CN104407080B - Portable GC Capillary Column Modules - Google Patents

Abstract

Portable gas chromatography capillary column module of the invention possesses：Capillary column skeleton, circular hole has been axially formed from one end towards the other end；Block, is connected to described one end of the capillary column skeleton；Heater element, is inserted in the circular hole；Capillary column, is wound on the outer surface of the diaphragm；Barrel shrond, the inside configuration capillary column skeleton；Muff, covers on outside the finger-type cylinder being combined into by the barrel shrond and the block.

Description

Portable GC Capillary Column Modules

technical field

The invention relates to the field of gas chromatography analysis and testing, in particular to a portable gas chromatography capillary column module for gas chromatography.

Background technique

Capillary columns are responsible for the separation of mixed substance components in gas chromatography (GC), and are the key components of GC. The separation of substances by the capillary column needs to be carried out at a certain temperature. The heating/cooling rate and temperature uniformity of the chromatographic column are two important indicators of GC, which determine the separation ability and analysis speed of the GC. Therefore, it is necessary to heat the capillary column and temperature control design.

The traditional furnace-type GC is to wind the capillary column into 7-8 inches of coils and hang it in a larger furnace, wrap the furnace with thick (3-5cm) insulation cotton, and heat the inside with a heating wire Air, the fan is used to exert force to make the air flow to heat/dissipate the chromatographic column. Currently, the mainstream desktop heating methods on the market belong to this type. Due to the limitation of the furnace box structure, this type of device has large volume, heavy weight, large heat capacity, large power consumption, and slow heating and cooling speed.

In recent years, portable or modular compact chromatographic column systems have appeared. The heating method of such devices is generally to heat the chromatographic column by heat conduction. For example, U.S. Patent US8043565 and China CN02215114.1 are representatives of thermal pillow heat transfer. This type of device is to cast the heating device on a base with high thermal conductivity. The base is equipped with a cover plate, and the chromatographic column is placed in the groove of the base. In the groove, the base acts as a thermal pillow for conducting heat to the chromatographic column, and the chromatographic column can be operated by opening the upper cover. This type of device reduces the volume and power consumption compared with the furnace box type device. However, the introduction of the base and the cover increases the heat capacity, and the base and the cover are much lower than the temperature rise rate of the heater, thus affecting the temperature rise rate of the chromatographic column. On the other hand, the heating devices respectively affect the temperature uniformity of the groove of the base, It will affect the column separation effect. Low thermal mass (LTM) technology overcomes the defects of thermal pillow heating technology. LTM technology is an invention patent of RVM company (related patent numbers: US5782964, US6209386, US6490852, US6530260). LTM technology is a combination of heating wire, capillary column and temperature sensor. Interwoven on a thin tube that can pass through the coolant, to ensure that the capillary column, the heating wire, and the thin tube are in contact with each other, realizing ultra-fast heating and rapid cooling of the chromatographic column. The thin tube can be coiled into a ring of 2 to 5 inches, which greatly reduces the coiled diameter of the chromatographic column. Agilent acquired RVM in 2008 and converted the patented LTM technology into a portable GC product. In 2012, Agilent made a patent layout of LTM technology in China (Patent No. CN10268842A). Taking the Agilent 222-5532LTM module (SN: US12280712) as an example, the volume is 150mm*153mm*53mm (length*width*height), the power consumption is 300W, the heating rate is 1800°C/min, and the cooling rate is <1min. The pinnacle class GC column module. However, LTM technology also has its drawbacks: (1) The winding method of its capillary column and heating wire is complicated and must be realized by a professional winding device. Choice; (2) The heating wire and the chromatographic column are fixed as one, and the user cannot disassemble it. Once the chromatographic column or the heating wire is damaged, the entire module must be replaced; (3) The LTM module is expensive (one module is about 5,000 US dollars), thus restricting the user's choice of more chromatographic columns; (4) The winding method cannot make the diameter of the chromatographic column disk smaller (2 to 5 inches).

Contents of the invention

The present invention is proposed to solve the problems existing in the above-mentioned prior art, and its purpose is to provide a portable gas chromatography capillary column module, which can ensure the rapid temperature rise and rapid cooling of the chromatographic column under the condition of low power consumption. On the one hand, the size of the chromatographic column module is more compact and portable, and it is easy to replace accessories such as chromatographic columns and heating elements, and has an easy-to-install/detachable insulation cover to facilitate the replacement of internal components. In addition, the modular chromatographic column system is not only It can be interconnected with various injectors and detectors, and the modules can be connected in parallel or in series to expand the application functions of the modules.

In order to achieve the above object, the present invention provides a portable gas chromatography capillary column module, characterized in that it has:

A bobbin-shaped capillary column framework, a circular hole is formed along the axial direction of the capillary column framework from one end to the other end, and the end face of the other end is closed;

a cap connected to the one end of the capillary column skeleton;

a heating device inserted into the circular hole of the capillary column skeleton;

a capillary column tightly wound on the outer surface of the capillary column skeleton; and

a cylindrical shell, the lower end of which is closed and the upper end is open, the capillary column skeleton is arranged in the cylindrical shell coaxially with the cylindrical shell, and the bottom end surface of the cylindrical shell and the capillary A gap is reserved between the bottom end faces of the column skeleton.

In addition, in the portable gas chromatographic capillary column module of the present invention, it is further equipped with: a thermal insulation cover covering the finger-shaped cylinder composed of the cylindrical shell and the cap.

In addition, in the portable gas chromatography capillary column module of the present invention, both ends of the capillary column framework have protruding eaves, and the cap is in the shape of a disc with an external protruding eaves.

In addition, in the portable gas chromatography capillary column module of the present invention, there is also a temperature measuring device arranged on the capillary column skeleton.

In addition, in the portable gas chromatograph capillary column module of the present invention, there is also thermal conductive paste for coupling the gap between the capillary column frame and the heating device.

In addition, in the portable gas chromatography capillary column module of the present invention, there is also a protective film arranged on the outer wall of the capillary column skeleton and between the protruding eaves at the one end and the protruding eaves at the other end, The capillary column is tightly wound on the outer surface of the protective film.

In addition, in the portable gas chromatography capillary column module of the present invention, a sealing ring is provided between the protruding outer eaves of the cap and the upper end of the cylindrical shell, thereby connecting the cylindrical shell and the cap The sealing is to realize the sealing between the cylindrical shell and the skeleton of the capillary column, and a circumferential space surrounding the capillary column is formed between the cylindrical shell and the skeleton of the capillary column.

In addition, in the portable gas chromatography capillary column module of the present invention, at both ends of the circumference diameter of the capillary column frame wound with the capillary column, two heat conduction tubes are arranged along the axial direction of the capillary column frame. The silicone rubber strip, thus, divides the circumferential space into two parts, forming the required cooling air path.

In addition, in the portable gas chromatography capillary column module of the present invention, the cap is provided with a heating device outlet port for leading out the wire of the heating device, a temperature measuring device for leading out the wire of the temperature measuring device An outlet port, a capillary column inlet port connected to one end of the capillary column, a capillary column outlet port connected to the other end of the capillary column, and an inlet nozzle and an outlet port respectively connected to two parts of the circumferential space The mouth is provided with holes corresponding to the above-mentioned ports respectively on the thermal insulation cover.

In addition, in the portable gas chromatography capillary column module of the present invention, the capillary column skeleton is formed of a light alloy material with high thermal conductivity.

In addition, in the portable gas chromatography capillary column module of the present invention, the diameter of the winding part of the capillary column framework is 20mm-80mm, and the height is 20mm-200mm.

In addition, in the portable gas chromatography capillary column module of the present invention, the heating device is a heating rod or a heating film.

In addition, in the portable gas chromatography capillary column module of the present invention, the heat-conducting paste is heat-conducting silicone grease.

In addition, in the portable gas chromatography capillary column module of the present invention, the thermal conductive paste is graphite film or indium foil.

In addition, in the portable gas chromatographic capillary column module of the present invention, the temperature measuring device is a high-precision patch-type platinum resistor, which is attached to the wall of the winding part of the capillary column skeleton.

In addition, in the portable gas chromatography capillary column module of the present invention, the protective film is a silica gel film or a ceramic fiber cloth.

In addition, in the portable gas chromatography capillary column module of the present invention, the capillary column is a metal capillary column, an MXT column or a fused silica column.

Furthermore, in the portable gas chromatography capillary column module of the present invention, the capillary column is wound in such a manner that each turn is closely arranged.

Furthermore, in the portable gas chromatography capillary column module of the present invention, the capillary column is wound in such a manner that the turns are spaced at predetermined intervals.

In addition, in the portable gas chromatography capillary column module of the present invention, the cylindrical shell is formed of an alloy material with low thermal conductivity and the inner wall is a mirror surface.

In addition, in the portable gas chromatography capillary column module of the present invention, the inner diameter of the cylinder housing is slightly smaller than the diameter of the cap and slightly larger than the diameter of the capillary column skeleton, and the cap just covers the cylinder The upper end surface of the housing, and the cylindrical housing is slightly higher than the capillary column skeleton.

In addition, in the portable gas chromatography capillary column module of the present invention, the sealing ring is formed of a material with high temperature resistance and low thermal conductivity.

In addition, in the portable gas chromatography capillary column module of the present invention, the jacket of the heat preservation jacket is cut and sewn from high temperature resistant polyimide fiber cloth, and the inside of the jacket is filled with gas with excellent thermal insulation performance. Gel, the shape of the heat preservation cover matches the shape of the finger-shaped chromatographic column module, including an upper circular cap and a lower cylindrical sleeve, and the upper circular cap and the lower cylindrical sleeve are tightly connected by buckles connect.

In addition, the present invention provides a portable gas chromatography capillary column module, characterized in that,

with a portable GC capillary column module as described above,

The portable gas chromatography capillary column module is two, that is, a first portable gas chromatography capillary column module and a second portable gas chromatography capillary column module whose properties are different from the first portable gas chromatography capillary column module,

Using a two-way modulator to connect the capillary column outlet port of the first portable gas chromatography capillary column module to the capillary column inlet port of the second portable gas chromatography capillary column module in series, the first portable The capillary column inlet port of the gas chromatography capillary column module is connected to a sampler, and the capillary column outlet port of the second portable gas chromatography capillary column module is connected to a detector.

In addition, the present invention provides a portable gas chromatography capillary column module, characterized in that,

Having a plurality of portable gas chromatography capillary column modules as described above, and the properties of the plurality of portable gas chromatography capillary column modules are the same,

The capillary column outlet port of each of the plurality of portable gas chromatography capillary column modules is connected to the capillary column inlet port of another portable gas chromatography capillary column module through a two-way modulator, and the first one The capillary column inlet port of the portable gas chromatography capillary column module and the capillary column outlet port of the last portable gas chromatography capillary column module are suspended.

In addition, the present invention provides a portable gas chromatography capillary column module, characterized in that,

with a portable GC capillary column module as described above,

The portable gas chromatography capillary column module is two, that is, the first portable gas chromatography capillary column module and the second portable gas chromatography capillary column module, and the first portable gas chromatography capillary column module and the second portable gas chromatography capillary column module The column module has the same properties,

The capillary column inlet port of the first portable gas chromatography capillary column module and the capillary column inlet port of the second portable gas chromatography capillary column module are connected to the same injector, and the first portable The capillary column outlet port of the gas chromatography capillary column module and the capillary column outlet port of the second portable gas chromatography capillary column module are respectively connected to different detectors.

As mentioned above, the present invention is designed in consideration of reducing heat capacity and energy consumption from various aspects: (1) The design of the sealed space formed by the cavity frame with high thermal conductivity and the cylindrical shell with low thermal conductivity reduces the heat capacity; (2) The heating device directly heats the capillary column through conduction, which can realize rapid temperature rise; (3) The mirror surface design of the cylindrical shell can reduce heat radiation loss; (4) The airgel insulation layer can effectively prevent convective heat loss. Combining the above four aspects, while reducing power consumption, it also achieves ultra-fast heating. In addition, the present invention adopts the ingenious design of the cooling circulation channel so that the module has the function of rapid cooling.

In addition, the heat insulation system of the present invention adopts a sleeve type: the cover is made of high-temperature-resistant polyimide fiber cloth, filled with airgel, which is safe and non-toxic, and has a good heat preservation effect; the cover is equipped with buckles for easy detachment; There are metal air holes to facilitate internal device leads. The sleeve design overcomes the defect that the heat transfer and insulation device is not easy to disassemble.

In addition, the design of the present invention takes into account the convenience of disassembly of each device: the heating device can be replaced by taking off the insulation cover; the skeleton is pulled out from the cylindrical shell, and the chromatographic column is exposed in front of the eyes, which is convenient for replacement. It is convenient to replace the device, and overcomes the defects that the chromatographic column cannot be replaced by the existing module, and the whole module is scrapped after some accessories are damaged.

In addition, the present invention is small in size and modular, and can expand the application function of modules through series/parallel connection.

Description of drawings

Fig. 1 A is a schematic longitudinal sectional view of the portable gas chromatography capillary column module of the present invention.

Fig. 1B is a schematic cross-sectional view of the middle part of the module in Fig. 1A.

Figure 1C is a schematic diagram of the cap.

Fig. 2A and Fig. 2B are schematic diagrams of the application examples of expanding the modules of the present invention into comprehensive two-dimensional or tandem chromatography.

Fig. 3A and Fig. 3B are schematic diagrams of the application example of expanding the modules of the present invention into parallel chromatography.

Explanation of reference signs:

1 Capillary column skeleton

2 caps

3 heating device

4 temperature measuring device

5 thermal paste

6 capillary columns

7 Protective film

8 cylinder housing

9 sealing ring

10 Thermal silicone rubber strips

11 Scalloped sealing area

12 arc-shaped sealing area

13 Heating device lead-out port

14 Outlet port of temperature measuring device

15 Capillary column inlet port

16 Capillary column outlet port

17 Air intake nozzle

18 Air outlet

19 heat sink

20 thermal sleeves

21 two-pass modulator

22 injectors

23 detectors

24 three-way valve

25 Another detector.

detailed description

Hereinafter, the portable gas chromatography capillary column module of the present invention will be described in detail with reference to the accompanying drawings.

Figure 1A is a schematic longitudinal sectional view of a portable gas chromatography capillary column module of the present invention (hereinafter, sometimes referred to as a module of the present invention), and Figure 1B is a schematic transverse sectional view of the middle part of the module in Figure 1A.

Specifically, as shown in FIGS. 1A and 1B , the portable gas chromatography capillary column module of the present invention has: a capillary column framework 1 with a bobbin shape with protruding eaves at both ends, from one end of the capillary column framework 1 toward its The other end is formed with a round hole along the axial direction of the capillary column skeleton 1, and the end face of the other end is closed; a disc-shaped cap 2 with a protruding outer eaves is connected to one end of the capillary column skeleton 1, which is shown in FIG. 1A Connected to the upper end of the capillary column frame 1; the heating device 3 is inserted into the round hole of the capillary column frame 1; the temperature measuring device 4 is arranged on the capillary column frame 1 and is located between the capillary column frame 1 and the heating device 3; heat conduction Paste 5 is used to couple the gap between the capillary column frame 1 and the heating device 3; the protective film 7 is arranged on the outer wall of the capillary column frame 1, and, as shown in FIG. 1A, the protective film 7 is located on the capillary column frame 1 Between the two protruding eaves; the capillary column 6 is tightly wound on the outer surface of the protective film 7; the cylindrical shell 8 has a closed lower end and an open upper end, and the capillary column skeleton 1 is coaxial with the cylindrical shell 8. It is arranged in the cylindrical shell 8, and, as shown in Figure 1A, there is a gap between the bottom end surface of the cylindrical shell 8 and the bottom end surface of the capillary column skeleton 1; Between the eaves and the upper end of the cylindrical shell 8, the cylindrical shell 8 and the cap 2 are sealed to realize the sealing between the cylindrical shell 8 and the capillary column skeleton 1, and an enclosure is formed between the cylindrical shell 8 and the capillary column skeleton 1 The circumferential space of the capillary column 1; two heat-conducting silicone rubber strips 10 are respectively arranged at both ends of the circumference diameter of the capillary column skeleton 1 wound with the capillary column 6 and extend along the axial direction of the capillary column skeleton 1, and the above-mentioned circumference The space is divided into two parts to form the required cooling air path; the thermal insulation cover 20 is covered outside the finger-shaped cylinder formed by the cylindrical shell 8 and the cap 2 .

In addition, Figure 1C is a schematic diagram of the cap. As shown in Figure 1C, six holes are opened on the cap 2 as ports for the lead-out pipeline: two of the ports lead out the heating device and the temperature detector wire respectively, and two of the ports are capillary column ends, which are respectively connected to the sampler and the detector. device, the other two are ventilation ports, one air inlet and one air outlet. That is, the above-mentioned six holes are respectively the heating device lead-out port 13 for leading out the wire of the heating device 3, the temperature-measuring device lead-out port 14 for leading the temperature-measuring device 4 out, and one end of the capillary column 6. The capillary column inlet port 15, the capillary column outlet port 16 connected with the other end of the capillary column 6, and the gas inlet nozzle 17 and the gas outlet nozzle 18 respectively connected with the two parts of the circumferential space. In addition, six corresponding air holes are reserved on the insulation cover 20 for pipelines to be led out.

As shown in Figure 1A, in the present invention, the capillary column framework 1 is, for example, a traditional bobbin shape, with protruding eaves at both ends, which can prevent the capillary column from slipping, and the upper end surface center of the capillary column framework 1 along the framework A circular hole is opened in the axial direction, and the lower end surface of the capillary column skeleton 1 is closed. Correspondingly, the cap 2 is, for example, in the shape of a disc with a protruding outer eave, and is integrally connected with the capillary column framework 1 on the upper end surface of the capillary column framework 1 . The capillary column skeleton 1 is made of light alloy material with high thermal conductivity, such as magnesium aluminum alloy and the like. Holes communicating with the air inlet nozzle 17 and the air outlet nozzle 18 are respectively formed on the protruding eaves of the capillary column skeleton 1, so that the air inlet nozzle 17 and the air outlet nozzle 18 communicate with the above-mentioned circumferential space. In addition, the capillary column skeleton and the cap are not limited to the above-mentioned structures, and of course other structures may be used as long as the functions played in the present invention can be realized.

In addition, in the present invention, the winding part of the capillary column skeleton 1, that is, the part between the two protruding eaves, has a diameter of 20mm-80mm and a height of 20mm-200mm. In addition, the pipe wall and the protruding eaves at both ends are required to be as thin as possible without deforming the skeleton, so as to reduce the heat capacity and facilitate rapid heating/cooling.

In the present invention, the heating device 3 can be any heating device that can follow the shape of the cavity of the capillary column skeleton 1, for example, a heating rod or a heating film, etc., and is not particularly limited. Preferably, the heating rod can be directly inserted into the central hole of the frame, which is convenient for replacement. A heat conduction paste 5 is provided between the heating device 3 and the capillary column skeleton 1 , and the function of the heat conduction paste 5 is to closely couple the heating device such as a heating rod and the capillary column skeleton 1 to realize fast and uniform heating of the capillary column 6 . Heat conduction paste 5 can use heat conduction silicone grease, the working temperature is -50 ~ 480 ℃, the price is cheap, easy to apply, and graphite film or indium foil can also be used. Both of them have good ductility and thermal conductivity and higher working temperature. The working temperature is 0~3000℃, and the working temperature of indium foil is 0~2080℃, but the price of both is slightly higher.

In addition, the temperature measuring device 4 is a high-precision chip-type platinum resistor, which is closely attached to the wall of the winding part of the capillary column skeleton 1 . However, it is not limited thereto, and may be other temperature measuring devices.

In the present invention, the protective film 7 is set on the outer periphery of the capillary column skeleton 1. The protective film 7 can be a high-temperature-resistant silica gel film, or a high-temperature-resistant ceramic fiber cloth with a thickness of 0.5 to 1 mm to increase the skeleton. The unique friction and elastic effect not only facilitates the easy winding of the capillary column, but also solves the problem that the capillary column may be broken due to tension or slipped due to relaxation due to expansion or contraction of the skeleton under heating and cooling.

In addition, in the present invention, it is preferable that the capillary column 6 adopts a metal capillary column or an MXT column. Such a capillary column is different from the quartz column used in patent documents CN1877319A and CN10268842A. The metal column is made of stainless steel, and the inner wall of the tube is treated as The inert layer is coated with a chromatographic stationary phase, and the outer wall of the tube is coated with a high-temperature resistant insulating layer with a micron-level thickness. Metal capillary columns have better toughness and strength than traditional quartz capillary columns, so they can be wound with a smaller radius of curvature. In addition, this kind of capillary column does not break under pressure, can withstand higher temperatures than quartz columns, and has a longer life. In addition, in the present invention, the capillary column 6 can also be a fused silica column.

In addition, regarding the winding of the capillary column, it can be wound in such a manner that each turn is closely arranged, or can be wound in such a manner that each turn is separated by a predetermined interval, and the total length of the capillary column is, for example, 5 m to 30 m. However, the present invention can also use the traditional quartz capillary column, which needs to be wound with a skeleton with a larger radius.

In the present invention, the cylindrical shell 8 is made of an alloy material with low thermal conductivity, and the inner wall of the cylinder is a mirror surface, thereby reducing the radiation loss of internal heat. In addition, with regard to the wall thickness of the cylindrical shell 8, it can be made thinner under the condition of sufficient load bearing, so as to reduce the heat capacity.

In the present invention, the inner diameter of the cylindrical shell 8 is slightly smaller than the diameter of the circular cap 2 protruding from the upper end of the capillary column skeleton 1 and slightly larger than the diameter of the capillary column skeleton 1, and the cap 2 just covers the upper end surface of the cylindrical shell 8 , the cylindrical shell 8 is slightly higher than the capillary column frame 1, that is, there is a small gap between the bottom end surface of the cylindrical shell 8 and the bottom end surface of the capillary column frame 1.

In addition, the sealing ring 9 is made of high temperature resistant rubber or other high temperature resistant and low thermal conductivity materials. The diameter of the sealing ring 9 is the same as the inner diameter of the cylindrical shell 8, and it is set under the cap 2 to realize the sealing between the cylindrical shell 8 and the capillary column frame 1, forming a gap between the cylindrical shell 8 and the capillary column frame 1 Narrow circumferential sealing space.

A layer of high-temperature-resistant silica gel strip 10 is respectively pasted on the two ends of the circumference of the capillary column framework 1 of the wound capillary column 6 with a diameter symmetrical along the axis of the framework. On the one hand, the chromatographic column can be compacted; The circumferential sealed space between the cartridge shell 8 and the capillary column frame 1 is divided into two fan arc-shaped sealing areas 11, 12, and the two fan arc-shaped areas 11, 12 are communicated through the gap on the bottom end surface of the capillary column frame 1. Each of the upper end surfaces corresponding to the fan arc-shaped regions is punched with an air hole to form a gas path for cooling the capillary column 6 .

In addition, the six ports on the cap, of which the heating device and the temperature measuring device port leading out are connected with high temperature resistant wires, the two ports leading out of the capillary column 6 are sealed with graphite pressure rings, and the two capillary column joints can be connected through a double-way The injector 22/detector 23 can also be connected in series or in parallel to other modules to realize module function expansion. The air inlet nozzle 17 and the air outlet nozzle 18 are arranged on the edge of the cap 2, respectively connected to the two fan arcs in the cylindrical shell 8. When the capillary column 6 needs to cool down, the cooling medium enters a fan-shaped area between the capillary column skeleton 1 and the cylindrical shell 8 through the air inlet 17 and flows through another fan-shaped area from the bottom. area, and finally flow out from the gas outlet 18 on the edge of the cap 2 to realize rapid cooling of the capillary column 6 . The cooling method can be realized by connecting the refrigerant (such as liquid CO2 or liquid nitrogen) to the gas nozzle, or by connecting the gas pump to the gas nozzle to achieve rapid ventilation.

In addition, regarding the thermal insulation cover 20, the cover is cut and sewn from high temperature resistant polyimide fiber cloth, and the inside of the cover is filled with airgel with excellent thermal insulation performance. Insulation effect. The cutting shape of the insulation cover matches the shape of the finger-shaped chromatographic column module, including the upper cap and the lower cylinder cover. The two parts are tightly connected by buckle loops, and the insulation cover can be removed by loosening the buckle loops.

The size of the existing Agilent portable chromatography module is 150mm*153mm*53mm, (L*W*H). The minimum size of the chromatographic module of the present invention is 60mm*70mm (2R*H), which further reduces the size of the chromatographic column system and realizes portability and modularization.

The working principle of the portable gas chromatography capillary column module of the present invention: the single finger module of the present invention can be used as a whole, and multiple finger modules can be connected in series or in parallel, and the same or different chromatographic columns can be used to expand the chromatographic Applications. For example: (1) Use a double pass to connect two or more modules of the same capillary column in series to increase the length of the capillary column to achieve the separation of complex components; (2) Use a modulator to connect two modules of different capillary columns in series Form a comprehensive two-dimensional chromatographic system; (3) Use a multi-pass to connect multiple modules of different types of capillary columns in parallel to unconnected detectors, which can realize parallel detection of multiple types of components at the same time and improve analysis efficiency. Combined with series or parallel connection, the finger-shaped capillary column modules are independently heated and temperature-controlled, which facilitates different temperature settings and facilitates different measurements. Each finger module in series or parallel connection can be removed from the whole machine as a whole, which is convenient for loading and unloading.

In addition, the present invention prefers a highly elastic metal capillary column, which can be wound with a radius of curvature of 5 mm without breaking, so the chromatographic column module can be made smaller. In addition, the quartz capillary column is very brittle, and its outer wall has a certain elasticity after being coated with a layer of polyimide film. This layer of polyimide film will age under long-term high temperature, causing the capillary column to become brittle and easy to break, while the metal The capillary column will not break under long-term high temperature. The use of metal capillary column solves the problem that the quartz column is easy to break during long-term high-temperature work under a small radius of curvature, and improves the life of the chromatographic column module.

Example 1

As shown in FIG. 1A and FIG. 1B , in this embodiment 1, the capillary column 6 is described by taking an MXT column with a specification of 5 m×0.25 mm i.d.×0.25 μm as an example. Due to the good elasticity of the capillary column 6, a thinner capillary column skeleton can be selected. The cap 2 is integrally connected with the capillary column framework 1 on the upper end surface of the capillary column framework 1 . The heating device 3 is inserted in the cavity of the capillary column framework 1 and coupled with the capillary column framework 1 through a thermal conductive paste 5 . The temperature measuring device 4 is closely attached to the inner wall of the capillary skeleton 1, and the heating device 3 and the temperature measuring device 4 are respectively drawn from the heating device outlet port 13 and the temperature measuring device outlet port 14 on the cap 2 and connected to the power supply and the temperature controller. The precise temperature control of the capillary column 6 is realized by using the PID algorithm. The capillary column 6 has a total length of 5m and an outer diameter of about 0.4mm. It is wound on the capillary column skeleton 1 in a single layer in a tightly arranged form. When the winding radius of curvature is 21, the height of the winding turns is about 30mm. The two ends of the capillary column 6 Joints reserved for a certain length are led out from the capillary column inlet port 15 and the capillary column outlet port 16 respectively. A protective film 7 is arranged between the capillary column framework 1 and the capillary column 6, and the protective film 7 is closely attached to the capillary column framework 1 to increase the friction and elasticity of the capillary column framework 1 and prevent the capillary column 6 from slipping. And the effect of the impact on the capillary column 6 due to the deformation of the capillary column skeleton 1 . Two heat-conducting silicone rubber strips 10 are closely attached to both sides of the capillary column framework 1 wound with the capillary column 6 along the axial direction of the framework. On the one hand, they play a role in fixing the capillary column 6. The circumferential gap formed between the skeletons 1 is divided into two fan-shaped sealing areas 11 and 12, and the two fan-shaped areas 11 and 12 are connected through the gap on the bottom end surface of the capillary column skeleton 1, and the two fan-shaped areas 11 and 12 are respectively connected with the cap The gas inlet nozzle 17 and the gas outlet nozzle 18 on the 2 are connected, and the cooling device 19 communicating with the gas inlet nozzle 17 and the gas outlet nozzle 18 respectively forms an air path for cooling the capillary column 6 . The upper end surface of the cylindrical shell 8 and the protruding outer eaves of the cap 2 are sealed by a sealing ring 9. The cylindrical shell 8 is made of an alloy material with low thermal conductivity, and the inside is a mirror surface to prevent heat from radiating outward. The capillary column 6 is suspended in the sealed space, forming a circumferential gap of about 3-5 mm between the cylindrical shell 8 and the capillary column frame 1 and communicating with the gap at the bottom of the capillary column frame 1 . Insulation cover 20 is made up of corresponding lower cylinder cover and upper circular block cap, is closely connected as a whole by buckle loop, and the upper circular block cap of thermal insulation cover 20 reserves corresponding six metal air holes for convenient lead-in. The sheath of the thermal insulation cover 20 is made of high temperature resistant polyimide fiber cloth, filled with airgel, and covered outside the finger-shaped cylinder formed by the cylindrical shell 8 and the cap 2 to form a complete gas chromatography For the capillary column module, the total volume of the module in this embodiment is about 60mm*70mm (2R*H). In addition, in the reverse order: take off the insulation cover 20, pull down the shell 8, and all components are exposed in front of the eyes, which is convenient for disassembly and replacement.

Example 2

Similarly, this embodiment adopts the capillary column module as shown in Fig. 1A and Fig. 1B. Quartz column with μm size. All the capillary columns 6 are long in length and poor in elasticity, so the size of the capillary column skeleton 1 is larger than that of the embodiment 1. Apart from that, all other devices and their assembly in this embodiment are completely the same as those in Embodiment 1, and will not be repeated here. The total volume of the module in this embodiment is about: 100mm*100mm (2R*H).

Example 3

In this embodiment, it is an application embodiment of expanding two modules of the present invention into a comprehensive two-dimensional gas chromatography module.

Fig. 2A and Fig. 2B are schematic diagrams of an application example in which the modules of the present invention are extended to comprehensive two-dimensional or tandem chromatography in this embodiment. As shown in FIGS. 2A and 2B , the single module in FIG. 2A is the module shown in FIGS. 1A and 1B . The capillary column properties of the two module assemblies are different. Connect the capillary column outlet port 16 of the first module (the module on the left in FIG. 15 are connected in series, the capillary column inlet port 15 of the first module is connected to the injector 22, the capillary column outlet port 16 of the second module is connected to the detector 23, and by adjusting the two-way modulator 21 in the middle, the two modules form Comprehensive two-dimensional gas chromatography module.

Example 4

In this embodiment, it is an application embodiment of multi-module series connection.

As shown in FIG. 2A and FIG. 2B , the single module in FIG. 2A is the module shown in FIG. 1A and FIG. 1B . Capillary columns with identical properties are configured in multiple modules, and the middle modulator 21 is a simple two-pass modulator. The two modules are connected in series through the two-pass modulator 21 to double the length of the capillary column. However, the present invention is not limited to two In this way, multiple modules can be connected in series to form a longer capillary column, which can enhance the separation ability of the capillary column and can be used for sample analysis of complex components.

Example 5

In this embodiment, it is an application embodiment in which two modules are connected in parallel.

Fig. 3A and Fig. 3B are schematic diagrams of an application example in which the modules of the present invention are expanded into parallel chromatography. As shown in FIG. 3A and FIG. 3B , the single module in FIG. 3A is the module shown in FIG. 1A and FIG. 1B , and capillary columns with identical properties can be assembled in the two modules. The sample injector 22 is respectively connected to the capillary column inlet ports 15 of the two modules through a three-way valve 24 to realize the parallel connection of the two chromatographic column modules. The two modules are respectively connected to two detectors 23 and 25 with different properties, and a single sample injection can realize the simultaneous detection of multiple separation components. Traditional single-detector spectrometers often need to replace detectors for repeated sample injection tests when different components are required to be detected. This method of connecting two modules in parallel overcomes the current limited response ability of a single detector to material components. defects, greatly improving the detection capability of a single measurement.

As mentioned above, the invention of the present application has been described, but it is not limited thereto. It should be understood that various combinations and various changes can be made to the above-mentioned embodiments within the scope of the spirit of the present invention. For example, each component can be designed according to needs. Its shape or structure, in addition, for example, components such as insulation cover, temperature measuring device, thermal paste or protective film can also be removed from the structure of the portable gas chromatography capillary column module as described above according to needs.

Claims (26)

1. a kind of portable gas chromatography capillary column module, it is characterised in that possess：

The capillary column skeleton of bobbin shape, from one end towards the other end being axially formed along the capillary column skeleton Circular hole, and the other end end face closing；

Block, is connected to described one end of the capillary column skeleton；

Heater element, is inserted in the circular hole of the capillary column skeleton；

Capillary column, is closely wound on the outer surface of the capillary column skeleton；And

Barrel shrond, its lower end closed and upper end open, and the capillary column skeleton is in the mode coaxial with the barrel shrond Configure in the barrel shrond, and between the bottom face of the barrel shrond and the bottom face of the capillary column skeleton Remain with gap.

2. portable gas chromatography capillary column module as claimed in claim 1, it is characterised in that

It is also equipped with：Muff, covers on outside the finger-type cylinder being combined into by the barrel shrond and the block.

3. portable gas chromatography capillary column module as claimed in claim 2, it is characterised in that

The two ends of the capillary column skeleton are with protrusion eaves, also, the block is the disc with outer protrusion eaves.

4. portable gas chromatography capillary column module as claimed in claim 3, it is characterised in that

Also there is the temperature measuring device being arranged on the capillary column skeleton.

5. portable gas chromatography capillary column module as claimed in claim 4, it is characterised in that

Also having is used for the heat-conducting cream of the slot-coupled between the capillary column skeleton and the heater element.

6. portable gas chromatography capillary column module as claimed in claim 5, it is characterised in that

Also with the protrusion eaves and the other end being arranged on the outer wall of the capillary column skeleton and positioned at described one end Diaphragm between protrusion eaves,

The capillary column is closely wound on the outer surface of the diaphragm.

7. portable gas chromatography capillary column module as claimed in claim 6, it is characterised in that

Sealing ring is provided between eaves and the upper end of the barrel shrond outside the protrusion of the block, thus, by the cylinder Shell and the cap sealed, realize the sealing between the barrel shrond and the capillary column skeleton, outside the cylinder The circuferential spacing for surrounding the capillary column is formed between shell and the capillary column skeleton.

8. portable gas chromatography capillary column module as claimed in claim 7, it is characterised in that

At the circle diameter two ends of the capillary column skeleton for being wound with the capillary column, along the capillary column skeleton Axial direction be respectively arranged with two heat-conducting silicon rubber bars, thus, the circuferential spacing is divided into two parts, the drop needed for being formed Wet road.

9. portable gas chromatography capillary column module as claimed in claim 8, it is characterised in that

It is provided with for the heater element of the wire extraction of the heater element to be drawn into port, for by described in the block The temperature measuring device that the wire of temperature measuring device is drawn draws the capillary column arrival end of one end connection of port and the capillary column The capillary column outlet port of the other end connection of mouth and the capillary column and two parts with the circuferential spacing The suction nozzle and outlet nozzle for connecting respectively,

Hole corresponding with above-mentioned port respectively is provided with the muff.

10. the portable gas chromatography capillary column module as described in any one of claim 1~9, it is characterised in that

The capillary column skeleton is formed by thermal conductivity light alloy material high.

The 11. portable gas chromatography capillary column module as described in any one of claim 1~9, it is characterised in that

A diameter of 20mm~80mm of the winding portion of the capillary column skeleton, is highly 20mm~200mm.

The 12. portable gas chromatography capillary column module as described in any one of claim 1~9, it is characterised in that

The heater element is heating rod or heating film.

The 13. portable gas chromatography capillary column module as described in any one of claim 5~9, it is characterised in that

The heat-conducting cream is heat-conducting silicone grease.

14. portable gas chromatography capillary column modules as claimed in claim 13, it is characterised in that

The heat-conducting cream is graphite film or indium foil.

The 15. portable gas chromatography capillary column module as described in any one of claim 4~9, it is characterised in that

The temperature measuring device is high-precision SMD RTD, is attached on the wall of the winding portion of the capillary column skeleton.

The 16. portable gas chromatography capillary column module as described in any one of claim 6~9, it is characterised in that

The diaphragm is pellosil or ceramic fiber cloth.

The 17. portable gas chromatography capillary column module as described in any one of claim 1~9, it is characterised in that

The capillary column is metal capillary post, MXT posts or vitreous silica post.

The 18. portable gas chromatography capillary column module as described in any one of claim 1~9, it is characterised in that

The capillary column is wound in the compact arranged mode of every circle.

The 19. portable gas chromatography capillary column module as described in any one of claim 1~9, it is characterised in that

The capillary column winds in the way of each circle separates predetermined space.

The 20. portable gas chromatography capillary column module as described in any one of claim 1~9, it is characterised in that

The barrel shrond is formed by the low alloy material of thermal conductivity factor and inwall is minute surface.

The 21. portable gas chromatography capillary column module as described in any one of claim 1~9, it is characterised in that

The internal diameter of the barrel shrond is more slightly smaller than the diameter of the block and more slightly larger than the diameter of the capillary column skeleton, described Block just covers the upper surface of the barrel shrond, also, the barrel shrond is more slightly higher than the capillary column skeleton.

22. portable gas chromatography capillary column modules as claimed in claim 7, it is characterised in that

The sealing ring is formed by the low thermal conducting material of high temperature resistant.

The 23. portable gas chromatography capillary column module as described in any one of claim 2~9, it is characterised in that

The set skin of the muff cuts sewing and forms using resistant to elevated temperatures polyimide fiber cloth, in set intracutaneous portion filling There is the aeroge that heat-insulating property is excellent,

The shape of the muff is engaged with the profile of the finger-type chromatographic column module, including upper circular block and lower cylinder Set, the upper circular block and the lower cylindrical sleeve are closely connected by button loop.

A kind of 24. portable gas chromatography capillary column modules, it is characterised in that

Possess the portable gas chromatography capillary column module described in any one of claim 1~23,

The portable gas chromatography capillary column module is two i.e. the first portable gas chromatography capillary column module and category The property second portable gas chromatography capillary column module different from the first portable gas chromatography capillary column module,

With a bilateral modulator by the capillary column port of export of the first portable gas chromatography capillary column module Mouth is connected in series with the capillary column ingress port of the second portable gas chromatography capillary column module, and described first The capillary column ingress port of portable gas chromatography capillary column module is connected to injector, second Portable gas The capillary column outlet port of phase chromatography capillary string modules is connected to detector.

A kind of 25. portable gas chromatography capillary column modules, it is characterised in that

Possess the portable gas chromatography capillary column module described in any one of multiple claims 1~23, and it is multiple The attribute of the portable gas chromatography capillary column module is identical,

The capillary column outlet port of each of multiple portable gas chromatography capillary column modules and another The capillary column ingress port of the portable gas chromatography capillary column module is connected by a bilateral modulator, the One capillary column ingress port of the portable gas chromatography capillary column module is described portable with last The capillary column outlet port of gas-phase chromatographic capillary column module is hanging.

A kind of 26. portable gas chromatography capillary column modules, it is characterised in that

Possess the portable gas chromatography capillary column module described in any one of claim 1~23,

The portable gas chromatography capillary column module is two i.e. the first portable gas chromatography capillary column module and the Two portable gas chromatography capillary column modules, and the first portable gas chromatography capillary column module and described second The attribute of portable gas chromatography capillary column module is identical,

The capillary column ingress port of the first portable gas chromatography capillary column module and described second portable The capillary column ingress port of gas-phase chromatographic capillary column module is connected to same injector, also, described first just Take the capillary column outlet port and the second portable gas chromatography capillary of formula gas-phase chromatographic capillary column module The capillary column outlet port of post module is connected to different detectors.