CN112557591A - Dynamic mixed gas full-component flow calibration system and calibration method - Google Patents
Dynamic mixed gas full-component flow calibration system and calibration method Download PDFInfo
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- G01F—MEASURING VOLUME, VOLUME FLOW, MASS FLOW OR LIQUID LEVEL; METERING BY VOLUME
- G01F25/00—Testing or calibration of apparatus for measuring volume, volume flow or liquid level or for metering by volume
- G01F25/10—Testing or calibration of apparatus for measuring volume, volume flow or liquid level or for metering by volume of flowmeters
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Abstract
A dynamic mixed gas full-component flow calibration system and a calibration method are provided, wherein the calibration system comprises: the gas injection unit comprises a gas-carrying pipeline and a plurality of calibration gas pipelines; each pipeline is provided with a flow controller for realizing the dynamic adjustment of gas injection; the mixed flow unit is connected with each pipeline of the gas injection unit and is used for mixing the multi-path gas conveyed by the gas injection unit; the mass spectrum post-calibration unit is connected with the mixed flow unit through a mixing pipeline and is used for sampling and detecting mixed gas output by the mixed flow unit; the processing unit is electrically connected with the mass spectrum post-calibration unit; the method is used for processing data obtained by the mass spectrum post-calibration unit by utilizing an equivalent characteristic spectrum method, and obtaining the flow and concentration results of different components in the dynamically adjusted mixed gas in real time. The invention can provide the flow and the concentration of all components in the calibrated mixed gas, and the flow comprises mass flow, volume flow and molar flow.
Description
Technical Field
The invention relates to the technical field of gas detection, in particular to a dynamic mixed gas all-component flow calibration system and a calibration method.
Background
The gas analyzer is used as the most basic detection device, and has the main functions of judging the component types in the mixed gas, determining the content of specific components by various technical means (such as spectrum, chromatogram, mass spectrum, electrochemistry and the like), and generally giving the concentration of the specific components. In order to accurately and reliably detect the content of each component, a gas analyzer must be effectively calibrated to determine various physical parameters of the analyzer, such as detection sensitivity and the like. The premise of calibration is that a known and accurate gas component mixing calibration system is required, by means of which reasonable and effective gas distribution of gas components relevant to detection range and precision can be provided.
At present, the mixed gas calibration method suitable for the gas analysis instrument has the following difficulties:
(1) the dynamic range of a specific component is very wide
The gas components in the reaction process dynamically change in real time, and the dynamic change range of the component content is larger for a complex reaction system, so that the mixed gas with wide concentration or flow range can be accurately configured in the calibration process.
(2) The trace gas phase component is susceptible to the high content of the gas phase component
For complex reaction processes, the gas analyzer is simultaneously faced with various gas phase components at a certain time, and contains a large amount of complex trace mixed gas (ppm level) and high concentration (more than 10%) of conventional gas. In the detection process, the content of trace gas is often seriously interfered by gas-phase components with large concentration, so that the detection result is drifted.
(3) Objective limitation of range of calibration for gas corrosivity
NH may be present in a multi-component dynamic gas3、NOx、SOxThe corrosive gas difficult to detect, such as HF, and the like, is characterized by multiple types, but the content is extremely low, generally ppm level or even ppb level, and the gas has quite strong corrosivity.
(4) Easy adsorption, reduction and phase change gases can cause larger deviation
For multi-component mixed gas, under the conditions of different temperatures, pressures, component types and the like, phenomena such as adsorption, reduction, phase change and the like can be generated, and if the effects are not effectively eliminated in the calibration process, great deviation can be formed. E.g. H at ambient temperature2Is very easy to permeate andadsorbed on stainless steel pipeline, water vapor is easy to condense on the pipeline surface, CO and CH4And the carbon-containing reducing gas is easy to generate reactions such as carbon deposition and deterioration, and the gas is very easy to generate errors when the flow rate or the concentration is calibrated. As shown in fig. 1.
(5) The 'dead volume' problem when the diffusion of gas and the counter-current diffusion effect form calibration
The transport process of gases follows Fick's law, relying on concentration to drive the diffusion effect between different components. For the dynamic calibration process of gas components, the diffusion and the countercurrent diffusion among the components are relatively serious, if gas calibration equipment and pipeline arrangement are not good, a large amount of dead volume is generated, and unexpected interference is generated on the calibration of trace gas.
At present, in some prior arts, different multi-component gas measurement devices and methods are designed for solving the above difficulties, and although the multi-component gas measurement devices and methods play a certain role in mixed gas calibration, the multi-component gas measurement devices and methods are developed based on component concentrations of mixed gas, and the multi-component gas mixed calibration which dynamically changes in real time also has technical or principle defects.
For example:
(1) principle defects: for the calibration method after combined gas distribution, the concentration is usually adopted as the calibration parameter of the gas phase component, and the concentration is used as the relative quantity, so that only the mass flow can more effectively represent the dynamic change of the multi-component gas. As shown in fig. 2 and 3, the concentration of the gas 2 actually increases in flow rate while decreasing in the second stage, and the concentration actually decreases in flow rate while increasing in the third stage, but the results are completely opposite if the change in concentration of the gas 2 is used as a judgment of the magnitude and the trend of the change. Therefore, the existing gas calibration system takes the concentration of the gas as a calibration object, and cannot provide effective and reliable data support for accurately calibrating the analysis equipment.
(2) The technical defects of the gas mixing process are as follows: a common gas mixing system uses a flow meter as a mixing calibration tool, and the value of the flow meter is used as the final gas mixing result. The existing dynamic calibration method is to use a high-precision mass flowmeter, record the content of gas through the flowmeter, and calculate to obtain the content of actual mixed gas. The corrosive gas needs to be distributed with low concentration, so that the error of the trace gas is increased according to geometric multiples, and the result error is beyond a controllable range.
When the trace gas components are calibrated, a dead volume is easily formed in a transmission pipeline of a gas mixing system, the gas mixing system is also easily influenced by gas flow with high content and pressure fluctuation, diffusion and countercurrent diffusion effects are generated, great signal vibration and drift are often formed after gas mixing, and the signal-to-noise ratio of the signal vibration and the drift cannot be effectively ensured.
(3) Defects of the instrument equipment: at present, gas analyzers for post-calibration of mixed gases include electrochemical, infrared, ultraviolet, gas chromatography, mass spectrometry and other devices. Among them, the working principle of electrochemical, infrared, ultraviolet and gas chromatography instruments determines the concentration of different components as the detection parameter, and this problem explains the reason of limitation in the above principle defects.
Based on the above analysis, the existing calibration system has not yet achieved the requirements for real-time dynamically changing multi-component gas mixture calibration. Therefore, it is necessary to develop a dynamic mixed gas component flow calibration system.
Disclosure of Invention
In view of the above, the present invention provides a dynamic mixed gas full component flow calibration system and a calibration method, which are intended to at least partially solve at least one of the above mentioned technical problems.
In order to achieve the purpose, the technical scheme of the invention comprises the following steps:
as an aspect of the present invention, there is provided a dynamic mixed gas full component flow calibration system, including:
the gas injection unit comprises a gas-carrying pipeline and a plurality of calibration gas pipelines; each pipeline is provided with a flow controller for realizing the dynamic adjustment of gas injection;
the mixed flow unit is connected with each pipeline of the gas injection unit and is used for mixing the multi-path gas conveyed by the gas injection unit;
the mass spectrum post-calibration unit is connected with the mixed flow unit through a mixing pipeline and is used for sampling and detecting mixed gas output by the mixed flow unit;
the processing unit is electrically connected with the mass spectrum post-calibration unit; the method is used for processing data obtained by the mass spectrum post-calibration unit by utilizing an equivalent characteristic spectrum method, and obtaining the flow and concentration results of different components in the dynamically adjusted mixed gas in real time.
As another aspect of the present invention, there is also provided a calibration method using the dynamic mixed gas full component flow calibration system as described above, including the following steps:
the flow controller dynamically adjusts the gas flow injected by each pipeline in the gas injection unit;
the gas of each pipeline in the gas injection unit is mixed in the mixed flow unit;
the mass spectrum post-calibration unit samples and detects the mixed gas output by the mixed flow unit;
the processing unit is used for processing the data obtained by the calibration unit after the mass spectrum by using an equivalent characteristic spectrum method, and obtaining the flow and concentration results of different components in the dynamically adjusted mixed gas in real time.
Based on the technical scheme, compared with the prior art, the invention has at least one or one part of the following beneficial effects:
(1) the flow and the concentration of all components in the calibrated mixed gas can be given, and the flow comprises mass flow, volume flow and molar flow;
(2) the calibration of trace gas can be provided with high precision, and the concentration of the gas can be lower than 100ppb level;
(3) the gas mixed flow unit, the self-cleaning unit, the flow controller and the pipeline are made of anti-corrosion materials, so that the problems of gas adsorption, permeation, corrosion, dead volume and the like which cannot be solved by a conventional calibration instrument are solved;
(4) the calibration system carries out post-calibration by using a high-precision mass spectrum quantitative method, really realizes high-precision verification of the result, and has small error of a linear calibration coefficient and strong anti-interference performance;
(5) the calibration system is suitable for accurate calibration of all gas analysis instruments in the market, and can be widely applied to various fields of energy, chemical industry, medicine and the like.
Drawings
FIG. 1 is a schematic diagram illustrating the effect of an easily adsorbable, reducible, phase-change gas on gas calibration;
FIG. 2 is a schematic diagram showing the flow rate variation of each component in the mixed gas during calibration according to the conventional calibration technique;
FIG. 3 is a schematic diagram illustrating the concentration variation of each component of the mixed gas during the calibration process according to the conventional calibration technique;
FIG. 4 is a schematic diagram of a dynamic mixed gas full component flow calibration system in an embodiment of the present invention;
FIG. 5 is a flow chart of a dynamic mixed gas full component flow calibration method in an embodiment of the present invention;
FIG. 6 shows CH in example 1 of the present invention4A calibrated mass spectrum three-dimensional map;
FIG. 7 shows CH in example 1 of the present invention4A calibrated normalization map;
FIG. 8 shows CH in example 1 of the present invention4Calibrating flow program setting and mass spectrum detection analysis data comparison graph;
FIG. 9 shows an ultra-low flow rate H in example 2 of the present invention2S, calibrating flow program setting and mass spectrum detection analysis data comparison graph;
FIG. 10 shows the ultralow concentration H in example 2 of the present invention2S, calibrating a concentration and temperature data comparison diagram;
FIG. 11 shows N in example 3 of the present invention2Ar and N with flow rate changing according to step flow rate in temperature rising process2With CO2The mass spectrum three-dimensional map of the mixed gas of (1);
FIG. 12 shows N in example 3 of the present invention2Ar and N with flow rate changing according to step flow rate in temperature rising process2With CO2The mass spectrum three-dimensional desorption spectrum of the mixed gas;
FIG. 13 shows N in example 3 of the present invention2Ar and N with flow rate changing according to step flow rate in temperature rising process2With CO2The mass spectrum data signal of each component in the mixed gas is followedA time variation graph;
FIG. 14 shows N in example 3 of the present invention2Ar and N with flow rate changing according to step flow rate in temperature rising process2With CO2A comparison graph of the calibration flow program setting and mass spectrum detection analysis data of each component in the mixed gas is obtained;
FIG. 15 is a three-dimensional chromatogram of a carrier gas calibration mass spectrum without a self-cleaning process in comparative example 1 of the present invention.
In the above figures, the reference numerals have the following meanings:
1. a gas cylinder; 2. a pre-valve; 3. a flow controller; 4. a buffer ring; 51. a mixed flow gas collection cavity; 52. a spoiler; 6. a vacuum pump; 7. a vacuum pump prepositive electromagnetic valve; 8. a mass spectrum prepositive electromagnetic valve; 9. a post-mass spectrometry calibration unit; 10. a processing unit; 11. a heat tracing band.
Detailed Description
In order that the objects, technical solutions and advantages of the present invention will become more apparent, the present invention will be further described in detail with reference to the accompanying drawings in conjunction with the following specific embodiments.
As one aspect of the present invention, as shown in fig. 4, there is provided a dynamic mixed gas full component flow calibration system, including:
the gas injection unit comprises a gas-carrying pipeline and a plurality of calibration gas pipelines; each pipeline is respectively provided with a flow controller 3 for realizing the dynamic adjustment of gas injection;
the mixed flow unit is connected with each pipeline of the gas injection unit and is used for mixing multi-path gas conveyed by the gas injection unit;
the mass spectrum post-calibration unit 9 is connected with the mixed flow unit through a mixing pipeline and is used for sampling and detecting mixed gas output by the mixed flow unit;
the processing unit 10 is electrically connected with the mass spectrum post-calibration unit 9; the method is used for processing the data obtained by the mass spectrum post-calibration unit 9 by using an equivalent characteristic spectrum method, and obtaining the flow and concentration results of different components in the dynamically adjusted mixed gas in real time.
In the embodiment of the present invention, 1 calibration gas pipeline may be provided, but is not limited to this, and 2, 3 or more calibration gas pipelines may also be provided, and may be increased or decreased according to the actual situation.
As shown in fig. 4, the gas supply is directly supplied by gas cylinders 1 for 1 gas carrying pipeline and 2 calibration gas pipelines.
In the embodiment of the invention, the contents of the components in the mixed gas, including parameters such as concentration and flow, are calibrated by the calibration system, and the real values of the different gas components after dynamic mixing are accurately calculated by means of high-precision quantitative analysis data of the calibration unit 9 and the processing unit 10 after mass spectrometry.
In an embodiment of the invention, the calibration system further comprises a self-cleaning unit comprising: a heat tracing band 11 and a vacuum pump 6; wherein the content of the first and second substances,
the heat tracing band 11 is coated on a pipeline of the calibration system and the mixed flow unit;
the vacuum pump 6 is connected with the mixing pipeline through a vacuumizing pipeline; wherein, a vacuum pump prepositive electromagnetic valve 7 is arranged on the vacuum pumping pipeline; and a mass spectrum prepositive electromagnetic valve 8 is arranged on a mixing pipeline between the vacuumizing pipeline and the mass spectrum post-calibration unit 9.
In the embodiment of the invention, the heat tracing band 11 is used as a temperature control heating component, can realize constant temperature and variable temperature heating between normal temperature and 300 ℃, is used for removing gas adsorbed on the inner parts of the pipeline and the mixed flow unit, and the temperature of the heat tracing band is controlled by the control module.
In the embodiment of the invention, the vacuum pump 6 can reach the vacuum degree in the calibration system to 10-1Pa, ensuring that the concentration of impurity gas in the calibration system is reduced to ppb level in the calibration process, and avoiding the influence of the dead volume of gas in the calibration system; the vacuum extraction is controlled by a control module, a mass spectrum preposed electromagnetic valve 8 in front of a mass spectrum post-calibration unit 9 is closed, a vacuum pump preposed electromagnetic valve 7 in front of a vacuum pump 6 is opened, and the vacuum pump 6 is started to extract impurity gas in the calibration system; meanwhile, the air tightness of the gas mixing unit can be judged by utilizing the vacuum pumping function, and if the vacuum degree of the calibration system cannot reach the standard in a specified procedure, the problem of gas leakage of the calibration system is shown.
In the embodiment of the present invention, the processing unit 10 further includes a control module, wherein the control module is electrically connected to the flow controller 3, the heat tracing band 11, the vacuum pump pre-solenoid valve 7 and the mass spectrum pre-solenoid valve 8 in the calibration system respectively.
In the embodiment of the invention, each pipeline of the gas injection unit on one side of the flow controller 3 close to the mixed flow unit is respectively provided with a buffer ring 4; in this embodiment, the buffer ring 4 is composed of a spiral pipeline, so as to prevent severe pressure fluctuation caused by large flow change from affecting the service life and the calibration precision of the flow controller.
In the embodiment of the invention, the flow controller 3 is provided with a front valve on each pipeline of the gas injection unit at the side far away from the flow mixing unit. The front valve 2 can be selected from a solenoid valve or a manual valve.
In the embodiment of the invention, the pipeline of each pipeline of the calibration system is made of an anti-corrosion material; the pipeline adopts corrosion-resistant material, weakens the destruction of corrosive gas.
In an embodiment of the invention, the flow controller 3 is an anti-corrosion flow controller; the flow controller 3 can be an anti-corrosion flow controller, and can also be a corrosion-resistant flow controller in a part of pipelines, and the corrosion-resistant flow controller is partially selected according to requirements, so that the cost can be saved.
In an embodiment of the invention, the range is different between the plurality of flow controllers; and flexible control of flow range is realized.
The carrier gas line is filled with an inert gas such as argon or helium, but is not limited thereto, and nitrogen may be used.
In the embodiment of the present invention, the mixed flow unit includes a mixed flow air collecting chamber 51 and a spoiler 52, and the spoiler 52 is disposed in the mixed flow air collecting chamber 51.
In the embodiment of the present invention, the inner diameter of the mixed flow gas collecting cavity 51 is greater than or equal to 10 times of the inner diameter of the pipeline used by the pipeline of the gas injection unit; for ensuring the stability of the pressure.
In an embodiment of the present invention, the spoiler 52 may be, but is not limited to, a spiral sheet; the spiral plate is used as a spoiler, so that the flow resistance is reduced, and the rapid and uniform mixing can be realized.
The mass spectrum post-calibration unit 9 comprises mass spectra of the types of quadrupole mass spectrum, ion trap mass spectrum, time-of-flight mass spectrum or multiplex mass spectrum. In the embodiment of the invention, the mixed gas is directly sampled and detected by using the capillary tube, and the mass spectrum signal is transmitted to the processing unit. And simultaneously storing and processing the detection data and carrying out real-time quantitative analysis by using a processing unit, and obtaining the flow and the concentration of different components in the mixed gas in real time by adopting an equivalent feature spectrum (ECSA).
In the embodiment of the invention, the invention is characterized by solving the principle problem in distinction from other conventional gas mixers. And performing secondary calibration on the mixed gas by using the high-precision mass spectrum after quantitative calibration, calculating a linear value by using a step peak and a linear curve, and finally determining a calibration coefficient to obtain a secondary calibration result so as to ensure the data accuracy of gas mixing and calibration.
As another aspect of the present invention, there is also provided a calibration method using the dynamic mixed gas full component flow calibration system as described above, including the following steps:
the flow controller dynamically adjusts the gas flow injected by each pipeline in the gas injection unit;
the gas of each pipeline in the gas injection unit is mixed in the mixed flow unit;
the mass spectrum post-calibration unit samples and detects the mixed gas output by the mixed flow unit;
the processing unit is used for processing the data obtained by the calibration unit after the mass spectrum by using an equivalent characteristic spectrum method, and obtaining the flow and concentration results of different components in the dynamically adjusted mixed gas in real time.
In the embodiment of the invention, the working principle mainly depends on a mass spectrometry quantitative analysis method, namely an equivalent feature spectrum (ECSA), the flow and the concentration of different components in the mixed gas are detected in real time, the post-calibration and detection functions of a mass spectrometry post-calibration unit are realized, the miscellaneous gas in a gas mixing system can be accurately diagnosed, and the content of all gas-phase components in the mixed gas, including the flow (mass flow, volume flow and molar flow) and the concentration, can be calibrated at high precision.
The mixed gas calibration link mainly utilizes different flow matching to realize real-time calibration of different content ranges and different types of gases. Before the operation of the mixed gas calibration link, closing the preposed electromagnetic valve of the vacuum pump, opening the preposed electromagnetic valve of the mass spectrum, starting the carrier gas path flow controller and setting default flow; then selecting the temperature of the gas mixing system, wherein gas mixing calibration can be executed at normal temperature or within a fixed temperature range, the selection of the temperature is determined by the type of gas, the gas which is easy to permeate, adsorb and reduce needs to be executed at a higher temperature, and then starting temperature control heating to ensure that the gas mixing system reaches the set temperature; setting a dynamic flow control program which changes along with time aiming at different gas paths and gas types, and calibrating various gases one by one; and detecting and analyzing the flow and concentration of different components in the mixed gas in real time by using a mass spectrum post-calibration unit and a processing unit.
When the mixed gas carrier gas process is diagnosed, a high-purity inert gas is used as the carrier gas, for example, 99.999% of Ar and He are used as purge gases, the working ionization energy of a mass spectrum in the detection process is 70eV, the main peak and the fragmentation peak of the Ar and the He in the mass spectrum detection do not have cross overlapping with other gases, the mass-to-nuclear ratio m/z of the main peak of the Ar is 40, the fragmentation peak m/z is 20, the mass-to-nuclear ratio m/z of the main peak of the He is 4, and the fragmentation peak m/z is 3, so that the air component and other gas components can be clearly distinguished, wherein the characteristic pattern peak positions of the air component are mass-to-nuclear ratios m/z 14, 16, 28, 32 and the like, and the characteristic pattern peak positions of the water are mass-to-nuclear ratios m/z 16, 17, 18. Therefore, the flow of the carrier gas can be selected according to the precision requirement of the calibration gas, the higher the precision requirement is, the lower the content of the required miscellaneous gas is, the flow of the carrier gas is reduced, and the reduction process of the miscellaneous gas in the purging process can be clearly observed.
In the mixed gas calibration process, high-purity inert gas is also used as carrier gas, for example, 99.999% of Ar and He are used as purge gas, the working ionization energy of the mass spectrum in the detection process is 70eV, the flow rate of the carrier gas is fixed at a set value, the set value is determined by the precision of the calibration gas, and the higher the precision requirement is, the lower the flow rate of the carrier gas is. And calibrating the flow setting of the gas, and sequentially setting from low to high according to the precision and the range of the flow controller, wherein if the range of the flow controller is 0-200 ml/min, the flow program is set to be integer multiples of 0, 10, 20, 40, 80, 160ml/min and the like, and each flow value is kept for 10-30 min. Then, the mass spectrum is used for quantitatively analyzing the flow of different components, and the response time of each flow dynamic change is given, so that the characteristics of diffusion and countercurrent expansion in the calibration system can be mastered, and the reliability of each calibration is ensured.
In an embodiment of the present invention, before performing calibration, the calibration method further includes:
and obtaining a characteristic spectrum of the calibration gas and the relative sensitivity of the calibration gas to the carrier gas by using a calibration system.
In an embodiment of the present invention, in the calibration method, obtaining the characteristic map of the calibration gas includes:
measuring mass spectrum data of a calibration gas with a mass-to-nuclear ratio in a range of 1-100 by using a mass spectrum post-calibration unit of the calibration system;
and obtaining a characteristic spectrum of the calibration gas based on the mass spectrum data.
In the embodiment of the invention, a mass flow controller which utilizes carrier gas and each calibration gas one by one is filled with a specific amount of gas, and the flow input adopts a step signal; detecting signals with a mass-to-nuclear ratio in a range of 1-100 by using a mass-spectrometric calibration unit; and acquiring the characteristic maps of the carrier gas and each calibration gas.
Wherein, betaj，kThe profile of a particular gas k is given in equation (1) below, which is a set of vectors that represent the abundance of the gas at the mass-to-nuclear ratio m/z j. HjThe intensity of the mixed ion current at m/z j is measured for mass spectra.
Representing the characteristic ion current intensity of gas k.
In an embodiment of the present invention, in the calibration method, obtaining the relative sensitivity of the calibration gas phase to the carrier gas comprises:
and determining the response time of the calibration system under different flow rates.
In the inventionIn the embodiment, a carrier gas such as N is used2The mass flow controller of (2) is filled with a specific amount of gas, and the flow input adopts a step signal. The specific amount of gas may be a high flow rate or a low flow rate; if the stability of the signal cannot be confirmed at a low flow rate, the stability of the signal must be confirmed by doubling the holding time of the specific flow rate. By using N2The signal variation characteristics of the proton-nuclear ratio 28 determine the response time at different flow rates.
In the embodiment of the invention, the relative sensitivity can be determined by inputting carrier gas at a fixed flow rate by utilizing the control of a flow controller and inputting calibration gas in a flow rate dynamic regulation mode meeting the response time;
and measuring mass spectrum data of the calibration gas with the mass-nuclear ratio of 1-100 by using a mass spectrum post-calibration unit of the calibration system, and determining the relative sensitivity of the calibration gas to the carrier gas.
In the examples of the present invention, the following formula (2), αr，kBeing the sensitivity of the gas k with respect to the gas r,
representing the volumetric flow of gases r, k, respectively.
And analyzing the mass spectrum in the calibration link by using the characteristic spectrum and the relative sensitivity of the gas to obtain the volume flow and the mass flow of various gases.
In an embodiment of the present invention, it is,
a vector consisting of the volume flow rates of the plurality of gases;
a vector consisting of the relative sensitivities of the gases; according to the volume flow obtained in the above formula (3)
Further, mass flow of the gas k at different time i is calculated by mass spectrum data
As in the above formula (4) (. rho)kIs the density of gas k at normal temperature.
In the embodiment of the present invention, in the calibration process, as shown in fig. 5, the calibration method may further include the steps of pre-purging, early self-cleaning preparation, late self-cleaning maintenance, and post-purging.
In the embodiment of the invention, the pre-purging link mainly has the function of replacing miscellaneous gases in the calibration system by carrier gases, wherein the carrier gases are high-purity inert gases (with the concentration of 99.999 percent), such as Ar and He. During pre-purging operation, the carrier gas pipeline is purged firstly, specific flow is kept, then the carrier gas is used for purging other calibrated gas pipelines of the calibration system one by one, dynamic change of each pipeline is monitored by the mass spectrum post-calibration unit in the purging process, and the purging gas pipeline is replaced after signals are stable.
In the embodiment of the invention, the main function of the early self-cleaning preparation link is to replace the dead volume of miscellaneous gas in the mixed gas by using carrier gas, eliminate gases which are easy to adsorb, permeate and reduce, protect the safety of each gas circuit and avoid the corrosion of corrosive gas. Before the operation of the early self-cleaning preparation link, firstly closing other flow controllers except the gas carrying pipeline, starting temperature control heating, setting the temperature to be generally higher than 150 ℃, and monitoring a gas flow signal by a mass spectrum post-calibration unit until the gas flow signal is stable after the set temperature is reached; then closing the flow controller and the mass spectrum preposed electromagnetic valve of the gas carrying pipeline, and opening the preposed electromagnetic valve of the vacuum pump; then starting a vacuum pump, and vacuumizing the calibration system; and if the vacuum degree reaches 0.1Pa, keeping for 30 minutes, stopping the early self-cleaning preparation operation link, and if the vacuum degree cannot reach, checking the air tightness of the gas mixing system.
In the embodiment of the invention, the later self-cleaning maintenance mainly eliminates easy-to-permeate, adsorption and reduction gases and corrosive gases, effectively maintains the reliability of equipment and prolongs the service life of the system. The later self-cleaning maintenance is similar to the earlier self-cleaning preparation link, firstly, other flow controllers except the gas carrying pipeline are closed, temperature control heating is started, the temperature is generally set to be higher than 150 ℃, and after the set temperature is reached, a gas flow signal is monitored by a mass spectrum until the gas flow signal is stable; then closing the flow controller and the mass spectrum preposed electromagnetic valve on the gas carrying pipeline, and opening the preposed electromagnetic valve of the vacuum pump; then starting a vacuum pump, and vacuumizing the calibration system; if the degree of vacuum reaches 0.1Pa, the vacuum is maintained for 30 minutes and then stopped, and if the degree of vacuum cannot reach the degree of vacuum, the airtightness of the calibration system needs to be checked.
In the embodiment of the invention, the main function of the post-blowing link is to replace impure gas in the calibration system by carrier gas, wherein the carrier gas is high-purity inert gas (with the concentration of 99.999 percent), such as Ar and He, and the inside of the system is kept clean and dry. The post-purging operation is similar to pre-purging, the carrier gas pipeline is purged firstly, specific flow is kept, then the carrier gas is used for purging other pipelines of the calibration system one by one, the dynamic change of each gas circuit is monitored by using the mass spectrum in the purging process, the purging gas circuit is replaced after the signal is stable, the whole post-purging operation is finished, and the system is closed.
In the embodiment of the invention, by adopting the calibration method, the 'dead volume', diffusion and countercurrent diffusion effects can be effectively eliminated, the accurate calibration of the component content spanning 5-6 orders of magnitude is realized, and the working state of the calibration system is kept and maintained.
The technical solution of the present invention is further described below with reference to specific examples, but it should be noted that the following examples are only for illustrating the technical solution of the present invention, but the present invention is not limited thereto.
Example 1
(1) Reducing gas CH4Calibration example (2)
High-purity CH with the concentration of 99.999 percent is injected in the calibration process4With Ar gas, purging with Ar for 1 hr before calibration, and adopting fixed value for Ar flow during calibration, CH4The flow program is designed for multi-step flow as shown in fig. 8.
By analyzing the pattern shift in FIG. 6, it can be seen that Ar and CH4Although the Ar flow is fixed, the characteristic peak m/z is 40 and still has a large change, fig. 6 objectively illustrates that the mass spectrometry mechanism is a typical Multiple Input Multiple Output (MIMO) nonlinear relationship, and a conventional calibration and analysis method based on linear assumption causes severe distortion of data.
By using an ECSA method, normalizing the spectrum with the characteristic peak m/z of Ar being 40 as a denominator to obtain a normalized mass spectrum, as shown in fig. 7, the normalized mass spectrum adaptively corrects the tilt trend and non-linear relationship in fig. 6, as shown in fig. 7, and simultaneously, Ar and CH are in parallel4The change of the characteristic peak and the change of the broken peak are completely consistent with the change of the respective flow, which also indicates that the data processing means of the ECSA conforms to the testing working principle of the mass spectrum.
The flow reliability was verified by further data processing and a perfect match between the two was seen, particularly in CH, with the programmed flow value pairs such as shown in FIG. 84In the process of flow switching, the response time of the test is very short, and the two are kept highly consistent.
Example 2
(2) Trace corrosive gas H2Calibration example of S
By using the method, various gas analyzers are calibrated by using the dynamic mixed gas all-component flow calibration system, and finally, a real and reliable calibration result can be obtained. In all gas analysis and detection processes, the accuracy of a calibration result is a key, if a problem occurs in a calibration link, the analysis result is seriously influenced, the actual flow or concentration of the escaping gas cannot be really obtained, the result is greatly wrong, and the calibration difficulty of corrosive trace gas is high.
Utilize onThe method is used for preparing trace H2S gas calibration to realize ultralow concentration H2The calibration of S gas, as shown in FIGS. 9 and 10, can be as low as 100ppb level with a volume flow rate close to 10-3ml/min, in order to ensure the test precision and higher signal-to-noise ratio (S/N is more than or equal to 10), 1ppm level is generally adopted as a reasonable measuring range for measurement.
It can be clearly seen from fig. 9 and 10 that when the trace gas is calibrated, the actual flow rate is in a fluctuation state, mainly due to the influence of various factors such as diffusion, countercurrent diffusion, adsorption, pneumatic vibration and the like, and the signal-to-noise ratio and the precision of the trace gas calibration signal can be effectively ensured.
Example 3
(3) Three kinds of gases Ar and N2With CO2Example of mixed calibration
The method can be used for calibrating the dynamic full component flow of various gases, and a real and reliable calibration result can be obtained. When multi-component gas is calibrated, due to the simultaneous dynamic change of gas flow, detection signals of the multi-component gas have great influence on each other, and if the concentration or flow of each component in the mixed gas is calibrated directly by means of the detection signals of the analysis equipment, serious mechanism errors are generated.
By the pair of Ar and N2With CO2Dynamic hybrid calibration of (1), wherein only N2The flow rate changes according to step flow rate in the temperature rise process, the mass spectrum of the flow rate changes as shown in 11 and 12, and CO is already mixed in figure 122And N2The overlap of Ar and CO is resolved, and although Ar and CO can be clearly seen in the three-dimensional mass spectrogram2The set flow rate of (2) is not changed, but the mass spectrum signal thereof also generates a mechanical accompanying change, and FIG. 13 shows Ar and CO more clearly2The trend of change of (c). Meanwhile, due to the changes of temperature and pressure, the signal in fig. 13 generally exhibits a characteristic of drifting downward with temperature, i.e., a temperature-dependent characteristic, and if the changes are not effectively analyzed, the accuracy and reliability of calibration are seriously affected.
The real gas flow can be directly analyzed by using the calibration system, and the real parameters of the calibration gas are given, rather than simply relying on the setting of a flow controller. The flow rate change in fig. 14 can actually reflect the response time of the flow rate change process.
The series of correction methods can be used for correcting the parameters of the mixed gas more accurately, eliminating the problems of secondary reaction, adsorption, condensation and the like of various gases in the mixing process and ensuring the precision of the multi-component dynamic mixed gas.
Comparative example 1
In order to verify the effects of diffusion and countercurrent diffusion, a dynamic mixed gas full-component flow calibration system is used for calibrating carrier gas, the carrier gas is high-purity Ar gas with the concentration of 99.999%, and a flow program is designed into multi-step flow, as shown by grey lines in FIG. 15; this calibration process does not employ a self-cleaning procedure.
As can be clearly seen from fig. 15, since no self-cleaning link is adopted, the characteristic peak-to-nucleus ratio m/z 40 in the three-dimensional mass spectrum of Ar is gradually increased along with the time, and is completely inconsistent with the multi-step flow rate. The main problem is that the system takes time to reduce the "dead volume" and gas diffusion effects.
Similarly, CH shown in FIGS. 6 and 74In the calibration, because a self-cleaning link is adopted, the flow of various gases in the diagram is basically consistent with the change turning point of mass spectrum data. This also indicates that the self-cleaning of the calibration system is very important during the mixed gas calibration process, and the self-cleaning process should be monitored by the actual high-precision gas analyzer to confirm the cleanliness of the interior with actual parameters, rather than relying on human guessing or defaults.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A dynamic mixed gas full-component flow calibration system is characterized by comprising:
the gas injection unit comprises a gas-carrying pipeline and a plurality of calibration gas pipelines; each pipeline is provided with a flow controller for realizing the dynamic adjustment of gas injection;
the mixed flow unit is connected with each pipeline of the gas injection unit and is used for mixing the multi-path gas conveyed by the gas injection unit;
the mass spectrum post-calibration unit is connected with the mixed flow unit through a mixing pipeline and is used for sampling and detecting mixed gas output by the mixed flow unit;
the processing unit is electrically connected with the mass spectrum post-calibration unit; the method is used for processing data obtained by the mass spectrum post-calibration unit by utilizing an equivalent characteristic spectrum method, and obtaining the flow and concentration results of different components in the dynamically adjusted mixed gas in real time.
2. The dynamic mixed gas full component flow calibration system as claimed in claim 1, wherein the calibration system further comprises a self-cleaning unit, the self-cleaning unit comprising: heat tracing band and vacuum pump; wherein the content of the first and second substances,
the heat tracing band is coated on the pipeline of the calibration system and the mixed flow unit;
the vacuum pump is connected with the mixing pipeline through a vacuumizing pipeline; wherein, a vacuum pump preposed electromagnetic valve is arranged on the vacuum pumping pipeline; and a mass spectrum prepositive electromagnetic valve is arranged on the mixing pipeline between the vacuumizing pipeline and the mass spectrum post-calibration unit.
3. The system for calibrating the full component flow of a dynamic mixed gas as claimed in claim 2, wherein the processing unit further comprises a control module, wherein the control module is electrically connected to the flow controller, the heat tracing band, the vacuum pump pre-solenoid valve and the mass spectrum pre-solenoid valve in the calibration system respectively.
4. The system for calibrating the full component flow of the dynamic mixed gas according to claim 1, wherein the flow controllers are provided with a buffer ring on each pipeline of the gas injection unit on the side close to the flow mixing unit;
and each pipeline of the gas injection unit on one side of the flow controller, which is far away from the mixed flow unit, is provided with a front valve.
5. The dynamic mixed gas full component flow calibration system as claimed in claim 4,
pipelines of all pipelines of the calibration system are made of anti-corrosion materials;
the flow controller is an anti-corrosion flow controller;
the range between a plurality of the flow controllers is different;
inert gas is introduced into the gas carrying pipeline.
6. The dynamic mixed gas full component flow calibration system as claimed in claim 1,
the mixed flow unit comprises a mixed flow gas collecting cavity and a spoiler, and the spoiler is arranged in the mixed flow gas collecting cavity.
7. The dynamic mixed gas full component flow calibration system as claimed in claim 6,
the inner diameter of the mixed flow gas collecting cavity is more than or equal to 10 times of the inner diameter of a pipeline adopted by a pipeline of the gas injection unit;
the spoiler adopts a spiral plate;
the mass spectrum post-calibration unit comprises mass spectrums of four-pole mass spectrum, ion trap mass spectrum, time-of-flight mass spectrum or multiple mass spectrum and the like.
8. A calibration method using the dynamic mixed gas full component flow calibration system as claimed in any one of claims 1 to 7, comprising the steps of:
the flow controller dynamically adjusts the gas flow injected by each pipeline in the gas injection unit;
the gas of each pipeline in the gas injection unit is mixed in the mixed flow unit;
the mass spectrum post-calibration unit samples and detects the mixed gas output by the mixed flow unit;
the processing unit is used for processing the data obtained by the calibration unit after the mass spectrum by using an equivalent characteristic spectrum method, and obtaining the flow and concentration results of different components in the dynamically adjusted mixed gas in real time.
9. The calibration method according to claim 8,
before the calibration, the calibration method further comprises:
and obtaining a characteristic spectrum of the calibration gas and the relative sensitivity of the calibration gas to the carrier gas by using the calibration system.
10. Calibration method according to claim 9,
in the calibration method, obtaining the characteristic spectrum of the calibration gas comprises the following steps:
measuring mass spectrum data of a calibration gas with a mass-nuclear ratio of 1-100 by using a mass spectrum post-calibration unit of the calibration system;
obtaining a characteristic map of the calibration gas based on the mass spectrum data;
in the calibration method, obtaining the relative sensitivity of the calibration gas phase to the carrier gas comprises:
determining the response time of the calibration system under different flow rates;
inputting carrier gas at a fixed flow rate by utilizing the control of a flow controller, and inputting calibration gas in a flow rate dynamic regulation mode meeting the response time;
and measuring mass spectrum data of the calibration gas with the mass-nuclear ratio of 1-100 by using a mass spectrum post-calibration unit of the calibration system, and determining the relative sensitivity of the calibration gas to the carrier gas.
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