阅读说明：本技术 一种用于便携式绝缘油色谱分析仪的微填充柱及其制备方法与应用 (Micro-filling column for portable insulating oil chromatographic analyzer and preparation method and application thereof ) 是由 李文琦 连鸿松 郑东升 赖永华 刘慧鑫 郭志斌 刘旭 王国库 张远闯 于 2019-11-13 设计创作，主要内容包括：本发明涉及一种用于便携式绝缘油色谱分析仪的微填充柱及其制备方法与应用。一套色谱柱管包括第一色谱柱柱长为2.5m,第二色谱柱柱长为1m；第三色谱柱柱长0.2m,所述第一、第二色谱柱并联后和第三色谱柱串联使用；第一、第二色谱柱采用外径1.59mm,内径1.02mm不锈钢色谱柱管。第三色谱柱采用外径3mm内径2mm聚四氟乙烯管；第一色谱柱内部担体为GDX502和Hayesep N 质量比例为1:1 混合填充,采用100～120目担体。第二色谱柱内部采用80～100目Unibeads C和100～120目GDX502串联填充,先填充Unibeads C,后填充GDX502填充长度各一半。第三色谱柱内部填充硅烷化白色101载体。本发明的微填充色谱柱比传统填充柱的体积缩小一半,能有效的减少了仪器的整体体积,同时出峰速度比传统填充柱提高一倍。(The invention relates to a micro-filling column for a portable insulating oil chromatographic analyzer and a preparation method and application thereof. The set of chromatographic column tubes comprises a first chromatographic column with the length of 2.5m and a second chromatographic column with the length of 1 m; the length of the third chromatographic column is 0.2m, and the first chromatographic column and the second chromatographic column are connected in parallel and then are connected in series with the third chromatographic column for use; the first chromatographic column and the second chromatographic column adopt stainless steel chromatographic column tubes with the outer diameter of 1.59mm and the inner diameter of 1.02 mm. The third chromatographic column adopts a polytetrafluoroethylene tube with the outer diameter of 3mm and the inner diameter of 2 mm; the inner support of the first chromatographic column is formed by mixing and filling GDX502 and Hayesep N in a mass ratio of 1:1, and a 100-120-mesh support is adopted. And (3) serially filling 80-100-mesh Unibeads C and 100-120-mesh GDX502 in the second chromatographic column, wherein the Unibeads C are filled firstly, and then half of the GDX502 is filled. The third chromatographic column is filled with silanized white 101 carrier. Compared with the traditional packed column, the volume of the micro packed chromatographic column is reduced by half, the whole volume of the instrument can be effectively reduced, and the peak output speed is doubled.)

1. The utility model provides a little packing post for portable insulating oil chromatographic analyzer which characterized in that: comprises a set of chromatographic column tubes, wherein the set of chromatographic column tubes comprises a first chromatographic column tube, and the column length is 2.5 m; a second chromatographic column tube, the column length is 1 m; a third chromatographic column tube, the column length is 0.2 m; and the first chromatographic column tube and the second chromatographic column tube are connected in parallel and then are connected in series with the third chromatographic column tube.

2. The micro-packed column for a portable insulating oil chromatograph according to claim 1, wherein: the first chromatographic column tube and the second chromatographic column tube are stainless steel chromatographic column tubes subjected to surface inert treatment, and the inner diameter of the first chromatographic column tube and the inner diameter of the second chromatographic column tube are 0.8-1.2 mm; the length is 1 m-3 m.

3. The micro-packed column for a portable insulating oil chromatograph according to claim 1, wherein: and the third chromatographic column tube adopts a polytetrafluoroethylene tube with the outer diameter of 3mm and the inner diameter of 2mm as the chromatographic column tube.

4. A method for preparing a micro-packed column for a portable insulating oil chromatograph according to any one of claims 1 to 3, comprising: the method comprises the following steps:

step S1: coiling the first chromatographic column tube and the second chromatographic column tube into a spiral shape with the diameter of 10 cm;

step S2: respectively introducing 100mL/min high-purity nitrogen into the first chromatographic column tube and the second chromatographic column tube, purging for 5min, and continuously oscillating by using a vibrating rod in the purging process to remove mechanical impurities in the pipeline;

step S3: sleeving a signboard at a position 10cm away from the outlet of the first chromatographic column tube and the second chromatographic column tube to serve as a mark, filling silanized glass silk floss with the length of 5mm, and filling a steel wire with the outer diameter of 0.8mm into the first chromatographic column tube and the second chromatographic column tube to the depth of 15 mm; cutting a 316L stainless steel mesh grid of 200 meshes into strips with the width of 5mm, rolling the strips into stainless steel wire mesh rolls with the outer diameter of about 0.9mm, respectively plugging the stainless steel wire mesh rolls into the outlets of the first chromatographic column and the second chromatographic column, and plugging steel wires into the stainless steel wire mesh rolls with the depth of 5mm from the outlets; sleeving a signboard at a position 5cm away from an outlet of the third chromatographic column tube to make an outlet mark, cutting the third chromatographic column tube into strips with the width of 10mm by using a 120-mesh 316 stainless steel woven net, rolling the strips into steel wire rolls with the diameter of 2mm, and filling the steel wire rolls into the third chromatographic column tube, wherein the depth of the third chromatographic column tube is 20mm away from the outlet; then plugging a stainless steel liner tube with the outer diameter of 2mm and the length of 20 mm;

step S4: preparing a supporter of the first chromatographic column: respectively weighing 0.25g of GDX502 and HayesepN by a precision balance according to the mass ratio of 1:1, putting into a beaker for mixing; adding 2mL of acetone into the beaker, and fully stirring and uniformly mixing the acetone with a small glass rod for later use; the acetone is added to reduce the adsorption of the supporter during filling;

step S5: preparing a supporter for carrying out a second chromatographic column: firstly weighing 0.25g of Unibeads C carrier, and then weighing 0.1g of GDX502 carrier for later use;

step S6: packing preparation for the third chromatography column was performed: weighing 0.2g of silanized white 101 supporter for later use;

step S7: filling a first chromatographic column, namely connecting an inlet of a first chromatographic column tube into the lower part of a sealing funnel, unscrewing an upper cover of the sealing funnel, transferring the carrier weighed and mixed in the step S4 to the sealing funnel by using a measuring spoon, and screwing down the upper cover of the sealing funnel; opening a nitrogen steel valve bottle for ventilation, adjusting the output pressure of a pressure reducing valve of the nitrogen steel bottle to be 0.25Mpa, gradually opening a flow stabilizing valve to a rotor flowmeter to display the flow to be 10 mL/min; vibrating the first chromatographic column tube and the sealing funnel by using a vibrating rod; when the material is not discharged any more, the pressure reducing valve is closed to output for 30 minutes, and then the steel cylinder valve is opened repeatedly and the vibration is carried out until the supporter in the sealing funnel is not reduced any more; completing the loading of the first carrier;

step S8: closing the pressure reducing valve output of the nitrogen steel cylinder, disconnecting the sealing funnel and the chromatographic column tube, slightly inclining the inlet of the first chromatographic column downwards, and pouring out the supporter with the column length of about 1.5cm by slight oscillation; filling the silanized glass wool and the stainless steel wire coil in sequence according to the step S3 to make an entrance mark; completing the packing of the first chromatographic column;

step S9: filling a second chromatographic column, namely connecting an inlet of a tube of the second chromatographic column to the lower part of the sealing funnel, unscrewing an upper cover of the sealing funnel, adding the Unibeads C carrier weighed in the step S5 into the sealing funnel by using a measuring spoon, and screwing down the upper cover of the sealing funnel; opening a switch of the nitrogen steel cylinder for ventilation, adjusting the output pressure of a pressure reducing valve of the nitrogen steel cylinder to be 0.25Mpa, gradually opening a flow stabilizing valve to a rotor flowmeter to display the flow to be 15 mL/min; vibrating the chromatographic column tube and the sealing funnel by using a vibrating spear; after the supporter completely enters the column tube, closing the pressure output of the pressure reducing valve, unscrewing the upper cover of the sealing funnel, and putting the weighed GD502 supporter; the pressure output of the pressure reducing valve of the steel cylinder is opened again, the chromatographic column and the sealing funnel are vibrated until the supporter is not reduced obviously any more, and the filling of the second kind of supporter is completed;

step S10: closing the pressure reducing valve output of the nitrogen steel cylinder, disconnecting the sealing funnel and the second chromatographic column tube, slightly inclining the inlet of the second chromatographic column downwards, and pouring out the supporter with the column length of 1.5cm through slight oscillation; filling the silanized glass wool and the stainless steel wire coil in sequence according to the step S3, and making an entrance mark; completing packing of the second chromatography column;

step S11: packing of the third chromatographic column: replacing the joint corresponding to the lower part of the sealing funnel and the outer diameter of the third chromatographic column; adding the supporter prepared in the step S6 into a sealing funnel, and screwing down a sealing upper cover; opening a switch of the nitrogen steel cylinder for ventilation, adjusting the output pressure of a pressure reducing valve of the nitrogen steel cylinder to be 0.25Mpa, gradually opening a flow stabilizing valve to a rotor flowmeter to display the flow to be 40 mL/min; vibrating the chromatographic column tube and the sealing funnel by using a vibrating spear; completing the filling process of the third chromatographic column after the supporter completely enters the column tube;

step S12: closing the pressure reducing valve output of the nitrogen steel cylinder, disconnecting the sealing funnel and the chromatographic column tube, slightly inclining the inlet of the third chromatographic column downwards, and lightly shaking to pour out a supporter with the column length of 3 cm; according to the method for plugging the outlet of the third chromatographic column in the step S3, sequentially filling a stainless steel wire coil and a liner tube, and making an inlet mark to finish the filling of the third chromatographic column;

step S13: aging the first and second column, connecting the chromatographic column into the aging box, and introducing 99.999% high-purity N into the column inlet₂Introducing air at 50 ℃ for 1 hour at the flow rate of 10-15 mL/min, heating to 150 ℃ at the flow rate of 2 ℃/min, and aging for 8 hours;

aging the third chromatographic column, connecting the chromatographic column into a chromatographic column aging box, and introducing 99.999% high-purity N into a column inlet₂The flow rate is 40-60 mL/min, and aeration is carried out at 80 ℃ for 4 hours.

5. The use of the micro-packed column for a portable insulating oil chromatograph according to claim 1, wherein: the first chromatographic column tube and the second chromatographic column tube are connected in parallel and then are connected in series with the third chromatographic column tube for use, and the third chromatographic column tube is a protective column and is used for adsorbing trace transformer oil entering an instrument in an analysis process and can be replaced regularly.

Technical Field

The invention relates to the field of electric insulating oil chromatographic analysis, in particular to a micro-packed column for a portable insulating oil chromatographic analyzer and a preparation method and application thereof.

Background

The chromatographic analysis of transformer insulating oil is an indispensable means for monitoring the faults of oil-filled equipment in the power industry. Most conventional packed columns or capillary columns are currently used in the chromatographic analysis of insulating oils to perform the analysis of gas concentrations in insulating oil samples. A packed column commonly used for packed column analysis methods was packed using a stainless steel tube having an outer diameter of 3mm and an inner diameter of 2 mm. Usually, a one-needle sample injection mode is adopted, and a double-column parallel gas circuit flow or a single-column gas circuit flow can be formed. At present, a double-column parallel gas circuit is commonly adopted, and one column in the process is used for analyzing carbon monoxide and carbon dioxide. The other column was used for hydrocarbon analysis.

In addition, in a common single-column analysis process, carbon monoxide and carbon dioxide are easy to influence the peak appearance of hydrocarbon components, and meanwhile, hydrocarbon substances are adsorbed differently when passing through a converter, so that the analysis result of the hydrocarbon is influenced. The peak-out speed is not convenient to further shorten, and is not suitable for portable instruments.

The chromatographic analysis of insulating oil can also be realized by adopting a capillary tube, and the separation of different components is realized by generally adopting a molecular sieve column and an alumina column which are connected in series and switching through a six-way valve. The capillary column has high cost and difficult preparation. The column has small capacity and is easily polluted by insulating oil. The required column length is long, and the whole volume is large, so that the column is not suitable for portable instruments.

When conventional packed columns are used in portable chromatography instruments, there is a large amount of carrier gas. The chromatographic column has large volume, is not suitable for portable instruments, and has the problems of low analysis speed, large amount of samples required by analysis and the like.

Disclosure of Invention

In view of the above, the present invention provides a micro-packed column for a portable insulating oil chromatograph, and a preparation method and an application thereof, which can use a smaller chromatographic column box and is more suitable for portable chromatography, thereby effectively reducing the overall volume of the instrument, increasing the analysis speed, and improving the overall working efficiency.

The invention is realized by adopting the following scheme: a micro-packed column for a portable insulating oil chromatographic analyzer comprises a set of chromatographic column tubes, wherein the set of chromatographic column tubes comprises a first chromatographic column tube, and the column length is 2.5 m; a second chromatographic column tube, the column length is 1 m; a third chromatographic column tube, the column length is 0.2 m; and the first chromatographic column tube and the second chromatographic column tube are connected in parallel and then are connected in series with the third chromatographic column tube.

Furthermore, the first chromatographic column tube and the second chromatographic column tube are stainless steel chromatographic column tubes subjected to surface inert treatment, and the inner diameter of the first chromatographic column tube and the inner diameter of the second chromatographic column tube are 0.8-1.2 mm; the length is 1 m-3 m.

Furthermore, the third chromatographic column tube adopts a polytetrafluoroethylene tube with the outer diameter of 3mm and the inner diameter of 2mm as the chromatographic column tube.

Further, the invention also provides a preparation method of the micro-filling column for the portable insulating oil chromatographic analyzer, which comprises the following steps:

step S1: coiling the first chromatographic column tube and the second chromatographic column tube into a spiral shape with the diameter of 10 cm; the chromatographic column tubes are stainless steel chromatographic column tubes with inert-treated surfaces, the outer diameters of the two chromatographic column tubes are both 1.59mm, and the inner diameters of the two chromatographic column tubes are both 1.02 mm;

step S1: coiling the first chromatographic column tube and the second chromatographic column tube into a spiral shape with the diameter of 10 cm;

step S2: respectively introducing 100mL/min high-purity nitrogen into the first chromatographic column tube and the second chromatographic column tube, purging for 5min, and continuously oscillating by using a vibrating rod in the purging process to remove mechanical impurities in the pipeline;

step S3: sleeving a signboard at a position 10cm away from the outlet of the first chromatographic column tube and the second chromatographic column tube to serve as a mark, filling silanized glass silk floss with the length of 5mm, and filling a steel wire with the outer diameter of 0.8mm into the first chromatographic column tube and the second chromatographic column tube to the depth of 15 mm; cutting a 316L stainless steel mesh grid of 200 meshes into strips with the width of 5mm, rolling the strips into stainless steel wire mesh rolls with the outer diameter of about 0.9mm, respectively plugging the stainless steel wire mesh rolls into the outlets of the first chromatographic column and the second chromatographic column, and plugging steel wires into the stainless steel wire mesh rolls with the depth of 5mm from the outlets; sleeving a signboard at a position 5cm away from an outlet of the third chromatographic column tube to make an outlet mark, cutting the third chromatographic column tube into strips with the width of 10mm by using a 120-mesh 316 stainless steel woven net, rolling the strips into steel wire rolls with the diameter of 2mm, and filling the steel wire rolls into the third chromatographic column tube, wherein the depth of the third chromatographic column tube is 20mm away from the outlet; then plugging a stainless steel liner tube with the outer diameter of 2mm and the length of 20 mm;

step S4: preparing a supporter of the first chromatographic column: respectively weighing 0.25g of GDX502 and HayesepN by a precision balance according to the mass ratio of 1:1, putting into a beaker for mixing; adding 2mL of acetone into the beaker, and fully stirring and uniformly mixing the acetone with a small glass rod for later use; the acetone is added to reduce the adsorption of the supporter during filling;

step S5: preparing a supporter for carrying out a second chromatographic column: firstly weighing 0.25g of Unibeads C carrier, and then weighing 0.1g of GDX502 carrier for later use;

step S6: packing preparation for the third chromatography column was performed: weighing 0.2g of silanized white 101 supporter for later use;

step S7: filling a first chromatographic column, namely connecting an inlet of a first chromatographic column tube into the lower part of a sealing funnel, unscrewing an upper cover of the sealing funnel, transferring the carrier weighed and mixed in the step S4 to the sealing funnel by using a measuring spoon, and screwing down the upper cover of the sealing funnel; opening a nitrogen steel valve bottle for ventilation, adjusting the output pressure of a pressure reducing valve of the nitrogen steel bottle to be 0.25Mpa, gradually opening a flow stabilizing valve to a rotor flowmeter to display the flow to be 10 mL/min; vibrating the first chromatographic column tube and the sealing funnel by using a vibrating rod; when the material is not discharged any more, the pressure reducing valve is closed to output for 30 minutes, and then the steel cylinder valve is opened repeatedly and the vibration is carried out until the supporter in the sealing funnel is not reduced any more; completing the loading of the first carrier;

step S8: closing the pressure reducing valve output of the nitrogen steel cylinder, disconnecting the sealing funnel and the chromatographic column tube, slightly inclining the inlet of the first chromatographic column downwards, and pouring out the supporter with the column length of about 1.5cm by slight oscillation; filling the silanized glass wool and the stainless steel wire coil in sequence according to the step S3 to make an entrance mark; completing the packing of the first chromatographic column;

step S9: filling a second chromatographic column, namely connecting an inlet of a tube of the second chromatographic column to the lower part of the sealing funnel, unscrewing an upper cover of the sealing funnel, adding the Unibeads C carrier weighed in the step S5 into the sealing funnel by using a measuring spoon, and screwing down the upper cover of the sealing funnel; opening a switch of the nitrogen steel cylinder for ventilation, adjusting the output pressure of a pressure reducing valve of the nitrogen steel cylinder to be 0.25Mpa, gradually opening a flow stabilizing valve to a rotor flowmeter to display the flow to be 15 mL/min; vibrating the chromatographic column tube and the sealing funnel by using a vibrating spear; after the supporter completely enters the column tube, closing the pressure output of the pressure reducing valve, unscrewing the upper cover of the sealing funnel, and putting the weighed GD502 supporter; the pressure output of the pressure reducing valve of the steel cylinder is opened again, the chromatographic column and the sealing funnel are vibrated until the supporter is not reduced obviously any more, and the filling of the second kind of supporter is completed;

step S10: closing the pressure reducing valve output of the nitrogen steel cylinder, disconnecting the sealing funnel and the second chromatographic column tube, slightly inclining the inlet of the second chromatographic column downwards, and pouring out the supporter with the column length of 1.5cm through slight oscillation; filling the silanized glass wool and the stainless steel wire coil in sequence according to the step S3, and making an entrance mark; completing packing of the second chromatography column;

step S11: packing of the third chromatographic column: replacing the joint corresponding to the lower part of the sealing funnel and the outer diameter of the third chromatographic column; adding the supporter prepared in the step S6 into a sealing funnel, and screwing down a sealing upper cover; opening a switch of the nitrogen steel cylinder for ventilation, adjusting the output pressure of a pressure reducing valve of the nitrogen steel cylinder to be 0.25Mpa, gradually opening a flow stabilizing valve to a rotor flowmeter to display the flow to be 40 mL/min; vibrating the chromatographic column tube and the sealing funnel by using a vibrating spear; completing the filling process of the third chromatographic column after the supporter completely enters the column tube;

step S12: closing the pressure reducing valve output of the nitrogen steel cylinder, disconnecting the sealing funnel and the chromatographic column tube, slightly inclining the inlet of the third chromatographic column downwards, and lightly shaking to pour out a supporter with the column length of 3 cm; and (5) according to the method for plugging the outlet of the third chromatographic column in the step S3, sequentially filling a stainless steel wire coil and a liner tube, and making an inlet mark to finish the filling of the third chromatographic column.

Step S13: aging the first and second column, connecting the chromatographic column into the aging box, and introducing 99.999% high-purity N into the column inlet₂The flow rate is 10-15 mL/min, the air is introduced at 50 ℃ for 1 hour, the temperature is raised to 150 ℃ according to the speed of 2 ℃/min, and the aging is carried out for 8 hours. Aging the third chromatographic column, connecting the chromatographic column into a chromatographic column aging box, and introducing 99.999% high-purity N into a column inlet₂The flow rate is 40-60 mL/min, and aeration is carried out at 80 ℃ for 4 hours.

Furthermore, the micro-packed column for the portable insulating oil chromatographic analyzer can prolong the service time of carrier gas of the portable insulating oil chromatographic analyzer; the first chromatographic column tube and the second chromatographic column tube are connected in parallel and then are connected in series with the third chromatographic column tube for use, and the third chromatographic column tube is a protective column and is used for adsorbing trace transformer oil entering an instrument in an analysis process and can be replaced regularly.

Compared with the prior art, the invention has the following beneficial effects:

(1) the invention adopts the micro-packed column with smaller inner diameter, so the using amount of carrier gas is less, the flow rate of 20mL/min after the double columns are connected in parallel is reduced by half compared with the flow rate of the conventional packed column, and the using time of the carrier gas of the portable insulating oil chromatographic analyzer is prolonged.

(2) The column efficiency of the micro-packed chromatographic column adopted by the invention is higher than that of the traditional packed column with the inner diameter, the time for analyzing the peak of 7 components is shortened by half compared with the traditional packed column, and the working efficiency is improved.

(3) The chromatographic column has small volume, is reduced by half compared with the traditional packed column, can use a smaller column box, is more suitable for portable chromatography, and effectively reduces the whole volume of an instrument. While reducing the power consumption required to heat the chromatograph. The overall power consumption of the instrument is reduced.

Drawings

Fig. 1 is a schematic diagram of a filling process of a micro-packed column according to an embodiment of the present invention, in which 1 is a nitrogen cylinder, 2 is a pressure reducing valve of the nitrogen cylinder, 3 is a flow stabilizing valve, 4 is a rotor flow meter, 5 is a sealing funnel, and 6 is a chromatographic column.

Fig. 2 is a schematic structural diagram of a sealing funnel of a micro-packed column according to an embodiment of the present invention, in which 51 is an upper cover, 52 is a sealing ring, 53 is an air inlet, 54 is a funnel body, 55 is a sealing gasket, 56 is an interchangeable joint, and 57 is a chromatography column.

Fig. 3 is a flow chart of the gas path using process of the micro-packed column according to the embodiment of the present invention.

FIG. 4 is a peak-appearing spectrum of the micro-packed column according to the embodiment of the present invention.

Detailed Description

The invention is further explained below with reference to the drawings and the embodiments.

As shown in fig. 1 and 2, the present embodiment provides a micro-packed column for a portable insulating oil chromatograph, comprising a set of chromatographic column tubes, wherein the set of chromatographic column tubes comprises a first chromatographic column tube, and the column length is 2.5 m; a second chromatographic column tube, the column length is 1 m; a third chromatographic column tube, the column length is 0.2 m; and the first chromatographic column tube and the second chromatographic column tube are connected in parallel and then are connected in series with the third chromatographic column tube.

In the embodiment, the first chromatographic column tube and the second chromatographic column tube are stainless steel chromatographic column tubes subjected to surface inert treatment, and the inner diameter of the first chromatographic column tube and the inner diameter of the second chromatographic column tube are 0.8-1.2 mm; the length is 1 m-3 m.

In this embodiment, the third chromatography column tube adopts a polytetrafluoroethylene tube with an outer diameter of 3mm and an inner diameter of 2mm as the chromatography column tube.

Preferably, the present application provides a method for preparing a micro-packed column for a portable insulating oil chromatograph, comprising the following steps:

step S1: coiling the first chromatographic column tube and the second chromatographic column tube into a spiral shape with the diameter of 10 cm;

step S2: respectively introducing 100mL/min high-purity nitrogen into the first chromatographic column tube and the second chromatographic column tube, purging for 5min, and continuously oscillating by using a vibrating rod in the purging process to remove mechanical impurities in the pipeline;

step S3: sleeving a signboard at a position 10cm away from the outlet of the first chromatographic column tube and the second chromatographic column tube to serve as a mark, filling silanized glass silk floss with the length of 5mm, and filling a steel wire with the outer diameter of 0.8mm into the first chromatographic column tube and the second chromatographic column tube to the depth of 15 mm; cutting a 316L stainless steel mesh grid of 200 meshes into strips with the width of 5mm, rolling the strips into stainless steel wire mesh rolls with the outer diameter of about 0.9mm, respectively plugging the stainless steel wire mesh rolls into the outlets of the first chromatographic column and the second chromatographic column, and plugging steel wires into the stainless steel wire mesh rolls with the depth of 5mm from the outlets; sleeving a signboard at a position 5cm away from an outlet of the third chromatographic column tube to make an outlet mark, cutting the third chromatographic column tube into strips with the width of 10mm by using a 120-mesh 316 stainless steel woven net, rolling the strips into steel wire rolls with the diameter of 2mm, and filling the steel wire rolls into the third chromatographic column tube, wherein the depth of the third chromatographic column tube is 20mm away from the outlet; then plugging a stainless steel liner tube with the outer diameter of 2mm and the length of 20 mm;

step S4: preparing a supporter of the first chromatographic column: respectively weighing 0.25g of GDX502 and HayesepN by a precision balance according to the mass ratio of 1:1, putting into a beaker for mixing; adding 2mL of acetone into the beaker, and fully stirring and uniformly mixing the acetone with a small glass rod for later use; the acetone is added to reduce the adsorption of the supporter during filling;

step S5: preparing a supporter for carrying out a second chromatographic column: firstly weighing 0.25g of Unibeads C carrier, and then weighing 0.1g of GDX502 carrier for later use;

step S6: packing preparation for the third chromatography column was performed: weighing 0.2g of silanized white 101 supporter for later use;

step S7: filling a first chromatographic column, namely connecting an inlet of a first chromatographic column tube into the lower part of a sealing funnel, unscrewing an upper cover of the sealing funnel, transferring the carrier weighed and mixed in the step S4 to the sealing funnel by using a measuring spoon, and screwing down the upper cover of the sealing funnel; opening a nitrogen steel valve bottle for ventilation, adjusting the output pressure of a pressure reducing valve of the nitrogen steel bottle to be 0.25Mpa, gradually opening a flow stabilizing valve to a rotor flowmeter to display the flow to be 10 mL/min; vibrating the first chromatographic column tube and the sealing funnel by using a vibrating rod; when the material is not discharged any more, the pressure reducing valve is closed to output for 30 minutes, and then the steel cylinder valve is opened repeatedly and the vibration is carried out until the supporter in the sealing funnel is not reduced any more; completing the loading of the first carrier;

step S8: closing the pressure reducing valve output of the nitrogen steel cylinder, disconnecting the sealing funnel and the chromatographic column tube, slightly inclining the inlet of the first chromatographic column downwards, and pouring out the supporter with the column length of about 1.5cm by slight oscillation; filling the silanized glass wool and the stainless steel wire coil in sequence according to the step S3 to make an entrance mark; completing the packing of the first chromatographic column;

step S9: filling a second chromatographic column, namely connecting an inlet of a tube of the second chromatographic column to the lower part of the sealing funnel, unscrewing an upper cover of the sealing funnel, adding the Unibeads C carrier weighed in the step S5 into the sealing funnel by using a measuring spoon, and screwing down the upper cover of the sealing funnel; opening a switch of the nitrogen steel cylinder for ventilation, adjusting the output pressure of a pressure reducing valve of the nitrogen steel cylinder to be 0.25Mpa, gradually opening a flow stabilizing valve to a rotor flowmeter to display the flow to be 15 mL/min; vibrating the chromatographic column tube and the sealing funnel by using a vibrating spear; after the supporter completely enters the column tube, closing the pressure output of the pressure reducing valve, unscrewing the upper cover of the sealing funnel, and putting the weighed GD502 supporter; the pressure output of the pressure reducing valve of the steel cylinder is opened again, the chromatographic column and the sealing funnel are vibrated until the supporter is not reduced obviously any more, and the filling of the second kind of supporter is completed;

step S10: closing the pressure reducing valve output of the nitrogen steel cylinder, disconnecting the sealing funnel and the second chromatographic column tube, slightly inclining the inlet of the second chromatographic column downwards, and pouring out the supporter with the column length of 1.5cm through slight oscillation; filling the silanized glass wool and the stainless steel wire coil in sequence according to the step S3, and making an entrance mark; completing packing of the second chromatography column;

step S11: packing of the third chromatographic column: replacing the joint corresponding to the lower part of the sealing funnel and the outer diameter of the third chromatographic column; adding the supporter prepared in the step S6 into a sealing funnel, and screwing down a sealing upper cover; opening a switch of the nitrogen steel cylinder for ventilation, adjusting the output pressure of a pressure reducing valve of the nitrogen steel cylinder to be 0.25Mpa, gradually opening a flow stabilizing valve to a rotor flowmeter to display the flow to be 40 mL/min; vibrating the chromatographic column tube and the sealing funnel by using a vibrating spear; completing the filling process of the third chromatographic column after the supporter completely enters the column tube;

step S12: closing the pressure reducing valve output of the nitrogen steel cylinder, disconnecting the sealing funnel and the chromatographic column tube, slightly inclining the inlet of the third chromatographic column downwards, and lightly shaking to pour out a supporter with the column length of 3 cm; and (5) according to the method for plugging the outlet of the third chromatographic column in the step S3, sequentially filling a stainless steel wire coil and a liner tube, and making an inlet mark to finish the filling of the third chromatographic column.

Step S13: aging the first and second column, connecting the chromatographic column into the aging box, and introducing 99.999% high-purity N into the column inlet₂The flow rate is 10-15 mL/min, the air is introduced at 50 ℃ for 1 hour, the temperature is raised to 150 ℃ according to the speed of 2 ℃/min, and the aging is carried out for 8 hours. Aging the third chromatographic column, connecting the chromatographic column into a chromatographic column aging box, and introducing 99.999% high-purity N into a column inlet₂The flow rate is 40-60 mL/min, and aeration is carried out at 80 ℃ for 4 hours.

Preferably, the embodiment also provides an application of the micro-filling column for the portable insulating oil chromatographic analyzer, wherein the micro-filling column for the portable insulating oil chromatographic analyzer is used for prolonging the service time of carrier gas of the portable insulating oil chromatographic analyzer; the first chromatographic column tube and the second chromatographic column tube are connected in parallel and then are connected in series with the third chromatographic column tube for use, and the third chromatographic column tube is a protective column and is used for adsorbing trace transformer oil entering an instrument in an analysis process and can be replaced regularly.

Preferably, in this embodiment, the flow rate ratio of the first chromatographic column to the second chromatographic column is about 6: 4. Controlled by the length and packing density of the column. The matching is done by recording the rotameter flow rate at the completion of the filling.

Preferably, in this embodiment, the following apparatus is used to pack the micro-packed column: comprises a nitrogen steel cylinder 1, a nitrogen pressure reducing valve, a flow stabilizing valve, a rotor flowmeter and a sealing funnel; the outlets of the three chromatographic column tubes are all emptied during filling, the interface of the nitrogen steel cylinder 1 is provided with a nitrogen steel cylinder pressure reducing valve 2, the outlet of the nitrogen steel cylinder pressure reducing valve 2 is connected to a flow stabilizing valve 3, the outlet of the flow stabilizing valve 3 is connected to a sealing funnel 5, and a rotor flow meter 4 is arranged between the sealing funnel 5 and the flow stabilizing valve 3; the inlets of the three chromatographic column tubes during filling are connected with the sealing funnel 5. The sealing funnel 5 comprises an openable upper lid 51 with a sealing ring 52. The funnel body 54 is made of a visible transparent material, and can be made of quartz glass or hard plastic, and the bottom of the funnel body 54 is provided with a replaceable joint 56 which is connected with a sealing gasket 55 and used for matching with chromatographic column tubes with different outer diameters to realize quick connection and sealing.

Preferably, the practical application method of the micro-packed column in this embodiment is as follows:

in the embodiment, the column 1# adopts the column length of 2.5m, the internal carrier is mixed and filled with GDX502+ Hayesep N in the mass ratio of 1:1, and a carrier of 100-120 meshes is adopted. The 2# column is filled with 100-120 mesh GDX502 and 80-100 mesh Unibeads C molecular sieves inside the column with the length of 1m in series. Due to the adoption of the micro-packed column with smaller inner diameter, the column efficiency is higher than that of the conventional packed column. Meanwhile, the use amount of carrier gas is reduced because the inner diameter of the column is small. In order to improve the anti-pollution capability, a third chromatographic column is arranged to be used as a protective column to adsorb trace transformer oil brought in during sample injection. In the present embodiment, the gas path flow shown in fig. 3 is adopted for the micro-packed column, and in the gas path flow, the micro-packed column 1 (1 # column) as the first chromatographic column and the micro-packed column 2 (2 # column) as the second chromatographic column are used in parallel. The two chromatographic columns take the resistance matching into consideration according to the resistance condition of the supporter in the filling process. The split ratio is about 6: 4.

a pressure stabilizing valve 1 is designed at the inlet of the carrier gas, and a flow stabilizing valve and a back pressure valve are connected behind the pressure stabilizing valve. The constant pressure of the sample inlet in the sample introduction process is ensured. A third chromatographic column is arranged between the outlet of the sample inlet and the shunt tee, and the shunt tee can be simultaneously provided with a column 1 and a column 2 in parallel. Column No. 1 is used for analysis of hydrocarbons including methane (CH)₄) Ethylene (C)₂H₄) Ethane (C)₂H₆) Acetylene (C)₂H₂). Column 2 for separating hydrogen (H)₂) Carbon monoxide (CO) and carbon dioxide (CO)₂）。

The outlet of column No. 1 was connected to FID detector 1 for the detection of hydrocarbons (see FID1 spectrum in fig. 4). No. 2 column outlet connected with micro-pool TCD detector for detecting H₂(see TCD spectrum in FIG. 4), followed by the needle valve 1. For correcting the balance of column No. 1 and column No. 2. After-connection for CO and CO₂A Ni catalytic methanation reformer for converting into methane. To facilitate analysis of CO and CO with a FID2 detector₂(see FID2 spectrum in FIG. 4).

To improve FID sensitivity, the peak shape was optimized. A tail blowing gas path is added in the gas path and consists of a pressure stabilizing valve 2, a needle valve 3, a needle valve 4 and the like, in order to save nitrogen carrier gas, air which is relatively easy to obtain is adopted as tail blowing gas, and the flow rate of the tail blowing gas is about 10mL/min per path.

The gas circuit flow is adopted to carry out peak output test by using mixed standard gas. The peak appearance is shown in FIG. 4 and Table 1. The three spectra in fig. 4 were obtained from FID1, FID2, and TCD detectors, respectively.

Tests prove that the analytical sensitivity of a chromatograph adopting the micro-packed column can meet the requirement of GB/T17623.

TABLE 1 micro-packed column data table for peak appearance

Peak height name	Standard gas concentration ppm	Peak height mv	Sensitivity of the probe	Retention time min
					H2	1047	2.472	4.924	0.150
CO	1006	16.806	1.748	0.618
					CO2	3022	15.5	6.29	3.240
CH4	101	29.462	0.0535	0.600
					C2H4	101	39.228	0.04	1.712
C2H6	100	33.508	0.0465	2.005
					C2H2	50.2	13.73	0.056	2.590

The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.