CN111679014A - Method and detection equipment for detecting chromatographic column bearing high-concentration sample pollution in real time - Google Patents

Method and detection equipment for detecting chromatographic column bearing high-concentration sample pollution in real time Download PDF

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CN111679014A
CN111679014A CN202010705808.5A CN202010705808A CN111679014A CN 111679014 A CN111679014 A CN 111679014A CN 202010705808 A CN202010705808 A CN 202010705808A CN 111679014 A CN111679014 A CN 111679014A
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sample
signal
chromatographic column
gas
concentration
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康明丽
周长
马鹏杰
康贺贺
康永升
苏旭刚
周子琦
刘阳
刘金成
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Zhengzhou Annuo Scientific Instrument Co ltd
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Zhengzhou Annuo Scientific Instrument Co ltd
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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02Column chromatography
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02Column chromatography
    • G01N30/04Preparation or injection of sample to be analysed
    • G01N30/06Preparation
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02Column chromatography
    • G01N30/04Preparation or injection of sample to be analysed
    • G01N30/24Automatic injection systems
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02Column chromatography
    • G01N30/50Conditioning of the sorbent material or stationary liquid
    • G01N30/52Physical parameters
    • G01N30/54Temperature
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02Column chromatography
    • G01N30/86Signal analysis
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02Column chromatography
    • G01N30/86Signal analysis
    • G01N30/8658Optimising operation parameters

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Abstract

The invention relates to a method and a device for detecting a chromatographic column bearing high-concentration sample pollution in real time. The method aims to solve the problem that in the prior art, a chromatographic column is polluted by a high-concentration sample, so that the sample cannot be normally detected or the detection value is inaccurate in the later period. The method comprises the steps of signal acquisition, conditioning, conversion and calculation, and the acquired signals are analyzed to control the heating of the chromatographic column and the opening and closing of the air passage in corresponding states. Has the advantages that: the high concentration automatic detection can prevent the subsequent sample analysis accuracy caused by the high concentration sample polluting the chromatographic column; different signals generated by different manufacturers and different types of chromatographs can be processed and converted, so that real-time detection is achieved; when high-concentration pollution is detected, the freezing sample injector has other functions except purging, and the problem of cross pollution of the pipelines of the sample injector is solved.

Description

Method and detection equipment for detecting chromatographic column bearing high-concentration sample pollution in real time
Technical Field
The invention relates to the field of sample detection equipment, in particular to a method and detection equipment for detecting a chromatographic column bearing high-concentration sample pollution in real time.
Background
The gas chromatographic column is a chromatographic column in which gas is carried by carrier gas, and the components are separated by the chromatographic column with different retention properties to the components in the mixture to be detected, and are sequentially introduced into a detector to obtain the detection signals of the components. According to the sequence of leading in the detector, the components can be distinguished by comparison, and the content of each component can be calculated according to the peak height or peak area. Chromatography uses a chromatographic column to separate the mixture first, and then a detector to detect the separated components in sequence. In the technology, the aging of the chromatographic column is to heat the chromatographic column to 30-50 ℃ below the maximum use temperature of the chromatographic column under the condition of introducing carrier gas, and then carry out high-temperature baking to remove some organic substances remained in the chromatographic column.
In recent years, along with the increasing importance of environmental pollution problems in various industries, related departments also issue corresponding national standards to detect the pollution degree of the environment, namely organic volatile matters in organized and unorganized exhaust gas are detected, most detection units detect the organic volatile matters by using modified gas chromatography or special gas chromatography, and due to the uncertainty of components and concentration in the gas, when high-concentration polluted gas enters the gas chromatography, the chromatographic column is polluted. When the chromatographic column is polluted, the temperature of the gas chromatographic column incubator needs to be artificially raised so as to reach an aged chromatographic column and eliminate the pollution.
At the present stage, the complexity of manual sample introduction is greatly reduced along with the popularization of a gas automatic sample injector, the working state which is not needed to be attended is almost achieved, but when a high-concentration sample enters the gas chromatography, the high-concentration sample cannot be found in time, and the temperature of a chromatographic column incubator cannot be increased to age the chromatographic column. Leading to the subsequent other gas samples to enter the polluted chromatographic column, and directly influencing the detection of the subsequent other gas samples and the detection accuracy.
Disclosure of Invention
The invention aims to solve the problem that a high-concentration sample pollutes a chromatographic column when gas is analyzed by gas chromatography in the prior art, so that the sample cannot be normally detected or the detection value is inaccurate at the later stage.
The specific scheme of the invention is as follows: a method for detecting the pollution of a chromatographic column bearing a high-concentration sample in real time comprises the following steps:
(1) signal acquisition: the concentration value of the sample gas is reflected on a micro-voltage signal in the output signal of the gas chromatography detector, the micro-voltage signal in the gas chromatography signal output by the detector is intercepted, and a signal for feeding back the concentration of the sample is intercepted from the gas chromatography output signal to obtain micro-voltage information A;
(2) signal conditioning: the micro-voltage information A is amplified in a multistage sectional mode to form micro-voltage information B after passing through an integrated operational amplifier, and the micro-voltage information B forms micro-voltage information C after passing through a filter amplifier;
(3) signal conversion: the micro-voltage information C is converted into a digital signal D through an AD converter, and an analog signal is converted into a digital signal;
(4) signal filtering and calculation: the signal filtering adopts an anti-pulse interference average value filtering algorithm, a digital signal D is connected with a data display device on a digital circuit, the signal filtering adopts an anti-pulse interference average value filtering algorithm, the anti-pulse interference average value algorithm compares N sampling signals firstly to obtain the maximum value and the minimum value, eliminates the maximum value and the minimum value, then carries out average calculation to calculate a sample concentration value E, E = (A0 + A1+ … A20) -AMAX-AMIN)/19, wherein A0-A20 represents a sampling value; AMAX represents the maximum sample value; AMIN represents the minimum sample value; 19 denotes the number of sample values;
(5) monitoring the sample concentration value: and taking the stability of the monitoring baseline as a reference, stopping the automatic sampler for alarming when the concentration value of the sample is greater than or equal to the alarm concentration value, automatically or manually intervening, increasing the temperature of the gas chromatographic column incubator, increasing the temperature by 20 ℃ again to age the chromatographic column, and purging the sample injection pipeline until the concentration value of the sample is recovered to be normal, wherein the baseline is recovered to be stable. The major fluctuation here mainly refers to the fluctuation of the non-horizontal state visible to the naked eye.
In step (1), the micro-voltage signal is intercepted using a shielded twisted pair.
In step (5), the sample concentration value returns to normal standard, that is, the electric signal gradually approaches to the original zero value and does not have large fluctuation, that is, the positive and negative fluctuation is less than 20 microvolts.
The application also relates to equipment for detecting the chromatographic column bearing the high-concentration sample pollution in real time, which comprises an information monitoring and transmitting mechanism, a control mechanism, a chromatographic gas path mechanism and a sample injector gas path mechanism communicated with the inlet of the chromatographic gas path mechanism; the chromatographic gas circuit mechanism comprises a chromatographic column, a temperature control box for arranging the chromatographic column and a detector connected with the chromatographic column; the information monitoring and transmitting mechanism sequentially comprises a signal amplifying plate, a signal converter and a chromatographic workstation along the electric information transmitting direction, wherein the input end of the signal amplifying plate is connected with the detector, and the output end of the signal amplifying plate is also connected with a signal collecting plate of the control mechanism; the control mechanism comprises a main control board, the input end of the main control board is connected with the signal acquisition board, and the output end of the main control board is connected with an upper computer of the sample injector and an on-off switch corresponding to each component in the gas circuit mechanism of the sample injector; the sample injector gas circuit mechanism comprises a sampling loop and a purging loop which are opened by one of the connection of a sample injection valve and a two-position three-way electromagnetic valve, wherein the sampling loop comprises a container for loading sampling gas and connecting the sample injection valve and a vacuum pump, and the purging loop comprises an inert gas container and a pressure stabilizing valve and a flow stabilizing valve which are connected with the inert gas container.
The sampling loop comprises at least two sampling gas containers, the outlet of each sampling gas container is used as a branch pipeline and is connected in parallel with the inlet of the selector valve, and the outlet of the selector valve is connected with the sample injection valve.
An electric heating device is arranged in the temperature control box, and a circuit of the electric heating device is connected with the output end of the main control panel.
The detector is connected with the signal amplification plate through two shielding stranded wires, the shielding stranded wires form a double-wire loop, and a single twist is arranged at the midpoint of the double-wire loop. Although the twisted pair technology is the term of the prior art, the interference can be effectively eliminated and the measurement accuracy is improved after the twisted pair technology is used in the technology, so that the method has the beneficial effects. And an air resistance is arranged between the air inlet of the vacuum pump and the two-position three-way valve.
The signal amplification board is sequentially provided with an LC filter circuit a, an input signal amplification circuit b, a signal conditioning circuit c, a primary filter circuit d and a secondary filter circuit e, wherein the input signal amplification circuit b and the signal conditioning circuit c are respectively connected in parallel with an independent branch filter circuit f.
The invention has the beneficial effects that:
the high concentration automatic detection can prevent the subsequent sample analysis accuracy caused by the high concentration sample polluting the chromatographic column;
different signals generated by different manufacturers and different types of chromatographs can be processed and converted, so that real-time detection is achieved;
when high-concentration pollution is detected, the freezing sample injector has other functions except purging, so that the problem of cross pollution of the pipelines of the sample injector is solved;
the automatic temperature rise and aging of the chromatographic column are realized, the working steps are simple and easy to operate, and when the sample concentration signal reaches the alarm value set by a user, the operation software of the sample injector can automatically freeze all other functions and buttons except for pipeline purging, so that the cross contamination of the pipeline of the automatic sample injector caused by misoperation is prevented. Until the chromatographic column is aged, operating the sample injector to normally run after the baseline is stabilized again;
the anti-pulse interference average value algorithm compares N sampling signals to obtain the maximum value and the minimum value, eliminates the maximum value and the minimum value and then carries out average calculation, so that the interference of interference signals on useful signals can be well eliminated. After signal filtering, calculating according to a circuit to calculate a sample concentration value;
the temperature drift of the voltage reference circuit can reach 5ppm, so that the equipment can be ensured to have no more than 200ppm influence on measurement in the change range of the environmental temperature within the normal environmental temperature change; the shielded twisted pair wires introduce signals into the device, and the anti-interference capability of the signals can be enhanced. The interference of interference signals to parallel lines is realized by setting a reasonable lay length with total interference current I =0 because the conditions of the two lines are the same, so that the purpose of eliminating the interference is achieved.
Drawings
FIG. 1 is a flow chart of the operation of the present invention;
FIG. 2 is an overall block diagram of the present invention;
FIG. 3 is a schematic view of the control mechanism of the present invention;
FIG. 4 is a schematic diagram of the gas path mechanism of the sample injector of the present invention;
FIG. 5 is a schematic structural diagram of an information monitoring and transmitting mechanism according to the present invention;
FIG. 6 is a schematic diagram of the structure of the chromatographic gas path mechanism in the present invention;
FIG. 7 is a schematic diagram of a circuit structure on a signal amplification board according to the present invention;
fig. 8 is a schematic diagram of an AD converter in the present invention;
FIG. 9 is a flow chart of a sampling phase;
FIG. 10 is a schematic view of a sample injection stage;
FIG. 11 is a schematic view of a purge phase;
FIG. 12 is a schematic diagram of the connection of the double shielded strands;
FIG. 13 is a schematic view of the structure of a gas chromatography column and a temperature controlled box section;
1. a control mechanism; 2. a sample injector gas circuit mechanism; 3. an information monitoring and transmitting mechanism; 4. a chromatographic gas circuit mechanism; 5. a temperature control box; 6. an electric heating device; 7. a thermometer;
a. an LC filter circuit; b. an input signal amplifying circuit; c. a signal conditioning circuit; d. a first-stage filter circuit; e. a second stage filter circuit; f. a branch filter circuit; g. inputting a signal;
101. an injector upper computer; 102. a main control panel; 103. a signal acquisition board;
201. a vacuum pump; 202. an air outlet of the vacuum pump; 203. a vacuum pump inlet; 204. a discharge port; 205. air resistance; 206. a two-position three-way electromagnetic valve; 207. a selector valve; 208. a standard gas container; 209. a sample injection valve; 210. a flow stabilizing valve; 211. a pressure maintaining valve; 212. an inert gas inlet;
301. a chromatography workstation; 302. a signal converter; 303. a signal amplification board;
401. a first carrier gas inlet; 402. a second carrier gas inlet; 403. a detector; 404. a chromatographic column;
in fig. 12, US signal voltage, RS load impedance.
Detailed Description
The preferred embodiments of the present invention will be described in conjunction with the accompanying drawings, and it will be understood that they are described herein for the purpose of illustration and explanation and not limitation.
Example 1
A method for detecting the pollution of a chromatographic column bearing a high-concentration sample in real time comprises the following steps:
(1) signal acquisition: the concentration value of the sample gas is reflected on a micro-voltage signal in the output signal of the gas chromatography detector 403, the micro-voltage signal in the gas chromatography signal output by the detector 403 is intercepted, and a signal for feeding back the concentration of the sample is intercepted from the gas chromatography output signal to obtain micro-voltage information A;
(2) signal conditioning: the micro-voltage information A is amplified in a multistage sectional mode to form micro-voltage information B after passing through the integrated operational amplifier, and the micro-voltage information B forms micro-voltage information C after passing through the filter amplifier;
(3) signal conversion: the micro-voltage information C is converted into a digital signal D through an AD converter, and an analog signal is converted into a digital signal;
(4) signal filtering and calculation: the signal filtering adopts an anti-pulse interference average value filtering algorithm, a digital signal D is connected with a data display device on a digital circuit, the signal filtering adopts an anti-pulse interference average value filtering algorithm, the anti-pulse interference average value algorithm compares N sampling signals firstly to obtain the maximum value and the minimum value, eliminates the maximum value and the minimum value, then carries out average calculation to calculate a sample concentration value E, E = (A0 + A1+ … A20-AMAX-AMIN)/19, wherein A0-A20 represents a sampling value; AMAX represents the maximum sample value; AMIN represents the minimum sample value; 19 denotes the number of sample values;
(5) monitoring the sample concentration value: and taking the stability of the monitoring baseline as a reference, stopping the automatic sampler for alarming when the concentration value of the sample is greater than or equal to the alarm concentration value, automatically or manually intervening, increasing the temperature of the incubator of the gas chromatographic column 404, increasing the temperature by 20 ℃ again to age the chromatographic column 404, and purging the sample injection pipeline until the concentration value of the sample is recovered to be normal, and the baseline is recovered to be stable.
In step (1), the micro-voltage signal is intercepted using a shielded twisted pair comprising two shielded wires twisted at least once to shield the interference signal.
In step (5), the sample concentration value returns to normal standard, namely that the electric signal gradually approaches the original zero value and does not fluctuate greatly.
The application also relates to equipment for detecting the chromatographic column bearing the high-concentration sample pollution in real time, which comprises an information monitoring and transmitting mechanism 3, a control mechanism 1, a chromatographic gas circuit mechanism 4 and a sample injector gas circuit mechanism 2 communicated with the inlet of the chromatographic gas circuit mechanism 4; wherein the chromatographic gas circuit mechanism 4 comprises a chromatographic column 404, a temperature control box for arranging the chromatographic column 404 and a detector 403 connected with the chromatographic column 404; the information monitoring and transmitting mechanism 3 sequentially comprises a signal amplification board 303, a signal converter 302 and a chromatographic workstation 301 along the electric information transmission direction, the input end of the signal amplification board 303 is connected with a detector 403, and the output end of the signal amplification board 303 is also connected with the signal acquisition board 103 of the control mechanism 1; the control mechanism 1 comprises a main control panel 102, the input end of the main control panel 102 is connected with a signal acquisition panel 103, and the output end of the main control panel 102 is connected with an injector upper computer 101 and an on-off switch corresponding to each component in the injector gas circuit mechanism 2; the sample injector gas circuit mechanism 2 comprises a sampling loop and a purging loop which are alternatively opened and connected through a sample injection valve 209 and a two-position three-way electromagnetic valve 206, wherein the sampling loop comprises a container for loading sampling gas and connected with the sample injection valve 209, and a vacuum pump 201, and the purging loop comprises an inert gas container, a pressure stabilizing valve 211 and a flow stabilizing valve 210 which are connected with the inert gas container.
The sampling loop comprises at least two containers for sampling gas, the outlet of each sampling gas container is connected in parallel with the inlet of the selector valve 207 as a branch pipeline, and the outlet of the selector valve 207 is connected with the sample injection valve 209. An electric heating device 6 is arranged in the temperature control box 5, and a circuit of the electric heating device 6 is connected with the output end of the main control panel 102. The detector 403 and the signal amplification board 303 are connected via two shielding strands, which form a two-wire loop. An air resistance 205 is arranged between the air inlet of the vacuum pump 201 and the two-position three-way valve.
The signal amplification board 303 is sequentially provided with an LC filter circuit a, an input signal amplification circuit b, a signal conditioning circuit c, a primary filter circuit d, and a secondary filter circuit e, wherein the input signal amplification circuit b and the signal conditioning circuit c are respectively connected in parallel with an independent branch filter circuit f.
The electric sample injection valve 209, also known as an electric rotary valve or an electric rotary valve, is mainly controlled by a stepping motor and is applied to automatic parts for sample collection, sample injection or flow path conversion. The inert flow path of the electric sample injection valve 209 can be used for various corrosive samples, and the materials in the valve body are matched with each other, so that sealing and leakage prevention can be effectively formed.
In the working process, the working principle of the sample injector is as follows:
and pushing each group of sample gas with a fixed volume into chromatographic analysis by the gas injector in a flow sample injection mode, namely sampling and injecting, and then sampling and injecting the next sample after the chromatographic analysis is finished.
In the sampling process: the sample is filled into the quantification loop in preparation for sample injection. The selection valve 207 is switched to be communicated with the container, the sampling valve 209 is switched to be in a sampling state to be communicated with the quantitative ring, the two-position three-way electromagnetic valve 206 is switched to be communicated with the flow path of the vacuum pump 201, and the vacuum pump 201 stops after working for corresponding time according to the value calculated by the program, so that the quantitative ring is filled with the sample amount.
In the sample introduction process: the sample injection valve 209 is switched to communicate the carrier gas with the dosing loop, the sample is pushed into the gas chromatograph for analysis, and when the substance passes through the detector 403, a voltage signal is generated and displayed on the workstation in the form of a spectrogram after passing through the signal amplifier and the signal converter 302.
In the purging process: when the sample enters the detector 403, the signal acquisition board 103 detects that the voltage signal of the detector 403 after passing through the signal amplification board 303 exceeds the set voltage value, the sample injector alarms, freezes other functions and starts the purging function of the sample injector, the purging function of the sample injector is started by using inert gas, and meanwhile, the incubator of the chromatographic column 404 is started to automatically heat up.
According to the principle of the sample injector, when the response voltage value of the sample entering the detector 403 is lower than the set alarm voltage value, the sample injector sequentially samples, injects and analyzes each sample. Until all samples were done. When the sample with too high concentration appears in the sample, namely the response voltage value of the sample after passing through the detector 403 is higher than the set alarm voltage value, the sample injector generates an alarm and stops all actions, and prompts a user to take down the current sample and execute the purging function. Besides the purging function, all the other operation keys are in a frozen state, so that misoperation of a client is prevented. Meanwhile, signals are output externally, and a chromatographic temperature-rising column incubator is started. In which the voltage value to which the detector 403 responds fluctuates significantly over time when the chromatographic column 404 is contaminated with a high concentration of sample. As the column oven is raised for a certain period of time, the electrical signal will gradually approach the original zero value, i.e., the baseline. When the signal acquisition board 103 in the sample injector acquires the electric signal and continuously stabilizes at zero for a certain time, the freezing of the operation interface of the sample injector is released, so that the sample injector can continue to work until all samples are taken.
In the process, an RS232 and an Ethernet communication interface are reserved on the equipment, and the measured sample concentration value can be sent to the monitoring software by adopting any communication mode.
In the process, the monitoring software can display the current sample concentration value and can set an alarm sample concentration value. When the sample concentration value is larger than or equal to the alarm concentration value, the automatic sample injector stops to alarm, meanwhile, automatic or manual intervention is performed, the temperature of the incubator of the gas chromatographic column 404 is raised, the chromatographic column 404 is aged, and a sample injection pipeline is purged to prepare for subsequent sample injection. Meanwhile, when the sample concentration signal reaches the alarm value set by the user, the injector operating software can automatically freeze all other functions and buttons except for purging the pipeline, so that the cross contamination of the pipeline of the automatic injector caused by misoperation is prevented. Until the column 404 aging is complete, the operational injector is operating normally after baseline re-stabilization.
In fig. 12, Us Is the source of the interference signal, and the interference currents Is generated on the two leads L1 and L2 of the two wires as I1 and I2, respectively. Since L1 is closer to the interferer, I1 is much larger than I2, I = I1-I2 ≠ 0, and there is a disturbing current. Interference of the interfering signal on the twisted pair loop is shown in fig. 2. Unlike fig. 1, the two-wire loop is twisted once at the midpoint location. Disturbance currents I11 and I12 are present at L1, disturbance currents I21 and I22 are present at L2, and a disturbance current I = I21+ I22-I11-I12, and since the conditions of the two lines are the same, the total disturbance current I = 0. Therefore, the purpose of eliminating interference can be achieved as long as a reasonable lay length is set. US signal voltage, RS load impedance.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (9)

1. A method for detecting the pollution of a chromatographic column bearing a high-concentration sample in real time is characterized by comprising the following steps:
signal acquisition: the concentration value of the sample gas is reflected on a micro-voltage signal in an output signal of the gas chromatography detector (403), the micro-voltage signal in the gas chromatography signal output by the detector (403) is intercepted, and a signal for feeding back the concentration of the sample is intercepted from the gas chromatography output signal to obtain micro-voltage information A;
signal conditioning: the micro-voltage information A is amplified in a multistage sectional mode to form micro-voltage information B after passing through an integrated operational amplifier, and the micro-voltage information B forms micro-voltage information C after passing through a filter amplifier;
signal conversion: the micro-voltage information C is converted into a digital signal D through an AD converter, and an analog signal is converted into a digital signal;
signal filtering and calculation: the signal filtering adopts an anti-pulse interference average value filtering algorithm, a digital signal D is connected with a data display device on a digital circuit, the signal filtering adopts an anti-pulse interference average value filtering algorithm, the anti-pulse interference average value algorithm compares N sampling signals firstly to obtain the maximum value and the minimum value, the maximum value and the minimum value are removed, then the average calculation is carried out, and the sample concentration value E is calculated, wherein E = (A0 + A1+ … A20) -AMAX-AMIN)/1; wherein A0-A20 represent sample values; AMAX represents the maximum sample value; AMIN represents the minimum sample value; 19 denotes the number of sample values;
(5) monitoring the sample concentration value: and taking the stability of the monitoring baseline as a reference, stopping the automatic sampler for alarming when the concentration value of the sample is greater than or equal to the alarm concentration value, automatically or manually intervening, increasing the temperature of an incubator of the gas chromatographic column (404), increasing the temperature by 20 ℃ again to age the chromatographic column (404), and purging the sample injection pipeline until the concentration value of the sample is recovered to be normal, and the baseline is recovered to be stable.
2. The method of real-time detection of contamination of a chromatographic column carrying a high concentration of sample as recited in claim 1, wherein: in step (1), the micro-voltage signal is intercepted using a shielded twisted pair.
3. The method of real-time detection of contamination of a chromatographic column carrying a high concentration of sample as recited in claim 1, wherein: in step (5), the sample concentration value returns to normal standard, that is, the electric signal gradually approaches to the original zero value, namely the fluctuation of the electric signal is less than plus or minus 20 microvolts.
4. The utility model provides an equipment of real-time detection bearing high concentration sample pollution chromatographic column which characterized in that: the device comprises an information monitoring and transmitting mechanism (3), a control mechanism (1), a chromatographic gas circuit mechanism (4) and a sample injector gas circuit mechanism (2) communicated with an inlet of the chromatographic gas circuit mechanism (4);
wherein the chromatographic gas path mechanism (4) comprises a chromatographic column (404), a temperature control box for arranging the chromatographic column (404) and a detector (403) connected with the chromatographic column (404);
the information monitoring and transmitting mechanism (3) sequentially comprises a signal amplification board (303), a signal converter (302) and a chromatographic work station (301) along the electric information transmission direction, the input end of the signal amplification board (303) is connected with a detector (403), and the output end of the signal amplification board (303) is also connected with a signal acquisition board (103) of the control mechanism (1);
the control mechanism (1) comprises a main control board (102), the input end of the main control board (102) is connected with the signal acquisition board (103), and the output end of the main control board (102) is connected with a sample injector upper computer (101) and an on-off switch corresponding to each component in the sample injector air circuit mechanism (2);
the sample injector gas circuit mechanism (2) comprises a sampling loop and a purging loop which are connected through a sample injection valve (209) and a two-position three-way electromagnetic valve (206) and are opened alternatively, wherein the sampling loop comprises a container for loading sampling gas and connected with the sample injection valve (209) and a vacuum pump (201), and the purging loop comprises an inert gas container, a pressure stabilizing valve (211) and a flow stabilizing valve (210) which are connected with the inert gas container.
5. The apparatus for real-time detection of contamination of a chromatographic column carrying a high concentration of sample according to claim 4, wherein: the sampling loop comprises at least two containers for sampling gas, the outlet of each sampling gas container is connected in parallel with the inlet of a selector valve (207) as a branch pipeline, and the outlet of the selector valve (207) is connected with the sample injection valve (209).
6. The apparatus for real-time detection of contamination of a chromatographic column carrying a high concentration of sample according to claim 4, wherein: an electric heating device (6) is arranged in the temperature control box (5), and a circuit of the electric heating device (6) is connected with the output end of the main control board (102).
7. The apparatus for real-time detection of contamination of a chromatographic column carrying a high concentration of sample according to claim 4, wherein: the detector (403) and the signal amplification board (303) are connected through two shielding stranded wires.
8. The apparatus for real-time detection of contamination of a chromatographic column carrying a high concentration of sample according to claim 4, wherein: and an air resistance (205) is arranged between the air inlet of the vacuum pump (201) and the two-position three-way valve.
9. The apparatus for real-time detection of contamination of a chromatographic column carrying a high concentration of sample according to claim 4, wherein: the signal amplification board (303) is sequentially provided with an LC filter circuit a, an input signal amplification circuit b, a signal conditioning circuit c, a primary filter circuit d and a secondary filter circuit e, wherein the input signal amplification circuit b and the signal conditioning circuit c are respectively connected in parallel with an independent branch filter circuit f.
CN202010705808.5A 2020-07-21 2020-07-21 Method and detection equipment for detecting chromatographic column bearing high-concentration sample pollution in real time Pending CN111679014A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117130297A (en) * 2023-10-25 2023-11-28 北京豪思生物科技股份有限公司 Upper computer control method, device and equipment of liquid chromatograph

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117130297A (en) * 2023-10-25 2023-11-28 北京豪思生物科技股份有限公司 Upper computer control method, device and equipment of liquid chromatograph
CN117130297B (en) * 2023-10-25 2023-12-29 北京豪思生物科技股份有限公司 Upper computer control method, device and equipment of liquid chromatograph

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