阅读说明：本技术 一种非甲烷总烃的检测装置以及检测方法 (Detection device and detection method for non-methane total hydrocarbons ) 是由 朱敏 熊新兴 刘欢 卯红伟 于 2018-07-31 设计创作，主要内容包括：本发明涉及气体测量领域,尤其涉及一种非甲烷总烃的检测装置以及检测方法。气瓶连接着十通阀,十通阀伸出并列的管道连接着定量环A组(3)以及定量环B组(4),所述的定量环A组(3)连接着总烃柱(5)；所述的定量环B组(4)连接着甲烷柱(7)；所述的总烃柱(5)以及甲烷柱(7)各自连接着FID氢气焰离子化检测器。本发明通过根据多种定量环的设置控制样品进样体积,样品利用十通阀分别进入定量环,随载气进入气相色谱检测装置中分析。本发明主要包括十通阀、多种定量环、气相色谱检测装置。本发明根据多种定量环的设置控制样品进样体积,有效的达到精准稀释的目的,省去手动稀释的步骤,极大地提高了检测效率,操作方便。(The invention relates to the field of gas measurement, in particular to a detection device and a detection method for non-methane total hydrocarbons. The gas cylinder is connected with a ten-way valve, the ten-way valve extends out of parallel pipelines to be connected with a quantitative ring A group (3) and a quantitative ring B group (4), and the quantitative ring A group (3) is connected with a total hydrocarbon column (5); the quantitative ring B group (4) is connected with a methane column (7); the total hydrocarbon column (5) and the methane column (7) are respectively connected with an FID hydrogen flame ionization detector. The sample injection volume of the sample is controlled according to the arrangement of various quantitative rings, and the sample respectively enters the quantitative rings by utilizing the ten-way valve and enters the gas chromatography detection device along with the carrier gas for analysis. The invention mainly comprises a ten-way valve, a plurality of quantitative rings and a gas chromatography detection device. The invention controls the sample introduction volume according to the setting of various quantitative rings, effectively achieves the aim of accurate dilution, omits the step of manual dilution, greatly improves the detection efficiency and has convenient operation.)

1. The detection device for the non-methane total hydrocarbons is characterized by comprising a gas cylinder, wherein the gas cylinder is connected with a ten-way valve, the ten-way valve extends out of parallel pipelines and is connected with a quantitative ring A group (3) and a quantitative ring B group (4), and the quantitative ring A group (3) is connected with a total hydrocarbon column (5); the quantitative ring B group (4) is connected with a methane column (7); the total hydrocarbon column (5) and the methane column (7) are respectively connected with an FID hydrogen flame ionization detector.

2. The apparatus for detecting non-methane total hydrocarbons according to claim 1, wherein two FID hydrogen flame ionization detectors are connected to the detector bridge; the FID hydrogen flame ionization detector described above is communicatively coupled to the data processing system.

3. The apparatus for detecting non-methane total hydrocarbons according to claim 1, wherein the quantitative ring group A (3) comprises a quantitative ring (A1), both ends of the quantitative ring (A1) are connected with a three-way valve (a 1) and a three-way valve (a 2), the quantitative ring (A2) is connected with a three-way valve (a 1) and a three-way valve (a 2), and the quantitative ring (A3) is connected with a three-way valve (A3) and a three-way valve (a 4); the quantitative ring B group comprises a quantitative ring (B1) connected with a three-way valve (B1) and a three-way valve (B2), a quantitative ring (B2) connected with a three-way valve (B1) and a three-way valve (B2), and a quantitative ring (B3) connected with a three-way valve (B3) and a three-way valve (B4).

4. A detection method of non-methane total hydrocarbons, characterized in that, by using the device of any one of claims 1 to 3, the quantitative ring group A (3) and the quantitative ring group B (4) are respectively controlled by a control system, and each three-way valve of the quantitative ring group is provided with a switch to control the opening or closing of a gas circuit;

the device is provided with a double-column flow path, namely a total hydrocarbon column and a methane column, and a quantitative ring A group for the total hydrocarbon column and a quantitative ring B group for the methane column which are selected are respectively arranged, the sample introduction is controlled by a ten-way valve, when the valve is in a sample introduction state, the sample introduction is carried out by an air bag or a glass injector, so that the quantitative ring A group and the quantitative ring B group are respectively filled with a sample, and redundant gas flows out from a waste gas pipeline; when the valve is rotated to the running state, the detection key is simultaneously opened; at the moment, the sample is separated by a total hydrocarbon column and a methane column along with the carrier gas, and then enters an FID hydrogen flame ionization detector for analysis and calculation to obtain a result value.

5. When the hydrogen flame ionization detector analyzes that the concentration of the non-methane total hydrocarbons in the waste gas is higher than a preset value, determining a dilution multiple according to a concentration exceeding range, and selecting a corresponding quantitative ring, wherein a control system corresponding to the quantitative ring opens a group A and a group B of the quantitative ring, and other quantitative rings are in a closed state; controlling the sample introduction volume to be equal to the dilution multiple of the sample gas, and enabling the sample gas to respectively pass through a total hydrocarbon column and a methane column and enter a detector for analysis to obtain a corresponding response value; when the hydrogen flame ionization detector analyzes that the concentration of the non-methane total hydrocarbons in the waste gas is low or normal, the sample can be directly injected, the quantitative ring A1 and the quantitative ring B1 are opened through a control system corresponding to the quantitative ring, and other quantitative ring groups are closed; the sample gas respectively passes through the total hydrocarbon column and the methane column and enters a detector for analysis to obtain corresponding response values.

6. The method for detecting non-methane total hydrocarbons according to claim 4, wherein the above detection is performed by gas chromatography under the following conditions: filling a column: a total hydrocarbon column and a methane column; nitrogen gas: high-purity nitrogen with the purity of more than 99.999 percent; methane standard gas, hydrocarbon-removed air, and the like.

7. The method according to claim 5, wherein the total hydrocarbons other than methane are detected,

sample inlet temperature: 120 ℃; column temperature: 80 ℃; detector temperature: 120 ℃; carrier gas flow: 20 ml/min.

8. The method according to claim 5, wherein the total hydrocarbons other than methane are detected,

calibration of the methane gasThe series is as follows: diluting the methane standard gas with high purity nitrogen gas step by step to prepare 5 calibration series with concentration gradient, wherein the concentrations of the calibration series are 50, 100, 200, 400 and 800 mg/m respectively ³。

Technical Field

The invention relates to the field of gas measurement, in particular to a detection device and a detection method for non-methane total hydrocarbons.

Background

The total term of non-methane total hydrocarbons, i.e., carbon hydrocarbons other than methane [ mainly C2-C8 ] includes substances such as alkanes, alkenes, aromatics, and oxygenated hydrocarbons. The hydrocarbon substances are inflammable and explosive, and the non-methane total hydrocarbon in the atmosphere not only directly threatens the health of human beings, but also causes photochemical smog under certain conditions, thereby causing serious negative effects on human beings and the environment on which the human beings live. At present, common petroleum products are a mixture of various carbon hydrocarbon compounds, and light components of the common petroleum products are extremely volatile under certain vapor pressure, so that the petroleum products from the source to the whole transportation system and even a user terminal have serious non-methane total hydrocarbon pollution problems to related workplaces.

The emission standards of atmospheric pollution established by countries and places all make regulations on emission limits of non-methane total hydrocarbons. The detection process of non-methane total hydrocarbons is generally field sampling and laboratory analysis. In-situ sampling generally adopts an aluminum foil gas collecting bag or a glass syringe, which mainly has the advantages of low price, convenient carrying, good air tightness and the like, and laboratory analysis generally adopts a gas chromatograph with a hydrogen Flame Ionization Detector (FID) for analysis, which has the advantages of high accuracy, good repeatability, short detection period and the like.

The laboratory analysis is to analyze the total hydrocarbon value and the methane value through a total hydrocarbon column and a methane column respectively, and the subtraction of the results is the non-methane total hydrocarbon value. The sample introduction mode generally comprises direct sample introduction and sample introduction after treatment, and for a sample with the concentration within the range of a calibration curve, the gas bag sample is directly injected into chromatographic analysis; for a high-concentration waste gas sample, dilution treatment is required, and then chromatographic analysis is performed. The sample dilution method generally comprises an instrument dilution method and a manual dilution method, the instrument dilution method is expensive in equipment cost and high in requirement on a sample container, so the common dilution method in the laboratory is the manual dilution method, namely, a 100ml glass syringe is used for respectively pumping a certain amount of sample gas and dilution gas to be fully mixed, and an appropriate concentration value is determined according to actual conditions.

The non-methane total hydrocarbon in the laboratory detection waste gas is generally detected by transporting a sample to the laboratory by using an air bag or a glass injector for analysis and detection, and in the analysis process of a large amount of waste gas samples, the following problems are easy to occur in high-concentration waste gas samples: 1. the instrument is easy to overload; 2. the problems that the baseline fluctuation of the instrument is large and the sensitivity and the upper limit of detection are influenced are caused; 3. easy residue and easy pollution to chromatographic columns, sample inlets, detectors and the like.

The invention aims at the detection and analysis of gas-collecting bags or glass syringes in laboratories, and because the gas-collecting bags or glass syringes are small in volume, the collected samples are too small in volume and difficult to dilute by using equipment, and the manual dilution technology is the most common dilution means at present. However, for gas, the gas molecules are more active, the fluidity is large, the sampling is difficult, and the quantification is not easy. Manual dilution suffers from several drawbacks: 1. large error and low accuracy; 2. the operation is inconvenient, and the pressure reducing valve attached to the gas cylinder is not easy to control; 3. insufficient mixing of gases, etc.

Disclosure of Invention

The purpose of the invention is as follows: in order to provide a detection device and a detection method for non-methane total hydrocarbons with better effects, the specific purpose is to see a plurality of substantial technical effects of the concrete implementation part.

In order to achieve the purpose, the invention adopts the following technical scheme:

the detection device for the non-methane total hydrocarbons is characterized by comprising a gas cylinder, wherein the gas cylinder is connected with a ten-way valve, the ten-way valve extends out of parallel pipelines and is connected with a quantitative ring A group and a quantitative ring B group, and the quantitative ring A group is connected with a total hydrocarbon column; the quantitative ring B group is connected with a methane column; the total hydrocarbon column and the methane column are each connected to a FID hydrogen flame ionization detector.

The invention further adopts the technical scheme that two FID hydrogen flame ionization detectors are connected with a detector bridge circuit; the FID hydrogen flame ionization detector described above is communicatively coupled to the data processing system.

The invention further adopts the technical scheme that the quantitative ring A group comprises a quantitative ring, two ends of the quantitative ring are connected with a three-way valve and a three-way valve, the quantitative ring is connected with the three-way valve and the three-way valve, and the quantitative ring is connected with the three-way valve and the three-way valve; the quantitative ring B group comprises a quantitative ring which is connected with a three-way valve and a three-way valve, the quantitative ring is connected with the three-way valve and the three-way valve, and the quantitative ring is connected with the three-way valve and the three-way valve.

A detection method of non-methane total hydrocarbon is characterized in that by using the device, a quantitative ring group A and a quantitative ring group B are respectively controlled by a control system, and each three-way valve of the quantitative ring group is provided with a switch to control the opening or closing of a gas circuit;

the device is provided with a double-column flow path, namely a total hydrocarbon column and a methane column, and a quantitative ring A group for the total hydrocarbon column and a quantitative ring B group for the methane column which are selected are respectively arranged, the sample introduction is controlled by a ten-way valve, when the valve is in a sample introduction state, the sample introduction is carried out by an air bag or a glass injector, so that the quantitative ring A group and the quantitative ring B group are respectively filled with a sample, and redundant gas flows out from a waste gas pipeline; when the valve is rotated to the running state, the detection key is simultaneously opened; at the moment, the sample is separated by a total hydrocarbon column and a methane column along with the carrier gas, and then enters an FID hydrogen flame ionization detector for analysis and calculation to obtain a result value.

When the hydrogen flame ionization detector analyzes that the concentration of the non-methane total hydrocarbons in the waste gas is higher than a preset value, determining a dilution multiple according to a concentration exceeding range, and selecting a corresponding quantitative ring, wherein a control system corresponding to the quantitative ring opens a group A and a group B of the quantitative ring, and other quantitative rings are in a closed state; controlling the sample introduction volume to be equal to the dilution multiple of the sample gas, and enabling the sample gas to respectively pass through a total hydrocarbon column and a methane column and enter a detector for analysis to obtain a corresponding response value; when the hydrogen flame ionization detector analyzes that the concentration of the non-methane total hydrocarbons in the waste gas is low or normal, the sample can be directly injected, the quantitative ring A1 and the quantitative ring B1 are opened through a control system corresponding to the quantitative ring, and other quantitative ring groups are closed; the sample gas respectively passes through the total hydrocarbon column and the methane column and enters a detector for analysis to obtain corresponding response values.

The further technical scheme of the invention is that the detection is carried out by using a meteorological chromatography, and the detection conditions are as follows: filling a column: a total hydrocarbon column and a methane column; nitrogen gas: high-purity nitrogen with the purity of more than 99.999 percent; methane standard gas, hydrocarbon-removed air, and the like.

The further technical scheme of the invention is that the injection port temperature is as follows: 120 ℃; column temperature: 80 ℃; detector temperature: 120 ℃; carrier gas flow: 20 ml/min.

The invention is as followsThe one-step technical scheme is that the calibration series of the methane gas is as follows: diluting the methane standard gas with high purity nitrogen gas step by step to prepare 5 calibration series with concentration gradient, wherein the concentrations of the calibration series are 50, 100, 200, 400 and 800 mg/m respectively ^3。

Compared with the prior art, the invention adopting the technical scheme has the following beneficial effects: the sample injection volume of the sample is controlled according to the arrangement of various quantitative rings, and the sample respectively enters the quantitative rings by utilizing the ten-way valve and enters the gas chromatography detection device along with the carrier gas for analysis. The invention mainly comprises a ten-way valve, a plurality of quantitative rings and a gas chromatography detection device. The invention controls the sample introduction volume according to the setting of various quantitative rings, effectively achieves the aim of accurate dilution, omits the step of manual dilution, greatly improves the detection efficiency and has convenient operation.

Drawings

To further illustrate the present invention, further description is provided below with reference to the accompanying drawings:

FIG. 1 is a schematic structural view of the present invention;

wherein: 1. a gas cylinder; 2. a ten-way valve; 3. quantification of loop a group; 4. quantification of loop B group; 5. a total hydrocarbon column; 6. a methane column; an FID hydrogen flame ionization detector; 8. a detector bridge circuit; 9. a data processing system.

Detailed Description

The present invention will be further illustrated with reference to the accompanying drawings and specific embodiments, which are to be understood as merely illustrative of the invention and not as limiting the scope of the invention. In the description of the present invention, it should be noted that the terms "center", "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer", "top", "bottom", and the like indicate orientations or positional relationships based on those shown in the drawings, and are only for convenience of description and simplicity of description, but do not indicate or imply that the referred device or element must have a specific orientation, be constructed in a specific orientation, and be operated, and thus, should not be construed as limiting the present invention. Furthermore, unless expressly stated or limited otherwise, the terms "mounted," "connected," and "connected" are to be construed broadly, as they may be fixedly connected, detachably connected, or integrally connected, for example; can be mechanically or electrically connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meanings of the above terms in the present invention can be understood in specific cases to those skilled in the art.

The patent provides a plurality of parallel schemes, and different expressions belong to an improved scheme based on a basic scheme or a parallel scheme. Each solution has its own unique features.

The invention controls the sample injection volume according to the setting of quantitative rings with various specifications, and mainly comprises two groups of quantitative ring A (for a total hydrocarbon column) and quantitative ring B (for a methane column): quantitative loop A1(1mL), quantitative loop A2(0.1mL), quantitative loop A3(0.05mL), quantitative loop B1(1mL), quantitative loop B2(0.1mL), and quantitative loop B3(0.05mL), wherein the appropriate quantitative loop is selected according to the range of the excess concentration, and the dilution ratio is generally controlled to be 10-20 times. The quantitative rings are controlled to be opened or closed by a control system, and a sample enters the selected quantitative rings by using a ten-way valve and enters the gas chromatography detection device along with the carrier gas for analysis. The invention mainly comprises a ten-way valve, quantitative rings with various specifications, a hydrogen flame ionization detector and a gas chromatography detection device. The invention controls the sample introduction volume according to the arrangement of various quantitative rings, omits the step of manual dilution, greatly improves the detection efficiency and has convenient operation.

1. A device for detecting non-methane total hydrocarbons in waste gas comprises a ten-way valve, a gas pipeline, a control system corresponding to a quantitative ring, a hydrogen flame ionization detector and a quantitative ring. The ten-way valve is respectively connected with two quantitative ring A groups (for total hydrocarbon columns) and quantitative ring B groups (for methane columns), the quantitative ring A group comprises two ends of a quantitative ring A1 which are connected with a three-way valve a1 and a three-way valve a2, the quantitative ring A2 is connected with a three-way valve a1 and a three-way valve a2, and the quantitative ring A3 is connected with a three-way valve A3 and a three-way valve a 4; the quantitative loop group B comprises a quantitative loop B1 connected with a three-way valve B1 and a three-way valve B2, a quantitative loop B2 connected with a three-way valve B1 and a three-way valve B2, and a quantitative loop B3 connected with a three-way valve B3 and a three-way valve B4. And the carrier gas respectively enters a total hydrocarbon column and a methane column through a quantitative ring, finally enters an FID hydrogen flame ionization detector to respectively measure the result values of the total hydrocarbon and the methane, and the result values are subtracted to obtain the concentration value of the non-methane total hydrocarbon.

The quantitative ring groups are respectively controlled by a control system, each valve of the quantitative ring groups is provided with a switch to control the opening or closing of the air passage, and the three-way valve a1, the three-way valve a2, the three-way valve a3, the three-way valve a4, the three-way valve b1, the three-way valve b2, the three-way valve b3 and the three-way valve b4 are respectively provided with control switches.

The device is provided with a double-column flow path, namely a total hydrocarbon column and a methane column, and is respectively provided with a selected quantitative ring A group (for the total hydrocarbon column) and a selected quantitative ring B group (for the methane column), wherein the sample introduction is controlled by a ten-way valve, when the valve is in a sample introduction state, the sample introduction is carried out by using an air bag or a glass injector, so that the quantitative ring A group and the quantitative ring B group are respectively filled with a sample, and redundant gas flows out from a waste gas pipeline; when the valve is rotated to the running state, the detection key is simultaneously opened. At the moment, the sample is separated by a total hydrocarbon column and a methane column along with the carrier gas, and then enters an FID hydrogen flame ionization detector for analysis and calculation to obtain a result value.

When the hydrogen flame ionization detector analyzes that the concentration of the non-methane total hydrocarbons in the waste gas is higher than a preset value, the corresponding quantitative rings are selected according to the dilution times determined by the concentration exceeding range, the control system corresponding to the quantitative rings opens the group A and the group B of the quantitative rings, and other quantitative rings are in a closed state. Controlling the sample introduction volume to be equal to the dilution multiple of the sample gas, and enabling the sample gas to respectively pass through a total hydrocarbon column and a methane column and enter a detector for analysis to obtain a corresponding response value; when the hydrogen flame ionization detector analyzes that the concentration of the non-methane total hydrocarbons in the waste gas is low or normal, the sample can be directly fed, the quantitative rings A1 and B1 are opened through the control system corresponding to the quantitative rings, and other quantitative ring groups are closed. The sample gas respectively passes through the total hydrocarbon column and the methane column and enters a detector for analysis to obtain corresponding response values.

The device of the invention is provided with: FID hydrogen flame ionization detector, packed column: a total hydrocarbon column and a methane column; nitrogen gas: high-purity nitrogen with the purity of more than 99.999 percent; methane standard gas, hydrocarbon-removed air, and the like.

The optimal reference conditions for the gas chromatography apparatus were obtained experimentally: sample inlet temperature: 120 ℃; column temperature: 80 ℃; detector temperature: 120 ℃; carrier gas flow: 20 ml/min.

Calibration series: diluting the methane standard gas with high purity nitrogen gas step by step to prepare 5 calibration series with concentration gradient, wherein the concentrations of the calibration series are 50, 100, 200, 400 and 800 mg/m respectively ³。

In general terms: the invention relates to a device for detecting non-methane total hydrocarbons in waste gas, which mainly solves the problems of instrument overload, influence on data accuracy, instrument pollution and the like caused by the large concentration of a sample collected by an air bag or a glass injector in a laboratory. The sample injection volume of the sample is controlled according to the arrangement of various quantitative rings, and the sample enters the quantitative rings by using the ten-way valve and enters the gas chromatography detection device along with the carrier gas for analysis. The invention mainly comprises a ten-way valve, a plurality of quantitative rings and a gas chromatography detection device. The invention controls the sample injection volume according to the setting of various quantitative rings, saves the step of manual dilution, greatly improves the detection efficiency, is convenient to operate and has popularization and application values.

The invention is described in more detail below with reference to specific embodiments: