CN102879506B - Automatic gas sampling device and using method thereof - Google Patents
Automatic gas sampling device and using method thereof Download PDFInfo
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- CN102879506B CN102879506B CN201210388090.7A CN201210388090A CN102879506B CN 102879506 B CN102879506 B CN 102879506B CN 201210388090 A CN201210388090 A CN 201210388090A CN 102879506 B CN102879506 B CN 102879506B
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Abstract
The invention relates to an automatic gas sampling device and a using method thereof. The device provided by the invention comprises a shell, wherein the shell is internally provided with a gas channel system and a circuit system; the gas channel system comprises a first electromagnetic valve, a second electromagnetic valve, a pressure sensor, a tee joint, a six-way valve and a vacuum pump; the circuit system comprises the first electromagnetic valve, the second electromagnetic valve, the pressure sensor and a computer; the first electromagnetic valve and the second electromagnetic valve are electrically connected with the I/O (input/output) switch control unit of the computer; and the pressure sensor is electrically connected with the analogue/digital converter of the computer. The gas automatic sampling device provided by the invention can be widely applied to automatic sampling for gas chromatograph analysis of gas samples, prevents the pollution of environment on tested sample gases, and effectively improves the utilization ratio of sample gases and analyzing instruments.
Description
Technical field
The present invention relates to a kind of gas automatic sampling device and using method, in particular, the present invention relates to a kind of negative-pressure gas automatic sampling apparatus for gas analysis instrument injection port front end.
Background technology
Gas chromatographic technique is a kind of efficient, sensitive, separate analytical technique fast, can separate in a short period of time tens kinds of even potpourris of hundreds of component, therefore it is the outstanding person in all multi-methods of analytical gas, is one of the Main Means of gas analysis and method.Adopt component concentration in gas chromatograph analytical gas, generally have two kinds of input modes of gas sampling syringe hand sampling or six-way valve auto injection.Syringe sampling method is simple, flexibly, but exist sealing poor, there is the shortcoming such as recoil and infiltration, sample introduction less stable.When analytic target pressure is during lower than atmospheric pressure, syringe hand sampling can entrained air component be affected the accuracy of test result.Commercial valve injection system adopts type of flow sample introduction, although easy to operate, favorable reproducibility be not suitable for normal pressure/negative pressure sample analysis, and gas consumption is large.Therefore, form a set of negative pressure automatic sampling device that is applicable to gaseous sample by research, this device has great importance for gas analysis.
Summary of the invention
The present invention has overcome the deficiencies in the prior art, provide and solve one by pressure sensing technology, vacuum pump and the combination of electromagnetism automatic transfer valve, for sample analysis instrument front end, and by and sample analysis instrument between data transmission, by the pressure change in gas circuit and and computer control system between data transmission, gaseous sample is derived to sample introduction automatically, simultaneously automatic sampling apparatus and the using method thereof of monitoring record sample feeding pressure.
For solving above-mentioned technical matters, the present invention by the following technical solutions:
A kind of gas automatic sampling device, comprising: housing; It is characterized in that: described enclosure interior comprises: air-channel system and Circuits System;
Described air-channel system comprises: sample analysis instrument, coupling arrangement, air extractor, sampling receptacle, and described sampling receptacle, air extractor and sample analysis instrument three are connected by coupling arrangement; On described coupling arrangement, be provided with at least one solenoid valve;
Described Circuits System comprises: for measuring sensor, the computer control system of air-channel system pressure size, for monitoring and control air-channel system; Described sensor signal output terminal is connected with computer control system; Described solenoid valve is connected with computer control system.
Further technical scheme is that coupling arrangement comprises: a three-way connection; The first interface of described three-way connection is connected with air extractor by first conduit, and first solenoid valve for controlling first conduit open circuit and opening circuit is set on described first conduit; The second interface of described three-way connection is connected with sample analysis instrument by second conduit; The 3rd interface of described three-way connection is connected with sensor signal input end; Described coupling arrangement also comprises the 3rd conduit for connecting sampling receptacle and sample analysis instrument, and second solenoid valve for controlling the 3rd conduit open circuit and opening circuit is set on the 3rd conduit.
Further technical scheme is that computer control system comprises: I/O switch control unit, A/D converter; Described I/O switch control unit is electrically connected with the first solenoid valve and the second solenoid valve; Described A/D converter is connected with sensor electrical, for reading and record the measured value of described sensor.
Further technical scheme is that coupling arrangement is the stable material of physico-chemical property.
Further technical scheme is that sensor is pressure transducer.
Further technical scheme is that sample analysis instrument is gas chromatograph.
Further technical scheme is that air extractor is vacuum pump.
Further technical scheme is a kind of using method of negative-pressure gas automatic sampling apparatus, comprises the following steps: automatic sampling apparatus is set;
Confirmatory sample container valve is under closed condition, and described the first solenoid valve and the second solenoid valve are opened, and start described air extractor; In the time being vacuum in described air-channel system, close described the first solenoid valve;
Open sampling receptacle switch, after pressure is stablized in described air-channel system, close described the second solenoid valve;
By described sample analysis instrument, rotate the six-way valve in sample analysis instrument, in the quantitative ring of described six-way valve, sample enters detecting instrument, and described computer control system reads and stores air-channel system pressure values by described pressure transducer simultaneously;
After sample introduction finishes, described six-way valve is got back to the front state of sample introduction, and described the first solenoid valve is opened, and starts air extractor by after sample pumps in described air-channel system, closes described the first solenoid valve.
Compared with prior art, the invention has the beneficial effects as follows: the coupling arrangement of air-channel system of the present invention all adopts the stable material of materialization, can effectively reduce the absorption of component in gas circuit in sample.Pressure transducer on sample air-channel system of the present invention can be measured the pressure in air-channel system, and pressure values can be transferred to computer control system and preserve for quantitative calculating.The first solenoid valve on air-channel system of the present invention and the opening and closing of the second solenoid valve can, by Sample introduction sampling system, realize the detection to the subatmospheric sample of pressure, have avoided the interference of environmental gas.Circuits System of the present invention has realized the data communication of each parts and computer control system, by regulating the rotation of six-way valve on the folding of the first solenoid valve, the second solenoid valve and sample analysis instrument, has realized auto injection.Effectively avoid the interference of environmental gas to testing sample, improved the utilization factor of sample.Can not only meet the analysis of negative-pressure gas sample, and energy automatic sampling, the unattended operation of Realization analysis instrument, saves human resources.
Brief description of the drawings
Fig. 1 is one embodiment of the invention air-channel system structural representation.
Fig. 2 is one embodiment of the invention structural representation.
Embodiment
Below in conjunction with accompanying drawing, the present invention is further elaborated.
As shown in Figure 1, Fig. 1 shows the air-channel system structural representation of one embodiment of the invention.One embodiment of the present of invention negative-pressure gas automatic sampling apparatus comprises housing, and enclosure interior comprises air-channel system and Circuits System; Air-channel system structural representation as shown in Figure 1, comprises sample analysis instrument 7, and the sample analysis instrument of the present embodiment is gaseous sample analytical instrument, can be gas analyzer or gas detecting instrument; As preferred embodiment, the sample analysis instrument of the present embodiment is gas chromatograph, gas chromatograph comprises a six-way valve 8, quantitative ring one end of six-way valve is connected with air extractor 9 by conduit, and the other end of the quantitative ring of six-way valve is connected with the switch valve 6 on sampling receptacle 5 by another root conduit.The air extractor of the present embodiment can be vacuum pump or the device with air extracting function, and the air extractor of this enforcement is vacuum pump.Air extractor is by first interface of first conduit connecting tee joint 4, as preferred embodiment, the present embodiment is provided with the first solenoid valve 1 on first conduit, the first solenoid valve 1 can be electrically connected with computer control system by data line, computer control system is automatically controlled it and is opened or closed, and has realized first conduit open circuit and closed robotization; Second interface of three-way connection is connected with quantitative ring one end of the six-way valve on gas chromatograph by second conduit.The 3rd interface of three-way connection be connected for the sensor 3 of measuring air-channel system pressure size.On gas chromatograph, the other end of the quantitative ring of six-way valve is connected with a valve port of the switch valve 6 on sampling receptacle 5 by the 3rd conduit, and another port of switch valve 6 is connected with sampling receptacle mouth.Sampling receptacle 5 is a gas sampling tank in the present embodiment.As preferred embodiment, the present embodiment is provided with for controlling the 3rd conduit open circuit and the second closed solenoid valve 2 for connecting on the 3rd conduit of quantitative ring one end and sampling receptacle, the second solenoid valve 2 is electrically connected with computer control system by data line, computer control system is controlled the opening and closing of the second solenoid valve automatically, has realized robotization open circuit and the closure of the 3rd conduit.When air-channel system has sample gas to enter, gas chromatograph 7 is controlled six-way valve 8 and is rotated, and in the quantitative ring of six-way valve 8, gaseous sample is brought into detecting instrument by the carrier gas A in gas chromatograph, carries out subsequent analysis.As preferred embodiment, conduit, jointing and sampling receptacle in the present embodiment all adopt physico-chemical property stabilizing material, as glass, stainless steel material etc., wherein taking stainless steel material as excellent.The air-channel system parts of the present embodiment are strictly sealing all, to keep the primary characteristic of gaseous sample, and shortens the pipeline that gaseous sample is carried as far as possible.
As shown in Figure 2, Fig. 2 shows the structural representation of one embodiment of the invention, is the structural representation that the air-channel system of the present embodiment is combined with Circuits System.The Circuits System of the present embodiment comprises sensor 3, the computer control system 10 for measuring air-channel system pressure size, for monitoring and control air-channel system; In this enforcement, sensor 3 is to realize the sensor of measuring air-channel system pressure size, says more specifically pressure transducer.Pressure transducer 3 signal input parts are connected with three-way connection 4, and pressure transducer 3 signal output parts are connected with computer control system.Computer control system in the present embodiment comprises: I/O switch control unit, A/D converter; I/O switch control unit is electrically connected by data line respectively with the first solenoid valve 1 and the second solenoid valve 2; A/D converter is electrically connected by data line with sensor 3, and A/D converter is for reading and record the measured value of described sensor.Computer control system in the present embodiment can also be PLC or integrated circuit block, or is other devices that can realize data processing and Presentation Function.
The course of work of the present embodiment is: air-channel system is in the charging stage, by vacuum pump by six-way valve quantitatively the pressure drop in ring and connecting line be low to moderate minimumly, the gaseous sample in sample can just can enter into that six-way valve is quantitative to be encircled and connecting line like this.In the time that air-channel system has sample gas to enter, gas chromatograph 7 is controlled six-way valve 8 and is rotated, and during six-way valve 8 quantitatively encircles, gaseous sample is brought into detecting instrument by the carrier gas A in gas chromatograph, carries out subsequent analysis.Whole sample introduction process sample gas and extraneous gas isolation, can not be polluted.Concrete, the using method of the present embodiment negative-pressure gas automatic sampling apparatus comprises the following steps: (1) first, opens the first solenoid valve and the second solenoid valve, keeps 6 of the switch valves of sample can in closed condition.Start vacuum pump, make the pressure drop in quantitative ring and the connecting line of six-way valve on gas chromatograph be low to moderate vacuum.(2) keep the second solenoid valve in open mode, close the first solenoid valve, open the switch valve of sample can, because the gas pressure intensity in sample can is greater than the gas pressure intensity in quantitative ring and the connecting line of six-way valve, the gaseous sample in sample can be derived smoothly.After pressure sensor readings is stable, close the first solenoid valve 1.(3) gas chromatograph control six-way valve rotates, six-way valve quantitatively in ring gaseous sample brought into detecting instrument by the carrier gas in gas chromatograph, carry out subsequent analysis, described computing machine reads by pressure transducer 3 and stores air-channel system pressure values simultaneously.(4) after sample introduction finishes, six-way valve is got back to the front state of sample introduction, and the first solenoid valve is opened, and after gaseous sample pumps in air-channel system, closes the first solenoid valve.
After above-mentioned 4 processes finish, complete single injected sampling process.When next sample introduction, operate according to (2) (3) (4) step.
The whole negative-pressure gas automatic sample handling system operation of the present embodiment is simple and easy, it is little, easy to maintenance to take up room, operating cost is low, has wide market outlook.Under the prerequisite of not introducing secondary pollution, can effectively improve the utilization factor of gaseous sample gas, realize the object accurately detecting.Can not only meet the analysis of negative-pressure gas sample, and energy automatic sampling, the unattended operation of Realization analysis instrument, saves human resources.
The present invention is for the gas analysis of carrying out in the laboratory such as conventional sense, the process detection of industrial enterprise of the scientific research of research institutions, government's part, can not only meet the analysis of gaseous sample, and energy automatic sampling, the unattended operation of Realization analysis instrument, saves human resources.
" embodiment ", " another embodiment ", " embodiment " that spoken of in this manual, etc., refer to specific features, structure or the feature described in conjunction with this embodiment and be included at least one embodiment that the application's generality describes.In instructions, multiple local appearance statement of the same race is not necessarily to refer to same embodiment.Furthermore, while describing a specific features, structure or feature in conjunction with any embodiment, what advocate is to realize this feature, structure or feature in conjunction with other embodiment also to fall within the scope of the invention.
Although with reference to the multiple explanatory embodiment inventing, invention has been described here, but, should be appreciated that, those skilled in the art can design a lot of other amendment and embodiments, within these amendments and embodiment will drop on the disclosed principle scope and spirit of the application.More particularly, in the scope of, accompanying drawing open in the application and claim, can carry out multiple modification and improvement to the building block of subject combination layout and/or layout.Except modification that building block and/or layout are carried out with improving, to those skilled in the art, other purposes will be also obvious.
Claims (6)
1. a gas automatic sampling device, comprising: housing; It is characterized in that: described enclosure interior comprises:
Air-channel system and Circuits System;
Described air-channel system comprises: sample analysis instrument (7), coupling arrangement, air extractor (9), sampling receptacle (5), and described sampling receptacle (5), air extractor (9) and sample analysis instrument (7) three are connected by coupling arrangement; On described coupling arrangement, be provided with at least one solenoid valve;
Described Circuits System comprises: for measuring sensor (3), the computer control system (10) of air-channel system pressure size, for monitoring and control air-channel system; Described sensor (3) one end is connected with coupling arrangement, and described sensor (3) signal output part is connected with computer control system (10); Described solenoid valve is connected with computer control system (10); Described coupling arrangement comprises: a three-way connection (4); The first interface of described three-way connection (4) is connected with air extractor (9) by first conduit, and first solenoid valve (1) for controlling first conduit open circuit and opening circuit is set on described first conduit; The second interface of described three-way connection (4) is connected with sample analysis instrument (7) by second conduit; The 3rd interface of described three-way connection (4) is connected with sensor (3); Described coupling arrangement also comprises the 3rd conduit for connecting sampling receptacle (5) and sample analysis instrument (7), and second solenoid valve (2) for controlling the 3rd conduit open circuit and opening circuit is set on the 3rd conduit.
2. a kind of gas automatic sampling device according to claim 1, is characterized in that described computer control system comprises: I/O switch control unit, A/D converter; Described I/O switch control unit is electrically connected with the first solenoid valve (1) and the second solenoid valve (2); Described A/D converter is electrically connected with sensor (3), for reading and record the measured value of described sensor.
3. a kind of gas automatic sampling device according to claim 1, is characterized in that described coupling arrangement adopts the stable material of physico-chemical property to make.
4. a kind of gas automatic sampling device according to claim 1, is characterized in that described sensor (3) is pressure transducer.
5. a kind of gas automatic sampling device according to claim 1, is characterized in that described sample analysis instrument (7) is gas chromatograph.
6. a kind of gas automatic sampling device according to claim 1, is characterized in that described air extractor (9) is vacuum pump.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201210388090.7A CN102879506B (en) | 2012-10-12 | 2012-10-12 | Automatic gas sampling device and using method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201210388090.7A CN102879506B (en) | 2012-10-12 | 2012-10-12 | Automatic gas sampling device and using method thereof |
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| CN102879506A CN102879506A (en) | 2013-01-16 |
| CN102879506B true CN102879506B (en) | 2014-07-16 |
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| CN107544412B (en) * | 2017-09-12 | 2023-05-23 | 国网福建省电力有限公司 | Control circuit of automatic sample injection device for oil chromatography test |
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| CN111239308A (en) * | 2020-01-07 | 2020-06-05 | 常州磐诺仪器有限公司 | Online high-vacuum negative-pressure gas sampling system and method |
| CN111189948A (en) * | 2020-01-07 | 2020-05-22 | 常州磐诺仪器有限公司 | High-vacuum negative-pressure sample injection system and method |
| CN111220742A (en) * | 2020-03-23 | 2020-06-02 | 中国工程物理研究院材料研究所 | Micro sample gas automatic sampling system for gas chromatography |
| CN111474284A (en) * | 2020-04-09 | 2020-07-31 | 中国工程物理研究院材料研究所 | Feed gas pretreatment and automatic sample introduction system for gas chromatography |
| CN112213270B (en) * | 2020-09-29 | 2021-10-19 | 湖北鑫英泰系统技术股份有限公司 | Stirring speed control method and device based on viscosity |
| CN112924605B (en) * | 2021-03-10 | 2023-11-14 | 中国人民解放军91315部队 | Automatic sample injection system and method |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4116046A (en) * | 1977-08-05 | 1978-09-26 | Hoffmann-La Roche Inc. | Liquid chromatography system |
| US20020146350A1 (en) * | 2001-02-02 | 2002-10-10 | Jiunn-Guang Lo | Real time monitoring system |
| CN2807257Y (en) * | 2005-06-07 | 2006-08-16 | 淄博祥龙测控技术有限公司 | Automatic sampling device of tube bundle chromatogram gas analyzing equipment |
| CN101339172A (en) * | 2008-08-14 | 2009-01-07 | 北京大学 | Low pressure gas automatic sampling device and use method |
| CN101750450A (en) * | 2008-12-17 | 2010-06-23 | 中国科学院大连化学物理研究所 | Automatic sampling device for array capillary electrophoresis |
| CN101949906A (en) * | 2010-08-09 | 2011-01-19 | 四川省环境监测中心站 | Decompressed purge-and-trap processing equipment for non-volatile organic compound in water sample and processing method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3322420B2 (en) * | 1992-07-20 | 2002-09-09 | 三菱重工業株式会社 | Automatic gas sampling method and automatic gas analysis method |
| JP3596651B2 (en) * | 1997-03-31 | 2004-12-02 | 東京瓦斯株式会社 | Gas analyzer and analysis method thereof |
-
2012
- 2012-10-12 CN CN201210388090.7A patent/CN102879506B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4116046A (en) * | 1977-08-05 | 1978-09-26 | Hoffmann-La Roche Inc. | Liquid chromatography system |
| US20020146350A1 (en) * | 2001-02-02 | 2002-10-10 | Jiunn-Guang Lo | Real time monitoring system |
| CN2807257Y (en) * | 2005-06-07 | 2006-08-16 | 淄博祥龙测控技术有限公司 | Automatic sampling device of tube bundle chromatogram gas analyzing equipment |
| CN101339172A (en) * | 2008-08-14 | 2009-01-07 | 北京大学 | Low pressure gas automatic sampling device and use method |
| CN101750450A (en) * | 2008-12-17 | 2010-06-23 | 中国科学院大连化学物理研究所 | Automatic sampling device for array capillary electrophoresis |
| CN101949906A (en) * | 2010-08-09 | 2011-01-19 | 四川省环境监测中心站 | Decompressed purge-and-trap processing equipment for non-volatile organic compound in water sample and processing method thereof |
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Application publication date: 20130116 Assignee: Hai Tian Industrial Co., Ltd. of science town of Sichuan Province Assignor: Inst. of Chemical Material, Chinese Inst. of Engineering Physics Contract record no.: 2015510000059 Denomination of invention: Automatic gas sampling device and using method thereof Granted publication date: 20140716 License type: Exclusive License Record date: 20150604 |
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