Method and apparatus for measuring NOx gas concentration

• US 6,695,964 B1
• Filed: 06/07/2000
• Issued: 02/24/2004
• Est. Priority Date: 12/02/1996
• Status: Expired due to Term

• Current Assignee: NGK Spark PLUG Company Limited (Niterra Co., Ltd.)
• Original Assignee: NGK Spark PLUG Company Limited (Niterra Co., Ltd.)
• Inventors: Ando, Masashi, Ishida, Noboru, Okumura, Tatsuo, Ootuka, Takaki, Sato, Yoshikuni, Sugaya, Satoshi, Nadanami, Norihiko, Oshima, Takafumi
• Primary Examiner(s): Nguyen, Nam
• Assistant Examiner(s): Olsen, Kaj K.
• Application Number:
  US09/588,504
• Time in Patent Office: 1,357 Days
• Field of Search: 204/424, 204/425, 204/426, 205/781, 205/784, 205/788, 73/233.1
• US Class Current: 205/781
• CPC Class Codes: G01N 27/4074 for detection of gases other than oxygen

Abstract

Method and sensor for measuring accurate measurement of NOx concentration in an exhaust gas containing O₂,H₂O, CO₂ and NOx and a NOx gas concentration sensor. A first oxygen pump cell sufficiently pumps out oxygen in a measurement gas such as not to decompose NOx. A pair of electrodes is provided on an inner side and an outer side of a second measurement chamber into which the gas is introduced from a first measurement chamber via a diffusion resistance. A voltage is impressed across the paired electrodes for decomposing NOx in the second measurement chamber to dissociate oxygen which causes the current to flow in a second oxygen ion pump cell. The NOx gas concentration is measured for this current. The voltage impressed across the paired electrodes of the second oxygen ion pump cell is set so as not to dissociate H₂O and CO₂ present in the second measurement chamber.

Claims

1. A NOx gas concentration sensor for measuring the NOx concentration in an exhaust gas comprising NOx, O₂, CO₂ and H₂O, comprising:

(a) a ceramic body comprising an electrolyte having an electrically controllable conducting rate of oxygen ion;

(b) a first pair and a second pair of electrodes formed on said ceramic body;

(c) a flow channel in said ceramic body for passage of the exhaust gas;

(d) means for extracting said O₂ from the exhaust gas via said ceramic body to outside the flow channel so as to form a residual gas in said flow channel;

(e) means for applying a first voltage and a second voltage across the first pair and the second pair of electrodes, respectively, said first voltage maximizing a gain by the dissociation of the NOx gas contained in said residual gas without substantial dissociation of the H₂O gas contained in said residual gas and said second voltage maximizing a gain by the dissociation of the NOx gas contained in said residual gas with substantial dissociation of the H₂O gas contained in said residual gas;

(f) means for measuring a first current flowing between said first pair of electrodes across which said first voltage is applied;

(g) means for measuring a second current flowing between said second pair of electrodes across which said second voltage is applied; and

(h) means for determining the NOx concentration in the exhaust, said determination of the NOx gas concentration being based on the first current being corrected by the second current.

2. The NOx gas concentration sensor as defined in claim 1, wherein said flow channel there is disposed a third pair of electrodes that extracts said O₂ of the exhaust gas out of the flow channel along the flowing direction of the exhaust gas, and

wherein the third pair of electrodes has an electrode length relative to the entire length of the flow channel as follows:

electrode length/entire length=¼

to ¾

.

3. The sensor as defined in claim 2, wherein the third pair of electrodes comprises a component inhibiting the NOx from dissociation.

4. The NOx gas concentration sensor as defined in claim 1, wherein said flow channel comprises a first flow channel in which said residual gas is formed, and a second flow channel in which NOx is dissociated, the first flow channel comprising a gas flow restrictor, the second flow channel comprising an inlet communicating to the first flow channel, and

wherein an electrode disposed in the first flow channel for extracting the O₂ of the exhaust gas out of the first flow channel extends from the vicinity of the gas flow restrictor disposed in the first flow channel until at most a position closer to said gas flow restrictor than the inlet of the second flow channel.

5. The NOx gas concentration sensor as defined in claim 1 wherein

said ceramic body is formed of plural ceramic layers laminated together;

said flow channel including a first flow channel for forming residual gas and a second flow channel for dissociating NOx, said first and second flow channels extending along the surface of said laminated ceramic layers;

said first and second flow channels communicating with each other by a flow channel extending in the laminating direction of said ceramic layers.

6. The NOx gas concentration sensor as defined in claim 1 wherein an oxygen concentration detecting electrode for detecting the oxygen concentration in said flow channel is formed on said ceramic body facing said flow channel, and wherein an oxygen concentration for generating a reference potential versus said oxygen concentration detection electrode is formed on said ceramic body outside of said flow channel;

said oxygen concentration reference electrode being an auto-generating reference electrode across which a voltage is impressed for transporting oxygen towards said reference electrode for providing a constant oxygen concentration around said electrode.

7. The NOx gas concentration sensor as defined in claim 1 wherein one of the electrodes provided in said flow channel for extracting the O₂ of the exhaust gas to the outside of said flow channel is sealed or covered, said one of the electrodes is provided with a gas diffision resistance.

8. The NOx gas concentration sensor as defined in claim 1 wherein, in one of the electrodes is provided in said, flow channel for extracting the O₂ of the exhaust gas from said flow channel to the outside of said flow channel.

9. The sensor as defined in claim 1 wherein the voltage is applied to an extent that does not substantially dissociate H₂O and CO₂ in the residual gas below about 450 mV at about 700°

C.

10. The sensor as defined in claim 1 wherein said extrating oxygen is carried out without substantial decomposition of NOx in the exhaust gas.

11. The sensor as defined in claim 1, wherein the voltage applied across the electrodes is about 450±

50 mV.

12. The sensor as defined in claim 1, wherein the voltage applied across the electrode is about 450 mV.

13. The sensor as defined in claim 1, wherein the NOx gas contained in the residual gas includes NO.

14. A method for measuring a NOx gas concentration, comprising:

providing an apparatus having a first measurement chamber into which an exhaust gas comprising O₂, H₂O, CO₂ and NOx is introduced via a first diffusion resistance;

measuring an oxygen partial pressure in the exhaust gas in said first measurement chamber with an oxygen partial pressure detection electrode;

pumping out a portion of said O₂ in said exhaust gas from said first measurement chamber to form a residual gas in said first measurement chamber, said pumping being carried out with a first oxygen ion pump cell, based on a potential of said oxygen partial pressure detection electrode, to an extent such that said pumping substantially does not decompose NOx in the exhaust gas;

introducing the residual gas into a second measurement chamber from said first measurement chamber via a second diffusion resistance;

measuring a first current and a second current flowing through a second oxygen ion pump cell and a third oxygen ion pump cell, respectively; and

determining the NOx concentration in the exhaust gas based on the first current being corrected by the second current.

15. The method for measuring a NOx gas concentration as defined in claim 14, wherein the voltage impressed across said second oxygen ion pump cell is about 450±

50 mV, wherein the electrode provided outside the second oxygen ion pump cell is exposed to the exhaust gas being measured.

16. The method for measuring a NOx gas concentration as defined in claim 14, wherein the voltage impressed across said second oxygen ion pump cell is set to 400 to 500 mV, wherein the electrode provided outside the second oxygen ion pump cell is not exposed to the exhaust gas being measured.

17. The method for measuring a NOx gas concentration as defined in any one of claims 14, wherein said O₂ in the exhaust gas is pumped out from the first measurement chamber so that the potential of said oxygen partial pressure detection electrode will be 150 to 450 mV.

18. The method as defined in claim 14, wherein the voltage impressed across the second oxygen ion pump cell is controlled in the range of about dc 450 mV or less.

19. A NOx gas concentration sensor, comprising:

a first measurement chamber into which an exhaust gas comprising O₂, H₂O, CO₂ and NOx is introduced via a first diffusion resistance;

an oxygen partial pressure detection electrode for measuring the oxygen partial pressure in the exhaust gas in said first measurement chamber;

a first oxygen ion pump cell for pumping out said O₂ in said exhaust gas in said first measurement chamber therefrom, based on a potential of said oxygen partial pressure detection electrode, to a sufficient extent such as not to substantially decompose NOx in the exhaust gas and form a residual gas in the first measurement chamber;

a second measurement chamber into which the residual gas is introduced from said first measurement chamber via a second diffusion resistance;

a second oxygen ion pump cell having first paired electrodes on inner and outer sides of said second measurement chamber and a first current flowing through said second oxygen ion pump cell, said first current being caused under a first voltage impressed across the first paired electrodes of said second oxygen ion pump cell;

a third oxygen ion pump cell having second paired electrodes on the inner and outer sides of a third measurement chamber and a second current flowing through said third oxygen ion pump cell, said second current being caused on impression of a second voltage across said second paired electrodes;

the first voltage is set at a value that substantially prevents dissociation of H₂O present in said second measurement chamber, the second voltage is set at a value that substantially allows dissociation of H₂O present in said third measurement chamber, and means for determining the NOx concentration based on the first current being corrected by the second current.

20. The sensor as defined in claim 19, wherein the voltage impressed across the second oxygen ion pump cell is controlled in the range of about dc 450±

50 mV.

21. The sensor as defined in claim 20, wherein the voltage impressed across the second oxygen ion pump cell is controlled in the range of about dc 450 mV or less.

22. An NOx gas concentration sensor comprising:

a first measurement chamber into which an gas comprising O₂, H₂O, CO₂ and NOx is introduced via a first diffusion resistance;

an oxygen partial pressure detection electrode for measuring the oxygen partial pressure in the exhaust gas in said first measurement chamber;

a first oxygen ion pump cell for pumping out the oxygen in said exhaust gas in said first measurement chamber therefrom, based on a potential of said oxygen partial pressure detection electrode, under the condition that does not allow substantial decomposition of NO in the first measurement chamber;

a second measurement chamber into which a gas is introduced from said first measurement chamber via a second diffusion resistance;

a second oxygen ion pump cell having first paired electrodes on inner and outer sides of said second measurement chamber, wherein said second oxygen ion pump cell flows a current caused by oxygen dissociated on decomposition of NOx in said second measurement chamber on application of a voltage across said first paired electrodes, said current having a first current under a first voltage;

a third oxygen ion pump cell having second paired electrodes on the inner and outer sides of a third measurement chamber and a second current flowing through said third oxygen ion pump cell, said second current being caused on impression of a second voltage across said second paired electrodes; and

means for determining the NOx gas concentration based on the first current being corrected by the second current.

23. The sensor as defined in claim 22, wherein the temperature of the electrolyte is controlled so that said H₂O and said CO₂ in the residual gas do not substantially dissociate on the surface of the electrode and a maximum gain of NOx detection is obtained.

24. The sensor as defined in claim 23, wherein said voltage is in the range of 300 mV to dc 500 mV.

25. The sensor as defined in claim 23, wherein said voltage is in the range of about dc 450±

50 mV.

26. The sensor as defined in claim 22, wherein said temperature is at least 700°

C.

27. The sensor as defined in claim 22, wherein said voltage is in the range of from dc 300 mV to dc 500 mV.

28. The sensor as defined in claim 22, wherein said voltage is in the range of about dc 450±

50 mV.

29. The sensor as defined in claim 22, wherein said high temperature is at least 800°

C.

30. The sensor as defined in claim 22, wherein said high temperature is above 700 up to 900°

C.

31. A method for determining a NOx concentration in an exhaust gas comprising O₂, H₂O, CO₂ and NOx employing an electrically controlled electrochemical cell comprising at least a first oxygen ion conductive solid electrolyte body and a second oxygen ion conductive solid electrolyte body, said method comprising:

(1) flowing the exhaust gas through a flow channel formed in the first oxygen ion conductive solid electrolyte body and the second oxygen ion conductive solid electrolyte body,

(2) forming a residual gas that has a different NO concentration than that of the exhaust gas at a high temperature while the exhaust gas travels through the flow channel,

(3) contacting said residual gas with a first catalytic electrode to which a first dc voltage that does not substantially dissociate H₂O and CO₂ but dissociates NO is applied to produce a first current,

(4) contacting said residual gas with a second catalytic electrode to which a second dc voltage that does substantially dissociate H₂O and NO is applied to produce a second current,

(5) determining the NOx concentration in the exhaust gas based on the current flowing through the electrolyte body, and based on the first current being corrected by the second current, and

(6) applying the dc voltage across the catalytic electrode and an electrode that is formed outside of the electrolyte body in the range of about dc 450±

50 mV and a maximum gain of NOx detection is obtained, said maximum gain of NOx being determined by a current gain of NOx at a given voltage applied as said dc voltage.

32. The method as defined in claim 31, wherein said flow channel has at least one reservoir formed adjacent to said flow channel and a catalytic electrode formed on a wall of the reservoir.

33. The method as defined in claim 32, wherein an additional electrode is formed around an inlet of the reservoir, wherein a negative voltage is applied to said additional electrode so that said O₂ concentration in the flow channel is detected to control the oxygen concentration of the residual gas flowed in the reservoir.

34. The method as defined in claim 32, wherein said reservoir is formed in between two oxygen ion conductive solid electrolyte bodies that are electrically insulated from each other.

35. The method as defined in claim 34, wherein said oxygen ion conductive solid electrolyte bodies are heated at a temperature of above 700 and up to 900°

C.

36. The method as defined in claim 31, wherein said flow channel has another electrode formed on a wall of said flow channel, wherein a negative polarity of a voltage is applied to said another electrode so that said O₂ in the flow channel is extracted out of the flow channel through the electrolyte body to lower an oxygen concentration of the residual gas flowed in the channel.

37. The method as defined in claim 36, wherein a surface of said another electrode is parallel to a surface of the catalytic electrode.

38. The method as defined in claim 31, wherein said electrolyte body is heated at a temperature of at least 700°

C.

39. The method as defined in claim 31, wherein said electrolyte body is heated at a temperature of at least 800°

C.

40. The method as defined in claim 31, wherein the dc voltage is less than about 450 mV.