Solid sample organic carbon content data collection method, system, equipment and application

Abstract

The present invention belongs to the technical field of data processing of organic carbon content in solid samples such as soil and sediment, and discloses a method, system, equipment and application for collecting data on organic carbon content in solid samples, turning off the automatic acquisition termination function of the electric signal of the instrument; retaining the peak curve slope detection function, setting a lower slope threshold, and monitoring the slope change in real time; the curve regresses to the baseline, and when the preset slope threshold is reached, a dialog box pops up to indicate whether to end the analysis or continue the analysis according to the detection setting time; the operator determines that the data collection is completed, chooses to end the analysis, and performs the detection of the next sample; the operator determines that the data collection is not completed, chooses to continue the analysis, and the instrument continues to collect data according to the detection setting time until the end; the detection of the next sample is performed. The present invention saves about 4 minutes per sample, which improves work efficiency; for samples of complex matrices, the accuracy of the detection results and the precision of the sample repeatability measurement are improved.

Description

Technical Field

[0001] The present invention belongs to the technical field of organic carbon content data processing in solid samples such as soil and sediment, and in particular relates to a solid sample organic carbon content data collection method, system, equipment and application. Background Art

[0002] At present, the main working principle of the existing instrument (Shimadzu TOC-L+SSM5000) when analyzing solid samples is as follows: using the high-temperature catalytic combustion method, the weighed sample is injected into the TC combustion tube filled with an oxidation catalyst and heated to 900°C. The TC in the sample is burned and decomposed into carbon dioxide. The combustion product is introduced into the non-infrared gas analysis unit (NDR) pool through the carrier gas, and the carbon dioxide is detected. The detection peak area of ​​NDIR is calculated in the data processing part. Since the peak area is proportional to the TC concentration in the sample, the relationship between TC concentration and peak area is obtained in advance using TC standard substances, and the TC concentration in the sample can be determined. Secondly, the sample is acid-lyzed with phosphoric acid at 200°C, and the carbonate is converted into carbon dioxide, which is introduced into the detector through the carrier gas and the IC concentration is calculated in the same way as the TC detection method. The difference between total carbon and inorganic carbon is the total organic carbon content.

[0003] The existing instrument (Shimadzu TOC-L+SSM5000) has the following defects:

[0004] ① In the actual operation process, when the sample chamber is opened to add or replace samples, air is introduced into the entire system. The sensitive NDIR detector can detect trace amounts of carbon dioxide in the air, causing baseline fluctuations. Each time the sample is replaced, it is necessary to wait for about 2 minutes for the carbon dioxide peak in the air to come out and the baseline to stabilize before the actual sample test can begin. If the actual sample is tested without waiting for the carbon dioxide in the air to be detected and the baseline to be stable, it is easy to cause the actual sample test to end prematurely (the system defaults to the end of the baseline zeroing test process), and the sample test fails.

[0005] ② During the determination process, inorganic carbon reacts slowly with phosphoric acid due to reasons such as the matrix effect of the sample, which directly affects the peak time and peak shape of the detection process. When the electrical signal of the detector approaches the baseline, the system defaults to the end of the detection process and the data acquisition process is terminated.

[0006] ③The instrument collection time setting is useless.

[0007] Through the above analysis, the problems and defects of the prior art are as follows:

[0008] (1) The existing instrument data acquisition is in automatic termination mode, that is, the data acquisition is terminated when the slope change of the electrical signal is detected to be less than a fixed value within a specified time; when the sample is replaced, it is necessary to wait for the air peak for about 2 minutes, which reduces work efficiency.

[0009] (2) For samples with slow reactions, data collection ends prematurely and the measurement results cannot objectively reflect the inorganic carbon content of the actual samples, which ultimately leads to inaccurate determination of organic carbon content.

[0010] The difficulty in solving the above problems and defects is: how to turn off the automatic termination of data collection and switch to manual mode and automatic mixed mode.

[0011] The significance of solving the above problems and defects is:

[0012] (1) During the sample replacement process, there is no need to wait and the measurement can be performed directly, which greatly improves work efficiency.

[0013] (2) The integrity of sample data collection is achieved, greatly improving the accuracy of the results.

[0014] (3) The system realizes the selectivity of manual termination and automatic data collection to meet the measurement requirements of different types of samples. Summary of the invention

[0015] In view of the problems existing in the prior art, the present invention provides a method, system, equipment and application for collecting data on organic carbon content of solid samples.

[0016] The present invention is implemented as follows: a method for collecting data on organic carbon content of solid samples, the method comprising:

[0017] Calculate the instantaneous slope of the peak curve on the visual interface and monitor the change of the slope;

[0018] Turn off the automatic acquisition termination function of the instrument, record the data of the curve changes and monitor the slope;

[0019] Determine whether to terminate or continue data collection based on the curve returning to the baseline.

[0020] The present invention turns off the automatic collection termination function of the instrument, allowing data to be collected all the time, and can detect the carbon dioxide subsequently reacted by samples of complex matrices, thereby ensuring work efficiency and the accuracy of the detection results.

[0021] Furthermore, the solid sample organic carbon content data collection method comprises the following steps:

[0022] The first step is to turn off the instrument's automatic signal acquisition termination function;

[0023] The second step is to retain the peak curve slope detection function, set a lower slope threshold, and monitor the slope change in real time;

[0024] In the third step, the curve returns to the baseline. When the preset slope threshold is reached, a dialog box pops up to indicate whether to end the analysis or continue the analysis according to the detection setting time.

[0025] In the fourth step, the operator determines that data collection is complete, chooses to end the analysis, and proceeds to the next sample test; if the operator determines that data collection is not complete, he chooses to continue the analysis, and the instrument continues to collect data according to the time set for the test until it is completed; then proceed to the next sample test.

[0026] In the present invention, the first step ensures continuous data collection and ensures the accuracy of the measurement results of carbon dioxide in slow-reacting samples. The second step is to monitor whether data collection is completed and give a dialog box signal in the third step; the fourth step is to make a choice based on the operator's experience to improve efficiency.

[0027] Furthermore, the solid sample organic carbon content data collection method sets a threshold to determine whether a protrusion in the signal curve can become a peak; during the process, the signal curve has ups and downs, resulting in changes in the slope of the curve. If the slope of the curve is greater than the set slope sensitivity, it is the starting point of the peak; when the slope of the curve drops below the slope sensitivity, it is the end point of the peak, and the peak is between the starting point and the end point.

[0028] Methods for determining whether a protrusion in a signal curve can become a peak include:

[0029] The formula for calculating the starting point of the curve peak is:

[0030]

[0031] div(i, j) represents the calculated objective coefficient between the current curve peak i and the set curve peak j, time(i), time(j) represent the data time from the beginning to the change of the current curve peak i and the set curve peak j respectively, the numerator is the absolute value of the time difference between the current curve peak i and the set curve peak j, and the denominator is the sum of the time changes between the current curve peak i and the set curve peak j;

[0032] The formula for calculating the endpoint of the curve peak is:

[0033] αdiv(i,j)+βy i +λy j ;

[0034] Where div(i,j) represents the end point correlation between the current curve peak i and the set curve peak j, y i and j They represent the memory rates of curve peaks i and j respectively; α, β, λ are the weight values ​​of the features.

[0035] Further, the data collection process curve slope calculation equation of the solid sample organic carbon content data collection method is as follows: the curve equation formed by the measurement result signal is f(x, y) = 0, P(X, Y) is any point on the curve, and the slope of the point on the curve is calculated to find the derivative of the function f(x, y) = 0 at x = X;

[0036] The equation f(x,y)=0 determines a function y=y(x). Substituting y=y(x) into the equation yields the identity f[x,y(x)]=0. Finding the total derivative of this function yields;

[0037] like

[0038] Calculate the slope:

[0039]

[0040] Using this calculation model, the slope of the curve can be easily and accurately calculated in real time, and the curve changes can be monitored in real time.

[0041] Another object of the present invention is to provide a computer device, which includes a memory and a processor, wherein the memory stores a computer program, and when the computer program is executed by the processor, the processor executes the steps of the solid sample organic carbon content data collection method.

[0042] Another object of the present invention is to provide a computer-readable storage medium storing a computer program, wherein when the computer program is executed by a processor, the processor executes the steps of the solid sample organic carbon content data collection method.

[0043] Another object of the present invention is to provide an information data processing terminal, which is used to implement the steps of the solid sample organic carbon content data collection method.

[0044] Another object of the present invention is to provide a solid sample organic carbon content data acquisition system for implementing the solid sample organic carbon content data acquisition method, the solid sample organic carbon content data acquisition system comprising:

[0045] Function closing module, used to close the electric signal automatic acquisition termination function;

[0046] The slope change monitoring module is used to retain the peak curve slope detection function, set a lower slope threshold, and monitor the slope change in real time;

[0047] The detection time setting module is used for curve regression baseline. When the preset slope threshold is reached, a dialog box pops up to indicate whether to end the analysis or continue the analysis according to the detection setting time.

[0048] The data collection end judgment module is used for the operator to judge that the data collection is completed, choose to end the analysis, and proceed to the next sample test; if the operator judges that the data collection is not completed, he chooses to continue the analysis, and the instrument continues to collect data according to the time set for the test until it is completed; and the next sample test is carried out.

[0049] Another object of the present invention is to provide an application of the solid sample organic carbon content data collection method in the organic carbon content data processing in soil samples.

[0050] Another object of the present invention is to provide an application of the solid sample organic carbon content data acquisition method in the organic carbon content data processing in sediment samples.

[0051] Combining all the above technical solutions, the advantages and positive effects of the present invention are as follows: the data acquisition method established by the present invention does not need to wait for the carbon dioxide peak in the air during the replacement of different samples, which can save about 4 minutes for each sample and greatly improve the work efficiency; for samples with complex matrices, the data collection is complete and objective, which greatly improves the accuracy of the detection results and the precision of the sample repeatability measurement.

[0052] Table 1 Comparison of data of sample measurements before and after application of the present invention

[0053]

[0054] It can be seen from the test data in Table 1 that the present invention has little effect on the measurement results of TC. The reason is that TC is measured at 900°C and the combustion is sufficient. For IC, due to reasons such as the sample matrix, the reaction with phosphoric acid is slow, resulting in the early termination of the data collection process, incomplete collection of the original IC data, and a smaller final data, resulting in a larger TOC value.

[0055] The results of the C21042P sample determination in Table 1 are examples of sample determination before and after the application of the present invention. After comparison, the accuracy of the detection is significantly improved.

[0056] After using the present invention, data collection is complete, and the IC content can be objectively reflected, and the data accuracy is high. Taking the standard sample GSS-8 as an example, the reference TOC value is 0.30%, the original calculation result is 0.694%, and the current result is 0.303%, which is relatively accurate. BRIEF DESCRIPTION OF THE DRAWINGS

[0057] Figure 1It is a flow chart of a method for collecting data on organic carbon content of solid samples provided in an embodiment of the present invention.

[0058] Figure 2 It is a structural schematic diagram of a solid sample organic carbon content data acquisition system provided by an embodiment of the present invention;

[0059] Figure 2 In: 1. Function shutdown module; 2. Slope change monitoring module; 3. Detection time setting module; 4. Data collection end judgment module.

[0060] Figure 3 It is a flow chart of the implementation of the method for collecting data on organic carbon content of solid samples provided in an embodiment of the present invention.

[0061] Figure 4 It is a schematic diagram of the peak shape of carbon dioxide in the air generated when the sample is replaced according to an embodiment of the present invention.

[0062] Figure 5 It is a schematic diagram of the peak shape of data collection during the measurement of the original sample provided by an embodiment of the present invention (taking C210420015 as an example).

[0063] Figure 6 It is a schematic diagram of the peak shape (taking C210420015 as an example) of sample measurement data collection after application of the present invention provided by an embodiment of the present invention. DETAILED DESCRIPTION

[0064] In order to make the purpose, technical solution and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with the embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention.

[0065] In view of the problems existing in the prior art, the present invention provides a method, system, device and application for collecting data on organic carbon content of solid samples. The present invention is described in detail below in conjunction with the accompanying drawings.

[0066] like Figure 1 As shown, the method for collecting data on organic carbon content of solid samples provided by the present invention comprises the following steps:

[0067] S101: Turn off the automatic acquisition termination function of the electrical signal of the instrument (Shimadzu TOC-L + SSM5000);

[0068] S102: retain the peak curve slope detection function, set a lower slope threshold, and monitor the slope change in real time;

[0069] S103: When the curve returns to the baseline and reaches the preset slope threshold, a dialog box pops up to indicate whether to end the analysis or continue the analysis according to the detection setting time;

[0070] S104: The operator determines that data collection is completed, chooses to end the analysis, and proceeds to the next sample test; the operator determines that data collection is not completed, chooses to continue the analysis, and the instrument continues to collect data according to the time set for the test until it is completed; and proceeds to the next sample test.

[0071] The method for collecting data on organic carbon content of solid samples provided by the present invention can also be implemented by ordinary technicians in the industry using other steps. Figure 1 The method for collecting data on organic carbon content in solid samples provided by the present invention is only a specific embodiment.

[0072] like Figure 2 As shown, the solid sample organic carbon content data acquisition system provided by the present invention comprises:

[0073] Function closing module 1, used to close the electric signal automatic acquisition termination function;

[0074] The slope change monitoring module 2 is used to retain the peak curve slope detection function, set a lower slope threshold, and monitor the slope change in real time;

[0075] Detection time setting module 3 is used for curve regression baseline. When the preset slope threshold is reached, a dialog box pops up to indicate whether to end the analysis or continue the analysis according to the detection setting time;

[0076] The data collection end judgment module 4 is used for the operator to judge that the data collection is completed, select to end the analysis, and proceed to the next sample test; if the operator judges that the data collection is not completed, he / she chooses to continue the analysis, and the instrument continues to collect data according to the detection setting time until it is completed; and proceeds to the next sample test.

[0077] The technical solution of the present invention is further described below in conjunction with the accompanying drawings.

[0078] like Figure 3 As shown, the data collection method for organic carbon content of solid samples of the present invention calculates the instantaneous slope of the peak curve of the visual interface and monitors the change of the slope; turns off the automatic collection termination function of the instrument and changes to the selectability of whether to terminate data collection or continue data collection according to the curve regression baseline.

[0079] In the present invention, the visualization of the instrument's electrical signal - "peak" is usually based on the concept of "slope sensitivity", that is, a threshold is set in advance to determine whether the protrusion of the signal curve can become a peak. During the measurement process, the signal curve will fluctuate, resulting in changes in the slope of the curve. If the slope of the curve is greater than the set slope sensitivity, it is the starting point of the peak. When the slope of the curve drops below the slope sensitivity, it is the end point of the peak. The peak is between the starting point and the end point.

[0080] Methods for determining whether a protrusion in a signal curve can become a peak include:

[0081] The formula for calculating the starting point of the curve peak is:

[0082]

[0083] div(i, j) represents the calculated objective coefficient between the current curve peak i and the set curve peak j, time(i), time(j) represent the data time from the beginning to the change of the current curve peak i and the set curve peak j respectively, the numerator is the absolute value of the time difference between the current curve peak i and the set curve peak j, and the denominator is the sum of the time changes between the current curve peak i and the set curve peak j;

[0084] The formula for calculating the endpoint of the curve peak is:

[0085] αdiv(i,j)+βy i +λy j ;

[0086] Where div(i,j) represents the end point correlation between the current curve peak i and the set curve peak j, y i and j They represent the memory rates of curve peaks i and j respectively; α, β, λ are the weight values ​​of the features.

[0087] The calculation equation of the curve slope of the data acquisition process of the instrument (Shimadzu TOC-L+SSM5000) of the present invention is as follows: Assume that the curve equation formed by the measurement result signal is f(x,y)=0, P(X,Y) is any point on the curve, and calculate the slope of the point on the curve. That is, to find the derivative of the function f(x,y)=0 at x=X. Assume that the equation f(x,y)=0 determines a function y=y(x), and substitutes y=y(x) into the equation to get the identity f[x,y(x)]=0. Find the total derivative of this function, and you get;

[0088] like

[0089] Calculate the slope:

[0090]

[0091] The technical effects of the present invention are described in detail below in conjunction with experiments.

[0092] The data acquisition method established by the present invention does not need to wait for the carbon dioxide peak in the air during the replacement of different samples, which can save about 4 minutes for each sample and greatly improve the work efficiency; for samples with complex matrices, the data acquisition is complete and objective, which greatly improves the accuracy of the detection results and the precision of the sample repeatability measurement.

[0093] Figure 4 It is a schematic diagram of the peak shape of carbon dioxide in the air generated when the sample is replaced according to an embodiment of the present invention.

[0094] Figure 5 It is a schematic diagram of the peak shape of data collection during the measurement of the original sample provided by an embodiment of the present invention (taking C210420015 as an example).

[0095] Figure 6 It is a schematic diagram of the peak shape (taking C210420015 as an example) of sample measurement data collection after application of the present invention provided by an embodiment of the present invention.

[0096] Table 1 Comparison of data of sample measurements before and after application of the present invention

[0097]

[0098] It can be seen from the test data in Table 1 that the present invention has little effect on the measurement results of TC. The reason is that TC is measured at 900°C and the combustion is sufficient. For IC, due to reasons such as the sample matrix, the reaction with phosphoric acid is slow, resulting in the early termination of the data collection process, incomplete collection of the original IC data, and a smaller final data, resulting in a larger TOC value.

[0099] After using the present invention, data collection is complete, and the IC content can be objectively reflected, and the data accuracy is high. Taking the standard sample GSS-8 as an example, the reference TOC value is 0.30%, the original calculation result is 0.694%, and the current result is 0.303%, which is relatively accurate.

[0100] It should be noted that the embodiments of the present invention can be implemented by hardware, software, or a combination of software and hardware. The hardware part can be implemented using dedicated logic; the software part can be stored in a memory and executed by an appropriate instruction execution system, such as a microprocessor or dedicated design hardware. It can be understood by a person of ordinary skill in the art that the above-mentioned devices and methods can be implemented using computer executable instructions and / or contained in a processor control code, such as a carrier medium such as a disk, CD or DVD-ROM, a programmable memory such as a read-only memory (firmware), or a data carrier such as an optical or electronic signal carrier. Such code is provided on the carrier medium. The device and its modules of the present invention can be implemented by hardware circuits such as very large-scale integrated circuits or gate arrays, semiconductors such as logic chips, transistors, etc., or programmable hardware devices such as field programmable gate arrays, programmable logic devices, etc., can also be implemented by software executed by various types of processors, and can also be implemented by a combination of the above-mentioned hardware circuits and software, such as firmware.

[0101] The above description is only a specific implementation mode of the present invention, but the protection scope of the present invention is not limited thereto. Any modifications, equivalent substitutions and improvements made by any technician familiar with the technical field within the technical scope disclosed by the present invention and within the spirit and principle of the present invention should be covered by the protection scope of the present invention.

Claims

1. A method for collecting data on organic carbon content of solid samples, characterized in that: The solid sample organic carbon content data collection method comprises: Calculate the instantaneous slope of the peak curve on the visual interface and monitor the change of the slope; Turn off the automatic acquisition termination function of the instrument, record the data of the curve changes and monitor the slope; Determine whether to terminate or continue data collection based on the curve regression baseline; The solid sample organic carbon content data collection method comprises the following steps: The first step is to turn off the instrument's automatic signal acquisition termination function; The second step is to retain the peak curve slope detection function, set a lower slope threshold, and monitor the slope change in real time; In the third step, the curve returns to the baseline. When the preset slope threshold is reached, a dialog box pops up to ask whether to end the analysis or continue the analysis according to the detection setting time; Step 4: If the data collection is completed, choose to end the analysis and proceed to the next sample test; if the data collection is not completed, choose to continue the analysis, and the instrument will continue to collect data according to the time set for the test until it is completed; then proceed to the next sample test; The solid sample organic carbon content data acquisition method sets a threshold to determine whether a protrusion in the signal curve can become a peak; during the process, the signal curve has ups and downs, resulting in changes in the slope of the curve. If the slope of the curve is greater than the set slope sensitivity, it is the starting point of the peak; when the slope of the curve drops below the slope sensitivity, it is the end point of the peak, and the peak is between the starting point and the end point.

2. The method for collecting data on organic carbon content of solid samples according to claim 1, characterized in that: Methods for determining whether a protrusion in a signal curve can become a peak include: The formula for calculating the starting point of the curve peak is: div(i,j) represents the calculated objective coefficient of the current curve peak i and the set curve peak j, time(i) and time(j) represent the data time from the beginning to the change of the current curve peak i and the set curve peak j respectively, the numerator is the absolute value of the time difference between the current curve peak i and the set curve peak j, and the denominator is the sum of the time changes between the current curve peak i and the set curve peak j; The formula for calculating the endpoint of the curve peak is: αdiv(i,j)+βy i +λy j ; Where div(i,j) represents the end point correlation between the current curve peak i and the set curve peak j, y i and j They represent the memory rates of curve peaks i and j respectively; α, β, λ are the weight values ​​of the features.

3. The method for collecting data on organic carbon content of solid samples according to claim 1, characterized in that: The slope calculation equation of the curve of the data collection process of the solid sample organic carbon content data collection method is as follows: the curve equation formed by the measurement result signal is f(x, y) = 0, P(X, Y) is any point on the curve, and the slope of the point on the curve is calculated to find the derivative of the function f(x, y) = 0 at x = X; The equation f(x,y)=0 determines a function y=y(x). Substituting y=y(x) into the equation yields the identity f[x,y(x)]=0. Finding the total derivative of this function yields; like Calculate the slope:

4. A computer device, characterized in that: The computer device includes a memory and a processor, the memory stores a computer program, and when the computer program is executed by the processor, the processor executes the steps of the solid sample organic carbon content data collection method according to any one of claims 1 to 3.

5. A computer-readable storage medium storing a computer program, wherein when the computer program is executed by a processor, the processor executes the steps of the method for collecting data on organic carbon content of solid samples according to any one of claims 1 to 3.

6. An information data processing terminal, characterized in that: The information data processing terminal is used to implement the steps of the solid sample organic carbon content data collection method according to any one of claims 1 to 3.

7. A solid sample organic carbon content data acquisition system for implementing the solid sample organic carbon content data acquisition method according to any one of claims 1 to 3, characterized in that: The solid sample organic carbon content data acquisition system comprises: Function closing module, used to close the electric signal automatic acquisition termination function; The slope change monitoring module is used to retain the peak curve slope detection function, set a lower slope threshold, and monitor the slope change in real time; The detection time setting module is used for curve regression baseline. When the preset slope threshold is reached, a dialog box pops up to ask whether to end the analysis or continue the analysis according to the detection setting time; The data collection end judgment module is used for the operator to judge that the data collection is completed, choose to end the analysis, and proceed to the next sample test; if the operator judges that the data collection is not completed, he chooses to continue the analysis, and the instrument continues to collect data according to the time set for the test until it is completed; and the next sample test is carried out.

8. Application of the method for collecting data on organic carbon content in solid samples as claimed in any one of claims 1 to 3 in processing data on organic carbon content in soil samples or in processing data on organic carbon content in sediment samples.

Images