CN1313823C - Apparatus and process for improving detection sensitivity by modulating outlet pressure or flow of chromatographic column - Google Patents
Apparatus and process for improving detection sensitivity by modulating outlet pressure or flow of chromatographic column Download PDFInfo
- Publication number
- CN1313823C CN1313823C CNB2004100940282A CN200410094028A CN1313823C CN 1313823 C CN1313823 C CN 1313823C CN B2004100940282 A CNB2004100940282 A CN B2004100940282A CN 200410094028 A CN200410094028 A CN 200410094028A CN 1313823 C CN1313823 C CN 1313823C
- Authority
- CN
- China
- Prior art keywords
- column
- pressure
- modulator
- chromatographic
- chromatographic column
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Abstract
The present invention discloses a device and a method for modulating the outlet pressure or the flow quantity of chromatographic columns for enhancing detecting sensitivity, which belongs to the improving techniques of chromatographic instrument detection. In the device, a concentrating column and a modulator are arranged between an outlet of a chromatographic column and a detector, and a feedback pipeline is arranged. In the process of the method, when components enter the concentrating column, the pressure or the flow quantity of the concentrating column is enhanced for causing the sample components entering the concentrating column to be compressed in a small volume unit; the samples are fast sent in the detector for obtaining high detection sensitivity. The present invention has the advantages that the method is suitable for not only mass type detectors, but also concentration type detectors, has no need of large changes of the existing chromatographic instruments and only needs the arrangements of the concentrating column and the modulator in the implementation process; the modulator can remarkably enhance the sensitivity of chromatographic instrument detectors, and the method is especially suitable for the detection of trace substances.
Description
Technical field
The present invention relates to a kind of device and method of modulating chromatographic column top hole pressure or flow raising detection sensitivity, belong to the improvement technology that chromatograph detects.
Background technology
How to improve the chromatograph detection sensitivity and be always the chromatogram worker and constantly make great efforts the technical field studied.The research that detection sensitivity is improved mainly concentrates on the device and chromatograph of detecting device, sample pre-treatments at present.Though the detection sensitivity of chromatographic detector improves constantly, chromatograph is become trace materials is separated and one of the most effective analytical instrument that detects.But increasing research object is had higher requirement to the chromatograph detector sensitivity in real work, and the sensitivity of existing chromatographic detector is difficult to reach this requirement, so need more, better method and device further improves chromatographic detection sensitivity.
Summary of the invention
The object of the present invention is to provide a kind of device and method of modulating chromatographic column top hole pressure or flow raising detection sensitivity, this device and operating process are simple, can effectively improve chromatographic detection sensitivity.
The present invention is realized by following technical proposals.A kind of device based on modulation chromatographic column top hole pressure or flow raising chromatograph detection sensitivity, it is characterized in that, endpiece in chromatographic column 3 is provided with evaporating column 4 to the pipeline between detecting device 10 imports, the length of evaporating column 4 is determined by the wideest chromatographic peak of bands of a spectrum in the analytic sample component; On the associated line bypass 6 is set between the import of chromatographic column 3 outlets and evaporating column 4, this bypass 6 connects modulator 5, this modulator comprises pressure-regulating valve and flow control valve, modulator 5 is provided with the associated line 9 with source of the gas 1 outlet, be provided with the associated line 7 that enters the mouth with chromatographic column 3, constitute backfeed loop; Modulator 5 is provided with the associated line 8 with detecting device 10 inlets, constitutes backfeed loop.
Above-mentioned evaporating column can be inertia post or common chromatographic column.
Adopt said apparatus to realize the method for modulation chromatographic column top hole pressure and flow, its process feature comprises following process:
After the sample component of chromatographic column outflow enters evaporating column, regulate the pressure-regulating valve of modulator, improve the pressure of evaporating column, backfeed loop guarantees that the pressure reduction that chromatographic column enters the mouth and the pressure reduction of outlet is preceding with improving evaporating column pressure is constant; The flow control valve of regulating modulator guarantees the flow of detecting device and improves the preceding flow of evaporating column pressure constant; The sample component that enters evaporating column is compressed, smaller volume, and sample is more promptly sent in the detecting device, thereby obtains higher detection sensitivity.
Below the present invention is elaborated:
Embodiment of the present invention are at outlet of gas chromatograph chromatographic column and detecting device link position, increase the suitable evaporating column of a segment length, and the length of this evaporating column must be able to be held the component of bands of a spectrum broadening maximum in the sample component.Be connected with pressure or flow modulation device simultaneously in chromatographic column outlet and evaporating column connecting portion.This device can independently be controlled the pressure and the flow of evaporating column.Variation for fear of evaporating column pressure, flow exerts an influence to analytical column and detecting device, and pressure, fluence modulators also are connected with feedback gas circuit pipeline with chromatographic column inlet and detecting device porch respectively.The feedback gas circuit can compensate control to analytical column and detecting device upward pressure, flow, to guarantee that the pressure or the flow of analytical column and detecting device remain unchanged when the pressure of evaporating column or flow change.After sample component flowed into evaporating column fully, pressure, flow modulation device improved the pressure or the flow of evaporating column rapidly.Pressure or flow increase the sample sets branch of back on evaporating column and are compressed in the littler volume, and sample concentration obtains corresponding raising, and sample component also can be purged at faster speed and enter detecting device simultaneously.For concentration detector, be improved owing to enter the sample component concentration of detecting device, so the detection sensitivity of detecting device is improved accordingly.To mass flow rate sensitive detector, not only exist sample concentration to improve and effect that detector sensitivity is improved; Because sample component flows into detecting device at faster speed, the sample component quality that flows into detecting device in the unit interval is significantly increased simultaneously, the detection sensitivity of outcome quality type detecting device can get a greater increase.The use of feedback assembly can be avoided causing the flow rate fluctuation to the pressure reduction and the detecting device of analytical column when modulation evaporating column pressure, and keeps them and be in constant substantially state, thereby guarantees the normal analysis of analytical column and the normal detection of detecting device.
The invention has the advantages that this method is not only applicable to mass flow rate sensitive detector, also be applicable to concentration detector, in implementation process, do not need existing chromatograph is carried out big change; Only evaporating column and modulator need be set.Can significantly improve the sensitivity of chromatographic detector by modem devices.The enforcement of this method is specially adapted to the detection of trace materials.
Description of drawings
Fig. 1 is apparatus of the present invention structured flowchart.
Among the figure: 1-source of the gas, 2-injector, 3-chromatographic column, 4-evaporating column, 5-modulator, 6-evaporating column control pipeline, 7-chromatographic column feedback line, 8-detecting device feedback line, 9-modulator source gas line, 10-detecting device.
The spectrogram that Fig. 2 obtains with existing methods analyst for engine discharging tail gas.
The spectrogram that Fig. 3 obtains with the inventive method analysis for engine discharging tail gas.
The analysis of spectra that Fig. 4 obtains with existing analytical approach for the enanthic acid sample.
The spectrogram that Fig. 5 obtains with the inventive method analysis for the enanthic acid sample.
Horizontal ordinate is chromatographic retention (min) in the spectrogram, and ordinate is the response (pA) of chromatographic component on detecting device.
Embodiment
Embodiment one:
Operating conditions
Gas chromatographic column: HP-5,30m * 0.32mm * 0.25 μ m
Detecting device: FID, 250 ℃ of temperature
Column temperature: temperature programme keeps 4min for 65 ℃, is warming up to 280 ℃ with 15 ℃/min
Injector: split sampling, split ratio 1: 1,250 ℃ of temperature
Sample: I. C. engine discharging tail gas (containing environmental pollutants such as trace stable hydrocarbon, aromatic hydrocarbons)
Sample size: 100 μ L
Under normal operating condition, chromatographic column endpiece carrier gas flux is 1mL/min, and the stratographic analysis result shows that the spectrum peak all presents flat peak, and detection sensitivity is low, sees Fig. 2.
Use modulator, chromatographic column 3:HP-5,24m * 0.32mm * 0.25 μ m, evaporating column 4:HP-5,6m * 0.32mm * 0.25 μ m.When working time during at 4.58min, the component of retention time between 4.6-4.98min enters evaporating column fully under normal operating condition, and control by the flow of 5 pairs of evaporating columns 4 of modulator this moment, and flow is heightened to 5ml/min.The component detection sensitivity that the result enters evaporating column has all obtained corresponding raising, and sensitivity improves 3-6 doubly, sees Fig. 3.
Embodiment two:
Operating conditions
Gas chromatographic column: HP-5,30m * 0.32mm * 0.25 μ m
Detecting device: FID, 250 ℃ of temperature
Column temperature: temperature programme keeps 4min for 65 ℃, is warming up to 280 ℃ with 15 ℃/min
Injector: split sampling, split ratio 1: 20,250 ℃ of temperature
Sample: enanthic acid
Sample size: 0.2 μ L
Under normal operating condition, chromatographic column endpiece carrier gas flux is 1ml/min, and the stratographic analysis result shows that the spectrum peak presents the peak that lolls, and detection sensitivity is low, sees Fig. 4.
Use modulator, chromatographic column 3:HP-5,24m * 0.32mm * 0.25 μ m, evaporating column 4:HP-5,6m * 0.32mm * 0.25 μ m.When working time during at 8.1min, retention time has entered evaporating column fully at the enanthic acid of 8.6min under normal operating condition, and control by the flow of 5 pairs of evaporating columns 4 of modulator this moment, and flow is heightened to 5mL/min.The component detection sensitivity that the result enters evaporating column has all obtained corresponding raising, and sensitivity has improved 8 times.See Fig. 5.
Claims (3)
1, a kind of device based on modulation chromatographic column top hole pressure or flow raising chromatograph detection sensitivity, it is characterized in that, endpiece in chromatographic column (3) is provided with evaporating column (4) to the pipeline between detecting device (10) import, the length of evaporating column (4) is determined by the wideest chromatographic peak of bands of a spectrum in the analytic sample component; On the associated line bypass (6) is set between the import of chromatographic column (3) outlet and evaporating column (4), this bypass (6) connects modulator (5), this modulator comprises pressure-regulating valve and flow control valve, modulator (5) is provided with and the associated line (9) of source of the gas (1) outlet and the associated line (7) of chromatographic column (3) inlet, constitutes backfeed loop; Modulator (5) is provided with the associated line (8) with detecting device (10) inlet, constitutes backfeed loop.
2, by the described device of claim 1, it is characterized in that evaporating column is inertia post or common chromatographic column based on modulation chromatographic column top hole pressure or flow raising chromatograph detection sensitivity.
3, a kind of described device of claim 1 that adopts is realized based on the method for modulating chromatographic column top hole pressure or flow raising chromatograph detection sensitivity, its feature comprises following process: after the sample component of chromatographic column outflow enters evaporating column, regulate the pressure-regulating valve of modulator, improve the pressure of evaporating column, backfeed loop guarantees that the pressure reduction of the chromatographic column entrance and exit pressure reduction preceding with improving evaporating column pressure is constant; The flow control valve of regulating modulator guarantees the flow of detecting device and improves the preceding flow of evaporating column pressure constant; The sample component that enters evaporating column is compressed, smaller volume, and sample is more promptly sent in the detecting device, thereby obtains higher detection sensitivity.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100940282A CN1313823C (en) | 2004-12-27 | 2004-12-27 | Apparatus and process for improving detection sensitivity by modulating outlet pressure or flow of chromatographic column |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100940282A CN1313823C (en) | 2004-12-27 | 2004-12-27 | Apparatus and process for improving detection sensitivity by modulating outlet pressure or flow of chromatographic column |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1632564A CN1632564A (en) | 2005-06-29 |
| CN1313823C true CN1313823C (en) | 2007-05-02 |
Family
ID=34847786
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004100940282A Expired - Fee Related CN1313823C (en) | 2004-12-27 | 2004-12-27 | Apparatus and process for improving detection sensitivity by modulating outlet pressure or flow of chromatographic column |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1313823C (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2537915B (en) * | 2015-04-30 | 2019-08-14 | Thermo Fisher Scient Bremen Gmbh | Method and apparatus for preconcentrating a gaseous sample |
| CN114324718A (en) * | 2021-12-20 | 2022-04-12 | 杭州谱育科技发展有限公司 | Organic sulfur detection method based on chromatographic technique |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1291724A (en) * | 1969-08-27 | 1972-10-04 | Pye Ltd | Improvements in or relating to apparatus for determining the presence of substances carried by a stream of carrier fluid |
| DE2840612A1 (en) * | 1978-09-18 | 1980-03-27 | Siemens Ag | Flow diversion between two chromatograph columns - using pressure differential system with pressure reducers on carrier gas mounted either side of capillary connection |
| WO1990009585A1 (en) * | 1989-02-16 | 1990-08-23 | Siemens Aktiengesellschaft | Process and device for controlling the carrier gas pressure in a valveless separating column circuit in gas chromatography |
| US20030100124A1 (en) * | 2000-12-19 | 2003-05-29 | Jan Beens | Modulator for gas chromatography |
-
2004
- 2004-12-27 CN CNB2004100940282A patent/CN1313823C/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1291724A (en) * | 1969-08-27 | 1972-10-04 | Pye Ltd | Improvements in or relating to apparatus for determining the presence of substances carried by a stream of carrier fluid |
| DE2840612A1 (en) * | 1978-09-18 | 1980-03-27 | Siemens Ag | Flow diversion between two chromatograph columns - using pressure differential system with pressure reducers on carrier gas mounted either side of capillary connection |
| WO1990009585A1 (en) * | 1989-02-16 | 1990-08-23 | Siemens Aktiengesellschaft | Process and device for controlling the carrier gas pressure in a valveless separating column circuit in gas chromatography |
| US5379629A (en) * | 1989-02-16 | 1995-01-10 | Siemens Aktiengesellschaft | Method and apparatus for regulating the carrier gas pressure for separation column arrangements in gas chromatography |
| US20030100124A1 (en) * | 2000-12-19 | 2003-05-29 | Jan Beens | Modulator for gas chromatography |
Non-Patent Citations (4)
| Title |
|---|
| 全二维气相色谱在刑事技术中的应用 丁军凯，黄丽，刑事技术，第6期 2003 * |
| 全二维气相色谱技术及其进展 许国旺，叶芬，孔宏伟，色谱，第19卷第2期 2001 * |
| 气相色谱的电子压力控制技术 蓝云峰，陈正夫，上海环境科学，第16卷第11期 1997 * |
| 气相色谱的电子压力控制技术 蓝云峰，陈正夫，上海环境科学，第16卷第11期 1997;全二维气相色谱技术及其进展 许国旺，叶芬，孔宏伟，色谱，第19卷第2期 2001;全二维气相色谱在刑事技术中的应用 丁军凯，黄丽，刑事技术，第6期 2003 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1632564A (en) | 2005-06-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1255680C (en) | Liquid phase chromatograph | |
| CN1648657A (en) | Liquid chromatograph | |
| US5435169A (en) | Continuous monitoring of organic pollutants | |
| US20060115904A1 (en) | Partial modulation via pulsed flow modulator for comprehensive two-dimensional liquid or gas chromatography with multiple modulation periods | |
| CN1520330A (en) | System and method for high throughput sample propn. and analysis using column chromatography | |
| US8371152B2 (en) | Helium conservation device for a gas chromatograph | |
| CN103698452B (en) | A kind of portable gas chromatography-GC-MS | |
| CN105717065B (en) | The continuous monitoring device and its method of work of non-methane total hydrocarbons | |
| WO2002056006A2 (en) | High throughput high performance chromatography system | |
| CN1313823C (en) | Apparatus and process for improving detection sensitivity by modulating outlet pressure or flow of chromatographic column | |
| Yang et al. | Multiplex gas chromatography with a hollow fiber membrane interface for determination of trace volatile organic compounds in aqueous samples | |
| TR201811105T4 (en) | Method and instrumentation for comprehensive multidimensional chromatography separations using a micro flow modulator. | |
| CN108254476A (en) | The analysis method of anion-content in a kind of ultra trace component | |
| EP0989401A8 (en) | Method and devices for improving the flash dynamic combustion reaction for the elemental analysis of C H N S O | |
| EP0989401A9 (en) | Method and devices for improving the flash dynamic combustion reaction for the elemental analysis of C H N S O | |
| US6475437B1 (en) | Method and system for preparing samples for gas chromatography | |
| CN214278048U (en) | double-FID detection device for analyzing methane and non-methane total hydrocarbons | |
| CN2585232Y (en) | On-line analysing device for propylene ammonia oxidation resultant | |
| CN211627463U (en) | Online thermal desorption gas circuit system | |
| CN1173177C (en) | Dynamic preconcentration method for small volume gas sample | |
| CN203772816U (en) | Two-dimensional liquid chromatography-mass spectrometer for detecting strong polar compounds | |
| JPS6197567A (en) | Sample preprocessor | |
| KR20210141308A (en) | On-line system for improving detection level of analytes by liquid chromatography and analysis method using the same | |
| CN1207276C (en) | In-situ analysis method of propylene ammoxidizing product | |
| CN2439025Y (en) | Dynamic pre-concentrating apparatus for gas sample |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |