CN1065529A - The method of capillary supercritical fluid chromatography desolventizing and desolventizing split sampling system thereof - Google Patents
The method of capillary supercritical fluid chromatography desolventizing and desolventizing split sampling system thereof Download PDFInfo
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- CN1065529A CN1065529A CN 91106366 CN91106366A CN1065529A CN 1065529 A CN1065529 A CN 1065529A CN 91106366 CN91106366 CN 91106366 CN 91106366 A CN91106366 A CN 91106366A CN 1065529 A CN1065529 A CN 1065529A
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Abstract
The invention belongs to the method and the split sampling system field thereof of desolventizing in the capillary supercritical fluid chromatography.The method of desolventizing is the six-way valve sampling of adopting in the liquid chromatography commonly used, and solvent constant temperature evaporation in quantity tube removes the method for big portion solvent.Separate system is made up of sampling valve, shunting resistance gauge, capillary resistance device, butt connector, well heater etc.Be characterized in shunting resistance gauge and be with diameter is a kind of porous resistance gauge of 5 to 10 compositions of steel wire of 0.3 millimeter 0.1 millimeter of stainless-steel tube interpolation.Desolventizing method coupled columns of the present invention is imitated and is not quantitatively had influence, the split sampling system, and stream is unimpeded, and qualitative precision is 1%, good stability, batching is analyzed quantitative error and is not more than 2%.
Description
The invention belongs to the six-way valve sampling that utilizes phase chromatography-use in the capillary supercritical fluid chromatography, sample is in quantity tube, through an analytical cycle, the Desolventizing method of constant temperature solvent evaporated and capillary supercritical fluid chromatography desolventizing shunting the carrying out system field of forming by sampling valve, shunting resistance gauge, capillary resistance device, butt connector thereof.
Common sample all need be used dissolution with solvents during capillary supercritical fluid chromatography was analyzed, because the capillary column capacity is limit, solvent all enters with the overload amount and causes solvent peak seriously to trail in the post, influences the detection of eluting peak the earliest and quantitatively, so wish can remove solvent behind the sample introduction.Desolventizing is just in developing a kind of method, has reported the gap method of withing a hook at the end, four-way valve column sample injection method, and post solvent emptying method.But these methods all will be reequiped sampling system, and troublesome poeration.
One of purpose of the present invention, studying does not exactly a kind ofly need to change the Desolventizing method of capillary supercritical fluid chromatography simple to operate to sampling valve.
Capillary supercritical fluid chromatography split sampling system is the critical component of capillary supercritical fluid chromatography, directly influences separation efficiency and quantitative precision.Present most of instrument adopts split sampling, and the shunting resistance gauge is to adopt the capillary resistance device, and the disadvantage of capillary resistance device is that easy the freezing of outlet blocked, and produces the not smooth phenomenon of stream.
Two of task of the present invention is exactly to study the high capillary supercritical fluid chromatography shunting desolventizing sampling system of unimpeded simple in structure, the easy to operate quantitative precision of a kind of stream.
In order to reach purpose of the present invention, the inventor adopts following technical characterictic to finish task of the present invention.
The method of capillary supercritical fluid chromatography desolventizing of the present invention: in capillary supercritical fluid chromatography is analyzed, the most frequently used solvent is a methylene chloride, the boiling point of this solvent is 36 ℃, at room temperature (25 ℃), volatility is very strong, utilize the volatile characteristic of solvent, with liquid chromatography six-way valve sampling commonly used, in the quantity tube of 10 microlitres, throw the liquid sample of certain volume into, (less than 10 microlitres) allow the solvent spontaneous evaporation, through certain hour (analytical cycle), promptly can fall most of solvent evaporation, rotating valve sample introduction then just can obtain sample peak behind the desolventizing.
Capillary supercritical fluid chromatography desolventizing split sampling system: comprise the system that sampling valve, shunting resistance gauge, capillary resistance device, butt connector, well heater etc. are formed.
Below the present invention will be further described with reference to the accompanying drawings:
Fig. 1 is a capillary supercritical fluid chromatography desolventizing split sampling system schematic
Fig. 2 is a porous shunting resistance gauge synoptic diagram
The synoptic diagram of Fig. 3 butt connector
Fig. 4 is a Rheodyne six-way valve desolventizing flow circuit diagram
Fig. 5 desolventizing time and post thereof are imitated, and biphenyl is quantitative influences figure
Biphenyl chromatogram before and after Fig. 6 desolventizing
Fig. 1 is of the present invention a kind of by six-way injection valve (1), diversion three-way (2), shunting resistance gauge (3), flame ionization detector heater (4), capillary column (5), to pressing connector (6), tail blows threeway (7), capillary resistance device (8), the capillary supercritical fluid chromatography desolventizing split sampling system that flame ionization detector (9) forms.
Accompanying drawing 2 is porous shunting resistance gauges, and wherein (10) are 0.3 millimeter stainless steel tube for internal diameter, and (11) are that 5 to 10 internal diameters of interpolation are 0.1 millimeter steel wire, the compression place of (12) pipe. (13) be CO2Gas because the shunting resistance gauge of single hole blocks easily, is made the porous type of accompanying drawing 2 to the shunting resistance gauge, and is heated to certain temperature, can guarantee not condensation of high-boiling components obstruction.
The resistance gauge of making is at N2Measure its flow velocity, N under the pressure2Flow velocity and 100 kilograms per centimeter2CO
2, the pass of 200 ℃ of flow velocitys is FN2＝0.53Fco
2For flame ionic detector, flow rate of mobile phase is advisable the N of resistance gauge with 25 to 35 millimeters/minute2Be 40 to 60 millimeters/minute under the flow velocity room temperature. The porous resistance gauge places the heater of detector, and temperature is minimum at 300 ℃, and often the phase uses, the emptying flow speed stability, and non-obstruction phenomenon produces.
When sampling, mobile phase directly advances pillar by passage 2,3, inject a certain amount of sample (less than 10 microlitres) by 4 to quantity tube with syringe, allow at room temperature natural evaporation of solvent, by 6 emptying (seeing accompanying drawing 4A), stop certain hour (analytical cycle) after, be 60 ° of sample injections of rotatable valve, stream is that 2143(sees accompanying drawing 4B) sample behind the desolventizing in the quantity tube is swept in the post analyze, after sample introduction was complete, it is for subsequent use that valve is gone to the sampling location.
Accompanying drawing 5 is that desolventizing time and coupled columns thereof are imitated, the quantitative impact of biphenyl.
Accompanying drawing 6 is chromatograms of biphenyl before and after the desolventizing.
Embodiment 1, utilize method of the present invention to desolventizing time and coupled columns thereof imitate, quantitative influence.
Experiment condition: 4 meters * 100 microns SE-54 quartz elasticity crosslinking columns, system controlled by computer SB-2 micro-injection pump, CO
2Be moving phase, pressure 130 kilograms per centimeter before the post
2, 88 ℃ of column temperatures, flame ionization detector, the temperature of shunting resistance gauge is 320 ℃, split ratio is 8: 1, gas flow rate: H
230 ml/min, nitrogen (tail blows) 30 ml/min, air 400 ml/min, carbon dioxide linear speed=3 cels, note bar device: 5 millivolts, chart speed 4 centimeters/minute, sample 0.1%, biphenyl dichloromethane solution, sample size 0.4 microlitre.
Experiment condition above utilizing measured for 0.1% biphenyl dichloromethane solution desolventizing time, and the post of biphenyl is imitated and quantitative data sees Table 1.
Table 1 desolventizing time, sample peak area and column effect relation
| The desolventizing time | 0 | 5 | 10 | 15 | 20 | 25 | 30 | 35 |
| The solvent peak area | － | 103 | 103 | 89 | 77 | 55 | 18 | 4 |
| The biphenyl peak area | － | 2.1 | 2.6 | 2.2 | 2.1 | 2.1 | 2.1 | 2.3 |
| Post is imitated (η) | 5000 | 5400 | － | － | － | － | 5400 | 5400 |
As can be seen from Table 1, being that solvent solvent in the quantity tube in 20 to 25 minutes can evaporate major part by blow-down pipe 1 with the methylene chloride under 25 ℃, to the peak area of biphenyl, coupled columns is imitated does not all have influence.
The experiment condition sample is C
22-C
28Pressure 145 kilograms per centimeter before the alkane, post
2, all the other conditions are identical with embodiment 1, the results are shown in Table 2, table 3
From table 2 data as can be seen, the qualitative precision of retention time is not more than 1%, and the stable fine of capillary supercritical fluid chromatography desolventizing split sampling of the present invention system is described.
Show from table 3 data, the quantitative accuracy of peak area be 1.53% with addition relatively, hand computation, the not correction up factor, relative error are 1.93%, within chromatogram quantification error allowed band, systematic quantification accuracy height of the present invention have been described.
Can illustrate that by top two embodiment (more than these two certainly) method of of the present invention six logical palace gate quantity tube constant temperature evaporation desolventizings is that a kind of coupled columns is imitated, quantitatively do not had influence, not need sampling valve is done any change, easy and simple to handle, be easy to use.The method of six-way valve quantity tube constant temperature evaporation desolventizing of the present invention can also be applied to gas chromatography and liquid chromatography desolventizing.
The split sampling system that porous shunting resistance gauge of the present invention constitutes, stream is unimpeded, and qualitative precision is 1%, join sample analysis quantitative error and be not more than 2%, be that a kind of stream is unimpeded, simple in structure, easy to operate, the capillary supercritical fluid chromatography desolventizing split sampling system that quantitative precision is high.
Claims (12)
1, the method for capillary supercritical fluid chromatography desolventizing is characterized in that utilizing the six-way valve sampling of phase chromatography-use, and sample is in quantitatively seeking, and through an analytical cycle, constant temperature evaporates the method for most of solvent.
2, the method for capillary supercritical fluid chromatography desolventizing according to claim 1 is characterized in that quantitatively the volume of battalion is 10 microlitres, and sample size is less than 10 microlitres.
3, the method for capillary supercritical fluid chromatography desolventizing according to claim 1 is characterized in that sample described in the battalion is being 10 to 25 minutes through an analytical cycle quantitatively.
4, the method for capillary supercritical fluid chromatography desolventizing according to claim 1 is characterized in that the temperature of described sample in quantitatively seeking is 20～35 ℃.
5, a kind of capillary supercritical fluid chromatography desolventizing split sampling system that is made up of sampling valve (1), shunting resistance gauge (2), capillary resistance device (3), butt connector (4), well heater (5) is characterized in that adopting porous shunting resistance gauge.
6, capillary supercritical fluid chromatography desolventizing split sampling according to claim 5 system is characterized in that the porous shunting resistance gauge that described shunting resistance gauge is made up of the several steel wires of stainless steel pipe interpolation.
7, capillary supercritical fluid chromatography desolventizing split sampling according to claim 5 system is characterized in that the pipe diameter of described porous shunting resistance gauge is 0.3 millimeter.
8, capillary supercritical fluid chromatography desolventizing split sampling according to claim 5 system is characterized in that the quantity of the interpolation steel wire of described porous shunting resistance gauge is 5 to 10.
9, capillary supercritical fluid chromatography desolventizing split sampling according to claim 5 system is characterized in that every gauge of wire in the described porous shunting resistance gauge is 0.1 millimeter.
10, capillary supercritical fluid chromatography desolventizing split sampling according to claim 5 system is characterized in that an end of described porous shunting resistance gauge compresses.
11, capillary supercritical fluid chromatography desolventizing split sampling according to claim 5 system is characterized in that described porous shunting resistance gauge is to be placed in the well heater of detecting device.
12, capillary supercritical fluid chromatography desolventizing split sampling according to claim 5 system is characterized in that the temperature of described porous shunting resistance gauge is minimum at 300 ℃.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 91106366 CN1065529A (en) | 1991-04-01 | 1991-04-01 | The method of capillary supercritical fluid chromatography desolventizing and desolventizing split sampling system thereof |
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| CN 91106366 CN1065529A (en) | 1991-04-01 | 1991-04-01 | The method of capillary supercritical fluid chromatography desolventizing and desolventizing split sampling system thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1329005C (en) * | 2003-12-05 | 2007-08-01 | 中国科学院大连化学物理研究所 | Thyroid disease auxiliary diagnosis instrument and its application |
| CN100419421C (en) * | 2004-01-05 | 2008-09-17 | 大赛璐化学工业株式会社 | Method of substance separation by supercritical fluid chromatography and vapor liquid separator for use therein |
| CN101206197B (en) * | 2006-12-22 | 2011-04-06 | 中国科学院大连化学物理研究所 | System for on-line desalinization, enrichment and mass spectrum of Double tap upgrade liquid chromatogram |
-
1991
- 1991-04-01 CN CN 91106366 patent/CN1065529A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1329005C (en) * | 2003-12-05 | 2007-08-01 | 中国科学院大连化学物理研究所 | Thyroid disease auxiliary diagnosis instrument and its application |
| CN100419421C (en) * | 2004-01-05 | 2008-09-17 | 大赛璐化学工业株式会社 | Method of substance separation by supercritical fluid chromatography and vapor liquid separator for use therein |
| CN101206197B (en) * | 2006-12-22 | 2011-04-06 | 中国科学院大连化学物理研究所 | System for on-line desalinization, enrichment and mass spectrum of Double tap upgrade liquid chromatogram |
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