CN117929556A - Dioxin on-line detection method applied to single channel or double channels - Google Patents

Dioxin on-line detection method applied to single channel or double channels Download PDF

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CN117929556A
CN117929556A CN202311701499.4A CN202311701499A CN117929556A CN 117929556 A CN117929556 A CN 117929556A CN 202311701499 A CN202311701499 A CN 202311701499A CN 117929556 A CN117929556 A CN 117929556A
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value
enumeration
concentrator
dimensional
array
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CN117929556B (en
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汤绍富
李楠
陈涛
林杰
王浩
赵有涛
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Zhejiang Fuchunjiang Environmental Technology Research Co ltd
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Abstract

The invention discloses a dioxin online detection method applied to single channels or double channels, and relates to the technical field of dioxin online detection. The method comprises the following steps: the cooperative work of the gas chromatograph, the first pre-concentrator and/or the second pre-concentrator is realized in a single-channel mode or a double-channel mode; selecting the running serial numbers of the first pre-concentrator and the second pre-concentrator and the serial numbers of the sampling analysis cold trap; corresponding to each cold trap in the single-channel mode and the double-channel mode, calculating the proportional relation between the quality and the peak area value of the standard gas, and obtaining a standard slope value; data acquisition is carried out, and peak area values are calculated; and determining a cold trap to be analyzed, obtaining a corresponding calibration slope value, and calculating a dioxin concentration value by combining the peak area value. The invention has the characteristics of flexible detection mode, low cost and the like.

Description

Dioxin on-line detection method applied to single channel or double channels
Technical Field
The invention relates to the technical field of online detection of dioxin, in particular to an online detection method of dioxin applied to single channels or double channels.
Background
The existing online dioxin detection equipment put into the market is mainly applied to single-channel emission source detection and faces the diversification of emission reduction requirements of garbage incineration enterprises. The existing single-channel dioxin on-line detection equipment cannot meet the application requirements of the existing complex enterprises, for example, garbage incineration enterprises generally have 2 to 3 incinerator production lines, if manufacturers perform process improvement or equipment transformation to realize the incineration process analysis of different furnace numbers, the analysis can only be realized by switching sampling pipelines, but the mode has the defects of long time period, high labor cost and the like, and the multi-incinerator incineration process analysis cannot be performed in real time. In addition, if multiple dioxin on-line detection equipment is purchased to realize multiple emission sources detection, the defects of high price, high equipment maintenance cost and the like exist.
Disclosure of Invention
In order to solve at least one technical problem in the background art, the invention aims to provide the dioxin on-line detection method applied to single channel or double channels, and the method has the characteristics of flexible detection mode, low cost and the like.
In order to achieve the above purpose, the present invention provides the following technical solutions:
a dioxin on-line detection method applied to single channel or double channels comprises the following steps:
WS1, the cooperative work of a gas chromatograph, a first pre-concentrator and/or a second pre-concentrator is realized in a single-channel mode or a double-channel mode;
WS2, selecting the running serial numbers of the first pre-concentrator and the second pre-concentrator and the serial numbers of the sampling analysis cold trap;
WS3, corresponding to each cold trap in the single-channel mode and the double-channel mode, calculating the proportional relation between the quality of the standard gas and the peak area value, and obtaining a standard slope value;
WS4, data acquisition is carried out, and peak area values are calculated;
WS5, determining a cold trap to be analyzed, obtaining a corresponding calibration slope value, and calculating a dioxin concentration value by combining the peak area value.
In some embodiments of the present invention, in the single channel mode, the carrier gas enters one of the first pre-concentrator and the second pre-concentrator, controls the one of the first pre-concentrator and the second pre-concentrator to alternately perform sampling analysis, and triggers the gas chromatograph to operate when the gas chromatograph reaches an analysis heating state; under the dual-channel mode, carrier gas sequentially enters the first pre-concentrator and the second pre-concentrator, the first pre-concentrator and the second pre-concentrator are controlled to alternately perform sampling analysis, and the gas chromatograph is triggered to work when the first pre-concentrator and the second pre-concentrator reach an analysis heating state.
In some embodiments of the present invention, the specific steps of selecting the operation serial numbers of the first preconcentrator, the second preconcentrator, and the sampling analysis cold-trap serial numbers are as follows:
C01: a Boolean control, a preconcentrator enumeration control, a sampling enumeration control and an analysis enumeration control are placed in a LabVIEW front panel cluster control, and the cluster control is added into an array to form a one-dimensional cluster array control; the preconcentrator enumeration control provides enumeration constants T1 and T2; the sampling enumeration control and the analysis enumeration control both provide enumeration constant cold traps A, B, C and D;
C02: the front panel clicks an enumeration control to select a preconcentrator serial number, a sampling serial number and a cold trap serial number;
c03: judging whether the current one-dimensional cluster array control is used for checking whether an enabling button and a preconcentrator sequence number are repeated or whether sampling analysis cold trap sequence numbers are not matched; comprising the following steps:
C031, obtaining the value of a one-dimensional cluster array control, and obtaining an enabling Boolean value and a cold trap serial number enumeration value;
C032: judging whether the starting Boolean value is true, if true, adding a Boolean true constant into the one-dimensional Boolean array B1, judging whether the length of the one-dimensional Boolean array B1 is smaller than 1, if so, not selecting a Boolean value starting button, and meanwhile, if the starting Boolean value is true, adding a preconcentrator serial number enumeration value into the one-dimensional enumeration array M1;
C033: judging whether the number value of the pre-concentration instrument after unbinding is equal to an enumeration constant value T1, if so, adding a Boolean constant into B2 in a one-dimensional Boolean array, judging whether the length of B2 is greater than 1, if so, repeating the Boolean variable B1 as true by the number of the pre-concentration instrument, and if so, judging the number of the cold trap;
C034, acquiring an enabling Boolean value, a preconcentrator serial number enumeration value, a sampling enumeration value and an analysis enumeration value in a one-dimensional cluster array, performing difference calculation on the sampling enumeration value and the analysis enumeration value, judging whether the absolute value is larger than 1, outputting a judging result as a one-dimensional Boolean array B3, searching whether a true constant exists in the one-dimensional Boolean array B3, and if the true constant exists, setting an overrun Boolean variable B3 as the true;
C035: judging whether the sampling enumeration value is equal to the analysis enumeration value, outputting a judging result as a one-dimensional Boolean array B4, searching whether the one-dimensional Boolean array B4 has true constants, if so, repeating at least one group of sampling and analysis sequence numbers in the representative parameters, and if so, repeating the sampling analysis sequence numbers, and repeating the Boolean variable B2 to be true;
C036: judging whether the enabling Boolean is true, if true, adding the current analysis enumeration value into a one-dimensional enumeration array M2, adding the current sampling enumeration value into a one-dimensional enumeration array M3, and merging the one-dimensional enumeration array M2 and the one-dimensional enumeration array M3 after adding the elements into a new one-dimensional enumeration array M4;
c04: judging whether the pre-concentration instrument is repeatedly configured, and if so, prompting reconfiguration; otherwise, judging whether the sampling analysis sequence number is repeated or exceeds the limit, if so, prompting reconfiguration, otherwise, judging the length of the one-dimensional enumeration array M1, and if the length is greater than 1, judging that the single-channel Boolean variable B4 is true;
C05: after the sequence configuration is completed, the integer sequence identification variable BI is initialized to 0.
In some embodiments of the invention, the step of calculating the proportional relationship between the mass of the target gas and the peak area value is as follows:
L1: judging whether the single-channel Boolean variable B4 is true, if true, calling a single-channel flow calibration module, otherwise, calling a double-channel flow calibration module;
L2: if the flow is calibrated in a single channel, writing a plurality of groups of corresponding cold trap test standard gas peak area values and the mass of a certain volume concentration standard gas of the first preconcentrator or the second preconcentrator in operation, and performing linear fitting to obtain slope parameters, namely corresponding cold trap calibration slope values;
L3: if the flow is calibrated by multiple channels, writing the peak area value of the cold trap test standard gas and the mass of the index gas with a certain volume concentration corresponding to multiple groups of the first pre-concentrator and the second pre-concentrator which are operated, and performing linear fitting to obtain slope parameters, namely the calibrated slope values corresponding to the cold traps.
In certain embodiments of the present invention, the specific method of step L2 is as follows:
l201: writing the sampling volume of the pre-concentrator in a ml column of a front panel table control, and writing the peak area values of different cold trap test standard gases in a T1-A, T1-B or T2-C, T-D column;
L202: obtaining the mass of a subscript gas with a certain volume concentration;
l203: and performing linear fitting, wherein the input variable X is a quality one-dimensional array SQZ of the standard gas, the input variables Y1 and Y2 are peak area value one-dimensional arrays SFS1 and SFS2 corresponding to the cold trap serial numbers, and slope parameters K1 and K2 after linear fitting are the standard slope values of the corresponding cold traps and are spliced into a one-dimensional array SXL.
In certain embodiments of the present invention, the specific method of step L3 is as follows:
l301: filling the front panel form control ml1 and ml2 columns with the sampling volume of the pre-concentrator, and writing the peak area values of different cold trap test standard gases in the T1-A, T1-B, T2-C, T-D columns;
l302: obtaining the mass of a subscript gas with a certain volume concentration;
L303: and performing linear fitting, wherein input variables X1 and X2 are quality one-dimensional arrays DQZ and DQZ of standard gas, input variables Y1, Y2, Y3 and Y4 are peak area value one-dimensional arrays DFS1, DFS2, DFS3 and DFS4 corresponding to cold trap serial numbers, and slope parameters K1, K2, K3 and K4 after linear fitting are calibration slope values corresponding to the cold traps and are spliced into a one-dimensional array DXL.
In some embodiments of the present invention, the method for calculating the quality of the target gas is as follows:
Wherein: the mass of the index gas is the i-th group sampling volume; m is the concentration of standard gas; /(I) Sampling volume for the i group of preconcentrators; /(I)Is the molar mass of the standard gas.
In certain embodiments of the invention, the peak area value is calculated as follows:
G301: introducing standard gas or flue gas into a pre-concentration instrument and a gas chromatograph for enrichment concentration and separation, then introducing the sample gas or flue gas into a mass spectrometer, and ionizing substances by a laser;
G302: two cursor base lines are arranged at the left side and the right side of the flight time of the indicator And/>Cursor baseline/>Two cursor base lines/>, are arranged on the left sideAnd/>Cursor baseline/>Two cursor base lines/>, are arranged on the right sideAnd/>；
G303: obtaining cursor base lineAnd/>Mean LA and cursor baseline/>, within intervalAnd/>Average RA within the interval;
G304: calculating a cursor baseline And/>The signal approximation noise value between the two is calculated as follows:
G305: calculating the magnitude of a coarse peak area value FM by adopting a trapezoidal rule method;
g306: the final peak area value XF is calculated as follows:
。
In some embodiments of the present invention, the method for obtaining the calibration slope value is as follows:
E1: judging whether the output voltage of the gas chromatograph is triggered or not, if so, determining that the current mode is a single-channel mode or a double-channel mode according to the running cold trap serial number;
e2: if the single-channel mode is adopted, whether the first pre-concentration instrument or the second pre-concentration instrument is operated is further judged;
e3: obtaining a calibration slope value corresponding to a cold trap of an operating preconcentrator;
E4: after the first slope value acquisition is completed, adding 1 to the sequence identification variable BI, performing the next calibration slope acquisition when the next gas chromatograph triggers, judging whether the single-channel Boolean variable B4 is true after the next calibration slope acquisition and the sequence identification variable BI adding 1 operation are completed, if true, judging whether the identification variable BI is greater than or equal to 2, if the condition is met, resetting the sequence identification variable BI to 0, if the single-channel Boolean variable B4 is false, judging whether the identification variable BI is greater than or equal to 4, and if the judgment result is true, resetting the sequence identification variable BI to 0.
In some embodiments of the present invention, the method for calculating the dioxin concentration value is as follows:
Substituting the calibrated slope value into the correlation model for calculation to obtain a dioxin concentration value, wherein the calculation formula is as follows:
wherein F represents the peak area value of an indicator in the waste incineration flue gas;
K represents a standard gas calibration slope value;
Representing the sampling volume of the flue gas;
Representing the flue gas volume conversion coefficient;
a represents an influence factor corresponding to the concentration of an indicator in the flue gas;
B represents a constant coefficient factor corresponding to the concentration of an indicator in the flue gas;
Represents the initial oxygen content of the flame-retardant air;
indicating the measured oxygen content of the flue gas;
y represents the calculated dioxin concentration value.
Compared with the prior art, the invention has the beneficial effects that:
(1) The invention can realize the selection of two detection modes of a single channel and a double channel, and has the advantages of flexible detection mode, low cost and the like compared with the single channel dioxin detection method;
(2) According to the invention, through setting of time sequence configuration, any single-channel furnace number detection and double-channel detection sequence selection can be performed, so that the method has high flexibility and can meet complex application requirements of enterprises.
Drawings
FIG. 1 is a flow chart of an on-line detection method of the present invention.
FIG. 2 is a diagram of the overall hardware system architecture of the present invention.
FIG. 3 is a schematic diagram of the hardware connections of the gas phase preconcentrator control of the present invention.
Fig. 4 is a schematic diagram of a gas phase preconcentrator collaborative triggering flow under a dual-channel mode according to the present invention.
FIG. 5 is a schematic diagram of the cooperative control flow of the gas phase preconcentrator of the present invention.
Fig. 6 and 7 are schematic flow calibration data entry diagrams and operation timing diagrams of the preconcentrator after different timing configurations in a single-channel operation mode.
Fig. 8 and 9 are schematic flow calibration data entry diagrams and operation timing diagrams of the preconcentrator after different timing configurations in the dual-channel operation mode of the present invention.
FIG. 10 is a flowchart illustrating the high-speed board average data sampling mode of the present invention.
FIG. 11 is a flow chart of the data acquisition operation state of the present invention.
FIG. 12 is a diagram showing the peak area calculation cursor interval position according to the present invention.
Fig. 13 and 14 are schematic diagrams of calibration slope acquisition after different time sequences are configured in a single-channel operation mode of the present invention.
Fig. 15 and 16 are schematic diagrams of calibration slope acquisition after different time sequences are configured in the dual-channel operation mode of the present invention.
In the figure: 1-1, an upper computer; 1-2, a laser; 1-3, gas chromatograph; 1-4, a low-speed board card; 1-5, a first preconcentrator; 1-6, a second preconcentrator; 1-7, a high-speed board card; 1-8, mass spectrometer; 2-7, a gas carrying cylinder; 2-8, a first electromagnetic valve; 2-9, a second electromagnetic valve; 2-10, a quartz tee joint.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Referring to fig. 1, the embodiment provides a method for online detecting dioxin applied to single channel or dual channels, which includes the following steps:
WS1, the cooperative work of a gas chromatograph, a first pre-concentrator and/or a second pre-concentrator is realized in a single-channel mode or a double-channel mode;
WS2, selecting the running serial numbers of the first pre-concentrator and the second pre-concentrator and the serial numbers of the sampling analysis cold trap;
WS3, corresponding to each cold trap in the single-channel mode and the double-channel mode, calculating the proportional relation between the quality of the standard gas and the peak area value, and obtaining a standard slope value;
WS4, data acquisition is carried out, and peak area values are calculated;
WS5, determining a cold trap to be analyzed, obtaining a corresponding calibration slope value, and calculating a dioxin concentration value by combining the peak area value.
Specifically, as shown in fig. 2 and 3, first, before step S1, the method further provides an upper computer 1-1, a laser 1-2, a gas chromatograph 1-3, a first preconcentrator 1-5, a second preconcentrator 1-6, and a mass spectrometer 1-8. The specific hardware module is connected as follows:
The input and output ends of the upper computer 1-1 are connected with the input ends of the gas chromatograph 1-3, the first pre-concentration instrument 1-5 (T1), the second pre-concentration instrument 1-6 (T2) and the low-speed board card 1-4, the output end of the gas carrying bottle 2-7 is connected with the carrier gas input end of the gas chromatograph 1-3 through a copper pipeline, the carrier gas output end of the gas chromatograph 1-3 is respectively connected with the input ends of the first electromagnetic valve 2-8 and the second electromagnetic valve 2-9 through copper pipelines, and the output ends of the first electromagnetic valve 2-8 and the second electromagnetic valve 2-9 are connected with the carrier gas input ends of the first pre-concentration instrument 1-5 and the second pre-concentration instrument 1-6. The sample output ends of the first pre-concentration instrument 1-5 and the second pre-concentration instrument 1-6 are connected with the input end of the quartz tee joint 2-10 through a transmission line, the output end of the quartz tee joint 2-10 is connected with the input end of the gas chromatograph 1-3 chromatographic column, the AI1 input end of the low-speed board card 1-4 is connected with the AO output end of the gas chromatograph 1-3, the AO1 output end, the AO2 output end, the AO3 output end, the AO4 output end and the AO5 output end of the low-speed board card 1-4 are respectively connected with the input ends of the gas chromatograph 1-3, the first electromagnetic valve 2-8, the first pre-concentration instrument 1-5, the second electromagnetic valve 2-9 and the second pre-concentration instrument 1-6.
The method comprises the following steps:
WS1, gas phase preconcentration control
The cooperative work of the gas chromatograph, the first pre-concentrator and/or the second pre-concentrator is realized in a single-channel mode or a double-channel mode;
Under a single-channel mode, carrier gas enters one of a first pre-concentrator and a second pre-concentrator, one of the first pre-concentrator and the second pre-concentrator is controlled to alternately perform sampling analysis, and the gas chromatograph is triggered to work when the carrier gas reaches an analysis heating state;
Under the dual-channel mode, carrier gas sequentially enters the first pre-concentrator and the second pre-concentrator, the first pre-concentrator and the second pre-concentrator are controlled to alternately perform sampling analysis, and the gas chromatograph is triggered to work when the first pre-concentrator and the second pre-concentrator reach an analysis heating state.
Taking a dual-channel mode as an example, as shown in fig. 4 and 5, the control flow of the first preconcentrator 1-5 and the second preconcentrator 1-6 triggering the gas chromatograph 1-3 is as follows:
s1: the upper computer 1-1 monitors the state of the first pre-concentrator 1-5 in real time through serial port communication, and judges whether the first pre-concentrator 1-5 is in an analysis heating state or not;
S2: the upper computer 1-1 monitors the state of the second pre-concentration instrument 1-6 in real time through serial port communication, and judges whether the second pre-concentration instrument 1-6 is in an analysis heating state or not;
S3: the upper computer 1-1 sequentially achieves analysis heating states according to the first pre-concentration instrument 1-5 and the second pre-concentration instrument 1-6, and assigns voltage AO1;
s4: the low-speed board AO1 channel outputs a signal to realize the triggering of the gas chromatograph 1-3.
As shown in fig. 4 and 5, the gas chromatograph 1-3 triggers the control flow of the first pre-concentrator 1-5 and the second pre-concentrator 1-6 in the dual-channel mode as follows:
T1: the upper computer 1-1 acquires analog input signals of the gas chromatograph 1-3 in real time through an AI1 channel of the low-speed board card 1-4;
T2: the upper computer 1-1 judges whether the gas chromatograph 1-3 is in a gas phase preparation state according to the real-time acquired voltage value, and assigns voltage AO3 or AO5 according to the software set operation time sequence;
t3: the low-speed board card 1-4 sends voltage to the first concentrator 1-5 through the AO3, and the first pre-concentrator 1-5 runs a method sequence;
t4: the low speed board 1-4 sends a voltage to the second concentrator 1-6 via the AO5, and the second preconcentrator 1-6 runs a sequence of methods.
The operation triggering modes of the first concentrator 1-5 and the second concentrator 1-6 are in two modes of rising edge triggering and falling edge triggering, and the triggering modes are set through upper computer software.
As shown in fig. 3 and 5, when the upper computer 1-1 monitors that the first preconcentrator 1-5 is in a ready-to-analyze state, the AO2 channel of the low-speed board card 1-4 outputs a 5V high level, the AO4 outputs a low level, the first electromagnetic valve 2-8 is opened, carrier gas (argon) is introduced into the first preconcentrator 1-5, and when the second preconcentrator 1-6 is in a ready-to-analyze state, the AO2 channel of the low-speed board card 1-4 outputs a low level, the AO4 outputs a high level, the second electromagnetic valve 2-9 is opened, and carrier gas (argon) is introduced into the second preconcentrator 1-6.
Through the control of the gas phase pre-concentration instrument, the gas chromatograph and the pre-concentration instrument can work cooperatively under the single-channel and double-channel acquisition modes, the pre-concentration instrument alternately performs cold trap analysis under the double-channel mode, cold trap sampling is performed simultaneously, the cold trap analysis interval is 20min, and the pre-concentration instrument performs single cold trap alternate sampling analysis under the single-channel mode.
In the single-channel mode, the low-speed board card performs one-channel electromagnetic valve control, performs one-channel gas chromatograph and preconcentrator cooperative control, and has an overall cooperative control flow similar to that of the double channels, and is not described herein.
WS2, timing configuration
And selecting the running serial numbers of the first pre-concentrator and the second pre-concentrator and the serial numbers of the sampling analysis cold trap. The method comprises the following specific steps:
Table 1 below shows the definitions of the partial variables involved in the present invention:
table 1: variable definition
C01: a Boolean control, a preconcentrator enumeration control (enumeration constants are T1 and T2), a sampling enumeration control (enumeration constants are cold trap A, cold trap B, cold trap C and cold trap D) and an analysis enumeration control (enumeration constants are cold trap A, cold trap B, cold trap C and cold trap D) are placed in a LabVIEW front panel cluster control, and the cluster control is added into an array to form a one-dimensional cluster array control;
C02: the front panel clicks an enumeration control to select a preconcentrator serial number, a sampling serial number and a cold trap serial number;
The preconcentrators T1 and T2 represent the sequence of detecting the furnace numbers, if the serial numbers of the preconcentrators of the first cluster control and the second cluster control of the cluster array are T1 and T2, the detection of the furnace smoke of the No. 1 furnace is firstly carried out, and then the detection of the furnace smoke of the No. 2 furnace is carried out, and similarly, if the serial numbers of the preconcentrators of the first cluster control and the second cluster control of the cluster array are T2 and T1, the detection of the furnace smoke of the No. 2 furnace is firstly carried out, and then the detection of the furnace smoke of the No. 1 furnace is carried out.
C03: judging whether the current one-dimensional cluster array control is used for checking whether an enabling button and a preconcentrator sequence number are repeated or whether sampling analysis cold trap sequence numbers are not matched; comprising the following steps:
C031: acquiring a value of a one-dimensional cluster array control, circularly indexing the value of an ith (i= … … N) one-dimensional cluster array For, unbinding the acquired value parameter by a name unbinding function, wherein the unbinding value is an enabling Boolean value and a cold trap serial number enumeration value;
c032: judging whether the unbundled starting Boolean value is true, if true, adding a Boolean true constant in a one-dimensional Boolean array B1[ N ] by using an array insertion function, judging whether the length of B1[ N ] is smaller than 1 by using an array size function, if smaller than 1, not selecting a Boolean starting button, and meanwhile, if true, adding a preconcentrator sequence number enumeration value into a one-dimensional enumeration array M1[ N ] by using the array insertion function;
C033: judging whether the number value of the pre-concentration instrument after unbinding is equal to an enumeration constant value T1, if so, adding a Boolean true constant in a B2[ N ] in a one-dimensional Boolean array by using an array insertion function, judging whether the length of the B2[ N ] is greater than 1 by using an array size function, if so, repeating the Boolean variable B1 as true by the number of the pre-concentration instrument, and if so, judging the number of the cold trap;
C034, for cyclic index (i= … … N) one-dimensional cluster array values, unbinding the acquired value parameters through a 'unbinding by name' function, wherein the unbinding values are an enabling Boolean value, a preconcentrator serial number enumeration value, a sampling enumeration value and an analysis enumeration value, respectively converting the sampling enumeration value and the analysis enumeration value into shaping values, then carrying out difference value calculation on the converted results, judging whether the absolute value is greater than 1, outputting the judging result as a one-dimensional Boolean array B3[ N ], searching whether a one-dimensional Boolean array B3[ N ] has true constant through a 'searching one-dimensional array' function, and if yes, obtaining an overrun Boolean variable B3 as true;
The sampling enumeration values are cold trap A, cold trap B, cold trap C and cold trap D, the corresponding constants are 0, 1,2 and 3, the corresponding constants of the analysis enumeration values are 0, 1,2 and 3, if the number exceeds the limit, the difference between the sampling sequence number and the analysis sequence number is larger than 1, and the difference between the default cold trap and the analysis enumeration value of the T1 pre-concentration instrument T2 pre-concentration instrument is 1.
C035: for circularly judging whether the sampling enumeration value is equal to the analysis enumeration value, outputting a judging result as a one-dimensional Boolean array B4[ N ], searching whether the one-dimensional Boolean array B4[ N ] has true constant through a one-dimensional array searching function, if so, at least one group of sampling and analysis sequence numbers in the representative parameters are repeated, and if the sampling analysis sequence numbers are repeated, the sampling analysis sequence number repeated Boolean variable B2 is true;
C036: and (3) For circularly judging whether the starting Boolean is true, if true, adding the current analysis enumeration value into the one-dimensional enumeration array M2[ N ] through an array insertion function, adding the current sampling enumeration value into the one-dimensional enumeration array M3[ N ] through an array insertion function, and merging the one-dimensional enumeration array M2[ N ] and the one-dimensional enumeration array M3[ N ] after adding the elements into a new one-dimensional enumeration array M4[ N ] through an array creation function.
C04: the user clicks a determination button to judge whether the pre-concentrator serial number repeat Boolean variable B1 is true, if true, a dialog box is prompted (the pre-concentrator serial number is repeated, please perform configuration selection |), if false, whether the value obtained after OR operation of the sampling analysis serial number repeat Boolean variable B2 and the overrun Boolean variable B3 is true is judged, if true, the dialog box is prompted (the sampling analysis serial number is selected to be repeated or overrun, please perform configuration |), if false, the length of the one-dimensional enumeration array M1[ N ] is judged through an array size function, and if the length is larger than 1, the single-channel Boolean variable B4 is true;
C05: after the sequence configuration is completed, the integer sequence identification variable BI is initialized to 0.
If the single-channel Boolean variable B4 is true, the single-channel dioxin on-line detection is performed, and if the single-channel Boolean variable B4 is false, the double-channel dioxin on-line detection is performed.
WS3, flow calibration
And calculating the proportional relation between the quality and the peak area value of the standard gas corresponding to each cold trap in the single-channel mode and the double-channel mode to obtain the standard slope value. As shown in fig. 6, 7, 8 and 9, the specific steps are as follows:
L1, judging whether a single-channel Boolean variable B4 is true, if true, performing single-channel flow calibration module call by LabVIEW upper computer software by using a function of starting asynchronous call, and if false, performing multi-channel flow calibration module call;
L2: if the single-channel flow calibration is performed, a first value of a one-dimensional enumeration array M1[ N ] of the serial number of the preconcentrator is obtained by using an index array function during software initialization, if the first value is equal to an enumeration constant value T1, the column head of the front panel table control is 'ml, T1-A, T-B', and if the first value is not equal to the enumeration constant value T1, the column head of the front panel table control is 'ml, T2-C, T2-D';
L201: writing the sampling volume of the pre-concentrator in a ml column of a front panel form control, writing the peak area values of standard gas of different cold trap tests in a T1-A, T-1-B or T2-C, T-D column, and filling data into at least 5 groups;
l202: the mass of the subscript gas with a certain volume concentration is obtained, and the conversion formula is as follows:
（i=0,1,2……N）
Wherein:
: the calculated mass at the i-th set of sample volumes is in ug;
m: the standard gas concentration is ppbv;
: the sampling volume of the i group of preconcentrators is in ml;
: the molar mass of the standard gas.
L203: and performing linear fitting by using a 'linear fitting' function in LabVIEW, wherein an input variable X is a one-dimensional array SQZ [ N ] of gas quality numbers, input variables Y1 and Y2 are one-dimensional arrays SFS1[ N ] and SFS2[ N ] of peak areas corresponding to cold trap serial numbers, a linear fitting method is selected as a 'least square method', and a slope parameter K1 and a slope parameter K2 after linear fitting are spliced into a one-dimensional array SXL [ N ].
And L3, if the flow is calibrated by multiple channels, the column head of the front panel table control is 'ml 1, T1-A, T1-B, ml2, T2-C, T2-D'.
L301: filling the front panel form control ml1 and ml2 columns with the sampling volume of the pre-concentrator, filling the T1-A, T1-B, T2-C, T2-D columns with the standard gas peak area values written into different cold trap tests, and filling at least 5 groups of data;
l302: obtaining the mass of a subscript gas with a certain volume concentration;
L303: and performing linear fitting by using a 'linear fitting' function in LabVIEW, wherein input variables X1 and X2 are one-dimensional arrays DQZ [ N ] and DQZ [ N ] of gas quality numbers, input variables Y1, Y2, Y3 and Y4 are one-dimensional arrays DFS1[ N ], DFS2[ N ], DFS3[ N ] and DFS4[ N ] of peak areas corresponding to cold trap serial numbers, a linear fitting method is selected as a 'least square method', and slope parameters K1, K2, K3 and K4 after linear fitting are spliced into a one-dimensional array DXL [ N ].
WS4, data acquisition
And adopting a high-speed board card 1-7 with the model number of Spectrum M4i.2210-x8 to collect data and calculate peak area values.
The specific implementation steps of data acquisition and calculation are as follows:
G1: the software is initialized to carry out acquisition parameter setting, equipment name connection is carried out through initializing equipment vi, parameter setting is carried out through general configuration setting vi, the signal detection range is set to +/-2500mv, and the signal coupling mode is DC; vi sets the trigger channel as external trigger through analog input, the trigger mode is rising edge trigger, the trigger voltage is 1V, and the sampling rate is 1.25GS/s;
As shown in fig. 10, in the average sampling mode, that is, the board card performs data collection once after receiving the trigger signal outside the laser, and places the collected data in the onboard memory after the average processing, and then when the sampling frequency reaches the sampling mean value n, the summation processing is performed inside the board card, in the sampling mode, the board card collects n times, the upper computer collects an accumulated value of the average value of n times, the upper computer collects a period of 0.1 x n (s in unit), in the sampling mode, the signal noise value is smaller, the signal distribution has better uniformity, and more accurate peak area results are convenient to obtain.
And G2: as shown in fig. 11, the data acquisition part adopts a state machine framework through While circulation, and the states are respectively: the method comprises the following steps of starting, judging state information, reading data, setting parameters and stopping the five states:
G201: a start state ①, vi, inputting the initialized board parameter input variable, outputting the board parameter output variable, and entering a state message judgment state;
G202: a status message judging status ②, through error checking, vi reads whether the boolean value of error occurrence is true, if true, then enters a stop status, exits the state machine cycle, ends the current data acquisition, enters the next data acquisition processing, if not true, judges that the status of the read board card is read, if true, enters a data reading status, if false, judges whether the user presses a stop acquisition button, if not presses the stop acquisition button, then enters a status message judging status ② all the time, and ends the current status and enters the stop status until the user clicks the stop acquisition;
G203: the data read state ③ reads vi reads the one-dimensional array RA [ N ] of the on-board memory, converts the one-dimensional array into a voltage value (in V), and the conversion formula is as follows:
Wherein:
: representing the voltage value of the ith sampling point of a one-dimensional array
: Representing the data value sampled by the ith sampling point of a one-dimensional array
N: representing the sampling mean
N: is the size of the sampling number
G204: parameter setting state ④, stopping through the channel, vi, closing the current high-speed board card acquisition channel, delaying for 1S, performing initialization parameter writing (the parameterized writing is the same as the G1 step), and exiting the current state machine circulation after the initialization parameter writing is completed;
The state is executed in the LabVIEW upper computer event structure, and when the user changes the size of the sampling mean value n, an event structure mean value change event branch enters the state to initialize parameters.
G205: and stopping the state ⑤, exiting the current state machine cycle, ending the current data acquisition, and entering the next data acquisition.
The initialization devices mentioned in the data acquisition calculations, vi, general configuration settings, vi, average statistics settings, vi, analog input settings, vi, startup, vi, error checking, vi, read card status, vi, cache data reading, vi, channel stop, channel shut-off vi are LabVIEW packages provided by the manufacturer, developed and integrated in the data acquisition calculations in the upper computer program.
S3: the peak area value was calculated as follows:
G301: introducing standard gas or flue gas into a pre-concentration instrument and a gas chromatograph for enrichment concentration and separation, then introducing the sample gas or flue gas into a mass spectrometer, and ionizing substances by a laser;
G302: as shown in FIG. 12, two cursor baselines are arranged on the left and right sides of the flight time of the indicator in the upper computer system interface oscillogram control And/>Cursor baseline/>Two cursor base lines/>, are arranged on the left sideAnd/>Cursor baseline/>Two cursor base lines/>, are arranged on the right sideAnd/>；/>
G303: obtaining a cursor baseline through a function of 'obtaining waveform subset' and a function of 'average' of LabVIEWAnd/>Obtaining a cursor baseline/>, by means of a 'acquire waveform subset' function and a 'mean' function of LabVIEWAnd/>Average RA within the interval;
the software firstly obtains a one-dimensional array of ordinate signal values in a cursor baseline interval through a function of obtaining a waveform subset, and then obtains an average value of the one-dimensional array of ordinate signal values, namely a Y-coordinate average value in the cursor interval through a function of obtaining an average value, wherein the function of obtaining the waveform subset and the function of obtaining the average value are both LabVIEW software self-contained packaging functions.
G304: calculating a cursor baselineAnd/>The signal approximation noise value between the two is calculated as follows:
G305: calculating the magnitude of the peak area FM by using a trapezoidal rule method through a 'unitary value integral' function of LabVIEW;
Wherein: the two input variables of LabVIEW 'unitary value integral' function are respectively the Double voltage signal value one-dimensional array V [ N ] (N=0, 1,2 … …) collected by the high-speed board card and the sampling step length dt of the data in the one-dimensional array V [ N ];
wherein: dt= （/>Is the high-speed board sampling rate); )
G306: the signal peak area XF is calculated as follows:
Because the high-speed board card is provided with noise signals, the obtained peak area value FM is subtracted by the noise signal value ZS, and the calculation accuracy of the signal peak area value can be improved, so that the accuracy of dioxin calculation is improved.
WS5, dioxin calculation
And determining a cold trap to be analyzed, obtaining a corresponding calibration slope value, and calculating a dioxin concentration value by combining the peak area value.
As shown in fig. 13, 14, 15, and 16, the method for obtaining the calibration slope value is as follows:
E1: judging whether the output voltage of the gas chromatograph AO1 is greater than the trigger voltage (rising edge trigger or falling edge trigger), if so, analyzing the enumerated value through an index array function index, wherein the input variable of the index array function is a one-dimensional enumerated array M4[ N ], the index serial number is an integer sequence identification variable BI (the initial value is 0), the index value is a cold trap enumerated value to be analyzed currently, and converting the cold trap enumerated value into a serial number integer value LJ through a long integer function;
E2: judging whether the single-channel Boolean variable B4 is true or not, judging whether the sequence number integer value LJ is more than or equal to 2 or not, if true, performing T2 pre-concentration instrument detection, and if false, performing T1 pre-concentration instrument detection;
e3: indexing and calibrating the slope value through an index array function, wherein the input variable of the index array function is a one-dimensional slope calibration array SXL [ N ], the index sequence number is a sequence number integer value LJ, the index value is a cold trap calibration slope value to be analyzed currently, and if the index value is single-channel detection and the sequence number integer value LJ is more than or equal to 2, the index sequence numbers of a cold trap C and a cold trap D are LJ-2; if the multi-channel detection is performed, acquiring a cold trap calibration slope value by using an index sequence number value LJ;
(if single-channel detection is performed, the corresponding enumeration constant values of cold trap C and cold trap D are 2 and 3, and the length of single-channel calibration one-dimensional array SXL [ N ] is 2, so if the index serial numbers are 2 and 3, the index acquired cold trap calibration value is 0, which can cause calculation errors of dioxin
E4: after the first slope value acquisition is completed, adding 1 to a sequence identification variable BI, performing next calibration slope acquisition when the next gas chromatograph is triggered, judging whether a single-channel Boolean variable B4 is true or not after the next calibration slope acquisition and the sequence identification variable BI adding 1 operation are completed, if true, judging whether the identification variable BI is greater than or equal to 2, if the condition is met, resetting the sequence identification variable BI to 0, if the single-channel Boolean variable B4 is false, judging whether the identification variable BI is greater than or equal to 4, and if the judgment result is true, resetting the sequence identification variable BI to 0;
e5: substituting the calibrated slope value into the correlation model for calculation to obtain a dioxin concentration value, wherein the calculation formula is as follows:
wherein F represents the peak area value of an indicator in the waste incineration flue gas;
K represents a standard gas calibration slope value;
the unit of the sampling volume of the flue gas is ml;
Representing the flue gas volume conversion coefficient;
a represents an influence factor corresponding to the concentration of an indicator in the flue gas;
B represents a constant coefficient factor corresponding to the concentration of an indicator in the flue gas;
Represents the initial oxygen content of the flame-retardant air;
indicating the measured oxygen content of the flue gas;
y represents the calculated dioxin concentration value.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.

Claims (10)

1. The online dioxin detection method applied to single channel or double channels is characterized by comprising the following steps of:
WS1, the cooperative work of a gas chromatograph, a first pre-concentrator and/or a second pre-concentrator is realized in a single-channel mode or a double-channel mode;
WS2, selecting the running serial numbers of the first pre-concentrator and the second pre-concentrator and the serial numbers of the sampling analysis cold trap;
WS3, corresponding to each cold trap in the single-channel mode and the double-channel mode, calculating the proportional relation between the quality of the standard gas and the peak area value, and obtaining a standard slope value;
WS4, data acquisition is carried out, and peak area values are calculated;
WS5, determining a cold trap to be analyzed, obtaining a corresponding calibration slope value, and calculating a dioxin concentration value by combining the peak area value.
2. The method for online detection of dioxin applied to single channel or double channels according to claim 1, wherein in the single channel mode, carrier gas enters one of a first pre-concentrator and a second pre-concentrator, controls one of the first pre-concentrator and the second pre-concentrator to alternately perform sampling analysis, and triggers the gas chromatograph to operate when the carrier gas reaches an analysis heating state; under the dual-channel mode, carrier gas sequentially enters the first pre-concentrator and the second pre-concentrator, the first pre-concentrator and the second pre-concentrator are controlled to alternately perform sampling analysis, and the gas chromatograph is triggered to work when the first pre-concentrator and the second pre-concentrator reach an analysis heating state.
3. The method for online detection of dioxin applied to single channels or double channels according to claim 1, wherein the specific steps of operation serial numbers of the first pre-concentrator and the second pre-concentrator and sampling analysis cold trap serial number selection are as follows:
C01: a Boolean control, a preconcentrator enumeration control, a sampling enumeration control and an analysis enumeration control are placed in a LabVIEW front panel cluster control, and the cluster control is added into an array to form a one-dimensional cluster array control; the preconcentrator enumeration control provides enumeration constants T1 and T2; the sampling enumeration control and the analysis enumeration control both provide enumeration constant cold traps A, B, C and D;
C02: the front panel clicks an enumeration control to select a preconcentrator serial number, a sampling serial number and a cold trap serial number;
c03: judging whether the current one-dimensional cluster array control is used for checking whether an enabling button and a preconcentrator sequence number are repeated or whether sampling analysis cold trap sequence numbers are not matched; comprising the following steps:
C031, obtaining the value of a one-dimensional cluster array control, and obtaining an enabling Boolean value and a cold trap serial number enumeration value;
C032: judging whether the starting Boolean value is true, if true, adding a Boolean true constant into the one-dimensional Boolean array B1, judging whether the length of the one-dimensional Boolean array B1 is smaller than 1, if so, not selecting a Boolean value starting button, and meanwhile, if the starting Boolean value is true, adding a preconcentrator serial number enumeration value into the one-dimensional enumeration array M1;
C033: judging whether the number value of the pre-concentration instrument after unbinding is equal to an enumeration constant value T1, if so, adding a Boolean constant into B2 in a one-dimensional Boolean array, judging whether the length of B2 is greater than 1, if so, repeating the Boolean variable B1 as true by the number of the pre-concentration instrument, and if so, judging the number of the cold trap;
C034, acquiring an enabling Boolean value, a preconcentrator serial number enumeration value, a sampling enumeration value and an analysis enumeration value in a one-dimensional cluster array, performing difference calculation on the sampling enumeration value and the analysis enumeration value, judging whether the absolute value is larger than 1, outputting a judging result as a one-dimensional Boolean array B3, searching whether a true constant exists in the one-dimensional Boolean array B3, and if the true constant exists, setting an overrun Boolean variable B3 as the true;
C035: judging whether the sampling enumeration value is equal to the analysis enumeration value, outputting a judging result as a one-dimensional Boolean array B4, searching whether the one-dimensional Boolean array B4 has true constants, if so, repeating at least one group of sampling and analysis sequence numbers in the representative parameters, and if so, repeating the sampling analysis sequence numbers, and repeating the Boolean variable B2 to be true;
C036: judging whether the enabling Boolean is true, if true, adding the current analysis enumeration value into a one-dimensional enumeration array M2, adding the current sampling enumeration value into a one-dimensional enumeration array M3, and merging the one-dimensional enumeration array M2 and the one-dimensional enumeration array M3 after adding the elements into a new one-dimensional enumeration array M4;
c04: judging whether the pre-concentration instrument is repeatedly configured, and if so, prompting reconfiguration; otherwise, judging whether the sampling analysis sequence number is repeated or exceeds the limit, if so, prompting reconfiguration, otherwise, judging the length of the one-dimensional enumeration array M1, and if the length is greater than 1, judging that the single-channel Boolean variable B4 is true;
C05: after the sequence configuration is completed, the integer sequence identification variable BI is initialized to 0.
4. The method for online detection of dioxin applied to single or double channels according to claim 3, wherein the step of calculating the proportional relationship between the mass of the standard gas and the peak area value is as follows:
L1: judging whether the single-channel Boolean variable B4 is true, if true, calling a single-channel flow calibration module, otherwise, calling a double-channel flow calibration module;
L2: if the flow is calibrated in a single channel, writing a plurality of groups of corresponding cold trap test standard gas peak area values and the mass of a certain volume concentration standard gas of the first preconcentrator or the second preconcentrator in operation, and performing linear fitting to obtain slope parameters, namely corresponding cold trap calibration slope values;
L3: if the flow is calibrated by multiple channels, writing the peak area value of the cold trap test standard gas and the mass of the index gas with a certain volume concentration corresponding to multiple groups of the first pre-concentrator and the second pre-concentrator which are operated, and performing linear fitting to obtain slope parameters, namely the calibrated slope values corresponding to the cold traps.
5. The online detection method of dioxin applied to single channels or double channels according to claim 4, wherein the specific method of step L2 is as follows:
l201: writing the sampling volume of the pre-concentrator in a ml column of a front panel table control, and writing the peak area values of different cold trap test standard gases in a T1-A, T1-B or T2-C, T-D column;
L202: obtaining the mass of a subscript gas with a certain volume concentration;
l203: and performing linear fitting, wherein the input variable X is a quality one-dimensional array SQZ of the standard gas, the input variables Y1 and Y2 are peak area value one-dimensional arrays SFS1 and SFS2 corresponding to the cold trap serial numbers, and slope parameters K1 and K2 after linear fitting are the standard slope values of the corresponding cold traps and are spliced into a one-dimensional array SXL.
6. The online detection method of dioxin applied to single channels or double channels according to claim 4, wherein the specific method of step L3 is as follows:
l301: filling the front panel form control ml1 and ml2 columns with the sampling volume of the pre-concentrator, and writing the peak area values of different cold trap test standard gases in the T1-A, T1-B, T2-C, T-D columns;
l302: obtaining the mass of a subscript gas with a certain volume concentration;
L303: and performing linear fitting, wherein input variables X1 and X2 are quality one-dimensional arrays DQZ and DQZ of standard gas, input variables Y1, Y2, Y3 and Y4 are peak area value one-dimensional arrays DFS1, DFS2, DFS3 and DFS4 corresponding to cold trap serial numbers, and slope parameters K1, K2, K3 and K4 after linear fitting are calibration slope values corresponding to the cold traps and are spliced into a one-dimensional array DXL.
7. The online detection method of dioxin applied to single channel or double channels according to claim 5 or 6, wherein the calculation method of the quality of the standard gas is as follows:
Wherein: the mass of the index gas is the i-th group sampling volume; m is the concentration of standard gas; /(I) Sampling volume for the i group of preconcentrators; /(I)Is the molar mass of the standard gas.
8. The online detection method of dioxin applied to single channel or double channels according to claim 1, characterized in that the peak area value calculation step is as follows:
G301: introducing standard gas or flue gas into a pre-concentration instrument and a gas chromatograph for enrichment concentration and separation, then introducing the sample gas or flue gas into a mass spectrometer, and ionizing substances by a laser;
G302: two cursor base lines are arranged at the left side and the right side of the flight time of the indicator And/>Cursor baseline/>Two cursor base lines/>, are arranged on the left sideAnd/>Cursor baseline/>Two cursor base lines/>, are arranged on the right sideAnd/>；
G303: obtaining cursor base lineAnd/>Mean LA and cursor baseline/>, within intervalAnd/>Average RA within the interval;
G304: calculating a cursor baseline And/>The signal approximation noise value between the two is calculated as follows:
G305: calculating the magnitude of a coarse peak area value FM by adopting a trapezoidal rule method;
g306: the final peak area value XF is calculated as follows:
。
9. The online detection method of dioxin applied to single channel or double channels according to claim 1, wherein the method for obtaining the calibration slope value is as follows:
E1: judging whether the output voltage of the gas chromatograph is triggered or not, if so, determining that the current mode is a single-channel mode or a double-channel mode according to the running cold trap serial number;
e2: if the single-channel mode is adopted, whether the first pre-concentration instrument or the second pre-concentration instrument is operated is further judged;
e3: obtaining a calibration slope value corresponding to a cold trap of an operating preconcentrator;
E4: after the first slope value acquisition is completed, adding 1 to the sequence identification variable BI, performing the next calibration slope acquisition when the next gas chromatograph triggers, judging whether the single-channel Boolean variable B4 is true after the next calibration slope acquisition and the sequence identification variable BI adding 1 operation are completed, if true, judging whether the identification variable BI is greater than or equal to 2, if the condition is met, resetting the sequence identification variable BI to 0, if the single-channel Boolean variable B4 is false, judging whether the identification variable BI is greater than or equal to 4, and if the judgment result is true, resetting the sequence identification variable BI to 0.
10. The online detection method of dioxin applied to single channel or double channels according to claim 1 or 9, wherein the calculation method of the concentration value of dioxin is as follows:
Substituting the calibrated slope value into the correlation model for calculation to obtain a dioxin concentration value, wherein the calculation formula is as follows:
wherein F represents the peak area value of an indicator in the waste incineration flue gas;
K represents a standard gas calibration slope value;
Representing the sampling volume of the flue gas;
Representing the flue gas volume conversion coefficient;
a represents an influence factor corresponding to the concentration of an indicator in the flue gas;
B represents a constant coefficient factor corresponding to the concentration of an indicator in the flue gas;
Represents the initial oxygen content of the flame-retardant air;
Indicating the measured oxygen content of the flue gas;
y represents the calculated dioxin concentration value.
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