CN102262137A - Gas chromatography method for high pressure liquid - Google Patents
Gas chromatography method for high pressure liquid Download PDFInfo
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- CN102262137A CN102262137A CN2010101831625A CN201010183162A CN102262137A CN 102262137 A CN102262137 A CN 102262137A CN 2010101831625 A CN2010101831625 A CN 2010101831625A CN 201010183162 A CN201010183162 A CN 201010183162A CN 102262137 A CN102262137 A CN 102262137A
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Abstract
The invention relates to a gas chromatography method for a high pressure liquid, mainly solving the problems existing in the present gas chromatography methods for the high pressure liquid of complicate devices and operations when using a water bath vaporizer for pre-evaporating a sample. The method comprises the following steps: (a) filling a high pressure liquid sample selected from volatile high pressure liquids in a storage high pressure liquid tank (1); (b) allowing the high pressure liquid sample in the storage high pressure liquid tank (1) to enter a sampling inlet end (4) of a four-way liquid sampling valve (5) through a filter (3); (c) allowing the sample to come out from a sampling outlet end of the four-way liquid sampling valve through the sampling inlet end (4) of a four-way liquid sampling valve and a micro quantification tube (8) arranged in the four-way liquid sampling valve (5), then allowing the sample to pass through a sampling vent end (7) of a damping tube (6) for venting and sampling, flushing the micro quantification tube (8) for several seconds with the high pressure liquid sample, then collecting a quantitative high pressure liquid sample; and (d) operating a sampling handle of the four-way liquid sampling valve (5) to rotate the built-in micro quantification tube (8) to a carrier gas line, allowing the sample to enter a gas chromatograph (11) for analysis. The method disclosed in the invention can be used in the industrial production of the gas chromatography of the high pressure liquid.
Description
Technical field
The present invention relates to a kind of method of gas chromatographic analysis highly pressurised liquid, be used to analyze highly pressurised liquid sample such as C
4Alkene, propylene, liquefied petroleum gas (LPG), dimethyl ether etc.
Background technology
Gc analysis highly pressurised liquid sample such as C
4When alkene, propylene, liquefied petroleum gas (LPG), dimethyl ether etc., sample introduction is the key of impact analysis data accuracy and precision with separating.C
4Highly pressurised liquid products such as alkene liquid condition normally in the process that stores, thereby adopt steel cylinder to take liquid sample analysis usually.Because the boiling point of each component is different with saturated vapor pressure in these highly pressurised liquid samples, and very easily vaporization under normal temperature and pressure conditions, can not adopt conventional fluid injector sample introduction, so during these samples of gas chromatographic analysis, how representational liquid sample being imported chromatograph is the key point that guarantees to analyze data accuracy.Because the composition of gas phase and liquid phase there are differences in the sample, thus can not directly take the gas phase of sample partly to analyze, otherwise can cause weight component analysis result's serious distortion.
Recommended water-bath vaporization sampling device in GB/T 6017-2008 " the mensuration vapor-phase chromatography of industrial butadiene purity and the hydrocarbon impurities " national standard.When this is this class highly pressurised liquid sample of present stratographic analysis, the general input mode of Cai Yonging.Adopt water-bath vaporization sampling device, equipment complexity, operation are comparatively loaded down with trivial details, if misoperation cause sample vaporization inhomogeneous easily, thereby representative distortion influences the accuracy of quantitative analytical data.
Summary of the invention
Technical matters to be solved by this invention is equipment complexity, the comparatively loaded down with trivial details problem of operation when in the past adopting the pre-vaporized sample of water-bath vapourizing unit in the gas chromatographic analysis highly pressurised liquid method.A kind of method of new gas chromatographic analysis highly pressurised liquid is provided.This method has device and sets up simple, processing ease, quantitative characteristic of accurate.
For addressing the above problem, the technical solution used in the present invention is as follows: a kind of method of gas chromatographic analysis highly pressurised liquid may further comprise the steps: the highly pressurised liquid sample that (a) will be selected from easy vaporization pours into and stores in the highly pressurised liquid jar 1; (b) will store highly pressurised liquid sample in the highly pressurised liquid jar 1 through behind the filtrator 3, enter the sampling inlet end 4 of four-way liquid sampling valve 5; (c) sample is through the sampling inlet end 4 of four-way valve, the four-way liquid sampling valve 5 built-in micro quantitative determination pipes 8 of flowing through are taken a sample from the sampling outlet end outflow of four-way valve and through sampling emptying end 7 emptying of damper tube 6, treat that highly pressurised liquid sample wash micro quantitative determination pipe after 8 several seconds, promptly takes quantitative highly pressurised liquid sample; (d) operation four-way liquid sampling valve 5 sample introduction handles rotate to the carrier gas circuit with built-in micro quantitative determination pipe 8, and sample enters gas chromatograph 11 and analyzes.
In the technique scheme, store highly pressurised liquid jar 1 and be directly connected to filtrator 3 and can take a sample and carry out stratographic analysis.
Adopt the method for gas chromatographic analysis highly pressurised liquid of the present invention, store highly pressurised liquid jar 1 and be directly connected to filtrator 3, be inverted and store highly pressurised liquid jar 1 Open valve 2, sample promptly relies on self pressure current through entering the micro quantitative determination pipe 8 of four-way liquid sampling valve 5 behind the filter 3 and through damper tube 6 emptying, because the resistance of damper tube 6 can quantitatively be taked micro-highly pressurised liquid sample.Stainless steel sintering core aperture in the metallic filter 3 is 2～4 μ m, with the mechanical impurity that may exist in the filtering sample, and the protection sampling valve.Treat that the sample wash quantity tube is after 8 several seconds, quantity tube 8 is promptly taked the highly pressurised liquid sample, operation four-way liquid sampling valve 5 is about to built-in miniature quantity tube 8 and switches to carrier gas line, and the split sampling mouth 12 that the micro-highly pressurised liquid sample of accurately taking is imported into chromatogram carries out stratographic analysis.The stainless steel capillary 13 that connects four-way liquid sampling valve 5 and chromatogram split sampling mouth 12 directly is inserted into the internal lining pipe middle part of split sampling mouth 12, diffusional effect before can effectively suppressing the vaporized expanding of highly pressurised liquid sample and spreading the post that is caused is improved separating effect.The method of gas chromatographic analysis highly pressurised liquid of the present invention need not adopt the pre-vapourizing units of sample such as water-bath vaporization, has simplified operation steps, has avoided the vaporization that exists in the vaporescence not exclusively or the uncertain factor such as inhomogeneous of vaporizing.
Use the method for gas chromatographic analysis highly pressurised liquid of the present invention to be used to analyze highly pressurised liquid 1,3-butadiene sample, the recovery of standard model is between 94.0%～112.8%, and the analytic variance of 5 mensuration is all less than 3.4%; The highly pressurised liquid 1,3-butadiene sample analysis of certain enterprise, the absolute value of the relative difference of 2 measurement results is all less than 6.5%.Method of the present invention is adopted in the quantitative analysis results explanation, and quantitatively accurately, the precision of data is good, has obtained better technical effect.
Description of drawings
Fig. 1 is the device schematic flow sheet of gas chromatographic analysis highly pressurised liquid method of the present invention.
Fig. 2 analyzes the chromatogram of highly pressurised liquid sample 1,3-butadiene for adopting apparatus of the present invention.
1 for storing the highly pressurised liquid jar among Fig. 1,2 is outlet valve, 3 is filtrator, 4 is the sampling inlet end of four-way liquid sampling valve, 5 is four-way liquid sampling valve, 6 is damper tube, and 7 are sampling emptying end, and 8 is the built-in micro quantitative determination pipe of liquid sampling valve, 9 are carrier gas, 10 is the carrier gas endpiece of four-way liquid sampling valve, and 11 is gas chromatograph, and 12 is chromatogram split sampling mouth, 13 for connecting the Stainless Steel Capillary bobbin of four-way liquid sampling valve and chromatogram split sampling mouth, 14 is the shunting outlet of split sampling mouth, and 15 is capillary chromatographic column, and 16 is flame ionization ditector.
1 is propane among Fig. 2, and 2 is propylene, and 3 is isobutane, and 4 is propadiene, 5 is normal butane, and 6 is acetylene, and 7 is anti--2-butylene, 8 is the 1-butylene, and 9 is isobutylene, and 10 is suitable-2-butylene, 11 is isopentane, and 12 is 1, the 2-butadiene, 13 is propine, and 14 are-n-pentane, and 15 is 1, the 3-butadiene, 16 is vinylacetylene, 17 is the 1-butine.
Workflow among Fig. 1 is: when preparing sample introduction, the outlet valve 2 that connects storage highly pressurised liquid jar 1 is to filtrator 3, be inverted and store highly pressurised liquid jar 1, open outlet valve 2, the highly pressurised liquid sample promptly relies on self pressure outflow, the micro quantitative determination pipe 8 that the four-way liquid sampling valve 5 of flowing through is built-in is by sampling emptying end 7 emptying of damper tube 6.Treat that fluid sample flushing quantity tube is after the several seconds, after observing in the damper tube 6 fluid sample and flowing out, operation four-way liquid sampling valve 5, rotary handle, the micro quantitative determination pipe 8 that the liquid sampling valve is built-in switches between the carrier gas endpiece 10 of chromatogram carrier gas 9 and four-way liquid sampling valve, promptly by the Stainless Steel Capillary bobbin 13 importing chromatogram split sampling mouths 14 of carrier gas 9 by connecting four-way liquid sampling valve and chromatogram split sampling mouth, sample enters capillary chromatographic column 15 separation and is detected by flame ionization ditector 16 the micro-highly pressurised liquid sample of quantitatively taking after shunting outlet 12 vaporizations and shunting.
The present invention is further elaborated below by embodiment.
Embodiment
[embodiment 1]
Press the flow process of Fig. 1, adopt highly pressurised liquid sample feeding analytical equipment of the present invention to analyze the standard model of highly pressurised liquid 1,3-butadiene, the sample ligand composition sees Table 1, and the instrument chromatographic condition sees Table 2, and chromatogram is seen Fig. 2, and quantitative analysis results sees Table 3.
The combo of table 1 highly pressurised liquid sample 1,3-butadiene becomes
| Hydrocarbon component | Concentration/(mg/kg) | Hydrocarbon component | Concentration/(mg/kg) |
| Propane | 329.0 | Isobutylene | 1675.0 |
| Propylene | 319.4 | Suitable-the 2-butylene | 33400 |
| Isobutane | 850.0 | N-pentane | 192.6 |
| Normal butane | 722.0 | Propine | 31.0 |
| Propadiene | 2108 | The 1-butine | 40.0 |
| Instead-the 2-butylene | 926.0 | Vinylacetylene | 29.0 |
| The 1-butylene | 1658.0 | 1,3-butadiene | Balance |
Table 2 is analyzed the chromatographic condition of highly pressurised liquid sample 1,3-butadiene
The quantitative analysis results of table 3 highly pressurised liquid sample 1,3-butadiene
| Component | Measured value, mg/kg | The recovery, % | 5 determination and analysis variances, % |
| Propane | 320.0 | 97.3 | 1.6 |
| Propylene | 323.0 | 101.1 | 2.1 |
| Isobutane | 809.1 | 95.2 | 1.4 |
| Propadiene | 225.0 | 106.7 | 3.4 |
| Normal butane | 718.1 | 99.5 | 1.7 |
| Instead-the 2-butylene | 948.4 | 102.4 | 1.3 |
| The 1-butylene | 1658.1 | 100.0 | 0.6 |
| Isobutylene | 1685.7 | 100.6 | 0.3 |
| Suitable-the 2-butylene | 3516.5 | 105.3 | 0.9 |
| Propine | 29.1 | 94.0 | 2.7 |
| N-pentane | 186.0 | 96.6 | 1.7 |
| Vinylacetylene | 32.7 | 112.8 | 2.7 |
| The 1-butine | 45.0 | 112.6 | 2.0 |
The data declaration of table 3, the recovery of standard model are between 94.0%～112.8%, and the analytic variance of 5 mensuration is all less than 3.4%, and the accuracy of setting analysis and data precision are good.
[embodiment 2]
Press the flow process of Fig. 1, adopt the sample of highly pressurised liquid 1,3-butadiene of the methods analyst enterprise of gas chromatographic analysis highly pressurised liquid of the present invention, quantitative analysis results relatively sees Table 4.
The quantitative analysis results of table 4 highly pressurised liquid 1,3-butadiene sample
The data declaration of table 4, the good separation of the sample of highly pressurised liquid 1,3-butadiene, the absolute value of the relative difference of 2 measurement results are all less than 6.5%, and quantitative repeatability is good.
Claims (2)
1. the method for a gas chromatographic analysis highly pressurised liquid may further comprise the steps: the highly pressurised liquid sample that (a) will be selected from easy vaporization pours into and stores in the highly pressurised liquid jar (1); (b) will store highly pressurised liquid sample in the highly pressurised liquid jar (1) through filtrator (3) after, enter the sampling inlet end (4) of four-way liquid sampling valve (5); (c) sample is through the sampling inlet end (4) of four-way valve, the built-in micro quantitative determination pipe (8) of the four-way liquid sampling valve (5) of flowing through is taken a sample from the sampling outlet end outflow of four-way valve and through sampling emptying end (7) emptying of damper tube (6), treat that highly pressurised liquid sample wash micro quantitative determination pipe after (8) several seconds, promptly takes quantitative highly pressurised liquid sample; (d) operation four-way liquid sampling valve (5) sample introduction handle rotates to the carrier gas circuit with built-in micro quantitative determination pipe (8), and sample enters gas chromatograph (11) and analyzes.
2. the method for gas chromatographic analysis highly pressurised liquid according to claim 1 is characterized in that storing highly pressurised liquid jar (1) and is directly connected to filtrator (3) and can takes a sample and carry out stratographic analysis.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103454362A (en) * | 2013-08-22 | 2013-12-18 | 中国石油天然气股份有限公司 | Online chromatographic reduced-pressure sample injection device and method |
| CN105911185A (en) * | 2016-04-20 | 2016-08-31 | 徐州市产品质量监督检验中心 | Method for detecting the contents of dimethyl ether and various hydrocarbon components in liquefied petroleum gas |
| CN108020484A (en) * | 2016-10-31 | 2018-05-11 | 中国石油化工股份有限公司 | A kind of method of quick measurement crude oil saturated vapor pressure |
| CN108205041A (en) * | 2016-12-16 | 2018-06-26 | 中国石油天然气股份有限公司 | Method for analyzing sulfur-containing compounds in liquefied gas |
| CN110146606A (en) * | 2019-05-06 | 2019-08-20 | 北京水木滨华科技有限公司 | A kind of preprocess method of highly pressurised liquid component |
| CN110286164A (en) * | 2019-05-06 | 2019-09-27 | 北京水木滨华科技有限公司 | A kind of qualitative and quantitative detecting method and detection device of liquid material |
| CN110286165A (en) * | 2019-05-06 | 2019-09-27 | 北京水木滨华科技有限公司 | A kind of qualitative and quantitative analysis method of highly pressurised liquid material |
| CN114910572A (en) * | 2021-02-10 | 2022-08-16 | 上海中化科技有限公司 | Sample introduction device and method, and quantitative analysis device and method |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103454362A (en) * | 2013-08-22 | 2013-12-18 | 中国石油天然气股份有限公司 | Online chromatographic reduced-pressure sample injection device and method |
| CN105911185A (en) * | 2016-04-20 | 2016-08-31 | 徐州市产品质量监督检验中心 | Method for detecting the contents of dimethyl ether and various hydrocarbon components in liquefied petroleum gas |
| CN105911185B (en) * | 2016-04-20 | 2019-02-05 | 徐州市质量技术监督综合检验检测中心 | A kind of method of dimethyl ether and each hydrocarbon component content in detection liquefied petroleum gas |
| CN108020484A (en) * | 2016-10-31 | 2018-05-11 | 中国石油化工股份有限公司 | A kind of method of quick measurement crude oil saturated vapor pressure |
| CN108205041A (en) * | 2016-12-16 | 2018-06-26 | 中国石油天然气股份有限公司 | Method for analyzing sulfur-containing compounds in liquefied gas |
| CN110146606A (en) * | 2019-05-06 | 2019-08-20 | 北京水木滨华科技有限公司 | A kind of preprocess method of highly pressurised liquid component |
| CN110286164A (en) * | 2019-05-06 | 2019-09-27 | 北京水木滨华科技有限公司 | A kind of qualitative and quantitative detecting method and detection device of liquid material |
| CN110286165A (en) * | 2019-05-06 | 2019-09-27 | 北京水木滨华科技有限公司 | A kind of qualitative and quantitative analysis method of highly pressurised liquid material |
| CN110286165B (en) * | 2019-05-06 | 2020-07-24 | 北京水木滨华科技有限公司 | Qualitative and quantitative analysis method for high-pressure liquid material |
| CN114910572A (en) * | 2021-02-10 | 2022-08-16 | 上海中化科技有限公司 | Sample introduction device and method, and quantitative analysis device and method |
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Application publication date: 20111130 |