15. Yes.

  When the oxygen-containing air that has entered through the opening of the air hole 15 comes into contact with the filter membrane 4 a, it can permeate in the thickness direction of the filter membrane 4 a and dissolve in the electrolyte solution 12. Conversely, oxygen generated by the counter electrode 5 through the reaction described later passes through the thickness direction of the filter film 4 a and is released from the air holes 15.

  A recess is formed in the side plate 10b that presses the filter film 4b on which the working electrode 7 is disposed. The opening of the recess is pressed against the filter film 4b so that the filter film 4b is exposed in the recess. The storage part 18 is comprised by the space of the fixed volume formed by the recessed part and the filter film | membrane 4b.

  The side plate 10b is formed with two vent holes 13 and 14 penetrating from the outer periphery to the storage portion 18, and one of the vent holes 13 is an intake side and the other vent hole 14 is an exhaust side. When the sample gas containing nitrogen oxide is supplied to the reservoir 18, the nitrogen oxide gas in the sample gas passes through the filter film 4b and reaches the interface between the working electrode 7 and the filter film 4b. Depending on the potential, the nitrogen oxide gas causes an oxidation reaction or a reduction reaction at the interface between the working electrode 7 and the filter film 4b.

  Reference numeral 20 in FIG. 3 is a nitrogen oxide gas measuring device using the gas sensor 1, and includes the gas sensor 1, an operational amplifier 24, a reference voltage source 26, and an ammeter 27.

Leads are connected to the working electrode 7, the counter electrode 5, and the comparison electrode 6 of the gas sensor 1, and the working electrode 7 is connected to a constant potential (here, ground potential) by the lead, and the counter electrode 5 is an operational amplifier. The comparison electrode 6 is connected to the inverting input terminal of the operational amplifier 24. The working electrode 7 can also be connected to a controllable voltage source instead of the ground potential.
The output terminal of the reference voltage source 26 is connected to the non-inverting input terminal of the operational amplifier 24.

  In the gas sensor 1, the potential of the comparison electrode 6 can be controlled by the potential of the counter electrode 5, and the potential of the comparison electrode 6 decreases when the potential of the counter electrode 5 decreases and increases when it increases.

Therefore, since the negative feedback circuit is configured by connecting the gas sensor 1 and the operational amplifier 24, the potential of the counter electrode 5 is set so that the comparison electrode 5 becomes equal to the output voltage Va of the reference voltage source 26 by the operation of the operational amplifier 24. Is controlled.
Since the potential of the working electrode 7 is the ground potential, the potential of the working electrode 7 with respect to the potential of the electrolytic solution 12 is −Va.

  An ammeter 27 is inserted between the counter electrode 5 and the output terminal of the operational amplifier 24. Since the input current of the operational amplifier 24 is negligibly small, the current flowing through the ammeter 27 is equal to the current flowing between the counter electrode 5 and the working electrode 7.

  When measuring the concentration of nitric oxide as nitrogen oxide, the potential of the working electrode 7 with respect to the comparison electrode 6 is set to a potential capable of oxidizing nitric oxide, and when measuring the concentration of nitrogen dioxide, the working electrode 7 Is set to a potential at which nitrogen dioxide can be reduced.

The air in contact with the surface of the filter membrane 4a penetrates the filter membrane 4a in the thickness direction, contacts the back surface of the comparison electrode 6, and becomes equal to the equilibrium potential of the following oxidation-reduction reaction.
O ₂ (air) + 4H ⁺ + 4e ⁻ ⇔ 2H ₂ O
This equilibrium potential is about 1.05 V as an actual measurement value when measured with reference to a standard hydrogen electrode (NHE).

  In the case of nitric oxide, the potential of the working electrode 7 with respect to the potential of the reference electrode 6 is set to a potential between +100 mV and +600 mV (Va = −100 mV to −600 mV). It becomes + 1.15V- + 1.65V which added 1.05V to the electric potential.

First, the case of nitric oxide will be described. In the working electrode 7, the following oxidation reaction (1a) occurs.
_{NO + 2H 2 O → NO 3} - + 4H + + 3e - ...... (1a)
At the counter electrode 5, the following reduction reaction (1b) occurs due to oxygen contained in the air.
3 / 4O ₂ + 3H ⁻ + 3e ⁻ → 3 / 2H ₂ O (1b)

The oxidation current of nitric oxide generated by the above equations (1a) and (1b) flows in the direction of flowing into the output terminal of the operational amplifier 24.
Since the oxidation current depends on the concentration of nitric oxide, the concentration of nitric oxide in the gas existing in the reservoir 18, that is, the concentration of nitric oxide in the sample gas supplied to the reservoir 18 is known. be able to.

  A display device 41 is connected to the ammeter 27, and a current value measured by the ammeter 27 is converted into a nitric oxide concentration by a circuit (not shown) and displayed as a nitric oxide concentration by the display device 41.

However, when nitrogen dioxide is contained in the sample gas, if the working electrode 7 has a potential at which the oxidation reaction of nitric oxide occurs, the nitrogen dioxide is also oxidized at the working electrode 7 according to the following reaction formula (2a), and oxidized. Current flows.
NO ₂ + H ₂ O → NO ₃ ⁻ + 2H ⁺ + e ⁻ (2a)
At the counter electrode 5, as shown in the following reaction formula (2b), a reduction reaction of oxygen contained in the air occurs.
1/4 O ₂ + H ⁻ + e ⁻ → 1/2 H ₂ O (2b)

Therefore, in practice, the value of the measured current Ia flowing through the ammeter 27 is determined by the oxidation current I _{NO of} nitrogen monoxide according to the expressions (1a) and (1b), and the oxidation of nitrogen dioxide according to the expressions (2a) and (2b). Although current I _NO2 is added value _{(Ia = I NO + I NO2} ), the nitrogen dioxide, is 1/3 the number of electrons generated per molecule of nitric oxide, also occurs at the working electrode 7 oxide Since the reaction rate of the reaction is also low, the magnitude of the oxidation current I _{NO2 that} flows due to the oxidation of nitrogen dioxide is about 1/4 to 1/5 of the value of the oxidation current I _NO that flows in the case of the same concentration of nitric oxide. .

Next, when measuring the concentration of nitrogen dioxide, the potential of the working electrode 7 is set to a potential at which the reduction reaction of nitrogen dioxide occurs at the working electrode 7.
Specifically, the potential of the working electrode 7 is set to a potential between −100 mV to −500 mV (Va = + 100 mV to +500 mV) with respect to the potential of the comparison electrode 6. In this case, the potential of the working electrode 7 with respect to the standard hydrogen electrode is + 0.55V to + 0.95V obtained by adding 1.05V.

At this potential, nitrogen dioxide is reduced at the working electrode 7 according to the following equation (3), and the reduction potential flows to the ammeter 27: NO ₂ + 2H ⁺ + 2e ⁻ → NO + H ₂ O (3a)
At this time, the water oxidation reaction shown in the following formula (3b) occurs at the counter electrode 5.
H ₂ O → 2H ⁺ + 2e ⁻ + 1 / 2O ₂ (3b)
The generated oxygen is released to the air holes 15 and the storage unit 18.

  Since the reduction current of nitrogen dioxide flowing according to equations (3a) and (3b) depends on the concentration of nitrogen dioxide, the reduction current value can be converted into the concentration of nitrogen dioxide.

  The display device 41 connected to the ammeter 27 is configured to be able to display the nitrogen dioxide concentration. The nitrogen dioxide concentration is obtained from the measured value of the ammeter 27 and the concentration is displayed on the display device 41.

  When the potential of the working electrode 7 with respect to the potential of the comparative electrode 6 is in the range of −100 mV to −500 mV, nitric oxide is neither oxidized nor reduced, so only the reduction current of nitrogen dioxide is generated and there is no influence of nitric oxide. The reduction current is a direction that flows out from the operational amplifier 24.

  Combustion exhaust gas may contain high concentrations of carbon monoxide in addition to nitrogen oxides. In the conventional potentiostatic gas sensor using gold as a working electrode material, carbon monoxide A current close to 100 ppm flows in terms of oxide concentration.

Normally, the concentration of carbon monoxide is relatively low in a state close to complete combustion where the concentration of nitrogen oxide is high, but the concentration of carbon monoxide is high in the incomplete combustion state where the concentration of nitrogen oxide is low. .
Therefore, if the nitrogen oxide concentration is low, it cannot be measured accurately.

  In contrast, in the gas sensor of the present invention using graphite as a working electrode, the reaction activity of graphite against carbon monoxide is very small, so that carbon monoxide hardly reacts, and the interference effect of 10% carbon monoxide is 1 ppm. Since this is a negligible level below, accurate nitrogen oxide concentration measurement is possible.

  Furthermore, combustion exhaust gas using a fuel containing sulfur S such as light oil or heavy oil, for example, exhaust gas of a diesel engine, contains hydrogen sulfide and sulfur dioxide which are components due to S.

These sulfur compounds do not exist at concentrations as high as carbon monoxide or hydrogen (H ₂ ), and at most about 100 ppm, but in a potentiostatic gas sensor using gold as a working electrode material, the concentration of nitrogen oxides There was a problem of giving an interference effect corresponding to a concentration exceeding 200 ppm in terms of conversion.

Phenomenon Further, if the controlled potential electrolysis type gas sensor in which the gold working electrode material, was only briefly exposed (1-2 min) in H ₂ S, the output to nitrogen oxides is increased 20% to 30% Is seen.

This phenomenon recovers when left for about a day, but it is difficult to accurately measure the concentration of nitrogen oxides in the presence of H ₂ S. As a countermeasure against these problems, a method of measuring after removing H ₂ S and SO ₂ with a remover can be considered. However, there is a problem of selecting a remover that can remove only a specific gas, and further removal. There was a maintenance problem with the life of the agent.

On the other hand, in a potentiostatic gas sensor using graphite as a working electrode, the interference effect between 100 ppm of H ₂ S and SO ₂ is 20 ppm or less in terms of nitrogen oxide concentration, and is exposed to H ₂ S. However, since the sensitivity to nitrogen oxides does not change at all, it is possible to accurately measure the nitrogen oxide concentration.

  Table 1 below is a comparison between a gas sensor using gold as a working electrode as in the prior art and the gas sensor 1 of the present invention using graphite as the working electrode 7. Measurement conditions were set to the conditions for measuring these two types of gas sensors (potential of working electrode 7 = 400 mV), the test gas having the compounds and concentrations shown in the table were measured, and the current value was It is shown in the table in terms of nitric oxide. The influence of the interference gas is smaller in the sensor 1 of the present invention.

Table 2 below shows that the prior art sensor using gold and the sensor of the present invention using graphite were set to the measurement conditions of nitric oxide (potential of the working electrode 7 = 400 mV). And then supplying 100 ppm of H ₂ S for 2 minutes, and again supplying nitrogen monoxide with the same concentration of 500 ppm and measuring the current, compared to before H ₂ S supply Indicates the magnitude of the error (increase) in the later measured value. The error of the sensor 1 of the present invention is extremely small.

In addition, under the measurement condition of nitric oxide, NO ₂ also shows output, so it is affected by interference of NO ₂ , but under the measurement condition of nitrogen dioxide, the concentration of nitrogen dioxide is not affected by the interference of nitric oxide. Therefore, if the current value obtained under the measurement condition of nitric oxide is corrected using the current value obtained under the measurement condition of nitrogen dioxide concentration, the accurate concentration of nitric oxide can be known.

For example, determine the concentration A _NO2 nitrogen dioxide from the measured current measured under conditions of nitrogen dioxide concentration, the concentration A of the nitrogen oxides obtained from measured current measurement conditions of nitric oxide, the concentration of nitrogen dioxide A _NO2 the subtracting influence coefficient (= 1/4 to 1/5) times the value of the nitrogen dioxide, the concentration a _NO of nitrogen monoxide is obtained.

  Accordingly, two types of voltage sources are prepared in the reference voltage source 26 of the measuring device 20, and first, the concentration of the nitrogen dioxide is measured by setting the potential of the comparison electrode 6 to a potential at which the reduction reaction of nitrogen dioxide occurs. The output voltage of the reference voltage source 26 is changed to a potential at which oxidation reaction of nitric oxide occurs, and the total nitrogen oxide concentration of nitrogen monoxide and nitrogen dioxide is measured, and the nitrogen dioxide concentration is corrected from the nitrogen oxide concentration. Thus, an accurate concentration of nitric oxide can be obtained. Two types of reference voltage sources may be prepared and switched.

The display device 41 can be configured to display both the nitric oxide concentration and the nitrogen dioxide concentration, and the measurement result can be displayed.
However, when measuring nitric oxide and nitrogen dioxide by changing the potential of the reference electrode 6, it takes time until the measurement current becomes stable.

  The code | symbol of FIG. 2 is the gas sensor of the 2nd example of this invention, and it can perform the said correction | amendment, without switching a reference voltage as mentioned above.

If the same reference numerals are given to the same members as those of the gas sensor 1 of the first example and the description thereof is omitted, the gas sensor 2 of the second example has the first and second working electrodes 7 ₁ , 7 on the surface of the filter film 4b. ₂ are closely arranged. The first and second working electrodes 7 ₁ and 7 ₂ are the same as the working electrode 7 of the gas sensor 1 of the first example divided into two.

The first and second working electrodes 7 ₁ and 7 ₂ are film-like electrodes that contain carbon as a main component and are capable of penetrating an electrolytic solution. The same members as the gas sensor 1 of the first example such as the filter films 4a and 4b and the counter electrode 6 are the same material.
The first and second working electrodes 7 ₁ and 7 ₂ are insulated from each other, and leads are connected to the first and second working electrodes 7 ₁ and 7 ₂ , the counter electrode 5, and the comparison electrode 6, respectively. .

  4 indicates a measurement circuit using the gas sensor 2 of the second example. The measurement circuit 30 includes the gas sensor 2, a main operational amplifier 33, and first and second sub operational amplifiers 31. , 32.

The comparison electrode 6 is connected to the inverting input terminal of the main operational amplifier 31, and the counter electrode 5 is connected to the output terminal of the main operational amplifier 31.
The non-inverting input terminal of the main operational amplifier 31 is connected to the main reference voltage source 36, the main reference voltages V ₁ to a reference voltage source 36 is output is input.

With such a connection, a negative feedback circuit including the main operational amplifier 33 and the gas sensor 2 is configured. When the main operational amplifier 33 operates, the counter electrode 6 has the same potential as the main reference voltage V _1. The potential of 5 is controlled.

The first and second working electrodes 7 ₁ and 7 ₂ are connected to the inverting input terminals of the first and second sub operational amplifiers 31 and 32. The output terminals of the first and second sub-operational amplifiers 31 and 32 are connected to their own inverting input terminals to form a negative feedback circuit. As a result, the first and second working electrodes 7 ₁ , 7 _second potential is controlled to be equal to the potential of the non-inverting input terminal.
The non-inverting input terminals of the first and second sub operational amplifiers 31 and 32 are connected to a constant potential.

Here, the non-inverting input terminal of the first auxiliary operational amplifier 31 is connected to the secondary reference voltage source 37, the secondary reference voltage V ₂ sub reference voltage source 37 outputs is input, the second sub The non-inverting input terminal of the operational amplifier 32 is connected to the ground potential (the non-inverting input terminal of the second sub operational amplifier 31 can also be connected to a controllable voltage source).

Since the potential of the comparison electrode 6 is the main reference voltage V ₁ , the potential E ₁ of the first working electrode 7 ₁ with respect to the comparison electrode 6 becomes V ₂ −V ₁ , and the second working electrode 7 ₂ with respect to the comparison electrode 6 has The potential E ₂ is −V ₁ .

Accordingly, the oxidation reaction of nitrogen monoxide produced in the first working electrode _71, in order to cause the reduction reaction of nitrogen dioxide in the second working electrode 7 _{2,
E 1 = V 2 -V 1 =} + 100mV~ + 600mV
E ₂ = −V ₁ = −100 mV to −500 mV
You can do it.

First and second ammeters 38 and 39 are inserted between the output terminals and the inverting input terminals of the first and second sub operational amplifiers 31 and 32, respectively. amplifier 31 operates, first, the second working electrode 7 _1, 7 oxidation current and reduction current flowing through the _2, first, configured to be respectively measured by the second working electrode 7 _1, 7 ₂ Has been.

In the first and second working electrodes 7 ₁ and 7 ₂ , the oxidation reaction and the reduction reaction represented by the above formulas (1a) and (2a) respectively proceed, and the first and second ammeters 38 and 39 respectively. Thus, the oxidation current and the reduction current are measured.

  In the measuring device 30 using the gas sensor 2 of the second example, since the voltage is not switched, the concentration of nitric oxide and the concentration of nitrogen dioxide can be measured continuously. Further, since it is not necessary to wait for the measurement until the gas sensor is stabilized, it is possible to cope with a sudden change in the concentration of nitrogen oxides.

Further, using the measured values of the reduction current flowing through the second working electrode 7 _2, the value of the oxidation current flowing in value as the first working electrode ₇₁ at the same time the reduction current corrected, the concentration of the exact nitric oxide You can ask for it.

  The first and second ammeters 38 and 39 are connected to the display device 42, and the oxidation current value and the reduction current value measured by the first and second ammeters 38 and 39 are expressed as monoxide. Nitrogen concentration (corrected concentration or non-corrected concentration) and nitrogen dioxide concentration are respectively converted and displayed on the display device 42.

Next, the relationship between the electrolyte solution 12 of the present invention using a working electrode containing carbon as a main component and the measurement target gas will be described.
First, the case of nitric oxide will be described. Table 3 below shows the comparison results of the measured values of the gas sensor of the present invention when the acidic electrolytic solution 12 and the neutral electrolytic solution 12 were used and nitrogen monoxide gas was the measurement target.

  A platinum electrode was used as a reference electrode and a counter electrode. A 4.25 mol / L aqueous sulfuric acid solution was used as the acidic electrolytic solution 12, and a 7.4 mol / L lithium chloride aqueous solution was used as the neutral electrolytic solution. The potential of the working electrode 7 with respect to the comparative electrode 6 is set to +400 mV, and the oxidation current due to the oxidation reaction of nitric oxide is measured.

When 500 ppm of nitric oxide gas was flowed, an oxidation current of 99.5 μA was obtained in the case of an aqueous sulfuric acid solution, and an oxidation current of 6.5 μA was obtained in the case of an aqueous lithium chloride solution. Since the measurement accuracy increases as the oxidation current obtained increases, an acidic electrolytic solution is preferred.
On the other hand, the smaller the measured value in the case of flowing an interference gas such as carbon monoxide, the higher the accuracy. Therefore, the acidic electrolytic solution is still preferable.

  From the above results, it can be seen that an acidic electrolytic solution is suitable for measuring nitric oxide.

Next, the case of nitrogen dioxide will be described. Table 4 below shows the comparison results of the measured values of the gas sensor of the present invention when nitrogen dioxide gas is the measurement target.
Similarly to the above, a platinum electrode is used for the reference electrode and the counter electrode, a 4.25 mol / L sulfuric acid aqueous solution is used as the acidic electrolyte solution 12, and a 7.4 mol / L chloride is used as the neutral electrolyte solution. An aqueous lithium solution was used.

  The potential of the working electrode 7 with respect to the comparative electrode 6 is set to −300 mV, and the oxidation current due to the oxidation reaction of nitric oxide is measured.

  When 500 ppm of nitrogen dioxide gas is flowed, the output current of the neutral electrolyte is about ½ of the output current of the acidic electrolyte, but the interference effect of interference gases such as CO is small. An electrolytic solution can also be used.

  When the current values measured by the ammeters 27, 38, 39 are converted into the concentration of nitrogen monoxide or nitrogen dioxide and displayed on the display devices 41, 42, corrections such as temperature compensation are added as necessary. May be.

First example gas sensor of the present invention Second example gas sensor of the present invention Measuring circuit using the gas sensor of the first example of the present invention Measuring circuit using the gas sensor of the second example of the present invention

Explanation of symbols

1, 2 ... Gas sensor 3 ... Container body 12 ... Electrolyte 7 ... Working electrode 7 ₁ ... First working electrode 7 ₂ ... Second working electrode 8b ... Filter membrane 5 ... Counter electrode 6 ... ... Comparative electrodes 41, 42 ... Display devices 20, 30 ... Measuring devices

Claims (9)

An electrolyte contained in the container body;
A working electrode whose surface is in contact with the electrolyte solution and is capable of penetrating the electrolyte solution;
A filter membrane that is in contact with the back surface of the working electrode and is permeable to gas;
A counter electrode in contact with the electrolyte and a reference electrode,
A gas sensor configured such that a gas to be measured contained in a sample gas in contact with the filter membrane passes through the filter membrane, a chemical reaction occurs by the working electrode, and a current flows through the working electrode;
The working electrode is a gas sensor whose main component is carbon. A gas sensor according to claim 1;
An ammeter connected to the working electrode;
A circuit for setting the potential of the working electrode with respect to the comparison electrode to a potential at which nitric oxide is oxidized at the working electrode;
A gas concentration measuring device comprising: a display device that displays the nitric oxide concentration obtained from the measured value of the ammeter. The gas sensor according to claim 1 or 2,
An ammeter connected to the working electrode;
A circuit for setting the potential of the working electrode with respect to the comparison electrode to a potential at which nitrogen dioxide is reduced by the working electrode;
A gas concentration measuring device comprising: a display device for displaying a nitrogen dioxide concentration obtained from a measured value of the ammeter. An electrolyte contained in the container body;
First and second working electrodes whose surfaces are in contact with the electrolyte solution and are capable of penetrating the electrolyte solution,
A filter membrane that is in contact with the back surface of the first and second working electrodes and allows gas to permeate;
A counter electrode in contact with the electrolyte and a reference electrode;
The gas to be measured contained in the sample gas in contact with the filter membrane permeates the filter membrane, a chemical reaction is generated by the first and second working electrodes, and currents flow through the first and second working electrodes, respectively. A gas sensor configured to flow through,
The first and second working electrodes are gas sensors whose main component is carbon. A gas sensor according to claim 4;
First and second ammeters respectively connected to the first and second working electrodes;
The potential of the first working electrode with respect to the comparison electrode is set to a potential at which nitric oxide is oxidized at the first working electrode,
A circuit for setting the potential of the second working electrode with respect to the comparison electrode to a potential at which nitrogen dioxide is reduced by the second working electrode;
A gas concentration measuring device having a nitric oxide concentration obtained from a measured value of the first ammeter and a display device for displaying the nitrogen dioxide concentration obtained from the measured value of the second ammeter. A counter electrode, a reference electrode, and a working electrode mainly composed of carbon and disposed on the filter membrane are brought into contact with the electrolytic solution, and a sample gas is brought into contact with the filter membrane at the back surface position of the working electrode. Nitric oxide contained in the filter membrane is transmitted in the thickness direction of the filter membrane,
Controlling the potential of the counter electrode, and setting the potential of the working electrode with respect to the comparison electrode to a potential at which an oxidation reaction of nitric oxide occurs at the working electrode;
A method for measuring a nitrogen oxide concentration, wherein an oxidation current flowing through the working electrode is measured and a concentration of the nitric oxide is obtained from the oxidation current. A counter electrode, a reference electrode, and a working electrode mainly composed of carbon and disposed on the filter membrane are brought into contact with the electrolytic solution, and a sample gas is brought into contact with the filter membrane at the back surface position of the working electrode. Nitrogen dioxide contained in the filter membrane in the thickness direction of the filter membrane,
Controlling the potential of the counter electrode, and setting the potential of the working electrode with respect to the reference electrode to a potential at which a reduction reaction of nitrogen dioxide occurs at the working electrode;
A method for measuring a nitrogen oxide concentration by measuring an oxidation current flowing through the working electrode and obtaining a concentration of the nitrogen dioxide from the oxidation current. The counter electrode, the reference electrode, and the first and second working electrodes, each having carbon as a main component and disposed on the filter membrane, are brought into contact with the electrolytic solution,
By controlling the potential of the counter electrode, the potential of the first working electrode with respect to the comparison electrode is set to a potential at which oxidation reaction of nitric oxide occurs at the first working electrode, and the second with respect to the comparison electrode The potential of the working electrode is set to a potential at which the reduction reaction of nitrogen dioxide occurs at the second working electrode,
A sample gas is brought into contact with the filter membrane, and nitrogen monoxide and nitrogen dioxide contained in the sample gas are transmitted in the thickness direction of the filter membrane,
A method for measuring a nitrogen oxide concentration, wherein a concentration of nitrogen monoxide and a concentration of nitrogen dioxide in the sample are determined from an oxidation current flowing through the first working electrode and a reduction current flowing through the second working electrode.   The method for measuring a nitrogen oxide concentration according to claim 8, wherein the nitrogen monoxide concentration is corrected using a measured value of the reduction current.

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