阅读说明：本技术 便携式气相色谱-气质联用仪快速温控装置 (Portable gas chromatography-mass spectrometer rapid temperature control device ) 是由 肖育 郭锡岩 姚如娇 景加荣 朱勇勇 陈元 于 2021-09-26 设计创作，主要内容包括：本发明提供了一种便携式气相色谱-气质联用仪快速温控装置,主要涉及为便携式气相色谱仪和便携式气相色谱质谱联用仪提供快速温度回调的装置和方法,具体来说是通过半导体制冷片的方式,让有效工作面接近色谱柱区域,以半导体制冷片效工作面快速制冷的方式吸收色谱柱加热丝和环境中的多余热量,达到快速降温的效果。本发明通过一个装置可以实现短时间内让色谱系统的温度回落至初始状态,同时还可以在某些对于程序模式升温速度要求较高的应用中作为辅助升温手段,提升升温效率,为体积空间有限的便携式气相色谱仪和便携式气相色谱质谱联用仪的快速降温升温提供高效、便捷、可靠的解决方案。(The invention provides a rapid temperature control device for a portable gas chromatography-gas chromatograph-mass spectrometer, and mainly relates to a device and a method for providing rapid temperature adjustment for the portable gas chromatography and the portable gas chromatography-mass spectrometer, in particular to a device and a method for providing rapid temperature adjustment for the portable gas chromatography and the portable gas chromatography-mass spectrometer, wherein an effective working surface is close to a chromatographic column area in a semiconductor refrigeration sheet mode, and redundant heat in a chromatographic column heating wire and the environment is absorbed in a semiconductor refrigeration sheet effective working surface rapid refrigeration mode, so that the effect of rapid temperature reduction is achieved. The invention can realize that the temperature of the chromatographic system falls back to the initial state in a short time through one device, and can be used as an auxiliary heating means in certain applications with higher requirements on the temperature rising speed of a program mode, thereby improving the heating efficiency and providing an efficient, convenient and reliable solution for the rapid temperature reduction and heating of a portable gas chromatograph with limited volume space and a portable gas chromatograph-mass spectrometer.)

1. The utility model provides a quick temperature control device of portable gas chromatography-gas chromatograph-mass spectrometer which characterized in that, includes gas chromatography column and semiconductor refrigeration piece, wherein:

the gas chromatographic column is provided with a heating device and a temperature measuring device;

the working surface of the semiconductor refrigeration piece is flush with the gas chromatographic column or has a distance with the gas chromatographic column.

2. The portable GC-MS of claim 1, wherein the semiconductor cooling plate is connected to the outer wall of the apparatus via a heat transfer mechanism.

3. The portable GC-MS of claim 2, wherein the heat transfer mechanism comprises a heat sink.

4. The portable GC-MS of claim 2, wherein the heat transfer mechanism is connected to the opposite side of the heating surface of the semiconductor cooling plate.

5. The portable GC-MS of claim 1, wherein the number of the semiconductor cooling plates is one or more.

6. The rapid temperature control device for the portable gas chromatography-mass spectrometer as claimed in claim 5, wherein when the number of the semiconductor cooling plates is plural, the plural semiconductor cooling plates cool or heat synchronously.

7. The portable GC-MS of claim 1, wherein the heating device and the temperature measuring device are wound around the gas chromatography column.

8. The portable GC-MS of claim 1, wherein the heating device comprises a platinum wire or a nickel alloy wire.

9. The portable GC-MS of claim 1, wherein the temperature measuring device is a PT100 temperature sensor.

10. The portable gas chromatography-mass spectrometer rapid temperature control device according to claim 1,

the heating device is connected with an external power supply and a control wire of the heating wire;

the temperature measuring device is connected with a temperature measuring power supply and a control line.

Technical Field

The invention relates to the technical field of gas chromatography and gas chromatography-mass spectrometer analyzers, in particular to a portable rapid temperature control device for a gas chromatography-mass spectrometer.

Background

Among a plurality of analysis and test methods, chromatography and chromatography-mass spectrometry are considered as detection technologies which have high specificity and high sensitivity and are widely applied, and at present, gas chromatographs and gas chromatography-mass spectrometers are widely applied to the fields of environmental protection industry, electronic industry, textile industry, petrochemical industry, essence and spice industry, medical and pharmaceutical industry, agriculture, food safety and the like.

The gas chromatography is a chromatography using gas as a mobile phase, and after a sample enters a chromatographic column, due to different adsorption force of an adsorbent to each component, the running speed of each component in the chromatographic column is different after a certain time. The less strongly adsorbed component is readily desorbed first from the column and enters the detector, while the most strongly adsorbed component is least readily desorbed and therefore leaves the column last. In this way, the components are separated from each other in the column and sequentially detected and recorded in the detector. Due to the fast transport speed of the sample in the gas phase, the components of the sample can reach equilibrium between the mobile phase and the stationary phase instantaneously. In addition, a large number of substances can be selected as stationary phases, so that the gas chromatography is a separation and analysis method with high analysis speed and high separation efficiency. Particularly, after the mass spectrometer is adopted as a detector, the method has the advantages of high analysis sensitivity, wide application range and the like, namely a gas chromatography-mass spectrometry combined method. The gas chromatograph-mass spectrometer combines the characteristics of gas chromatograph and mass spectrometer to complete the accurate analysis of the components and content in the tested matter. In the gas chromatography-mass spectrometer, the gas chromatography still works as an independent module, and the mass spectrometer is used as a rear-end detector and is connected with the mass spectrometer through a gas interface.

The traditional gas chromatograph and gas chromatograph-mass spectrometer has large volume, high power consumption and strict requirements on working environment and personnel operation, and cannot meet the requirements of emergency monitoring and field analysis, particularly the growing field rapid application scenes of rapid response, mobile monitoring, simple maintenance and easy use, so the development of portable instruments becomes the development trend in the field of first-line analytical instruments. The miniaturized gas chromatograph and gas chromatograph-mass spectrometer combined instrument has the characteristics of light weight, small volume, low power consumption and the like, and has great advantages and potentials in the aspects of portability, timeliness, simplicity and cost, so that the miniaturization of the instrument becomes an important trend for the development of analytical instruments.

The high-end instrument market represented by miniaturized mass spectrometry is currently completely monopolized by a few foreign instrument companies due to the lack of own products, such as hapeisite from Inficon, and tori T-9 from PerkinElmer. In order to change the unfavorable current situation of long-term dependence on imported instruments and comprehensively improve the level and detection capability of on-site emergency monitoring equipment in China, the existing planning clearly points out ' promotion of miniaturization, portability and specialization of universal instruments such as chromatography and mass spectrometry ', enhancement of environmental event emergency technology and equipment development and improvement of the technical level of ecological environment monitoring '. With the strong support and investment of the country on high-end analytical instruments, the domestic mass spectrometry technology is in the high-speed development period, and series breakthrough is made on the core technology and products, such as Panuo portable gas chromatography PCG-86, Hangzhou light collection portable chromatography mass spectrometry combination instrument Mars-400 series and the like.

Because the chromatographic column and the gas interface need to maintain a certain temperature or heat according to a certain program mode, and a peripheral auxiliary heating and temperature control device is required in a common chromatographic device to construct and maintain a temperature field required by the chromatographic column or the gas interface, the volume and the power consumption of the chromatographic device are huge. One important indicator is the uniformity of the temperature distribution of the column. Only the chromatographic column with uniform temperature distribution can ensure that the analysis result has high repeatability and precision every time, otherwise, retention time drift can be caused, and the phenomena of supercooling condensation and overheating decomposition of a sample at the local position of the chromatographic column can occur when the temperature distribution is serious. In the traditional gas chromatograph/gas chromatograph-mass spectrometer, in order to ensure the temperature condition of a chromatographic column, a large column incubator 101 is adopted, smooth stainless steel with high light reflection performance is adopted on the peripheral surface of a box body, heat-preservation quartz wool is wrapped inside the box body, the chromatographic column 102 is located in the center of a cavity, and a fan 103 is arranged on the back side of the chromatographic column, as shown in fig. 1 below. The column oven is designed to ensure the constant temperature effect of the chromatographic column 102, and the fan 103 can ensure the uniformity of the environmental temperature.

The portable gas chromatograph/mass spectrometer is the same in structure as a traditional gas chromatograph/mass spectrometer, the portable gas chromatograph/mass spectrometer also needs a temperature control system to keep warm for a chromatographic column and a gas interface, but the portable gas chromatograph/mass spectrometer is limited by the size, only a heating wire 202 and a temperature measuring wire 203 which are wound in parallel can be wound on the chromatographic column 201, the constant temperature of the chromatographic column is maintained through mechanisms such as PT100 temperature measurement feedback adjustment on-off of the heating wire, and in part of models, the temperature can be maintained even by adopting a mode of adding a heat preservation and insulation layer inside. The portable large-fan design is different from the design of a large internal fan of a desktop instrument, the portable internal space is small, the heating and the heat preservation are easy, but the heat dissipation is difficult, the heat dissipation can be completed only by opening a heat dissipation opening and a small fan, long-time waiting and recovery are needed between two adjacent experiments, the special requirements of outdoor field operation are met, the rain and water drop invasion are strictly limited, and the scheme of opening the heat dissipation opening and the small fan is difficult to implement. These conditions all limit the rapid switching between two different operating conditions when used in the field.

The semiconductor refrigerating chip is also called as thermoelectric refrigerating chip, and is a heat pump. Its advantages are no slide part, limited space, high reliability and no pollution of refrigerant. By utilizing the Peltier effect of semiconductor materials, when direct current passes through a galvanic couple formed by connecting two different semiconductor materials in series, heat can be absorbed and released at two ends of the galvanic couple respectively, and the aim of refrigeration can be fulfilled. The refrigerating technology which generates negative thermal resistance is characterized by no moving parts and higher reliability. At present, in the field of gas chromatography, the semiconductor refrigeration chip is rarely applied, and is mainly used in full-two-dimensional gas chromatography (CN106940352A), traditional low-temperature chromatography (CN1412504) and enrichment devices (CN209264371U), and has no application in portable gas chromatography and portable gas chromatography mass spectrometry.

Disclosure of Invention

Aiming at the defects in the prior art, the invention aims to provide a portable gas chromatography-gas chromatograph-mass spectrometer rapid temperature control device.

The invention provides a portable gas chromatography-gas chromatograph-mass spectrometer rapid temperature control device, which comprises a gas chromatography column and a semiconductor refrigerating piece, wherein:

the gas chromatographic column is provided with a heating device and a temperature measuring device;

the working surface of the semiconductor refrigeration piece is flush with the gas chromatographic column or has a distance with the gas chromatographic column.

Preferably, the semiconductor chilling plate is connected to the outer wall of the instrument through a heat transfer mechanism.

Preferably, the heat transfer mechanism comprises a heat sink.

Preferably, the opposite surface of the heating surface of the semiconductor refrigeration piece is connected with the heat transfer mechanism.

Preferably, the number of the semiconductor chilling plates is one or more.

Preferably, when the number of the semiconductor refrigerating sheets is multiple, the multiple semiconductor refrigerating sheets synchronously refrigerate or heat.

Preferably, the heating device and the temperature measuring device are wound on the gas chromatography column.

Preferably, the heating means comprises a platinum wire or a nickel alloy wire.

Preferably, the temperature measuring device adopts a PT100 temperature sensor.

Preferably, the heating device is connected with an external power supply and a control wire of the heating wire;

the temperature measuring device is connected with a temperature measuring power supply and a control line.

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

1. the invention can effectively improve the falling speed of the temperature, and can assist in temperature rise in certain specific applications, thereby improving the efficiency of program mode temperature rise.

2. The invention can complete the temperature of the chromatographic system to fall back to the initial state in a short time, quickly complete the next test preparation and is suitable for the field quick response application.

3. The invention can be used as an auxiliary heating means in certain applications with higher requirements on the temperature rising speed of the program mode, and the temperature rising efficiency is improved.

4. The invention has small volume, no moving parts and high reliability, and is suitable for portable instruments.

Drawings

Other features, objects and advantages of the invention will become more apparent upon reading of the detailed description of non-limiting embodiments with reference to the following drawings:

fig. 1 is a structural diagram and a structural schematic diagram of a column oven in a conventional gas chromatography module.

FIG. 2 is a schematic diagram of a temperature control structure of a chromatography column in a portable gas chromatography module.

Fig. 3 is a schematic front view of a structure according to a first embodiment of the present invention.

Fig. 4 is a schematic side view of the first embodiment of the invention.

Fig. 5 is a schematic structural diagram in the second embodiment of the present invention.

Fig. 6 is another schematic structural diagram in the second embodiment of the present invention.

The figures show that:

gas chromatography module 101

Front opening 102

Rear side port 103

Capillary chromatography column 201

Heating wire 202

Temperature measuring line 203

External power supply and control wire 204 for heating wire

Thermometric power supply and control line 205

Capillary chromatography column 301

Heating wire 302

Temperature measuring line 303

External power supply and control wire 304 for heating wire

Thermometric power and control line 305

Semiconductor chilling plate 306

Detailed Description

The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that it would be obvious to those skilled in the art that various changes and modifications can be made without departing from the spirit of the invention. All falling within the scope of the present invention.

As shown in fig. 1 to 6, the rapid temperature control device for a portable gas chromatograph-mass spectrometer according to the present invention includes a gas chromatographic column and a semiconductor refrigeration plate, and for convenience of subsequent description, a side of the semiconductor refrigeration plate close to the gas chromatographic column is defined as a working side. Wherein the main structure of the gas chromatographic column comprises a heating structure and a temperature measuring structure, the heating structure can adopt a heating wire generally, the temperature measuring structure adopts a platinum wire combined PT100 temperature measuring form generally, and the gas chromatographic column, the heating structure and the temperature measuring structure can be wound together, pressed or independently arranged in the same space and other forms. The distance L between the working surface of the semiconductor refrigeration piece and the surface of the gas chromatographic column is not less than 0, namely the working surface of the semiconductor refrigeration piece is flush with the gas chromatographic column or the surface of the gas chromatographic column is away from the working surface of the semiconductor refrigeration piece by a certain distance, so that cold air or hot air emitted from the working surface of the semiconductor refrigeration piece can fully contact the gas chromatographic column, and the functions of rapid cooling or auxiliary heating are achieved. Because the semiconductor refrigeration piece can be in a refrigeration or heating mode, the working surface of the semiconductor refrigeration piece not only can be used as a cold source, but also can be used as a heat source. In the analysis of certain SVOC or substances with higher boiling points, the requirement on the temperature programming of the chromatographic column is higher, at the moment, the working surface of the semiconductor refrigerating sheet can be adjusted to be in a heating mode, and the auxiliary heating structure can rapidly heat the chromatographic column.

Further, the present invention discloses a portable gas chromatography/mass spectrometer rapid cooling control device, and the following describes the details of the present invention with a specific implementation example of a typical portable gas chromatography structure.

The first embodiment is as follows: as shown in fig. 3, 301 is a capillary chromatographic column, 302 is a heating wire, which may be a platinum wire, a nickel alloy wire, etc., 303 is a temperature measurement wire, which may be a platinum wire, etc., adopting PT100 temperature measurement, etc., 304 is a heating wire external power supply and control wire, 305 is a temperature measurement power supply and control wire, and 306 is a semiconductor refrigeration sheet structure. In a portable gas chromatograph-mass spectrometer, a parallel winding mode of a heating wire, a temperature measuring wire and a chromatographic column is usually adopted to ensure the volume, namely the heating wire 302 and the temperature measuring wire 303 wound in parallel are wound on the chromatographic column 301, and the constant temperature of the chromatographic column is maintained by adjusting the on-off mechanism of the heating wire through PT100 temperature measurement feedback. In order to further increase the cooling and heating speed, a semiconductor refrigeration sheet 306 is placed in the central area, as shown in fig. 4, the distance L from the working surface of the semiconductor refrigeration sheet 306 to the surface of the gas chromatography column 301 is greater than or equal to 0, that is, the working surface of the semiconductor refrigeration sheet is flush with the gas chromatography column or the surface of the gas chromatography column is away from the working surface of the semiconductor refrigeration sheet by a certain distance, so that the cold source temperature or the heat source temperature on the working surface of the semiconductor refrigeration sheet can be uniformly received by the gas chromatography column 301, and the effect of rapidly cooling or heating is achieved. Meanwhile, the working surface of the semiconductor refrigerating sheet and the opposite surface of the working surface are completely in an opposite state, namely the working surface is in a refrigerating mode, namely the opposite surface of the working surface is in a heating mode, and the working surface is in a heating mode, namely the opposite surface of the working surface is in a refrigerating mode, so that the opposite surface of the working surface is actually an adverse factor to the actual requirement of the system, and is required to be connected to an instrument foreign currency 308 through a heat transfer structure 307 such as a radiating fin and the like to conduct an unnecessary heat source or cold source to the outside of the instrument, thereby reducing the influence on the work of the instrument.

Example two: as shown in fig. 5 and 6, the number N of the semiconductor refrigeration pieces used in the portable gas chromatography/mass spectrometer rapid cooling control device and method is greater than or equal to 1, that is, the number of the semiconductor refrigeration pieces that can be used is 1, 2, 3 or even more, depending on the specific application scenario. The semiconductor refrigerating sheets used at the same time are not limited in placement position and mode, and can be placed in a central area or positions right below a chromatographic column and the like, but the working state of the working surface of each semiconductor refrigerating sheet is guaranteed to be consistent, namely synchronous refrigeration or heating is realized.

The invention can complete the temperature of the chromatographic system to fall back to the initial state in a short time, quickly complete the next test preparation and is suitable for the field quick response application. The temperature-raising device can be used as an auxiliary temperature-raising means in certain applications with higher requirements on the temperature-raising speed of the program mode, and the temperature-raising efficiency is improved. The volume is small and exquisite, no moving part, and the reliability is high, is fit for using in portable instrument.

In the description of the present application, it is to be understood that the terms "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", and the like indicate orientations or positional relationships based on those shown in the drawings, and are only for convenience in describing the present application and simplifying the description, but do not indicate or imply that the referred device or element must have a specific orientation, be constructed in a specific orientation, and be operated, and thus, should not be construed as limiting the present application.

The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes or modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention. The embodiments and features of the embodiments of the present application may be combined with each other arbitrarily without conflict.