CN114910572A - Sample introduction device and method, and quantitative analysis device and method - Google Patents
Sample introduction device and method, and quantitative analysis device and method Download PDFInfo
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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
-
- 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
- G01N30/16—Injection
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- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Sampling And Sample Adjustment (AREA)
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
Abstract
The invention provides a sample introduction device and method, and a quantitative analysis device and method. The sample introduction device comprises a first pipeline, a second pipeline and a heating device, wherein the heating device is used for heating the second pipeline, an outlet of the first pipeline is connected with an inlet of the second pipeline, and the first pipeline is a capillary pipeline. The invention also discloses a quantitative analysis device comprising the sample introduction device and a method for carrying out sample introduction by adopting the sample introduction device. The invention realizes the accurate calibration of the relative mass correction factor between the multi-component wide boiling range organic mixture, and has stable experimental result and high accuracy.
Description
Technical Field
The invention relates to a sample introduction device and method, and a quantitative analysis device and method.
Background
A large number of samples to be analyzed in the fields of petrochemical industry, pesticide analysis and the like belong to multi-component wide boiling range organic mixtures, so that the rapid and accurate quantitative analysis of the multi-component wide boiling range organic mixtures is a crucial problem in the fields of petrochemical industry, pesticide analysis and the like.
The multi-component wide boiling range organic mixture has the characteristics of complex components, large boiling point difference among the components and the like, some multi-component wide boiling range organic mixtures simultaneously contain components which are gas at normal temperature and normal pressure and components which are liquid at normal temperature and normal pressure, and the rapid and accurate quantitative analysis of the multi-component wide boiling range organic mixtures is difficult to realize by adopting the conventional detection device and method.
Quantitative analysis of organic mixtures requires accurate calibration of the relative mass correction factors between the components, which is typically determined by formulating a standard gas or liquid and calibrating by chromatographic analysis. However, the boiling points and volatility of each component in the wide boiling range organic mixture are obviously different, and the standard gas or liquid composition can be obviously influenced by the changes of temperature, pressure and the like, so that the relative mass correction factor cannot be accurately calibrated, and the accuracy and reliability of the quantitative analysis of the multi-component wide boiling range organic matter are greatly limited.
The on-line gas distribution method can realize simultaneous calibration of relative mass correction factors among all components by simultaneously gasifying a wide boiling range organic mixture and then bringing the mixture gas into chromatographic analysis by utilizing carrier gas. However, the method has the defects of large analysis error, complex operation of the gas distribution method, large influence of external conditions such as temperature, gas flow rate and other factors on the accuracy and stability of an analysis result, and the like.
Chinese patent publication No. CN109738529A discloses a method for preparing a multi-component organic mixture standard gas by a dynamic gas distribution method, and drawing a standard curve of standard gas concentration versus chromatographic peak area by chromatographic analysis, wherein the concentration range of each component in the method depends on the saturated vapor pressure of the component, the preparation range is narrow, and the application in industrial scenes is limited; meanwhile, each component in the standard gas needs a complex gas distribution system, and meanwhile, the method is used for collecting gas sample introduction, so that the error is large, the composition concentration is greatly influenced by the gasification temperature and the carrier gas flow rate, and the calibration result is not high.
Chinese patent publication No. CN109655545A discloses a static gas distribution method, which also uses gas to sample, resulting in inaccurate chromatographic analysis results. Moreover, the concentration of the static gas distribution method is measured by pressure, so that the accuracy is low; and the diffusion difference of gases with different components exists, so that the result error of chromatographic analysis is larger.
The existing liquid sample feeding device also has the defects of low accuracy and stability of analysis results. As shown in fig. 1, guo jing cloud introduces a typical sample injection device for multicomponent wide boiling range liquid-liquefied petroleum gas (see "study on chromatographic analysis of liquefied petroleum gas composition" [ J ], "chemical industry of petroleum and natural gas, 2015,44(001):87-92), which adopts a liquid sample injection mode, wherein a sample is led out from an inverted liquefied gas steel cylinder 11 through a pipeline, the liquid sample is gasified in a constant temperature water bath 12 and then enters a chromatograph through a pipeline outlet 13 for analysis, and the pipeline outlet 13 is connected with a chromatograph sample injector.
Disclosure of Invention
The invention aims to solve the technical problem of improving the accuracy and stability of the quantitative analysis result of the multi-component wide boiling range organic mixture. The invention provides a sample introduction device and method, and a quantitative analysis device and method. The method realizes accurate calibration of the relative mass correction factor between the multi-component wide boiling range organic mixture, and has stable experimental result and high accuracy.
In order to solve the technical problem, the invention adopts the following technical scheme:
the invention provides a sample introduction device which comprises a first pipeline, a second pipeline and a heating device, wherein the heating device is used for heating the second pipeline, an outlet of the first pipeline is connected with an inlet of the second pipeline, and the first pipeline is a capillary pipeline.
In the invention, the sample injection device is used for injecting the liquid sample into the gas chromatograph or the mass spectrometer. The first conduit may be a commercially available capillary conduit. The first tubing has an inlet and an outlet, the inlet of the first tubing for connection to a sample storage device for storing a liquid sample. The liquid sample is input into the first pipeline through the inlet of the first pipeline, under the pressure reduction and throttling action of the first pipeline, the liquid sample with different components and initial pressure (namely the pressure of the liquid sample in the sample storage device, when the sample storage device is a pressurized standard liquid steel cylinder, the initial pressure is the gas pressure filled in the pressurized standard liquid steel cylinder) can maintain the liquid state in the first pipeline and can be partially gasified, and the formed sample is conveyed into the second pipeline through the outlet of the first pipeline. The second line is a sample transfer line conventional in the art, and the sample can be completely vaporized in the second line and input to a gas chromatograph or mass spectrometer. The second pipeline is provided with an inlet and an outlet, the inlet of the second pipeline is connected with the outlet of the first pipeline, and the outlet of the second pipeline is used for connecting a gas chromatograph or a mass spectrometer.
Wherein the inner diameter of the first pipeline is generally below 500 μm, usually below 200 μm, preferably 10-200 μm, more preferably 20-150 μm, and most preferably 20-100 μm.
Wherein the length of the first pipeline can be more than 20cm, when the initial pressure of the liquid sample is 2-15Mpa, such as 2-5Mpa, and such as 2-3Mpa, preferably 20-150cm, and more preferably 30-150 cm. The first pipeline is preferably a pipeline with the inner diameter of 20-100 mu m and the length of 30-150 cm.
Wherein, the length of the second pipeline can be 10cm-150cm, preferably 20cm-100 cm. The internal diameter of the second pipeline can be 1mm-25.4mm, and preferably 3mm-12 mm. The second pipeline is preferably a pipeline with the inner diameter of 3-12mm and the length of 20-100 cm.
The second pipeline and the first pipeline may be made of conventional pipeline materials in the art, such as quartz, glass, stainless steel, and the like. The first pipeline is preferably a glass capillary tube, a quartz capillary tube or a stainless steel capillary tube. The second pipeline and the first pipeline can be made of the same material or different materials.
The first pipe is made by a conventional method in the art, such as integral molding, for example, two substrates (such as steel material, etc.) are respectively provided with capillary grooves, and the surfaces of the two substrates with the capillary grooves are connected together in a face-to-face manner (such as welding, etc.), so that the capillary grooves are combined into a capillary pipe.
The outlet of the first pipeline and the inlet of the second pipeline are connected in a manner that the outlet of the first pipeline is opposite to the inlet of the second pipeline, and the outlet of the first pipeline is directly connected (i.e. not connected through a connecting piece) or connected through a connecting piece (e.g. a tee joint, etc.); alternatively, a portion of the first line is inserted into the second line via the inlet of the second line, the outlet of the first line being located within the second line, preferably a portion of the first line is inserted into the second line via the inlet of the second line, the outlet of the first line being located within the second line. When the outlet of the first pipeline is positioned in the second pipeline, one part of the first pipeline extends into the second pipeline, at the moment, the inlet of the second pipeline is connected with the side wall of the first pipeline, the first pipeline and the second pipeline form a sleeve, and the second pipeline can protect the first pipeline.
The connection mode of the outlet of the first pipeline and the inlet of the second pipeline can be a pipeline connection mode which is conventional in the field, such as welding, welding or connection by means of a joint (such as a tee joint and the like). The second pipeline and the first pipeline can be connected after being formed respectively, and can also be connected during forming, namely the second pipeline and the first pipeline can be integrally formed.
In the present invention, the heating device is a heating device capable of heating the pipeline, which is conventional in the art. The heating device may be a device capable of heating a part of the second line (for example 1/2 second line) or the entire second line, preferably at least a whole of the gasified part of the second line from the outlet of the first line to the outlet of the second line (i.e. a heat tracing heating device). The heating device is more preferably a device capable of heating the entire second pipeline, and is further preferably a heating device provided on the outer surface of the entire second pipeline to heat the entire second pipeline. Heating whole second pipeline can guarantee that the heating is even, work as liquid sample when being high boiling point sample, heat whole second pipeline and more do benefit to the even gasification state that maintains the sample to improve the degree of accuracy and the stability of analysis result. Wherein, the heating device can adopt a heating device conventional in the field, such as an electric heating device, a heat-conducting oil heating device, a steam heating device, a water bath heating device and the like. The heating device is preferably an electric heating belt, and more preferably an electric heating belt wound on the outer wall of the whole second pipeline.
In the invention, the sample injection device can also comprise a gas carrying pipeline, and the second pipeline is connected with the gas carrying pipeline. Preferably, the carrier gas line is connected to the second line at a location such that the carrier gas flows through the outlet of the first line. The carrier gas line is a line conventional in the art for conveying a carrier gas. And the carrier gas pipeline is used for conveying carrier gas to the second pipeline, and carrying the gasified liquid sample into a gas chromatograph or a mass spectrometer for quantitative analysis.
The connection between the carrier gas pipeline and the second pipeline may be any pipeline connection conventional in the art, such as welding, soldering, or connecting by means of a joint (e.g., a tee joint, etc.). The air-carrying pipeline and the second pipeline can be formed respectively and then connected, and can also be connected simultaneously during forming, namely the air-carrying pipeline and the second pipeline can be integrally formed.
The length of the carrier gas pipeline can be the length of the carrier gas pipeline which is conventional in the field, and can be, for example, 10cm-120cm, preferably 20cm-100 cm. The internal diameter of the carrier gas pipeline can be 1mm-12mm, and is preferably 3mm-8 mm. The carrier gas pipeline is preferably a pipeline with the inner diameter of 3-8mm and the length of 20-100 cm. The material of the gas carrying pipeline can be the material of the pipeline which is conventional in the field, such as quartz, glass, stainless steel and the like. The material of the gas-carrying pipeline and the second pipeline can be the same or different.
Wherein, a flowmeter can be arranged on the gas carrying pipeline. The flow meter is a flow meter for measuring the flow of gas as is conventional in the art. The flowmeter can be arranged at any position on the gas carrying pipeline, and the position can be used for measuring the gas flow.
Wherein, the sample injection device can also comprise a device for storing carrier gas, and the device for storing carrier gas is connected with the carrier gas pipeline. The device for storing the carrier gas can be a carrier gas steel cylinder.
In the invention, the sample introduction device can also comprise a sample storage device, and the sample storage device is connected with the inlet of the first pipeline. The sample storage device may be a storage device capable of storing a liquid sample as is conventional in the art, preferably a sample storage device for storing a liquefied gas sample as is conventional in the art, such as a pressurized target liquid cylinder. The sample storage device can also be a reaction device, a mixing device, a separation device, an extraction device and the like which can store liquid samples, such as a reaction device, a mixing device, a separation device, an extraction device and the like which are conventional in the fields of petrochemical industry, pesticide analysis and the like. The sample storage device may be arranged in a forward orientation or may be inverted, preferably in a forward orientation. The sample storage device can be an atmospheric device or a pressurizing device (e.g., a pressurized cylinder) that can be filled with a gas having a pressure greater than atmospheric pressure, such as a gas having a pressure of 1-5MPa, such as a gas having a pressure of 1-3MPa, and such as a gas having a pressure of 2 MPa. The gas is non-reactive with the liquid in the sample storage device and may be, for example, nitrogen or an inert gas.
The connection between the sample storage device and the inlet of the first pipeline may be a conventional connection in the art, for example, the sample storage device is provided with an outlet pipeline or a sampling device, and the outlet pipeline or the sampling device is connected with the inlet of the first pipeline. The outlet line may be an outlet line as is conventional in the art, which may be arranged at an outlet of the sample storage device, the outlet line having an inlet arranged in the sample storage device and an outlet, the outlet of the outlet line being connected to the inlet of the first line. The inlet of the outlet line is located below the liquid level in the sample storage device. The sampling device can be a conventional sampling device in the fields of petrochemical industry, pesticide analysis and the like, and preferably is an online sampling device. The sampling device can sample from the interior of a reaction device, a mixing device, a separating device, an extracting device, a storage device and the like which contain liquid and are conventional in the fields of petrochemical industry, pesticide analysis and the like, and convey the sample to the first pipeline.
The invention also provides a quantitative analysis device which comprises the sample introduction device and a gas chromatograph or a mass spectrometer, wherein a sample introduction port of the gas chromatograph or the mass spectrometer is connected with an outlet of the second pipeline of the sample introduction device.
The connection mode of the sample inlet of the gas chromatograph or the mass spectrometer and the outlet of the second pipeline of the sample introduction device can be a conventional connection mode in the field.
The gas chromatograph is conventional in the art, such as a chromatograph equipped with a capillary column, a chromatograph equipped with a packed column, and a chromatograph equipped with both columns.
The invention also provides a sample introduction method, which adopts the sample introduction device and comprises the following specific steps: inputting a liquid sample into a first pipeline, heating a second pipeline by using a heating device, and introducing a sample after the sample output by the first pipeline enters the second pipeline and is gasified in the second pipeline; the liquid sample contains or does not contain a substance which is gaseous at normal temperature and normal pressure, when the liquid sample does not contain the substance which is gaseous at normal temperature and normal pressure, the second pipeline is filled with carrier gas, and the gasified sample is carried by the carrier gas for sample injection; when the liquid sample contains a substance which is gaseous at normal temperature and normal pressure, the second pipeline can be filled with carrier gas or not, and preferably, the second pipeline is filled with carrier gas. When the second pipeline is filled with carrier gas, the gasified liquid sample is carried by the carrier gas for sample injection.
In the invention, the liquid sample can be maintained in a liquid state or partially gasified in the first pipeline, and the formed liquid state or partially gasified sample is conveyed to the second pipeline through the outlet of the first pipeline and can be completely gasified in the second pipeline for sample introduction.
In the present invention, when the initial pressure of the liquid sample is 2 to 15MPa, such as 2 to 5MPa, and further such as 2 to 3MPa, the length of the first line is preferably 20 to 150cm, more preferably 30 to 150 cm.
In the present invention, the liquid sample may be a liquid mixture, such as an organic liquid mixture, for example, a standard or a sample to be analyzed in the field of petrochemical or pesticide analysis, such as multi-component wide boiling range organic mixtures in the fields of petrochemical, pesticide analysis, etc., such as liquefied petroleum gas, propylene-butyraldehyde-isobutyraldehyde mixtures (propylene carbonylation to butyraldehyde), etc., preferably, the liquid sample is a mixture of at least one of low-boiling-point organic substances including but not limited to ethane, propane, butane, isobutane, pentane, isopentane, n-butene, isobutene, butadiene, propylene, dimethyl ether and the like and at least one of high-boiling-point organic substances including but not limited to methyl acetate, ethyl acetate, ethanol, methanol, propanol, butanol, tert-butanol, toluene, tert-butylamine, dimethylamine, cyclohexane, tetrahydrofuran, acetic acid and the like. When the sample contains a substance that is gaseous at normal temperature and pressure, the sample needs to be pressurized to be liquid.
Wherein, when the liquid sample is a standard product, the liquid sample can be prepared by a method conventional in the field, and is preferably prepared by a mass method.
In the present invention, the heating device heats at least the entire vaporizing portion of the second pipeline, the vaporizing portion extending from the outlet of the first pipeline to the outlet of the second pipeline. Preferably, the heating device heats the whole second pipeline.
Wherein, the heating temperature of the heating device can be a conventional temperature in the art for heating and vaporizing the liquid sample, such as 180-200 ℃, further such as 140-160 ℃, further such as 150 ℃.
The carrier gas flow rate described in the present invention may be a conventional carrier gas flow rate suitable for use in a quantitative analysis device in the art, such as 30-80mL/min, further such as 40-60mL/min, further such as 50 mL/min. The carrier gas flow rate can be adjusted by a flow meter.
In the present invention, the time for introducing the carrier gas may be the same as, before or after the heating device is turned on.
In the present invention, the liquid sample may be introduced into the first conduit in a manner conventional in the art, for example, the liquid sample is forced into the first conduit by a gas filled in a pressurized sample storage device at a pressure greater than atmospheric pressure.
In the invention, the sample injection is to a gas chromatograph or a mass spectrometer.
The invention also provides a quantitative analysis method, which comprises the following steps: and (3) injecting the liquid sample by adopting the injection method, and carrying out quantitative analysis.
In the invention, the quantitative analysis is carried out by adopting a gas chromatograph or a mass spectrometer. The analysis method is a gas chromatography analysis method or a mass spectrometry analysis method which is conventional in the field.
In the present invention, when the liquid sample is a liquid mixture, the quantitative analysis method further includes: relative mass correction factors between different components are calculated based on the content (e.g. mass fraction) of each component in the liquid mixture and the results of the quantitative analysis (e.g. peak area measured by gas chromatography).
The above preferred conditions can be arbitrarily combined to obtain preferred embodiments of the present invention without departing from the common general knowledge in the art.
The reagents and starting materials used in the present invention are commercially available.
The positive progress effects of the invention are as follows:
1. according to the invention, the liquid sample is input into the second pipeline through the capillary, so that the samples with different boiling points can be completely gasified, the temperature fluctuation degree caused by gasification heat absorption is reduced, the stability of the measured relative mass correction factor is high, and the detection result is accurate.
2. The heating device can gasify the sample in the second pipeline, and when the heating device heats the whole gasification part of the second pipeline, the problems that heavy components in the gasified sample are liquefied and adhered to the wall when meeting cold, light components escape and the like can be avoided, the uniformity degree of the concentration of the gasified sample is improved, the components of the sample are ensured to stably enter chromatographic analysis, and the stability and the accuracy of a detection result are further improved; when the heating device heats the whole second pipeline, the concentration uniformity degree of the gasified sample, particularly the high-boiling-point sample, can be further improved, and therefore the stability and the accuracy of the detection result are further improved.
3. The sample injection method can utilize carrier gas to carry the sample for sample injection, and when the liquid sample does not contain gaseous substances at normal temperature and normal pressure, the carrier gas is used for carrying the sample for rapid sample injection. When the liquid sample contains gaseous substances at normal temperature and normal pressure, the carrier gas is used for carrying the sample for sample injection, so that the problems of wall adhesion due to the fact that heavy components in the gasified sample are liquefied again when being cooled, escape of the light components and the like can be avoided, the uniformity degree of the concentration of the gasified sample is improved, and the stability and accuracy of a detection result are ensured.
4. The method can prepare multi-component standard solution by adopting a quality method, and has the advantages of high accuracy, simple operation, easy implementation and wide application range.
5. The method is simple and convenient to operate, can greatly improve the accuracy of the analysis of the multi-component organic matter, and can effectively improve the aspects of operability, data accuracy, stability and the like compared with the traditional method.
Drawings
Fig. 1 is a schematic structural diagram of a sample injection device disclosed in the prior document "investigation of liquefied petroleum gas composition chromatography technology". Wherein 11 is a liquefied gas steel cylinder, 12 is a water bath heating device, and 13 is a pipeline outlet; a is container valve, B, C is flow control valve.
FIG. 2 is a schematic view of a sample injection device in embodiment 1 of the present invention.
FIG. 3 is a schematic view of a quantitative analyzer in example 2 of the present invention.
Fig. 4 is a schematic view of a sample injection device in embodiment 3 of the present invention.
In fig. 2-4, 1 is a pressurized standard liquid steel cylinder, 2 is a first pipeline, 3 is a second pipeline, 4 is an electric heating belt, 5 is a gas chromatograph, 6 is a carrier gas steel cylinder, 7 is a flow meter, 8 is an outlet pipeline, 9 is a carrier gas pipeline, and 10 is a three-way joint.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. Experimental procedures without specifying specific conditions in the following examples were selected in accordance with conventional procedures and conditions, or in accordance with commercial instructions. The method can change the flow rate and the type of the carrier gas, the heat preservation temperature, the adjustment of related chromatographic parameters and the like aiming at different organic mixtures, and still belongs to the protection scope of the invention.
The chromatographic conditions for the gas chromatography of the following examples and comparative examples were as follows: the sample measurement chromatogram is an Agilent 8890 chromatogram, the sample measurement conditions are that the temperature of a chromatographic gasification chamber is 260 ℃, the temperature of a detection chamber is 280 ℃, the temperature of a column chamber is provided with a programmed heating program, the initial temperature is 70 ℃, the temperature is kept constant for 1min, then the temperature is increased to 210 ℃ at the speed of 10 ℃/min, the temperature is kept constant for 10min, the temperature is automatically reduced, and the sample measurement is carried out by selecting a proper split-flow ratio.
EXAMPLE 1 sample introduction device
As shown in fig. 2, the sample injection device of the present embodiment includes a pressurized standard liquid steel bottle 1, a first pipeline 2, a second pipeline 3, an electric heating band 4, a carrier gas steel bottle 6, a flow meter 7, an outlet pipeline 8, a carrier gas pipeline 9, and a three-way joint 10.
The pressurized standard liquid steel cylinder 1 is arranged in the positive direction. The outlet of the pressurized marking liquid steel cylinder 1 is provided with an outlet pipeline 8, the outlet pipeline 8 is provided with an inlet and an outlet, the inlet of the outlet pipeline 8 is arranged in the pressurized marking liquid steel cylinder 1, and the outlet of the outlet pipeline 8 is connected with the inlet of the first pipeline 2. The inlet of the outlet line 8 is located below the liquid level in the pressurized target liquid cylinder 1.
The first pipeline 2 is a capillary pipeline with the inner diameter of 50 mu m and the length of 100 cm. The inner diameter of the second pipeline 3 is 3mm, and the length is 50 cm. The first pipeline 2 is made of quartz, and the second pipeline 3 is made of stainless steel. First pipeline 2 and second pipeline 3 all have entry and export, the entry of second pipeline 3 is connected the first interface of three way connection 10, three way connection 10 for this field conventional three way connection can, the entry of first pipeline 2 with the exit linkage of export pipeline 8, the lateral wall of first pipeline 2 with three way connection 10's second interface connection, a part of first pipeline 2 passes three way connection 10 via the entry of second pipeline 3 stretch into in the second pipeline 3, the export of first pipeline 2 is located in second pipeline 3. The first pipeline 2 and the second pipeline 3 form a sleeve, and the second pipeline 3 can protect the first pipeline 2. And the outlet of the second pipeline 3 is connected with a gas chromatograph.
The carrier gas steel cylinder 6 is connected with an inlet of a carrier gas pipeline 9, an outlet of the carrier gas pipeline 9 is connected with a third interface of the three-way joint 10, and a flowmeter 7 is arranged on the carrier gas pipeline 9. The carrier gas line 9 is used for conveying carrier gas to the second line 3. The outlet of the carrier gas pipeline 9 is positioned on the left side of the outlet of the first pipeline 2, the carrier gas flows through the outlet of the first pipeline 2, and a sample coming out of the outlet of the first pipeline 2 can be immediately mixed with the carrier gas, so that the mixing is more sufficient and uniform. The gas carrying pipeline 9 is a stainless steel pipeline with the inner diameter of 3mm and the length of 50 cm.
The electric heating tape 4 is wound on the outer wall of the whole second pipeline 3, namely from the joint of the second pipeline 3 and the three-way joint 10 to the joint of the second pipeline 3 and the gas chromatograph. The electric heating belt 4 is used for heating the whole second pipeline 3 so as to ensure that the second pipeline 3 is uniformly heated and has no cooling point.
EXAMPLE 2 quantitative analysis device
As shown in fig. 3, the quantitative analysis device of the present embodiment includes the sample injection device of embodiment 1, and further includes a gas chromatograph 5. And a sampling tube of the gas chromatograph 5 is connected with an outlet of the second pipeline 3 of the sampling device.
EXAMPLE 3 sample introduction device
As shown in fig. 4, the sample injection device of the present embodiment includes a first pipeline 2, a second pipeline 3, and an electric heating tape 4. The first pipeline 2, the second pipeline 3 and the electric heating belt 4 are the same as the embodiment 1. The inlet of the second pipeline 3 is connected with the first interface of the pipe joint, the side wall of the first pipeline 2 is connected with the second interface of the pipe joint, a part of the first pipeline 2 passes through the pipe joint and extends into the second pipeline 3 through the inlet of the second pipeline 3, and the outlet of the first pipeline 2 is positioned in the second pipeline 3. The first pipeline 2 and the second pipeline 3 form a sleeve, and the second pipeline 3 can protect the first pipeline 2. The electric heating tape 4 is wound on the outer wall of the whole second pipeline 3, namely from the joint of the second pipeline 3 and the pipe joint to the joint of the second pipeline 3 and the gas chromatograph. The electric heating belt 4 is used for heating the whole second pipeline 3 so as to ensure that the second pipeline 3 is uniformly heated and has no cooling point.
When the device is used, the inlet of the first pipeline 2 is connected with the outlet of the outlet pipeline of the pressurized standard liquid steel cylinder, and the pressurized standard liquid steel cylinder is arranged in the forward direction. The outlet of the pressurized standard liquid steel cylinder is provided with an outlet pipeline, the outlet pipeline is provided with an inlet and an outlet, and the inlet of the outlet pipeline is arranged in the pressurized standard liquid steel cylinder. The inlet of the outlet pipeline is positioned below the liquid level in the pressurized standard liquid steel cylinder. And connecting the outlet of the second pipeline with a gas chromatograph.
The pipe joint can be a two-way joint or a three-way joint which is conventional in the field, when the pipe joint is the three-way joint and is used, the third interface of the pipe joint is connected with the outlet of the carrier gas pipeline, the inlet of the carrier gas pipeline is connected with the carrier gas steel cylinder, and the carrier gas pipeline is provided with a flowmeter. The carrier gas line is used to convey carrier gas to the second line 3. The outlet of the carrier gas pipeline is positioned on the left side of the outlet of the first pipeline 2, the carrier gas flows through the outlet of the first pipeline 2, and the sample from the outlet of the first pipeline 2 can be immediately mixed with the carrier gas, so that the mixing is more sufficient and uniform. The gas-carrying pipeline is a stainless steel pipeline with the inner diameter of 3mm and the length of 50 cm.
Example 4
The sample injection device in example 1 was used for sample injection and quantitative analysis. And connecting a sampling tube of the gas chromatograph with an outlet of a second pipeline of the sample injection device.
Preparing 58.43% and 41.57% standard liquid samples of isobutene and cyclohexane by mass method in a pressurized standard liquid steel cylinder, charging 2MPa of nitrogen into the pressurized standard liquid steel cylinder, connecting the pressurized standard liquid steel cylinder with a first pipeline, opening a switch of the pressurized standard liquid steel cylinder, pressing the standard liquid sample into the first pipeline through an outlet pipeline of the pressurized standard liquid steel cylinder, starting an electric heating belt to heat the second pipeline, controlling the heating temperature to be 150 ℃, opening a carrier gas steel cylinder, introducing carrier gas into the second pipeline, controlling the flow rate of the carrier gas (nitrogen) to be 50mL/min through a flowmeter, allowing the sample output by the first pipeline to enter a second pipeline and be gasified in the second pipeline, allowing the gasified sample carried by the nitrogen to enter a gas chromatograph together for quantitative analysis, completing chromatographic analysis every 20 minutes, and determining the peak area according to the mass fraction of each component and the peak area measured by the chromatograph when preparing the standard liquid sample, and calculating and calibrating relative quality correction factors among different components. The results are shown in Table 1.
Table 1:
the method is used for continuously collecting ten samples, and has good data reproducibility and small fluctuation.
Example 5
The sample injection device in example 1 was used for sample injection and quantitative analysis. And connecting a sampling tube of the gas chromatograph with an outlet of a second pipeline of the sample introduction device.
Preparing standard liquid samples of 45.08 percent and 54.92 percent of isobutene and cyclohexane by a mass method in a pressurized standard liquid steel cylinder, adding 2MPa of nitrogen into the pressurized standard liquid steel cylinder, connecting the pressurized standard liquid steel cylinder with a first pipeline, opening a switch of the pressurized standard liquid steel cylinder, pressing the standard liquid sample into the first pipeline through an outlet pipeline of the pressurized standard liquid steel cylinder, starting an electric heating belt to heat the second pipeline, controlling the heating temperature to be 150 ℃, opening a carrier gas steel cylinder, introducing carrier gas into the second pipeline, controlling the flow rate of the carrier gas (nitrogen) to be 50mL/min by a flowmeter, allowing the sample output by the first pipeline to enter the second pipeline and be gasified in the second pipeline, allowing the nitrogen to carry the gasified sample together into a gas chromatograph to perform quantitative analysis, completing chromatographic analysis every 20 minutes, and determining the mass fraction of each component and the peak area by the chromatograph when the standard liquid sample is prepared, and calculating and calibrating relative quality correction factors among different components. The results are shown in Table 2.
Table 2:
eleven samples are continuously collected by using the method, the data reproducibility is good, and the fluctuation is small.
The relative mass correction factors of isobutene/cyclohexane measured by standard liquids with different mass compositions are very close, and the result shows that the method is an accurate and reliable online quantitative analysis method for the multi-component low-boiling-point organic mixture.
Example 6
The sample injection device in example 1 was used for sample injection and quantitative analysis. And connecting a sampling tube of the gas chromatograph with an outlet of a second pipeline of the sample introduction device.
Through a mass method, a standard liquid sample of isobutene-cyclohexane-tert-butylamine with the mass fractions of 53.43 percent, 36.69 percent and 9.88 percent is put into a pressurized standard liquid steel cylinder, 2MPa of nitrogen is added into the pressurized standard liquid steel cylinder, the pressurized standard liquid steel cylinder is connected with a first pipeline, a switch of the pressurized standard liquid steel cylinder is opened, the standard liquid sample is pressed into the first pipeline through an outlet pipeline of the pressurized standard liquid steel cylinder, an electric heating belt is started to heat the second pipeline, the heating temperature is controlled to be 150 ℃, a carrier gas steel cylinder is opened, carrier gas is introduced into the second pipeline, the flow rate of the carrier gas (nitrogen) is controlled to be 50mL/min through a flowmeter, the sample output by the first pipeline enters the second pipeline and is gasified in the second pipeline, the nitrogen carries the gasified sample together with the gasified sample to enter a gas chromatograph for quantitative analysis, an automatic sampling program is set, chromatographic analysis is completed every 20 minutes, and calculating and calibrating relative mass correction factors among different components according to the mass fractions of the components when the standard liquid sample is prepared and peak areas measured by chromatography. The results are shown in Table 3.
Table 3:
the method is used for continuously acquiring data, has good data reproducibility and can accurately calibrate the relative mass correction factor among the multi-component organic mixtures.
Example 7
The sample injection device in this embodiment is similar to that of embodiment 1, except that the electrical heating tape is wound in the middle of the second pipeline (i.e., 1/2 for the length) to the connection between the second pipeline and the gas chromatograph.
Preparing a standard liquid sample of isobutene-cyclohexane-tert-butylamine with the mass fractions of 53.43%, 36.69% and 9.88% in a pressurized standard liquid steel cylinder by a mass method, adding 2MPa of nitrogen into the pressurized standard liquid steel cylinder, connecting the pressurized standard liquid steel cylinder with a first pipeline, opening a switch of the pressurized standard liquid steel cylinder, pressing the standard liquid sample into the first pipeline through an outlet pipeline of the pressurized standard liquid steel cylinder, starting an electric heating belt to heat a second pipeline, controlling the heating temperature to be 150 ℃, and heating the standard liquid sample from the middle part of the second pipeline to the connecting part of the second pipeline and a gas chromatograph. Opening a carrier gas steel cylinder, introducing carrier gas into the second pipeline, controlling the flow rate of the carrier gas (nitrogen) to be 50mL/min through a flowmeter, enabling the sample output by the first pipeline to enter the second pipeline and be gasified in the second pipeline, enabling the nitrogen to carry the gasified sample to enter a gas chromatograph together for quantitative analysis, setting an automatic sampling program, completing chromatographic analysis every 20 minutes, and calculating and calibrating relative mass correction factors among different components according to the mass fraction of each component and the peak area measured by the chromatogram when preparing a standard liquid sample. As shown in table 4.
Table 4:
example 8:
the sample introduction device in this example is similar to example 1 except that the first tubing has an inner diameter of 25 μm and a length of 50 cm. And the electric heating belt is wound in the middle of the second pipeline (namely 1/2 of the length) to the joint of the second pipeline and the gas chromatograph. Preparing a standard liquid sample of isobutene-cyclohexane-tert-butylamine with the mass fractions of 53.43%, 36.69% and 9.88% in a pressurized standard liquid steel cylinder by a mass method, adding 3MPa of nitrogen into the pressurized standard liquid steel cylinder, connecting the pressurized standard liquid steel cylinder with a first pipeline, opening a switch of the pressurized standard liquid steel cylinder, pressing the standard liquid sample into the first pipeline through an outlet pipeline of the pressurized standard liquid steel cylinder, starting an electric heating belt to heat a second pipeline, controlling the heating temperature to be 150 ℃, and heating the standard liquid sample from the middle of the second pipeline to the joint of the second pipeline and a gas chromatograph. Opening a carrier gas steel cylinder, introducing carrier gas into a second pipeline, controlling the flow rate of the carrier gas (nitrogen) to be 50mL/min through a flowmeter, enabling a sample output by a first pipeline to enter the second pipeline and be gasified in the second pipeline, enabling the nitrogen to carry the gasified sample to enter a gas chromatograph together for quantitative analysis, setting an automatic sampling program, completing chromatographic analysis every 20 minutes, and calculating and calibrating relative mass correction factors among different components according to the mass fraction of each component and the peak area measured by the chromatogram when preparing a standard liquid sample. The experimental data are shown in table 5.
Table 5:
the method is used for continuously acquiring data, has good data reproducibility, and can accurately calibrate the relative mass correction factor among the multi-component organic mixtures.
Example 9:
the sample injection device in this example is similar to example 1, except that the first tubing has an inner diameter of 100 μm and a length of 150 cm. And the electric heating tape is wound in the middle of the second pipeline (namely 1/2 of the length) to the joint of the second pipeline and the gas chromatograph.
Preparing a standard liquid sample of isobutene-cyclohexane-tert-butylamine with the mass fractions of 53.43%, 36.69% and 9.88% in a pressurized standard liquid steel cylinder by a mass method, adding 2MPa of nitrogen into the steel cylinder, connecting the pressurized standard liquid steel cylinder with a first pipeline capillary, opening a switch of the pressurized standard liquid steel cylinder, pressing the standard liquid sample into the first pipeline through an outlet pipeline of the pressurized standard liquid steel cylinder, starting an electric heating belt to heat the second pipeline, controlling the heating temperature to be 150 ℃, and heating the standard liquid sample from the middle part of the second pipeline to the connecting part of the second pipeline and the gas chromatograph. Opening a carrier gas steel cylinder, introducing carrier gas into the second pipeline, controlling the flow rate of the carrier gas (nitrogen) to be 50mL/min through a flowmeter, enabling the sample output by the first pipeline to enter the second pipeline and be gasified in the second pipeline, enabling the nitrogen to carry the gasified sample to enter a gas chromatograph together for quantitative analysis, setting an automatic sampling program, completing chromatographic analysis every 20 minutes, and calculating and calibrating relative mass correction factors among different components according to the mass fraction of each component and the peak area measured by the chromatogram when preparing a standard liquid sample. The experimental data are shown in table 6.
Table 6:
the method is used for continuously acquiring data, has good data reproducibility and can accurately calibrate the relative mass correction factor among the multi-component organic mixtures.
Example 10
Standard liquids of isobutylene and cyclohexane were injected and quantitatively analyzed at 58.43% and 41.57% by mass using an apparatus and method similar to example 4, except that no nitrogen gas was introduced during the injection.
Preparing standard liquid samples of isobutene and cyclohexane with the mass fractions of 58.43% and 41.57% in a pressurized standard liquid steel cylinder by a mass method, adding 2MPa of nitrogen into the pressurized standard liquid steel cylinder, connecting the pressurized standard liquid steel cylinder with a first pipeline, opening a switch of the pressurized standard liquid steel cylinder, pressing the standard liquid sample into the first pipeline through an outlet pipeline of the pressurized standard liquid steel cylinder, starting an electric heating belt to heat a second pipeline, controlling the heating temperature to be 150 ℃, allowing the sample output by the first pipeline to enter the second pipeline and be gasified in the second pipeline, allowing the gasified sample to enter a gas chromatograph for quantitative analysis, setting an automatic sampling program, completing chromatographic analysis every 20 minutes, calculating and calibrating relative mass correction factors among different components according to the mass fractions of the components and peak areas measured by the chromatograph when the standard liquid sample is prepared, the results are shown in Table 7.
Table 7:
by comparing example 4, when the sample to be tested contains a substance which is gas (isobutene) at normal temperature and normal pressure, accurate and stable test data can be obtained by introducing carrier gas or not, but the introduction of carrier gas is helpful to improve the stability of chromatographic test data.
Example 11
The sample introduction device in this example is similar to example 6 except that the first tube has an inner diameter of 50 μm and a length of 150 cm.
Preparing a standard liquid sample of isobutene-cyclohexane-tert-butylamine with the mass fractions of 53.43%, 36.69% and 9.88% in a pressurized standard liquid steel cylinder by a mass method, adding 2MPa of nitrogen into the steel cylinder, connecting the pressurized standard liquid steel cylinder with a first pipeline capillary, opening a switch of the pressurized standard liquid steel cylinder, pressing the standard liquid sample into the first pipeline through an outlet pipeline of the pressurized standard liquid steel cylinder, starting an electric heating belt to heat the second pipeline, controlling the heating temperature to be 150 ℃, and heating the standard liquid sample from the middle part of the second pipeline to the connecting part of the second pipeline and the gas chromatograph. Opening a carrier gas steel cylinder, introducing carrier gas into the second pipeline, controlling the flow rate of the carrier gas (nitrogen) to be 50mL/min through a flowmeter, enabling the sample output by the first pipeline to enter the second pipeline and be gasified in the second pipeline, enabling the nitrogen to carry the gasified sample to enter a gas chromatograph together for quantitative analysis, setting an automatic sampling program, completing chromatographic analysis every 20 minutes, calculating and calibrating relative correction factors and relative mass correction factors among different components according to the mass fraction of each component and the peak area measured by the chromatogram when preparing a standard liquid sample, and enabling the results to be shown in Table 8.
Table 8:
comparative example 1
Standard liquids of isobutylene and cyclohexane were sampled and quantitatively analyzed at 58.43% and 41.57% by mass using an apparatus and method similar to example 4, except that the first line of the sampling apparatus was replaced with a 1/4 inch stainless steel tube.
Preparing standard liquid samples of isobutene and cyclohexane with the mass fractions of 58.43% and 41.57% in a pressurized standard liquid steel cylinder by a mass method, adding 2MPa of nitrogen into the pressurized standard liquid steel cylinder, connecting the pressurized standard liquid steel cylinder with a 1/4 stainless steel tube, opening a switch of the pressurized standard liquid steel cylinder, pressing the standard liquid sample into the 1/4 stainless steel tube through an outlet pipeline of the pressurized standard liquid steel cylinder, starting an electric heating belt to heat the second pipeline, controlling the heating temperature to be 150 ℃, opening a carrier gas steel cylinder, controlling the flow rate of carrier gas (nitrogen) to be 50mL/min by a flowmeter, inputting the sample in the 1/4 stainless steel tube into the second pipeline for gasification, carrying the gasified sample into a gas chromatograph together with the nitrogen for quantitative analysis, setting an automatic sampling program, completing chromatographic analysis every 20 minutes, and according to the mass fractions of components when the standard liquid sample is prepared and the peak area measured by the chromatograph, relative mass correction factors between different components are calculated and calibrated, and the detection results are shown in table 9.
Table 9:
an 1/4-inch stainless steel tube is used for replacing a capillary tube, the measured data deviation is obvious, and the difference between the relative mass correction factor of the isobutene/cyclohexane and the relative mass correction factor of the example 4 is large, so that an accurate test result cannot be obtained.
Comparative example 2
Standard liquids of isobutylene and cyclohexane were injected and quantitatively analyzed using an apparatus and method similar to example 4 at 58.43% and 41.57% by mass, except that no electric heating tape was turned on during injection.
Preparing standard liquid samples of isobutene and cyclohexane with mass fractions of 58.43% and 41.57% in a pressurized standard liquid steel cylinder by a mass method, adding 2MPa of nitrogen into the pressurized standard liquid steel cylinder, connecting the pressurized standard liquid steel cylinder with a first pipeline, opening a switch of the pressurized standard liquid steel cylinder, pressing the standard liquid sample into the first pipeline through an outlet pipeline of the pressurized standard liquid steel cylinder, opening a carrier gas steel cylinder, controlling the flow rate of the carrier gas (nitrogen) to be 50mL/min by a flowmeter, allowing the sample output by the first pipeline to enter a second pipeline and be gasified in the second pipeline, allowing the gasified sample carried by the nitrogen to enter a gas chromatograph together for quantitative analysis, setting an automatic sampling program, completing chromatographic analysis every 20 minutes, calculating and calibrating relative mass correction factors among different components according to the mass fractions of the components and peak areas measured by the chromatograph when preparing the standard liquid sample, the results are shown in Table 10.
Table 10:
under the condition of no heating and heat preservation, substances with higher boiling points are easy to condense and liquefy and adhere to the pipe wall, so that the analysis result is inaccurate.
Claims (10)
1. The sampling device is characterized by comprising a first pipeline, a second pipeline and a heating device, wherein the heating device is used for heating the second pipeline, an outlet of the first pipeline is connected with an inlet of the second pipeline, and the first pipeline is a capillary pipeline.
2. The sample introduction device according to claim 1, wherein the inner diameter of the first conduit is less than 200 μm, preferably 10-200 μm, more preferably 20-150 μm, most preferably 20-100 μm;
and/or, the length of the first pipeline is more than 20cm, the sample injection device is used for injecting the liquid sample into the gas chromatograph or the mass spectrometer, and when the initial pressure of the liquid sample is 2-15Mpa, such as 2-5Mpa, and further such as 2-3Mpa, the length of the first pipeline is preferably 20-150cm, and more preferably 30-150 cm.
3. The sample introduction device according to claim 1 or 2, wherein the length of the second pipeline is 10cm to 150cm, preferably 20cm to 100 cm;
and/or the inner diameter of the second pipeline is 1mm-25.4mm, preferably 3mm-12 mm;
and/or the first pipeline is a glass capillary tube, a quartz capillary tube or a stainless steel capillary tube;
and/or the outlet of the first pipeline is connected with the inlet of the second pipeline in a manner that the outlet of the first pipeline is arranged opposite to the inlet of the second pipeline, and the outlet of the first pipeline is directly connected with the inlet of the second pipeline or is connected with the inlet of the second pipeline through a connecting piece; alternatively, a portion of the first conduit is inserted into the second conduit via an inlet of the second conduit, and an outlet of the first conduit is located within the second conduit.
4. The sample introduction device according to claim 1, wherein the heating device is a device capable of heating a part of the second pipeline or the whole second pipeline; preferably, the heating device is a device capable of heating at least the whole gasification part of the second pipeline, and the gasification part is from the outlet of the first pipeline to the outlet of the second pipeline; more preferably, the heating device is a device capable of heating the whole second pipeline, and further preferably, the heating device is a heating device arranged on the outer surface of the whole second pipeline to heat the whole second pipeline;
and/or the heating device is an electric heating device, a heat conduction oil heating device, a steam heating device or a water bath heating device; the heating device is preferably an electric heating belt, and more preferably an electric heating belt wound on the outer wall of the whole second pipeline;
and/or the sample introduction device further comprises a gas carrying pipeline, and the second pipeline is connected with the gas carrying pipeline;
and/or, the sample introduction device further comprises a sample storage device, and the sample storage device is connected with the inlet of the first pipeline.
5. The sample introduction device according to claim 4, wherein the carrier gas line is connected to the second line at a position such that the carrier gas flows through the outlet of the first line;
and/or a flow meter is arranged on the gas carrying pipeline;
and/or the sample introduction device further comprises a device for storing carrier gas, and the device for storing carrier gas is connected with the carrier gas pipeline.
6. The sample introduction device according to claim 4, wherein the sample storage device is a storage device capable of storing a liquid sample, preferably a pressurized standard liquid steel cylinder; or a reaction device, a mixing device, a separation device or an extraction device capable of storing a liquid sample;
and/or, the sample storage device is positively disposed;
and/or the sample storage device is an atmospheric device or a pressurizing device, and preferably, the pressurizing device is filled with gas with the pressure higher than the atmospheric pressure;
and/or the sample storage device is provided with an outlet pipeline or a sampling device, and the outlet pipeline or the sampling device is connected with the inlet of the first pipeline; preferably, the inlet of the outlet line is located below the liquid level in the sample storage device; preferably, the sampling device is an online sampling device.
7. A quantitative analysis device, comprising the sample introduction device as claimed in any one of claims 1 to 6 and a gas chromatograph or a mass spectrometer, wherein a sample introduction port of the gas chromatograph or the mass spectrometer is connected with an outlet of the second pipeline of the sample introduction device.
8. A sample introduction method, characterized in that the sample introduction device of any one of claims 1 to 6 is adopted, and the specific steps comprise: inputting a liquid sample into a first pipeline, heating a second pipeline by using a heating device, and introducing the sample output by the first pipeline into the second pipeline, gasifying the sample in the second pipeline and then injecting the sample; the liquid sample contains or does not contain a substance which is gaseous at normal temperature and normal pressure, when the liquid sample does not contain the substance which is gaseous at normal temperature and normal pressure, the second pipeline is filled with carrier gas, and the gasified sample is carried by the carrier gas for sample injection; when the liquid sample contains a substance which is gaseous at normal temperature and normal pressure, the second pipeline is communicated with or not communicated with a carrier gas.
9. The sample introduction method according to claim 8, wherein the length of the first tubing is 20-150cm, preferably 30-150cm, when the initial pressure of the liquid sample is 2-15Mpa, such as 2-5Mpa, such as 2-3 Mpa;
and/or the liquid sample is a mixture of at least one of ethane, propane, butane, isobutane, pentane, isopentane, n-butene, isobutene, butadiene, propylene and dimethyl ether and at least one of methyl acetate, ethyl acetate, ethanol, methanol, propanol, butanol, tert-butanol, toluene, tert-butylamine, dimethylamine, cyclohexane, tetrahydrofuran and acetic acid;
and/or the liquid sample is a standard product or a sample to be analyzed in petrochemical or pesticide analysis, and when the liquid sample is the standard product, the liquid sample is prepared by a mass method;
and/or the heating device at least heats the whole gasification part of the second pipeline, and the gasification part is started from the outlet of the first pipeline to the outlet of the second pipeline; preferably, the heating device heats the whole second pipeline;
and/or the heating temperature of the heating device is 180-;
and/or the flow rate of the carrier gas is 30-80mL/min, such as 40-60mL/min, such as 50 mL/min;
and/or, the liquid sample is pressed into the first pipeline by the gas with the pressure higher than the atmospheric pressure in the pressurized sample storage device;
and/or the sample injection is to a gas chromatograph or a mass spectrometer.
10. A method of quantitative analysis, comprising: a liquid sample is injected by the injection method of claim 8 or 9 for quantitative analysis.
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