Catalytic adsorption and oxidation based carbon monoxide sensor and detection method

• US 6,550,310 B1
• Filed: 11/28/2000
• Issued: 04/22/2003
• Est. Priority Date: 11/28/2000
• Status: Active Grant

• Current Assignee: Honeywell International Inc.
• Original Assignee: Honeywell International Inc.
• Inventors: Alderman, Richard A., Bonne, Ulrich, Liu, Di-Jia
• Primary Examiner(s): Larkin, Daniel S.
• Assistant Examiner(s): CYGAN, MICHAEL T
• Application Number:
  US09/724,534
• Time in Patent Office: 875 Days
• Field of Search: 73/310.5, 73/310.6, 73/310.7, 73/250.1, 73/250.5, 73/232.1, 73/233.1, 73/233.2, 732/041.7
• US Class Current: 73/31.05
• CPC Class Codes: G01N 25/30 using electric temperature-responsive elements
• CPC Class Codes: G01N 33/004 for CO, CO2

Abstract

A high-sensitivity carbon monoxide sensor is shown and described. The sensor includes a sensing element having a catalyst dispersed over a metal oxide layer. The catalyst is capable of adsorbing carbon monoxide. The sensing element can also include a heater and a temperature sensor. A flow sensor is provided for sensing a flow rate of gas directed at the sensing element. The signal processing module is coupled to the flow sensor and the temperature sensor. A flow sensor sends signals indicative of the flow rate to the processing module while the temperature sensor sends signals indicative of the temperature of the sensing element to the processing module. After carbon monoxide has been adsorbed onto the catalyst and metal oxide layer for a fixed time period, the heater is activated to heat the sensing element above the light-off temperature or at least as high as the oxidation temperature of the adsorbed carbon monoxide. As a result, an exothermic oxidation of the adsorbed carbon monoxide takes place, which results in an increase in the temperature of the sensing element. This increase in the temperature of the sensing element is used to determine the amount of accumulated adsorbed carbon monoxide which, in conjunction with the flow rate and the fixed time period, is used to calculate the carbon monoxide concentration in the gas flow.

Claims

1. A carbon monoxide sensor comprising:

a sensing element;

a flow sensor for sensing a flow rate of gas towards the sensing element;

a signal processing module in communication with the flow sensor and the sensing element;

the sensing element comprising a catalyst dispersed over a metal oxide layer, the catalyst capable of adsorbing carbon monoxide onto the metal oxide layer;

the flow sensor sending a signal indicative of the flow rate to the processing module;

the sensing element sending a signal indicative of the temperature of the sensing element to the processing module;

the processing module measuring the carbon monoxide in accordance with the flow rate signal and the temperature signal.

2. The carbon monoxide sensor of claim 1 further comprising a heater wherein, after carbon monoxide has been adsorbed onto the metal oxide layer, the heater heats the sensing element to a first temperature that is at least as high as the oxidation temperature of carbon monoxide adsorbed onto the metal oxide layer, thereby resulting in an exothermic oxidation of said carbon monoxide adsorbed onto the metal oxide layer and an increase in temperature of the sensing element to a second temperature.

3. The carbon monoxide sensor of claim 2 wherein the heater is capable of heating the sensing element to a third temperature of at least 200°

C. for regenerating the catalyst.

4. The carbon monoxide sensor of claim 1 wherein the processing module determines accumulated carbon monoxide CO_ACC in accordance with the increase in temperature and, wherein the processing module determines carbon monoxide concentration C_CO in accordance with the following equation:

5. The carbon monoxide sensor of claim 1 wherein the catalyst is selected from the group consisting of Ag, Au, Ru, Rh, Pd, Ir, Pt, metallic alloys thereof and mixtures thereof.

6. The carbon monoxide sensor of claim 1 wherein the catalyst comprises Pt.

7. The carbon monoxide sensor of claim 1 wherein the catalyst comprises Ru.

8. The carbon monoxide sensor of claim 1 wherein the catalyst comprises a RuPt alloy.

9. The carbon monoxide sensor of claim 1 wherein the catalyst comprises a RuIr alloy.

10. The carbon monoxide sensor of claim 1 wherein the metal oxide layer comprises at least one refractory metal oxide.

11. The carbon monoxide sensor of claim 1 wherein the metal oxide layer comprises a metal oxide selected from the group consisting of alumina, silica, titania and zirconia.

12. The carbon monoxide sensor of claim 1 further comprising a filter disposed upstream of the sensing element.

13. The carbon monoxide sensor of claim 1 further comprising a filter disposed upstream of the flow rate sensor so that the flow rate sensor is disposed between the filter and the sensing element.

14. The carbon monoxide sensor of claim 1 wherein the metal oxide layer is a first metal oxide layer and the sensing element further comprises a second metal oxide layer disposed on top of the catalyst and the first metal oxide layer.

15. The carbon monoxide sensor of claim 14 wherein the second metal oxide layer comprises a metal oxide selected from the group consisting of NiO, ZnO and MnO₂, and mixtures thereof.

16. The carbon monoxide sensor of claim 1 further comprising a reference sensing element comprising the catalyst dispersed over a layer of the metal oxide, the reference sensing element further comprising a heater;

the carbon monoxide sensor further comprising a low temperature carbon monoxide oxidation catalyst dispersed on a substrate, the low temperature carbon monoxide oxidation catalyst and substrate being disposed upstream of the reference sensing element;

the reference sensing element being coupled to the processing module.

17. A method of detecting a presence of carbon monoxide in a gas comprising the following steps:

exposing a catalyst dispersed onto a metal oxide layer to the gas that comprises carbon monoxide, the catalyst capable of adsorbing carbon monoxide onto the metal oxide layer;

adsorbing at least a portion of the carbon monoxide in the gas onto the metal oxide layer;

heating the catalyst and metal oxide layer to a first temperature that is at least as high as the oxidation temperature of carbon monoxide adsorbed onto the first metal oxide layer, thereby resulting in an exothermic oxidation of said carbon monoxide adsorbed onto the metal oxide layer and an increase in temperature of the metal oxide layer;

using the temperature increase of the metal oxide layer, thereby indicating the presence of carbon monoxide in the gas.

18. The method of claim 17 wherein the catalyst and metal oxide layer form part of a sensing element that further comprises a heater for heating the metal oxide layer.

19. The method of claim 18 wherein a signal processing module is coupled to the sensing element.

20. The method of claim 17 further comprising the steps of:

sensing a flow rate of gas that engages the catalyst and metal oxide layer over a fixed time period;

calculating a cumulative value for the carbon monoxide adsorbed onto the metal oxide layer from the increase in temperature of the metal oxide layer due to the exothermic oxidation of the carbon monoxide;

calculating a volume of gas by multiplying the flow rate by the fixed time period;

calculating a concentration of carbon monoxide in the gas as a function of the cumulative value and the volume.

21. The method of claim 20 wherein the catalyst is a first catalyst, wherein the method further comprises the step of providing a reference cumulative value provided by a reference sensing element comprising the first catalyst dispersed over a layer of the metal oxide, and by providing a second catalyst dispersed on a substrate, the second catalyst and substrate being disposed upstream of the reference sensing element, the second catalyst being a low temperature carbon monoxide catalyst which thereby oxidizes substantially all carbon monoxide in the gas that reaches the reference sensing element;

heating the reference sensing element to the first temperature;

recording any temperature increase of the reference sensing element above the first temperature;

calculating a reference value from said temperature increase;

reducing the cumulative value for the carbon monoxide gas by the reference cumulative value.

22. The method of claim 21 wherein the reducing step is performed by differential amplification.

23. The method of claim 17 wherein the catalyst is selected from the group consisting of Ag, Au, Ru, Rh, Pd, Ir, Pt, metallic alloys thereof and mixtures thereof.

24. The method of claim 17 wherein the metal oxide layer comprises at least one refractory metal oxide.

25. The method of claim 17 wherein the metal oxide layer comprises a metal oxide selected from the group consisting of alumina, silica, titania and zirconia, and mixtures thereof.

26. The method of claim 17 further comprising the step of filtering the gas before it reaches the metal oxide layer.

27. The method of claim 17 further comprising the step of regenerating the catalyst by heating the catalyst and metal oxide layer to a temperature of at least 200°

C.

28. A carbon monoxide sensor comprising:

a sensing element;

a flow sensor for sensing a flow rate of gas towards the sensing element;

a filter disposed upstream of the flow rate sensor so that the flow rate sensor is disposed between the filter and the sensing element;

a signal processing module in communication with the flow sensor and the sensing element;

the sensing element comprising a catalyst dispersed over a first metal oxide layer, the catalyst capable of adsorbing carbon monoxide onto the first metal oxide layer, the sensing element further comprising a second metal oxide layer disposed on top of the catalyst and first oxide layer, the sensing element further comprising a heater;

the flow sensor sending signals indicative of the flow rate to the processing module;

the sensing element sending signals indicative of the temperature of the sensing element to the processing module;

whereby, after carbon monoxide has been adsorbed onto the first metal oxide layer, the heater heats the sensing element to a first temperature that is at least as high as the oxidation temperature of carbon monoxide adsorbed onto the first metal oxide layer, thereby resulting in an exothermic oxidation of said carbon monoxide adsorbed onto the first metal oxide layer and an increase in temperature of the sensing element to a second temperature.

29. The carbon monoxide layer of claim 28 wherein the first metal oxide has a surface area ranging from about 50 m²/g to about 300 m²/g.

30. The carbon monoxide sensor of claim 28 further comprising a reference sensing element and, the reference sensing element comprising the catalyst dispersed over a layer of the first metal oxide, the reference sensing element further comprising a heater;

the carbon monoxide sensor further comprising a low temperature carbon monoxide oxidation catalyst dispersed on a substrate, the low temperature carbon monoxide oxidation catalyst and substrate being disposed upstream of the reference sensing element;

the reference sensing element being coupled to the processing module.

31. A method of detecting a presence of carbon monoxide in an exhaust stream comprising the following steps:

exposing a catalyst dispersed onto a metal oxide layer to the exhaust stream, the catalyst capable of adsorbing carbon monoxide onto the metal oxide layer;

adsorbing at least a portion of the carbon monoxide in the exhaust stream onto the metal oxide layer;

sensing a flow rate of the exhaust stream that engages the catalyst and metal oxide layer over a fixed time period;

heating the metal oxide layer to a first temperature that is at least as high as the oxidation temperature of carbon monoxide adsorbed onto the metal oxide layer, thereby resulting in an exothermic oxidation of said carbon monoxide adsorbed onto the metal oxide layer and an increase in temperature of the metal oxide layer;

using the temperature increase of the metal oxide layer, thereby indicating the presence of carbon monoxide in the exhaust stream;

calculating a cumulative value for the carbon monoxide adsorbed onto the metal oxide layer from the increase in temperature of the metal oxide layer due to the exothermic oxidation of the carbon monoxide;

calculating a volume of exhaust stream by multiplying the flow rate by the fixed time period;

calculating a concentration of carbon monoxide in the exhaust stream as a function of the cumulative value and the volume.

32. The method of claim 31 wherein the catalyst is a first catalyst, and wherein the method further comprises the step of providing a reference cumulative value by providing a reference sensing element comprising a second catalyst dispersed over a second metal oxide, and by providing a third catalyst dispersed on a substrate, the third catalyst and substrate being disposed upstream of the reference sensing element, the third catalyst being a low temperature carbon monoxide catalyst which thereby oxidizes substantially all carbon monoxide in the exhaust stream that reaches the reference sensing element;

heating the reference sensing element to the first temperature;

recording any temperature increase of the sensing element above the first temperature;

calculating a reference value from said temperature increase;

reducing the cumulative value for the carbon monoxide exhaust stream by the reference value.