EP4078171A1

EP4078171A1 - Improved measurement of gases

Info

Publication number: EP4078171A1
Application number: EP19914204.3A
Authority: EP
Inventors: Geoffrey Stephen Henshaw
Original assignee: Aeroqual Ltd
Current assignee: Aeroqual Ltd
Priority date: 2019-12-16
Filing date: 2019-12-16
Publication date: 2022-10-26
Also published as: GB2606062A; WO2021123864A1; GB2606062B; GB202205084D0

Abstract

Interference signals from other gases in an air sample are eliminated by flowing an air sample directly to an electrochemical gas sensor and subsequently flowing an air sample through a selective scrubber and removing the target gas of interest before flowing the sample to the electrochemical gas sensor. The difference in responses of the electrochemical gas sensor is directly proportional to the concentration of the target gas of interest in the air sample.

Description

Improved Measurement of Gases BACKGROUND OF THE INVENTION

The measurement of low levels of gases in ambient air by electrochemical gas sensors is made difficult due to interferences such as humidity, temperature and other gases to which electrochemical sensors respond.

SUMMARY OF THE INVENTION

The invention solves the problem and compensates for those interferences by using a comparative measurement between two different states. The first state is one in which the sensor responds to a sample of air which includes the gas of interest plus the combination of interferences. The second state is one in which the gas of interest is removed from the sample using a selective scrubber, and the sensor responds to the combination of interferences. The concentration of the gas of interest in the incoming air sample is proportional to the difference between the electrochemical sensor signals in first and second states. This can be achieved with a new measurement system as described herein.

BRIEF DESCRIPTION OF THE DRAWINGS

Figure 1 is a schematic representation of the apparatus, system and method of the invention. DETAILED DESCRIPTION

Figure 1 is a schematic representation of the apparatus, system and method of the invention. In Figure 1, the numeral 1 represents an optional selective scrubber. Element 2 is a selective scrubber for the gas of interest to be determined. Element 3 represents a valve or a combination of valves that can be controlled to switch at a specific interval between the gas streams to the electrochemical sensor 5 in a housing. Element 4 represents a nafion tubing to buffer humidity. Pump 6 brings the air flow to the electrochemical sensor 5. T 7 allows the incoming air sample 8 to be routed through scrubber 2 or directly to the sensor. Valve 3 either directs the incoming air sample 8 or the sample which has been scrubbed by the target gas scrubber 2 through the humidity buffer 4 to the electrochemical sensor or directs the incoming air sample 8 through the humidity buffer 4 to electrochemical sensor 5, bypassing the scrubber. The concentration of the gas of interest in the incoming air sample is proportional to the difference between the electrochemical sensor signals in first and second states.

The electrochemical sensors 5 that may be deployed in the improved instrument include sensors for the measurement of SO2, EES, CO, NH₃, O₃ and NO2. Suitable selective scrubbers 2 depend on the gas of interest.

Example 1. Measurement of SO2 was improved by using an electrochemical sensor 5 such as Alphasense SO2 -AF, a three-way solenoid valve 3 to switch sample flow between lines 10 and 11. Line 10 bypasses the selective target gas scrubber 2. Line 11 draws the incoming gas through scrubber 2. Scrubber 1 is a piece of PTFE tubing containing 0.2g of silver wool. Scrubber 2 contains lOg of marble (calcium and magnesium carbonate). The difference in response from the electrochemical sensor 5 when presented the air sample directly or via the scrubber 2 was found to be proportional to SO2 concentration, and the measurement was substantively free of interference from temperature and humidity changes and carbon monoxide.

In other examples, a different scrubber 2 would be used to remove a different target gas and to eliminate its inclusion in gases sensed in sensor 5.

In other examples, plural scrubbers 2 are used with plural parallel lines 11. Switch 3 may have plural input connections for plural lines 11 to select individual lines 11, and the different individual lines 11 have different scrubbers 2 for connection to sensor 5.

In other examples, plural switches are connected between plural scrubbers and switch 3 to select specific scrubbers.

In one example, a device for determining the concentration of a target gas in ambient air transfers the sample air through an optional selective scrubber 1 to an electrochemical sensor 5. A solenoid valve 3 or valves cycles the air to the sensor 5 via a direct path 10 or a path 11 containing a selective scrubber 2. Electronics control the position of the valve 3 or valves and measure the sensor response at a sample interval between five and one thousand seconds after the valve 3 switches the sample flow.

The new method determines the concentration of a target gas in ambient air. The gas concentration is proportional to the difference in sensor signals between when the gas sample flows directly to the sensor 5 and when the gas sample flows via the selective scrubber 2 to the sensor.

The sensor signal after a predetermined time of sample flow through the scrubber 2 to the sensor 5 represents the signal of the sensor in the absence of the target gas. The sensor signal after a predetermined time of sample flow directly to the sensor represents the signal of the sensor in the presence of the target gas.

In other examples, the electrochemical sensor is for the measurement of S0₂, H₂S, CO, NH₃, 0₃ or N0₂.

For the measurement of S0₂, the first optional scrubber 1 is a catalyst containing a silver catalyst, Mn0₂ catalyst, potassium iodide or ferrous sulphate for the scrubbing of ozone and N0₂, and selective scrubber 2 contains activated carbon, marble chips, calcium carbonate or an adsorbent for acidic gases.

For the measurement of H₂S, the first optional scrubber 1 is a catalyst containing a silver catalyst, Mn0₂ catalyst or potassium iodide for the scrubbing of ozone and N0₂, and selective scrubber 2 contains activated carbon or iron oxides or a purafil chemisorbent for H₂S.

The invention provides a device for determining the concentration of a target gas in ambient air 8 which transfers the sample air through an optional selective scrubber 1 to an electrochemical sensor 5, via a solenoid valve 3 or valves which cycles the air to the sensor via a direct path or a path containing a selective scrubber 2. Electronics control the position of the valve 3 or valves and measure the sensor 5 response at a sample interval between 5 and 1000 seconds after the valve 3 switches the sample flow.

The invention provides a method of determining the concentration of a target gas in ambient air and where the gas concentration is proportional to the difference in sensor signals between when the gas sample flows directly to the sensor or flows via the selective scrubber 2.

In the new method the sensor signal after a predetermined time of sample flow through the scrubber 2 to the sensor 5 represents the signal of the sensor in the absence of the target gas. The sensor signal after a predetermined time of sample flow directly to the sensor 5 represents the signal of the sensor in the presence of the target gas.

In the new method the sensor signal after a predetermined time of sample flow through the scrubber 2 to the sensor 5 represents the signal of the sensor in the presence of the target gas, and the sensor signal after a predetermined time of sample flow directly to the sensor 5 represents the signal of the sensor in the absence of the target gas.

The invention provides a new device with the electrochemical sensor 5 for the measurement of SO2, H2S, CO, NH3, O3 or NO2.

In a new device as described herein for the measurement of SO2, the selective scrubber 1 includes a catalyst containing a silver catalyst, a Mn02 catalyst, potassium iodide or ferrous sulphate for the scrubbing of ozone and NO2, and selective scrubber 2 contains activated carbon, marble chips, calcium carbonate or an adsorbent for acidic gases.

In a new device described herein for the measurement of ]¾S, the selective scrubber 1 includes a catalyst containing a silver catalyst, a MnC>2 catalyst, potassium iodide or ferrous sulphate for the scrubbing of ozone and NO2, and selective scrubber 2 contains activated carbon, iron oxides or a purafil chemisorbent for H2S.

While the invention has been described with reference to specific embodiments, modifications and variations of the invention may be constructed without departing from the scope of the invention, which is defined in the following claims.

Claims

I claim:

1. Apparatus comprising: an instrument for measurement of one or more target gases in a sample, further comprising: a first path having a first inlet and a first outlet, at least one additional second path having a second inlet and a second outlet, at least one multiple- way valve having a first input port connected to the first outlet, having a second input port connected to the second outlet and having an output port, a connection connected to the output port, a gas sensor connected to the connection, a flow inducer connected to the instrument for flowing the gases in the first and second paths through the valve, the connection and the gas sensor, and a selective gas scrubber in the second path for removing a target gas from the sample.

2. The apparatus of claim 1, further comprising a gas flow divider having an inlet port and outlet ports connected to the first and second inlets of the paths.

3. The apparatus of claim 2, wherein the flow divider is a T.

4. The apparatus of claim 2, further comprising an input gas scrubber connected to the inlet port of the gas flow divider for removing selected gases from the sample.

5. The apparatus of claim 4, wherein the selected gases removed by the input gas scrubber are O₃ and NO₂.

6. The apparatus of claim 1, wherein the flow inducer is a pump connected to the gas sensor for drawing the sample through the gas sensor from the multiple- way valve and through the first or second path as determined by a condition of the multiple-way valve.

7. The apparatus of claim 6, wherein the multiple-way valve is a three-way valve.

8. The apparatus of claim 1, further comprising a humidity buffer in the connection between the output port of the multiple- way valve and the gas sensor.

9. The apparatus of claim 1, wherein the selective gas scrubber is selected to remove SO₂ or 1¾S from the sample.

10. Apparatus comprising a device for determining the concentration of a target gas in ambient air which transfers samples of the air to an electrochemical sensor, via a solenoid valve or valves which cycles the air to the sensor via a direct path or a path containing a selective scrubber of the target gas, electronics to control positions of the valve or valves and to measure the sensor responses at sample intervals between 5 and 1000 seconds after the valve switches the sample flow.

11. The apparatus of claim 1, comprising a method of determining the concentration of a target gas in ambient air comprising a device, wherein target gas concentration is proportional to a difference in sensor signals between when the gas sample flows directly to the sensor or flows to the sensor via the selective scrubber of the target gas.

12. The apparatus of claim 11, wherein the sensor signal after a predetermined time of sample flow through the selective scrubber of the target gas to the sensor represents a signal of the sensor in the absence of the target gas, and a sensor signal after a predetermined time of sample flow directly to the sensor represents the signal of the sensor in the presence of the target gas.

13. The apparatus of claim 10, wherein the electrochemical sensor is for the measurement of SO2, H2S, CO, NH3, O3 or NO2.

14. The apparatus of claim 10, wherein the device is for the measurement of SO2, wherein the selective scrubber contains activated carbon, marble chips, calcium carbonate or a adsorbent for acidic gases.

15. The apparatus of claim 10, further comprising an optional selective scrubber connected to inlets of the paths.

16. The apparatus of claim 15, wherein the selective scrubber comprises a catalyst containing a silver catalyst or Mn02 catalyst or potassium iodide or ferrous sulphate for the scrubbing of ozone and NO2.

17. The apparatus of claim 10, wherein the device is for the measurement of H2S, wherein the optional selective scrubber comprises a catalyst containing a silver catalyst, MnC>2 catalyst, potassium iodide or ferrous sulphate for the scrubbing of ozone and NO2 and the selective scrubber of the target gas comprises activated carbon, iron oxides or a purafil chemisorbent for H2S.

18. A method comprising: determining the concentration of a target gas in ambient air which transfers the sample air through an optional selective scrubber to an electrochemical sensor, via a solenoid valve or valves which cycles the air to the sensor via a direct path, and subsequently by a second path containing a selective scrubber, removing the target gas in the selective scrubber, and providing electronics to control the position of the valve or valves and to measure the sensor responses at a sample interval between 5 and 1000 seconds after the valve switches the sample flow.

19. The method of claim 18, wherein the gas concentration is proportional to the difference in sensor signals between when the gas sample flows directly to the sensor or flows via the selective scrubber.

20. The method of claim 19, wherein the sensor signal after a predetermined time of sample flow through the scrubber to the sensor represents the signal of the sensor in the absence of the target gas, and the sensor signal after a predetermined time of sample flow directly to the sensor represents the signal of the sensor in the presence of the target gas.