CN114917885A - Capillary gas chromatographic column for realizing xylene isomer baseline separation and preparation method and application thereof - Google Patents
Capillary gas chromatographic column for realizing xylene isomer baseline separation and preparation method and application thereof Download PDFInfo
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/281—Sorbents specially adapted for preparative, analytical or investigative chromatography
- B01J20/282—Porous sorbents
- B01J20/285—Porous sorbents based on polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
- B01D53/025—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with wetted adsorbents; Chromatography
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3092—Packing of a container, e.g. packing a cartridge or column
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Abstract
The invention discloses a capillary gas chromatographic column for realizing xylene isomer baseline separation and a preparation method and application thereof. The fixed phase of the capillary gas chromatographic column is a nano material with a hierarchical pore structure, and nano particles are uniformly embedded in the inner wall of the capillary column. The prepared nano material is dissolved in an organic solvent, is dynamically coated in a capillary chromatographic column at a constant flow rate, and is finally cured at high temperature to obtain the capillary chromatographic column. The capillary column is used for separating xylene isomers, the meta-position/para-position separation degree is up to 15.2, and meanwhile, the prepared capillary gas chromatographic column can achieve excellent separation effects on other benzene substituted isomers and alkane isomers, so that a new solution is provided for efficient separation of the same isomer.
Description
Technical Field
The invention belongs to the technical field of chromatographic separation, and particularly relates to a capillary gas chromatographic column for realizing xylene isomer baseline separation, and a preparation method and application thereof.
Background
Xylene is an important chemical raw material, is a manufacturing raw material of polyester resin, plasticizer and the like, and is widely used for organic solvents, synthetic medicines, coatings, resins, explosives, pesticides and the like. Meanwhile, xylene is also one of environmental pollutants, which mainly comes from waste water and waste gas of production plants of organic synthesis, synthetic rubber, paint and dye, synthetic fiber, petroleum processing, pharmacy, cellulose and the like, and the unsealed production equipment and the ventilation and air exchange of workshops. Belongs to low-toxicity chemical substances, has serious toxicity to the hematopoietic system and the nervous system of people, and can cause acute poisoning by inhaling a large amount of high-concentration xylene vapor for a long time. In industrial production, anticorrosive paint with xylene as solvent is painted inside sealed tank, and the paint has no good ventilation and great amount of xylene vapor accumulated to result in acute poisoning of the operator. The isolation and characterization of these structural isomers is therefore of great importance in the fields of industry and environmental science.
Xylene isomers exist in ortho, meta and para positions respectively, and because the isomers have similar properties and small boiling point difference, the xylene isomers are difficult to separate and measure by common physical and chemical methods. Capillary column Gas Chromatography (GC) has the advantages of strong separation capability, high sensitivity and accuracy, environmental friendliness and the like, and is one of important methods for analyzing and determining complex samples in the fields of chemistry and chemical engineering, petrifaction, food, medicine, environmental monitoring and the like. At present, the common commercial chromatographic columns such as HP-5 and VF-WAXMS are difficult to realize the baseline separation of xylene isomers, the complete baseline separation is difficult to realize by using novel porous materials such as Metal Organic Frameworks (MOFs), Metal Organic Nanosheets (MONs) and porous organic cages, and the like, and the isomer separation is still a great challenge in the petrochemical industry, so that the development of a porous material gas chromatographic column with sensitive nanometer space and selective binding sites is urgently needed to realize the baseline separation of xylene isomers and isomers of the same kind.
Disclosure of Invention
The purpose of the invention is as follows: in order to solve the technical problems, the invention provides a capillary gas chromatographic column for realizing xylene isomer baseline separation, a preparation method and application thereof, the chromatographic column can realize the highest separation degree of the prior three xylene isomers and ethylbenzene mixture, the meta-position/para-position separation degree is as high as 15.2, and the chromatographic column also has good separation performance on other similar isomer materials.
The technical scheme is as follows: the stationary phase of the capillary gas chromatographic column for realizing the xylene isomer baseline separation is an octahedral nanomaterial with a multi-stage pore structure, nanoparticles are uniformly embedded in the inner wall of the capillary column, and pores with different sizes are formed by defects generated by trifluoroacetic acid serving as a regulator in the material structure.
The invention also provides a preparation method of the capillary column for realizing the xylene isomer baseline separation, which comprises the steps of dissolving the prepared nano material in an organic solvent, dynamically coating the nano material in the capillary column at a constant flow rate, and finally curing at high temperature to obtain the capillary column.
Specifically, the preparation method comprises the following steps:
(1) synthesizing a hierarchical porous nano material as a stationary phase: ZrCl with certain concentration is prepared 4 Mixing the solution with a terephthalic acid solution, adding a certain amount of trifluoroacetic acid, uniformly mixing, reacting at high temperature to obtain a white UiO-66 nano material, cooling, centrifuging, washing and drying to obtain a hierarchical porous nano material;
(2) preparing a capillary gas chromatographic column with the inner wall coated with a hierarchical pore material: ultrasonically dispersing the hierarchical porous nano material obtained in the step (1) in an organic solvent, pushing the hierarchical porous nano material into a pretreated capillary chromatographic column at a constant speed by using a syringe pump, dynamically coating the capillary chromatographic column on the inner wall of the capillary chromatographic column, then carrying out programmed heating and aging treatment on the capillary column in an inert atmosphere, cooling to room temperature to obtain the capillary gas chromatographic column, installing the capillary gas chromatographic column in a gas chromatographic phase, and carrying out sensitive detection on a benzene isomer or carrying out efficient separation on a benzene isomer mixture.
Wherein, in the step (1), the concentration of zirconium tetrachloride in the zirconium tetrachloride solution is 8-11 mg/mL, and the concentration of the terephthalic acid solution is 8-11 mg/mL.
The pretreatment of the capillary chromatographic column in the step (2) comprises the following steps: the inner wall of the capillary column is silanized by APTES and then kept at 120 ℃ for 2-5 h.
When in dynamic coating, the injection rate is 3mL/h to 5 mL/h.
When the heat treatment is carried out in the inert atmosphere, the inert atmosphere is one or a mixture of several of nitrogen, helium or argon according to any proportion.
The specific mode of the programmed temperature-rising aging treatment in the step (2) is as follows: under inert atmosphere, the initial temperature is 20-50 ℃, the temperature is raised to 250 ℃ at the speed of 2-10 ℃/min, and the temperature is kept for 2-8 h.
The invention finally provides the use of a capillary gas chromatography column for separating other isomers, such as the chlorotoluene isomer, the dichlorobenzene isomer, the hexane isomer, the octane isomer or the decane isomer.
The capillary chromatographic gas chromatographic column is connected into a gas chromatograph, after the initial temperature, the heating rate and the temperature retention time are set, a trace amount of separation target substances are injected into the chromatographic column by a trace amount injector from an injection port, and the chromatographic peak of the corresponding separation substances can be obtained after the test is started for a plurality of minutes by clicking.
In the preparation method of the gas chromatographic column, ZrCl is used 4 The preparation method is characterized in that the material is a metal source, terephthalic acid is an organic ligand, trifluoroacetic acid is used as a regulator, a white powdery hierarchical pore material is prepared by a solvothermal method, and the material is filled on the inner wall of a capillary tube in a dynamic coating manner to serve as a stationary phase. The material has regular and uniform appearance and is uniformly embedded in the inner wall of the quartz capillary column. The stationary phase material contains rich pore channels, different adsorption sites can be provided, and the obtained capillary column has high column efficiency and excellent circulation stability.
The prepared hierarchical porous material is used as a gas chromatographic column of a stationary phase, and has the following advantages: the highest separation degree of the mixture of three xylene isomers and ethylbenzene at present is realized, and the meta-position/para-position separation degree is as high as 15.2; secondly, the material used as the stationary phase has better stability, the structure can not be damaged under acid, alkali and water environments, and the material is high temperature resistant; the material has pore channels with different pore sizes, the pore channel structures are beneficial to the transmission and diffusion of separated objects, and meanwhile, the material can provide corresponding pore channels and acting force for the objects with different sizes and properties, thereby realizing the separation of the mixture; the material particles used as the stationary phase have larger specific surface area, which is beneficial to adsorbing the target; the size of the stationary phase material is small and uniform, the fineness of the filler in the woolen yarn pipe is improved, and the column efficiency is greatly improved; the prepared capillary chromatographic column has extremely high stability and repeatability.
Has the advantages that: compared with the prior art, the technical scheme of the invention has the following remarkable advantages: the capillary gas chromatographic column prepared by the method is coated with the hierarchical pore structure nano particles and is used for gas chromatographic separation, so that the highest separation degree of the separation of three xylene isomers and ethylbenzene mixtures at present is realized, and the meta-position/para-position separation degree can be up to 15.2; the stationary phase material has high yield and uniform size of nanoparticles, is uniformly embedded in the inner wall of the capillary column, and the capillary gas chromatographic column has the advantages of simple and convenient preparation operation, low cost, excellent performance and capability of realizing large-scale production; meanwhile, the capillary gas chromatographic column can realize excellent separation effect on other benzene substituted isomers and alkane isomers, is a gas chromatographic separation material with great potential, and has wide application prospect in analysis and detection of chemical pollutants.
Drawings
FIG. 1 is a SEM photograph of a longitudinal section of a capillary gas chromatography column obtained in example 1 of the present invention;
FIG. 2 is an SEM image of a cross-section of a capillary gas chromatography column prepared in example 1 of the present invention;
FIG. 3 is an SEM image of a stationary phase material of a capillary gas chromatography column according to example 2 of the present invention;
FIG. 4 is a TEM image of the stationary phase material of the capillary gas chromatography column obtained in example 2 of the present invention;
FIG. 5 is a TGA profile of the stationary phase material of a capillary gas chromatography column made in example 3 of the instant invention;
FIG. 6 is a nitrogen adsorption spectrum of a stationary phase material of a capillary gas chromatography column according to example 3 of the present invention;
FIG. 7 is a pore size distribution diagram of a stationary phase material of a capillary gas chromatography column according to example 3 of the present invention;
FIG. 8 is a gas chromatographic separation chart of a capillary gas chromatographic column prepared in example 1 of the present invention for a mixture of three xylene isomers and ethylbenzene;
FIG. 9 is a gas chromatographic separation spectrum of a capillary gas chromatographic column prepared in example 2 of the present invention for a mixture of three isomers of chlorotoluene;
FIG. 10 is a gas chromatographic separation pattern of a capillary gas chromatographic column of three dichlorobenzene isomers according to the invention obtained in example 3;
FIG. 11 is a gas chromatography separation chart of a capillary gas chromatography column on a mixture of n-hexane, n-heptane, n-octane, n-nonane and n-decane, obtained in example 4 of the present invention;
FIG. 12 is a gas chromatographic separation profile of a capillary gas chromatographic column prepared in example 5 of the present invention for a mixture of three hexane isomers;
FIG. 13 is a gas chromatographic separation profile of a mixture of three octane isomers using a capillary gas chromatographic column prepared in example 6 of the present invention;
FIG. 14 gas chromatography separation of a mixture of three decane isomers by a capillary gas chromatography column prepared in example 7 of the present invention.
Detailed Description
The technical solution of the present invention is further described below with reference to the accompanying drawings and examples.
The technical solutions of the present invention are further described in detail by the following specific examples, but it should be noted that the following examples are only used for describing the content of the present invention and should not be construed as limiting the scope of the present invention. Wherein, the gas chromatograph used in the invention is Agilent GC7890B, and the reagent used is analytically pure or chromatographically pure.
Example 1
A preparation method of a gas chromatographic column for realizing baseline separation of xylene isomers comprises the following steps:
1) preparing a hierarchical pore UiO-66 nano material: weigh 45.00mg of ZrCl 4 Dissolving in 5mL of N, N-dimethylformamide, and dissolving 50.00mg of terephthalic acid in 5mL of N, N-dimethylformamideIn formamide, the prepared ZrCl is added 4 The solution was mixed with terephthalic acid solution, 0.5mL trifluoroacetic acid was added and mixed by sonication. The resulting mixture was transferred to a vertical glass vial having a capacity of 20mL and reacted at 120 ℃ for 72 hours. After cooling to room temperature, centrifugally washing the mixture for three times by using N, N-dimethylformamide to obtain a final product;
2) preparing a capillary chromatographic column with a multilevel pore material coated on the inner wall: ultrasonically dispersing 2mg of the prepared material in 1mL of methanol, pushing the material into a pretreated capillary chromatographic column at a constant speed of 4.5mL/h by using an injection pump, heating the capillary column to 250 ℃ by a program of 2 ℃/min in a nitrogen atmosphere after the material is injected, and keeping the temperature for 6h to obtain the capillary gas chromatographic column.
Example 2
A preparation method of a gas chromatographic column for realizing baseline separation of xylene isomers comprises the following steps:
1) preparing a hierarchical pore UiO-66 nano material: 45.50mg of ZrCl were weighed 4 Dissolving in 5mL of N, N-dimethylformamide, dissolving 50.00mg of terephthalic acid in 5mL of N, N-dimethylformamide, and mixing the obtained ZrCl 4 The solution was mixed with terephthalic acid solution, 0.5mL trifluoroacetic acid was added and mixed by ultrasound. The resulting mixture was transferred to a 20 mL-volume upright glass vial and reacted at 120 ℃ for 72 hours. After cooling to room temperature, centrifugally washing the mixture for three times by using N, N-dimethylformamide to obtain a final product;
2) preparing a capillary chromatographic column with the inner wall coated with a hierarchical pore material: ultrasonically dispersing 2mg of the prepared material in 1mL of methanol, pushing the material into a pretreated capillary chromatographic column at a constant speed of 4.5mL/h by using an injection pump, heating the capillary column to 250 ℃ by a program of 2 ℃/min in a nitrogen atmosphere after the material is injected, and keeping the temperature for 6h to obtain the capillary gas chromatographic column.
Example 3
A preparation method of a gas chromatographic column for realizing baseline separation of xylene isomers comprises the following steps:
1) preparing a hierarchical pore UiO-66 nano material: weigh 45.00mg of ZrCl 4 Dissolving in 5mL of N, N-dimethylformamide, dissolving 50.40mg of terephthalic acid in 5mL of N, N-dimethylformamide, and mixing the obtained ZrCl 4 The solution was mixed with terephthalic acid solution, 0.5mL trifluoroacetic acid was added and mixed by sonication. The resulting mixture was transferred to a 20 mL-volume upright glass vial and reacted at 120 ℃ for 72 hours. After cooling to room temperature, centrifugally washing the mixture for three times by using N, N-dimethylformamide to obtain a final product;
2) preparing a capillary chromatographic column with a multilevel pore material coated on the inner wall: ultrasonically dispersing 2mg of the prepared material in 1mL of methanol, pushing the material into a pretreated capillary chromatographic column at a constant speed of 4.5mL/h by using an injection pump, heating the capillary column to 250 ℃ by a program of 2 ℃/min in an argon atmosphere after the material is injected, and keeping the temperature for 6h to obtain the capillary gas chromatographic column.
Example 4
A preparation method of a gas chromatographic column for realizing baseline separation of xylene isomers comprises the following steps:
1) preparing a hierarchical pore UiO-66 nano material: 44.70mg of ZrCl were weighed 4 Dissolving in 5mL of N, N-dimethylformamide, dissolving 49.00mg of terephthalic acid in 5mL of N, N-dimethylformamide, and mixing the obtained ZrCl 4 The solution was mixed with terephthalic acid solution, 0.5mL trifluoroacetic acid was added and mixed by sonication. The resulting mixture was transferred to a 20 mL-volume upright glass vial and reacted at 120 ℃ for 72 hours. After cooling to room temperature, centrifugally washing the mixture for three times by using N, N-dimethylformamide to obtain a final product;
2) preparing a capillary chromatographic column with the inner wall coated with a hierarchical pore material: ultrasonically dispersing 2mg of the prepared material in 1mL of methanol, pushing the material into a pretreated capillary chromatographic column at a constant speed of 4.5mL/h by using an injection pump, heating the capillary column to 250 ℃ by a program of 2 ℃/min in a nitrogen atmosphere after the material is injected, and keeping the temperature for 6h to obtain the capillary gas chromatographic column.
Example 5
A preparation method of a gas chromatographic column for realizing baseline separation of xylene isomers comprises the following steps:
1) preparing a hierarchical pore UiO-66 nano material: 45.80mg of ZrCl were weighed out 4 Dissolving in 5mL of N, N-dimethylformamide, dissolving 51.00mg of terephthalic acid in 5mL of N, N-dimethylformamide, and adding ZrCl 4 The solution was mixed with terephthalic acid solution, 0.5mL trifluoroacetic acid was added and mixed by ultrasound. The resulting mixture was transferred to a vertical glass vial having a capacity of 20mL and reacted at 120 ℃ for 72 hours. Cooling to room temperature, and centrifuging and washing with N, N-dimethylformamide for three times to obtain a final product;
2) preparing a capillary chromatographic column with the inner wall coated with a hierarchical pore material: ultrasonically dispersing 2mg of the prepared material in 1mL of methanol, pushing the material into a pretreated capillary chromatographic column at a constant speed of 4.5mL/h by using an injection pump, heating the capillary column to 250 ℃ by a program of 2 ℃/min in a nitrogen atmosphere after the material is injected, and keeping the temperature for 6h to obtain the capillary gas chromatographic column.
Example 6
A preparation method of a gas chromatographic column for realizing baseline separation of xylene isomers comprises the following steps:
1) preparing a hierarchical pore UiO-66 nano material: weigh 45.00mg of ZrCl 4 Dissolving in 5mL of N, N-dimethylformamide, dissolving 50.00mg of terephthalic acid in 5mL of N, N-dimethylformamide, and dissolving the thus-prepared ZrCl 4 The solution was mixed with terephthalic acid solution, 0.5mL trifluoroacetic acid was added and mixed by ultrasound. The resulting mixture was transferred to a 20 mL-volume upright glass vial and reacted at 120 ℃ for 72 hours. Cooling to room temperature, and centrifuging and washing with N, N-dimethylformamide for three times to obtain a final product;
2) preparing a capillary chromatographic column with a multilevel pore material coated on the inner wall: ultrasonically dispersing 2mg of the prepared material in 1mL of methanol, pushing the material into a pretreated capillary chromatographic column at a constant speed of 4.0mL/h by using an injection pump, heating the capillary column to 250 ℃ by a program of 2 ℃/min in a nitrogen atmosphere after the material is injected, and keeping the temperature for 6h to obtain the capillary gas chromatographic column.
Example 7
A preparation method of a gas chromatographic column for realizing baseline separation of xylene isomers comprises the following steps:
1) preparing a hierarchical pore UiO-66 nano material: weigh 45.00mg of ZrCl 4 Dissolving in 5mL of N, N-dimethylformamide, dissolving 50.00mg of terephthalic acid in 5mL of N, N-dimethylformamide, and dissolving the thus-prepared ZrCl 4 The solution was mixed with terephthalic acid solution, 0.5mL trifluoroacetic acid was added and mixed by ultrasound. The resulting mixture was transferred to a 20 mL-volume upright glass vial and reacted at 120 ℃ for 72 hours. After cooling to room temperature, centrifugally washing the mixture for three times by using N, N-dimethylformamide to obtain a final product;
2) preparing a capillary chromatographic column with a multilevel pore material coated on the inner wall: ultrasonically dispersing 2mg of the prepared material in 1mL of methanol, pushing the material into a pretreated capillary chromatographic column at a constant speed of 5.0mL/h by using an injection pump, heating the capillary column to 250 ℃ by a program of 2 ℃/min in a nitrogen atmosphere after the material is injected, and keeping the temperature for 6h to obtain the capillary gas chromatographic column.
Example 8
A preparation method of a gas chromatographic column for realizing baseline separation of xylene isomers comprises the following steps:
1) preparing a hierarchical pore UiO-66 nano material: weigh 45.00mg of ZrCl 4 Dissolving the above-mentioned raw materials in 5mL of N, N-dimethylformamide, dissolving 50.00mg of terephthalic acid in 5mL of N, N-dimethylformamide, and adding ZrCl 4 The solution was mixed with terephthalic acid solution, 0.5mL trifluoroacetic acid was added and mixed by ultrasound. The resulting mixture was transferred to a 20 mL-volume upright glass vial and reacted at 120 ℃ for 72 hours. After cooling to room temperature, centrifugally washing the mixture for three times by using N, N-dimethylformamide to obtain a final product;
2) preparing a capillary chromatographic column with the inner wall coated with a hierarchical pore material: ultrasonically dispersing 2mg of the prepared material in 1mL of methanol, pushing the material into a pretreated capillary chromatographic column at a constant speed of 4.5mL/h by using an injection pump, heating the capillary column to 250 ℃ by a program of 5 ℃/min in a nitrogen atmosphere after the material is injected, and keeping the temperature for 2h to obtain the capillary gas chromatographic column.
Example 9
A preparation method of a gas chromatographic column for realizing baseline separation of xylene isomers comprises the following steps:
1) preparing a hierarchical pore UiO-66 nano material: weigh 45.00mg of ZrCl 4 Dissolving in 5mL of N, N-dimethylformamide, dissolving 50.00mg of terephthalic acid in 5mL of N, N-dimethylformamide, and mixing the obtained ZrCl 4 The solution was mixed with terephthalic acid solution, 0.5mL trifluoroacetic acid was added and mixed by ultrasound. The resulting mixture was transferred to a 20 mL-volume upright glass vial and reacted at 120 ℃ for 72 hours. After cooling to room temperature, centrifugally washing the mixture for three times by using N, N-dimethylformamide to obtain a final product;
2) preparing a capillary chromatographic column with the inner wall coated with a hierarchical pore material: ultrasonically dispersing 2mg of the prepared material in 1mL of methanol, pushing the material into a pretreated capillary chromatographic column at a constant speed of 4.5mL/h by using an injection pump, heating the capillary column to 250 ℃ by a program of 10 ℃/min in a nitrogen atmosphere after the material is injected, and keeping the temperature for 4h to obtain the capillary gas chromatographic column.
Example 10
A preparation method of a gas chromatographic column for realizing baseline separation of xylene isomers comprises the following steps:
1) preparing a hierarchical pore UiO-66 nano material: weigh 45.00mg of ZrCl 4 Dissolving the above-mentioned raw materials in 5mL of N, N-dimethylformamide, dissolving 50.00mg of terephthalic acid in 5mL of N, N-dimethylformamide, and adding ZrCl 4 The solution was mixed with terephthalic acid solution, 0.5mL trifluoroacetic acid was added and mixed by ultrasound. The resulting mixture was transferred to a 20 mL-volume upright glass vial and reacted at 120 ℃ for 72 hours. After cooling to room temperature, the reaction mixture was separated from N, N-dimethylformamideWashing with heart for three times to obtain final product;
2) preparing a capillary chromatographic column with the inner wall coated with a hierarchical pore material: ultrasonically dispersing 2mg of the prepared material in 1mL of methanol, pushing the material into a pretreated capillary chromatographic column at a constant speed of 5mL/h by using an injection pump, heating the capillary column to 250 ℃ by a program of 5 ℃/min in a nitrogen atmosphere after the material is injected, and keeping the temperature for 6h to obtain the capillary gas chromatographic column.
Example 11
A preparation method of a gas chromatographic column for realizing baseline separation of xylene isomers comprises the following steps:
1) preparing a hierarchical pore UiO-66 nano material: weigh 45.30mg of ZrCl 4 Dissolving the above-mentioned raw materials in 5mL of N, N-dimethylformamide, dissolving 50.90mg of terephthalic acid in 5mL of N, N-dimethylformamide, and adding ZrCl 4 The solution was mixed with terephthalic acid solution, 0.5mL trifluoroacetic acid was added and mixed by sonication. The resulting mixture was transferred to a 20 mL-volume upright glass vial and reacted at 120 ℃ for 72 hours. Cooling to room temperature, and centrifuging and washing with N, N-dimethylformamide for three times to obtain a final product;
2) preparing a capillary chromatographic column with the inner wall coated with a hierarchical pore material: ultrasonically dispersing 2.3mg of the prepared material in 1mL of methanol, pushing the material into a pretreated capillary chromatographic column at a constant speed of 3.5mL/h by using an injection pump, heating the capillary column to 250 ℃ at a program of 10 ℃/min in a nitrogen atmosphere after the material is injected, and carrying out heat treatment, and keeping the temperature for 8h to obtain the capillary gas chromatographic column.
The capillary column and the stationary phase hierarchical pore nanometer material prepared by the embodiment are physically characterized by adopting the paths of SEM, TGA and the like. Cross-sectional SEM images of the column (fig. 1, 2) show that the multi-pore nanoparticles are uniformly embedded in the inner wall of the capillary column. From the SEM (figure 3) and TEM (figure 4) of the stationary phase hierarchical pore nano material, the size of the material is uniform, and the material is a nano-scale three-dimensional particle. The TGA profile (fig. 5) shows that the stationary phase nanomaterial is stable at higher temperatures, with a calculated defect number of 2.79. ByAs can be seen from the nitrogen adsorption spectrum of FIG. 6, the material has large specific surface area, high porosity and a BET specific surface area value of 835.86m 2 The adsorption capacity is strong. According to the pore size distribution spectrogram (figure 7) of the material, the sample has rich pore channels and is mixed with micropores with different pore size grades. FIG. 8 is a gas chromatogram obtained from the separation of a mixture of p-xylene and ethylbenzene using a capillary gas chromatography column prepared in example 3, which achieves the highest separation reported to date, with a meta/para separation as high as 15.2. FIG. 9 is a gas chromatogram of a p-chlorotoluene mixture separated by a capillary gas chromatography column prepared in example 5, with a m/p separation degree as high as 10.62. FIG. 10 is a gas chromatogram obtained by separating a p-dichlorobenzene mixture by using a capillary gas chromatography column prepared in example 6, and the degree of separation m/p is 11.20. The capillary column not only realizes extremely high separation degree on the benzene isomers, but also has extremely excellent separation capability on alkane mixtures. FIG. 11 is a gas chromatogram obtained by separating a mixture of linear paraffins from C6 to C10 using a capillary gas chromatography column prepared in example 4. FIG. 12 is a gas chromatogram obtained from the separation of a mixture of hexane isomers by means of a capillary gas chromatography column prepared in example 2, with a degree of separation of 3-methylpentane/n-hexane as high as 46.38. FIG. 13 is a gas chromatogram obtained by separating an octane isomer mixture using a capillary gas chromatography column prepared in example 8, and the degree of separation of 2, 4-dimethylhexane/n-octane was 7.01. FIG. 14 is a gas chromatogram obtained by separating a decane isomer mixture by means of the capillary gas chromatography column prepared in example 10, and the degree of separation of 3, 3-dimethyloctane/n-decane was 6.61. The results show that the capillary column has good application prospect for separating the isomer.
TABLE 1 separation of several benzene isomers by different capillary columns
| Xylene isomers | Isomers of chlorotoluene | Dichlorobenzene isomers | |
| The UiO-66 capillary column | 15.20 | 10.62 | 11.20 |
| Commercial pillar VF-WAXMS | 0.47 | 0 | 1.32 |
| Commercial column HP-5MS | 0 | 0.62 | 0.93 |
Claims (9)
1. A capillary gas chromatographic column for realizing xylene isomer baseline separation is characterized in that a fixed phase of the capillary gas chromatographic column is a nano material with a hierarchical pore structure, and nano particles are uniformly embedded in the inner wall of the capillary column.
2. The method for preparing a capillary column for effecting baseline separation of xylene isomers according to claim 1, comprising the steps of:
(1) synthesizing a hierarchical porous nano material as a stationary phase: ZrCl with a certain concentration is prepared 4 Mixing the solution with terephthalic acid solution, adding a certain amount of trifluoroacetic acid, and uniformly mixingReacting at a room temperature to obtain a white UiO-66 nano material, cooling, and then centrifugally washing and drying to obtain a hierarchical pore nano material;
(2) preparing a capillary gas chromatographic column with the inner wall coated with a hierarchical pore material: ultrasonically dispersing the hierarchical porous nano material obtained in the step (1) in an organic solvent, pushing the hierarchical porous nano material into a pretreated capillary chromatographic column at a constant speed by using an injection pump, dynamically coating the capillary chromatographic column on the inner wall of the capillary chromatographic column, then carrying out programmed heating and aging treatment on the capillary column in an inert atmosphere, and cooling to room temperature to obtain the capillary gas chromatographic column.
3. The method of claim 2, wherein the ZrCl is formed in step (1) 4 The solvents of the solution and the terephthalic acid solution are both N, N-dimethylformamide.
4. The method of claim 2, wherein the ZrCl is formed in step (1) 4 ZrCl in solution 4 The concentration of (b) is 8mg/mL to 11 mg/mL.
5. The method for preparing a capillary gas chromatography column for realizing baseline separation of xylene isomers according to claim 2, wherein the concentration of the terephthalic acid solution in the step (1) is 8mg/mL to 10 mg/mL.
6. The method for preparing a capillary gas chromatography column for realizing baseline separation of xylene isomers according to claim 2, wherein the pretreatment of the capillary gas chromatography column in the step (2) is performed by silanizing the inner wall of the capillary column with APTES and then keeping the inner wall at 120 ℃ for 2-5 h.
7. The method for preparing a capillary gas chromatographic column as claimed in claim 2, wherein the inert atmosphere in the step (2) is one or more of nitrogen, helium or argon mixed in any proportion.
8. The method for preparing a capillary gas chromatographic column as claimed in claim 2, wherein the specific manner of the programmed temperature-rising aging treatment in the step (2) is as follows: the initial temperature is 20-50 ℃, the temperature is raised to 250 ℃ at the speed of 2-10 ℃/min, and the temperature is kept for 2-8 h.
9. Use of a capillary gas chromatography column for effecting baseline separation of xylene isomers, according to claim 1, for separating other isomers, characterized in that said isomers are chlorotoluene isomers, dichlorobenzene isomers, hexane isomers, octane isomers or decane isomers.
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| CN116351405A (en) * | 2023-04-18 | 2023-06-30 | 大连中汇达科学仪器有限公司 | Gas-phase capillary column using UiO-66 as adsorbent and manufacturing method and application thereof |
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| CN109464998A (en) * | 2018-12-18 | 2019-03-15 | 南京师范大学 | Capillary gas chromatographic column and its preparation method and application based on two-dimensional metallic organic backbone nanometer sheet |
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| CN111821960A (en) * | 2020-07-24 | 2020-10-27 | 北京工商大学 | Liquid chromatography stationary phase based on metal organic framework composite material and preparation method thereof |
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