CN217587073U - Low-heat-capacity miniature chromatographic column box device and atmospheric organic matter online measuring device - Google Patents
Low-heat-capacity miniature chromatographic column box device and atmospheric organic matter online measuring device Download PDFInfo
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Abstract
The application provides a miniature chromatographic column case device of low heat capacity includes: the device comprises one or more than two low-heat-capacity micro chromatographic column boxes, wherein each low-heat-capacity micro chromatographic column box comprises a box body and a chromatographic column arranged in the box body; and a heating unit; the one or more than two low heat capacity micro chromatographic column boxes are integrated in the same control device; the application also provides an online measuring device for the atmospheric organic matters. The utility model discloses can carry out many post incubator integrated design according to measuring material kind demand, can integrate a plurality of (2 and above) miniature post incubators in a module, can satisfy the high accuracy programming requirement of the different materialization characteristic organic matters of polytype. The low-heat-capacity miniature chromatographic column box device is small in design volume, and can be subjected to unified circuit gas circuit control, so that independent program temperature rise control of each column temperature box is realized, and the column temperature boxes are mutually independent and mutually unified.
Description
Technical Field
The utility model belongs to the technical field of environmental monitoring, especially, miniature chromatographic column case device of low heat capacity, atmospheric organic matter on-line measuring device.
Background
Atmospheric organics are quite complex and can exist in both the gas phase and the particulate phase. Organic materials can be classified into Volatile Organic Compounds (VOCs), semi-Volatile Organic Compounds (SVOCs), and particulate phase Organic Compounds (Organic Aerosol OA) according to their volatility. Under normal temperature and pressure, VOCs mainly exist in the atmosphere in a gaseous state, SVOCs exist in both a gas phase and a particle phase, and OA mainly exists in the particle phase.
The gas phase/particle phase organic matter is an important precursor for the generation of near-surface ozone and fine particles, namely O in the atmosphere 3 VOCs, SVOCs and OA can be mutually converted to form dynamic balance under certain conditions, and the composite pollution process of the atmosphere is influenced. The online real-time measurement of the atmospheric gas phase and particle phase organic matters is the basis for researching the pollution characteristics, sources and material conversion of the atmospheric organic matters, and effective O3 and PM are formulated 2.5 The pollution control strategy has important scientific significance and practical effect. However, the knowledge and measurement means of concentration distribution and substance conversion in the atmosphere of various organic substances, especially VOCs, SVOCs and OA, are not comprehensive at present.
At present, almost no direct synchronous online measurement technology for VOCs, SVOCs and OA multi-species organic matters exists at home and abroad, and the synchronous measurement of the three substances is mainly offline measurement, namely, VOCs, SVOCs and OA are subjected to long-time large-flow active pump suction by adopting various stainless steel tanks, adsorbents and filter membranes, and then are taken to a laboratory for a series of offline post-treatment and detection. Compared with the organic matter offline sampling technologies such as adsorbent sampling, derivative adsorption sampling, stainless steel tank sampling, filter membrane sampling and the like, the online measurement technology has obvious advantages in the aspects of measurement time resolution, real-time performance of data, economy and the like. However, the existing online monitoring equipment is difficult to meet the synchronous real-time monitoring requirement of atmospheric multi-component organic matters (especially semi-volatile organic matters and granular phase organic matters), and a device for online identifying chemical compositions and realizing quantitative analysis of the chemical compositions aiming at SVOCs and OA is not provided in China.
The online measurement method for VOCs, SVOCs or OA single species at home and abroad mainly comprises the following means. The online measurement method of VOCs is mature, and detection is basically carried out by combining adsorbent enrichment with GCMS. But the online measurement method for large-molecular SVOCs and OA is relatively lacked. For the OA on-line measurement technology of large molecular weight, an on-line aerosol thermal desorption gas chromatography (TAG device) is mainly used, and organic components in a particle phase can be measured on line from a molecular level. The TAG device was first reported by Williams et al (2006) at the university of California, berkeley, california. Subsequently, goldstein et al performed a series of studies to improve the TAG device: such as two-dimensional chromatography, a semi-volatile organic compound measuring device (SV-TAG), an on-line derivatization device, and the like. For the SVOCs on-line measurement technology of middle volatile substances, most of the existing detection methods can only measure the total amount of semi-volatile organic compounds, or obtain the gas content by subtracting the content difference between the total amount and the particle phase, such as two-position gas chromatography, a semi-volatile organic compound measuring device (SV-TAG) and the like, but the indirect measurement of the gas phase SVOC causes larger errors.
Gas chromatography has become one of the most widely used methods for analyzing compounds because of its high sensitivity, stable operation and inexpensive price of analytical instruments. The conventional gas chromatograph is usually large in volume and mainly applied to an analysis laboratory, so that the wider application environment of the gas chromatograph is greatly limited. The most important reason for the large size of gas chromatographs is their large column box. The general chromatographic column box mainly controls the temperature of air in the column box in a radiation heat conduction mode, and the efficiency is relatively low. However, in practice, the volume of the chromatographic column is relatively small, and necessary temperature control can be directly performed on the chromatographic column, so that a miniaturized and portable chromatographic column box is realized, further the miniaturization of the chromatograph is promoted, and the wide application prospect of the chromatograph is expanded.
SUMMERY OF THE UTILITY MODEL
The utility model provides a solve the defect that prior art exists, provide a miniature chromatographic column case device of low heat capacity, reliable and stable and temperature control precision is high.
The utility model discloses technical scheme as follows:
1. a low heat capacity mini chromatography column cassette apparatus comprising:
one or more than two low heat capacity micro chromatographic column boxes,
the low heat capacity micro chromatographic column box comprises a box body and a chromatographic column arranged in the box body; and a heating unit;
the one or more than two low heat capacity micro chromatographic column boxes are integrated in the same control device;
preferably, the volume of the box is 5cm × 20cm × 10cm.
2. The low heat capacity mini chromatography column box apparatus according to item 1,
the heating unit is a resistance wire wound outside the chromatographic column;
preferably, the resistance wire is an insulating resistance wire, and the resistance wire can heat the chromatographic column to 50-350 ℃;
further preferably, the resistance wire can enable the temperature rise rate of the chromatographic column to be 2-60 ℃/min, and the resistance wire can enable the temperature control precision of the chromatographic column to be +/-0.2 ℃.
3. The low heat capacity mini chromatography column box apparatus according to item 1,
the low heat capacity micro chromatographic column box also comprises a heat preservation unit;
preferably, the heat preservation unit is arranged inside the box body and on the periphery of the box body;
further preferably, the heat preservation unit is a heat preservation material wound inside and around the box body;
still further, the thermal insulation material is selected from aluminum silicate ceramic fiber cotton.
4. The low heat capacity mini chromatography column cartridge device according to item 3,
the low heat capacity micro chromatographic column box also comprises a heat dissipation unit; the heat dissipation unit is positioned at the bottom of the box body;
preferably, the heat dissipation unit is a fan.
5. The low heat capacity mini chromatography column cartridge device according to item 4,
the chromatographic column is a metal capillary column and is selected from one of an RTX-624 chromatographic column, an RTX-5 chromatographic column and an RTX-5 chromatographic column.
6. The low heat capacity micro cartridge apparatus according to item 5,
the low heat capacity micro chromatographic column box comprises a first transmission pipeline, and a sample flowing out of the chromatographic column is collected on a main transmission pipeline through the first transmission pipeline;
preferably, the main transfer line comprises:
a line for connecting a chromatography column;
a support tube for supporting the stainless steel pipeline;
the heating layer is wound on the frame type supporting pipe;
the heat insulation layer is wound on the periphery of the main transmission flow path;
further preferably, the heat-resistant temperature of the main transfer channel is 150 to 350 ℃.
7. An atmospheric organic matter on-line measuring device comprises:
the atmospheric organic enrichment and desorption pretreatment device divides an atmospheric sample into volatile organic compounds, semi-volatile organic compounds and particle phase organic compounds;
the low heat capacity micro-chromatographic column box device of any one of items 1 to 6 connected to the pretreatment device;
a mass spectrometer;
the atmospheric organic matter enrichment and desorption pretreatment device is connected with the low-heat-capacity miniature chromatographic column box device through a fluid channel;
the low heat capacity miniature chromatographic column box is connected with a mass spectrometer through a four-way valve.
8. The atmospheric organic matter on-line measuring device according to item 7,
the pretreatment device for enrichment and desorption of the atmospheric organic matters comprises a pretreatment device for enrichment and desorption of volatile organic matters, a pretreatment device for enrichment and desorption of semi-volatile organic matters and a pretreatment device for enrichment and desorption of particle-phase organic matters;
the low heat capacity micro chromatographic column box device comprises a volatile organic matter low heat capacity micro chromatographic column box, a semi-volatile organic matter low heat capacity micro chromatographic column box and a particle phase organic matter low heat capacity micro chromatographic column box;
the low-heat-capacity micro-chromatographic column box for the volatile organic compounds is connected with the pre-enrichment and desorption treatment device for the volatile organic compounds, the low-heat-capacity micro-chromatographic column box for the semi-volatile organic compounds is connected with the pre-enrichment and desorption treatment device for the semi-volatile organic compounds, and the low-heat-capacity micro-chromatographic column box for the particle-phase organic compounds is connected with the pre-enrichment and desorption treatment device for the particle-phase organic compounds;
preferably, a first chromatographic column is arranged in the volatile organic low-heat-capacity micro chromatographic column box, a second chromatographic column is arranged in the semi-volatile organic low-heat-capacity micro chromatographic column box, and a third chromatographic column is arranged in the particle-phase organic low-heat-capacity micro chromatographic column box;
further preferably, the first chromatographic column is an RTX-624 chromatographic column, and the heating temperature is 50-250 ℃; the second chromatographic column is an RTX-5 chromatographic column, and the heating temperature is 50-300 ℃; the third chromatographic column is an RTX-5 chromatographic column, and the heating temperature is 50-350 ℃.
9. The atmospheric organic matter on-line measuring device according to item 8,
a first fluid channel is arranged between the volatile organic compound low heat capacity micro chromatographic column box and the volatile organic compound enrichment and pretreatment device, and preferably, the first fluid channel is a 1/32' flexible inerting stainless steel pipe with the inner diameter of 0.32 mm;
a second fluid channel is arranged between the semi-volatile organic matter low heat capacity micro chromatographic column box and the semi-volatile organic matter enrichment and desorption pretreatment device, and preferably, the second fluid channel is a 1/16' flexible inerting stainless steel tube with the inner diameter of 0.32 mm;
a third fluid channel is arranged between the particle-phase organic matter low-heat-capacity micro chromatographic column box and the particle-phase organic matter enrichment and desorption pretreatment device, and preferably, the third fluid channel is a 1/16' rigid inerting stainless steel tube with the inner diameter of 0.25 mm;
preferably, the second fluid passage and the third fluid passage each comprise:
a line for connecting to a chromatography column;
a support tube for supporting the stainless steel pipeline;
the heating layer is wound on the frame type supporting pipe;
the heat insulation layer is wound on the periphery of the fluid channel;
it is further preferred that the first and second liquid crystal compositions,
the heat-resistant temperature of the second fluid channel is 100-350 ℃;
the heat-resistant temperature of the third fluid channel is 100 to 350 ℃.
10. The on-line measuring device for atmospheric organics according to item 9,
the main transmission pipeline of the volatile organic low-heat capacity micro chromatographic column box and the main transmission pipeline of the semi-volatile organic low-heat capacity micro chromatographic column box are connected to a first four-way valve;
the main transmission pipeline of the particle-phase organic matter low heat capacity micro chromatographic column box is connected to the second four-way valve;
the first four-way valve is connected with the second four-way valve;
the second four-way valve is connected with the mass spectrometer through a first transmission channel;
preferably, the first transfer channel is a 1/16' rigid inerted stainless steel tube with an inner diameter of 0.25 mm.
Compared with the prior art, the utility model, following effect has:
(1) Based on the low heat capacity chromatographic technique, the low heat capacity miniature chromatographic column box device meeting the requirements of measuring substances with different characteristics is designed. This monitoring range that has not only expanded the device has still improved detection speed, and the device has small in size, the high characteristics of the rate of rising and falling temperature.
(2) The utility model discloses a miniature chromatographic column case device of low heat capacity can carry out many post thermostats integrated design according to measuring material kind demand, can integrate a plurality of (2 reach above) miniature post thermostats in a module, can satisfy the high accuracy programming requirement of the different materialization characteristic organic matters of multiple type. The low-heat capacity micro chromatographic column box device is small in design volume, and can be subjected to unified circuit gas circuit control, so that independent temperature programming control of each column temperature box is realized, and the column temperature boxes are independent and unified.
(3) The utility model discloses an online measuring device of atmosphere organic matter has introduced the combined type and has advanced kind technique, and this combined type advances kind technique can be connected the miniature chromatographic column case device of low heat capacity with the mass spectrograph, makes a mass spectrograph can satisfy the separation measurement demand of three types of material (VOCs, SVOCs and OA) promptly through the switching of valve. The composite sample injection technology can realize sequential sample injection of different substances or direct sample injection requirement of specific substances through control according to customer requirements.
(4) The utility model discloses an atmosphere organic matter on-line measuring device can realize that the many materials from gaseous phase to the granule looks are measured, satisfies present atmosphere combined pollution's measurement demand, provides data support for the science is treated pollution. Meanwhile, the whole volume of the atmospheric organic matter online measuring device is small, the transportation of instruments can be conveniently realized, and the purpose of monitoring substances from the north to the south and from cities to villages can be met according to the requirements of measured substances (gas phase or particle phase).
(5) Conventional chromatographic column case external physical dimension is about 300mm (length wide high), the utility model discloses the box minimum external physical dimension is about 5mm 5mm (length wide high), has reduced the box size greatly, reaches miniaturation mesh.
Drawings
FIG. 1 is a top view of a low heat capacity micro chromatography column box of the present invention;
FIG. 2 is a schematic structural view of a low heat capacity micro chromatographic column box device and a mass spectrometer of the invention;
FIG. 3 is a schematic structural diagram of the online measurement device for atmospheric organic compounds according to the present invention;
FIG. 4 is a schematic structural view of the main transfer flow path and the fluid channel of the present invention;
description of the symbols:
1, a high-precision temperature sensor; 2, high-temperature resistant insulated transmission pipelines; 3, heating a pipeline by a chromatographic column;
4, a heat radiation fan; 5, a heat preservation unit; 6 insulating resistance wires; 7 chromatographic column; 8, a box body;
a 15-VOCs chromatographic column box; 16-SVOCs chromatography column box; a 17-OA chromatography column box;
a first fluid path of 18-VOCs; 19-SVOCs second fluid channel; a 20-OA third fluid channel; 21-VOCs main transmission pipeline; 22-SVOCs main transmission pipeline; a 23-OA primary transport line;
24-a first transmission channel; 27-a first four-way valve; 28-a second four-way valve; 29-mass spectrum;
30-a volatile organic compound enrichment and desorption pretreatment device; 31-a semi-volatile organic matter enrichment desorption pretreatment device; 32-a particle phase organic matter enrichment and desorption pretreatment device; 34-silanized line; 35-support tube; 36-a heating layer; 37-insulating layer.
Detailed Description
Specific embodiments of the present invention will be described in more detail below with reference to the accompanying drawings. While specific embodiments of the invention are shown in the drawings, it will be understood that the invention may be embodied in various forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art.
According to the difference of the volatilization characteristics of the atmospheric organic matters, the atmospheric organic matters can be divided into volatile organic matters, semi-volatile organic matters and particle-phase organic matters. By respectively constructing the pretreatment and enrichment devices, designing a chromatographic separation integrated module (comprising a special chromatographic column and program temperature control) matched with the pretreatment and enrichment devices, and combining a mass spectrum detection module, a control device and a data processing software device, the real-time collection, enrichment, thermal analysis, separation and detection of the atmospheric volatile/semi-volatile/particle phase organic matters are finally realized, and a set of high-sensitivity online measurement device for the atmospheric low-concentration multi-component organic matters is formed.
Volatile Organic Compounds (VOCs): VOCs, according to the definition of the world health organization WHO, refer to various organic compounds having a boiling point of between 50 ℃ and 260 ℃ at atmospheric pressure (WHO, 1989)
Semi-volatile organics (SVOCs): SVOC is defined as an organic compound boiling between 240 ℃ and 400 ℃ (WHO, 1997).
Particulate phase Organic (OA): the Organic Aerosol (OA) is an important component in PM2.5 and accounts for 20-90% of the mass concentration of PM 2.5.
The utility model provides a miniature chromatographic column case device of low heat capacity, include:
comprises one or more than two low heat capacity micro chromatographic column boxes,
the low heat capacity micro chromatographic column box comprises a box body and a chromatographic column arranged in the box body; and a heating unit;
the one or more than two low heat capacity micro chromatographic column boxes are integrated in the same control device.
In some embodiments of the present invention, the low heat capacity micro chromatographic column box device comprises a volatile organic low heat capacity micro chromatographic column box, a semi-volatile organic low heat capacity micro chromatographic column box and a particle phase organic low heat capacity micro chromatographic column box.
Above-mentioned miniature chromatographic column case of low heat capacity is miniature column case, in order to reduce the whole volume of device, but extension arrangement's practicality, the utility model discloses carry out the minimizing design with every column case among the miniature chromatographic column case device of low heat capacity, use 5cm ~ 20cm 10 cm's cube as the miniature column case that bears of chromatographic column, for example can be 10cm 10cm 5 cm's column case, the column case adopts 316 stainless steel.
<xnotran> , 5cm*5cmm*5cm, 10cm*5cmm*5cm, 15cm*5cmm*5cm, 20cm*5cmm*5cm, 5cm*10cmm*5cm, 10cm*10cmm*5cm, 15cm*10cmm*5cm, 20cm*10cmm*5cm, 5cm*15cmm*5cm, 10cm*15cmm*5cm, 15cm*15cmm*5cm, 20cm*15cmm*5cm, 5cm*20cmm*5cm, 10cm*20cmm*5cm, 15cm*20cmm*5cm, 20cm*20cmm*5cm, 5cm*5cmm*10cm, 10cm*5cmm*10cm, 15cm*5cmm*10cm, 20cm*5cmm*10cm, 5cm*10cmm*10cm, 10cm*10cmm*10cm, 15cm*10cmm*10cm, 20cm*10cmm*10cm, 5cm*15cmm*10cm, 10cm*15cmm*10cm, 15cm*15cmm*10cm, 20cm*15cmm*10cm, 5cm*20cmm*10cm, 10cm*20cmm*10cm, 15cm*20cmm*10cm, 20cm*20cmm*10cm . </xnotran>
In some embodiments of the present invention, three low heat capacity micro chromatography column boxes are integrated: the design of the low heat capacity mini-chromatographic column box apparatus requires the continuous analysis of VOCs, SVOCs and OA samples to be accomplished. Therefore, an integrated design of three low heat capacity micro-chromatographic column boxes is required, and the three low heat capacity micro-chromatographic column boxes (namely, the VOCs column box, the SVOCs column box and the OA column box) are integrated in one low heat capacity micro-chromatographic column box device to perform uniform temperature programming, carrier gas pressure and flow control, so that the three modules can work cooperatively.
In some embodiments of the present invention, three chromatography column boxes, such as a volatile organic low heat capacity micro chromatography column box (i.e. a VOCs chromatography column box), a semi-volatile organic low heat capacity micro chromatography column box (i.e. a SVOCs chromatography column box) and a particle phase organic low heat capacity micro chromatography column box (OA chromatography column box), are placed in one module, and unified condition parameter control is performed thereon. The three low heat capacity micro chromatographic column boxes are independent and coordinated with each other, the independent conditions are different process rise conditions of different chromatographic columns, and the mutual coordination is realized by using the same control device to uniformly control the flow, the temperature and the pressure of the three column temperature boxes, namely, three sets of parameters are integrated into one integrated module, and the integrated module is controlled.
When the device is integrated, the arrangement among the three low heat capacity micro chromatographic column boxes can be set according to actual needs, and the route among sample transmission processes can be reduced as much as possible by a person skilled in the art.
The low heat capacity micro chromatographic column box device realizes the control of the flow, the voltage and the programmed temperature rise of the device through a control circuit. The control circuit adopts a double-CPU structure, the CPU1 is a CPU with an MCS51 framework and is mainly used for temperature control (including heating and temperature control) of a sample transmission flow path, a fluid channel and a transmission channel; the CPU2 adopts an ARM-structured CPU, is mainly used for temperature control, valve box temperature control and EPC pressure control of each low-heat-capacity micro chromatographic column box, and can also be used for start-stop control of a volatile organic matter enrichment and desorption pretreatment device, a semi-volatile organic matter enrichment and desorption pretreatment device and a particle-phase organic matter enrichment and desorption pretreatment device. The CPU1 and the CPU2 adopt I2C communication to transmit control and state information.
The main functions of the control circuit are as follows:
the coordination work of three chromatographic column box (a volatile organic matter low heat capacity micro chromatographic column box, a semi-volatile organic matter low heat capacity micro chromatographic column box and a particle-phase organic matter low heat capacity micro chromatographic column box) modules and a four-way valve switchable interface device is controlled; controlling each chromatographic column box module to carry out temperature programming, carrier gas pressure and flow according to respective set conditions; and sending and receiving starting and range rising signals and the like of atmospheric organic matter enrichment and desorption pretreatment devices (a volatile organic matter enrichment and desorption pretreatment device, a semi-volatile organic matter enrichment and desorption pretreatment device and a particle-phase organic matter enrichment and desorption pretreatment device).
Fig. 1 is a top view of the low heat capacity micro chromatography column box. The low heat capacity micro column box comprises a box body, a column 7 arranged in the box body and a heating unit. In some embodiments of the invention, the low heat capacity micro chromatographic column box adopts an LTM structure, namely a resistance wire winding heating structure, wherein the heating unit is a resistance wire 6 wound outside the chromatographic column, the resistance wire is an insulating resistance wire, in the invention, the insulating resistance wire is alternately wound on the chromatographic column layer by layer in a crossing manner, and the uniform and encrypted heating mode is adopted, so that the contact area between the chromatographic column and the resistance wire is greatly increased, the chromatographic column is uniformly heated, and the temperature gradient of each point in the column can be effectively reduced. By adopting the heating unit, the resistance wire can heat the chromatographic column to 50-350 ℃, the resistance wire can heat the chromatographic column at a temperature rise rate of 2-60 ℃/min, and the resistance wire can control the temperature of the chromatographic column to +/-0.2 ℃.
In some embodiments of the present invention, a 30m long column is straightened, a resistance wire is wound on the column layer by layer to ensure uniform contact between the column and the heating wire, and then the wound column is coiled and placed in a miniature column incubator of 10cm to 10cm.
As shown in fig. 1, the low heat capacity micro-chromatographic column box further comprises a heat preservation unit 5: the heat preservation unit 5 is arranged in the box body and on the periphery of the box body; the heat preservation unit is a heat preservation material wound inside and on the periphery of the box body. In order to reduce the temperature difference heat dissipation phenomenon of the low-heat-capacity micro chromatographic column box at high temperature, the inner part of the low-heat-capacity micro chromatographic column box and the outer surface of a chromatographic column are subjected to heat preservation design, and specifically, cellucotton with a good heat preservation effect is uniformly spread on each surface of the low-heat-capacity micro chromatographic column box, so that the temperature discrimination of the low-heat-capacity micro chromatographic column box at high-temperature separation is reduced. The heat preservation cotton is arranged on the inner layer of the chromatographic column, the outer layer of the chromatographic column after the resistance wire is wound and the inner surface of the low-heat-capacity miniature chromatographic column box. In order to enhance the heat preservation performance, the invention adopts the aluminum silicate ceramic fiber cotton heat preservation material which can resist 1000 ℃, and provides an excellent temperature environment and heat preservation capability, which is very beneficial to the improvement and control effect of the temperature characteristic of the whole column box.
As shown in fig. 1, the low heat capacity micro-chromatographic column box further comprises a heat dissipation unit: the heat dissipation unit is positioned at the bottom of the box body and is a heat dissipation fan 4. In the invention, the fan is arranged at the bottom of the low-heat-capacity micro chromatographic column box, and the chromatographic column is blown upwards by the fan during cooling, so that the temperature of the chromatographic column is reduced. The cooling of the low-heat capacity miniature chromatographic column box adopts a high-power direct-current fan air cooling mode, and the fast cooling of the chromatographic column box can be realized in view of the characteristic of small volume of the column incubator.
As shown in fig. 1, the low heat capacity micro-chromatographic column box further comprises a sensor 1, wherein the sensor is a high-precision temperature sensor, and the sensor is deeply inserted into the wound chromatographic column and is used for monitoring the real-time temperature of the chromatographic column. Still include chromatographic column heating pipeline 3 in the miniature chromatographic column case of low heat capacity, the both ends of heating pipeline and the resistance wire both ends of winding on the chromatographic column are connected, adopt direct current 24V resistance wire heating to realize the intensification of chromatographic column. In order to avoid the phenomena of melting of the outer skin and electric leakage of the pipeline in the high-temperature period of the column temperature box, the pipeline in the low-heat-capacity miniature chromatographic column box is wrapped by a high-temperature-resistant insulating material, namely the high-temperature-resistant insulating transmission pipeline 2, and all pipelines passing through the column temperature box are protected by the high-temperature-resistant insulating transmission pipeline. Wherein, the high temperature resistant insulating material is glass fiber high temperature sleeve.
In some embodiments of the present invention, the chromatographic column is a metal capillary column, and a silanized Restek stainless steel metal capillary column is used, and the chromatographic column is selected from one of a RTX-624 chromatographic column, a RTX-5 chromatographic column and a RTX-5 chromatographic column, and has the characteristics of good heat conductivity and difficult breakage when being coiled.
In some embodiments of the invention, the volatile organic compounds low heat capacity micro chromatographic column box (i.e. the VOCs chromatographic column box) adopts an RTX-624 chromatographic column, wherein the chromatographic column is a metal capillary column, the length of the column is 60m, the inner diameter of the column is 0.25mm, the thickness of the membrane is 1.4um, the maximum heating temperature is 250 ℃, and the maximum heating rate is 30 ℃/min.
In some embodiments of the invention, the low heat capacity micro chromatographic column box (i.e. SVOCs chromatographic column box) for semi-volatile organic compounds adopts RTX-5 chromatographic column, wherein the chromatographic column is a metal capillary column, the length of the column is 30m, the inner diameter is 0.25mm, the thickness of the membrane is 0.25um, the maximum heating temperature is 300 ℃, and the maximum heating rate is 30 ℃/min.
In some embodiments of the invention, the particle phase organic matter low heat capacity micro chromatographic column box (OA chromatographic column box) adopts an RTX-5 chromatographic column, wherein the chromatographic column is a metal capillary column, the length of the column is 30m, the inner diameter of the column is 0.25mm, the thickness of the membrane is 0.25um, the maximum heating temperature is 350 ℃, and the maximum heating rate is 60 ℃/min.
In some embodiments of the invention, the low heat capacity micro chromatography column box comprises a first transfer line, and the sample flowing out of the chromatography column is collected to a main transfer line through the first transfer line in a confluence mode. Each low heat capacity mini chromatography column box has its own main transfer line.
As shown in fig. 4, the main transmission pipeline sequentially includes, from inside to outside: stainless steel pipeline 34, frame type support pipe 35, heating layer 36 and heat preservation layer 37. Wherein, the stainless steel pipeline 34 is a stainless steel inerting pipeline used for connecting the chromatographic column and the four-way valve and used for transmitting the sample; a frame-type support tube 35 for supporting the stainless steel pipeline and internally laying an inerting pipeline; a heating layer 36 wound around the frame-type support tube; and the insulating layer 37 is wound on the periphery of the main conveying pipeline. The temperature control of the transmission pipeline adopts a closed loop control mode of thermocouple temperature measurement and direct current PWM heating. The heat-resistant temperature of the transmission pipeline is 150-350 ℃, certain high-boiling-point substances can be prevented from being condensed in the pipeline, and the transmission requirements of all samples of VOCs, SVOCs and OA can be met.
VOCs chromatographic column case includes first transmission line, adopts the mode of converging, will collect on VOCs chromatographic column case's main transmission line 21 from the sample of chromatographic column outflow through first transmission line.
The SVOCs column box includes a second transfer line, and the sample flowing out from the column is collected to the main transfer line 22 of the VOCs column box through the second transfer line in a confluence manner.
The OA chromatographic column box comprises a third transmission pipeline, and a sample flowing out of the chromatographic column is converged on the main transmission pipeline 23 of the VOCs chromatographic column box through the third transmission pipeline in a confluence mode.
As shown in FIG. 2 and FIG. 3, the present invention also provides an on-line measuring system for atmospheric organic compounds, which comprises
The atmospheric organic enrichment and desorption pretreatment device divides an atmospheric sample into volatile organic compounds, semi-volatile organic compounds and particle phase organic compounds;
the low heat capacity micro chromatographic column box system is connected with the pretreatment device;
a mass spectrometer;
the pre-treatment device for the enrichment and desorption of the organic matters in the atmosphere is connected with a low-heat-capacity miniature chromatographic column box system through a fluid channel;
the low heat capacity miniature chromatographic column box is connected with a mass spectrometer through a four-way valve.
As shown in fig. 2, in some embodiments of the present invention, the pretreatment apparatus for enrichment and desorption of atmospheric organic compounds includes a pretreatment apparatus 30 for enrichment and desorption of volatile organic compounds, a pretreatment apparatus 31 for enrichment and desorption of semi-volatile organic compounds, and a pretreatment apparatus 32 for enrichment and desorption of particulate organic compounds;
the low heat capacity micro chromatographic column box system comprises a volatile organic matter low heat capacity micro chromatographic column box 15, a semi-volatile organic matter low heat capacity micro chromatographic column box 16 and a particle-phase organic matter low heat capacity micro chromatographic column box 17;
as shown in fig. 3, the volatile organic compound low heat capacity micro chromatographic column box 15 is connected to the volatile organic compound enrichment and desorption pretreatment device 30, the semi-volatile organic compound low heat capacity micro chromatographic column box 16 is connected to the semi-volatile organic compound enrichment and desorption pretreatment device 31, and the particle phase organic compound low heat capacity micro chromatographic column box 17 is connected to the particle phase organic compound enrichment and desorption pretreatment device 32.
In some embodiments of the present invention, the volatile organic compound low heat capacity micro chromatographic column box 15 is provided with a first chromatographic column, RTX-624 chromatographic column, and the heating temperature is 50-250 ℃; a second chromatographic column and an RTX-5 chromatographic column are arranged in the semi-volatile organic low heat capacity micro chromatographic column box 16, and the heating temperature is 50-300 ℃; the particle phase organic matter low heat capacity micro chromatographic column box 17 is internally provided with a third chromatographic column and an RTX-5 chromatographic column, and the heating temperature is 50-350 ℃.
In some embodiments of the present invention, a first fluid channel 18 is disposed between the voc low heat capacity micro-chromatography column box and the voc pre-treatment device, that is, a first fluid channel of VOCs.
In some embodiments of the present invention, the first fluid channel may be any fluid channel known in the art, and in the present invention, the first fluid channel has an inner diameter of 0.32mm of 1/16 "flexible passivated stainless steel tube, or an inner diameter of 0.32mm of 1/32" flexible inerted stainless steel tube, or an inner diameter of 0.25mm of 1/32 "flexible passivated stainless steel tube, or an inner diameter of 0.25mm of 1/16" flexible passivated stainless steel tube; preferably a 1/32 "flexible inerted stainless steel tube with an internal diameter of 0.32 mm.
In some embodiments of the present invention, a second fluid channel 19, that is, an SVOCs second fluid channel, is disposed between the semi-volatile organic low heat capacity micro chromatographic column box 16 and the semi-volatile organic enrichment and desorption pre-processing device 31. The second fluid channel has a structure as shown in fig. 4, is a silanized stainless steel tube, and comprises a stainless steel pipeline 34, a frame-type support tube 35, a heating layer 36 and an insulating layer 37, wherein the stainless steel pipeline is used for connecting a chromatographic column; wherein the stainless steel pipeline is a stainless steel inerting pipeline and is used for connecting the chromatographic column and the four-way valve and transmitting a sample; the frame type supporting pipe is used for supporting the stainless steel pipeline and internally laying an inerting pipeline; the heating layer is wound on the frame type supporting pipe; and the insulating layer is wound on the periphery of the second fluid channel. The heat-resistant temperature of the second fluid channel is 100-350 ℃, so that high-boiling-point substances can be prevented from being condensed in the pipeline.
In some embodiments of the invention, the second fluid channel may be any fluid channel known in the art, in the present invention, the second fluid channel is a flexible passivated stainless steel tube with an inner diameter of 1/32 'of 0.32mm, or a flexible inerted stainless steel tube with an inner diameter of 1/16' of 0.32mm, or a flexible passivated stainless steel tube with an inner diameter of 1/32 'of 0.25mm, or a flexible passivated stainless steel tube with an inner diameter of 1/16' of 0.25 mm; preferably a 1/16 "flexible inerted stainless steel tube with an internal diameter of 0.32 mm.
In some embodiments of the present invention, a third fluid channel, that is, an OA third fluid channel, is disposed between the particle-phase organic matter low heat capacity micro-chromatography column box 17 and the particle-phase organic matter pre-enrichment and desorption treatment device 32; the third fluid channel has a structure as shown in fig. 4, is a silanized stainless steel tube, and comprises a stainless steel pipeline 34, a frame-type support tube 35, a heating layer 36 and an insulating layer 37, wherein the stainless steel pipeline is used for connecting a chromatographic column; wherein the stainless steel pipeline is a stainless steel inerting pipeline and is used for connecting the chromatographic column and the four-way valve and transmitting a sample; the frame type supporting pipe is used for supporting the stainless steel pipeline and internally laying an inerting pipeline; the heating layer is wound on the frame type supporting pipe; and the heat insulation layer is wound on the periphery of the third fluid channel. The heat-resistant temperature of the third fluid channel is 100-350 ℃, so that high-boiling-point substances can be prevented from being condensed in the pipeline.
In some embodiments of the invention, the third fluid channel may be any fluid channel known in the art, in the present invention, a 1/16 "rigid inerted stainless steel tube with an inner diameter of 0.25mm, or a 1/16" flexible passivated stainless steel tube with an inner diameter of 0.32mm, or a 1/32 "flexible passivated stainless steel tube with an inner diameter of 0.25 mm; preferably a 1/16' rigid inerted stainless steel tube with an internal diameter of 0.25 mm.
As shown in fig. 3, in some embodiments of the present invention, the main transfer lines of the voc low heat capacity mini-column boxes and the main transfer line of the semi-voc low heat capacity mini-column boxes are connected to a first four-way valve 27; the main transmission pipeline of the particle-phase organic matter low heat capacity micro chromatographic column box is connected to a second four-way valve 28; the first four-way valve is connected with the second four-way valve; the second four-way valve is connected to the mass spectrometer via a first transmission channel 24. The design of double four-way valves is adopted, and the sequential analysis of VOCs, SVOCs and OA by one mass spectrometer can be realized through the switching of the two four-way valves, the four-way valve in the invention adopts a high-temperature passivation four-way valve, the highest temperature can reach 350 ℃, and the sample adsorption can be effectively prevented; the whole four-way valve interface device can be heated to 300 ℃ to prevent the sample from being condensed and adsorbed.
In some embodiments of the invention, the first transfer channel may be any transfer channel known in the art, and in the present invention, the first transfer channel is preferably a 1/16 "rigid inerted stainless steel tube with an inner diameter of 0.25mm, a 1/16" flexible passivated stainless steel tube with an inner diameter of 0.32mm, or a 1/32 "flexible passivated stainless steel tube with an inner diameter of 0.25mm, or a 1/32" flexible passivated stainless steel tube with an inner diameter of 0.32mm, preferably a 1/16 "rigid inerted stainless steel tube with an inner diameter of 0.25 mm.
Wherein the inner diameters of the main transmission pipeline and the first fluid channel (or the second fluid channel or the third fluid channel) are matched with the inner diameter of the first transmission channel.
In some embodiments of the present invention, the four-way valve can be any type of four-way valve known in the art, such as a pneumatically or electrically controlled four-way valve, with the use of an electrically controlled high temperature four-way valve being preferred herein for ease of integrated circuit design.
In some embodiments of the present invention, the two four-way valves may be the same or different.
In some embodiments of the present invention, the method for enriching the volatile organic compounds in the atmospheric organic compounds in the pre-volatile organic compound enrichment and desorption processing device 30, enriching the semi-volatile organic compounds in the atmospheric organic compounds in the pre-semi-volatile organic compound enrichment and desorption processing device 31, and enriching the particulate phase organic compounds in the atmospheric organic compounds in the pre-particulate phase organic compound enrichment and desorption processing device 32 may be any method known to those skilled in the art. Preferably, in the invention, volatile organic compounds and semi-volatile organic compounds are enriched in the enrichment and desorption pretreatment device by adopting a low-temperature adsorption collection technology and then a high-temperature thermal desorption technology, and particle-phase organic compounds are collected by adopting a quartz filter membrane and enriched in the enrichment and desorption pretreatment device.
The invention also provides the application of the atmospheric organic matter on-line measuring system in the aspect of measuring the atmospheric organic matters.
The invention also provides an online measurement method of the online measurement system for the atmospheric organic matters, wherein the online measurement method comprises the following steps:
and (3) aging: aging and purging are carried out on the atmospheric organic matter enrichment and desorption pretreatment device and the transmission line;
a sampling step: enriching the atmospheric organic matters in the pretreatment device for enriching and desorbing the atmospheric organic matters;
a purging step: purging the pre-treatment device for enriching and desorbing the organic matters in the atmosphere and the transmission flow path;
a sample introduction step: and (3) bringing the enriched atmospheric organic matters in the step into a low heat capacity micro chromatographic column box system and a subsequent mass spectrometer, and separating and measuring the low heat capacity micro chromatographic column box system and the subsequent mass spectrometer.
In some embodiments of the present invention, the step of introducing sample comprises:
carrying the volatile organic compounds enriched in the sample introduction step into a low heat capacity micro chromatographic column box system of the volatile organic compounds for separation, and then, entering a mass spectrometer for measurement;
carrying the semi-volatile organic matters enriched in the sample introduction step into a low-heat-capacity micro chromatographic column box system of the semi-volatile organic matters for separation, and then, entering a mass spectrometer for measurement;
and carrying the particle phase organic matters enriched in the sample introduction step into a low heat capacity micro chromatographic column box system of the particle phase organic matters for separation, and then, entering a mass spectrometer for measurement.
In some embodiments of the present invention, in the aging step, the volatile organic compound enrichment and desorption pretreatment device 30, the semi-volatile organic compound enrichment and desorption pretreatment device 31, the particulate organic compound enrichment and desorption pretreatment device 32, and the transmission line thereof are sequentially subjected to carrier gas cleaning to remove the residual substances in the pipeline.
In some embodiments of the present invention, in the sampling step, volatile organic compounds in the atmospheric organic compounds are enriched in the pretreatment device for volatile organic compound enrichment and desorption, semi-volatile organic compounds in the atmospheric organic compounds are enriched in the pretreatment device for semi-volatile organic compound enrichment and desorption, and particulate-phase organic compounds in the atmospheric organic compounds are enriched in the pretreatment device for particulate-phase organic compound enrichment and desorption.
In some embodiments of the present invention, in the purging step, the pre-volatile organic compound enrichment and desorption processing device 30, the pre-semi-volatile organic compound enrichment and desorption processing device 31, the pre-particulate organic compound enrichment and desorption processing device 32, and the transmission line thereof are sequentially purged to remove the residual oxygen and other unwanted interfering gases.
In some embodiments of the present invention, the sample injection step comprises:
carrying the volatile organic compounds enriched in the sampling step into a low heat capacity micro chromatographic column box system for separation, and then entering a mass spectrometer for measurement;
carrying the enriched semi-volatile organic compounds in the sampling step into a low heat capacity micro chromatographic column box system for separation, and then entering a mass spectrometer for measurement;
and carrying the enriched particle phase organic matters in the sampling step into a low heat capacity micro chromatographic column box system for separation, and then, entering a mass spectrometer for measurement.
Thus, completing a sampling and analyzing cycle;
if the detection is needed to be continued, the operation is circulated.
In some embodiments of the present invention, the step of introducing sample comprises:
carrying the volatile organic compounds enriched in the sampling step into a low-heat-capacity micro chromatographic column box for separation, and then, entering a mass spectrometer for measurement;
carrying the semi-volatile organic matters enriched in the sampling step into a low-heat-capacity micro chromatographic column box for separation, and then, entering a mass spectrometer for measurement;
carrying the particle phase organic matters enriched in the sampling step into a particle phase organic matter low heat capacity micro chromatographic column box for separation, and then, entering a mass spectrometer for measurement;
completing a sampling and analyzing cycle;
if the detection is needed to be continued, the steps are circulated.
The low heat capacity micro chromatographic column box system can carry out multi-column incubator integrated design according to the requirement of measuring material types, namely 3 micro column incubators with different functions can be integrated in one module, and the high-precision program temperature rise requirement of various organic matters with different physical characteristics can be met. The low heat capacity micro chromatographic column box system is small in design volume, and can be subjected to unified circuit gas circuit control, so that independent program temperature rise control of each column temperature box is realized, and the column temperature boxes are independent and unified.
The online measurement system for the atmospheric organic matters can connect the low-heat-capacity micro chromatographic column box system with a mass spectrometer, namely, one mass spectrometer can meet the separation measurement requirements of three types of substances (VOCs, SVOCs and OA) through switching of two valves. According to the requirements of customers, the sequential sample injection of different substances or the direct sample injection requirement of specific substances is realized.
The on-line measurement system for the atmospheric organic matters can realize the measurement of a plurality of substances from gas phase to particle phase, meets the measurement requirement of the current atmospheric combined pollution, and provides data support for scientific pollution control. Meanwhile, the on-line measuring system for the atmospheric organic matters has small integral volume, can conveniently realize the transportation of instruments, and can meet the object of monitoring the substances from the north to the south and from cities to villages according to the demand of the measured substances (gas phase or particle phase).
Examples
Example 1 design of a volatile organic Low Heat Capacity Microchromatography column Box
The volatile organic compound low heat capacity micro chromatographic column box (VOCs chromatographic column box) comprises a box body, and an RTX-624 chromatographic column 7, a heating unit, a heat preservation unit 5 and a heat dissipation unit which are arranged inside the box body. The box body adopts a column box of 10cm × 5cm, and the column box adopts 316 stainless steel materials. The heating unit adopts an LTM structure, namely a resistance wire winding heating structure, specifically, an RTX-624 chromatographic column is straightened, insulating resistance wires 6 are wound on the chromatographic column layer by layer to ensure that the chromatographic column is uniformly contacted with a heating wire, and then the wound RTX-624 chromatographic column is coiled and placed in a miniature column temperature box of 10cm x 5 cm. By adopting the structure, the contact area of the RTX-624 chromatographic column and the resistance wire is greatly increased, so that the chromatographic column is uniformly heated, and the temperature gradient of each point in the column can be effectively reduced. The maximum temperature of the chromatographic column box can reach 330 ℃, the maximum heating rate can reach 60 ℃/min, the constant temperature precision is +/-0.2 ℃, and the analysis requirements of high-boiling point and low-volatility organic matter components in the atmosphere can be met by selecting 50W of heating power. The heat preservation unit 5 is arranged inside and outside the box body, and fiber cotton with a good heat preservation effect is uniformly spread on each surface of the low-heat-capacity micro chromatographic column box. The heat preservation cotton is arranged on the inner layer of the chromatographic column, the outer layer of the chromatographic column after the resistance wire is wound and the inner surface of the low-heat-capacity miniature chromatographic column box. In order to strengthen the heat preservation performance, the invention adopts an aluminum silicate ceramic fiber cotton heat preservation material which can resist 1000 ℃. The fan is located the bottom half, adopts high-power direct current fan air cooling mode, in view of the small characteristics of column incubator, can realize the rapid cooling of column case. Through the design, the miniature column box has the characteristics of small volume, high temperature rise and drop rate and convenience for integration.
The VOCs chromatographic column case comprises a first transmission pipeline, and a confluence mode is adopted, so that a sample flowing out of the chromatographic column is converged on a main transmission pipeline 21 of the VOCs chromatographic column case through the first transmission pipeline. The main transmission pipeline comprises from inside to outside in sequence: stainless steel pipeline 34, frame type support pipe 35, heating layer 36 and heat preservation layer 37. Wherein the stainless steel pipeline is a stainless steel inerting pipeline and is used for connecting the chromatographic column and the four-way valve and transmitting a sample; the frame type supporting pipe is used for supporting the stainless steel pipeline and internally laying an inerting pipeline; the heating layer is wound on the frame type supporting pipe; and the heat insulation layer is wound on the periphery of the main transmission pipeline. The temperature control of the transmission pipeline adopts a closed loop control mode of thermocouple temperature measurement and direct current PWM heating.
Example 2 design of Low Heat Capacity Microchromatography column Box for semi-volatile organic Compounds
Example 2 differs from example 1 in that the low heat capacity mini-column box of semi-volatile organic compounds (i.e. SVOCs column box) employs RTX-5 column, wherein the column length is 30m, the inner diameter is 0.25mm, the film thickness is 0.25um, the maximum heating temperature is 300 ℃, and the maximum heating rate is 30 ℃/min.
Example 3 design of particulate phase organic Low Heat Capacity Microchromatography column Box
Example 2 differs from example 1 in that,
the low heat capacity micro chromatographic column box (OA chromatographic column box) of the granular organic matter adopts an RTX-5 chromatographic column, wherein the column is 30m long, the inner diameter is 0.25mm, the film thickness is 0.25um, the maximum heating temperature is 350 ℃, and the maximum heating rate is 60 ℃/min.
Example 4
The volatile organic compound low heat capacity micro-chromatographic column box (VOCs chromatographic column box) of example 1, the semi-volatile organic compound low heat capacity micro-chromatographic column box (SVOCs chromatographic column box) of example 2 and the particle phase organic compound low heat capacity micro-chromatographic column box (OA chromatographic column box) of example 3 are sequentially placed in a low heat capacity micro-chromatographic column box system, a control circuit of the system adopts a double-CPU structure, and the CPU1 is a CPU with an MCS51 framework and is mainly used for temperature control (including heating and temperature control) of a sample transmission flow path, a fluid channel and a transmission channel; the CPU2 adopts an ARM framework CPU, is mainly used for temperature control, valve box temperature control and EPC pressure control of each low heat capacity micro chromatographic column box, and can also be used for start-stop control of a volatile organic matter enrichment and desorption pre-processing device, a semi-volatile organic matter enrichment and desorption pre-processing device and a particle phase organic matter enrichment and desorption pre-processing device. The CPU1 and the CPU2 adopt I2C communication to transmit control and state information.
Example 5 Online measurement method of atmospheric organic matter
In the aging step (1): and sequentially carrying out carrier gas cleaning on the volatile organic matter enrichment and desorption pretreatment device 30, the semi-volatile organic matter enrichment and desorption pretreatment device 31, the particle-phase organic matter enrichment and desorption pretreatment device 32 and a transmission line thereof, and removing residual substances in the pipeline.
In the sampling step (2), volatile organic compounds in the atmospheric organic compounds are sequentially enriched in the volatile organic compound enrichment and desorption pretreatment device, semi-volatile organic compounds are enriched in the semi-volatile organic compound enrichment and desorption pretreatment device, and particle-phase organic compounds are enriched in the particle-phase organic compound enrichment and desorption pretreatment device.
In the purging step (3), the volatile organic compound enrichment and desorption pretreatment device 30, the semi-volatile organic compound enrichment and desorption pretreatment device 31, the particle-phase organic compound enrichment and desorption pretreatment device 32, and the transmission line thereof are sequentially subjected to carrier gas nitrogen purging to remove residual oxygen and other redundant interference gases.
The step (4) of sample injection comprises the following steps
Step i: and (3) the Volatile Organic Compounds (VOCs) enriched in the step (2) enter a VOCs chromatographic column box through a first fluid channel for separation, the separated Volatile Organic Compounds (VOCs) are collected to a main transmission pipeline of the VOCs chromatographic column box through a first transmission pipeline of the VOCs chromatographic column box, and then enter a mass spectrometer through a first transmission channel for measurement through a BC port of a first four-way valve 27 and a BC port of a second four-way valve 28, so that the sampling and analysis circulation of the volatile organic compounds is completed. At the moment, the pre-treatment device for enrichment and desorption of semi-volatile organic compounds is in a focusing mode, the pre-treatment device for enrichment and desorption of granular phase organic compounds is in a thermal desorption mode, and the RTX-5 chromatographic column in the SVOCs chromatographic column box and the RTX-5 chromatographic column in the OA chromatographic column box are both in an initial low-temperature mode;
step ii: and (3) after VOCs are measured, allowing the semi-volatile organic compounds (SVOCs) enriched in the step (2) to enter an SVOCs chromatographic column box through a second fluid channel for separation, collecting the SVOCs on a main transmission pipeline of the SVOCs chromatographic column box through a first transmission pipeline of the SVOCs chromatographic column box by the separated semi-volatile organic compounds (SVOCs), and allowing the SVOCs to enter a mass spectrometer through a first transmission channel for measurement through a DC port of a first four-way valve 27 and a BC port of a second four-way valve 28, so that a sampling and analyzing cycle of the semi-volatile organic compounds is completed. At the moment, the pre-treatment device for enrichment and desorption of volatile organic compounds is in an aging mode, the pre-treatment device for enrichment and desorption of granular phase organic compounds is in a thermal desorption mode, and the RTX-624 chromatographic column in the VOCs chromatographic column box and the RTX-5 chromatographic column in the OA chromatographic column box are both in a low-temperature standby mode;
step iii: and (3) after SVOCs measurement is finished, the particle phase organic matters (OA) enriched in the step (2) enter an OA chromatographic column box through a third fluid channel for separation, the separated particle phase organic matters (OA) are collected on a main transmission pipeline of the OA chromatographic column box through a first transmission pipeline of the OA chromatographic column box, and then enter a mass spectrometer through a DC port of a second four-way valve 28 through a first transmission channel for measurement, so that a particle phase organic matter sampling and analyzing cycle is finished. At this time, the volatile organic compound enrichment and desorption pretreatment device 30 and the semi-volatile organic compound enrichment and desorption pretreatment device 31 are both in a standby mode;
completing a sampling and analyzing cycle;
if the detection is needed to be continued, the steps are circulated.
Claims (22)
1. A low heat capacity miniature chromatographic column box device, characterized in that includes:
one or more than two low heat capacity micro chromatographic column boxes,
the low heat capacity micro chromatographic column box comprises a box body and a chromatographic column arranged in the box body; and a heating unit;
the one or more than two low heat capacity micro chromatographic column boxes are integrated in the same control device.
2. The low heat capacity mini-chromatographic column box device of claim 1, wherein the box volume is 5cm x 5cm to 20cm x 10cm.
3. The low heat capacity micro chromatography column cassette apparatus of claim 1,
the heating unit is a resistance wire wound outside the chromatographic column.
4. The low heat capacity micro chromatography column cassette apparatus of claim 1,
the low heat capacity micro chromatographic column box further comprises a heat preservation unit.
5. The low heat capacity micro chromatography column cassette apparatus of claim 4, wherein the temperature retention unit is disposed inside and outside the cassette.
6. The low heat capacity micro chromatography column cassette apparatus of claim 4, wherein the thermal insulation unit is a thermal insulation material wound around the inside and the outside of the cassette.
7. The low heat capacity micro chromatography column cassette apparatus of claim 3,
the low heat capacity micro chromatographic column box also comprises a heat dissipation unit; the heat dissipation unit is located at the bottom of the box body.
8. The low heat capacity micro chromatography column cassette apparatus of claim 7, wherein the heat dissipating unit is a fan.
9. The low heat capacity micro chromatography column cassette apparatus of claim 4,
the chromatographic column is a metal capillary column and is selected from one of an RTX-624 chromatographic column, an RTX-5 chromatographic column and an RTX-5 chromatographic column.
10. The low heat capacity micro chromatography column cassette apparatus of claim 9,
the low heat capacity micro chromatographic column box comprises a first transmission pipeline, and a sample flowing out of the chromatographic column is collected on the main transmission pipeline through the first transmission pipeline.
11. The low heat capacity mini chromatography column cassette apparatus of claim 10 wherein said main transfer line comprises:
a line for connecting a chromatography column;
a support tube for supporting the stainless steel pipeline;
the heating layer is wound on the frame type supporting pipe;
and the insulating layer is wound on the periphery of the main transmission flow path.
12. An online measuring device for atmospheric organic matters is characterized by comprising:
an atmosphere sample is divided into an atmosphere organic enrichment desorption pretreatment device for volatile organic compounds, semi-volatile organic compounds and particle phase organic compounds;
a low heat capacity micro-cartridge apparatus according to any one of claims 1 to 11 connected to a pretreatment apparatus;
a mass spectrometer;
the atmospheric organic matter enrichment and desorption pretreatment device is connected with the low-heat-capacity miniature chromatographic column box device through a fluid channel;
the low heat capacity miniature chromatographic column box is connected with a mass spectrometer through a four-way valve.
13. The on-line measuring device for atmospheric organic compounds according to claim 12,
the pretreatment device for enrichment and desorption of the atmospheric organic matters comprises a pretreatment device for enrichment and desorption of volatile organic matters, a pretreatment device for enrichment and desorption of semi-volatile organic matters and a pretreatment device for enrichment and desorption of particle-phase organic matters;
the low heat capacity micro chromatographic column box device comprises a volatile organic matter low heat capacity micro chromatographic column box, a semi-volatile organic matter low heat capacity micro chromatographic column box and a particle phase organic matter low heat capacity micro chromatographic column box;
the device comprises a volatile organic matter low-heat-capacity micro chromatographic column box, a semi-volatile organic matter low-heat-capacity micro chromatographic column box, a particle-phase organic matter enrichment and desorption pretreatment device and a particle-phase organic matter enrichment and desorption pretreatment device.
14. The on-line measuring device for the atmospheric organic compounds according to claim 13, wherein the volatile organic compound low heat capacity micro-chromatographic column box is provided with a first chromatographic column, the semi-volatile organic compound low heat capacity micro-chromatographic column box is provided with a second chromatographic column, and the particulate phase organic compound low heat capacity micro-chromatographic column box is provided with a third chromatographic column.
15. The atmospheric organic matter on-line measuring device of claim 13, characterized in that the first chromatographic column is an RTX-624 chromatographic column; the second chromatographic column is an RTX-5 chromatographic column; the third chromatographic column is an RTX-5 chromatographic column.
16. The on-line measuring device for atmospheric organic compounds according to claim 13,
a first fluid channel is arranged between the volatile organic compound low-heat-capacity micro chromatographic column box and the volatile organic compound enrichment and desorption pretreatment device;
a second fluid channel is arranged between the semi-volatile organic matter low heat capacity micro chromatographic column box and the semi-volatile organic matter enrichment and desorption pretreatment device;
and a third fluid channel is arranged between the particle-phase organic matter low-heat-capacity micro chromatographic column box and the particle-phase organic matter enrichment and desorption pretreatment device.
17. The online atmospheric organic matter measurement device of claim 16, wherein the first fluid channel is a 1/32 "flexible inerted stainless steel tube with an inner diameter of 0.32 mm.
18. The on-line atmospheric organic matter measurement device of claim 16, wherein the second fluid channel is a 1/16 "flexible inerted stainless steel tube with an inner diameter of 0.32 mm.
19. The on-line measuring device for atmospheric organics of claim 16, wherein the third fluid channel is a 1/16 "rigid inerted stainless steel tube with an inner diameter of 0.25 mm.
20. The online atmospheric organic matter measurement device of claim 16, wherein the second fluid channel and the third fluid channel each comprise:
a line for connecting a chromatography column;
a support pipe for supporting the stainless steel pipeline;
the heating layer is wound on the frame type supporting pipe;
and the heat insulation layer is wound on the periphery of the fluid channel.
21. The on-line measuring device for atmospheric organics according to claim 16,
the main transmission pipeline of the volatile organic low-heat capacity micro chromatographic column box and the main transmission pipeline of the semi-volatile organic low-heat capacity micro chromatographic column box are connected to a first four-way valve;
the main transmission pipeline of the particle-phase organic matter low heat capacity micro chromatographic column box is connected to the second four-way valve;
the first four-way valve is connected with the second four-way valve;
and the second four-way valve is connected with the mass spectrometer through a first transmission channel.
22. The on-line measuring device for the atmospheric organics of claim 21, wherein the first transmission channel is a 1/16 "rigid inerting stainless steel tube with an inner diameter of 0.25 mm.
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