CN109716118B - Acetylene gas analysis equipment and method for underground cable - Google Patents
Acetylene gas analysis equipment and method for underground cable Download PDFInfo
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- G—PHYSICS
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
- G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
- G01N27/12—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a solid body in dependence upon absorption of a fluid; of a solid body in dependence upon reaction with a fluid, for detecting components in the fluid
- G01N27/129—Diode type sensors, e.g. gas sensitive Schottky diodes
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
- G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
- G01N27/12—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a solid body in dependence upon absorption of a fluid; of a solid body in dependence upon reaction with a fluid, for detecting components in the fluid
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/0004—Gaseous mixtures, e.g. polluted air
- G01N33/0009—General constructional details of gas analysers, e.g. portable test equipment
- G01N33/0027—General constructional details of gas analysers, e.g. portable test equipment concerning the detector
- G01N33/0036—Specially adapted to detect a particular component
Abstract
The application provides acetylene gas analysis equipment and an acetylene gas analysis method for underground cables. The device utilizes the gas to be analyzed to contact with an acetylene hydration catalyst, and the generated acetaldehyde is used for analyzing the acetylene content in the gas. Therefore, even a small amount of acetylene gas of about 10mL can be detected by the method, the detection limit is about 0.01ppm, the method can be used for accurate diagnosis, and the method is portable, so that the acetylene gas analysis can be directly carried out on site.
Description
Technical Field
The present invention relates to an acetylene gas analyzing apparatus and an acetylene gas analyzing method, and more particularly, to an acetylene gas analyzing apparatus and an acetylene gas analyzing method for an underground cable.
Background
Underground cable is a facility of burying the electric wire in the underground, and its component structure is complicated, can replace overhead communication and electric power transmission line, promotes the city pleasing to the eye, in the demand constantly increases. In addition, in order to reduce the possibility of complaints at the time of construction, when a new production yard is developed, cable facilities are previously erected in a public area inside the yard.
With the increasing demand for underground cable facilities in recent years, there has been an increasing demand for development of a convenient detection technique capable of discovering and preventing equipment failure in advance.
One of the conventional inspection techniques, gas from underground cable closure boxes is collected according to the method defined in ASTM D3612 and analyzed by Gas Chromatography (GC) in the laboratory. The collected gas is separated and measured by the above method, and the measured gas concentrations of hydrogen, carbon dioxide, methane, acetylene, etc. are used to determine whether the insulating oil is abnormal, whether the insulating paper is overheated, and the equipment is abnormal, such as arc discharge, and dielectric strength deterioration. However, in the method of gas analysis using Gas Chromatography (GC) in a laboratory, the gas in the junction box must be collected as a sample before being sent to the laboratory. Therefore, the handling process may affect the accuracy of the results, and the cost of the equipment for performing the gas chromatography is high, and the analysis only performed by experts is a disadvantage of this method.
In addition, there is an analysis method using a Flame Ionization Detector (FID) for the analysis of acetylene gas. However, if the sampled gas contains only a trace amount of acetylene, it is difficult to measure, and the sample needs to be transported from the site to a laboratory, and during the transportation process, the composition of the gas may change, which may reduce the analysis accuracy.
Therefore, in order to improve the accuracy of fault detection, a method for directly collecting samples on site and analyzing the samples is needed. More importantly, when the gas abnormality is detected by the detection personnel, the detection personnel can directly bring the detection personnel to the site for detection by the portable detection equipment.
The acetylene detecting devices currently available on the market can be classified into two types, i.e., a diffusion type detecting device for detecting gas diffused in air, and a suction type detecting device for detecting gas forcibly sucked by a pump or an air aspirator (air aspirator). In the case of the diffusion type detector, detection is performed by gas diffused in the air, and therefore the concentration of the gas to be analyzed must be very high, for example, the concentration must be at least 10,000ppm or more, and therefore it is not suitable for diagnosing abnormality of the electric power facility. Although the suction type detector has sensitivity superior to the diffusion type detector and can detect a concentration of several ppm to 1,000ppm, if the amount of a sample required for detection is several liters or more, the detector must be continuously sucked with the sample, and therefore, if only a small amount of gas is present inside the terminal box, analysis cannot be performed.
Therefore, the demand of underground cable acetylene gas analysis equipment which can complete acetylene gas detection by using a small amount of gas samples, can reduce the detection limit, increase the detection accuracy, is convenient to carry and can be directly analyzed on site is increasing at present.
Disclosure of Invention
Problems to be solved
The invention aims to provide acetylene gas analysis equipment for underground cables, which can analyze acetylene gas by using a trace amount of samples, reduces the detection lower limit, improves the detection precision, is convenient to carry and can directly perform gas analysis on site, and an analysis method thereof.
Means for solving the problems
One embodiment of the present application is an acetylene gas analysis apparatus for underground cables. A reaction zone in the equipment is used for storing an acetylene hydration catalyst solution, so that the gas to be analyzed can pass through the acetylene hydration catalyst to hydrate the acetylene in the gas into acetaldehyde; the measuring area is connected with the reaction area, when acetaldehyde is introduced into the measuring area, ZnO nanocrystals with the surfaces coated with amine gas-containing silane compounds are arranged on the inner wall of the measuring area and can react with the acetaldehyde to change the conductivity, and the change of the conductivity is measured at the position; in addition, a quantitative analysis area is provided, the conductivity variation obtained by detection is analyzed, the acetylene content in the gas to be analyzed is calculated, and the result is displayed.
Another embodiment in this application is a method for acetylene gas analysis of underground cables by first reacting a gas to be analyzed with an acetylene hydration catalyst and then using acetaldehyde produced by the reaction to calculate the acetylene content of the gas to be analyzed.
Effects of the invention
The application provides acetylene gas analysis equipment and an acetylene gas analysis method, which can detect acetylene gas even in a trace sample of 10mL, have a detection limit of 0.1ppm, can be used for precise diagnosis, are convenient to carry, can directly perform gas analysis on site and can detect the equipment fault condition in advance.
Drawings
Fig. 1 is a structure of an acetylene gas detecting apparatus according to the present application.
FIG. 2 is a simplified schematic diagram of a conventional gas chromatographic gas analysis method.
Fig. 3 is an overview of the acetylene gas analysis method used in the present application.
Detailed Description
One embodiment in this application is an acetylene gas analysis apparatus for underground cables. A reaction zone in the equipment is used for storing an acetylene hydration catalyst solution, so that the gas to be analyzed can pass through the acetylene hydration catalyst to hydrate the acetylene in the gas into acetaldehyde; the measuring area is connected with the reaction area, when acetaldehyde is introduced into the measuring area, ZnO nanocrystals with the surfaces coated with amine gas-containing silane compounds are arranged on the inner wall of the measuring area and can react with the acetaldehyde to change the conductivity, and the change of the conductivity is measured at the position; in addition, a quantitative analysis area is provided, the conductivity variation obtained by detection is analyzed, the acetylene content in the gas to be analyzed is calculated, and the result is displayed.
By the analysis method, even a trace sample of about 10mL can be used for detecting acetylene gas, the detection limit is 0.1ppm, the method can be used for precise diagnosis, is convenient to carry, can be directly used for gas analysis on site, and can detect the condition of equipment failure in advance.
Fig. 1 is a structure of an acetylene gas detecting apparatus according to the present application. Hereinafter, an acetylene gas analyzing apparatus in the example will be explained with reference to fig. 1.
The acetylene gas analyzing apparatus of the present application comprises three blocks of a hydration reaction zone (100), a conductivity measurement zone (200), and a quantitative analysis zone (300).
The hydration reaction zone (100) stores an acetylene hydration catalyst (101), and when the gas (G) to be analyzed is passed through the acetylene hydration catalyst in the hydration reaction zone, the acetylene in the gas (G) to be analyzed generates acetaldehyde through hydration reaction.
Specifically, the container for storing the acetylene hydration catalyst solution (101) in the hydration reaction zone (100) has a double-wall structure, and therefore, the effect of keeping the acetylene hydration catalyst solution warm is excellent, and the efficiency of converting acetylene in the gas (G) to be analyzed into acetaldehyde can be improved.
The hydration reaction zone (100) is not particularly limited in volume and may be between 50mL and 100 mL. Within this range, the device can be made more portable. In addition, the solution stored inside is beneficial to improving the durability and safety of equipment in terms of storing the acetylene hydration catalyst solution.
Specifically, the acetylene hydration catalyst solution (101) contains [ Ru ] in a concentration of 0.5mM-2.0mMⅢ(EDTA-H)Cl]2H2O catalyst, at a concentration of 0.5mM, 0.6mM, 0.7mM, 0.8mM, 0.9mM, 1.0mM, 1.1mM, 1.2mM, 1.3mM, 1.4mM, 1.5mM, 1.6mM, 1.7mM, 1.8mM, 1.9mM, or 2.0 mM. In the above case, the efficiency of converting acetylene in the gas (G) to be analyzed into acetaldehyde is excellent, the detection lower limit can be reduced, and the minimum amount of gas (G) to be analyzed required at the time of detection can be reduced.
In the examples, acetylene hydration catalyst [ RuⅢ(EDTA-H)Cl]2H2The reaction formula of the O solution converting acetylene in the gas (G) to be divided into acetaldehyde (hydration reaction) is shown in chemical formula 1.
[ chemical formula 1]
The reaction zone (100) is provided with a heater (103) which can keep the temperature of the acetylene hydration catalyst solution (101) at about 70 ℃ to 90 ℃, and in the temperature range, the efficiency of converting acetylene in the gas (G) to be analyzed into acetaldehyde is excellent, the sensitivity of the analysis equipment can be improved, and the detection lower limit is reduced.
The temperature of the acetylene hydration catalyst solution (101) is about 75 ℃ to 85 ℃, and may be adjusted to 75 + -0.1 ℃, 76 + -0.1 ℃, 77 + -0.1 ℃, 78 + -0.1 ℃, 79 + -0.1 ℃, 80 + -0.1 ℃, 81 + -0.1 ℃, 82 + -0.1 ℃, 83 + -0.1 ℃, 84 + -0.1 ℃ or 85 + -0.1 ℃. Within the above temperature range, the efficiency of conversion of acetylene to acetaldehyde in the gas (G) to be analyzed can be improved upward.
The hydration reaction zone (100) is provided with a mass flow regulator (104) which can regulate the injection speed of the gas (G) to be analyzed into the acetylene hydration catalyst solution (101), and the mass flow regulator (104) can regulate the injection speed of the gas (G) to be analyzed into the acetylene hydration catalyst solution (101) in the form of bubbles at a flow rate of about 20mL/s to 30mL/s, possibly 20mL/s, 21mL/s, 22mL/s, 23mL/s, 24mL/s, 25mL/s, 26mL/s, 27mL/s, 28mL/s, 29mL/s, 30 mL/s. Within this range, the efficiency of conversion of acetylene to acetaldehyde in the gas (G) to be analyzed is excellent, the detection lower limit can be lowered, and the minimum amount of the gas (G) to be analyzed required for detection can be reduced.
The interior of the hydration reaction zone (100) is divided into an upper space and a lower space, and a permselective membrane (105) which only allows gas to pass is arranged. The permselective membrane (105) is permeable only to gases, but not to the acetylene hydration catalyst solution (101). In the above case, acetaldehyde generated after the gas to be analyzed passes through the acetylene hydration catalyst solution (101) can be collected through the permselective membrane (105).
In the hydration reaction zone (100) there is also provided a piston (106) connected to the permselective membrane (105) to control the axial movement of the permselective membrane (105), in which case it is easier to regulate the pressure generated when the volume of the gas (G) to be analyzed containing acetaldehyde changes after passing through the permselective membrane (105) and it is also easier to control the amount of gas flowing into the conductivity measurement zone.
The hydration reaction zone (100) also has a discharge port (107) for discharging the acetylene hydration catalyst solution (101) and regulating the pressure in the vessel. Such a design makes it easier to adjust the pressure generated inside when injecting the gas (G) to be analyzed into the hydration reaction zone (100).
The pressure in the hydration reaction zone (100) should be about 0.5atm to 1.5atm, such as 0.5atm, 0.6atm, 0.7atm, 0.8atm, 0.9atm, 1.0atm, 1.1atm, 1.2atm, 1.3atm, 1.4atm or 1.5 atm. Within the above range, the efficiency of converting acetylene in the gas (G) to be analyzed into acetaldehyde is excellent, the rate of inflow of the gas (G) to be analyzed can be more easily adjusted, and the portability of the apparatus is improved.
In summary, a container for storing an acetylene hydration catalyst solution is provided in the hydration reaction zone (100), a heater (103) for adjusting the temperature of the acetylene hydration catalyst solution, a mass flow regulator (104) for adjusting the amount of a gas to be analyzed to be injected into the acetylene hydration catalyst solution, a selectively permeable membrane (105) for allowing only the gas to pass therethrough, and a discharge port (106) for discharging the acetylene hydration catalyst solution and adjusting the internal pressure are provided in the container. Therefore, the acetylene gas analyzing apparatus provided with the hydration reaction zone (100) is excellent in the efficiency of converting acetylene in the gas (G) to be analyzed into acetaldehyde, can adjust the inflow speed of the gas (G) to be analyzed, can lower the detection lower limit, and can lower the minimum amount (G) of the gas (G) to be analyzed required for detection.
The conductivity measuring region (200) is connected to the hydration reaction region (100) and is a reaction vessel. The gas (G) to be analyzed produces acetaldehyde after passing through the hydration reaction zone (100), and then flows therein.
The inner wall of the conductivity measuring region (200) is coated with ZnO nanocrystals (202) containing an amine gas silane compound, and the surfaces of the ZnO nanocrystals react with acetaldehyde flowing into the conductivity measuring region (200) to change the conductivity.
In the conductivity measurement region (200), the change in conductivity caused when ZnO nanocrystals coated with an amine gas-containing silane compound on the surface are reacted with acetaldehyde can be measured.
The change in conductivity of the conductivity measurement zone (200) results from the reversible reaction of amine gas (amine) with imine (imine) due to acetaldehyde.
The amine gas-containing silane compound is N- (2-aminoethyl) aminopropyltriethoxysilane (N- (2-aminoethyl) aminopropyltriethoxysilane). Under the condition, the bonding force and conductivity transmission degree of the ZnO nanocrystals and the silane compound containing the amine gas are excellent, and the sensitivity and detection accuracy of the analytical equipment can be improved.
In the examples, the amine gas-containing silane compound is N- (2-aminoethyl) aminopropyltriethoxysilane (N- (2-aminoethyl) aminopropyltriethoxysilane). The reversible reaction efficiency of amine gas (amine) and imine (imine) generated after the reaction with acetaldehyde is excellent, and the change of conductivity can be increased. The reaction occurred in the above case is shown in chemical formula 2.
[ chemical formula 2]
The conductivity measuring area (200) is provided with a light source (203) which can trigger the reaction of amine gas and acetaldehyde, and the reaction starting time and the reaction speed of the amine gas and the acetaldehyde can be adjusted.
Also in the conductivity measurement region (200) is a conductivity tester (204) for measuring the amount of change in conductivity after the gas to be analyzed is brought into contact with the ZnO nanocrystals whose surfaces are coated with the amine gas-containing silane compound.
In the conductivity measurement area (200), the acetylene content calculated from the change in conductivity is displayed in the quantitative analysis area (300). Therefore, the quantitative analysis section (300) is provided with a display device (301) for displaying the result value, and the type of the display device (301) is not particularly limited.
In the quantitative analysis section (300), the acetylene content in the gas (G) to be analyzed can be calculated by the following formula 1.
[ formula 1]
Ac(ppm)＝{Ec2/(Mw2/F)}-{Ec1/(Mw1/F)}
In formula 1, Ac is the amount of acetylene gas (unit: ppm) contained in the gas to be analyzed, Ec1 is the conductivity (unit: mho) measured before the start of analysis, Mw1 is the molecular weight (unit: g/mol) of an imine group (imine group), Ec2 is the conductivity (unit: mho) measured after the start of analysis, Mw2 is the molecular weight (unit: g/mol) of an amine group (amine group), and F is the Faraday constant (Faraday constant) (unit: C/mol).
In formula 1, "before starting the analysis" refers to a state before the gas (G) to be analyzed flows into the hydration reaction region (100), and "after starting the analysis" refers to a state after the gas (G) to be analyzed flows into the hydration reaction region (100), or may refer to a state after the amine gas and acetaldehyde react due to the light source in the conductivity measurement region (200).
In the examples, the amine gas-containing silane compound was N- (2-aminoethyl) aminopropyltriethoxysilane (N- (2-aminoethyl) aminopropyltriethoxysilane), the Faraday constant F was 96485(C/mol), the molecular weight of the Mw1 imine group (amine group) was 265.29(g/mol), and the molecular weight of the Mw2 amine group was 237.29 (g/mol). The acetylene content of the gas (G) to be analyzed can be calculated in the quantitative analysis region (300) by the following formula 1A.
[ formula 1A ]
Ac(ppm)＝(Ec2/0.002459)-(Ec1/0.002750)
In formula 1A, Ac is the amount of acetylene gas (unit: ppm) contained in the gas to be analyzed, Ec1 is the electrical conductivity (unit: mho) measured before the start of analysis, and Ec2 is the electrical conductivity (unit: mho) measured after the start of analysis. In formula 1A, the value of 0.002459(mg/mC) is calculated from 237.29/96485 ═ 0.002459, and the value of 0.002750(mg/mC) is calculated from 265.29/96485 ═ 0.002750.
The acetylene analysis equipment for the underground cable can detect the acetylene content in the gas (G) to be analyzed, and the detection limit is below 10ppm, possibly 10ppm, 5ppm, 1ppm or 0.1ppm, so that the equipment can be directly brought to the site, and even if only trace gas exists, the detection can be carried out.
The minimum amount of gas that can be analyzed by the acetylene analyzing apparatus for underground cables in the present application is about 5mL or more, for example, 5mL, 10mL, 15mL, 20mL, 25mL, 30mL, 35mL, 40mL, 45mL, 50mL or more. Therefore, the apparatus can be brought to the site directly, and even if only a trace amount of gas is collected, an abnormality can be detected.
Another embodiment of the present application is an analytical method in which a gas to be analyzed is contacted with an acetylene hydration catalyst to produce acetaldehyde, and the acetylene content of the gas is calculated. And this method must be performed by the aforementioned acetylene gas analyzing apparatus.
The method for analyzing acetylene gas comprises the steps of (a) contacting the gas to be analyzed with an acetylene hydration catalyst solution to collect the generated acetaldehyde, (b) reacting the acetaldehyde with ZnO nanocrystals of which the surfaces are coated with amine gas-containing silane compounds to measure the variation of the conductivity after the reaction, and (c) calculating the acetylene content in the gas to be analyzed through the variation of the conductivity.
Specifically, the aforementioned hydration reaction may be carried out at about 70 ℃ to 90 ℃. Within the above temperature range, the efficiency of converting acetylene to acetaldehyde in the gas (G) to be analyzed is excellent, and the sensitivity of the analyzing apparatus can be improved, reducing the detection margin.
The temperature of the hydration reaction is about 75 ℃ to 85 ℃, for example, it can be adjusted to 75. + -. 0.1 ℃, 76. + -. 0.1 ℃, 77. + -. 0.1 ℃, 78. + -. 0.1 ℃, 79. + -. 0.1 ℃, 80. + -. 0.1 ℃, 81. + -. 0.1 ℃, 82. + -. 0.1 ℃, 83. + -. 0.1 ℃, 84. + -. 0.1 ℃ or 85. + -. 0.1 ℃. Within the above temperature range, the efficiency of conversion of acetylene to acetaldehyde in the gas (G) to be analyzed can be further improved.
The acetylene hydration catalyst solution may contain 0.5mM to 2.0mM of [ RuⅢ(EDTA-H)Cl]2H2And (3) an O catalyst. In the above case, the efficiency of conversion of acetylene to acetaldehyde in the gas (G) to be analyzed is excellent, the detection lower limit can be lowered, and the minimum amount of gas (G) to be analyzed required at the time of detection can be reduced.
In addition, the above-mentioned acetylene gas analysis method is to react ZnO nanocrystals whose surfaces are coated with silane compounds containing amine gas with acetaldehyde, and measure the amount of change in electrical conductivity.
This reaction is a reversible reaction between amine gas (amine) and imine (imine) using acetaldehyde, and the amount of change in conductivity was measured.
In the above method, the amine gas-containing silane compound is N- (2-aminoethyl) aminopropyltriethoxysilane (N- (2-aminoethyl) aminopropyltriethoxysilane). Under the condition, the bonding force and the conductivity transmission degree of the ZnO nanocrystal and the silane compound containing the amine gas are excellent, and the sensitivity and the detection precision of analytical equipment can be improved.
Furthermore, the reaction of amine gas with acetaldehyde is triggered via a light source.
The acetylene content in the gas to be analyzed can be calculated by the following formula 1.
[ formula 1]
Ac(ppm)＝{Ec2/(Mw2/F)}-{Ec1/(Mw1/F)}
In formula 1, Ac is the amount of acetylene gas (unit: ppm) contained in the gas to be analyzed, Ec1 is the conductivity (unit: mho) measured before the start of the analysis, Mw1 is the molecular weight (unit: g/mol) of an imine group (imine group), Ec2 is the conductivity (unit: mho) measured after the start of the analysis, Mw2 is the molecular weight (unit: g/mol) of an amine group (amine group), and F is the Faraday constant (Faraday constant) (unit: C/mol).
The underground cable acetylene analysis equipment can detect the acetylene content in the gas (G) to be analyzed, the detection limit is 10ppm or less, and may be 10ppm, 5ppm, 1ppm or 0.1ppm, so that the equipment can be directly carried to the site, and even if only a trace amount of gas exists, the acetylene content can be detected.
The underground cable acetylene analysis apparatus of the present application can analyze a minimum amount of gas of about 5mL or more, for example, 5mL, 10mL, 15mL, 20mL, 25mL, 30mL, 35mL, 40mL, 45mL, 50mL or more. Therefore, the device can be carried to the site, and even if only a trace amount of gas is collected, the abnormality can be detected.
Examples
In the following embodiments, the configuration and operation method of the present application will be described in detail, however, the following description is for the purpose of assisting understanding of the present application, and the scope of the present application is not limited to the following embodiments. In addition, the contents not described in the specification are all those that can be inferred by those skilled in the art, and thus the description is omitted.
Example 1
The device comprises a hydration reaction zone, a double-wall container, a heater and a mass flow regulator, wherein the double-wall container can store acetylene hydration catalyst solution; a selectively permeable membrane that can collect air; and a discharge port for controlling the discharge amount of the aqueous acetylene hydration catalyst solution to adjust the internal pressure of the vessel.
After passing through the hydration reaction zone, the gas to be analyzed containing acetaldehyde flows into the conductivity measurement zone connected thereto. The inner wall of the conductivity measuring area is provided with ZnO nano crystals with the surfaces coated with amine gas-containing silane compounds, and the reaction of the ZnO nano crystals and acetaldehyde can be triggered by a light source.
In addition, the quantitative analysis region is connected to the conductivity measurement region, and the result of calculating the acetylene content in the gas to be analyzed through the amount of change in conductivity is shown here.
50mL of distilled water was filled in the hydration reaction zone and the inside air was removed by a piston, followed by addition of [ Ru ] with a concentration of 0.5mMⅢ(EDTA-H)Cl]2H2O catalyst solution, the temperature of the catalyst solution was controlled to 80. + -. 0.1 ℃ by a heater so that the pressure was 1atm and the inflow rate of the gas to be analyzed was 20 mL/min.
Using the acetylene gas analyzing apparatus of example 1, it was confirmed whether acetylene could be detected in a simulated environment of 1ppm acetylene.
Examples 2 to 12
Acetylene detection was carried out using the same apparatus as in example 1, except that the acetylene concentration, the catalyst aqueous solution concentration, the reaction pressure and the reaction temperature in the simulated environment were partially changed as shown in Table 1 below.
After the detection, the aqueous catalyst solutions of examples 2 to 12 were analyzed to confirm the hydration rate, and the results are shown in table 2 below.
[ TABLE 1]
[ TABLE 2]
| Hydration Rate (Mhr)-1) | |
| Example 2 | 0.78×103 |
| Example 3 | 1.51×103 |
| Example 4 | 2.07×103 |
| Example 5 | 2.42×103 |
| Example 6 | 0.34×103 |
| Example 7 | 0.72×103 |
| Example 8 | 1.22×103 |
| Example 9 | 1.54×103 |
| Example 10 | 0.77×103 |
| Example 11 | 1.23×103 |
| Example 12 | 1.52×103 |
Comparative example 1
The method comprises the steps of taking acetylene with the concentration of less than 1ppm in a simulated environment, putting the acetylene into a sampling bag as a sample, adjusting a gas flow and a quantitative loop (sample loop) for improving the detection low limit of a Gas Chromatography (GC) system installed in a laboratory, installing a collected sample, and injecting the collected sample into a gas chromatograph. A mass flow regulator and output controller are provided to regulate the flow rate of the sample. The sample is automatically cut off after being injected for a certain period of time (about 30 seconds) by the GC operation program, and the consumption of the sample is reduced as much as possible. The mass flow regulator injects the sample into the sampling bag at a predetermined flow rate (50 cc/min).
Comparative example 2
The lower limit of detection and the minimum amount of gas required for analysis were confirmed for a diffusion detector (NEW COSMOS, XP-3160), and the possibility of acetylene detection in a simulated environment of less than 1ppm acetylene was confirmed for the instrument.
Comparative example 3
The detection limit of the suction-type detector (Honeywell, MiniMaxX4) and the minimum amount of gas required for analysis were confirmed, and the possibility of acetylene detection in a simulated environment of less than 1ppm acetylene was confirmed.
[ TABLE 3 ]
Reference numerals:
100 hydration reaction zone
200 conductivity measurement zone
300 quantitative analysis region
Claims (16)
1. An acetylene gas analyzing apparatus for detecting underground electric cables, comprising:
a hydration reaction zone for hydration to acetaldehyde, containing an acetylene hydration catalyst solution, for passing a gas to be analyzed;
connecting the hydration reaction zone to make the inflowing acetaldehyde react with the ZnO nano-crystal which is arranged on the surface of the inner wall and is coated with the silane compound containing amine gas,
a conductivity measurement area that measures a change in conductivity; and
and the quantitative analysis area can calculate the acetylene content of the gas to be analyzed through the conductivity variation.
2. The acetylene gas analyzing device according to claim 1, wherein a heater capable of controlling the temperature of the acetylene hydration catalyst solution to be 70 ℃ to 90 ℃ is provided in the hydration reaction zone.
3. The acetylene gas analyzing device according to claim 1, wherein a mass flow regulator which can regulate the amount of the gas to be analyzed flowing into the acetylene hydration catalyst solution is provided in the hydration reaction zone.
4. The acetylene gas analyzing apparatus according to claim 1, wherein the catalyst [ Ru ] is contained in the acetylene hydration catalyst solution at a concentration of 0.5mM to 2.0mMⅢ(EDTA-H)Cl]2H2O。
5. The acetylene gas analyzing device according to claim 1, wherein a container for storing the acetylene hydration catalyst solution is provided in the hydration reaction zone, and a heater for adjusting the temperature of the acetylene hydration catalyst solution is provided in the container; a mass flow regulator capable of regulating the flow of the gas to be analyzed flowing into the acetylene hydration catalyst solution; a permselective membrane that can collect gases; and a discharge port through which the acetylene hydration catalyst solution can be discharged to maintain the pressure in the container.
6. Acetylene gas analysis device according to claim 5, characterized in that the permselective membrane is connected to a piston to control the axial movement of the permselective membrane (105).
7. The acetylene gas analyzing apparatus according to claim 1, wherein the amine gas-containing silane compound is N- (2-aminoethyl) aminopropyltrimethoxysilane.
8. The acetylene gas analyzing apparatus according to claim 1, wherein the conductivity measuring section uses a light source to trigger a reaction of amine gas with acetaldehyde.
9. An acetylene gas analysis method, comprising:
(a) the gas to be analyzed is contacted with the acetylene hydration catalyst solution, then the acetaldehyde generated after the reaction is collected,
(b) then the collected acetaldehyde reacts with ZnO nano crystal coated with amine silane compound on the surface, the conductivity variation generated after the reaction is measured, and
(c) and calculating the acetylene content in the gas to be analyzed through the conductivity variation.
10. The acetylene gas analysis method according to claim 9, wherein the hydration reaction temperature is between 70 ℃ and 90 ℃.
11. The acetylene gas analysis method according to claim 9, characterized in that the catalyst [ Ru ] in the acetylene hydration catalyst solutionⅢ(EDTA-H)Cl]2H2The concentration of O is between 0.5mM and 2.0 mM.
12. The method for analyzing acetylene gas according to claim 9, wherein the silane compound containing an amine gas is N- (2-aminoethyl) aminopropyltrimethoxysilane.
13. The acetylene gas analysis method according to claim 9, wherein the reaction of the amine gas with acetaldehyde is triggered by a light source.
14. The acetylene gas analysis method according to claim 9, wherein the lowest detected value is 0.1ppm when the acetylene content in the gas to be analyzed is calculated from the amount of change in conductivity.
15. The acetylene gas analysis method according to claim 9, characterized in that the minimum gas amount of the gas to be analyzed is 10 mL.
16. The acetylene gas analysis method according to claim 9, characterized in that the acetylene content in the gas to be analyzed is analyzed by calculating via the following formula 1:
[ formula 1]
Ac＝{Ec2/(Mw2/F)}-{Ec1/(Mw1/F)}
In formula 1, Ac is the amount of acetylene gas contained in the gas to be analyzed, and is in ppm; ec1 is the conductivity measured before the start of the analysis, in mho; mw1 is the molecular weight of the imine groups in g/mol; ec2 is the conductivity measured after the start of the analysis, in mho; mw2 is the molecular weight of the amine groups in g/mol; f is the Faraday constant in C/mol.
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