TWI700494B - Calibrator for calibrating gas sensing device, gas sensing device containing calibrator, and calibrating method - Google Patents

Abstract

A calibrator for calibrating a gas sensing device, comprising: a body and a gas generating unit housed in the body, the body being in communication with the gas sensing device, the gas generating unit having a gas generating solution, The gas generating solution can produce a calibration gas having a predetermined concentration and detectable by the gas sensing device. In addition, the present invention also provides a gas sensing device including a calibrator and a method of calibrating the gas sensing device.

Description

Calibrator for calibrating gas sensing device, gas sensing device containing the calibrator and calibration method

The invention relates to a calibrator for calibrating a gas sensing device, a gas sensing device containing the calibrator and a calibration method, in particular to a calibration gas capable of producing a calibration gas and calibrating the gas sensing device , And a gas sensing device and calibration method containing the calibrator.

The application field of gas sensor is very wide, whether it is industrial or household application, it can be used to detect the type and content of gas. However, since the gas sensor is easily affected by the ambient temperature, humidity or frequency of use during use, the measurement results of the sensed gas will be biased. Therefore, in order to ensure the accuracy of the measurement, it is generally measured Calibration is performed before or after the gas sensor is used for a predetermined period of time to ensure the accuracy of the gas sensor measurement. However, the standard gases generally used for gas sensor calibration are mostly filled in bulky high-pressure steel cylinders, which are not only dangerous and difficult to carry. It is easy and costly. Therefore, how to provide a calibration device that is low-cost, small in size, easy to carry, and can generate a specific concentration of standard calibration gas for calibrating the gas sensor, so that the gas sensor device can be more easily operated Correction is a problem to be solved by those skilled in the art.

Therefore, the purpose of the present invention is to provide a corrector for correcting a gas sensing device.

Therefore, the corrector of the present invention includes a body and a gas generating unit accommodated in the body.

The body communicates with the gas sensing device. The gas generating unit has a gas generating solution that can generate a calibration gas having a predetermined concentration and can be detected by the gas sensor, and the calibration gas sensing device can generate a calibration gas by using the measurement result of the calibration gas Used to calibrate the calibration parameters of the gas sensing device.

In addition, another object of the present invention is to provide a gas sensing device containing a corrector.

Therefore, the gas sensing device containing the corrector of the present invention includes a gas sensor and a corrector.

The gas sensor can be used to detect a predetermined gas molecule.

The corrector is in communication with the gas sensor, and includes a defining and a cavity Between the main body and a gas generating unit accommodated in the accommodating space, the gas generating unit includes a gas generating solution, the gas generating solution can generate a calibration gas having a predetermined concentration and can be detected by the gas sensing device, The gas sensor can use the measurement result of the calibration gas to generate a calibration parameter for calibrating the gas sensor device.

In addition, another object of the present invention is to provide a calibration method for a gas sensing device.

Therefore, the calibration method of the gas sensing device of the present invention includes the following steps.

Prepare the gas sensing device with the corrector as described above.

The gas generating unit is placed in the accommodating space, wherein the gas generating unit has a gas generating solution capable of generating the same calibration gas as the gas molecules sensed by the gas sensor.

The calibration gas generated by the gas generating solution is introduced into the gas sensor for sensing, and the measurement result of the calibration gas is used to generate a calibration parameter for calibrating the gas sensing device.

The effect of the present invention is that the gas sensor can be calibrated by a calibrator which is connected to the gas sensor and can be used to generate calibration gas with a predetermined type and concentration.

2: Gas sensor

21: Gas sensing film

22: Check the intake pipe

3: corrector

31: body

311: Wall

312: accommodation space

313: air outlet

314: exhaust port

32: Gas generating unit

321: Gas generating solution

322: Absorbent

33: Correct the intake pipe

34: Exhaust pipe

4: Air bag

5: Valve

The other features and effects of the present invention will be described in the embodiment with reference to the drawings Figure 1 is a schematic diagram illustrating a first embodiment of a gas sensing device containing a corrector according to the present invention; Figure 2 is a schematic diagram illustrating another structural aspect of the corrector according to the present invention; Figure 3 is a schematic diagram illustrating another connection between the corrector and the gas sensor of the present invention; Figure 4 is a schematic diagram illustrating a second embodiment of the gas sensing device containing the corrector according to the present invention; 5 is a current-time relationship diagram, illustrating the current-time relationship obtained by gas sensing using the first embodiment and the standard ammonia gas of the steel cylinder; Figure 6 is a current-time relationship diagram illustrating the first embodiment The current-time relationship obtained by gas sensing the calibrator of the example with the standard ammonia gas of the steel cylinder after being placed for 1 day; and Figure 7 is a current-time relationship diagram illustrating that the calibrator of the first embodiment is placed 7 After days, the current-time relationship obtained by gas sensing with the standard ammonia gas in the cylinder.

Before the present invention is described in detail, it should be noted that in the following description, similar elements are represented by the same numbers.

Referring to Figure 1, a first example of a gas sensing device containing a corrector of the present invention The embodiment includes a gas sensor 2 and a corrector 3.

The gas sensor 2 can be used to detect a predetermined gas molecule, has a gas sensing film 21 that can interact with the predetermined gas molecule, and a detection gas inlet pipe 22.

Specifically, the gas sensing film 21 can be used to detect, for example, but not limited to, amine gas, aldehyde gas, ketone gas, nitric oxide, ethanol, nitrogen dioxide, carbon dioxide, ozone, or sulfide gas. The amine gas is for example, but not limited to, ammonia, dimethylamine, or trimethylamine. The ketone gas is for example but not limited to acetone. The sulfide gas is, for example, but not limited to, hydrogen sulfide. The material of the gas sensing film 21 is selected from the group consisting of at least one sensing material having a functional group capable of sensing gas molecules to be detected. The functional group is selected from fluorenyl group, triphenylamine group and fluorenyl group-containing group, phenylene vinylene group, or dithiophene benzodithiophene group and thienothienyl group Department of the group. The sensing material with the functional group is for example but not limited to: poly(9,9-dioctylfluorene) [poly(9,9-dioctylfluorene), referred to as PFO], 9,9-dioctylfluorene-N -(4-butylphenyl)diphenylamine copolymer {poly[9,9-dioctylfluorene-co-N-(4-butylphenyl)diphenylamine]}, 9,9-dioctylfluorene-benzothiadiazole copolymer物[poly(9,9-dioctylfluorene-co-benzothiadiazole)], poly{4,8-bis[(2-ethylhexyl)thiophen-5-yl]benzo[1,2-b:4,5- b']Dithiophene-2,6-diyl.-tert-[2-(2'-ethylhexyl]thieno[3,4-b]thiophen-4,6-diyl}poly{[ 4,8-bis-(2-ethyl-hexyl-thiophene-5-yl)-benzo[1,2-b: 4,5-b']dithiophene-2,6-diyl]-alt-[2-( 2'-ethyl-hexanoyl)-thi eno[3,4-b]thiophen-4,6-diyl]}, referred to as PBDTTT-CT], poly{4,8-bis(5-(2-ethylhexyl)thiophen-2-yl)benzo[ 1,2-b; 4,5-b']Dithiophene-2,6-diyl-4-(2-ethylhexyl)-thieno[3,4-b]thiophene-2,6- Diyl}{poly[4,8-bis(5-(2-ethylhexyl)thiophene-2-yl)-benzo[1,2-b;4,5-b']dithiophene-2,6-diyl-4 -(2-ethylhexanoyl)-thieno[3,4-b]-thiophene)-2,6-diyl]}, or poly{4,8-bis(5-(2-ethylhexyl)thiophene-2-yl ) Benzo[1,2-b; 4,5-b']dithiophene-2,6-diyl-4-(2-ethylhexyloxycarbonyl)-3-fluoro-thieno[3, 4-b]thiophene-2,6-diyl)}{poly[4,8-bis(5-(2-ethylhexyl)thiophene-2-yl)-benzo[1,2-b; 4,5-b ']dithiophene-2,6-diyl-4-(2-ethylhexyloxycarbonyl)-3-fluoro-thieno[3,4-b]-thiophene))-2,6-diyl]} etc. The 9,9-dioctylfluorene-benzothiadiazole copolymer, for example, but not limited to: 9,9-dioctylfluorene-2,1,3-benzothiadiazole copolymer, or 9,9- Dioctylfluorene-1,2,3-benzothiadiazole copolymer, etc.

Preferably, the constituent material of the gas sensing film 21 is selected from poly(9,9-dioctylfluorene), 9,9-dioctylfluorene-N-(4-butylphenyl)diphenylamine copolymer Compound, 9,9-dioctylfluorene-benzothiadiazole copolymer, poly{4,8-bis[(2-ethylhexyl)thiophen-5-yl]benzo[1,2-b:4 ,5-b']Dithiophene-2,6-diyl.-tert-[2-(2'-ethylhexyl]thieno[3,4-b]thiophen-4,6-diyl} , Poly{4,8-bis(5-(2-ethylhexyl)thiophen-2-yl)benzo[1,2-b; 4,5-b']dithiophene-2,6-diyl- 4-(2-Ethylhexyl)-thieno[3,4-b]thiophen-2,6-diyl}, poly{4,8-bis(5-(2-ethylhexyl)thiophene- 2-yl)benzo[1,2-b;4,5-b']dithiophene-2,6-diyl-4-(2-ethylhexyloxycarbonyl)-3- Fluoro-thieno[3,4-b]thiophen-2,6-diyl)}, or any combination of the above, and the weight average molecular weight ranges from 5,000 to 300,000.

One end of the detection inlet pipe 22 is detachably connected with the gas sensor 2, and the other end can be used to input a gas to be measured for the gas sensor film 21 to detect.

Taking the gas sensor 2 as an example for detecting human breathing ammonia, the gas to be measured can be blown directly from the human body from the other end of the detection air inlet pipe 22 into the gas sensor 2 to use The gas sensing film 21 is used for detection; or, it is also possible to use a collector bag (not shown) that collects pre-treated (removed water vapor and carbon dioxide) breathing gas and the detection air inlet pipe 22 The other end is connected, and the gas to be tested can also be transported from the detection gas inlet pipe 22 to the gas sensor 2 for detection.

The corrector 3 is connected to the gas sensor 2 and can be used to calibrate the gas sensor 2.

In detail, the corrector 3 includes a body 31, a gas generating unit 32, a correcting inlet pipe 33, and an exhaust pipe 34. The main body 31 has a surrounding wall 311 defining an accommodating space 312, an air outlet 313 passing through the surrounding wall 311 and communicating with the accommodating space 312, and an exhaust port 314 passing through the surrounding wall 311. Wherein, both ends of the calibration gas inlet pipe 33 are respectively connected to the gas outlet 313 and the gas sensor 2, and the gas outlet pipe 34 is inserted into the gas outlet 314 and extends to the gas generating solution 321. Therefore, the calibration gas generated by the gas generating solution 321 in the accommodating space 312 can be transmitted to the gas sensor 2 through the calibration air inlet pipe 33, and external air can pass through the exhaust pipe 34 enters the gas generating solution 321.

It should be noted that the material or shape of the body 31 applicable to the first embodiment of the present invention is not particularly limited, as long as it can accommodate the gas generating unit 32 and does not react with the gas generating unit 32. can. In addition, because the main body 31 can be designed to accommodate the gas generating unit 32 that generates the calibration gas for the current calibration, the main body 31 can be flexibly selected with a smaller volume or a size suitable for the environment (for example, a suitable device can be selected. A small or portable container placed on the table), which is more convenient to use.

The gas generating unit 32 has a gas generating solution 321 accommodated in the accommodating space 312 of the body 31, and the gas generating solution 321 can be used to generate a calibration with a predetermined concentration and which can interact with the gas sensing film 21 gas. The calibration gas can enter the gas sensor 2 through the calibration gas inlet pipe 33, and the gas sensor 2 measures the calibration gas and obtains a calibration based on which the gas sensing film 21 can be calibrated. parameter.

It should be noted that the gas generating solution 321 is composed of a buffer solution and a substance that is soluble in the buffer solution and used to generate a calibration gas. The composition of the buffer solution and the calibration gas used to generate the calibration gas can be determined by the gas sensor. The type of gas sensed by the membrane 21 has different choices; and the concentration of the gas generating solution 321 can be adjusted according to the concentration of the required calibration gas, so that the required calibration gas can be generated by the gas generating solution 321. For example, when the gas sensing film 21 is used for sensing ammonia gas, the gas generating solution 321 may use an aqueous ammonia chloride solution as a buffer solution and produce Ammonia-generating ammonia water and ammonia chloride are mixed with the buffer solution. When the gas sensing film 21 senses acetic acid gas, the gas generating solution 321 can be a buffer solution of sodium acetate aqueous solution and added to the buffer solution Acetic acid that can produce acetic acid gas. It should be noted that the purpose of the buffer is to control the concentration of the generated calibration gas, and there are different options depending on the type of the generated calibration gas, and the buffer can be an aqueous solution or a non-aqueous solution. More specifically, taking the gas generating solution 321 as a solution containing ammonia water and ammonia chloride that can generate ammonia gas, the content ratio and total concentration of ammonia water and ammonia chloride in the solution can be adjusted to obtain the total concentration. The concentration of pre-generated ammonia (calibration gas).

Accordingly, when the gas sensor 2 is to be calibrated, the calibrator 3 can be used, and the gas generating unit 32 of the calibrator 3 can generate a calibration gas with a preset type and concentration. The calibration gas is used as a standard gas for calibrating the gas sensor 2 to calibrate the gas sensor 2.

In addition, it should be noted that in some implementations, the gas generating unit 32 may also have a certain temperature device for keeping the temperature of the accommodating space 312 of the body 31 at a preset temperature, which is beneficial for use in different environments. At this time, the gas concentration produced can still be accurately controlled.

In addition, in some embodiments, the gas sensing device may further include a pumping unit (not shown) arranged downstream of the gas sensor. The pumping unit can provide negative pressure so that the calibration gas can flow into the gas sensor 2 more stably.

Referring to FIG. 2, in some embodiments, the calibration intake pipe 33 and the exhaust The pipe 34 can also be provided with a valve 5 respectively, which serves as a flow switch for controlling whether the calibration gas enters the gas sensor 2 and whether the gas in the accommodating space 312 circulates with the outside.

Referring to FIG. 3, in some embodiments, the calibration gas inlet pipe 33 and the detection gas inlet pipe 22 may also be converged and communicated with each other before communicating with the gas sensor 2. In FIG. 3, one end of the detection gas inlet pipe 22 contains the gas collecting bag 4 of the gas to be measured, and the other end is first connected with the calibration gas inlet pipe 33 and then connected with the gas sensor 2 as an example. Therefore, in order to control the flow direction of the calibration gas and the gas to be measured after being connected, a place where the calibration gas inlet pipe 33 and the detection gas inlet pipe 22 converge can be provided to control the detection gas inlet pipe 22 and the calibration gas inlet pipe. The valve 5 where the gas in the pipe 33 flows. The valve 5 can be, for example, but not limited to a three-phase valve, so as to control whether the gas to be measured and the calibration gas enter the gas sensor 2.

Accordingly, when the gas sensing device of the present invention is used to measure the gas to be measured, the valve 5 can be turned to make the detection inlet pipe 22 communicate with the gas sensor 2, and at the same time, the calibration inlet is closed. The passage between the gas pipe 33 and the gas sensor 2 can introduce the gas to be measured into the gas sensor 2 to detect the gas to be measured.

When the gas sensor 2 is to be calibrated by the gas sensing device of the present invention, the gas generating solution 321 that can generate the same calibration gas as the gas molecules sensed by the gas sensor 2 is placed in The accommodating space 312, and rotating the valve 5, closes the passage between the detection inlet pipe 22 and the gas sensor 3, so that the calibration is The gas pipe 33 communicates with the gas sensor 2, and then the calibration gas generated by the gas generating solution 321 is introduced into the gas sensor 2, and then the gas sensor 2 can be used to sense the calibration gas and based on the sensing result A calibration parameter is obtained, and the gas sensor 2 is calibrated using the calibration parameter. The calibration parameter can be calculated by using the gas sensor 2 to measure the current change of the calibration gas to obtain a corresponding gas concentration value, and then the calculated gas concentration value and the standard calibration gas The concentration is compared to obtain the measured offset value, and then the calibration parameter of the gas sensor 2 is obtained.

Referring to FIG. 4, a second embodiment of the gas sensing device containing a corrector of the present invention is substantially the same as the first embodiment, except that the gas generating unit 32 of the corrector 3 of the second embodiment It also includes an absorbing member 322 disposed in the accommodating space 312 for absorbing liquid.

Specifically, the absorbent member 322 is made of a material that can absorb liquids and is breathable, such as super absorbent polymer or sponge, and can be in a single aggregate or composed of multiple small aggregates. Composition, the gas generating solution 321 is adsorbed by the absorbing member 322, so that the gas generating solution 321 will not flow freely, so as to avoid the problem of the gas generating solution 321 overflowing when the body 31 is poured. Safety of use. When the corrector 3 of the second embodiment is used, it is sufficient to make the absorbent 322 fully absorb the gas generating solution 321 to be completely wetted and place it in the containing space 312. In FIG. 4, the absorbent member 322 is composed of a plurality of small aggregates composed of sponge blocks, and the gas generating solution 321 has been adsorbed by the absorbent member 322 as an example. Obviously, the actual implementation is not limited to this form.

Next, the first embodiment of the present invention and the conventional steel cylinder are used to provide gas, and the gas sensor 2 is used for sensing, so as to measure the sensing current change of the gas sensor 2.

Wherein, the gas sensor 2 uses a gas sensing film 21 capable of sensing ammonia gas (the constituent material of the gas sensing film 21 is PBDTTT-CT) as an example, wherein the gas generating solution of the corrector 3 321 is capable of generating ammonia gas with a concentration of 500ppb, and the gas generating solution 321 of the corrector 3 is to take 0.036mL of 28% ammonia water and 24.9g of ammonia chloride, and then add DIwater to 1 liter , Derived from configuration. The cylinder provides 500ppb standard ammonia gas.

Referring to Figure 5, Figure 5 is the staggered use of the aforementioned cylinder to input 500ppb standard ammonia gas and the 500ppb calibration gas (ammonia) generated by the corrector 3 into the gas sensor 2 in different preset time intervals. The result of the sensed current measured by the sensor 2. In FIG. 5 (A) is the current sensing result of using a steel cylinder to input standard ammonia gas, and (B) is the current sensing result of using the calibration gas generated by the corrector 3 of the present invention to input the gas sensor 2.

It can be seen from the results in Fig. 5 that when standard ammonia gas is passed through a conventional steel cylinder, the measured current response value (response) is about 19%-20%, and the correction generated by the corrector 3 Gas, the current response value measured by the gas sensor 2 is also about 19%~22%. The measurement results of the two are roughly the same, and after a time interval (such as Fig. 5, the first measurement is about 1870 seconds, the last measurement is about 2870 seconds), the current response value measured by the gas sensor 2 can also be maintained at 19%~20%, showing the present invention The corrector 3 can indeed provide a stable calibration gas, and can calibrate the gas sensor 2.

Referring to Figures 6 and 7, Figure 6 shows the first embodiment of the present invention that can be used to generate ammonia gas corrector 3 after 1 day and 7 days, and then use the gas sensor 2 to the corrector 3 Current sensing results of the generated ammonia gas and standard cylinder ammonia gas. In FIGS. 6 and 7 (A) is the current sensing result of using a steel cylinder to input standard ammonia gas, and (B) is the current sensing result of using the calibration gas generated by the corrector 3 of the present invention. It can be seen from the measurement results in FIG. 7 that the current response value (~44%) of the corrector 3 of the present invention after being placed for 7 days can still maintain the same as the current measured by the corrector 3 after being placed for 1 day (Figure 6). The response value (~40%) is equivalent, which shows that the corrector 3 of the present invention can indeed provide a stable and long-lasting correction gas to correct the gas sensor 2.

In summary, the gas sensing device of the present invention including the corrector can calibrate the gas sensing device 2 through the correction gas generated by the corrector 3. The corrector 3 is low in cost, small in size, easy to carry, and easier to calibrate and use the gas sensing device, so it can indeed achieve the purpose of the invention.

However, the above are only examples of the present invention. When the scope of implementation of the present invention cannot be limited by this, all simple equivalent changes and modifications made in accordance with the scope of the patent application of the present invention and the content of the patent specification still belong to Within the scope of the patent for the present invention.

2‧‧‧Gas sensor

21‧‧‧Gas sensing film

22‧‧‧Detecting the intake pipe

3‧‧‧Correcter

31‧‧‧Ontology

311‧‧‧Wall

312‧‧‧accommodating space

313‧‧‧Exhaust port

32‧‧‧Gas generating unit

321‧‧‧Gas generating solution

33‧‧‧Correcting intake pipe

Claims (10)

A calibrator for calibrating a gas sensing device, comprising: a body and a gas generating unit accommodating the body, the body communicating with the gas sensing device, the gas generating unit having a gas generating solution, the gas The generating solution can generate a calibration gas having a predetermined concentration and can be detected by the gas sensing device, the gas generating solution includes a buffer solution for dissolving the calibration gas, and the gas sensing device can use the measurement of the calibration gas As a result, a calibration parameter for calibrating the gas sensing device is generated. The corrector according to claim 1, wherein the gas generating unit further has an absorbing member that is disposed in the accommodating space and can absorb the gas generating solution. The corrector according to claim 2, wherein the absorbing member is made of a material that can absorb liquid. A gas sensing device containing a corrector, comprising: a gas sensor, which can be used to detect a predetermined gas molecule; and a corrector, which is connected to the gas sensor, and includes a body defining an accommodating space and A gas generating unit accommodated in the accommodating space, the gas generating unit including a gas generating solution, the gas generating solution can generate a calibration gas having a predetermined concentration and can be detected by the gas sensor, the gas generating solution A buffer solution for dissolving the calibration gas is included, and the gas sensor can use the measurement result of the calibration gas to generate a calibration parameter for calibrating the gas sensor device. According to claim 4, the gas sensing device with a corrector, wherein the gas generating unit further has an absorption member which is arranged in the containing space and can absorb the gas generating solution. The gas sensing device containing a corrector according to claim 5, wherein the absorbent is made of a material that can absorb liquid. The gas sensing device containing a corrector according to claim 4, wherein the gas sensor has a gas sensing film and a detection gas inlet pipe, the gas sensing film can interact with the predetermined gas molecule, and the detection enters One end of the gas pipe is connected with the gas sensing membrane, and the other end can be used to input a gas to be measured. The gas sensing device containing a corrector according to claim 7, wherein the corrector has a correction inlet pipe connecting the gas sensor and the main body, and the detection inlet pipe and the correction inlet pipe are connected to each other The gas sensing device containing the corrector also includes a valve that can control the gas flow direction of the corrected intake pipe and the detection intake pipe. According to claim 4, the gas sensing device with a corrector further includes a gas extraction unit, which is arranged downstream of the gas sensor and can provide a negative pressure for the calibration gas to flow into the gas sensor. A method for calibrating a gas sensing device, comprising: preparing a gas sensing device containing a corrector as described in claim 4; placing the gas generating unit in the containing space, wherein the gas generating unit has a gas Generating a solution, wherein the gas generating solution can generate the same calibration gas as the gas molecules sensed by the gas sensor; and introducing the calibration gas generated by the gas generating solution into the gas sensor for sensing, and using the The measurement result of the calibration gas generates a calibration parameter for calibrating the gas sensing device.

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