CN1536359A - GC high-temperature high-pressure sample directly-sampling method and equipment - Google Patents
GC high-temperature high-pressure sample directly-sampling method and equipment Download PDFInfo
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- CN1536359A CN1536359A CNA03110102XA CN03110102A CN1536359A CN 1536359 A CN1536359 A CN 1536359A CN A03110102X A CNA03110102X A CN A03110102XA CN 03110102 A CN03110102 A CN 03110102A CN 1536359 A CN1536359 A CN 1536359A
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Abstract
The invention provides a gas-phase chromatographic sampling method and device which can online analyze high-temperature high-pressure gas-liquid mixing sampling source. The sample enters ten-way valve quantitative tube from the high-pressure sampling source (high-pressure kettle or container) through high-pressure resisting tube, and after filling up the tube, is directly placed in the air through damping tube or high-pressure, doubled-pressure, pressure-stabilizing valve, to keep the pressures of the quantitative tube and the sampling source consistent; at the same time it pours eluting solvent in the eluting solvent quantitative tube; turns the ten-way valve to the sampling position, so that the auxiliary carrier gas feeds the eluting solvent together with the sample into gas chromatographic sampler, then quantitatively analyzes by area normalization with response factor, and obtains the composition of high-pressure sample by primarily sampling. The device includes auxiliary carrier gas flow stabilizing system, high-temperature resisting ten-way valve, damping tube or high-pressure, pressure-doubling, pressure stabilizing valve, eluting solvent system and sample transmission capillary.
Description
Technical field
The present invention relates to a kind of gas chromatography sampling technique, particularly capillary gas chromatography sampling technique, relate in particular to the direct injected method that a kind of High Temperature High Pressure sample online acquisition and single injected sampling are finished the normalization quantitative test.
The invention still further relates to a kind of device of realizing that above-mentioned sample injection method is used.
Background technology
Gas chromatography has been widely used in the compartment analysis of all gases, fluid sample under normal pressure and middle pressure or the negative pressure.But the direct insertion technique for the direct analysis of some high pressure sample, particularly high pressure volatile liquid sample and high pressure solution-airmixture sample does not appear in the newspapers so far.Industrial gas liquid reaction is usually under high pressure carried out, and the variation of the composition of reactant and product under the differential responses condition in the analytical reactions process is very important to the control reaction conditions.
Traditional analytical approach adopts and in closed system high pressure sample is decompressed to normal pressure, is divided into gas-liquid two-phase, then divides the composition of gassing, liquid two-phase respectively, calculates each component concentration of solution-airmixture at last by material balance.The method complicated operation, influence factor is many, misses by a mile.Particularly to the mensuration of High Temperature High Pressure sample, in the process of sample cooling decompression, the heavy constituent wall sticking phenomenon in the sample can take place, and cause the light constituent sample introduction many, the problem that the heavy constituent sample introduction is few.If the solution-air biased sample after the step-down cooling is distinguished sample introduction again after gas-liquid separation, can when the fluid sample sample introduction, lose dissolved gas wherein again.Therefore traditional normal pressure analytical approach can not the real embodiment reaction conditions under the composition of (temperature of reaction and reaction pressure) reactant and product, or the composition of underground petroleum and rock gas oil gas compound sample.
Summary of the invention
The object of the present invention is to provide a kind of gas chromatography high pressure sample direct injected method and apparatus, be suitable for the analysis that High Temperature High Pressure volatile liquid, high pressure contain the liquid and the high temperature and high pressure gas-liquid mixing matter sample of dissolved gas.
Direct injected method and apparatus of the present invention, be directly to gather the High Temperature High Pressure sample, and single injected sampling just can be finished whole sample feedings, can provide the area normalization result of high pressure sample in the short time, quantitatively accurately, simple to operate, be specially adapted to the industrial On-line Control analysis of High Temperature High Pressure gas liquid reaction and the analysis of underground petroleum and rock gas oil gas compound sample composition.
Sample injection method of the present invention is to adopt the auxiliary carrier gas and the eluting solvent of regime flow that high pressure sample is introduced chromatogram ration analysis.(press still or high pressure vessel) enters the sample quantity tube of a valve through high pressure resistant pipe sample from the high pressure sample source, is full of the back by the direct emptying of damper tube or pass through the emptying of high pressure back pressure pressure maintaining valve again, and the pressure of quantity tube and the pressure of sample source are consistent; Simultaneously eluting solvent is injected the eluting solvent quantity tube; Rotating valve is to the sample introduction position, and auxiliary carrier gas is sent into eluting solvent and sample in the injector of gas chromatography together, can use the area normalization method quantitative test of band response factor, and single injected sampling directly draws the composition of high pressure sample.
The auxiliary carrier gas systems stabilisation adopts pressure maintaining valve and flow stabilizing valve control, and the system that makes keeps stable carrier gas flux under pressure changes, guaranteed the repeatability of sample introduction.
Damper tube or high pressure back pressure pressure maintaining valve are kept high pressure sample pressure in the sample collecting process constant, guarantees that the composition of sample is constant;
Eluting solvent adopts usually to good, the volatile solvent of sample dissolution, as alkane, alkene, ketone etc.Concrete as n-pentane, normal hexane, normal heptane, cyclohexane, acetone etc.Its effect is a residual sample in sample dissolution, compensator or trimmer pressure, elution samples quantity tube and the sample transfer tube in the sample introduction process, thereby the nothing that realizes sample is detained, without discrimination is introduced.
Apparatus of the present invention synoptic diagram is seen Fig. 1.This device mainly is made up of one tunnel auxiliary carrier gas steady flow system a, high temperature high voltage resistant ten-way valve b, damper tube or high pressure back pressure pressure maintaining valve c, the d of eluting solvent system and the sample introduction transfer capillary e that have a damper tube.1 of ten-way valve b directly links to each other with the thief hatch in high pressure sample source through a stainless-steel tube, 2 is the sample drain, " stainless-steel tube links to each other with damper tube or high pressure back pressure pressure maintaining valve c; connect a sample quantity tube f between 3 and 10; connect an eluting solvent quantity tube g between 6 and 9; eluting solvent enters among the wash-out quantity tube g through 8; 7 is the eluting solvent drain; auxiliary carrier gas is gone into ten-way valve b from 5 bit streams, and 4 of ten-way valve b are passed through a capillary e and link to each other with the injection port of gas chromatography through one 1/16.
Figure 1A is the process flow diagram of high pressure sample gatherer process, high pressure sample enters the sample quantity tube f of ten-way valve from high-voltage power supply, gather high pressure sample by the drain that has damper tube, simultaneously elute soln is injected wash-out quantity tube g, then ten-way valve is switched to the position shown in Figure 1B, auxiliary carrier gas promotes eluting solvent sample is introduced chromatogram ration analysis by transmission sample introduction pipe e.
Situation per sample, wash-out quantity tube g can adopt the internal diameter 25 μ m～elastic quartz capillary tube of 250 μ m or suitable stainless-steel tube.It is the introducing gas chromatography injection port that sample and eluting solvent is not had absorption that the sample transfer tube e that introduces the gas chromatography injector can adopt the elastic quartz capillary tube of fine inner diameter, its effect, can also directly insert in the pre-column as direct column sample injection pipe.
The present invention adopts high temperature high voltage resistant ten-way valve (200/300 ℃ of heatproof, withstand voltage 5000psi), directly links to each other with the high pressure sample source, simultaneously adds a high pressure damper tube or high pressure back pressure pressure maintaining valve c at sample drain (ten-way valve 2).By regulating drain flow or pressure, keep quantitative intraductal pressure consistent with high pressure sample source pressure.The high pressure sample of being gathered can be the high pressure volatile liquid, and high pressure solution-airmixture, high pressure contain the fluid sample of dissolved gas etc.Because the sample in the sample quantity tube is consistent with the sample composition in the high pressure sample source, thereby realized the gatherer process of high pressure sample.
For the High Temperature High Pressure sample collecting, sample delivery pipeline and this device need be incubated, constant with the composition that guarantees sample.
Description of drawings
Below by embodiment and accompanying drawing the present invention is done detailed narration, the present invention and classic method accuracy and accuracy relatively is described simultaneously.
Figure 1A is the sample collecting process.(autoclave or high pressure vessel) flows out high pressure sample from the high pressure sample source, and 1 by ten-way valve directly enters in the sample hose, because the drag effect of drain damper tube, keeps in the sample hose pressure consistent with the pressure in high pressure sample source; Eluting solvent is full of the wash-out pipe from 8;
Figure 1B is the sample introduction process, and ten-way valve is switched to Fig. 1 (B) position, and assist gas promotes eluent and sample is sent in gas chromatography vaporizer or the pre-column in the lump;
Fig. 2 is the chromatogram of valve injection hexene-1 liquid product under the normal pressure;
Fig. 3 is the chromatogram that micro syringe sample introduction hexene-1 liquid product is formed under the normal pressure;
Fig. 4 is the chromatogram that online valve is gathered the phase composition of hexene-1 reactant liquor under the 50kg pressure;
Fig. 5 is the chromatogram of micro syringe sample introduction hexene-1 reactant liquor phase composition under the normal pressure.
Embodiment
Embodiment 1: valve injection hexene-1 liquid product composition measuring under the normal pressure
The assist gas flow is controlled at 4mL/min with flow stabilizing valve, VALCO ten logical liquid phase valves, and the sample quantity tube adopts 25 μ m * 120mm quartz capillary, 0.1 μ L, the wash-out pipe adopts 100 μ m * 120mm quartz capillary, 0.5 μ L, and eluent adopts n-pentane, capillary sample introduction pipe adopts the quartz capillary of 50 μ m * 25cm, split sampling, split ratio 40: 1, analytical column is 30m * 0.53mm internal diameter * 1.5 μ m heavy caliber SE-54 quartz wool buttress shafts, detecting device is FID, and valve is to switch moment switching time.Chromatogram is seen Fig. 2.
Embodiment 2: micro syringe sample introduction hexene-1 liquid product composition measuring under the normal pressure
Adopt the micro syringe sample introduction, sample size 0.1 μ L, split sampling, split ratio 40: 1, analytical column is 30m * 0.53mm * 1.5 μ m heavy caliber SE-54 quartz wool buttress shafts, detecting device is FID.Chromatogram is seen Fig. 3.
Embodiment 3: online valve is gathered sample introduction and is measured hexene-1 reactant liquor phase composition mensuration under the 50kg pressure
The assist gas flow is controlled at 4mL/min with flow stabilizing valve, VALCO ten logical liquid phase valves, the sample quantity tube adopts 25 μ m * 120mm quartz capillary, 0.1 μ L, damper tube adopts 10m * 25 μ m quartz capillaries, the eluting solvent quantity tube adopts 100 μ m * 120mm quartz capillary, 0.5 μ L, eluent adopts n-pentane, and capillary sample introduction pipe adopts the quartz capillary of 50 μ m * 25cm, split sampling, split ratio 40: 1, analytical column is 30m * 0.53mm * 1.5 μ m heavy caliber SE-54 quartz wool buttress shafts, and detecting device is FID, and valve is to switch moment switching time.Chromatogram is seen Fig. 4.
Embodiment 4: the phase composition of micro syringe sample introduction hexene-1 reactant liquor is measured under the normal pressure
Adopt the micro syringe sample introduction, sample size 0.1 μ L, split sampling, split ratio 40: 1, analytical column is 30m * 0.53mm * 1.5 μ m heavy caliber SE-54 quartz wool buttress shafts, detecting device is FID.Chromatogram is seen Fig. 5.
Claims (8)
1, a kind of gas chromatography High Temperature High Pressure sample direct injected method, sample enters the sample quantity tube of valve from the high pressure sample source through high pressure resistant pipe, be full of the back by the direct emptying of damper tube or pass through the emptying of high pressure back pressure pressure maintaining valve again, the pressure of quantity tube and the pressure of sample source are consistent; Simultaneously eluting solvent is injected the eluting solvent quantity tube; Rotating valve is to the sample introduction position, and auxiliary carrier gas is sent into eluting solvent and sample in the injector of gas chromatography together, can use the area normalization method quantitative test of band response factor, and single injected sampling directly draws the composition of high pressure sample;
Damper tube or high pressure back pressure pressure maintaining valve are kept high pressure sample pressure in the sample collecting process constant, guarantees that the composition of sample is constant;
The auxiliary carrier gas systems stabilisation adopts pressure maintaining valve and flow stabilizing valve control, makes system keep stable carrier gas flux under pressure changes, and guarantees the repeatability of sample introduction;
Its effect of eluting solvent is a residual sample in compensator or trimmer pressure, elution samples quantity tube and the sample transfer tube in the sample introduction process, realizes that the nothing of sample is detained, without discrimination is introduced;
Promote valve to be switched to the sampling location after sample is transferred to the sample introduction transfer capillary fully at eluting solvent, valve is not more than 10s switching time.
2, sample injection method as claimed in claim 1 is characterized in that, described high pressure sample source is autoclave or high pressure vessel.
3, sample injection method as claimed in claim 1 is characterized in that, described eluting solvent is alkane, alkene or ketone.
As claim 1 or 3 described methods, it is characterized in that 4, described eluting solvent is n-pentane, normal hexane, normal heptane, cyclohexane or acetone.
5, sample injection method as claimed in claim 1 is characterized in that, described sample is various volatility, half volatile and the high temperature high pressure liquid that contains dissolved gas and gases at high pressure-liquid mixing matter sample.
6, a kind of gas chromatography high pressure sample direct injected device, it is characterized in that this device mainly is made up of one tunnel auxiliary carrier gas steady flow system, high temperature high voltage resistant ten-way valve, damper tube or the high pressure back pressure pressure maintaining valve, eluting solvent system and the sample introduction transfer capillary that have a damper tube;
Wherein, 1 of ten-way valve directly links to each other with the thief hatch in high pressure sample source through a stainless-steel tube, 2 is the sample drain, " stainless-steel tube links to each other with damper tube; connect a sample quantity tube between 3 and 10; connect an eluting solvent quantity tube between 6 and 9, and eluting solvent enters in the wash-out quantity tube through 8, and 7 be the eluting solvent drain; auxiliary carrier gas is gone into ten-way valve from 5 bit streams, and 4 of ten-way valve are passed through a capillary and link to each other with the injection port of gas chromatography through one 1/16.
7, device as claimed in claim 6 is characterized in that, 2 of described ten-way valve link to each other with high pressure back pressure pressure maintaining valve through stainless-steel tube.
8, device as claimed in claim 6 is characterized in that, the eluting solvent quantity tube that connects between 6 and 9 of the described ten-way valves is elastic quartz capillary tube or stainless-steel tube.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CNA03110102XA CN1536359A (en) | 2003-04-10 | 2003-04-10 | GC high-temperature high-pressure sample directly-sampling method and equipment |
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| CNA03110102XA CN1536359A (en) | 2003-04-10 | 2003-04-10 | GC high-temperature high-pressure sample directly-sampling method and equipment |
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| CN1536359A true CN1536359A (en) | 2004-10-13 |
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| CNA03110102XA Pending CN1536359A (en) | 2003-04-10 | 2003-04-10 | GC high-temperature high-pressure sample directly-sampling method and equipment |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007143907A1 (en) * | 2006-05-29 | 2007-12-21 | Accelergy Shanghai R & D Center Co., Ltd. | Sample collecting device |
| WO2009079059A1 (en) * | 2007-12-17 | 2009-06-25 | Services Petroliers Schlumberger | High pressure and high temperature chromatography |
| CN101113969B (en) * | 2006-07-27 | 2010-05-12 | 中国科学院大连化学物理研究所 | Sample feeder device of solid body and liquid example |
| CN101251517B (en) * | 2008-04-01 | 2011-01-19 | 南京特种气体厂有限公司 | Method and equipment for chromatographic analysis minim argon, nitrogen impurity in oxygen |
| CN102262137A (en) * | 2010-05-26 | 2011-11-30 | 中国石油化工股份有限公司 | Gas chromatography method for high pressure liquid |
| CN101617226B (en) * | 2007-02-22 | 2012-07-04 | 通用电气健康护理生物科学股份公司 | Rotation valve for sample injection |
| CN102749403A (en) * | 2011-04-20 | 2012-10-24 | 中国石油化工股份有限公司 | Special sampling device for online chromatographic analysis system |
| CN102928255A (en) * | 2012-11-14 | 2013-02-13 | 天津市先权工贸发展有限公司 | Liquid in-situ chromatographic sampling device inside high-temperature high-pressure reaction kettle and method of liquid in-situ chromatographic sampling device |
| CN101617225B (en) * | 2007-02-22 | 2013-03-06 | 通用电气健康护理生物科学股份公司 | Selection valve |
| CN105675776A (en) * | 2016-04-07 | 2016-06-15 | 中科合成油技术有限公司 | Stable online chromatogram sample feeding device and method |
| CN110487944A (en) * | 2019-08-16 | 2019-11-22 | 国家能源集团宁夏煤业有限责任公司 | The method of chromatographic detection apparatus and detection acetonitrile |
| US11852616B2 (en) | 2021-01-07 | 2023-12-26 | Saudi Arabian Oil Company | High pressure high temperature direct fluid injection to gas chromatography in a PVT system |
-
2003
- 2003-04-10 CN CNA03110102XA patent/CN1536359A/en active Pending
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007143907A1 (en) * | 2006-05-29 | 2007-12-21 | Accelergy Shanghai R & D Center Co., Ltd. | Sample collecting device |
| CN101113969B (en) * | 2006-07-27 | 2010-05-12 | 中国科学院大连化学物理研究所 | Sample feeder device of solid body and liquid example |
| CN101617225B (en) * | 2007-02-22 | 2013-03-06 | 通用电气健康护理生物科学股份公司 | Selection valve |
| CN101617226B (en) * | 2007-02-22 | 2012-07-04 | 通用电气健康护理生物科学股份公司 | Rotation valve for sample injection |
| EP2223100A1 (en) * | 2007-12-17 | 2010-09-01 | Services Pétroliers Schlumberger | High pressure and high temperature chromatography |
| WO2009079059A1 (en) * | 2007-12-17 | 2009-06-25 | Services Petroliers Schlumberger | High pressure and high temperature chromatography |
| CN101251517B (en) * | 2008-04-01 | 2011-01-19 | 南京特种气体厂有限公司 | Method and equipment for chromatographic analysis minim argon, nitrogen impurity in oxygen |
| CN102262137A (en) * | 2010-05-26 | 2011-11-30 | 中国石油化工股份有限公司 | Gas chromatography method for high pressure liquid |
| CN102749403A (en) * | 2011-04-20 | 2012-10-24 | 中国石油化工股份有限公司 | Special sampling device for online chromatographic analysis system |
| CN102749403B (en) * | 2011-04-20 | 2015-11-25 | 中国石油化工股份有限公司 | The special sampling apparatus of on-line chromatograph analytic system |
| CN102928255A (en) * | 2012-11-14 | 2013-02-13 | 天津市先权工贸发展有限公司 | Liquid in-situ chromatographic sampling device inside high-temperature high-pressure reaction kettle and method of liquid in-situ chromatographic sampling device |
| CN105675776A (en) * | 2016-04-07 | 2016-06-15 | 中科合成油技术有限公司 | Stable online chromatogram sample feeding device and method |
| CN110487944A (en) * | 2019-08-16 | 2019-11-22 | 国家能源集团宁夏煤业有限责任公司 | The method of chromatographic detection apparatus and detection acetonitrile |
| US11852616B2 (en) | 2021-01-07 | 2023-12-26 | Saudi Arabian Oil Company | High pressure high temperature direct fluid injection to gas chromatography in a PVT system |
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