CN111398495A - Novel trace and ultra-trace impurity component online chromatographic enrichment and analysis device - Google Patents
Novel trace and ultra-trace impurity component online chromatographic enrichment and analysis device Download PDFInfo
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- CN111398495A CN111398495A CN202010351788.6A CN202010351788A CN111398495A CN 111398495 A CN111398495 A CN 111398495A CN 202010351788 A CN202010351788 A CN 202010351788A CN 111398495 A CN111398495 A CN 111398495A
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/26—Conditioning of the fluid carrier; Flow patterns
- G01N30/28—Control of physical parameters of the fluid carrier
- G01N30/30—Control of physical parameters of the fluid carrier of temperature
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/24—Automatic injection systems
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/26—Conditioning of the fluid carrier; Flow patterns
- G01N30/28—Control of physical parameters of the fluid carrier
- G01N30/32—Control of physical parameters of the fluid carrier of pressure or speed
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/26—Conditioning of the fluid carrier; Flow patterns
- G01N30/38—Flow patterns
- G01N30/46—Flow patterns using more than one column
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/26—Conditioning of the fluid carrier; Flow patterns
- G01N30/28—Control of physical parameters of the fluid carrier
- G01N30/32—Control of physical parameters of the fluid carrier of pressure or speed
- G01N2030/328—Control of physical parameters of the fluid carrier of pressure or speed valves, e.g. check valves of pumps
Abstract
The invention provides a novel trace and ultra-trace impurity component online chromatographic enrichment and analysis device, which comprises: a sample introduction system; the vaporizing chamber is connected with the sample injection system; an enrichment system connected to the vaporization chamber; a holding box connected to the enrichment system; the sample collection system is connected with the heat preservation box, and the focusing trap is connected with the heat preservation box; a chromatography column system connected to the focusing trap; a detector connected to the chromatography column system; the sample introduction system, the vaporizing chamber, the enrichment system, the sample collection system, the focusing trap and the heat preservation box are respectively connected with respective controllers, and the controllers are connected with the chromatographic workstation and the display screen; the sample introduction system, the vaporizing chamber, the chromatographic analysis column system and the detector are connected to the chromatographic workstation. The whole device is very simple and convenient to install and connect, has extremely strong universality, and is suitable for analyzing the trace and ultra-trace impurity components of all gas, solid and liquid high-purity samples which can be analyzed by gas chromatography.
Description
Technical Field
The invention relates to the field of chemical analysis instruments, in particular to a novel trace and ultra-trace impurity component online chromatographic enrichment and analysis device.
Background
For the analysis of trace and ultra-trace impurity components, the unilateral dependence on high detector sensitivity and low detection limit of a specific detector is difficult to realize, and the universal method is realized by increasing the concentration by sample enrichment. The solid phase extraction technology of first enrichment, then analysis and then analysis is the most common analysis technology of trace analysis, is widely applied to environmental and petrochemical analysis, is a powerful enrichment method in analysis of trace gas, liquid and solid and impurity measurement, and can be used for off-line sampling analysis and on-line sampling analysis. However, the methods have extremely high requirements on enrichment materials and enrichment tubes, have certain adsorption capacity and are easy to resolve, and can not bring new impurities nor bring irreversible adsorption, so that the method is often difficult to obtain; especially for complex matrixes and mixtures, a plurality of enrichment materials are required to be mixed, and the proper recovery rate of all components is difficult to ensure; meanwhile, conditions such as thermal analysis or solvent elution are groped, and a large amount of experimental data is needed to verify the reliability of the method, so that time and labor are wasted.
CN203870078U discloses a gas chromatography separation system, couples adsorption desorption device, sampling pump and miniature chromatogram through six-way valve, has realized the online instant determination of gas sample, and response speed is fast, and the device can independently operate, and portable is favorable to handling and handling the incident. However, in the separation system, the adsorption and desorption device is still the key for enriching the target components, the sample directly enters the adsorption and desorption device, the interference of the sample background cannot be eliminated, the selection and condition optimization of the adsorption material are complex, and the requirement on the temperature of the cold trap is high.
CN207263702U discloses a gas chromatography on-line solid phase extraction device, which applies a wider on-line solid phase extraction technology in the field of liquid chromatography for the first time after separation of a gas chromatography column; the device adopts a solid phase extraction trap to enrich, focus and release components separated by the one-dimensional chromatographic column to enter a two-dimensional chromatographic column for separation and detection, has better selectivity and high detection sensitivity for low-content compounds. Although the device adopts the one-dimensional chromatographic column to solve the problem of sample background interference, the device still adopts a solid phase extraction trap essentially, the trapping of different components still depends on the selection of filling materials, and the requirement on refrigeration is higher.
The method is characterized in that the method comprises the following steps of (1) analyzing samples which are complicated and have high requirements like VOCs in air or water, wherein target components are easily interfered by adsorption materials, sample transmission relations and sample backgrounds, and meanwhile, the adsorption materials are expanded with heat and contracted with cold in the repeated heating process, so that the spacing among adsorption particles in an adsorption tube is not reproduced, the repeatability and reproducibility of a measurement result are low, and the reliability of the measurement result is influenced; but can also be applied because the background is air or purge carrier gas, and for samples such as high purity gas, high purity solvent and polymerization grade monomer, similar systems cannot be applied because the adsorption properties of the background components are similar or close to those of the impurity components. The invention directly adopts commercial/self-made gas chromatographic columns/tubes as an impurity enrichment system, solves the problem of interference of a sample background on enrichment and analysis of a target component by utilizing the separation capacity of gas chromatography, and the enrichment, analysis and sample analysis conditions can refer to the analysis conditions of the corresponding chromatographic columns and can be simply checked or simply adjusted without carrying out a large number of condition experiments; the chromatographic enrichment column can be repeatedly utilized through back flushing, and the cost is low; direct sample introduction and enrichment by adopting a chromatographic column avoid the adsorption loss of trace components with strong adsorption and irreversible adsorption on a pretreatment system and an adsorption cold trap; the device is ingenious in design, so that the installation and connection of the chromatographic enrichment column are very simple and convenient, a sample introduction system is flexible and selectable, the universality is extremely high, and the device is suitable for analyzing the trace and ultra-trace impurity components of all gas, solid and liquid high-purity samples which can be analyzed by gas chromatography. The novel online chromatographic enrichment-analysis device for trace and ultra-trace impurity components is not reported in the field of related analytical instruments.
Disclosure of Invention
The invention aims to provide a novel trace and ultra-trace impurity component online chromatographic enrichment and analysis device which can solve the problems that the selection of a selective adsorption material is difficult to find, the analysis condition is complex, the universality is poor and the background interference cannot be avoided when the trace and ultra-trace impurity components of the existing gas, solid and liquid high-purity samples are analyzed by adopting an enrichment thermal desorption technology.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows: a novel trace and ultra-trace impurity component online chromatographic enrichment and analysis device comprises:
a sample introduction system (1);
a vaporization chamber (21) connected to the sample injection system (1);
an enrichment system (3) connected to the vaporization chamber;
a heat preservation box (5) connected to the enrichment system;
a sample collection system (6) connected to the heat preservation box, and a focusing trap (4);
a chromatography column system (22) connected to the focused trap;
a detector (23) connected to the chromatography column system;
the sample introduction system (1), the vaporization chamber (21), the enrichment system (3), the sample collection system (6), the focusing trap (4) and the heat preservation box (5) are respectively connected to respective controllers, and the controllers are connected to the chromatographic workstation and the display screen;
the sample introduction system (1), the vaporization chamber (21), the chromatographic analysis column system (22) and the detector (23) are connected to a chromatographic workstation.
Further, the heat preservation box (5) is connected with the enrichment system (3), the sample collection system (6) and the focusing trap (4) through a four-way valve (51), and the four-way valve is an independent temperature control type four-way valve.
Furthermore, an enrichment column in the enrichment system (3) is a low-temperature refrigeration type enrichment column and/or a rapid heating type chromatographic column.
Furthermore, the focusing chromatographic column of the focusing trap (4) is a low-temperature refrigeration type focusing chromatographic column and/or a rapid heating type focusing chromatographic column.
Further, the sample collection system (6) is a heat-insulating cavity capable of measuring the gas sampling volume.
Furthermore, the sample injection structure of the sample injection system (1) is a gas valve sample injection structure, a liquid autosampler structure or a pressure control type structure.
Further, the apparatus further comprises: an electronic switch valve box (7) comprising a first electronic switch (71) mounted between the electronic pressure controller (24) and the four-way valve, a second electronic switch (72) between the sample collection system and the four-way valve.
The enrichment system is a single/multi-color spectrum column/tube combination which can be rapidly refrigerated and rapidly heated; the heat preservation box is connected with the enrichment system, the sample collection system and the focusing trap through a four-way valve; the chromatographic column system can be any single/multi-column chromatographic column combination, and can also be a self-made single/multi-color chromatographic column/tube combination which can be rapidly refrigerated and rapidly heated; the vaporization chamber and detector can be any commercially available GC vaporization chamber and detector. The enrichment column system is simple and convenient to assemble and install, has strong universality, and is suitable for enrichment monitoring of trace and ultra-trace impurity components in samples such as all liquid chromatographic grade solvents, food grade and medical grade solvents, high-purity gases, polymer grade chemical monomers and the like. The whole enrichment system can be independent of a chromatographic analysis system, is provided with an electronic control system, is used for automatically collecting a field sample, and can also be used together with a micro chromatograph for on-site online enrichment monitoring.
Compared with the prior art, the invention has the advantages that:
1. the whole device is very simple and convenient to install and connect, has extremely strong universality, and is suitable for analyzing the trace and ultra-trace impurity components of all gas, solid and liquid high-purity samples which can be analyzed by gas chromatography.
2. The whole enrichment system can be independent of the chromatographic analysis system and is provided with an electronic control system.
3. The method can be used for automatic collection of samples on site and can also be used for on-site online enrichment analysis.
Drawings
FIG. 1 is a schematic diagram of a novel trace and ultra-trace impurity component on-line chromatographic enrichment and analysis device of the invention.
FIG. 2 is an enrichment-analysis chromatogram of 1, 3-butadiene in application example 1 of the present invention.
FIG. 3 is an enrichment-analysis chromatogram of methanol in application example 2 of the present invention.
Detailed Description
The technical solution adopted by the present invention will be further explained with reference to the schematic drawings.
Referring to fig. 1, a novel on-line chromatographic enrichment and analysis device for trace and ultra-trace impurity components (hereinafter referred to as "the device") comprises: the sample injection system 1, sample injection system 1 can be gas injection valve or liquid autosampler, and gas injection valve can connect the headspace sample injector or sweep the trap. The sample introduction system 1 is connected to a chromatographic column incubator 2 through a pipeline, the chromatographic column incubator 2 comprises a vaporization chamber 21, a chromatographic analysis column system 22, a detector 23 and an electronic pressure controller 24, the chromatographic analysis column system 22 can be any commercial chromatographic column and combination thereof, the detector 23 can be any commercial detector and combination thereof, and the electronic pressure controller 24 can control flow and pressure. The vaporizing chamber 21 is connected to the sample feeding system 1, the enriching system 3 is connected to the vaporizing chamber 21, the enriching system 3 comprises an enriching chromatographic column system 31 which can be any commercial chromatographic column and combination thereof, and can be independently refrigerated and rapidly heated. The incubation box 5 is connected to the enrichment system 3, and the incubation box 5 is connected to the focusing trap 4, the sample collection system 6, the electronic pressure controller 24, and the focusing trap 4 comprises a focusing chromatography column system 41. The sample collection system 6 is connected to an electronic pressure controller 24, the focusing trap 4 is connected to a chromatography column system 22, and the chromatography column system 22 is connected to a detector 23.
The sample introduction system 1, the vaporizing chamber 21, the enrichment system 3, the sample collection system 6, the focusing trap 4 and the heat preservation box 5 are respectively connected with respective controllers, the controllers are connected with a chromatographic workstation and a display screen, the controllers are provided with microcomputers and electronic display screens, can control the sample introduction system 1, and can independently and automatically control the working states of the heat preservation box 5, the four-way valve 51, the electronic pressure controller 24 and the sample receiver (the sample collection system 6); all devices may be controlled by the controller 8 and transmit signals to the DCS.
The sample introduction system 1, the vaporization chamber 21, the chromatographic analysis column system 22 and the detector 23 are connected to a chromatographic workstation.
The heat preservation box 5 is connected with the enrichment system 3, the sample collection system 6 and the focusing trap 4 through a four-way valve 51, and the four-way valve 51 in the heat preservation box 5 can independently control the temperature.
The sample collection system 6 is a heat insulation cavity capable of measuring the sampling volume of gas, the sample collection system 6 formed by a constant temperature container can collect samples, the temperature can be independently controlled, and the total amount of the samples can be measured by adopting a flowmeter or a pressure measurement mode.
The enrichment column in the enrichment system 3 is a low-temperature refrigeration type enrichment column and/or a rapid heating type chromatographic column; the focusing chromatographic column of the focusing trap 4 is a low-temperature refrigeration type focusing chromatographic column and/or a rapid heating type focusing chromatographic column; the sample injection system 1, the vaporizing chamber 21, the chromatographic analysis column system 22, the detector 23 and the sample injection structure of the chromatographic workstation are a gas valve sample injection structure, a liquid autosampler structure or a pressure control type structure.
Referring to fig. 1, the apparatus further comprises: and the electronic switch valve box 7 comprises a first electronic switch 71 arranged between the electronic pressure controller 24 and the four-way valve, and a second electronic switch 72 arranged between the sample collection system and the four-way valve, wherein the first electronic switch 71 and the second electronic switch 72 are used for controlling the enrichment state, the analytic state and the blowback state of the enrichment system.
In specific use, after the sample introduction system 1 is installed, the outlet is directly connected into the vaporization chamber 21, the outlet pipeline of the vaporization chamber 21 passes through the chromatographic column incubator 2 to be connected with the inlet of the enrichment system 3, the outlet of the enrichment system 3 passes through the heat preservation box 5 to be connected with the interface A511 of the four-way valve 51, the interface C513 of the four-way valve 51 is connected with the electronic pressure controller 24, and the interface B512 of the four-way valve 51 passes through the heat preservation box 5 to be connected with the inlet of the focusing trap 4, then passes through the outlet of the focusing trap 4 to be connected with the chromatographic analysis column system 22, and then is connected. The port D514 of the four-way valve 51 is connected to the electronic pressure controller 24 and the sample collection system 6, respectively, by a three-way connection.
When the system is adopted to perform online enrichment analysis on high-purity gas, liquid chromatographic grade/food solvent or polymer grade monomer such as ethylene propylene and the like, the gas flow can be adjusted by a vacuum pump and a pressure controller/flowmeter at normal pressure for a gas sample so as to obtain the optimal enrichment effect; under pressure, the sample can directly pass through the enrichment column, and the flow rate of the gas passing through the chromatographic enrichment column is controlled by a post-column flow meter so as to obtain the optimal enrichment effect; or the volume of sample injection can be measured by adopting a quantitative ring to perform sample injection for multiple times. For liquid analysis, a liquid autosampler can be adopted to perform multiple sample injection and cumulatively measure the sample injection volume. For different sample analysis, the enrichment column can be any one or combination of a plurality of chromatographic columns, so that the target components are completely enriched; the analytical column can also be any one or combination of a plurality of chromatographic columns, and the detector selects according to the characteristics of the target components to ensure that the target components can be accurately, qualitatively and quantitatively analyzed; each sample analysis program has a back flushing function and a pipeline purging function of the enrichment column and the analysis column, so that the sample background is ensured not to influence the detection result, and no heavy component residue influence is generated in the next analysis. When the standard sample and the actual sample are measured, the detection limit of each component is less than 0.1nmol/mol, the accuracy is less than +/-10 percent, and the precision is less than 10 percent. The consistency of the analysis result of the target component and the actual content is very good.
The on-line chromatographic enrichment-analysis device using the novel trace and ultra-trace impurity components has the following three working modes:
(one) enrichment state: after the sample is injected and gasified by the sample injection system 1, the valve position of the four-way valve 51 is in the state that the interface A511 is communicated with the interface D514, the first electronic switch valve 71 is closed, and the second electronic switch valve 72 is opened, the system is in the target component enrichment state, all the target components are collected by the enrichment column system 31 in the low-temperature state, and the background gas in the analysis sample is collected by the sample collection system 6 and then discharged.
(II) analyzing the state: after the target components of the sample are enriched, the second electronic switch valve 72 is closed, the four-way valve 51 is rotated to enable the valve position interface A511 to be communicated with the interface B512, the temperature of the enrichment column is increased, the device is in a target component analysis state, and all the target components are heated and then analyzed out of the enrichment column and enter the low-temperature focusing trap.
(III) analyzing a back flushing state: when the valve position of the four-way valve 51 is restored to be in a state that the interface A511 is communicated with the interface D514, the second electronic switch valve 72 is closed, the first electronic switch valve 71 is opened and the pressure of the evaporation chamber is closed, the enrichment column system 31 is in a back flushing state, and heavy components are blown out in a back flushing mode; meanwhile, a valve position interface C513 of the four-way valve 51 is communicated with an interface B512, the temperature of the focusing chromatographic column system 41 is quickly raised, the target component is analyzed and then enters a chromatographic analysis column system 22 for separation, the target component is detected by a detector 23, and the device is in an analysis back flushing state.
The following experimental data were performed on the present system:
example 1:
the prepared 1, 3-butadiene standard sample is taken as an analysis sample, and the selection and optimization of back flushing conditions including the types and sizes of enrichment columns and analysis columns, the pressure of each pressure control point and the valve switching time, the temperature of each temperature control point, the process rate and the switching time, the flow control of each flow control point and the like are carried out on the novel online chromatographic enrichment-analysis device for trace and ultra-trace impurity components. The system is enriched and then separated for detection, and the optimized typical chromatographic analysis conditions are determined as shown in table 1.
TABLE 1 enrichment and analysis conditions
Under the optimized online chromatographic enrichment-analysis conditions of trace and ultra-trace impurity components, the prepared 1, 3-butadiene sample 1 is used as a calibration sample, the prepared 1, 3-butadiene sample 2 is used as an analyte, and the general system is evaluated, wherein the evaluation comprises the accuracy and repeatability of data analysis results and the stability of the system, and the analysis results are shown in table 2.
As can be seen from Table 2, when the system is used for carrying out on-line enrichment analysis on a 1, 3-butadiene sample, the relative standard deviation of continuous operation for 6 times is lower than 5 percent, the recovery rate is between 93.6 and 110.5 percent, and the analysis requirements of trace and ultra-trace components can be completely met.
TABLE 21, 3-butadiene test data
Example 2:
the purchased liquid chromatographic grade methanol sample is taken as an analysis sample, and the selection and optimization of back flushing conditions including the types and sizes of enrichment columns and analysis columns, the pressure of each pressure control point and the valve switching time, the temperature and the process rate and the switching time of each temperature control point, the flow control of each flow control point and the like are carried out on the novel online chromatographic enrichment-analysis device for trace and ultra-trace impurity components. The system was enriched and then tested separately, and the optimized typical chromatographic conditions were determined as shown in table 3.
TABLE 3 enrichment and analysis conditions
Under the optimized online chromatographic enrichment-analysis conditions of trace and ultra-trace impurity components, a liquid chromatographic grade methanol sample 1 is taken as a reference, dimethyl ether, ethanol, formaldehyde and methyl formate with different concentrations are added and then respectively taken as a calibrator and an analyte, the general system is evaluated, the accuracy and the repeatability of data analysis results and the stability of the system are included, and the analysis results are shown in table 4.
As can be seen from Table 4, when the system is used for online enrichment analysis of propylene samples, the relative standard deviation of the propylene samples continuously operated for 6 times is lower than 6.4 percent, the recovery rate is between 91.3 and 108.4 percent, and the system can completely meet the analysis requirements of trace and ultra-trace components.
Table 4 methanol test data
The above description is only a preferred embodiment of the present invention, and does not limit the present invention in any way. It will be understood by those skilled in the art that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (9)
1. A novel trace and ultra-trace impurity component online chromatographic enrichment and analysis device is characterized by comprising:
a sample introduction system (1);
a vaporization chamber (21) connected to the sample injection system (1);
an enrichment system (3) connected to the vaporization chamber;
a heat preservation box (5) connected to the enrichment system;
a sample collection system (6) connected to the heat preservation box, and a focusing trap (4);
a chromatography column system (22) connected to the focused trap;
a detector (23) connected to the chromatography column system;
the sample introduction system (1), the vaporization chamber (21), the enrichment system (3), the sample collection system (6), the focusing trap (4) and the heat preservation box (5) are respectively connected to respective controllers, and the controllers are connected to the chromatographic workstation and the display screen;
the sample introduction system (1), the vaporization chamber (21), the chromatographic analysis column system (22) and the detector (23) are connected to a chromatographic workstation.
2. The novel online chromatographic enrichment and analysis device for trace and ultra-trace impurity components according to claim 1, characterized in that the heat preservation box (5) is connected with the enrichment system (3), the sample collection system (6) and the focusing trap (4) through a four-way valve (51), and the four-way valve is an independent temperature control type four-way valve.
3. The novel online chromatographic enrichment and analysis device for trace and ultra-trace impurity components according to claim 1, characterized in that the enrichment column in the enrichment system (3) is a low-temperature refrigeration type enrichment column and/or a rapid-warming type chromatographic column.
4. The novel online chromatographic enrichment and analysis device for trace and ultra-trace impurity components according to claim 1, characterized in that the focusing chromatographic column of the focusing trap (4) is a low-temperature refrigeration type focusing chromatographic column and/or a rapid-heating type focusing chromatographic column.
5. The novel online chromatographic enrichment and analysis device for trace and ultra-trace impurity components according to claim 1, characterized in that the sample collection system (6) is a heat-insulating chamber capable of measuring gas sample injection volume.
6. The novel online chromatographic enrichment and analysis device for trace and ultra-trace impurity components according to claim 1, characterized in that the sample injection structure of the sample injection system (1) is a gas valve sample injection structure, a liquid autosampler structure or a pressure control structure.
7. The novel online chromatographic enrichment and analysis device for trace and ultra-trace impurity components according to claim 1, characterized in that the sample injection system (1) is a gas sample injection valve or a liquid autosampler.
8. The apparatus according to claim 7, wherein the gas injection valve is connected to a headspace injector or a purge trap.
9. The novel online chromatographic enrichment and analysis device for trace and ultra-trace impurity components according to claim 1, characterized by further comprising: an electronic switch valve box (7) comprising a first electronic switch (71) mounted between the electronic pressure controller (24) and the four-way valve, a second electronic switch (72) between the sample collection system and the four-way valve.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112763594A (en) * | 2020-12-15 | 2021-05-07 | 南京工业职业技术大学 | One-bit four-channel chromatographic on-line analysis system |
| CN113092798A (en) * | 2021-04-12 | 2021-07-09 | 四川中环联蜀环境咨询服务有限公司 | Automatic sample introduction device for gas detection |
| CN113702585A (en) * | 2021-08-26 | 2021-11-26 | 山东非金属材料研究所 | Automatic capturing and digesting device for trace metal elements in high-purity gas |
| 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 |
-
2020
- 2020-04-29 CN CN202010351788.6A patent/CN111398495A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112763594A (en) * | 2020-12-15 | 2021-05-07 | 南京工业职业技术大学 | One-bit four-channel chromatographic on-line analysis system |
| 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 |
| CN113092798A (en) * | 2021-04-12 | 2021-07-09 | 四川中环联蜀环境咨询服务有限公司 | Automatic sample introduction device for gas detection |
| CN113702585A (en) * | 2021-08-26 | 2021-11-26 | 山东非金属材料研究所 | Automatic capturing and digesting device for trace metal elements in high-purity gas |
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