A column chromatography sample online concentration device, method and application

Abstract

The purpose of the present invention is to provide a column chromatography sample online concentration device, method and application, which are used to overcome the problem of difficulty in analyzing volatile and semi-volatile components in chromatography products. The device comprises a hollow bracket (7), the open end of the hollow bracket (7) is connected to a gas pipeline (3) and a gas source (1), and a plurality of flow regulating valves (6) installed on the hollow bracket (7) are connected to a bronchial line (10); the hollow bracket (7) is connected to a chromatography column (4); and a gas path is formed by the gas source (1), the gas pipeline (3), the hollow bracket (7), the flow regulating valve (6), and the bronchial line (10). In a column chromatography separation experiment, the device continuously and controllably blows the gas flow into a product receiving container through the gas pipeline, so that the mobile phase in the product evaporates rapidly, thereby shortening the product concentration time and reducing the temperature of the collected sample, thereby providing a column chromatography experimental tool for chromatography-mass spectrometry analysis including samples from high-overmature areas.

Description

Technical Field

[0001] The invention relates to the field of column chromatography, and in particular to an online concentration device, method and application of column chromatography samples. Background Art

[0002] Column chromatography is a common method for purifying and separating organic or inorganic substances. It can be used to separate most organic compounds and is particularly suitable for separating complex natural products. Its separation capacity ranges from a few milligrams to hundreds of milligrams, so this method is suitable for separating and preparing samples.

[0003] At present, the oil and gas industry generally uses column chromatography to extract biomarker compounds from rocks. The industry standard implemented is SY / T 5119-2016 "Analysis of soluble organic matter in rocks and crude oil group components". The column chromatography device used only includes components such as the chromatography column and its iron stand (or a stand with similar functions). The function of the iron stand or stand is to support / clamp the chromatography column. The separated sample solution needs to evaporate the reagent at a certain temperature, quantify it, and then dissolve the sample with a solvent for chromatography-chromatography analysis.

[0004] However, due to the generally high maturity of organic matter in the current commercially exploitable shale oil field, Ro is between 1.1% and 1.6%, and this maturity window is the most favorable stage for the conversion of adsorbed oil into free oil in shale oil. Conventional sterane and terpane biomarker compounds in highly over-mature soluble organic matter have been severely degraded, and their content is too low. The use of existing column chromatography devices and methods for normal chromatography-mass spectrometry analysis often cannot accurately and qualitatively analyze their composition, nor can it be used to compare oil sources and evaluate the maturity of soluble organic matter through its composition, resulting in the almost ineffectiveness of the biomarker compound parameters extracted by conventional column chromatography.

[0005] At the same time, the kerogen in the rocks of high-overmature areas has been severely degraded, especially the lack of vitrinite components in marine strata, resulting in large errors in the vitrinite reflectance measured in high-overmature areas, making it difficult to make an accurate quantitative evaluation of the maturity of the strata. Therefore, the focus of scientific research has begun to shift to seeking methods to verify the maturity of crude oil and source rocks by measuring indicators such as adamantane and methylphenanthrene in soluble organic matter. However, in actual operation, the volatile components and semi-volatile substances in the products analyzed by column chromatography have either been completely volatilized and lost (such as adamantane) or have suffered a certain degree of loss, and the analysis results are often abnormal (such as methylphenanthrene), resulting in the limited application of existing column chromatography in judging the maturity of organic matter in high-overmature areas.

[0006] In order to avoid the problem of loss of volatile and semi-volatile components in the products of chromatography treatment, China Petroleum Exploration and Development Research Institute proposed SY / T 7470-2020 "Separation and Quantification Method of Diamond in Petroleum" in 2020. This method is mainly applicable to the analysis of diamond compounds in crude oil (rock extract analysis can refer to this method). In the method, the crude oil (or rock extract) solution is first centrifuged and ultrasonicated, and then the supernatant of the solution is taken for gas chromatography-mass spectrometry analysis to analyze the diamond compounds. However, this method has the following problems in application: ① When there are many heavy components in crude oil or soluble organic matter, the centrifugal method cannot effectively stratify the sample and it is not easy to sample; ② Because the sample is not separated, the sample contains multiple components, and the peaks of components with similar molecular weights in the chromatographic-mass spectrometry spectrum interfere with each other, affecting the quantitative results of the components; ③ Because there are many heavy components in the extracted sample, the experiment has a large loss on the chromatographic column; ④ This method is not suitable for direct analysis of rocks, and the process of extracting soluble organic matter from rocks and evaporating solvents with high polarity is very likely to cause component loss. Summary of the invention

[0007] The technical problem to be solved by the present invention is to overcome the difficulty in analyzing volatile and semi-volatile components in the existing chromatography products in the background technology, and to provide a column chromatography sample online concentration device, which continuously and controllably blows the gas flow into the product receiving container through the gas pipeline in the column chromatography separation experiment, so that the mobile phase in the product evaporates rapidly, which not only shortens the sample analysis time but also reduces the temperature of the collected product, and can effectively control the loss of volatile and semi-volatile components, and provide a column chromatography experimental tool for the chromatography-mass spectrometry analysis of samples in high-overmature regions. The present invention also provides a column chromatography sample online concentration method and application thereof.

[0008] The present invention can solve the problem by the following technical solution:

[0009] One of the purposes of the present invention is to provide an online concentration device for column chromatography samples, comprising an air pipeline and a hollow bracket, wherein one end of the hollow bracket has an opening, and the hollow bracket is provided with a plurality of openings for connecting flow regulating valves, and the hollow bracket is connected to the bronchial pipeline through each flow regulating valve; a chromatography column is installed on the hollow bracket; one end of the air pipeline is connected to a gas source, and the other end is connected to the open end of the hollow bracket; the gas source, the air pipeline, and the hollow bracket respectively form an air circuit with each flow regulating valve and the bronchial pipeline.

[0010] Preferably, a chromatography column is mounted on the hollow support via a fixing clamp; the fixing clamp is a butterfly clamp; and each flow regulating valve on the hollow support corresponds to a chromatography column.

[0011] Preferably, a receiving container is disposed at the lower portion of the chromatography column, and the receiving container is a vial; a boss is disposed at the end of the bronchial line, and the boss disposed on the bronchial line is utilized to fix the bronchial line at the opening of the receiving container; and the lower end of the chromatography column is inserted into the opening of the receiving container.

[0012] Preferably, both ends of the hollow bracket are supported and fixed by fixed brackets; the gas source is a gas cylinder filled with nitrogen or a compressed gas source filled with other compressed gases; and a dryer is connected to the gas pipeline.

[0013] Another object of the present invention also provides a column chromatography sample online concentration method, comprising:

[0014] Assemble the gas circuit of the device, install the chromatography column and the receiving container;

[0015] Chromatographic separation of samples and online concentration, control of online concentration time, separation sample environment temperature, and acquisition of chromatographic separation products;

[0016] Test the chromatographic separation product or seal it and store it at low temperature.

[0017] Preferably, the method for controlling the time of online concentration and the environmental temperature of the separated samples comprises:

[0018] Nitrogen is introduced into the receiving container through the gas path of the device. When the chromatographic separation product flows into the receiving container, the nitrogen gas flow is used to volatilize and carry away the separation reagent in the chromatographic separation product, thereby cooling and concentrating the product.

[0019] Preferably, the receiving container is pre-cooled before the chromatographically separated product flows into the receiving container; the method for pre-cooling the receiving container comprises:

[0020] Nitrogen is introduced into the receiving container containing the reagent through the gas path of the device, and the nitrogen gas flow volatilizes the reagent in the receiving container to pre-cool the receiving container;

[0021] Preferably, the method of online concentration during separation of a sample comprises:

[0022] During the separation of samples, the gas path of the online concentration device is connected to concentrate the separation product solution online. During the online concentration process, the flow rate of the gas flow can be dynamically adjusted using the flow control valve on the device to keep the liquid level in the receiving container stable.

[0023] Preferably, after the chromatography separation of the sample is completed, a certain amount of reagent solution is retained in the receiving container to keep the sample in a solution environment and inhibit the volatilization of light components in the sample.

[0024] The third object of the present invention also provides the application of the column chromatography sample online concentration method to directly separate adamantane from samples in high-overmature areas, and to separate saturated hydrocarbons and aromatic hydrocarbon components in soluble organic matter.

[0025] Preferably, the high-overmature area samples include shale oil samples and marine source rock samples with high maturity. The shale oil samples and marine source rock samples include block rock samples and crude oil samples.

[0026] Compared with the above background technology, the present invention has the following beneficial effects:

[0027] The device of the present invention can reduce the analysis time and the temperature of collecting products by concentrating products online during the column chromatography separation experiment, thus overcoming the problem of difficulty in analyzing volatile and semi-volatile components in the chromatography products.

[0028] The separated products have completed component separation, and there is no problem of mixing the components together, which avoids mutual interference between the peaks of the components. In addition, there are no heavy components such as asphaltene in the products, which reduces the loss of the chromatographic column.

[0029] The present invention ensures that the light components in the extracted product are always in a solution environment that can make them more stable, and there is no need to extract soluble organic matter from rock samples first, thereby effectively controlling the volatilization of the light components and ensuring that the light products in the rock can be extracted.

[0030] The device of the present invention provides a column chromatography experimental tool for chromatography-mass spectrometry analysis of samples from high-overmature areas (including shale oil samples with high maturity and marine source rock samples).

[0031] The hollow support used in the device of the present invention is used as a part of the air pipeline and also as a support for supporting the chromatography column, so that the process is simple and easy to operate.

[0032] The device of the present invention verifies the maturity of crude oil and source rock by measuring indicators such as adamantane in soluble organic matter, and makes an accurate quantitative evaluation of the maturity of the formation. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] Figure 1 It is a structural schematic diagram of the device of the present invention;

[0034] In the figure: 1: gas source; 2: dryer; 3: gas pipeline; 4: chromatography column; 5: fixing clamp; 6: flow regulating valve; 7: hollow bracket; 8: receiving container; 9: fixing bracket; 10: bronchial pipeline;

[0035] Figure 2 This is a curve showing the variation of the residual mass of a certain crude oil over time under room temperature and open conditions in an embodiment of the present invention;

[0036] Figure 3 This is a single adamantane chromatogram mass spectrum of a block sample with Ro=1.4% stored at room temperature extracted by the device of the present invention in an embodiment of the present invention;

[0037] Figure 4 The total ion current of the chromatographic mass spectrometer TIC of the product extracted from the rock by conventional extraction method;

[0038] Figure 5 This is a chromatographic mass spectrometry TIC total ion current diagram of the product extracted from the rock using the device of the present invention in the embodiment of the present invention;

[0039] Figure 6 It is the total ion current diagram of the chromatographic mass spectrometry TIC of the saturated hydrocarbon products extracted from crude oil in the embodiment of the present invention. DETAILED DESCRIPTION

[0040] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the present invention and the embodiments, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0041] In order to solve the problem of light component and semi-volatile loss in the products prepared by the existing technical solutions, the key factors affecting the loss of light components in soluble organic matter were found by tracking and analyzing the loss characteristics of light components in crude oil at room temperature. Figure 2 The curve of the residual mass of a certain crude oil (about 3g) changing with time under natural exposure is shown. It can be seen from the figure that the mass loss of the sample is 4.15% in 3h, 5.61% in 6h, 10.98% in 24h, 15.45% in 48h, and the final mass loss is more than 29.57%; the increase in the volatilization rate in the local interval of the curve is directly related to the increase in room temperature. The higher the temperature, the more obvious the increase in the local volatilization rate. That is, time is the key factor affecting the loss of light components in soluble organic matter. The loss increases with time, and the loss rate is the largest in the initial stage (about 1.38% / h for crude oil); temperature is also one of the factors affecting the loss rate of soluble organic matter. The higher the temperature, the greater the loss rate. Therefore, the loss of volatile and semi-volatile components in the chromatography product can be suppressed by shortening the sample analysis time and reducing the temperature during column chromatography.

[0042] Based on the above analysis results, Figure 1As shown, the present invention designs an online concentration device for column chromatography samples, including an air pipeline 3, a hollow bracket 7, one end of the hollow bracket 7 has an opening, the open end of the hollow bracket 7 is connected to one end of the air pipeline 3, and the other end of the air pipeline 3 is connected to a gas source 1, and the gas source 1 is a gas cylinder filled with nitrogen; the hollow bracket 7 has a plurality of openings, each opening is respectively connected to a flow regulating valve 6, and the hollow bracket 7 is connected to a bronchial line 10 through each flow regulating valve 6; the hollow bracket 7 is connected to a chromatography column 4 through a fixing clamp 5; the fixing clamp 5 is a butterfly clamp; the chromatography column 4 A receiving container 8 is placed at the lower part, and the receiving container 8 is a cillin bottle; a boss is provided at the end of the bronchial line 10, and the bronchial line 10 is fixed to the opening of the receiving container 8 by using the boss provided on the bronchial line 10, and the lower end of the chromatography column 4 is also inserted into the opening of the receiving container 8; both ends of the hollow bracket 7 are supported and fixed by fixed brackets 9; the fixed bracket 9 is a T-shaped tripod; the air pipeline 3 is connected to the dryer 2; the gas source 1, the air pipeline 3, the hollow bracket 7 and each flow regulating valve 6 and the bronchial line 10 respectively constitute an air path of an online concentration device.

[0043] The hollow bracket 7 is used as a part of the air pipeline and also as a bracket for supporting the chromatography column 4. The hollow bracket 7 is connected to the dryer 2 and the gas cylinder through the air pipeline 3. Several flow regulating valves 6 and butterfly clamps 5 are installed on the hollow bracket 7. The hollow bracket 7 is fixed on the experimental table through a T-shaped tripod 9; the bronchial line 10 led out of the flow regulating valve 6 is directly connected to the bottle mouth of the sample receiving container 8. A boss is provided at the end of the bronchial line 10 (the boss is formed by the pipeline diameter change). During use, the boss can be stuck on the bottle mouth of the receiving container 8 to prevent the bronchial line 10 from sliding off under the reaction force of the airflow; the butterfly clamp 5 is used to clamp the chromatography column 4 used for column chromatography experiments; a desiccant is installed in the dryer 2 to remove water vapor that may exist in the airflow and prevent the water vapor in the gas from generating condensed water in the cold environment of the receiving container 8.

[0044] When the column chromatography sample online concentration device is working, the gas is diverted through the hollow bracket 7 and the flow regulating valve 6 and then blown into the product receiving container 8 in a continuously and controllable manner, so that the mobile phase in the product evaporates rapidly. The mobile phase absorbs a large amount of heat during the volatilization process. The online concentration of samples shortens the sample analysis time and reduces the product collection temperature, thereby reducing the loss of light components in the product. At the same time, since the experimental product is simultaneously concentrated during the column chromatography process, the total volume of the product sample is reduced, and the smaller receiving container 8 can be used directly to receive the sample, and the loss of light components caused by repeated volatilization of reagents is avoided, which helps to shorten the experimental analysis time.

[0045] The main operating steps of using the column chromatography sample online concentration device of the present invention to perform a column chromatography experiment include:

[0046] ① Assemble the online concentration device: add the desiccant into the dryer 2; connect the gas source 1, the dryer 2, the hollow support 7 and the flow regulating valve 6 in sequence; fix the chromatography column 4 on the fixing clamp 5, and fill the chromatography column 4 with cotton and the activated stationary phase in sequence;

[0047] ② Install the receiving container: place the receiving container 8 below the chromatography column 4, fix the bronchial line 10 to the bottle mouth of the receiving container 8 using the boss on the bronchial line 10, and slightly insert the chromatography column 4 into the receiving container 8 to prevent the airflow from blowing down the receiving container 8 or the liquid flowing out of the chromatography column 4 from flying out with the airflow during operation;

[0048] ③ Pre-cooling of the receiving container: before separating the sample, the temperature of the receiving container 8 is lowered to prepare for receiving the sample;

[0049] ④ Sample separation and online concentration: Add the experimental sample into the chromatography column 4, separate the sample according to the experimental design, and connect the gas path of the online concentration device to concentrate the separated product solution online. During this process, the reagent in the product solution must not be evaporated; during the online concentration process, the flow rate of the gas flow can be dynamically adjusted using the flow control valve 6 on the device to keep the liquid level in the receiving container 8 stable;

[0050] ⑤ Test the product or seal it and store it at low temperature: After the experiment is over, a certain amount of reagent solution must still be retained in the receiving container 8. The separated product must not be concentrated to dryness. The retained reagent solution is used to keep the sample in a solution environment and inhibit the volatilization of light components in the sample. At this time, the separated product can be immediately tested in subsequent experiments; if it cannot be tested immediately, the sample can be sealed and stored at low temperature.

[0051] The order of the above steps can be fine-tuned according to actual needs.

[0052] The column chromatography sample online concentration device and the use method thereof of the present invention effectively control the loss of light components in soluble organic matter by shortening the separation and extraction time, lowering the sample environment temperature and maintaining the dissolved state of the product.

[0053] Example 1: Direct separation of adamantane from rocks using the column chromatography sample online concentration device of the present invention

[0054] like Figure 1 Assemble the column chromatography sample online concentration device in the manner shown.

[0055] A block of rock with Ro=1.4% stored at room temperature was selected and crushed at low temperature. 4g of rock powder was sieved and mixed with 2g of activated (dehydrated) silica gel.

[0056] Take a chromatography column 4 with a capacity of 50 ml and a diameter of 1 cm and a polytetrafluoroethylene valve, fix the chromatography column 4 on the butterfly clip of this device, and sequentially fill the bottom of the chromatography column 4 with absorbent cotton as a support and 3g of activated stationary phase silica gel and 2g of alumina, then quickly add the mixture of rock powder and silica gel into the chromatography column 4, and add n-hexane reagent, and quickly close the polytetrafluoroethylene valve when the n-hexane reagent is about to flow out of the polytetrafluoroethylene valve at the bottom of the chromatography column 4. Continue to add n-hexane reagent until it is about 5cm above the interface of the rock powder and silica gel mixture, cover and seal, and let it stand and soak for 8 hours;

[0057] Take the receiving container 8, add half a bottle of n-hexane reagent into the receiving container 8, place it under the chromatography column 4, and slightly insert the chromatography column 4 into the receiving container 8; use the boss at the end of the bronchial tube 10 to fix the air tube to the bottle mouth of the receiving container 8, and then slowly open the flow regulating valve 6 to volatilize the reagent in the receiving container 8 to lower its temperature, thereby completing the pre-cooling of the receiving container 8.

[0058] After the pre-cooling of the receiving container 8 is completed, the flow valve of the chromatography column 4 is opened to collect the adamantane sample. During this period, the flow regulating valve 6 can be dynamically adjusted according to the change of the liquid level in the receiving container 8 to keep the liquid level in the receiving container 8 relatively stable. Preferably, the solution can always be kept at about 2 ml. Avoid evaporating the reagent during the volatilization process. Since the light component is more stable in the solution environment (because the light component is in a dissolved state and is not easy to dissipate), a certain amount of reagent should always be retained.

[0059] After the experiment is finished, a certain amount of reagent solution needs to be retained in the receiving container 8, and then subsequent experimental analysis can be carried out on the separated products in the receiving container (or the samples can be sealed and stored at low temperature).

[0060] like Figure 3 The figure shows a monoadamantane chromatogram mass spectrum of a block sample of Ro=1.4% stored at room temperature extracted by the device of the present invention. As shown in the figure, the numbers 1-17 in the figure represent adamantane, 1-methyladamantane, 1,3-dimethyladamantane, 1,3,5-trimethyladamantane, 1,3,5,7-tetramethyladamantane, 2-methyladamantane, cis-1,4-dimethyladamantane, trans-1,4-dimethyladamantane, 1,3,6-trimethyladamantane, 1,2-dimethyladamantane, cis-1,3,4-trimethyladamantane, trans-1,3,4-trimethyladamantane, 1,2,5,7-tetramethyladamantane, 1-ethyladamantane, 1-ethyl-3-methyladamantane, 1-ethyl-3,5-dimethyladamantane, and 2-ethyl-adamantane. The carbon number range of monoadamantane is C 11~13 .

[0061] like Figure 4 , Figure 5As shown, a block rock sample with Ro=1.4% stored at room temperature was extracted by using a conventional extraction method and the method of the embodiment of the present invention, and the chromatographic mass spectrometry of the extracted products was compared. Figure 4 This is the total ion current of the chromatogram of the product extracted by conventional column chromatography. The peak is from C 15 Beginning; Figure 5 This is the total ion current diagram of the chromatographic sample online concentration device extracting the product. The peak is from C 10 By comparison, it can be seen that the column chromatography sample online concentration device can effectively retain the light components in the separated product.

[0062] Example 2: Separation of saturated hydrocarbons and aromatic hydrocarbon components from crude oil using an online concentration device

[0063] When using the column chromatography online sample concentration device of the present invention to separate crude oil, 50 mg of crude oil sample is put into a sample bottle containing an appropriate amount of n-hexane reagent, and after sealing the sample bottle with a cap, the sample bottle is put into ultrasound to dissolve the crude oil.

[0064] like Figure 1 The column chromatography sample online concentration device is assembled in the manner shown, and the bottom of the chromatography column 4 is filled with absorbent cotton as a support and 3g of activated stationary phase silica gel and 2g of alumina in sequence; the chromatography column 4 is slightly inserted into the receiving container 8; after the end of the bronchial line 10 is fixed to the bottle mouth of the receiving container 8, the flow regulating valve 6 is slowly opened, and n-hexane reagent is added to the chromatography column 4 in small amounts and multiple times to wet the stationary phase. The wetting reagent evaporates after flowing into the receiving container 8, thereby pre-cooling the receiving container 8.

[0065] When the pre-cooling of the receiving container 8 is completed, the crude oil after ultrasonic dissolution can be added to the chromatography column 4, and the saturated hydrocarbon components can be eluted with 30ml of n-hexane; after the separation of saturated hydrocarbons, the aromatic hydrocarbon receiving container 10 is replaced, and a n-hexane-dichloromethane (1:2) mixed solution is added to the chromatography column 4. At this time, the aromatic hydrocarbon receiving container 8 can achieve pre-cooling by volatilizing the n-hexane blank reagent eluted from the chromatography column 4; finally, the aromatic hydrocarbon components are eluted with 20ml of n-hexane-dichloromethane (1:2) mixed solution. During the separation of saturated hydrocarbon and aromatic hydrocarbon components, the flow regulating valve 6 can be dynamically adjusted according to the changes in the liquid level in the receiving container 8 to keep the liquid level in the receiving container 8 dynamically stable. After the experiment, a certain amount of reagent solution still needs to be retained in the receiving container 8, and then the separation product in the receiving container 8 can be subjected to subsequent experimental analysis (or sealed samples can be stored at low temperatures).

[0066] like Figure 6Shown is the chromatographic mass spectrum TIC total ion current diagram of saturated hydrocarbon products extracted from crude oil by the column chromatography sample online concentration device of the present invention. It can be seen from the figure that the separation product of the device can effectively retain C9 and subsequent light components.

[0067] Example 1 describes an implementation method for extracting biomarker compounds from rocks using a column chromatography sample online concentrator. Compared with the SY / T 5119-2016 "Analysis of soluble organic matter in rocks and crude oil group components" method described in the background, this column chromatography sample online concentrator is effective in retaining light components in the separation product; Example 2 describes an implementation method for extracting biomarker compounds from crude oil using a column chromatography sample online concentrator. Compared with the SY / T 7470-2020 "Separation and Quantification Method of Diamond in Petroleum" described in the background, this column chromatography sample online concentrator is suitable for separating various types of soluble organic matter including heavy crude oil, avoiding the problems of ineffective stratification of samples, mutual interference between component peaks, and large chromatographic column loss during centrifugal separation, and also avoiding the problem of easy loss of light components in the process of extracting soluble organic matter from the core and then centrifuging it.

[0068] It should be understood that although the chromatographic mass spectrometry TIC total ion current diagrams of the separated products in Examples 1 and 2 are from C9 or C 10 peak, but it does not mean that the separated product contains only C9 or C 10 The peaks in the TIC total ion flow chart are responses to ions with a set charge-to-mass ratio, and components before C9 are not detected in this embodiment. If a core or freshly produced crude oil is used and a full-scan chromatographic analysis is performed on the sample, separation products with smaller molecular weights can be detected.

[0069] Although this specification is described according to implementation modes, not every implementation mode includes only one independent technical solution. This description of the specification is only for the sake of clarity. Those skilled in the art should regard the specification as a whole. The technical solutions in each embodiment may also be appropriately combined to form other implementation modes that can be understood by those skilled in the art.

Claims

1. A column chromatography sample online concentration device, comprising a gas pipeline (3) and a hollow support (7), characterized in that: The hollow support (7) has an opening at one end, and a plurality of openings connected to flow regulating valves (6) are formed on the hollow support (7), and the hollow support (7) is connected to a bronchial line (10) through each flow regulating valve (6); a chromatography column (4) is installed on the hollow support (7); one end of the air line (3) is connected to a gas source (1), and the other end is connected to the open end of the hollow support (7); The gas source (1), the air pipeline (3), and the hollow support (7) respectively form an air circuit with each flow regulating valve (6) and the bronchial pipeline (10); The hollow support (7) is connected to the chromatography column (4) via a fixing clamp (5); each flow regulating valve (6) on the hollow support (7) corresponds to a chromatography column (4); A receiving container (8) is disposed at the bottom of the chromatography column (4); a boss is disposed at the end of the bronchial line (10); the bronchial line (10) is fixed to the opening of the receiving container (8) by utilizing the boss disposed on the bronchial line (10); the lower end of the chromatography column (4) is inserted into the opening of the receiving container (8); The gas source (1) is a gas cylinder containing compressed gas, and the compressed gas is nitrogen; Nitrogen is introduced into the receiving container (8) through the gas path of the device. When the chromatographic separation product flows into the receiving container (8), the nitrogen gas flow is used to volatilize and carry away the separation reagent in the chromatographic separation product, thereby cooling and concentrating the product. The device is used to directly separate adamantane from samples in high-overmature areas, or to separate saturated hydrocarbons and aromatic hydrocarbon components in crude oil; the samples in high-overmature areas include shale oil samples with higher maturity and marine source rock samples.

2. The column chromatography sample online concentration device according to claim 1, characterized in that: The two ends of the hollow support (7) are supported and fixed by fixed supports (9); and the air pipeline (3) is connected to a dryer (2).

3. A method for online concentration of column chromatography samples using the device according to any one of claims 1 to 2, characterized in that: include: Assembling the gas circuit of the device, installing the chromatography column (4) and the receiving container (8); Chromatographic separation of samples and online concentration, control of online concentration time, separation sample environment temperature, and acquisition of chromatographic separation products; Test the chromatographic separation product or seal it and store it at low temperature; The method for controlling the time of online concentration and the environmental temperature of the separated samples comprises: Nitrogen is introduced into the receiving container (8) through the gas path of the device. When the chromatographic separation product flows into the receiving container (8), the nitrogen gas flow is used to volatilize and carry away the separation reagent in the chromatographic separation product, thereby cooling and concentrating the product.

4. The column chromatography sample online concentration method according to claim 3, characterized in that : The receiving container (8) is pre-cooled before the chromatographically separated product flows into the receiving container (8); the method for pre-cooling the receiving container (8) is: Nitrogen is introduced into the receiving container (8) containing the reagent through the gas path of the device, and the nitrogen gas flow volatilizes the reagent in the receiving container (8) to pre-cool the receiving container (8).

5. The column chromatography sample online concentration method according to claim 3, characterized in that : A method for online concentration during separation of a sample, comprising: During the separation of the sample, the gas path of the online concentration device is connected to concentrate the separation product solution online. During the online concentration process, the flow rate of the gas flow is dynamically adjusted using the flow control valve (6) on the device to maintain a stable liquid level in the receiving container (8).

6. The method for online concentration of column chromatography samples according to claim 3, characterized in that: After the chromatography separation of the sample is completed, a certain amount of reagent solution is retained in the receiving container (8); the solution is used to keep the sample in a solution environment and inhibit the volatilization of light components in the sample.

7. Application of the column chromatography sample online concentration method according to any one of claims 3 to 6 in directly separating adamantane from samples in high-overmature regions, and in separating saturated hydrocarbons and aromatic hydrocarbon components in crude oil; the high-overmature region samples include shale oil samples with higher maturity and marine source rock samples.

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