CN113567602A - Detection method and detection device - Google Patents
Detection method and detection device Download PDFInfo
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- CN113567602A CN113567602A CN202010352393.8A CN202010352393A CN113567602A CN 113567602 A CN113567602 A CN 113567602A CN 202010352393 A CN202010352393 A CN 202010352393A CN 113567602 A CN113567602 A CN 113567602A
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/62—Detectors specially adapted therefor
- G01N30/64—Electrical detectors
- G01N30/68—Flame ionisation detectors
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/86—Signal analysis
- G01N30/8665—Signal analysis for calibrating the measuring apparatus
Abstract
The invention provides a detection method and corresponding detection equipment, which can reduce the types and the use amount of standard gas required to be used, simplify the correction operation or operation process and simultaneously implement detection by utilizing a more accurate correction curve. The detection method is a detection method for measuring the concentration of a target component in a sample by using a detection device, the detection device is provided with a storage device for storing a correction curve of the concentration, and the detection method comprises the following steps: step a, selecting a first concentration value and a first response value corresponding to the first concentration value in a correction curve to be corrected; b, using a detection device to measure a first standard sample with known concentration of the target component equal to the first concentration value to obtain a first correction value; step c, calculating a second correction value corresponding to the second concentration value according to the deviation of the first correction value relative to the first response value; and d, determining a corrected correction curve at least according to the second correction value.
Description
Technical Field
The invention relates to the technical field of analysis and detection, in particular to a detection method and detection equipment.
Background
Prior art test devices detect the concentration of a target component in a sample by testing the sample for a response to a prescribed action or input. For example, in a conventional VOC (Volatile Organic compound) online monitoring device having a Flame Ionization Detector (FID), an ion current is generated by an Ionization reaction generated in a hydrogen-air Flame, and the concentration of a VOC component in a sample gas is detected by calculating an integral area of an intensity of the ion current corresponding to the VOC component. Specifically, since the gas with different VOC concentration can correspond to different area responses of the FID, the VOC content in the sample can be reversely calculated according to the area response of the FID.
Some existing detection devices calibrate and store a calibration curve at the time of shipment, compare a response value with the calibration curve when a response (for example, intensity data, integrated area data, or the like) is detected at a measurement point, and determine a measurement result of a sample concentration by searching a concentration value corresponding to the response value in the calibration curve.
However, the calibration curve may be shifted according to the change of the environment. In the prior art, in order to correct a correction curve which deviates along with environmental changes, a maintenance worker needs to be sent to a measuring point, and the correction curve needs to be corrected on the spot by using a dynamic calibrator.
In such a conventional method for correcting the calibration curve, the operation flow or the operation flow is relatively complicated. In particular, when the calibration curve is not a straight line, the calibration curve cannot be accurately fitted by two-point calibration, such as zero gas (zero gas) and span gas (span gas) calibration. In order to perform multi-point calibration at or above three points, the operation and maintenance personnel are required to carry the dynamic calibration instrument and additional standard samples, or three or more standard samples are stored or prepared by the detection equipment, and calibration is also required to be performed on a plurality of concentration points in the corrected operation flow or operation flow.
Therefore, when the detection equipment is installed and the use environment is changed (such as equipment displacement) each time, maintenance personnel is required to arrive at the measuring point to implement correction of the correction curve, more types and usage of standard samples are required to be used in the correction process, the operation is complicated, and the operation and maintenance cost is high.
Therefore, in the process of correcting a non-linear calibration curve (for example, a concentration-area calibration curve obtained by performing VOC measurement with FID), it is an urgent need to reduce the types and the amounts of standard samples, reduce the complexity of the correction process, and improve the efficiency while ensuring the accuracy of the correction.
Disclosure of Invention
The inventors have found through extensive studies on the detection devices in the prior art that although some detection devices are affected by the environment and cause the deviation of the correction curve, the deviation of the correction curve as a whole follows a certain rule, that is, the degree of curvature of the correction curve after the deviation is approximately the same as that of the correction curve before the deviation.
Based on the above problems and findings, the present invention provides a detection method and a corresponding detection device, which can reduce the type and amount of the standard gas to be used, simplify the operation or operation process of correcting the calibration curve, and perform detection using a more accurate non-linear calibration curve.
The invention provides a detection method, which is a detection method for measuring the concentration of a target component in a sample by using detection equipment, wherein the detection equipment is provided with a storage device for storing a correction curve of the concentration, and the detection method comprises the following steps:
step a, selecting a first concentration value and a first response value corresponding to the first concentration value in a correction curve to be corrected;
b, using a detection device to measure a first standard sample with known concentration of the target component equal to the first concentration value to obtain a first correction value;
step c, calculating a second correction value corresponding to the second concentration value according to the deviation of the first correction value relative to the first response value;
and d, determining a corrected correction curve at least according to the second correction value.
According to the detection method of the present invention, the deviation of the first correction value from the first response value is the deviation of the response value corresponding to the same concentration point. The offset of one density point or a part of the density point on the correction curve can be continued to the calculation of the offset to the whole correction curve or the correction curve within a prescribed range based on the finding that the degree of curvature of the correction curve after offset is approximately the same as that of the correction curve before offset. Thus, the second correction value can be determined by calculation, not by experiment.
By using the calculation method to replace the method of using the standard sample for calibration in the prior art, the calibration steps for multiple standard samples which are originally required to be implemented can be omitted, so that the use of the standard samples is saved, and the operation or operation process is simplified.
In addition, by adopting the detection method provided by the invention, the concentration value of the standard sample used in correction does not need to be consistent with or matched with the concentration point used in multi-point correction in factory, and the flexibility of concentration selection in standard sample preparation is improved.
In some preferred embodiments of the present invention, step e is further included. In step e, using the detection device, measuring a second standard sample with the known concentration of the target component equal to zero to obtain a zero correction value; in step d, the corrected correction curve is determined based on at least the second correction value and the zero correction value.
The advantage of correcting the zero point of the calibration curve with a second standard sample of known concentration of the target component equal to zero, for example the zero gas normally provided by some detection devices, is that: in some embodiments, for example, in the embodiment of measuring the VOC concentration by FID, the slope has a larger variation range or ratio on the low concentration side of the calibration curve, and the calibration on the low concentration side of the calibration curve is assisted by zero gas, so that the accuracy of fitting the correction result to the actual curve can be improved. In addition, the correction is completed in the mode, the traditional device structure for two-point linear correction and part of software control flow can be used, and the cost for improving and upgrading hardware or software is reduced.
In some preferred embodiments of the present invention, the method further comprises step f. In step f, the corrected calibration curve is used to detect the concentration of the target component in the sample. The corrected correction curve is used for detection, so that a more accurate detection result can be obtained.
In some preferred embodiments of the present invention, the first standard sample is a span gas of the detection device. The range gas generally corresponds to a concentration point on the high concentration side, and the magnitude and the variation of the response value corresponding to the concentration point on the high concentration side are large, and accordingly, the amount or degree of the deviation can be reflected more accurately by the result obtained by calculation using the concentration point on the high concentration side. In addition, the measuring range gas is usually a gas type which is always provided for the detection equipment, so that the gas with specific concentration is not required to be independently prepared or stored for completing correction, and the device is convenient to popularize and use.
In some preferred embodiments of the present invention, the detection method includes performing the loop of steps a to d once every predetermined time interval, and saving the corrected calibration curve as the currently used calibration curve. Through the mode, the detection equipment automatically runs the correction program at a specified time interval, on one hand, operation and maintenance personnel do not need to be dispatched to reach a measurement point to complete correction on the spot, and therefore operation and maintenance cost is reduced; on the other hand, because the correction curve can be continuously and periodically updated, the detection equipment can be corrected and synchronized in time after the environment changes, and the measurement precision is guaranteed.
In some preferred embodiments of the present invention, the detecting device is an online monitoring device, and the online monitoring device performs step d on the site of the measuring point. The correction method is executed on the site of the measuring point, so that the correction result is more fit for the actual environment condition, and a correction curve which more accurately reflects the actual working condition of the measuring point is obtained.
In some preferred embodiments of the present invention, the offset in step c is a difference between the first correction value and the first response value. The second correction value is corrected by using the characteristic that the difference values at different positions on the correction curve are approximately the same, so that the curvature of the corrected correction curve and the curvature of the correction curve to be corrected can be basically kept consistent.
In some preferred embodiments of the present invention, the offset in step c is a ratio of the first correction value to the first response value. By correcting the second correction value using the characteristic that the proportional values at different positions on the correction curve are substantially the same, the response value of each density point of the corrected correction curve can be adjusted in a proportional manner, and the degree of curvature of the correction curve can be adjusted in a proportional manner.
In some preferred embodiments of the present invention, the correction curve is one or more of a polygonal line, a power function curve, an exponential function curve, or a polynomial function curve. The detection method provided by the technical scheme can be suitable for the correction of different types of concentration curves, particularly the concentration curves in a nonlinear form, and the forms of the correction curves can be accurately fitted.
In some preferred technical solutions of the present invention, the calibration curve to be corrected is a calibration curve pre-stored in the factory of the detection device. The detection method provided by the technical scheme is used for correcting the calibration curve prestored in the factory, so that the types and the use amount of standard gas required for correcting the calibration curve during initialization of the detection equipment can be effectively reduced, and the operation complexity of the initialization process is reduced.
In some preferred embodiments of the present invention, the detection device is an on-line monitoring device having a flame ionization detector. Experiments prove that for the same FID, the bending degree of the actual curve after the deviation is generated due to the environmental change is basically consistent with that of the correction curve before the environmental change, so that the correction curve of the FID can be corrected accurately by the detection method in the technical scheme.
Drawings
FIG. 1 is a diagram illustrating a relationship between calibration curves before and after correction in the prior art;
FIG. 2 is a flow chart of a detection method according to a first embodiment of the present invention;
FIGS. 3-6 are schematic diagrams of calibration curves at various stages of a detection method according to an embodiment;
FIG. 7 is a flowchart of a detection method according to a second embodiment of the present invention;
FIG. 8 is a diagram illustrating the relationship between the calibration curves before and after correction according to a third embodiment of the present invention;
fig. 9 is a schematic structural diagram of an online monitoring device according to an embodiment of the present invention.
Reference numerals: 1-an on-line monitoring device; 11-flame ionization detector; 12-a controller; 13-a storage device; 131-a calibration curve module; 132-curve compensation module.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Terms and explanations
Furthermore, the terms "first" and "second" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present application, "a plurality" means two or more unless specifically limited otherwise.
The term "calibration curve" is a curve used to describe the quantitative relationship between the concentration or amount of a substance to be measured and the response amount or other indicative amount of a corresponding detection device, and is usually obtained by plotting a standard sample with a chemically defined composition or structure through a whole analysis process. The term "curve" is a curve in the mathematical sense and does not limit that the curve must have a curvature greater than zero, in other words "curve" encompasses straight and non-straight lines. The term "multipoint" in the term "multipoint correction curve" means three or more sampling points. "concentration point" refers to a point on the calibration curve having a specific concentration value.
As used herein, the term "on-line monitoring device" refers to a device that is installed in the field at a measurement site and performs continuous or timed monitoring of an analyte.
In addition, it should be noted that, the names of "step a", "step c", "step d", etc. in this document are not intended to limit the execution sequence of the steps, but are given only for the convenience of description and reference. "steps a-d" means a process comprising "step a", "step b", "step c", and "step d", but is not limited to include only the above steps, and in some embodiments, "steps a-d" may also include steps such as "step e", "step f", and the like.
Implementation mode one
Fig. 1 is a schematic diagram showing a relationship between calibration curves before and after correction in the prior art, and it can be seen from fig. 1 that, in the prior art, a multi-point calibration curve, such as the multi-point calibration curve shown by a straight line formed by connecting a plurality of concentration points in fig. 1, is determined and stored when a detection device is shipped from a factory. When the detection device is put into use and installed on the site of a measurement point or after the detection device is moved, the actual curve is shifted, for example, to the position shown by the upper gray scale curve in fig. 1, because the use environment of the detection device changes.
In order to correct the multi-point calibration curve so that the multi-point calibration curve is more consistent with the actual curve after the environment changes, the existing detection method is to send a maintenance worker by a manufacturer of the detection device or a related party, carry a dynamic calibration instrument, re-determine the response values of the detection device corresponding to the multiple concentration points, and then fit the multi-point calibration curve according to the re-determined response values, such as the multi-point calibration curve shown by the dotted line formed by connecting the multiple concentration points in fig. 1.
However, the detection method adopted in the prior art is not only complicated in operation, but also requires that each concentration point correspondingly carries, stores or prepares a standard sample with corresponding concentration, thereby increasing the requirements on the type and the dosage of the standard sample.
In order to solve the above-mentioned problems in the prior art, the inventors have conducted extensive studies on the detection device in the prior art, and have found that, although the calibration curve of some detection devices may be shifted due to a change in the use environment or the like, the entire shift of the calibration curve follows a certain rule, that is, the degree of curvature of the calibration curve after the shift is substantially the same as that of the calibration curve before the shift. Based on the above problems and findings, the present embodiment provides a new detection method of a correction curve.
The detection device to which the detection method provided in this embodiment is applicable is a detection device for measuring the concentration of a target component in a sample, and the specific measurement method is not limited, and for example, measurement or statistics may be performed on a mathematical parameter, an optical parameter, an electromagnetic parameter, an acoustic parameter, a thermodynamic parameter, or any other suitable mathematical or physicochemical parameter.
The target component may be a volatile organic or any other suitable component. Volatile Organic Compounds (VOCs) can be measured using index parameters including, but not limited to, the following types: total Volatile Organic Compounds (TVOC), Total Organic Gas (TOG), non-methane organic gas (NMOG), hydrocarbons (THX), non-methane total hydrocarbons (NMHC), or benzene series (BTX), etc.
The detection method of the present embodiment is described with reference to fig. 2, and the detection method of the present embodiment includes the steps of:
step a, selecting a first concentration value c1 and a first response value A1 corresponding to the first concentration value c1 in a correction curve to be corrected;
b, using a detection device to measure a first standard sample with the concentration of the target component equal to the first concentration value c1 to obtain a first correction value;
step c, calculating a second correction value corresponding to the second concentration value according to the deviation of the first correction value relative to the first response value;
and d, determining a corrected correction curve at least according to the second correction value.
Fig. 3 is a schematic diagram of a calibration curve drawn to illustrate step a in the detection method according to the first embodiment of the present invention. Referring to fig. 3, first, a correction curve to be corrected in which the first density value c1 and the first response value a1 corresponding to the first density value c1 are selected through step a is illustrated.
The calibration curve to be corrected is a concentration calibration curve stored in the detection device, for example, a calibration curve pre-stored when the detection device is shipped from a factory or a calibration curve that has been corrected.
When the first concentration value c1 is selected in step a, the first concentration value c1 may be determined according to the concentration value of the standard sample owned by the detection device itself or the concentration value of another standard sample communicated with the detection device, for example, if the detection device itself or the detection device is communicated with several standard samples with different concentrations, one standard sample with a suitable concentration may be selected as the first standard sample, and the first concentration value c1 may be correspondingly determined according to the concentration of the first standard sample, for example, a concentration value equal to the concentration of the target component in the first standard sample may be selected as the first concentration value c 1. Of course, in some embodiments, the standard sample may be temporarily prepared by the detection device or carried by the operation and maintenance personnel, and in these embodiments, the first concentration value c1 may also be set manually or by reading data.
After the first concentration value c1 is determined, a first response value a1 corresponding thereto is determined. The first response value a1 may be obtained by calculation or search using a correction curve, or may be obtained by searching a data table corresponding to the correction curve, and the specific calculation or search method is not limited.
The unit of the first response value a1 may be a physicochemical unit directly detected by the detection device, for example, a unit of the specific parameter described above, such as a mathematical unit, an optical unit, an electromagnetic unit, an acoustic unit, a thermodynamic unit, or any other suitable mathematical, physicochemical unit, or other type of unit or unit after homogenization processing obtained by counting or processing the measurement result of the detection device.
Fig. 4 is a schematic diagram of a calibration curve drawn to illustrate step b in the testing method according to the first embodiment of the present invention, and referring to fig. 4, it can be seen that, after the first response value A1 is determined, step b is performed, that is, the testing apparatus is used to perform measurement on the first standard sample whose concentration of the target component is known to be equal to the first concentration value c1, thereby obtaining the first correction value A1 s.
In other words, in step b, the measurement of the entire analysis process is carried out using the first standard sample whose target component is the concentration c1, and the response of the detection device (or the statistical, processed result of the response) is obtained as the first correction value A1 s. The first correction value A1s has the same unit as the first response value A1, but the correction curve tends to shift due to environmental changes and other factors, typically A1s ≠ A1.
The first standard sample may be a standard sample prepared or stored in advance, in which the concentration ratios of the respective components are known, or a standard sample in which only a part of the components (including the target component to be measured) is known in concentration. The concentration of the target component being "known" indicates that the detection device has stored or can read the concentration of the target component in the standard sample.
Fig. 5 is a schematic diagram of a calibration curve drawn to illustrate step c in the detection method according to the first embodiment of the present invention. In the first detection method according to the first embodiment of the present invention, step c is performed after the first correction value A1s is obtained, i.e., a second correction value A2s corresponding to the second concentration value c2 is calculated at least according to the deviation of the first correction value A1s from the first response value A1.
Referring to fig. 5, the deviation of the first correction value A1s from the first response value A1 represents the degree of deviation of the first correction value A1s from the first response value A1, and does not limit the representation of the deviation. The offset may be represented by quantities including, but not limited to, forms such as, in some embodiments, the offset may be represented in the form of a difference Δ A (A1s-A1 or A1-A1 s); in other embodiments, the offset may also be represented in the form of a ratio of A1s/A1 or A1/A1 s; in other embodiments, the degree of offset may also be expressed in terms of a combination or variation of the two forms described above, for example to
(A0 represents the response value corresponding to the zero point in the calibration curve to be corrected, and A0s represents the zero-point correction value obtained by measurement on the standard sample having the concentration of zero).
The second correction value A2s may be obtained by co-calculation from the offset (e.g. the offset expressed in Δ a or ratio) and the second response value A2, for example by superimposing the same difference Δ a or multiplying by the same ratio A1s/A1 on the basis of the second response value A2. In some embodiments, the ratio value may also be adjusted to the ratio value shown in formula (1).
In order to complete the determination of the multi-point calibration curve, it is usually necessary to determine the corresponding correction values of three or more concentration points. In some embodiments, other ways of determining the correction value may follow the way of determining the second correction value A2s, or in other embodiments, other correction values corresponding to the concentration point may be determined based at least in part on the offset between the second correction value A2s and the second response value A2.
Referring to fig. 6, after the determination of the correction values corresponding to all the concentration points to be determined is completed, step d is executed to determine a corrected correction curve at least according to the second correction value A2 s.
The detection method provided in the present embodiment has been described above. In the present embodiment, the offset of one density point or a part of the density point on the calibration curve can be continued by calculation of the offset of the entire calibration curve or the calibration curve within a predetermined range based on the finding that the degree of curvature of the calibration curve after offset is substantially the same as that of the calibration curve before offset. Thus, the second correction value A2s may be determined by calculation, rather than by experiment.
According to the detection method in the embodiment, by using the calculation method to replace the method of using the standard sample calibration in the prior art, the calibration steps for multiple standard samples which are originally required to be implemented can be omitted, so that the use of the standard samples is saved, and the operation or operation flow is simplified.
As can be seen from fig. 3 to 6, with the detection method according to the present embodiment, the concentration value (i.e., c1) of the standard sample used for correction does not need to match the concentration point used for multipoint correction at the time of shipment, and flexibility in concentration selection when preparing the standard sample is improved.
As described above, by correcting the calibration curve pre-stored in the factory by using the detection method provided by the present embodiment, the type and amount of the standard sample required for correcting the calibration curve during initialization of the detection device can be effectively reduced, and the operation complexity of the initialization process can be reduced. By using the detection method provided by the embodiment to correct the previously corrected calibration curve, the calibration curve can be kept continuously updated, and the calibration curve can be kept continuously matched with the environmental change.
Second embodiment
Fig. 7 is a flowchart of a detection method in the second embodiment of the present invention.
The embodiment provides a detection method, which comprises the following steps:
step a, selecting a first concentration value c1 and a first response value A1 corresponding to the first concentration value c1 in a correction curve to be corrected;
step b, using a detection device, of carrying out a measurement on a first standard sample of which the concentration of the target component is known to be equal to a first concentration value c1, obtaining a first correction value A1 s;
step e, using a detection device to measure a second standard sample with the known concentration of the target component equal to zero to obtain a zero correction value A0 s;
step c, calculating a second correction value A2s corresponding to the second concentration value c2 according to the deviation of the first correction value A1s relative to the first response value A1;
d, determining a corrected correction curve at least according to the second correction value A2s and the zero correction value A0 s;
and f, detecting the concentration of the target component in the sample by using the corrected correction curve.
In the present embodiment, step e may be performed before step a, or may be performed after step a and before step d. Step d may be performed after any of step a, step b, step c or step e. Step c may be performed after step b. In other embodiments of the present invention, the execution order of the above steps may be changed as needed, and there is no particular requirement on the execution order.
According to the above embodiment, the zero point of the calibration curve is corrected by a second standard sample of known concentration of the target component equal to zero, for example, zero gas, which is always available in some detection devices. This has the advantage that: because the change amplitude or the proportion of the slope is larger on the low concentration side (the side with smaller concentration value) of the correction curve, if the second standard sample is used for assisting the calibration on the low concentration side of the correction curve, the accuracy of the fitting of the correction result to the actual curve can be improved. In addition, the correction is completed in the above mode, the traditional device structure for two-point linear correction or part of software control flow can be used, and the cost for improving and upgrading hardware or software is reduced. In addition, the corrected calibration curve is used for detection, so that more accurate detection results can be obtained.
Third embodiment
In addition to the second embodiment, a third embodiment of the present invention further provides a detection method. The detection method of the third embodiment is different from the second embodiment in that the first standard sample used is a span gas of the detection device.
The rest is the same as the second embodiment, and is not described herein again.
Fig. 8 is a schematic relationship diagram of the calibration curve before and after the correction in the third embodiment of the present invention.
Table 1 illustrates the parameters of the calibration curve to be corrected.
TABLE 1
The parameters of the corrected calibration curve are shown in table 2.
TABLE 2
In the present embodiment, a case where the multipoint calibration curve is a polygonal line will be described as an example. The broken line comprises a plurality of sections of straight lines which are successive from head to tail, and the expression of each section of straight line can be derived based on the parameters. For example, for a straight line in the interval of concentration 4 to concentration 5, the specific expression can be obtained according to the K value and the B value:
A＝(c-c4)*K+B＝(c-c4)*(A1s/A1)*(A5-A4)/(c5-c4)+A4*(A1s/A1)
wherein a represents a response value of the detection apparatus to the sample, for example, an area value of the flame ionization detector 11; c represents the concentration of the sample; A2-A5 are response values corresponding to the concentration points c 2-c 5 in the correction curve to be corrected.
According to the parameters, the expression of each section of straight line in the multipoint correction curve can be obtained, and the whole correction curve is obtained through integration.
Referring to fig. 8, since the range gas generally corresponds to the concentration point on the high concentration side, the magnitude of the response value corresponding to the concentration point on the high concentration side and the amount of change are large, and accordingly, the result obtained by calculation using the concentration point on the high concentration side can reflect the amount or degree of the deviation more accurately. In addition, the measuring range gas is usually a gas type which is always provided for the detection equipment, so that the gas with specific concentration does not need to be separately prepared or stored for completing correction, and the measurement and the operation are convenient.
In the first to third embodiments, the corrected correction curve may be determined based on the first correction value A1s and the second correction value A2 s. Since the first correction value A1s is used for the calculation of the second correction value A2s on the one hand and for the determination of the correction curve on the other hand, which is equivalent to substituting the actually measured first correction value A1s into two calculations, the weight of the first correction value A1s in the calculation process is increased, so that the correction result is more accurate.
In some embodiments of the present invention, the detection method comprises performing steps a to d once every a predetermined time interval, and saving the corrected calibration curve as the currently used calibration curve. Through the mode, the detection equipment automatically runs the correction program at a specified time interval, on one hand, operation and maintenance personnel do not need to be dispatched to reach a measurement point to complete correction on the spot, and the operation and maintenance cost is reduced; on the other hand, the calibration curve is continuously updated, so that the detection equipment can keep synchronization with the environmental change, and the measurement precision is improved. The predetermined time interval may be, for example, a day, a week, or a month, and may be flexibly adjusted according to the intensity of the environmental change at the measurement point, without any particular limitation.
In some embodiments of the present invention, the detection device is an online monitoring device 1, and the measurement site of the online monitoring device 1 may be a site where people are not normally living, such as near a factory, near a sewage discharge site, near a river, near a scenic spot, and the like. Even if the on-line monitoring device 1 is installed in these places, the on-line monitoring device can transmit and receive the detection information or the detection result by using a communication means or a device, thereby realizing real-time remote control detection and monitoring. At this time, when the detection method related to any embodiment of the present invention is used for the online monitoring device 1, it is not necessary to send operation and maintenance personnel to reach the measurement point to complete the correction, so as to reduce the operation and maintenance cost and ensure the continuous real-time stable operation monitoring of the online monitoring device 1. Further, the calibration curve is automatically corrected and updated and stored continuously at predetermined time intervals, so that the maintenance of the on-line monitoring apparatus 1 can be remotely managed and grasped.
In some embodiments of the invention, the correction curve is one or a combination of more of a polyline, a power function curve, an exponential function curve, or a polynomial function curve. The detection method provided by the embodiment of the invention can be suitable for the correction of different types of concentration curves, particularly nonlinear concentration curves, and the forms of the correction curves can be more accurately fitted.
In the first to third embodiments, the detection apparatuses may each be the on-line monitoring apparatus 1 having the flame ionization detector 11. Experiments prove that for the same flame ionization detector 11, the bending degree of the actual curve after the deviation is generated due to the environmental change is basically consistent with the bending degree of the correction curve before the environmental change, so that the correction curve of the flame ionization detector 11 can be corrected accurately by the detection method in the technical scheme.
The present embodiment also provides a detection device for performing detection using the above method, such as an on-line monitoring device 1 having a flame ionization detector 11.
Referring to fig. 9, the online monitoring device 1 includes a flame ionization detector 11, a controller 12, and a storage device 13, wherein a calibration curve module 131 is stored in the storage device 13, and the calibration curve module 131 stores a calibration curve or a data table and a functional relationship corresponding to the calibration curve. The storage device 13 further stores a curve correction module 132, the curve correction module 132 has instructions for the controller 12 to read and operate, and the controller 12 can control the online monitoring device 1 to perform the correction curve correction method according to one to three embodiments by operating the instructions of the curve correction module 132.
The present invention is not limited to the above preferred embodiments, and any modifications, equivalent substitutions and improvements made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (12)
1. A detection method for measuring a concentration of a target component in a sample using a detection apparatus having a storage device for storing a calibration curve of the concentration, characterized by comprising the steps of:
step a, selecting a first concentration value and a first response value corresponding to the first concentration value in a correction curve to be corrected;
step b, using the detection device, of carrying out a measurement on a first standard sample, of which the concentration of the target component is known to be equal to the first concentration value, obtaining a first correction value;
step c, calculating a second correction value corresponding to a second concentration value at least according to the deviation of the first correction value relative to the first response value;
and d, determining a corrected correction curve at least according to the second correction value.
2. The detection method of claim 1, further comprising
Step e, using the detection device to measure a second standard sample with known concentration of the target component equal to zero to obtain a zero correction value;
in the step d, a corrected correction curve is determined based on at least the second correction value and the zero correction value.
3. The detection method of claim 1, further comprising
And f, detecting the concentration of the target component in the sample by using the corrected correction curve.
4. The test method of claim 1, wherein the first standard sample is a span gas of the test device.
5. The detection method according to claim 1, wherein the steps a-d are performed once at intervals of a predetermined length of time, and the corrected calibration curve is stored as a currently used calibration curve.
6. The method of testing as claimed in claim 1 or 5, wherein said testing device is an on-line monitoring device, said on-line monitoring device performing said step d on-site at a measurement site.
7. The detection method according to claim 1, wherein the offset in step c is a difference between the first correction value and the first response value.
8. The detection method according to claim 1, wherein the offset in step c is a ratio of the first correction value to the first response value.
9. The detection method according to claim 1, wherein the correction curve is one or more of a polygonal line, a power function curve, an exponential function curve, or a polynomial function curve.
10. The inspection method according to claim 1, wherein the calibration curve to be corrected is a calibration curve pre-stored in the factory of the inspection apparatus.
11. A detection device, characterized in that it uses a detection method according to any one of claims 1-10.
12. The detection apparatus of claim 11, wherein the detection apparatus is an in-line monitoring apparatus having a flame ionization detector.
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| CN202010352393.8A CN113567602A (en) | 2020-04-28 | 2020-04-28 | Detection method and detection device |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114397396A (en) * | 2021-12-29 | 2022-04-26 | 杭州春来科技有限公司 | Automatic calibration method and system for VOCs detection and analysis |
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