CN213456762U - Online monitoring system for high-resolution high-sensitivity rapid determination of volatile organic compounds - Google Patents

Abstract

The utility model relates to an analytical testing instrument, concretely relates to high resolution high sensitivity spot test volatile organic compounds's on-line monitoring system. The device comprises a sampling joint and a reaction chamber, wherein the sampling joint is connected with a gas filter, a precision filter, a gas-liquid separator, a permeable membrane gas dryer and sixteen-way switching valves; the reaction chamber comprises an ion source glow discharge region, an ion source drift region, a first differential vacuum chamber and a reaction tube which are sequentially adjacent, the rear part of the reaction chamber is sequentially connected with a second differential vacuum chamber, an ion transmission region and a TOF detection region, a single lens is arranged in the ion transmission region, and the single lens is composed of three groups of electrodes which are arranged left and right; the upper part of the TOF detection area is communicated with a reflection area through a field-free drift area, and three groups of reflectors and detectors are arranged in the reflection area. The utility model discloses rational in infrastructure, the molecular weight scope of survey is wide, and resolution ratio, sensitivity are high, and detectable molecular weight is to decimal point back quadbit, and the testing process interference factor is few, and the piece produces fewly, easily analyzes, can realize the real-time quick accurate determination of Source of pollution waste gas.

Description

Online monitoring system for high-resolution high-sensitivity rapid determination of volatile organic compounds

Technical Field

The utility model relates to an analytical testing instrument, concretely relates to high resolution high sensitivity spot test volatile organic compounds's on-line monitoring system.

Background

With the promulgation of ten atmosphere conditions in China, the measurement of volatile organic compounds in air and waste gas becomes the key content of atmosphere monitoring, and most of the conventional modes for monitoring the emission of the volatile organic compounds of enterprises are ex-situ monitoring, namely collecting samples by using an air bag or an adsorption tube and bringing the samples back to a laboratory for analysis. This sampling approach has a number of drawbacks: after the sample is collected, the adsorption phenomenon of an air collecting bag or the incomplete desorption of an adsorption tube possibly exists, and the real numerical value of the pollutant discharged by an enterprise cannot be obtained; the sampling time and sampling place of the sampling mode are usually known by enterprises in advance, so that measures for interfering normal emission of pollutants exist, the enterprise is difficult to supervise, in order to obtain the situation of VOCs emitted by the enterprises in real time and provide reliable basis for government decision, the online monitoring method is widely applied, but the online monitoring method for VOCs which is applied more at the present stage mostly adopts gas chromatography tandem mass spectrometry or directly adopts an FID detector for detection, the detection methods can realize analysis on the gas collected by ambient air and a fixed pollution source, but the detection process needs to be preprocessed and separated by the gas chromatography and then analyzed by a mass spectrometer, the process consumes long time, the time interval of the obtained VOCs data is larger, the data is lack of continuity, and the method is almost incapable of continuously monitoring the concentration change trend of the acquired VOCs; and the cost is high, and the analysis process needs continuous carrier gas supply; in addition, the analytical instrument mostly adopts a destructive hard ionization EI ion source, and a spectrogram obtained in the determination is ion fragment information, so that the spectrogram is complex and difficult to analyze; in addition, the monitoring instrument has higher requirement on a monitored gas sample, the influence of moisture on a measurement result is larger, particularly, when the pollution source waste gas is measured, the measurement result has larger interference due to complex components and high content of components such as water, carbon dioxide and the like, the capability of measuring the multi-path pollution source waste gas is more limited, the simultaneous analysis of the multi-path gas is difficult to realize for a long time, and the practicability is poorer.

Based on the method, a proton transfer reaction mass spectrometer (PTR-MS) capable of rapidly measuring pollution source waste gas is applied. At present, PTR-MS which is developed more is developed, after a sample molecule and reaction gas are subjected to proton transfer reaction, the sample molecule is screened by a quadrupole rod and then detected by a detector, the method realizes the rapid detection of the VOCs gas, but has a plurality of problems, the molecule is screened by a four-stage rod mass filter, the molecular range is determined to be narrow, and the method is often used for determining the VOCs molecule with smaller molecular weight (less than 300); most PTR-like instruments today have low resolution and cannot achieve separation of isomeric forms (different species with the same mass number but different structures).

SUMMERY OF THE UTILITY MODEL

The utility model aims at not enough to prior art, the utility model aims at providing a high resolution high sensitivity spot test volatile organic compounds's on-line monitoring system, the molecular weight scope of survey is wide, and resolution ratio, sensitivity are high, but the molecular ion peak material of high resolution detection molecular weight accurate to the quadbit behind the decimal point, and the testing process interference factor is few, and the fragment ion is few, the spectrogram is simple, easily the analysis.

The utility model discloses an online monitoring system of high-resolution high sensitivity spot test volatility organic matter, including sampling joint and reaction chamber, sampling joint exit linkage gas filter, the gas filter export is through first gas-supply pipe connection precision filter, first gas-supply pipe periphery sets up first electrical heating area, the precision filter export connects gradually first-order vapour and liquid separator and second grade vapour and liquid separator through the pipeline, second grade vapour and liquid separator gas outlet connects the osmotic membrane gas desicator, the osmotic membrane gas desicator passes through the second gas-supply pipe and connects sixteen way diverter valve, the second gas-supply pipe periphery sets up second electrical heating area; the reaction chamber is provided with a reaction gas inlet, the reaction gas inlet is connected with an outlet of a first tee joint, two inlets of the first tee joint are respectively connected with a water vapor generating device and other reaction gas inlets, the reaction chamber comprises an ion source glow discharge area, an ion source drift area, a first differential vacuum chamber and a reaction tube which are adjacent in sequence, the rear part of the reaction chamber is sequentially connected with a second differential vacuum chamber, an ion transmission area and a TOF detection area, the first differential vacuum chamber is communicated with the reaction tube through a first small hole, the reaction tube is communicated with the second differential vacuum chamber through a second small hole, the second differential vacuum chamber is communicated with the ion transmission area through a third small hole, the ion transmission area is communicated with the TOF detection area through a differential diversion hole, equivalent divider resistors are arranged outside the reaction areas of the ion source drift area, the first differential vacuum chamber and the reaction tube, and the differential tail end of the first vacuum chamber is connected with a first mechanical pump, the tail end of the second differential vacuum cavity is connected with a second mechanical pump, a VOCs gas inlet is arranged on the wall of the reaction tube and close to the first differential vacuum cavity, the VOCs gas inlet is connected with the sixteen-way switching valve through a pipeline, a VOCs gas outlet is arranged on the second differential vacuum cavity, a single lens is arranged in the ion transmission area, the single lens is composed of three groups of electrodes which are arranged left and right, and each group of electrodes is composed of two electrodes which are opposite up and down; the upper part of the TOF detection area is communicated with the reflection area through a field-free drift area, an XY deflection plate is arranged in the field-free drift area, and three groups of reflectors and detectors are arranged in the reflection area.

Wherein:

first gas-supply pipe and second gas-supply pipe all adopt the teflon material for the sample transmission, greatly reduced the pipeline to volatile organic compounds' absorption, corrosion resistance good, gas delivery volume is big, reliable durable, guarantee the accuracy of sampling.

A first thermocouple temperature sensor is arranged corresponding to the first electric heating belt, and the first thermocouple temperature sensor and the first electric heating belt are both connected with a first temperature controller; a second thermocouple temperature sensor is arranged corresponding to the second electric heating belt, and the second thermocouple temperature sensor and the second electric heating belt are both connected with a second temperature controller; the first gas pipe is provided with a diaphragm pump.

The electric heating belt is used for heating the pipeline of the gas transmission pipe, and the temperature is accurately controlled through the sensing of the thermocouple temperature sensor and the temperature controller. The temperature of the front-end pipeline is controlled by a first thermocouple temperature sensor and a first temperature controller, and the temperature of the rear-end pipeline is controlled by a second thermocouple temperature sensor and a second temperature controller. The heating temperature of the gas pipe is adjusted to ensure that the material in the pipe maintains a gasification state, so that the high-temperature flue gas is prevented from being cooled, liquefied or solidified on the wall of the sampling device, the inner wall of the sampling pipe is narrow or liquid droplets remain, the sampling accuracy and the real representativeness are ensured, and the gas pipe is suitable for collecting volatile organic compounds in the high-temperature flue gas.

The gas filter adopts a cylindrical 316 stainless steel filter element for filtering, removes large particles in waste gas and purifies the gas.

The diaphragm pump is used for transmitting a gas sample to be detected, high sealing performance ensures that the gas sample has no leakage or dilution, and is reliable, durable and low in maintenance cost.

The precision filter adopts a glass fiber filter element for filtration, has small filtration resistance and large flux, can efficiently remove fine particles, achieves the aim of purifying and dedusting, and ensures that the waste gas entering the analysis equipment has no impurities.

The first-stage gas-liquid separator is connected with a second thermocouple temperature sensor and a second temperature controller.

The low-temperature cooling device is internally provided with a closed recyclable anti-freezing cooling liquid, the cooling liquid circularly flows in a cooling coil pipe in the primary gas-liquid separator to cool a gas sample, the anti-freezing cooling liquid is anti-frozen in winter, and the external temperature can still normally work below 0 ℃.

The low-temperature cooling device is used for refrigerating the cooling coil of the primary gas-liquid separator, removing water and oil in the gas to be detected at low temperature, and controlling the refrigerating temperature to be 4 +/-2 ℃ by the second temperature controller. Pollutant source waste gas passes through the low-temperature cooling coil pipe and realizes effectual gas-liquid separation, removes most of moisture and oil content in the gas that awaits measuring, prevents that moisture and oil content from adhering to the sampling pipeline inner wall, causes the pipeline narrowly, avoids the accuracy that follow-up gas sample collection can be influenced to the tar of the attached moisture of inner wall, oil content or solidification state, and the guarantee can be gathered and has real representative's sample.

The liquid outlet of the first-stage gas-liquid separator and the liquid outlet of the second-stage gas-liquid separator are both connected with the inlet of the peristaltic pump, and the outlet at the bottom of the peristaltic pump is provided with a drain pipe.

The second-stage gas-liquid separator is made of cylindrical glass in a room temperature environment, the top of the second-stage gas-liquid separator is provided with two branch pipe openings which are respectively an inlet and a gas outlet, and the bottom of the second-stage gas-liquid separator is provided with a branch pipe opening which is a liquid outlet. And the gas in the first-stage gas-liquid separator enters a second-stage gas-liquid separator, the moisture and the oil in the pollution source waste gas can be further removed through room temperature cooling, the treated gas is discharged from a gas outlet, and the liquid enters a peristaltic pump from a bottom branch pipe and is discharged. The second-stage gas-liquid separator can further remove moisture and oil in the pollution source waste gas through room temperature cooling, purify the pollution source waste gas, and the second-stage gas-liquid separator can also play a role in safety buffering of pollution source sample gas flow and stabilize the gas flow.

Equivalent voltage dividing resistors are arranged outside the ion source drift region, the first differential vacuum cavity and the reaction region of the reaction tube, direct current voltage is applied, and the direction of an electric field is from left to right along the axial direction of the drift tube; the reaction tube focus area is provided with high-frequency alternating voltage, and the direction of an electric field is in the radial direction of the drift tube.

Through the isolation effect of the first differential vacuum cavity, the influence of the pressure increase of the reaction tube on the ion source is reduced, and the air input of the reaction tube is increased to improve the sensitivity of the instrument.

The acceleration electric field area on the TOF detection area is communicated with the reflection area through the field-free drift area.

The ion transport zone is provided with a first turbomolecular pump and the TOF detection zone is provided with a second turbomolecular pump.

The reaction tube is divided into a reaction area with no blocking space and a focusing area.

The water vapor generation device comprises a water storage bottle, wherein a thermocouple and a heating wire are arranged inside the water storage bottle, a heat insulation layer is arranged outside the water storage bottle, the top of the water storage bottle is connected with one inlet of a first tee joint through a pipeline, and a water switch is arranged on the pipeline between the water storage bottle and the first tee joint; other reaction gas inlets are connected with one inlet of the first tee joint through a pipeline, and other reaction gas regulating switches are arranged on the pipelines between the other reaction gas inlets and the first tee joint; a flow meter and a flow regulating switch are arranged on a pipeline between the first three-way outlet and the reaction chamber.

A reaction gas inlet is arranged on the ion source drift region at a position opposite to the first differential vacuum cavity, and the flow regulating switch is connected with the reaction gas inlet; and the sixteen-way switching valve is provided with an air inlet pipe.

The single lens is formed by three groups of electrodes placed left and right, each group of electrodes is formed by two opposite electrodes from top to bottom, wherein the two ends of the electrodes are used as extraction lens electrodes, the middle electrode is used as a transmission lens electrode, and the voltages applied by the three groups of electrodes are respectively: the voltage range of the extraction lens electrode is-6V-0V, and the voltage range of the transmission lens electrode is-80V-110V.

The inside position that is close to differential water conservancy diversion hole at the TOF detection zone sets up Faraday cup, and TOF detection zone is inside to be equipped with four polar plates, and four polar plates are bottom plate, extraction polar plate, middle polar plate and acceleration electrode board, each polar plate voltage range by last under to in proper order: the voltage of the bottom plate is-100V-200V, pulse voltage is applied to the extraction polar plate, when ions to be detected enter the polar plate ion introduction area, the voltage value of the extraction polar plate is the same as that of the bottom plate, when the ions with the largest mass-to-charge ratio enter the ion introduction area after one sample introduction, the voltage value of the extraction polar plate is increased to-400V-450V, the voltage of the middle polar plate is-500V-650V, and the voltage of the acceleration polar plate is-1800V-2200V.

The anode voltage of the ion source glow discharge area is 400-550V, and the supply of the glow discharge causes the cathode voltage to float downwards to about 750V before the glow discharge is switched on but the plasma starts; below the anode set point. Therefore, if the anode voltage is 450V, the cathode voltage will drop to about-300V. When the plasma starts, the cathode voltage starts to change. At this time, the discharge potential between the anode and the cathode is maintained between 350V and 400V. The pressure of the glow discharge area of the ion source is 10-100Pa, and the discharge current is 4-6 mA; the pressure of the ion transport region was 10^-4In the mbar order of magnitude; pressure within TOF detection zone of 10^-5-10^-7In the mbar class.

The outside of the reaction chamber is coated with a heat-insulating layer, and the inside of the reaction chamber is provided with a heating wire, a fan and a temperature controller; the gas flow at the inlet of the reaction chamber is 3-14 mL/min; the inner diameter of the first small hole is 0.05-0.5 cm; the diameters of the second small hole and the third small hole are both 0.1-1.0cm, and the inner diameter of the differential flow guide hole is 1-1.5 mm.

The utility model discloses an isolation of first difference vacuum cavity reduces the influence of reaction tube pressure increase to the ion source, increases the reaction tube air input in order to improve instrument sensitivity. Because the concentration content of VOCs in the environmental air sample is low, in order to improve the accuracy of sample determination, the pressure in the reaction tube is set to be 5-10mbar, the first mechanical pump is used for pumping vacuum, the direct current voltage applied to two ends of the reaction zone of the reaction tube is 1.5-3KV, and the sample gas inlet amount is 200-; and simultaneously applying high-frequency alternating voltage to a focusing area of the reaction tube, wherein the frequency of the alternating voltage is 0.4-0.6MHz, and the amplitude of the voltage is 40-60V. The length of the reaction tube is 90-120 cm.

Three groups of reflectors are arranged in the reflecting area, each group of reflectors consists of a reflecting plate, a sleeve and annular polar plates, the reflecting plate is circular, the sleeve is perpendicular to the reflecting plate, two groups of annular polar plates are arranged on the inner wall of the sleeve and distributed up and down, the voltage of one group of annular polar plates close to the opening of the sleeve is-1800V-2200V, the voltage of one group of annular polar plates close to the reflecting plate is-1700V-1900V, and the voltage of the reflecting plate is 1800V-2000V; the three groups of reflectors are respectively a first reflector, a second reflector and a third reflector, the openings of the sleeves of the first reflector and the third reflector are upward, the opening of the sleeve of the second reflector is downward, the first reflector and the third reflector are positioned at two sides of the second reflector and have the same height, and the height of the second reflector is higher than that of the first reflector and that of the third reflector. The first reflector is located below the XY deflection plate.

The VOCs gas inlet is connected with sixteen-way switching valve by means of pipeline, the sixteen-way switching valve is connected with standard gas outlet and zero gas inlet pipe of dynamic gas diluter, at the same time it is connected with air inlet pipe, said air inlet pipe can be various ambient air inlet pipes or Suma tank, the standard gas steel cylinder and nitrogen steel cylinder are respectively connected with dynamic gas diluter by means of pipeline, on the pipeline between standard gas steel cylinder and dynamic gas diluter a first mass flowmeter and a first pressure reducing valve are set, on the pipeline between nitrogen steel cylinder and dynamic gas diluter a second mass flowmeter and a second pressure reducing valve are set, after the zero gas inlet pipe is connected with zero gas generator a sixteen-way switching valve is connected, the zero gas inlet pipe is connected with zero-gas pump, precooling dehydrator and molecular sieve which are set in the zero gas generator in turn and then connected with sixteen-way switching valve, on the second differential vacuum cavity a VOCs gas outlet is set, and through pipeline a gas-pumping, the second tee joint second interface is connected with the dynamic gas diluter waste gas outlet, and the third interface of the second tee joint is connected with the exhaust pipe, so that two paths of waste gas are evacuated through the exhaust pipe.

The detector is a double-microchannel plate detector, the double-microchannel plate detector is connected with a 4GTDC time digital conversion module, the 4GTDC time digital conversion module is connected with an industrial personal computer, and the industrial personal computer is simultaneously connected with a controller of the sixteen-channel switching valve and an electronic weather station and is remotely connected with a mobile phone or a computer terminal.

Wherein:

the ion source comprises an ion source glow discharge region and an ion source drift region, and the interior of the reaction tube is divided into a reaction region with no space blockage and a focusing region; the ion source is provided with a reaction gas inlet, the reaction gas inlet can be simultaneously connected with a water vapor inlet and other reaction gas inlets through a first tee joint, the water vapor generator and the adjusting control part thereof are connected with other reaction gas switches and the adjusting control part thereof through a tee joint ball valve, the rapid switching of various reaction gases can be realized only by switching the reaction gas inlets, and the ion source does not need to be replaced.

The reaction gas may be steam or O₂NO, etc., the gas flow at the inlet of the reaction chamber is 3-14mL/min, so that the reaction gas is positively ionized ([ H ]₃O]⁺、[O₂]⁺Or [ NO ]]⁺) The abundance of the ions reaches 1.6 multiplied by 10⁵Thus, the volatile organic compound molecule R is successfully converted into VOCs positive ions [ RH ]]⁺Or R⁺。

The first differential vacuum chamber serves a dual purpose, first, to further purify the reactant gas ions. And voltage is applied to the outside of the first differential vacuum cavity and is connected with equivalent resistance to divide voltage, and a uniform electric field is formed inside the first differential vacuum cavity. Under the action of electric field force, positive ions move towards the reaction tube, and neutral molecules do not have obvious orientation due to the fact that the neutral molecules do not move under the action of the electric field force and are pumped away through the molecular pump, so that the purpose that the ions of the reaction gas are continuously extracted from the reaction gas in the process of moving towards the reaction tube is achieved. Secondly, the pressure in the reaction tube can influence the ion source to a certain extent, so the pressure in the reaction tube which can be born by the ion source is limited, the pressure of the traditional drift tube can only reach 1-2mbar, the ion source and the reaction tube can be isolated to a greater extent by virtue of the first differential vacuum chamber, and the pressure in the reaction tube can reach 5-10mbar, so that the ion number density in the reaction tube can be improved, the sample introduction amount of the sample gas is increased to remarkably enhance the response value of measuring each VOCs substance, the sensitivity of the instrument is improved, and the accuracy of the measuring result is ensured. Through an ion motion simulation experiment, the ion current is monitored by using a Faraday cup arranged at the tail end of the reaction tube, the ion current intensity is 500nA when the first differential vacuum chamber is not arranged, and the ion current intensity is increased to 700nA when a low-concentration sample is measured by means of the action of the first differential vacuum chamber. Here the increased ion current intensity versus the increased sensitivity of the instrument is embodied in a significant reduction of the detection limit: the detection limit of the instrument can only reach a few ppt when the first differential vacuum cavity is not arranged, and the detection limit of each substance can reach the level below the ppt by arranging the differential vacuum cavity. The inner diameter of the first small hole is 0.05-0.5cm, and the reaction gas is further pumped from the rear part of the first small hole through a molecular pump, so that the unprotonated reaction gas entering the reaction tube is reduced to the maximum extent.

The inner wall of the reaction tube is modified, and the modified material can use polydimethylsiloxane to reduce the adsorption of VOCs molecules.

An equivalent voltage dividing resistor is arranged outside the reaction zone of the reaction tube to divide the direct current voltage outside the reaction tube, so that a uniform axial electric field is formed in the reaction tube, and axial power is provided for ion movement; the VOCs molecules collide with the positive ions of the reaction gas in the tube to react. The pressure in the reaction tube is set by a computer, the molecular pump is used for pumping vacuum, and the air inlet needle valve is controlled by the valve motor to deliver sample gas, so that the pressure in the reaction tube is constant, and the air inflow is constant. When the sample is measured, the pressure in the reaction tube is 5-10mbar, the direct current voltage applied to two ends of the reaction tube is 1.5-3KV, and the sample gas introduction amount is 200-; and simultaneously applying high-frequency alternating voltage to the focusing area, wherein the frequency of the alternating voltage is 0.4-0.6MHz, the amplitude of the voltage is 40-60V, and the voltage provides radial constraint force for the movement of ions so that the ions are focused to the center of the reaction tube, thereby increasing the ion number passing through the second differential vacuum pore. Through an ion motion simulation experiment, ion current is monitored by a Faraday cup, and the ion passing rate can be improved by 10 times through the focusing effect of the high-frequency alternating voltage arranged at the ion current. The length of the reaction tube is 90-120cm, and the increase of the length can increase the probability of collision of VOCs and reaction reagent ions, improve the reaction efficiency and improve the measurement sensitivity of an instrument.

The single lens is formed by placing three groups of electrodes left and right, each group of electrodes is two pieces which are opposite up and down, wherein, the two ends of the electrodes are extraction lens electrodes, the middle electrode is a transmission lens electrode, and the ion flow focusing is completed by adjusting the voltage value of the electrodes. The extraction lens electrode voltage is high, the transmission lens electrode voltage is low, and the voltages applied by the three groups of electrodes are respectively as follows: the voltage range of the extraction lens electrode is-6V-0V, and the voltage range of the transmission lens electrode is-80V-110V. The ion transport zone pressure is maintained at 10 by a first turbomolecular pump^-4In the mbar class.

The ion transmission area is communicated with the TOF detection area through differential diversion holes, the inner diameter of each differential diversion hole is 1-1.5mm, and the pressure in the TOF detection area is 10^-5-10^-7mbar grade, maintained with a second turbomolecular pump. And a Faraday cup is arranged in the TOF detection area and close to the differential diversion hole to monitor ion current, so that the ion utilization rate is improved. The TOF detection area is internally provided with four polar plates which are sequentially a bottom plate, an extraction polar plate, a middle polar plate and an acceleration polar plate from top to bottom, the space between the bottom plate and the extraction polar plate is an ion introduction area, the space between the extraction polar plate and the acceleration polar plate is an ion acceleration area, the acceleration area adopts double-field acceleration, the middle polar plate is separated by space, a first-stage acceleration area is arranged between the extraction polar plate and the middle polar plate, and a second-stage acceleration area is arranged between the middle polar plate and the acceleration polar plate. Voltage range of each plate: the voltage of the bottom plate is-100V-200V, pulse voltage is applied to the extraction polar plate, when ions to be detected enter the polar plate ion introduction area, the voltage value of the extraction polar plate is the same as that of the bottom plate, when the ions with the maximum mass-to-charge ratio (M/Z) enter the ion introduction area after one sample injection, the voltage value of the extraction polar plate is increased to-400V-450V, the voltage of the middle polar plate is-500V-650V, and the voltage of the acceleration polar plate is-1800V-2200V.

The XY deflection plate is composed of an X deflection plate and a Y deflection plate, the X deflection plate is positioned above the Y deflection plate and used for adjusting the ion beam entering the reflector to fly to the detector in the horizontal direction and guiding the ion beam to impact the detector to the maximum extent, and the detector realizes the detection of each group of ions.

The three groups of reflectors can improve ion transmittance, ions reach the detector for detection after three times of reflection, the ion flight path is increased, the ion focusing effect is enhanced, and the detection resolution is improved.

The detector is a double-microchannel plate detector, the directly output signal is an analog signal, and has a linear relation with the flight time and the ion quantity, so that the problem of larger time and amplitude errors of ions caused by signal distortion is solved by adopting a high-frequency sampling and transmission mode. The double-microchannel plate detector is connected with the 4GTDC time digital conversion module, the 4GTDC time digital conversion module is connected with the industrial personal computer, and the industrial personal computer is connected with the sixteen-path switching valve controller so as to control the sixteen-path switching valve. The TDC time digital conversion module samples the frequency of 4GHz, and accurately measures the time interval between the start and stop of the pulse signal. An electronic pulse signal of the flight time mass spectrum is converted into a fixed amplitude signal through a peak discriminator (CFD), the signal is recorded through a time-to-digital converter (TDC), data are processed through a computer, a mass spectrum peak in a formed flight time mass spectrum is very narrow, the rising edge of the peak is smaller than 1 nanosecond, and the signal bandwidth is more than 1-2 GHz.

The utility model discloses set up the effective transmission of long range of sample transmission line and preceding processing equipment assurance pollution sources waste gas, sampling joint exit linkage gas filter promptly, the gas filter export is through first gas-supply pipe connection precision filter, first gas-supply pipe periphery sets up first electrical heating area, the one-level vapour and liquid separator and second grade vapour and liquid separator are connected gradually through the pipeline in the precision filter export, second grade vapour and liquid separator gas outlet connects the osmotic membrane gas desicator, the osmotic membrane gas desicator passes through second gas-supply pipe connection sixteen way diverter valve, second gas-supply pipe periphery sets up second electrical heating area. The purification processes of dewatering, dedusting, deoiling and the like of the pollution source waste gas are completed through the arrangement, the monitoring equipment can complete the generation and purification of the positive ions of the reaction gas, and the purity of the reaction ions is improved.

The utility model can realize the generation and purification of positive ions of the reaction gas and improve the purity of the reaction ions through the action of the electric field applied outside the first differential vacuum cavity; the reaction with VOCs molecules is completed in the modified reaction tube, and the influence of pressure increase in the reaction tube on the ion source is reduced by virtue of the isolation effect of the first differential vacuum cavity, so that the sample air input is improved, the molecule number density in the tube is increased, the sensitivity of the instrument can be obviously improved, and the anti-adsorption effect of a modifier also plays an important role in improving the sensitivity of the instrument; the direct current applied to the reaction region of the reaction tube and the high-frequency alternating current applied to the focusing region can screen and focus ions generated by the reaction, increase the density of the ions entering the ion transmission region, and improve the resolution of the instrument. The focusing function and high transmittance of the single lens also have important contribution to improving the sensitivity and resolution of the instrument; the focused ion beam monitors ion current by a Faraday cup, so that the ion utilization rate is improved; the ion flow vertically enters a TOF detection area and then is reflected by three reflectors, so that the ion movement distance is increased, and the influence of different speed directions, different sizes (speed dispersion) and different positions (space dispersion) on the resolution when the ion flow enters is reduced; the precise design of the voltage value of each polar plate of the TOF area detector, particularly the adjustment of the peak shape by the middle polar plate and the high-resolution detection of the double-microchannel plate detector, plays an important role in improving the resolution of the instrument. The instrument generates few ion fragments, has low mass spectrum background noise, and can realize the rapid, high-sensitivity and high-resolution detection of the VOCs.

The method for measuring the content of VOCs by the online monitoring system comprises the following steps: connecting a sampling joint with a fixed pollution source waste gas exhaust cylinder, allowing the fixed pollution source waste gas to enter a gas filter for filtering under the action of a diaphragm pump from the sampling joint, then entering a first gas conveying pipe, heating the first gas conveying pipe by using a first electric heating belt until materials in the pipe are maintained in a gasification state, conveying the heated first gas conveying pipe to a precision filter under the action of the diaphragm pump, performing secondary fine filtration and dust removal, and removing fine particles; the gas without the particles enters a first-stage gas-liquid separator for first water and oil removal, the temperature of the first-stage gas-liquid separator is 4 ℃, and the first water and oil removal is carried outThe gas after water and oil removal enters a secondary gas-liquid separator for secondary water and oil removal, the secondary gas-liquid separator is at room temperature, the purified gas is discharged from a gas outlet, enters a permeable membrane gas dryer for drying and dehydration, enters a second gas pipe, enters a sixteen-way switching valve through the second gas pipe and then enters a reaction chamber for detection; the reaction gas ions generated in the ion source enter the reaction tube after passing through the first differential vacuum cavity to collide with the volatile organic compound molecules R in the sample to be detected, and then the reaction is carried out to generate positive ions [ RH ] to be detected]⁺Or [ R ]]⁺(ii) a A first differential vacuum chamber is arranged between the ion source drift region and the reaction tube, an equivalent divider resistor is arranged outside the first differential vacuum chamber, direct current voltage is applied and is connected with the equivalent resistor for dividing voltage, a uniform electric field is formed inside the first differential vacuum chamber, and reaction gas ions [ H ] are generated under the action of the electric field force₃O]⁺Or [ NO ]]⁺Or [ O ]₂]⁺Move to the reaction tube, and the reaction gas is neutral molecule H₂O or NO or O₂The motion of the first differential vacuum chamber is not obviously oriented under the action of the electric field force, the tail end of the first differential vacuum chamber is connected with a first mechanical pump, and the first mechanical pump pumps neutral molecules H in the reaction gas₂O or NO or O₂Prevention of neutral molecules H₂O or NO or O₂Entering a reaction tube; reaction-generated molecule [ RH ] to be detected]⁺Or R⁺Under the action of a uniform electric field in the reaction tube, the ion enters an ion transmission area through a second small hole, a single lens is arranged in the ion transmission area, the single lens is formed by placing three groups of electrodes left and right, each group of electrodes is formed by two electrodes which are opposite up and down, the two electrodes are extraction lens electrodes, the middle electrode is a transmission lens electrode, and the focusing of ion current is completed by adjusting the voltage value of the electrodes; the ions horizontally enter a TOF detection area after passing through a differential diversion hole after being focused, a Faraday cup is arranged in the TOF detection area and close to the differential diversion hole, the ions focused by a lens horizontally enter the TOF detection area, the ion flow is monitored by the Faraday cup and then enters the TOF detection area, and the ions with different mass-to-charge ratios are distinguished in the process of continuous movement; the acceleration electric field region at the upper part of the TOF detection region is connected with the reflection region through a field-free drift regionThe X-Y deflection plate is arranged in the field-free drift region, the ion beams entering the reflectors and flying to the detector are adjusted, three groups of reflectors are arranged in the reflection region, the ion beams are guided to impact the detector to the maximum extent, and the detector realizes the detection of each group of ions.

The reactive gas ion is [ H ]₃O]⁺Or [ O ]₂]⁺Or [ NO ]]⁺When the reactive gas ion is [ H ]₃O]⁺During the process, the water vapor generated by the water vapor generating equipment flows through the water switch, then flows through the first tee joint, enters the ion source glow discharge area of the reaction chamber through the reaction gas inlet, and is ionized by the hollow cathode lamp of the ion source to generate reaction gas ions (H)₃O]⁺When the reactive gas ion is [ O ]₂]⁺Or [ NO ]]⁺When is, O₂Or NO enters the ion source glow discharge area of the reaction chamber from other reaction gas inlets, and different reaction gases are ionized to generate reaction gas ions [ O ] by utilizing the hollow cathode lamp of the ion source₂]⁺Or [ NO ]]⁺。

Generated in ion source [ H₃O]⁺Or [ O ]₂]⁺Or [ NO ]]⁺The (positive ions of the reaction gas) enter the reaction tube after passing through the first differential vacuum cavity to collide with volatile organic molecules R in the sample to be detected, and the reaction is carried out to generate positive ions [ RH ] to be detected]⁺Or [ R ]]⁺(ii) a Generated in ion source [ H₃O]⁺(positive ions of the reaction gas) enter the reaction tube after passing through the first differential vacuum cavity to collide with VOCs molecules R in the sample to be detected, and the reaction is carried out to generate molecules to be detected [ RH ]]⁺(ii) a Generated in ion source [ O ]₂]⁺Or [ NO ]]⁺The positive ions of the reaction gas enter the reaction tube after passing through the first differential vacuum cavity to collide with VOCs molecules R in the sample to be detected, and the reaction is carried out to generate molecules to be detected [ R ]]⁺。

Preferably, the detailed procedure of the instrument for determining a gas sample containing VOCs is as follows:

gas that gathers from the pollution source loops through the pollution source sampling joint and gets into between the preliminary treatment, carries out the dewatering dust removal with waste gas through purifier between the preliminary treatment, specifically is: gas from the pollution sources collection gets into gas filter by the sampling joint and filters, with first gas transmission pipe with first electric heating tape heating to make intraductal material maintain the gasification state can, according to handling the material difference, the temperature is done corresponding adjustment, reduces the pipeline and adsorbs, prevents that the high temperature gas in the flue from meetting the sampling device wall that the temperature is low and taking place the cooling liquefaction or solidify, influences the accuracy that follow-up gas sample gathered. The temperature of the first gas conveying pipe is controlled by a first thermocouple temperature sensor and a first temperature control instrument, and the temperature of the second gas conveying pipe is controlled by a second thermocouple temperature sensor and a second temperature control instrument. The primary gas-liquid separator is cooled through a low-temperature cooling device arranged outside, the low-temperature cooling device cools a cooling coil in the primary gas-liquid separator to 4 ℃ for removing moisture and oil in the gas to be detected at low temperature, and the refrigerating temperature of 4 ℃ is controlled by a second temperature controller.

The sampling joint is connected with a fixed pollution source waste gas exhaust cylinder, and the fixed pollution source waste gas enters a first gas conveying pipe after being subjected to primary coarse filtration and dust removal of a gas filter under the pumping attraction of a diaphragm pump. The outside cladding of first gas-supply pipe has first electric heating area, and the temperature is controlled through first thermocouple temperature sensor and first temperature control appearance. The diaphragm pump provides power for the transmission of the fixed pollution source waste gas sample. And conveying the pollution source waste gas subjected to preliminary coarse filtration and dust removal to a precision filter under the pumping action of a diaphragm pump, and performing secondary fine filtration and dust removal to remove fine particles.

And (3) allowing the gas with the particulate matters removed to enter a primary gas-liquid separator for first water and oil removal, wherein the low temperature of 4 ℃ of the primary gas-liquid separator is controlled by a second thermocouple temperature sensor and a second temperature controller. Under the action of low temperature cooling, condensed liquid water and oil in the waste gas enter the peristaltic pump, and are drained and discharged under the rolling action of the peristaltic pump, and the water and oil are drained through the drain pipe. And the gas after the first water and oil removal enters a secondary gas-liquid separator, the gas is cooled at room temperature through the secondary gas-liquid separator, the second water and oil removal is started, the moisture and oil in the pollution source waste gas are further removed, the pollution source waste gas is purified, the purified gas is discharged from a gas outlet, and the liquid enters a peristaltic pump from a bottom branch pipe of the secondary gas-liquid separator and is discharged through a drain pipe. In addition, the secondary gas-liquid separator also plays a role in safely buffering the sample gas flow of the pollution source and stabilizing the gas flow. Gas after secondary gas-liquid condensation processing then gets into osmotic membrane gas dryer drying, carries out the final dehydration of gas sample, and through the dehydration of osmosis membrane method, volatile organic compounds can pass through the osmotic membrane smoothly in the gas, and water can not pass through the osmotic membrane, and the high dry purification of guarantee transmission pollution sources waste gas sample. The permeable membrane type gas dryer has the advantages of good drying effect, high efficiency and high speed.

And the sample gas after being dried and dewatered by the permeable membrane gas dryer enters a second gas pipe, preferably, the second gas pipe is accompanied with an explosion-proof heat tracing wire, and the temperature of the second gas pipe is controlled by a second thermocouple temperature sensor and a second temperature controller. The gas enters the sixteen-way switching valve through the second gas transmission pipe and then enters the reaction chamber for detection.

The reaction gas is first ionized in an ion source inside the reaction chamber to produce positive ions. The reaction chamber comprises an ion source glow discharge region, an ion source drift region, a first differential vacuum chamber and a reaction tube which are adjacent in sequence. The rear part of the reaction chamber is sequentially connected with a second differential vacuum cavity, an ion transmission area and a TOF detection area. The outside cladding heat preservation of reaction chamber, inside sets up heater strip, fan and temperature controller, and the heater strip heats it, and the fan promotes inside temperature equilibrium to control the temperature with the temperature controller. Since some volatile organic molecules cannot be measured by the reaction of hydrated protons, it is necessary to pass another reaction gas (O)₂NO, etc.) were measured. And the replacement of the reaction gas is usually accompanied with the replacement and debugging of the ion source, the operation is complex, and the requirement on technical personnel is high. Therefore, the ion source which is more convenient to operate is designed, the ion source is provided with a reaction gas inlet, the reaction gas inlet is connected with an outlet of a first tee joint, two inlets of the first tee joint are respectively connected with a water vapor generating device and other reaction gas inlets, the water vapor generating device comprises a water storage bottle, a thermocouple and a heating wire are arranged inside the water storage bottle, a heat preservation layer is arranged outside the water storage bottle, and the top of the water storage bottle passes through a pipelineOne inlet of the three-way joint is connected, and a water switch is arranged on a pipeline between the water storage bottle and the three-way joint; other reactive gas inlets (O)₂NO) is connected with one inlet of the first tee joint through a pipeline, and other reaction gas regulating switches are arranged on the pipelines between other reaction gas inlets and the first tee joint; a flow meter and a flow regulating switch are arranged on a pipeline between the first three-way outlet and the reaction chamber. Therefore, the rapid switching of the multiple reaction gases can be realized by only switching the gas inlets without replacing the ion source.

Taking water as a reaction reagent as an example, a water switch is opened, and in order to ensure the stability of the generation rate of the reaction ions, the water storage bottle is subjected to constant temperature control. The temperature of water in the water storage bottle is maintained at 40 ℃ under the heating action of the heating wire and the heat preservation action of the heat preservation groove, the continuous generation of saturated vapor with the constant pressure of 70mbar is ensured, and the gas flow is 3-14mL/min, so that the ion abundance of hydronium ions reaches 1.6 multiplied by 10⁵The above. The generated vapor flows through the water switch, then enters the ion source of the reaction chamber through the first tee joint, the flowmeter and the flow regulating switch, and is ionized to generate hydronium ions. In order to obtain better ionization efficiency of reaction gas, the anode voltage of the glow discharge area of the ion source needs to be ensured to be 400-550V, and the cathode voltage is caused to float downwards to about 750V by the supply of glow discharge before the plasma starts after the glow discharge is switched on; below the anode set point. Therefore, if the anode voltage is 450V, the cathode voltage will drop to about-300V. When the plasma starts, the cathode voltage starts to change. At this time, a voltage difference of the sustain discharge between the anode and the cathode is maintained between 350V and 400V. The pressure of the glow discharge area of the ion source is about 10-100Pa, and the discharge current is 4-6 mA. Generation of large quantities of H by cathode glow discharge]⁺、[H₃O]⁺And further reacting in the ion source drift region to generate high-purity [ H ]₃O]⁺. If other reaction gases are used, the gases enter the ion source through the first tee joint, the flowmeter and the flow regulating switch after passing through other reaction gas inlets, and the ion source does not need to be replaced.

Reaction gas ion generated by reaction [ H₃O]⁺Enter into reactionThe tube collides with VOCs molecules R, which represents the molecules, and reacts to generate molecules [ RH [ -]⁺. The reaction gas ions enter the reaction tube while being entrained with the water vapor to varying degrees. In order to reduce water molecules entering a reaction tube as much as possible and improve the purity of water and protons, a first differential vacuum chamber is designed and arranged between an ion source drift region and the reaction tube, and neutral reaction gas (H) is pumped out from the tail end of the first differential vacuum chamber by a first mechanical pump₂O、O₂NO, etc.).

The first differential vacuum cavity applies direct current voltage and is connected with equivalent resistance to divide voltage, and a uniform electric field is formed inside the first differential vacuum cavity. Under the action of electric field force, positive ions move to the reaction tube, while neutral molecules do not have obvious orientation due to the fact that the neutral molecules do not move under the action of electric field force, and therefore ions ([ H ] in the reaction gas are obtained₃O]⁺Or [ O ]₂]⁺Or [ NO ]]⁺) Continuously extracting the reaction gas in the process of moving to the reaction tube. Simultaneously, a first mechanical pump is used for pumping neutral molecules (H) in the reaction gas in the first differential vacuum chamber₂O、O₂NO, etc.), neutral molecules of the reaction gas are prevented from entering the reaction tube, and ions ([ H ] of the reaction gas entering the reaction tube are increased₃O]⁺Or [ O ]₂]⁺Or [ NO ]]⁺) The purity of the instrument is improved, and the sensitivity of the instrument is improved.

The function of the first differential vacuum chamber in improving the sensitivity of the sample measurement is not only reflected in improving the purity of the reactive gas ions, but also has another important function: the ion source and the reaction tube can be isolated to a greater extent without influencing the entrance of reaction gas ions into the reaction tube, thereby reducing the influence of the increase of the pressure in the reaction tube on the ion source. Therefore, when a sample is measured, the number density of molecules of the reaction tube and the voltage of the reaction tube are properly increased, the sample introduction amount of the sample gas is increased, so that the response value of measuring each VOCs is obviously enhanced, and the sensitivity of the instrument is improved. The specific operation is as follows: by means of the isolation effect of the differential vacuum cavity, the air inlet needle valve is controlled by the valve motor to improve the air input of the delivered sample gas, the number density of molecules in the reaction tube is increased, and the pressure in the reaction tube is regulated to be increased to 5-10 mbar. By means of the effect of increasing the ion current intensity of the first differential vacuum chamber, the sensitivity of the instrument is remarkably improved, and the detection limit is remarkably reduced: the detection limit of the instrument can only reach a few ppt when the first differential vacuum cavity is not arranged, and the detection limit of each substance can reach the level below the ppt by arranging the differential vacuum cavity.

The direct current voltage applied to two ends of the reaction zone of the reaction tube is 1.5-3KV, and an equivalent voltage-dividing resistor is arranged outside the reaction zone to divide the direct current voltage outside the reaction tube, so that a uniform electric field is formed in the reaction tube. Keeping the E/n within the range of 170-. And applying high-frequency alternating voltage to the focusing area, wherein the frequency of the alternating voltage is 0.4-0.6MHz, the amplitude of the voltage is 40-60V, and the voltage provides radial constraint force for the movement of ions, so that the ions are focused to the center of the reaction tube, and the number of the ions passing through the second differential vacuum small hole is increased. The material and length of the reaction tube have important influence on the sensitivity and resolution of the measurement of the instrument, and the reaction tube made of stainless steel can generate adsorption effect and memory effect, so that the inner wall of the reaction tube is modified by a polydimethylsiloxane coating, the adsorption and memory effect is reduced, and the measurement sensitivity is improved. The length of the reaction tube is designed to be 90-120cm, and the length can increase the probability of collision of VOCs and reaction reagent ions, improve the reaction efficiency and improve the measurement sensitivity of an instrument.

The vacuum degree in the reaction tube is maintained by a second mechanical pump, and the unreacted VOCs gas in a second differential vacuum cavity connected to the tail end of the reaction tube passes through a VOCs gas outlet, passes through a flowmeter, is pumped out by a suction pump and is emptied by a tee joint.

The ions of the substance to be detected generated by the reaction enter the ion transmission area through the second small hole under the action of the uniform electric field in the reaction tube, the diameter of the second small hole is 0.1-1.0cm, the ion transmission area is vacuumized by a turbo molecular pump, and the pressure of the ion transmission area is ensured to be 10^-4In the order of mbar. Ion current can have certain degree to diverge in the ion motion process, produces serious influence to instrument resolution ratio, based on this, utility model people considers the factor in ion throughput rate and ion beam focus two aspects comprehensively, and the ion transmission district of design uses single lens, and single lens places by three group's electrodes about and constitutes, and every group electrode is upper and lower relative two piecesWherein, the two end electrodes are extraction lens electrodes, the middle electrode is a transmission lens electrode, and the ion flow focusing is completed by adjusting the voltage value of the electrodes. The single lens has simple structure and high ion passing rate, and can achieve ideal focusing effect by accurately controlling the voltage values of the three groups of lens electrodes. The voltages applied by the three groups of electrodes are respectively as follows: the voltage range of the extraction lens electrode is-6V-0V, and the voltage range of the transmission lens electrode is-80V-110V. Therefore, a curved electric field is formed, positive ions or negative ions entering the electric field can be focused to form a concentrated ion flow, the problem of divergence of the ions is solved, the introduction efficiency of the ions is ensured, and the method has important contribution to improving the resolution of an instrument. Ion flow passes through level behind the differential water conservancy diversion hole and gets into the TOF detection zone after focusing, and differential water conservancy diversion downthehole diameter is 1-1.5mm, can guarantee the ion through-put rate, effectively keeps apart ion transmission district and TOF detection zone simultaneously, guarantees the high vacuum degree of TOF detection zone. The design of directly connecting the TOF detection area without using a quadrupole mass analyzer has remarkable advantages compared with the design of using a quadrupole mass analyzer, the traditional quadrupole mass analyzer mainly plays a role in ion screening, and the molecular weight which can be detected by the quadrupole mass analyzer can be much more than three hundred; the design solves the problem that the mass range of the monitoring ions of the quadrupole mass analyzer is small, and the design is a better choice in the aspect of monitoring VOCs macromolecules.

After ions focused by the lens horizontally enter the TOF detection area, an electric field is applied in the vertical direction, and the electric field force applied to different ions in the vertical direction does work the same, so that the ions with different mass-to-charge ratios (M/Z) have different moving speeds, the speed with large mass is slow, the speed with small mass is fast, and the ions with different mass-to-charge ratios (M/Z) can be continuously distinguished after moving for a certain distance. However, considering the fact that ions move, there is a velocity dispersion and a spatial dispersion of ions as they enter the TOF detection zone, severely limiting the sensitivity and resolution of the detector. For this reason, the measures we take in the TOF detection zone design to improve the sensitivity and resolution of the ion assay with respect to noise reduction are: the pressure of the TOF detection zone (ensuring high vacuum) was controlled to 10^-5-10^-7mbar grade, reduced stray ion to ion flightThe influence of the row. And a Faraday cup is arranged in the TOF detection area and close to the differential diversion hole to monitor ion current, so that the ion utilization rate is improved. The ion acceleration zone adopts double-field acceleration and is composed of four polar plates, wherein the four polar plates are sequentially a bottom plate, an extraction polar plate, a middle polar plate and an acceleration polar plate from top to bottom, the space between the bottom plate and the extraction polar plate is an ion introduction zone, the space between the extraction polar plate and the acceleration polar plate is an ion acceleration zone, the acceleration zone adopts double-field acceleration and is separated by the space of the middle polar plate, a first-stage acceleration zone is arranged between the extraction polar plate and the middle polar plate, and a second-stage acceleration zone is arranged between the middle polar plate and the acceleration polar plate. The middle polar plate plays an important role in adjusting ion peak shape and improving resolution: in the optimal voltage value range, when the voltage of the middle polar plate is smaller, the kinetic energy of the ions between the extraction polar plate and the middle polar plate is small, the initial acceleration speed of the ions is small, the movement time is prolonged, the peak shape is widened, and the resolution is reduced; the resolution can be improved by increasing the voltage of the intermediate electrode plate properly, increasing the preliminary acceleration speed of ions and reducing the motion time to narrow the peak shape, but the resolution is also reduced by excessively high voltage of the intermediate electrode plate. In the experiment, the optimal value of the middle electrode plate voltage is-600V when water is used as a reaction reagent and benzene in the air is measured, and when the middle electrode plate voltage is set to-490V, the peak height is 638 and the resolution is 3060; when the voltage is increased to-550V, the peak height is 952, and the resolution is 4647; when the voltage is increased to-570V, the peak height is 974, and the resolution is 4669; when the voltage is increased to-600V, the peak height is 1016, the resolution is 5012, and the resolution is the highest; when the voltage was increased to-620V, the peak shape was rather deteriorated.

And an XY deflection plate is arranged in the field-free drift region close to the accelerating electrode plate, and the ion beam entering the reflector and flying to the detector is adjusted to guide the ion beam to impact the detector to the maximum extent. In order to compensate the space dispersion and the energy dispersion of ions to a greater degree and improve the resolution, three groups of reflectors are used, the three groups of reflectors are respectively a first reflector, a second reflector and a third reflector, the sleeve openings of the first reflector and the third reflector are upward, the sleeve opening of the second reflector is downward, the first reflector and the third reflector are positioned on two sides of the second reflector and have the same height, the height of the second reflector is higher than that of the first reflector and the third reflector, namely the three groups of reflectors are positioned at three end points of an inverted V shape, the first reflector is positioned below an XY deflection plate, the three groups of reflectors and a detector are positioned at five end points of a W shape, the design increases the ion movement path, and the increase of the movement path can effectively compensate the space dispersion; the reflector can make the depth of ions with large initial energy entering the reflecting area deeper, the depth of ions with small initial energy entering the reflector shallower, faster ones have more distance and slower ones have less distance, and the same ions almost reach the detector at the same time after three times of reflection, so that the speed dispersion of the ions is compensated, and the resolution is improved. The three-level reflector is adopted, the compensation of ion space dispersion and initial energy dispersion is realized to a greater extent, and the resolution of the instrument is greatly improved; the double microchannel plate detector is adopted to improve the ion detection multiple, and has an important effect on improving the resolution of the instrument.

Arranging a Faraday cup at a position close to the differential diversion hole in the TOF detection area, and setting the voltage of each polar plate in the TOF detection area, wherein the voltage of a bottom plate, a middle polar plate and an accelerating polar plate maintains the set optimal values of-100V to-200V, -500V to-650V and-1800V to-2200V respectively, only the extraction polar plate adopts a pulse voltage form, when ion current continuously enters the ion introduction area of the bottom plate and the extraction polar plate, the voltage of the extraction polar plate is-100V to-200V and is the same as the voltage value of the bottom plate, no electric field exists between the extraction polar plate and the bottom plate at the moment, and ions transversely enter the ion introduction area; when ions with the largest mass-to-charge ratio (M/Z) enter an ion introduction area after one-time sample introduction, the voltage of an extraction electrode plate is increased to-400V-450V, and at the moment, the ion flow moves downwards under the action of an electric field, so that the ion flow can be modulated into a single ion group, the ion utilization rate is ensured, and the sensitivity is improved; the ion peak shape is adjusted by adjusting the voltage of the intermediate plate, so that the resolution is improved, when the voltage of the intermediate plate is lower, the initial acceleration speed of the ions is lower, the movement time is longer, the peak shape is wider, the resolution is reduced, and the initial acceleration speed of the ions is increased, the movement time is shorter, the peak shape is narrower and the resolution is improved by properly increasing the voltage of the intermediate plate; the ions primarily accelerated by the middle electrode plate are accelerated under the action of high voltage (-2000V) of the accelerating electrode plate, and obtain larger kinetic energy. The charged ions are then subjected to X/Y deflection to adjust the lateral position of the ion beam, directing the beam to impinge maximally on a detector. The ions then enter a field-free drift region and are continuously separated during the movement. The ions enter the reflecting region after passing through the field-free drift region, the voltage of a group of annular polar plates close to the sleeve opening is-1800V-2200V, the voltage of a group of annular polar plates close to the reflecting plate is-1700V-1900V, the voltage of a group of annular polar plates close to the sleeve opening is the same as that of the accelerating polar plate, the field-free drift region is formed between the polar plates, the voltage of the reflecting plate is 1800V-2000V, and the double reflecting regions provide media for effective reflection of the ions, so that the field-free drift region has important significance for compensating speed dispersion. In the region, ions are subjected to acting force opposite to the movement direction, gradually decelerated and reversely accelerated to enter the next ion reflection region, and after multi-stage reflection is finished, the ions are driven to the double microchannel plates and are detected by the high-resolution double microchannel plate detector.

The signal measured by the detector passes through a 4GTDC time-to-digital conversion module, the sampling frequency is 4GHz, and the time interval of the start and stop of the pulse signal is accurately measured. An electronic pulse signal of the flight time mass spectrum is converted into a fixed amplitude signal through a peak discriminator (CFD), the signal is recorded through a time-to-digital converter (TDC), data are processed through a computer, a mass spectrum peak in a formed flight time mass spectrum is very narrow, the rising edge of the peak is smaller than 1 nanosecond, and the signal bandwidth is more than 1-2 GHz.

To sum up, the utility model has the advantages of it is following:

(1) the utility model discloses the organic matter kind that can detect is extensive. Multiple reactive gases, e.g. H, can be selectively used without changing the ion source₂O、O₂NO, etc. are ionized.

(2) The utility model discloses can obviously improve the degree of accuracy of the gaseous sample survey of VOCs. The first differential vacuum chamber is additionally arranged between the ion source drift region and the reaction tube, and the influence of pressure increase in the reaction tube on the ion source is reduced through the isolation effect of the first differential vacuum chamber, so that the pressure in the reaction tube can be greatly increased, the sample air input is improved, the molecule number density in the tube is increased, and the detection accuracy is obviously improved.

(3) The utility model discloses can obviously improve the sensitivity of VOCs survey. The inner wall of the used reaction tube is modified by a coating, so that the adsorption effect of VOCs molecules can be reduced; applying high-frequency alternating voltage to the reaction tube focusing area to focus ion flow; the transmittance of ions entering a TOF detection area is further improved through secondary focusing of the ion transmission area, and ion current is monitored by a Faraday cup before the ion beams enter the TOF detection area, so that the ion utilization rate is improved; the instrument generates few ion fragments, the mass spectrum background noise is low, the sensitivity is high, and the spectrogram analysis is simple and convenient.

(4) The utility model discloses can improve the resolution ratio of VOCs survey. The three-stage reflector is combined with a double-microchannel plate detector, so that the ion movement path is increased, and the influence of different speed directions, different sizes (speed dispersion) and different positions (space dispersion) on the resolution when the ion flow enters is reduced; the precise design of the voltage value of each polar plate of the TOF detection area detector, particularly the effect of the middle polar plate on adjusting the ion peak shape and the high-resolution detection of the double-microchannel plate detector, plays an important role in improving the resolution of the instrument.

(5) The utility model discloses can realize the quick monitoring of VOCs concentration in the pollution sources waste gas, the survey is fast, and the result is accurate, but wide application in emergent monitoring management. Pretreatment equipment can realize the high-efficient nondestructive treatment to pollution source waste gas to directly get into detection device through sixteen ways diverter valve after purifying through the dust removal dewatering, carry out the nondestructive switching through computer control sampling gas pipeline, realize that single reaction time of flight mass spectrograph monitors the function of multitube way pollution source waste gas simultaneously. The data measurement speed is fast, and the concentration value of the VOCs component in the pollution source can be obtained within the millisecond range.

(6) The utility model discloses the transmission area is focused on with novel lens and need not to use traditional static four pole DCQ focus separation to avoid charged ion's loss, increased the scope of survey molecular weight, directly survey with the TOF detection zone at last, the accurate cooperation of each part of entire system realizes the high-resolution detection to the determinand molecule. Interference factors in the detection process are few; the ionization source is soft chemical ionization, the generation of fragments is less, the spectrogram is simple, the analysis is easy, the range of the measured molecular weight is wide, and the resolution and the sensitivity are high.

(7) The utility model discloses can realize the incessant monitoring that lasts to blowdown unit emission VOCs, provide data theory support for the environmental monitoring law enforcement of relevant department. The data acquisition interval can be several seconds, the time interval is small, the data continuity is strong, and the pollution discharge behavior of enterprises can be closely monitored.

Drawings

Fig. 1 is a schematic structural diagram of embodiment 1 of the present invention;

fig. 2 is a graph of the resolution test of the instrument in different voltages of the middle electrode plate in embodiment 1 of the present invention.

In the figure: 1-a heat preservation layer, 2-a water storage bottle, 3-a heating wire, 4-a thermocouple, 5-a water switch, 6-other reaction gas inlets, 7-other reaction gas regulating switches, 8-a first tee joint, 9-a flowmeter, 10-a flow regulating switch, 11-an ion source glow discharge area, 12-an ion source drift area, 13-a first differential vacuum chamber, 14-a reaction tube, 15-a second differential vacuum chamber, 16-an ion transmission area, 17-a Faraday cup, 18-a TOF detection area, 19-a bottom plate, 20-a VOCs gas inlet, 21-a first small hole, 22-a first mechanical pump, 23-an equivalent divider resistor, 24-a second small hole, 25-an electrode, 26-a field-free drift area and 27-XY deflection plates, 28-reflection area, 29-detector, 30-reflector, 31-sleeve, 32-annular polar plate, 33-reflector, 34-4GTDC time-to-digital conversion module, 35-second mechanical pump, 36-industrial computer, 37-sixteen-way switching valve, 38-molecular sieve, 39-precooling dehydrator, 40-oil-free pump, 41-zero gas inlet pipe, 42-dynamic gas diluter, 43-first mass flowmeter, 44-first pressure reducing valve, 45-standard gas steel cylinder, 46-second mass flowmeter, 47-second pressure reducing valve, 48-nitrogen steel cylinder, 49-exhaust pipe, 50-second tee joint, 51-air pump, 52-third small hole, 53-differential diversion hole, 54-extraction polar plate, 55-middle pole plate, 56-accelerating pole plate, 57-air inlet pipe, 58-reaction gas inlet, 59-VOCs gas outlet, 60-sampling joint, 61-gas filter, 62-first gas pipe, 63-first electric heating belt, 64-first thermocouple temperature sensor, 65-first temperature control instrument, 66-diaphragm pump, 67-precision filter, 68-first-stage gas-liquid separator, 69-second-stage gas-liquid separator, 70-peristaltic pump, 71-permeable membrane gas dryer, 72-second gas pipe, 73-second electric heating belt, 74-second thermocouple temperature sensor and 75-second temperature control instrument.

Detailed Description

The present invention will be further described with reference to the following examples.

Example 1

Substances such as propylene, acetone, 1, 3-butadiene, 1-butene, cyclohexane, benzene, acetaldehyde, acrolein, 2-propanol, methyl vinyl ketone, n-butanol, n-valeraldehyde, n-hexanal and the like were measured using water as a reaction gas.

An online monitoring system for high-resolution high-sensitivity rapid determination of volatile organic compounds comprises a sampling connector 60 and a reaction chamber, wherein an outlet of the sampling connector 60 is connected with a gas filter 61, an outlet of the gas filter 61 is connected with a precision filter 67 through a first gas pipe 62, a first electric heating belt 63 is arranged on the periphery of the first gas pipe 62, an outlet of the precision filter 67 is sequentially connected with a primary gas-liquid separator 68 and a secondary gas-liquid separator 69 through pipelines, a gas outlet of the secondary gas-liquid separator 69 is connected with a permeable membrane gas drier 71, the permeable membrane gas drier 71 is connected with a sixteen-way switching valve 37 through a second gas pipe 72, and a second electric heating belt 73 is arranged on the periphery of the second gas pipe 72; the reaction chamber is provided with a reaction gas inlet 58, the reaction gas inlet 58 is connected with the outlet of a first tee joint 8, two inlets of the first tee joint 8 are respectively connected with a water vapor generation device and other reaction gas inlets 6, the reaction chamber comprises an ion source glow discharge area 11, an ion source drift area 12, a first differential vacuum chamber 13 and a reaction tube 14 which are adjacent in sequence, the rear part of the reaction chamber is connected with a second differential vacuum chamber 15, an ion transmission area 16 and a TOF detection area 18 in sequence, the first differential vacuum chamber 13 is communicated with the reaction tube 14 through a first small hole 21, the reaction tube 14 is communicated with the second differential vacuum chamber 15 through a second small hole 24, the second differential vacuum chamber 15 is communicated with the ion transmission area 16 through a third small hole 52, the ion transmission area 16 is communicated with the detection area 18 through a differential diversion hole 53, the ion source drift area 12, the first differential vacuum chamber 13 and the reaction area of the reaction tube 14 are all provided with equivalent partial pressure resistors 23 outside, the tail end of the first differential vacuum cavity 13 is connected with a first mechanical pump 22, the tail end of the second differential vacuum cavity 15 is connected with a second mechanical pump 35, a VOCs gas inlet 20 is arranged on the wall of the reaction tube 14 and close to the first differential vacuum cavity 13, the VOCs gas inlet 20 is connected with a sixteen-way switching valve 37 through a pipeline, a VOCs gas outlet 59 is arranged on the second differential vacuum cavity 15, a single lens is arranged in the ion transmission area 16 and is composed of three groups of left and right electrodes 25, and each group of electrodes 25 is composed of two vertically opposite electrodes; the upper part of the TOF detection region 18 communicates with a reflection region 28 through a field-free drift region 26, an XY deflection plate 27 is provided in the field-free drift region 26, and three sets of reflectors 30 and detectors 29 are provided in the reflection region 28.

A first thermocouple temperature sensor 64 is arranged corresponding to the first electric heating belt 63, and the first thermocouple temperature sensor 64 and the first electric heating belt 63 are both connected with a first temperature controller 65; a second thermocouple temperature sensor 74 is arranged corresponding to the second electric heating belt 73, and both the second thermocouple temperature sensor 74 and the second electric heating belt 73 are connected with a second temperature controller 75; the first gas pipe 62 is provided with a diaphragm pump 66; the liquid outlet of the first-stage gas-liquid separator 68 and the liquid outlet of the second-stage gas-liquid separator 69 are both connected with the inlet of a peristaltic pump 70, and the outlet at the bottom of the peristaltic pump 70 is provided with a drain pipe.

The water vapor generation device comprises a water storage bottle 2, a thermocouple 4 and a heating wire 3 are arranged in the water storage bottle 2, a heat preservation layer 1 is arranged outside the water storage bottle 2, the top of the water storage bottle 2 is connected with one inlet of a first tee joint 8 through a pipeline, and a water switch 5 is arranged on the pipeline between the water storage bottle 2 and the first tee joint 8; the other reaction gas inlets 6 are connected with one inlet of the first tee joint 8 through pipelines, and other reaction gas regulating switches 7 are arranged on the pipelines between the other reaction gas inlets 6 and the first tee joint 8; a flow meter 9 and a flow regulating switch 10 are arranged on a pipeline between the outlet of the first tee joint 8 and the reaction chamber.

The VOCs gas inlet 20 is connected with sixteen-way switching valve 37 through a pipeline, the sixteen-way switching valve 37 is connected with a standard gas outlet and a zero gas inlet pipe 41 of a dynamic gas diluter 42, and is simultaneously connected with an air inlet pipe 57, the air inlet pipe 57 can be various ambient air inlet pipes or Suma tanks, a standard gas steel cylinder 45 and a nitrogen steel cylinder 48 are respectively connected with the dynamic gas diluter 42 through pipelines, a first mass flow meter 43 and a first pressure reducing valve 44 are arranged on the pipeline between the standard gas steel cylinder 45 and the dynamic gas diluter 42, a second mass flow meter 46 and a second pressure reducing valve 47 are arranged on the pipeline between the nitrogen steel cylinder 48 and the dynamic gas diluter 42, a sample inlet pipe 41 is sequentially connected with a non-oil pump 40, a precooling dehydrator 39 and a molecular sieve 38 arranged in the zero generator and then connected with the sixteen-way switching valve 37, and a VOCs gas outlet, the VOCs gas outlet 59 is sequentially connected with a suction pump 51 and a first interface of a second tee joint 50 through pipelines, a second interface of the second tee joint is connected with a waste gas outlet of the dynamic gas diluter 42, a third interface of the second tee joint 50 is connected with an exhaust pipe 49, and two paths of waste gases are evacuated through the exhaust pipe 49.

The detector 29 is a double-microchannel plate detector, the double-microchannel plate detector is connected with a 4GTDC time-to-digital conversion module 34, the 4GTDC time-to-digital conversion module 34 is connected with an industrial personal computer 36, and the industrial personal computer 36 is simultaneously connected with a controller of a sixteen-way switching valve 37 and an electronic weather station and is remotely connected with a mobile phone or a computer terminal.

The ion transport region 16 is provided with a first turbomolecular pump and the TOF detection region 18 is provided with a second turbomolecular pump.

A reaction gas inlet 58 is arranged on the ion source drift region at a position opposite to the first differential vacuum cavity, and the flow regulating switch is connected with the reaction gas inlet 58; the sixteen-way switching valve 37 is provided with an air intake pipe 57.

According to the volume ratio, a mixed standard gas containing 1ppm of propylene, acetone, 1, 3-butadiene, 1-butene, cyclohexane, benzene, acetaldehyde, acrolein, 2-propanol, methyl vinyl ketone, n-butanol, n-valeraldehyde and n-hexanal is prepared into standard gases with the concentrations of 10ppb, 20ppb, 100ppb, 200ppb, 400ppb and 1000ppb respectively. A standard gas is prepared from a standard gas in a standard gas cylinder 45 and nitrogen in a nitrogen cylinder 48 in a dynamic gas dilution instrument 42. And (3) carrying out detection after sample introduction is carried out from low concentration to high concentration in sequence, establishing a calibration curve according to the relation between the concentration and the response value, and calculating the concentration of each component in the sample from the calibration curve by measuring the response value of each component in the sample.

The determination process comprises the following steps:

connecting a sampling connector 60 with a fixed pollution source waste gas exhaust cylinder, allowing the fixed pollution source waste gas to enter a gas filter 61 for filtering under the action of a diaphragm pump 66 from the sampling connector 60, then entering a first gas pipe 62, heating the first gas pipe 62 by using a first electric heating belt 63 to enable materials in the pipe to maintain a gasification state, controlling the temperature of the first gas pipe 62 by using a first thermocouple temperature sensor 64 and a first temperature controller 65, conveying the gas to a precision filter 67 under the action of the diaphragm pump 66, performing secondary fine filtration and dust removal, and removing fine particles; the gas with the particles removed enters a primary gas-liquid separator 68 for first water and oil removal, the temperature of the primary gas-liquid separator 68 is 4 ℃, the gas after the first water and oil removal enters a secondary gas-liquid separator 69 for second water and oil removal, the secondary gas-liquid separator 69 is at room temperature, the purified gas is discharged from a gas outlet, enters an osmotic membrane gas dryer 71 for drying and dehydration, the dehydrated gas enters a second gas pipe 72, enters a sixteen-way switching valve 37 through the second gas pipe 72 and then enters a reaction chamber for detection.

The first tee joint 8 is communicated with a water vapor inlet, and other reaction gas inlets 6 are closed. And (5) starting a water switch 5, and controlling the water storage bottle 2 at a constant temperature in order to ensure the stability of the generation rate of the reaction ions. The temperature of water in the water storage bottle 2 is maintained at 40 ℃ under the heating action of the heating wire 3 and the heat preservation action of the heat preservation layer 1, the continuous generation of saturated vapor with the constant pressure of 70mbar is ensured, the flow of the used vapor is 4mL/min, the generated vapor flows through the water switch 5, then passes through the first tee joint 8, the flowmeter 9 and the flow regulating switch 10, then enters the ion source glow discharge area 11 in the reaction chamber through the reaction gas inlet, and is ionized by the hollow cathode lamp of the ion source to generate hydronium ions [ H ]₃O]⁺And ensures that the ion abundance of hydronium ion reaches 2.0 multiplied by 10⁵。

In order to obtain better ionization efficiency, the anode voltage of the ion source glow discharge region 11 is 450V, the cathode voltage is maximum-350V, and the anode and the cathodeThe discharge potential between the ion source and the ion source is maintained at 400V, the pressure of a glow discharge area 11 of the ion source is 100Pa, and the discharge current is 5 mA; generation of large quantities of H by cathode glow discharge]⁺、[H₃O]⁺And further reacting in the ion source drift region to generate high-purity [ H ]₃O]⁺. The reaction chamber before the sample is measured is heated by the heating wires arranged in the reaction chamber, the fan promotes the internal temperature to be balanced, the heat preservation layer coated outside keeps the temperature constant, and the temperature is strictly controlled by a temperature controller to be 100 ℃.

Ion source generated [ H ]₃O]⁺The water enters the reaction tube 14 with the length of 96cm after passing through the first differential vacuum chamber 13 and collides with VOCs molecules R to react, at the moment, the first differential vacuum chamber 13 effectively reduces the water molecules entering the reaction tube 14, and improves the water and protons H₃O]⁺The purity of the (D) has an important effect on improving the sensitivity of the instrument; the inner diameter of the first small hole 21 is 0.1cm, which can ensure that the reaction gas ions can effectively enter the reaction tube 14 and realize the isolation of the ion source and the reaction tube 14 to a greater extent. The reaction tube 14 is modified with polydimethylsiloxane to reduce the adsorption of organic molecules.

When a propylene, acetone, 1, 3-butadiene, 1-butene, cyclohexane, benzene, acetaldehyde, acrolein, 2-propanol, methyl vinyl ketone, n-butanol, n-valeraldehyde and n-hexanal gas sample is measured, the ion source and the reaction tube 14 can be separated to a greater extent through the first differential vacuum chamber 13, the influence of pressure increase in the reaction tube 14 on the ion source is reduced, the pressure in the reaction tube 14 is controlled to be increased to 10mbar through a computer, the voltage at two ends is set to be 3KV, the E/n is maintained at 175, and the sample feeding amount of the sample gas is 260ml/min, so that the ion number density in the reaction tube 14 is increased, and the response value of each substance to be measured is obviously enhanced. And simultaneously, high-frequency alternating voltage is applied to the focusing area, the frequency of the alternating voltage is 0.5MHz, the amplitude of the voltage is 55V, and the voltage provides radial constraint force for the movement of ions so that the ions are focused towards the center of the reaction tube, thereby increasing the ion number passing through the second differential vacuum small hole and improving the sensitivity of the instrument. In particular in terms of a significant reduction in detection limit: the detection limit of the apparatus can reach only a few ppt without providing the first differential vacuum chamber 13, and the detection limit of each substance can reach the ppt level or less by providing the first differential vacuum chamber 13.

Protonation products [ RH ] of propylene, acetone, 1, 3-butadiene, 1-butene, cyclohexane, benzene, acetaldehyde, acrolein, 2-propanol, methyl vinyl ketone, n-butanol, n-valeraldehyde, n-hexanal formed by the reaction]⁺Under the action of uniform electric field in the reaction tube 14, the ion beam passes through the second small hole 24 and the third small hole 52 with the diameter of 0.5cm and then enters the ion transmission area 16, the second small hole 24 and the third small hole 52 isolate the ion transmission area 16 from the reaction tube 14, and the ion transmission area 16 is vacuumized by the first turbo molecular pump to ensure that the pressure of the ion transmission area 16 is 10^-4mbar. The single lens is composed of three groups of left and right electrodes 25, each group of electrodes 25 is composed of two opposite electrodes, wherein the two end electrodes 25 are extraction lens electrodes, the middle electrode 25 is a transmission lens electrode, and the voltages applied by the three groups of electrodes 25 are respectively: the voltage of the extraction electrode is-3V and the voltage of the transmission electrode is-100V, so that the formed curved electric field is opposite to the [ RH ] of the entering electric field]⁺The focusing is carried out to form a concentrated ion flow, so that the problem of ion divergence is prevented, and the resolution of the instrument is improved. The focused ion flow horizontally enters a TOF detection zone 18 after passing through a differential diversion hole 53, the inner diameter of the differential diversion hole 53 is 1.0mm, the ion passing rate is ensured, an ion transmission zone and the TOF detection zone are effectively isolated, the second turbine molecular pump is used for vacuumizing, and the high vacuum degree of the TOF zone is 10^-7mbar。

The Faraday cup 17 is arranged in the TOF detection area 18 and close to the differential diversion hole 53, ion flow is monitored through the Faraday cup 17 when ions focused by the lens horizontally enter the TOF detection area 18 and then enter the TOF detection area 18, and ions with different mass-to-charge ratios (M/Z) are distinguished in the continuous movement process. The ion acceleration zone at the upper part of the TOF detection zone 18 is provided with four polar plates, the four polar plates are sequentially provided with a bottom plate 19, an extraction polar plate 54, a middle polar plate 55 and an acceleration polar plate 56 from top to bottom, the space between the bottom plate 19 and the extraction polar plate 54 is an ion introduction zone, the space between the extraction polar plate 54 and the acceleration polar plate 56 is an ion acceleration zone, the acceleration zone adopts double-field acceleration, the middle polar plate 55 is separated by space, a primary acceleration zone is arranged between the extraction polar plate 54 and the middle polar plate 55, and a secondary acceleration zone is arranged between the middle polar plate 55 and the acceleration polar plate 56. The optimal voltage values of the bottom plate 19, the middle polar plate 55 and the accelerating polar plate 56 are-150V, -600V and-2000V respectively, and the pulse voltage of the extraction polar plate 54 is as follows: when the ion current continuously enters the ion introducing region of the bottom plate 19 and the extraction polar plate 54, the voltage of the extraction polar plate 54 is-150V, when the ions with the largest mass-to-charge ratio (M/Z) enter the ion introducing region after one sample introduction, the voltage of the extraction polar plate is increased to-420V, and the ions obtain kinetic energy vertical to the incident direction. The optimum voltage of the middle plate is-600V, where the middle plate voltage plays a crucial role in improving resolution. In the experiment, when the voltage of the middle electrode plate is reduced, the peak shape of the middle electrode plate is widened, and the resolution is reduced; resolution can be improved by increasing the middle plate voltage. For the component benzene, when the middle plate voltage was set to-490V, the peak height was 638 and the resolution was 3060; when the voltage is increased to-550V, the peak height is 952, and the resolution is 4647; when the voltage is increased to-570V, the peak height is 974, and the resolution is 4669; when the voltage is increased to-600V, the peak height is 1016, and the resolution is 5012; when the voltage was increased to-650V, the peak shape was poor. After passing through the four plates, the ions are then redirected by XY deflector 27. The light-emitting diode enters a reflecting region 28 after passing through a field-free drift region 26, three groups of reflectors 30 are arranged in the reflecting region, each group of reflectors 30 consists of a reflecting plate 33, a sleeve 31 and annular polar plates 32, the reflecting plate 33 is circular, the sleeve 31 is perpendicular to the reflecting plate 33, two groups of annular polar plates 32 are arranged on the inner wall of the sleeve 31, the two groups of annular polar plates 32 are distributed up and down, the voltage of one group of annular polar plates 32 close to the opening of the sleeve is-2000V, the voltage of one group of annular polar plates 32 close to the reflecting plate 33 is-1800V, and the voltage of the reflecting plate 33 is 2000V; the three groups of reflectors 30 are respectively a first reflector, a second reflector and a third reflector, the sleeve openings of the first reflector and the third reflector are upward, the sleeve opening of the second reflector is downward, the first reflector and the third reflector are positioned at two sides of the second reflector and have the same height, and the height of the second reflector is higher than that of the first reflector and that of the third reflector.

The detector 29 is a double-microchannel plate detector, the double-microchannel plate detector is connected with a 4GTDC time-to-digital conversion module 34, the 4GTDC time-to-digital conversion module 34 is connected with an industrial personal computer 36, and the industrial personal computer 36 is connected with a sixteen-way switching valve controller 37; the pipeline between the zero gas inlet pipe 41 and the sixteen-way switching valve 37 is sequentially provided with an oil-free pump 40, a pre-cooling dehydrator 39 and a molecular sieve 38.

The signal measured by the detector 29 passes through a 4GTDC time-to-digital conversion module 34, the sampling frequency is 4GHz, the time interval between the start and the stop of the pulse signal is accurately measured, and the time interval is calculated and stored by an industrial personal computer 36. The method specifically comprises the following steps: the electronic pulse signal of the time-of-flight mass spectrum is converted into a fixed amplitude signal by a peak discriminator (CFD), and finally, the signal is recorded by a time-to-digital converter (TDC), and the data is processed and stored by a computer.

(1) The system resolution was monitored for various middle plate voltages measured at 1ppm benzene standard gas according to the above instrument conditions, and the results are shown in FIG. 2 and Table 1.

TABLE 1

Intermediate electrode plate voltage	m (benzene character peak)	Half peak width Δ M	Mass resolution R
				-490V	79.05478	0.02583	3060
-550V	79.05478	0.01701	4647
				-570V	79.05478	0.01693	4669
-600V	79.05478	0.01577	5012

Δ M in table 1: the half-peak width is calculated by using a calculation formula R of mass resolution R, wherein the mass resolution R is M/delta M, and the resolution values when different middle electrode plate voltages are calculated.

(2) The influence of the first differential vacuum chamber on the detection limit of the instrument, the detection limits of propylene, acetone, 1, 3-butadiene, 1-butene, cyclohexane, benzene, acetaldehyde, acrolein, 2-propanol, methyl vinyl ketone, n-butanol, n-valeraldehyde and n-hexanal are calculated before and after the vacuum chamber is set, and the results are shown in the following table 2:

TABLE 2

Through the above comparison experiment of the detection limits of the VOCs components in the presence or absence of the differential vacuum chamber, it can be found that the existence of the differential vacuum chamber reduces the detection limit of the substance by 1.8-10.7 times, which indicates that the first differential vacuum chamber plays a crucial role in improving the sensitivity of the instrument.

(3) Results of sample quantification

And (3) sampling from low concentration to high concentration in sequence to obtain mass spectrum response values of propylene, acetone, 1, 3-butadiene, 1-butene, cyclohexane, benzene, acetaldehyde, acrolein, 2-propanol, methyl vinyl ketone, n-butanol, n-valeraldehyde and n-hexanal components with different concentrations, wherein the concentration of each component is an abscissa, and the response value of each substance is an ordinate, and establishing an external standard method standard curve.

The correction equation between the response value Ai of each component and its concentration Ci is: and y is kx + b.

Ci＝(Ai-b)/k

Wherein Ci is the concentration of each volatile organic component in the sample, Ai is the response value of each component, k is the slope of the standard curve, and b is the intercept of the standard curve.

The linear fitting regression equation and the linear correlation coefficient of propylene, acetone, 1, 3-butadiene, 1-butene, cyclohexane, benzene, acetaldehyde, acrolein, 2-propanol, methyl vinyl ketone, n-butanol, n-valeraldehyde and n-hexanal in the standard gas are shown in Table 3. The results of the precision and accuracy measurements of the 13 VOCs are shown in table 3.

TABLE 3

The experimental results show that: by adopting the analysis equipment and the analysis method, H generated by water source₃O⁺As an ionizing reagent, the mass-to-nuclear ratio of the quantitative ions of each substance to be detected in Table 3 can be accurately measured to five positions after a decimal point, and the resolution is high; the linear correlation is good, and the linear correlation coefficient is greater than 0.992; the precision is high, the standard gas sample with the concentration of 0.75ppm is parallelly measured for 7 times, and the measured Relative Standard Deviation (RSD) is less than 9.8 percent; the accuracy is good, the recovery rate of the 13 substances to be detected reaches 86.7% -109%, and the recovery rate is obviously improved by 60% compared with that of the traditional method; the analysis speed is high, the qualitative and quantitative analysis of the VOCs in the gas sample can be completed within 50 seconds, compared with the traditional gas chromatography or gas chromatography mass spectrometry, the analysis of the VOCs requires 30 minutes to 1 hour, the analysis of the gas sample only requires 50 seconds, and the analysis efficiency of the sample is improved by 35-71 times.

The online VOCs monitoring instrument comprising the pretreatment facility is used for respectively measuring the VOCs gas sample collected by a certain chemical enterprise at an organized discharge port and comparing the VOCs gas sample with a sample without water and dust removal. Sampling is carried out through the same flue gas in the same time period between the sampling positions of the sixteen switching valves of the enterprise flue gas discharge port and the VOCs on-line monitoring system, the sampled flue gas is respectively measured by VOCs on-line monitoring system equipment, and whether difference exists in the whole analysis process of the sampling positions of the sixteen switching valves of the discharge port and the VOCs on-line monitoring system is observed. Respectively collecting the same flue gas in the same time period at a flue gas discharge port, before dewatering, after dewatering and at a sampling position of a sixteen-way switching valve of the VOCs online monitoring system, and analyzing the same flue gas by using VOCs online monitoring system analysis equipment. The results are shown in Table 4.

TABLE 4

The measured data shows that the change of the detected data of each component in the sampling analysis process of the sixteen-way switching valve from the discharge port to the VOCs on-line monitoring system is not large, and the relative deviation of the data of the waste gas discharge port and the data of the sampling position of the sixteen-way switching valve is less than 5.0 percent.

Example 2

With oxygen (O)₂) VOCs such as acrolein, acetone, ethyl acetate, vinyl acetate, ethylbenzene, carbon disulfide, acetaldehyde, 2-propanol, methyl vinyl ketone, n-butanol, n-valeraldehyde, and n-hexanal were measured as reaction gases.

An online monitoring system for high-resolution high-sensitivity rapid determination of volatile organic compounds comprises a sampling connector 60 and a reaction chamber, wherein an outlet of the sampling connector 60 is connected with a gas filter 61, an outlet of the gas filter 61 is connected with a precision filter 67 through a first gas pipe 62, a first electric heating belt 63 is arranged on the periphery of the first gas pipe 62, an outlet of the precision filter 67 is sequentially connected with a primary gas-liquid separator 68 and a secondary gas-liquid separator 69 through pipelines, a gas outlet of the secondary gas-liquid separator 69 is connected with a permeable membrane gas drier 71, the permeable membrane gas drier 71 is connected with a sixteen-way switching valve 37 through a second gas pipe 72, and a second electric heating belt 73 is arranged on the periphery of the second gas pipe 72; the reaction chamber is provided with a reaction gas inlet 58, the reaction gas inlet 58 is connected with the outlet of a first tee joint 8, two inlets of the first tee joint 8 are respectively connected with a water vapor generation device and other reaction gas inlets 6, the reaction chamber comprises an ion source glow discharge area 11, an ion source drift area 12, a first differential vacuum chamber 13 and a reaction tube 14 which are adjacent in sequence, the rear part of the reaction chamber is connected with a second differential vacuum chamber 15, an ion transmission area 16 and a TOF detection area 18 in sequence, the first differential vacuum chamber 13 is communicated with the reaction tube 14 through a first small hole 21, the reaction tube 14 is communicated with the second differential vacuum chamber 15 through a second small hole 24, the second differential vacuum chamber 15 is communicated with the ion transmission area 16 through a third small hole 52, the ion transmission area 16 is communicated with the detection area 18 through a differential diversion hole 53, the ion source drift area 12, the first differential vacuum chamber 13 and the reaction area of the reaction tube 14 are all provided with equivalent partial pressure resistors 23 outside, the tail end of the first differential vacuum cavity 13 is connected with a first mechanical pump 22, the tail end of the second differential vacuum cavity 15 is connected with a second mechanical pump 35, a VOCs gas inlet 20 is arranged on the wall of the reaction tube 14 and close to the first differential vacuum cavity 13, the VOCs gas inlet 20 is connected with a sixteen-way switching valve 37 through a pipeline, a VOCs gas outlet 59 is arranged on the second differential vacuum cavity 15, a single lens is arranged in the ion transmission area 16 and is composed of three groups of left and right electrodes 25, and each group of electrodes 25 is composed of two vertically opposite electrodes; the upper part of the TOF detection region 18 communicates with a reflection region 28 through a field-free drift region 26, an XY deflection plate 27 is provided in the field-free drift region 26, and three sets of reflectors 30 and detectors 29 are provided in the reflection region 28.

A first thermocouple temperature sensor 64 is arranged corresponding to the first electric heating belt 63, and the first thermocouple temperature sensor 64 and the first electric heating belt 63 are both connected with a first temperature controller 65; a second thermocouple temperature sensor 74 is arranged corresponding to the second electric heating belt 73, and both the second thermocouple temperature sensor 74 and the second electric heating belt 73 are connected with a second temperature controller 75; the first gas pipe 62 is provided with a diaphragm pump 66; the liquid outlet of the first-stage gas-liquid separator 68 and the liquid outlet of the second-stage gas-liquid separator 69 are both connected with the inlet of a peristaltic pump 70, and the outlet at the bottom of the peristaltic pump 70 is provided with a drain pipe.

Other reactive gases (O)₂) The inlet 6 is connected with one inlet of the first tee joint 8 through a pipeline, and other reaction gas regulating switches 7 are arranged on the pipelines between the other reaction gas inlets 6 and the first tee joint 8; a flow meter 9 and a flow regulating switch 10 are arranged on a pipeline between the outlet of the first tee joint 8 and the ion source drift region 12.

The VOCs gas inlet 20 is connected with sixteen-way switching valve 37 through a pipeline, the sixteen-way switching valve 37 is connected with a standard gas outlet and a zero gas inlet pipe 41 of a dynamic gas diluter 42, and is simultaneously connected with an air inlet pipe 57, the air inlet pipe 57 can be various ambient air inlet pipes or Suma tanks, a standard gas steel cylinder 45 and a nitrogen steel cylinder 48 are respectively connected with the dynamic gas diluter 42 through pipelines, a first mass flow meter 43 and a first pressure reducing valve 44 are arranged on the pipeline between the standard gas steel cylinder 45 and the dynamic gas diluter 42, a second mass flow meter 46 and a second pressure reducing valve 47 are arranged on the pipeline between the nitrogen steel cylinder 48 and the dynamic gas diluter 42, the zero gas inlet pipe 41 is sequentially connected with a zero gas pump 40 arranged in the zero gas generator, a precooling dehydrator 39 and a molecular sieve 38 and then connected with the sixteen-way switching valve 37, and the second differential vacuum cavity, the VOCs gas outlet 59 is sequentially connected with an air pump 51 and a first interface of a second tee joint 50 through pipelines, a second interface of the second tee joint is connected with a waste gas outlet of the dynamic gas diluter 42, a third interface of the second tee joint 50 is connected with an exhaust pipe 49, and two paths of waste gases are evacuated through the exhaust pipe 49.

The detector 29 is a double-microchannel plate detector, the double-microchannel plate detector is connected with a 4GTDC time digital conversion module 34, the 4GTDC time digital conversion module 34 is connected with an industrial personal computer 36, the industrial personal computer 36 is simultaneously connected with a sixteen-way switching valve 37 and an electronic weather station and is remotely connected with a mobile phone or a computer terminal, and the industrial personal computer 36 is connected with a controller of the sixteen-way switching valve 37.

The ion transport zone is provided with a first turbomolecular pump and the TOF detection zone is provided with a second turbomolecular pump.

According to the volume ratio, the mixed standard gas containing 1ppm of acrolein, acetone, ethyl acetate, vinyl acetate, ethylbenzene, carbon disulfide, acetaldehyde, 2-propanol, methyl vinyl ketone, n-butanol, n-valeraldehyde and n-hexanal is prepared into standard gases with the concentrations of 10ppb, 20ppb, 100ppb, 200ppb, 400ppb and 1000ppb respectively. A standard gas is prepared from a standard gas in a standard gas cylinder 45 and nitrogen in a nitrogen cylinder 48 in a dynamic gas dilution instrument 42. And (3) carrying out detection after sample introduction is carried out from low concentration to high concentration in sequence, establishing a calibration curve by fitting concentration and response values, and calculating the concentration of each VOCs according to the calibration curve by measuring the response value of each component in the sample.

The determination process comprises the following steps:

connecting a sampling connector 60 with a fixed pollution source waste gas exhaust cylinder, allowing the fixed pollution source waste gas to enter a gas filter 61 for filtering under the action of a diaphragm pump 66 from the sampling connector 60, then entering a first gas pipe 62, heating the first gas pipe 62 by using a first electric heating belt 63 to enable materials in the pipe to maintain a gasification state, controlling the temperature of the first gas pipe 62 by using a first thermocouple temperature sensor 64 and a first temperature controller 65, conveying the gas to a precision filter 67 under the action of the diaphragm pump 66, performing secondary fine filtration and dust removal, and removing fine particles; the gas with the particles removed enters a primary gas-liquid separator 68 for first water and oil removal, the temperature of the primary gas-liquid separator 68 is 4 ℃, the gas after the first water and oil removal enters a secondary gas-liquid separator 69 for second water and oil removal, the secondary gas-liquid separator 69 is at room temperature, the purified gas is discharged from a gas outlet, enters an osmotic membrane gas dryer 71 for drying and dehydration, the dehydrated gas enters a second gas pipe 72, enters a sixteen-way switching valve 37 through the second gas pipe 72 and then enters a reaction chamber for detection.

The first tee joint 8 is communicated with other reaction gas (O)₂) The inlet 6, the port of the first tee joint 8 connected with the water storage bottle 2 are closed, water vapor does not enter the instrument any more, and oxygen passes through other partsThe reaction gas enters an ion source glow discharge region 11 in the reaction chamber through a reaction gas inlet after passing through a first tee joint 8, a flowmeter 9 and a flow regulating switch 10 after passing through a reaction gas regulating switch 7 to be partially ionized to generate [ O ]₂]⁺And ensure that the ion abundance of oxygen ions reaches 2.0 multiplied by 10⁵。

In order to obtain better ionization efficiency, the anode voltage of the ion source glow discharge area 11 is 400V, the cathode voltage is maximally-300V, the discharge potential between the anode and the cathode is maintained at 400V, the pressure of the ion source glow discharge area 11 is 80Pa, and the discharge current is 3.2 mA; generation of large amounts of [ O ] by cathodic glow discharge₂]⁺And further reacting in the ion source drift region to generate high-purity O₂]⁺. The reaction chamber before the sample is measured is heated by the heating wires arranged in the reaction chamber, the fan promotes the internal temperature to be balanced, the heat preservation layer coated outside keeps the temperature constant, and the temperature is strictly controlled by a temperature controller to be 100 ℃.

Ion source generated [ O ]₂]⁺Enters a reaction tube 14 with the length of 96cm after passing through a first differential vacuum cavity 13 to collide with volatile organic molecules R, and then reacts to generate R⁺At this time, the first differential vacuum chamber 13 effectively reduces the oxygen molecules entering the reaction tube 14 and increases [ O ]₂]⁺The purity of the (D) has an important effect on improving the sensitivity of the instrument; the inner diameter of the first small hole 21 is 0.12cm, which can ensure that the reaction gas ions can effectively enter the reaction tube 14, and simultaneously realize the isolation of the ion source and the reaction tube 14 to a greater extent. The reaction tube 14 is modified with polydimethylsiloxane to reduce adsorption.

When a VOCs sample is measured, the ion source and the reaction tube 14 can be separated to a greater extent through the first differential vacuum cavity 13, the influence of pressure increase in the reaction tube 14 on the ion source is reduced, the pressure in the reaction tube 14 is controlled to be increased to 8mbar through a computer, the voltage at two ends is set to be 2.4KV, and the E/n is maintained at 170, so that the sample introduction amount of sample gas is increased to 250ml/min, the ion number density in the reaction tube 14 is increased, the response value of each substance to be measured is obviously enhanced, meanwhile, a high-frequency alternating voltage is applied to a focusing area, the frequency of the alternating voltage is 0.45MHz, the voltage amplitude is 52V, and the voltage provides a radial constraint force for ion movement, ions are focused to the center of the reaction tube, the number of ions passing through the second differential vacuum small hole is increased.

By reaction of [ R ]]⁺Under the action of uniform electric field in the reaction tube 14, the ion beam passes through the second small hole 24 and the third small hole 52 with the diameter of 0.42cm and then enters the ion transmission area 16, the second small hole 24 and the third small hole 52 separate the ion transmission area 16 from the reaction tube 14, and the ion transmission area 16 is vacuumized by the first turbo molecular pump to ensure that the pressure of the ion transmission area 16 is 10^-4mbar. The single lens is composed of three groups of left and right electrodes 25, each group of electrodes 25 is composed of two opposite electrodes, wherein the two end electrodes 25 are extraction lens electrodes, the middle electrode 25 is a transmission lens electrode, and the voltages applied by the three groups of electrodes 25 are respectively: the voltage of the extraction electrode is-5V, the voltage of the transmission electrode is-110V, and the curved electric field formed by the voltage is opposite to the R of the entering electric field]⁺The focusing is carried out to form a concentrated ion flow, so that the problem of ion divergence is prevented, and the resolution of the instrument is improved. The focused ion flow horizontally enters a TOF detection area 18 after passing through a differential flow guide hole 53, the inner diameter of the differential flow guide hole 53 is 1.1mm, the ion passing rate is ensured, an ion transmission area and the TOF detection area are effectively isolated, and the high vacuum degree of the TOF area is 10 by pumping vacuum of a second turbo molecular pump^{- 7}mbar。

The Faraday cup 17 is arranged in the TOF detection area 18 and close to the differential diversion hole 53, ion flow is monitored through the Faraday cup 17 when ions focused by the lens horizontally enter the TOF detection area 18 and then enter the TOF detection area 18, and ions with different mass-to-charge ratios (M/Z) are distinguished in the continuous movement process. Four polar plates are arranged in an ion acceleration zone on the TOF detection zone 18, the four polar plates are sequentially a bottom plate 19, an extraction polar plate 54, a middle polar plate 55 and an acceleration polar plate 56 from top to bottom, wherein the optimal voltage values of the bottom plate 19, the middle polar plate 55 and the acceleration polar plate 56 are-120V, -570V and-1900V respectively, and the pulse voltage of the extraction polar plate 54 is: when the ion current continuously enters the ion introducing region of the bottom plate 19 and the extraction polar plate 54, the voltage of the extraction polar plate 54 is-120V, and the ions (R) with the largest mass-to-charge ratio (M/Z) are injected once⁺) When entering the ion introduction zone, extractingThe plate voltage is raised to-400V and ions acquire kinetic energy perpendicular to the incident direction, and ions of different mass-to-charge ratios (M/Z) are distinguished in the process of continuous movement. The ion movement direction is then adjusted by the XY deflection plate 27. The ions enter a reflecting region 28 after passing through a field-free drift region 26, three groups of reflectors 30 are arranged in the reflecting region, each group of reflectors 30 consists of a reflecting plate 33, a sleeve 31 and annular polar plates 32, the reflecting plate 33 is circular, the sleeve 31 is perpendicular to the reflecting plate 33, two groups of annular polar plates 32 are arranged on the inner wall of the sleeve 31, the two groups of annular polar plates 32 are distributed up and down, the voltage of one group of annular polar plates 32 close to the opening of the sleeve is-1900V, the voltage of one group of annular polar plates 32 close to the reflecting plate 33 is-1800V, and the voltage of the reflecting plate 33 is 2000V; the three groups of reflectors 30 are respectively a first reflector, a second reflector and a third reflector, the sleeve openings of the first reflector and the third reflector are upward, the sleeve opening of the second reflector is downward, the first reflector and the third reflector are positioned at two sides of the second reflector and have the same height, and the height of the second reflector is higher than that of the first reflector and that of the third reflector.

The detector 29 is a double-microchannel plate detector, the double-microchannel plate detector is connected with a 4GTDC time digital conversion module 34, the 4GTDC time digital conversion module 34 is connected with an industrial personal computer 36, and the industrial personal computer 36 is simultaneously connected with a controller of a sixteen-way switching valve 37 and an electronic weather station and is remotely connected with a mobile phone or a computer terminal; the pipeline between the zero gas inlet pipe 41 and the sixteen-way switching valve 37 is sequentially provided with an oil-free pump 40, a pre-cooling dehydrator 39 and a molecular sieve 38.

The signal measured by the detector 29 passes through a 4GTDC time-to-digital conversion module 34, the sampling frequency is 4GHz, the time interval between the start and the stop of the pulse signal is accurately measured, and the time interval is calculated and stored by an industrial personal computer 36. The method specifically comprises the following steps: the electronic pulse signal of the time-of-flight mass spectrum is converted into a fixed amplitude signal by a peak discriminator (CFD), and finally, the signal is recorded by a time-to-digital converter (TDC), and the data is processed and stored by a computer.

A mixed gas sample containing 0.667ppm of acrolein, acetone, ethyl acetate, vinyl acetate, ethylbenzene, carbon disulfide, acetaldehyde, 2-propanol, methyl vinyl ketone, n-butanol, n-valeraldehyde, n-hexanal was measured, the concentration of each component was calculated by a linear regression equation, each substance was measured in parallel 7 times, and the recovery rate and the Relative Standard Deviation (RSD) were calculated, respectively, and the results are summarized in table 5:

TABLE 5

Through the experiment, the following results are found: o generated from an oxygen source₂ ⁺As an ionization reagent, the equipment and the analysis method are adopted, the mass-to-nuclear ratio detection of the quantitative ions of the 12 substances to be detected in the table 5 can be accurately measured to five decimal places, and the resolution ratio is high; the linear correlation is good, and the linear correlation coefficient is greater than 0.947; the accuracy is better, the recovery rate of 12 substances to be detected reaches 93.5-113%, and the recovery rate is obviously improved by 60% compared with the traditional method; the precision is high, and the relative standard A standard deviation RSD is less than 9.5%; the analysis speed is high, the qualitative and quantitative analysis of the VOCs in the gas sample can be completed within 50 seconds, and compared with the traditional gas chromatography or gas chromatography mass spectrometry, the analysis of the VOCs requires 30 minutes to 1 hour, and the sample analysis efficiency is improved by 35-71 times.

Example 3

The online monitoring system for rapidly determining volatile organic compounds with high resolution and high sensitivity is the same as that in the embodiment 2, and the difference is that the following parameters are different:

and (3) measuring the VOCs components in the waste gas of the fixed pollution source of the enterprise by using Nitric Oxide (NO) as a reaction gas.

The flow rate of the reaction gas NO is 7 mL/min; the pressure of the ion source glow discharge area is 0.9 mbar; the length of the reaction tube is 93cm, the vacuum degree in the reaction tube 14 is adjusted to be 10mbar, the temperature is 100 ℃, the voltage at two ends of the reaction tube 14 is 2.9kV, and the E/n in the tube is 170; the voltage of the single lens is respectively-2V for extracting electrode voltage, -101V for transmitting electrode voltage, and-130V for each polar plate voltage of TOF detection area, and the pulse voltage of the extracting polar plate is as follows: when the ion current continuously enters the ion introducing region of the bottom plate and the extracting polar plate, the voltage of the extracting polar plate is-130V, when the ions with the largest mass-to-charge ratio (M/Z) enter the ion introducing region after one sample introduction, the voltage of the extracting polar plate is increased to-400V, the voltage of the middle polar plate is-650V, the voltage of the accelerating polar plate is-2000V, the voltages of the two polar plates in the reflecting region are respectively-2000V and-1800V, and the voltage of the reflecting plate is 2000V.

The standard gas containing 1ppm of acrolein, acetone, ethyl acetate, vinyl acetate, ethylbenzene, carbon disulfide, acetaldehyde, 2-propanol, methyl vinyl ketone, n-butanol, n-valeraldehyde and n-hexanal is prepared into mixed standard gas with the concentration of 10ppb, 20ppb, 100ppb, 200ppb, 400ppb and 1000ppb respectively according to the volume ratio. The standard gas is prepared from VOCs standard gas in a standard gas cylinder 45 and nitrogen in a nitrogen cylinder 48 in a dynamic gas diluter 42. And (3) carrying out detection after sample introduction is carried out from low concentration to high concentration in sequence, establishing a calibration curve according to the relation between the concentration and the response value, and calculating the concentration of each component in the sample from the calibration curve by measuring the response value of each component in the sample.

The determination process comprises the following steps:

connecting a sampling connector 60 with a fixed pollution source waste gas discharge port, allowing the fixed pollution source waste gas to enter a gas filter 61 for filtering under the action of a diaphragm pump 66 from the sampling connector 60, then entering a first gas pipe 62, heating the first gas pipe 62 by using a first electric heating belt 63 to enable materials in the pipe to maintain a gasification state, controlling the temperature of the first gas pipe 62 by using a first thermocouple temperature sensor 64 and a first temperature controller 65, conveying the gas to a precision filter 67 under the action of the diaphragm pump 66, performing secondary fine filtration and dust removal, and removing fine particles; the gas with the particles removed enters a primary gas-liquid separator 68 for first water and oil removal, the temperature of the primary gas-liquid separator 68 is 4 ℃, the gas after the first water and oil removal enters a secondary gas-liquid separator 69 for second water and oil removal, the secondary gas-liquid separator 69 is at room temperature, the purified gas is discharged from a gas outlet, enters an osmotic membrane gas dryer 71 for drying and dehydration, the dehydrated gas enters a second gas pipe 72, enters a sixteen-way switching valve 37 through the second gas pipe 72 and then enters a reaction chamber for detection.

The first tee joint 8 is communicated with other reaction gas (NO) inlets 6, the port of the first tee joint 8 connected with the water storage bottle 2 is closed, water vapor does not enter the instrument any more, Nitric Oxide (NO) passes through the other reaction gas regulating switch 7, then passes through the first tee joint 8, the flowmeter 9 and the flow regulating switch 10, and then enters the ion source glow discharge area 11 in the reaction chamber through the reaction gas (NO) inlets to be partially ionized to generate [ NO ]]⁺And ensure [ NO]⁺The abundance of the ions reaches 2.0 multiplied by 10⁵。

In order to obtain better ionization efficiency, the anode voltage of the ion source glow discharge area 11 is 400V, the cathode voltage is maximally-300V, the discharge potential between the anode and the cathode is maintained at 400V, the pressure of the ion source glow discharge area 11 is 80Pa, and the discharge current is 3.2 mA; generation of large amounts of [ NO ] by cathode glow discharge]⁺And further reacting in the ion source drift region to generate high-purity [ NO ]]⁺. The reaction chamber before the sample is measured is heated by the heating wires arranged in the reaction chamber, the fan promotes the internal temperature to be balanced, the heat preservation layer coated outside keeps the temperature constant, and the temperature is strictly controlled by a temperature controller to be 100 ℃.

Ion source generated [ NO]⁺The nitrogen oxide enters the reaction tube 14 with the length of 96cm after passing through the first differential vacuum chamber 13 and collides with VOCs molecules R to react, at the moment, the first differential vacuum chamber 13 effectively reduces the nitrogen oxide molecules entering the reaction tube 14, and the NO is improved]⁺The purity of the (D) has an important effect on improving the sensitivity of the instrument; the inner diameter of the first small hole 21 is 0.12cm, which can ensure that the reaction gas ions can effectively enter the reaction tube 14, and simultaneously realize the isolation of the ion source and the reaction tube 14 to a greater extent. The reaction tube 14 is modified with polydimethylsiloxane to reduce adsorption.

When a VOCs sample is measured, the ion source and the reaction tube 14 can be separated to a greater extent through the first differential vacuum cavity 13, the influence of pressure increase in the reaction tube 14 on the ion source is reduced, the pressure in the reaction tube 14 is controlled to be increased to 8mbar through a computer, the voltage at two ends is set to be 2.4KV, and the E/n is maintained at 170, so that the sample introduction amount of sample gas is increased to 250ml/min, the ion number density in the reaction tube 14 is increased, the response value of each substance to be measured is obviously enhanced, meanwhile, a high-frequency alternating voltage is applied to a focusing area, the frequency of the alternating voltage is 0.45MHz, the voltage amplitude is 52V, and the voltage provides a radial constraint force for ion movement, ions are focused to the center of the reaction tube, the number of ions passing through the second differential vacuum small hole is increased.

By reaction of [ R ]]⁺Under the action of uniform electric field in the reaction tube 14, the ion beam passes through the second small hole 24 and the third small hole 52 with the diameter of 0.42cm and then enters the ion transmission area 16, the second small hole 24 and the third small hole 52 separate the ion transmission area 16 from the reaction tube 14, and the ion transmission area 16 is vacuumized by the first turbo molecular pump to ensure that the pressure of the ion transmission area 16 is 10^-4mbar. The single lens is composed of three groups of left and right electrodes 25, each group of electrodes 25 is composed of two opposite electrodes, wherein the two end electrodes 25 are extraction lens electrodes, the middle electrode 25 is a transmission lens electrode, and the voltages applied by the three groups of electrodes 25 are respectively: the voltage of the extraction electrode is-5V, the voltage of the transmission electrode is-110V, and the curved electric field formed by the voltage is opposite to the R of the entering electric field]⁺The focusing is carried out to form a concentrated ion flow, so that the problem of ion divergence is prevented, and the resolution of the instrument is improved. The focused ion flow horizontally enters a TOF detection area 18 after passing through a differential flow guide hole 53, the inner diameter of the differential flow guide hole 53 is 1.2mm, the ion passing rate is ensured, an ion transmission area and the TOF detection area are effectively isolated, and the high vacuum degree of the TOF area is 10 by pumping vacuum of a second turbo molecular pump^{- 7}mbar。

The Faraday cup 17 is arranged in the TOF detection area 18 and close to the differential diversion hole 53, ion flow is monitored through the Faraday cup 17 when ions focused by the lens horizontally enter the TOF detection area 18 and then enter the TOF detection area 18, and ions with different mass-to-charge ratios (M/Z) are distinguished in the continuous movement process. Four polar plates are arranged in an ion acceleration zone on the TOF detection zone 18, the four polar plates are sequentially a bottom plate 19, an extraction polar plate 54, a middle polar plate 55 and an acceleration polar plate 56 from top to bottom, wherein the optimal voltage values of the bottom plate 19, the middle polar plate 55 and the acceleration polar plate 56 are respectively-145V, -570V and-1900V, and the pulse voltage of the extraction polar plate 54 is: when the ion current continuously enters the ion introducing region of the bottom plate 19 and the extraction polar plate 54, the voltage of the extraction polar plate 54 is-120V, when the ions with the largest mass-to-charge ratio (M/Z) enter the ion introducing region after one sample introduction, the voltage of the extraction polar plate is increased to-410V, the ions obtain kinetic energy perpendicular to the incident direction, and the ions with different mass-to-charge ratios (M/Z) are distinguished in the process of continuous movement. The ion movement direction is then adjusted by the XY deflection plate 27. The ions enter a reflecting region 28 after passing through a field-free drift region 26, three groups of reflectors 30 are arranged in the reflecting region, each group of reflectors 30 consists of a reflecting plate 33, a sleeve 31 and annular polar plates 32, the reflecting plate 33 is circular, the sleeve 31 is perpendicular to the reflecting plate 33, two groups of annular polar plates 32 are arranged on the inner wall of the sleeve 31, the two groups of annular polar plates 32 are distributed up and down, the voltage of one group of annular polar plates 32 close to the opening of the sleeve is-1900V, the voltage of one group of annular polar plates 32 close to the reflecting plate 33 is-1800V, and the voltage of the reflecting plate 33 is 2000V; the three groups of reflectors 30 are respectively a first reflector, a second reflector and a third reflector, the sleeve openings of the first reflector and the third reflector are upward, the sleeve opening of the second reflector is downward, the first reflector and the third reflector are positioned at two sides of the second reflector and have the same height, and the height of the second reflector is higher than that of the first reflector and that of the third reflector.

The detector 29 is a double-microchannel plate detector, the double-microchannel plate detector is connected with a 4GTDC time digital conversion module 34, the 4GTDC time digital conversion module 34 is connected with an industrial personal computer 36, and the industrial personal computer 36 is simultaneously connected with a controller of a sixteen-way switching valve 37 and an electronic weather station and is remotely connected with a mobile phone or a computer terminal; the pipeline between the zero gas inlet pipe 41 and the sixteen-way switching valve 37 is sequentially provided with an oil-free pump 40, a pre-cooling dehydrator 39 and a molecular sieve 38.

The signal measured by the detector 29 passes through a 4GTDC time-to-digital conversion module 34, the sampling frequency is 4GHz, the time interval between the start and the stop of the pulse signal is accurately measured, and the time interval is calculated and stored by an industrial personal computer 36. The method specifically comprises the following steps: the electronic pulse signal of the time-of-flight mass spectrum is converted into a fixed amplitude signal by a peak discriminator (CFD), and finally, the signal is recorded by a time-to-digital converter (TDC), and the data is processed and stored by a computer.

The actual sample was measured, and the concentration of each component was calculated by a linear regression equation by performing the measurement in the same manner as in example 2 using NO as a reactive gas. The results of the measurement were as follows: acrolein 0.191ppm, acetone 0.204ppm, ethyl acetate 0.021ppm, vinyl acetate 0.017ppm, ethylbenzene 0.255ppm, carbon disulfide 2.336ppm, acetaldehyde 0.267ppm, 2-propanol 0.871ppm, methyl vinyl ketone 0.102ppm, n-butanol 0.101ppm, n-valeraldehyde 0.167ppm, n-hexanal 0.312 ppm. By using the online monitoring system and the online monitoring method, the VOCs of the waste gas sample can be rapidly determined within 50 seconds, the determination is rapid and convenient, and the discharge type and concentration of VOCs in the waste gas discharge port can be monitored in real time.

Claims (9)

1. The utility model provides a high-resolution high sensitivity short-term test volatile organic compounds's on-line monitoring system which characterized in that: the device comprises a sampling connector (60) and a reaction chamber, wherein an outlet of the sampling connector (60) is connected with a gas filter (61), an outlet of the gas filter (61) is connected with a precision filter (67) through a first gas pipe (62), a first electric heating belt (63) is arranged on the periphery of the first gas pipe (62), an outlet of the precision filter (67) is sequentially connected with a primary gas-liquid separator (68) and a secondary gas-liquid separator (69) through pipelines, a gas outlet of the secondary gas-liquid separator (69) is connected with a permeable membrane gas dryer (71), the permeable membrane gas dryer (71) is connected with a sixteen-way switching valve (37) through a second gas pipe (72), and a second electric heating belt (73) is arranged on the periphery of the second gas pipe (72); the reaction chamber is provided with a reaction gas inlet (58), the reaction gas inlet (58) is connected with an outlet of a first tee joint (8), two inlets of the first tee joint (8) are respectively connected with a water vapor generation device and other reaction gas inlets (6), the reaction chamber comprises an ion source glow discharge area (11), an ion source drift area (12), a first differential vacuum chamber (13) and a reaction tube (14) which are adjacent in sequence, the rear part of the reaction chamber is connected with a second differential vacuum chamber (15), an ion transmission area (16) and a TOF detection area (18) in sequence, the first differential vacuum chamber (13) is communicated with the reaction tube (14) through a first small hole (21), the reaction tube (14) is communicated with the second differential vacuum chamber (15) through a second small hole (24), the second differential vacuum chamber (15) is communicated with the ion transmission area (16) through a third small hole (52), the ion transmission area (16) is communicated with the TOF detection area (18) through a differential flow guide hole (53), equivalent divider resistors (23) are arranged outside reaction regions of an ion source drift region (12), a first differential vacuum chamber (13) and a reaction tube (14), the tail end of the first differential vacuum chamber (13) is connected with a first mechanical pump (22), the tail end of a second differential vacuum chamber (15) is connected with a second mechanical pump (35), a VOCs gas inlet (20) is arranged at a position, close to the first differential vacuum chamber (13), on the wall of the reaction tube (14), the VOCs gas inlet (20) is connected with sixteen-way switching valves (37) through a pipeline, a VOCs gas outlet (59) is arranged on the second differential vacuum chamber (15), a single lens is arranged in an ion transmission region (16), the single lens is composed of three groups of left and right electrodes (25), and each group of electrodes (25) is composed of two vertically opposite electrodes; an accelerating electric field area at the upper part of the TOF detection area (18) is communicated with a reflecting area (28) through a field-free drift area (26), an XY deflecting plate (27) is arranged in the field-free drift area (26), and three groups of reflectors (30) and detectors (29) are arranged in the reflecting area (28).

2. The on-line monitoring system for high resolution, high sensitivity and rapid determination of volatile organic compounds according to claim 1, characterized in that: a first thermocouple temperature sensor (64) is arranged corresponding to the first electric heating belt (63), and the first thermocouple temperature sensor (64) and the first electric heating belt (63) are both connected with a first temperature controller (65); a second thermocouple temperature sensor (74) is arranged corresponding to the second electric heating belt (73), and both the second thermocouple temperature sensor (74) and the second electric heating belt (73) are connected with a second temperature controller (75); a diaphragm pump (66) is arranged on the first gas pipe (62); the liquid outlet of the first-stage gas-liquid separator (68) and the liquid outlet of the second-stage gas-liquid separator (69) are both connected with the inlet of a peristaltic pump (70), and the outlet at the bottom of the peristaltic pump (70) is provided with a drain pipe.

3. The on-line monitoring system for high resolution, high sensitivity and rapid determination of volatile organic compounds according to claim 1, characterized in that: the water vapor generation device comprises a water storage bottle (2), a thermocouple (4) and a heating wire (3) are arranged inside the water storage bottle (2), a heat insulation layer (1) is arranged outside the water storage bottle (2), the top of the water storage bottle (2) is connected with one inlet of a first tee joint (8) through a pipeline, and a water switch (5) is arranged on the pipeline between the water storage bottle (2) and the first tee joint (8); other reaction gas inlets (6) are connected with one inlet of the first tee joint (8) through a pipeline, and other reaction gas regulating switches (7) are arranged on the pipeline between the other reaction gas inlets (6) and the first tee joint (8); a flow meter (9) and a flow regulating switch (10) are arranged on a pipeline between the outlet of the first tee joint (8) and the reaction chamber.

4. The on-line monitoring system for high resolution, high sensitivity and rapid determination of volatile organic compounds according to claim 1, characterized in that: the single lens is composed of three groups of left and right placed electrodes (25), each group of electrodes (25) is composed of two opposite electrodes, wherein, the two end electrodes (25) are extraction lens electrodes, the middle electrode (25) is a transmission lens electrode, and the applied voltages are respectively: the voltage range of the extraction lens electrode is-6V-0V, and the voltage range of the transmission lens electrode is-80V-110V.

5. The on-line monitoring system for high resolution, high sensitivity and rapid determination of volatile organic compounds according to claim 1, characterized in that: the inside position that is close to differential water conservancy diversion hole (53) at TOF detection zone (18) sets up Faraday cup (17), and TOF detection zone (18) is inside to be equipped with four polar plates, and four polar plates are bottom plate (19), extract polar plate (54), middle polar plate (55) and acceleration electrode board (56) by last bottom in proper order, each polar plate voltage range: the voltage of the bottom plate (19) is-100V-200V, pulse voltage is applied to the extraction polar plate (54), when ions to be detected enter the polar plate ion introduction area, the voltage value of the extraction polar plate (54) is the same as that of the bottom plate (19), when the ions with the largest mass-to-charge ratio enter the ion introduction area after one sample introduction, the voltage value of the extraction polar plate (54) is increased to-400V-450V, the voltage of the middle polar plate (55) is-500V-650V, and the voltage of the acceleration polar plate (56) is-1800V-2200V.

6. The on-line monitoring system for high resolution, high sensitivity and rapid determination of volatile organic compounds according to claim 1, characterized in that: the anode voltage of the ion source glow discharge area (11) is 400-550V, the discharge potential between the anode and the cathode is maintained between 350V and 400V, the pressure of the ion source glow discharge area (11) is 10-100Pa, and the discharge current is 4-6 mA; the pressure of the ion transport region (16) is 10^-4In the mbar order of magnitude; pressure within TOF detection zone (18) of 10^-5-10^-7mbar grade; the gas flow at the inlet of the reaction chamber is 3-14 mL/min; the inner diameter of the first small hole (21) is 0.05-0.5 cm; the diameters of the second small hole (24) and the third small hole (52) are both 0.1-1.0cm, and the inner diameter of the differential flow guide hole (53) is 1-1.5 mm.

7. The on-line monitoring system for high resolution, high sensitivity and rapid determination of volatile organic compounds according to claim 1, characterized in that:

the pressure in the reaction tube (14) is 5-10mbar, the voltage applied to the two ends of the reaction tube (14) is 1.5-3KV, and the sample gas inlet amount is 200-; the length of the reaction tube (14) is 90-120 cm;

three groups of reflectors (30) are arranged in the reflecting area, each group of reflectors (30) is composed of a reflecting plate (33), a sleeve (31) and annular polar plates (32), the reflecting plate (33) is circular, the sleeve (31) is perpendicular to the reflecting plate (33), two groups of annular polar plates (32) are arranged on the inner wall of the sleeve (31), the two groups of annular polar plates (32) are distributed up and down, the voltage of one group of annular polar plates (32) close to the opening of the sleeve ranges from minus 1800V to minus 2200V, the voltage of one group of annular polar plates (32) close to the reflecting plate (33) ranges from minus 1700V to minus 1900V, and the voltage of the reflecting plate (33) ranges from 1800V to 2000V; the three groups of reflectors (30) are respectively a first reflector, a second reflector and a third reflector, the openings of the sleeves of the first reflector and the third reflector are upward, the opening of the sleeve of the second reflector is downward, the first reflector and the third reflector are positioned on two sides of the second reflector and have the same height, and the height of the second reflector is higher than that of the first reflector and that of the third reflector.

8. The on-line monitoring system for high resolution, high sensitivity and rapid determination of volatile organic compounds according to claim 1, characterized in that: the VOCs gas inlet (20) is connected with sixteen switching valves (37) through a pipeline, the sixteen switching valves (37) are connected with a standard gas outlet and a zero gas inlet pipe (41) of a dynamic gas diluter (42), a standard gas steel cylinder (45) and a nitrogen steel cylinder (48) are respectively connected with the dynamic gas diluter (42) through pipelines, a first mass flowmeter (43) and a first pressure reducing valve (44) are arranged on the pipeline between the standard gas steel cylinder (45) and the dynamic gas diluter (42), a second mass flowmeter (46) and a second pressure reducing valve (47) are arranged on the pipeline between the nitrogen steel cylinder (48) and the dynamic gas diluter (42), the zero gas inlet pipe (41) is connected with the sixteen switching valves after being connected with a zero gas generator, a VOCs gas outlet (59) is arranged on a second differential vacuum cavity (15), and the VOCs gas outlet (59) is sequentially connected with a first interface of a gas suction pump (51) and a second tee (50) through a, the second interface of the second tee joint is connected with a waste gas outlet of the dynamic gas diluter (42), and the third interface of the second tee joint (50) is connected with an exhaust pipe (49).

9. The on-line monitoring system for high resolution, high sensitivity and rapid determination of volatile organic compounds according to claim 1, characterized in that: the detector (29) is a double-microchannel plate detector, the double-microchannel plate detector is connected with a 4GTDC time-to-digital conversion module (34), the 4GTDC time-to-digital conversion module (34) is connected with an industrial personal computer (36), and the industrial personal computer (36) is simultaneously connected with a controller of a sixteen-way switching valve (37) and an electronic weather station and is remotely connected with a mobile phone or a computer terminal.

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