Sample-weighing-free chemical quantitative analysis method, medium and equipment

Abstract

The invention provides a sample-weighing-free chemical quantitative analysis method, medium and equipment, and relates to the technical field of metallurgical chemical analys.The method comprises the steps that on the basis of at least two samples of a substance to be measured within the set mass range, the spectral intensity measured value of each element to be measured in each sample is obtained; acquiring a central mass concentration point and an extended mass concentration point in the mass concentration information database based on the mass concentration information database and the spectral intensity measurement value; based on the central mass concentration point, the extended mass concentration point and the corresponding standard spectral intensity point, obtaining a dynamic working curve of each to-be-measured element, and calculating a mass concentration measurement value of each to-be-measured element in each sample; and performing normalization calculation on the mass concentration measurement value of each element to be measured in the at least two samples to obtain a mass concentration report value of each element to be measured in the substance to be measured. The method can solve the problem that the existing analysis technology depends on accurate weighing of substances.

Description

Technical Field

[0001] The invention relates to the technical field of metallurgical chemical analysis, and in particular to a chemical quantitative analysis method, medium and equipment free of sample weighing. Background Art

[0002] The solution analysis method can obtain accurate quantitative analysis data for metallurgical slag and other test materials. However, in the specific analysis process, since the standard working curve is set for each mass concentration point of a fixed mass (such as 0.2000g), if the full process automated analysis is to be achieved, the key link is to solve the accuracy of automatic weighing of the material, which needs to be accurate to 0.0001g. The solution analysis method weighs a small amount of sample, usually 0.2000g, and its 1% deviation is only ±0.0010g at a 99% confidence level.

[0003] Under existing technical conditions, it is difficult to achieve the above-mentioned precision automatic weighing, and manual weighing is the only option. However, due to the influence of factors such as personnel movement, air flow and sample residue, the accuracy of material weighing may exceed the deviation of ±0.0010g. Inaccurate material mass will greatly reduce the accuracy of analytical measurement results. Summary of the invention

[0004] The problem solved by the present invention is that existing analysis technologies all rely on accurate weighing of substances, and inaccurate substance mass will greatly reduce the accuracy of analysis results.

[0005] In order to solve the above problems, the present invention provides a chemical quantitative analysis method, medium and equipment without sample weighing.

[0006] In a first aspect, the present invention provides a chemical quantitative analysis method without sample weighing, comprising the following steps:

[0007] Based on m groups of standard mass concentration points of each element to be measured in the substance to be measured and their corresponding standard spectral intensity points, a mass concentration information database of each element to be measured in the substance to be measured is obtained;

[0008] Based on at least two samples within a set mass range of the substance to be tested, obtaining a spectral intensity measurement value of each element to be tested in each sample;

[0009] Based on the mass concentration information database and the spectral intensity measurement value, a central mass concentration point and an extended mass concentration point in the mass concentration information database are obtained; wherein the central mass concentration point is a standard mass concentration point corresponding to a standard spectral intensity point in the mass concentration information database that is closest to the spectral intensity measurement value; and the extended mass concentration point is a standard mass concentration point in the mass concentration information database that extends 1 to n spans above and below the central mass concentration point, respectively, wherein n and m are both positive integers, n>1 and 2n+1 <m;

[0010] Based on the central mass concentration point and its corresponding standard spectral intensity point, and the extended mass concentration point and its corresponding standard spectral intensity point, a dynamic working curve of spectral intensity and mass concentration of each element to be measured is obtained; wherein, in the dynamic working curve, the weight of the central mass concentration point is not less than 30%;

[0011] Calculate the mass concentration measurement value of each element to be measured in each sample based on the dynamic working curve and the spectral intensity measurement value of each element to be measured in each sample;

[0012] The mass concentration measurement values ​​of each element to be measured in at least two samples are normalized and calculated using a normalized weight method to obtain the mass concentration reported value of each element to be measured in the substance to be measured.

[0013] Optionally, the value of n is 2, and the extended mass concentration points include a first extended mass concentration point extending 1 span above and below the central mass concentration point, and a second extended mass concentration point extending 2 spans above and below the central mass concentration point.

[0014] Optionally, in the dynamic working curve, the central mass concentration point and its corresponding spectral intensity point are read 3 times, the first extended mass concentration point and its corresponding spectral intensity point are read 2 times, and the second extended mass concentration point and its corresponding spectral intensity point are read once.

[0015] Optionally, in the mass concentration information database, the difference between every two adjacent standard mass concentration points is 2%-10%.

[0016] Optionally, obtaining the spectral intensity measurement value of each element to be detected in each sample based on at least two samples within a set mass range of the substance to be detected includes:

[0017] The substance to be tested is metallurgical slag. At least two samples of the metallurgical slag are chemically digested using different digestion processes to obtain corresponding chemical digestion solutions, and then the spectral intensity measurement value of the element to be tested in each chemical digestion solution is obtained.

[0018] Optionally, the at least two samples are chemically digested using different digestion processes to obtain corresponding chemical digestion solutions, including:

[0019] At least one portion of the sample is chemically digested using a polar organic solvent, nitric acid, and hydrofluoric acid in sequence to obtain a first digestion solution, and then a spectral intensity measurement value of the element to be measured in the first digestion solution is obtained;

[0020] At least one portion of the sample is chemically digested using a polar organic solvent and nitric acid in sequence to obtain a second digestion solution, and then a spectral intensity measurement value of the element to be measured in the second digestion solution is obtained.

[0021] Optionally, at least one of the samples is chemically digested with a polar organic solvent and nitric acid in sequence to obtain a second digestion solution, further comprising:

[0022] After a portion of the second digestion solution is mixed with a fluorine element detection reagent, an electrode method is used to obtain a measured value of the mass concentration of the fluorine element in the second digestion solution.

[0023] Optionally, the fluorine detection reagent includes the following components: trisodium citrate, potassium nitrate and neutralizing base.

[0024] Optionally, the normalization weight method is used to normalize the mass concentration measurement values ​​of each element to be measured in at least two samples to obtain the mass concentration reported value of each element to be measured in the substance to be measured, including:

[0025] Calculating a quantitative proportionality coefficient based on a first sum of mass concentration measurements of a selected element to be measured in one of the samples and a second sum of mass concentration measurements of the selected element to be measured in another sample;

[0026] Based on the quantitative proportional relationship coefficient, calculate the weighted value of the mass concentration of each element to be measured in one of the samples, and the weighted average value of the mass concentration of the selected element to be measured;

[0027] Calculating a third summation value based on the weighted average value of the mass concentration of the selected element to be measured and the weighted values ​​of the mass concentrations of other elements to be measured;

[0028] Calculating a weighting coefficient based on the third summation value and the mass concentration standard value of each element to be measured;

[0029] Based on the weighting coefficient, the mass concentration reported value of each element to be measured of the substance to be measured is calculated.

[0030] In a second aspect, the present invention further provides a computer-readable storage medium, in which a computer program is stored. When the computer program is executed by the processor, the processor executes the above-mentioned chemical quantitative analysis method without sample weighing.

[0031] In a third aspect, the present invention further provides a computer device, comprising a memory, a processor, and a computer program stored in the memory and executable on the processor, wherein the processor implements the above-mentioned chemical quantitative analysis method without sample weighing when executing the computer program.

[0032] The beneficial effects of the present invention compared to the prior art are:

[0033] The chemical quantitative analysis method of the present invention can be used to analyze the elements to be measured in metallurgical slag. The present invention is based on a mass concentration information database, and searches for the standard spectral intensity point closest to the spectral intensity measurement value of the element to be measured in the mass concentration information database to obtain a central mass concentration point, and then selects the extended mass concentration point located near the central mass concentration point in the mass concentration information database, and generates a dynamic working curve after weighting. Then, the spectral intensity measurement value of the element to be measured is substituted into the dynamic working curve to obtain the final mass concentration measurement value. In the fitting process of the dynamic working curve, each spectral intensity measurement value of each element to be measured corresponds to a new dynamic working curve, and the new dynamic working curve is not affected by the large changes in the weighing mass, and the mass concentration measurement value can be accurately reported. In this way, the errors caused by other interfering factors such as material weighing errors or matrix effects can be reduced, thereby improving the analysis accuracy of metallurgical slag when weighing is not required.

[0034] For the mass concentration measurement data of at least two samples without clear specific masses, since the specific masses of the samples are unknown, the results cannot be converted by the sample masses. Therefore, the present invention further uses the normalized weight method to weight the mass concentration measurement values ​​of at least two samples to obtain the mass concentration reported value. It has been verified that the relative error between the mass concentration reported value finally obtained by the present invention and the mass concentration standard value is within 3%, and it has a high analytical accuracy. In summary, the present invention can accurately obtain the mass concentration of each element to be measured in metallurgical slag without precise weighing of the substance. BRIEF DESCRIPTION OF THE DRAWINGS

[0035] Figure 1 The overall flow chart of the chemical quantitative analysis method in Example 1 of the present invention;

[0036] Figure 2 for Figure 1 Flowchart of normalization calculation in . DETAILED DESCRIPTION

[0037] In order to make the above-mentioned objects, features and advantages of the present invention more obvious and easy to understand, the specific embodiments of the present invention are described in detail below in conjunction with the accompanying drawings. Although certain embodiments of the present invention are shown in the accompanying drawings, it should be understood that the present invention can be implemented in various forms and should not be interpreted as being limited to the embodiments described herein. On the contrary, these embodiments are provided to provide a more thorough and complete understanding of the present invention. It should be understood that the drawings and embodiments of the present invention are only for exemplary purposes and are not intended to limit the scope of protection of the present invention.

[0038] Unless otherwise defined, all technical and scientific terms used in this application have the same meanings as those commonly understood by those skilled in the art to which this application belongs; the terms used in the specification of this application are only for the purpose of describing specific implementation methods and are not intended to limit this application;

[0039] The term "including" and its variations used in this article are open inclusions, that is, "including but not limited to"; the term "based on" is "based at least in part on"; the term "one embodiment" means "at least one embodiment"; the term "another embodiment" means "at least one other embodiment"; the term "some embodiments" means "at least some embodiments"; the term "optionally" means "optional embodiments". The relevant definitions of other terms will be given in the following description. It should be noted that the concepts of "first" and "second" mentioned in the present invention are used to distinguish different objects, rather than to describe a specific order or a primary and secondary relationship. In addition, the terms "first" and "second" are only used for descriptive purposes and cannot be understood as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Therefore, the features defined as "first" and "second" may explicitly or implicitly include one or more of the features. In the description of this application, unless otherwise specified, the meaning of "multiple" is two or more.

[0040] At present, the chemical solution analysis technology of related metallurgical slag generally requires quantitative weighing of slag materials, and at the same time, different detection methods are implemented for different elements to be tested. For example: calcium element adopts complexometric titration analysis, magnesium element adopts complexometric titration or atomic absorption analysis, aluminum adopts complexometric titration or spectrophotometry or ICP spectral analysis, silicon element adopts spectrophotometry, gravimetric analysis or ICP generation spectral analysis, fluorine element adopts electrochemical analysis, and iron element adopts spectrophotometry, oxidation titration analysis or ICP spectral analysis. Among them, the sum of calcium oxide, calcium fluoride, magnesium oxide, aluminum oxide, silicon dioxide, ferrous oxide, and manganese oxide in metallurgical slag exceeds 99%.

[0041] When using ICP-AES analysis technology to detect metallurgical slag chemical digestion solution, in general, the standard working curve is each mass concentration point set for the fixed mass of the substance (such as 0.2000g), and its matrix interference is also set for the fixed mass, and the optimal measurement range of the working curve established by each mass concentration point is also set for the fixed mass. Therefore, when the mass of the substance is less than 0.2000g, the established working curve will produce measurement deviation, and then deviate from the optimal measurement range. And different elements to be measured have different spectral line self-absorption phenomena, the higher the concentration, the more serious the self-absorption, and the matrix influence is also different, causing the measurement results to have a large deviation. Therefore, existing analysis techniques all rely on the accurate weighing of the substance, and inaccurate substance mass will greatly reduce the accuracy of the analysis and measurement results.

[0042] In view of the problems existing in the above-mentioned related technologies, the present invention provides a chemical quantitative analysis method, medium and equipment without sample weighing.

[0043] A chemical quantitative analysis method without sample weighing according to an embodiment of the present invention comprises the following steps:

[0044] S1: Based on m groups of standard mass concentration points of each element to be measured in the substance to be measured and their corresponding standard spectral intensity points, a mass concentration information database of each element to be measured in the substance to be measured is obtained.

[0045] S2: Based on at least two samples within a set mass range of the substance to be tested, obtain a spectral intensity measurement value of each element to be tested in each sample.

[0046] S3: Based on the mass concentration information database and the spectral intensity measurement value, obtain the central mass concentration point and the extended mass concentration point in the mass concentration information database; wherein the central mass concentration point is the standard mass concentration point corresponding to the standard spectral intensity point in the mass concentration information database that is closest to the spectral intensity measurement value; the extended mass concentration point is the standard mass concentration point in the mass concentration information database that extends (1 to n) spans above and below the central mass concentration point, wherein n and m are both positive integers, n>1 and 2n+1 <m。

[0047] S4: Based on the central mass concentration point and its corresponding standard spectral intensity point, as well as the extended mass concentration point and its corresponding standard spectral intensity point, a dynamic working curve of spectral intensity and mass concentration of each element to be measured is obtained; wherein, in the dynamic working curve, the weight of the central mass concentration point is not less than 30%.

[0048] S5: Calculate the mass concentration measurement value of each element to be measured in each sample based on the dynamic working curve and spectral intensity measurement value of each element to be measured in each sample.

[0049] S6: normalize the mass concentration measurement values ​​of each element to be measured in at least two samples by using a normalized weight method to obtain the mass concentration report value of each element to be measured in the substance to be measured.

[0050] The embodiment of the present invention is based on a mass concentration information database, and searches for a standard spectral intensity point closest to the spectral intensity measurement value of the element to be measured in the mass concentration information database to obtain a central mass concentration point, and then selects an extended mass concentration point located near the central mass concentration point in the mass concentration information database, and generates a dynamic working curve after weighting. Then, the spectral intensity measurement value of the element to be measured is substituted into the dynamic working curve to obtain the final mass concentration measurement value.

[0051] In a specific embodiment, the quantitative analysis method can be used to analyze the elements to be measured in metallurgical slag. In the above steps S3 and S4, each spectral intensity measurement value of each element to be measured corresponds to a new dynamic working curve, and the new dynamic working curve is not affected by the large changes in the weighing mass, and the mass concentration measurement value can be accurately reported. In this way, the error caused by other interfering factors such as material weighing error or matrix effect can be reduced, thereby improving the analysis accuracy of metallurgical slag when weighing is not required. For the mass concentration measurement value data of at least two samples without clear specific mass, since the specific mass of the sample is unknown, the result cannot be converted by the sample mass. Therefore, the present invention further uses the normalized weight method to weight the mass concentration measurement values ​​of at least two samples to obtain the mass concentration reported value. It has been verified that the relative error between the mass concentration reported value and the mass concentration standard value finally obtained by the present invention is within 3%, and has a high analysis accuracy. In summary, the present invention can accurately obtain the mass concentration of each element to be measured in metallurgical slag without precise material weighing.

[0052] It should be noted that the mass concentration information database is a plurality of groups of standard spectral intensity points and standard mass concentration points obtained by weighing the same slag sample at a sample mass of 0.2000g. It should be understood that the span between the standard mass concentration points in the mass concentration information database refers to the difference between each two adjacent standard mass concentration points in the mass concentration information database, and this difference is not fixed. Specifically, the two adjacent standard mass concentration points can be in any multiple relationship between 2 times and 10 times, or, as a preferred embodiment, the difference can fluctuate between 2% and 10%.

[0053] Specifically, when drawing the dynamic working curve, the extended mass concentration points that extend 1 span above and below the central mass concentration point are specifically the two standard mass concentration points adjacent to the central mass concentration point in the mass concentration information database; the extended mass concentration points that extend n spans above and below the central mass concentration point are specifically the two extended mass concentration points n spans away from the central mass concentration point in the mass concentration information database. When actually selecting points to draw the dynamic working curve, the number of extended mass concentration points should be reasonably controlled in combination with the specific position of the central mass concentration point in the m groups of standard mass concentration points in the mass concentration information database. And to ensure the fitting effect, the value of n should be no less than 2, and it should be ensured that each extended mass concentration point is symmetrically distributed about the central mass concentration point.

[0054] In some optional embodiments, the value of n can be 2, and the value of m can be 10. That is, the number of extended mass concentration points is 4 in total, and the 4 extended mass concentration points include 2 first extended mass concentration points extending 1 span above and below the central mass concentration point, and 2 second extended mass concentration points extending 2 spans above and below the central mass concentration point. Further, in this specific embodiment, when drawing the dynamic working curve, the central mass concentration point and its corresponding standard spectral intensity point are read 3 times, as a total of 3 independent data; each first extended mass concentration point and its corresponding standard spectral intensity point are read 2 times, as a total of 4 independent data; each second extended mass concentration point and its corresponding standard spectral intensity point are read once, as a total of 2 independent data. Thus, a total of 9 mass concentration points and their corresponding standard spectral intensity points are obtained, and the dynamic working curve is obtained by fitting these 9 mass concentration points and standard spectral intensity points.

[0055] In the dynamic working curve of the embodiment of the present invention, the central mass concentration point closest to the mass concentration base value occupies about 33% of the weight, the first extended mass concentration point second closest to the mass concentration base value occupies about 22% of the weight, and the second extended mass concentration point occupies only 11% of the weight. The dynamic working curve obtained by fitting in this way is established with the mass concentration base value of the element to be measured as the center. By increasing the weight of the central mass concentration point in the dynamic working curve fitting process, the model can pay more attention to this central mass concentration point, so that it can be given more consideration in prediction or analysis, which helps to improve the accuracy of the model and greatly reduce the calculation error of the mass concentration measurement value.

[0056] Optionally, when the substance to be tested is metallurgical slag, at least two samples of the metallurgical slag can be chemically digested using different digestion processes to obtain corresponding chemical digestion solutions, and then the spectral intensity measurement value of each element to be tested in each chemical digestion solution is obtained.

[0057] Furthermore, the following digestion process can be used to process at least two samples: at least one sample is chemically digested using a polar organic solvent, nitric acid and hydrofluoric acid in sequence to obtain a first digestion solution, and spectral intensity measurement values ​​of some elements to be measured in the first digestion solution are obtained; at least one sample is chemically digested using a polar organic solvent and nitric acid in sequence to obtain a second digestion solution, and spectral intensity measurement values ​​of some elements to be measured in the second digestion solution are obtained.

[0058] Preferably, the embodiment of the present invention can set two samples within a set mass range based on the same substance to be tested, and the set mass range can be 0.15-0.25g. One of them is chemically digested with polar organic solvents, nitric acid and hydrofluoric acid in sequence, and is used for the detection of elements such as calcium, magnesium, aluminum, silicon, iron, manganese, titanium, chromium, potassium, and sodium; the other is chemically digested with polar organic solvents and nitric acid only in sequence, and is used for the detection of calcium, magnesium, aluminum, silicon, iron, manganese, titanium, chromium, potassium, sodium and fluorine.

[0059] Optionally, in the above digestion process, the polar organic solvent can be ethanol, and after the substances are mixed, they can be mixed evenly by ultrasonic vibration. When one of the samples is chemically digested with a polar organic solvent, nitric acid and hydrofluoric acid in sequence, the added concentration of hydrofluoric acid is 0.1-2%. Hydrofluoric acid can destroy the silica gel in the digestion process and form fluorosilicic acid dissolved in the digestion solution. By limiting the added concentration of hydrofluoric acid to less than 2%, the phenomenon of digestion failure due to precipitation of fluorosilicate can be avoided.

[0060] Optionally, another sample is chemically digested with a polar organic solvent and nitric acid to obtain a second digestion solution, and then part of the second digestion solution can be mixed with a fluorine element detection reagent, and the mass concentration measurement value of the fluorine element in the second digestion solution can be obtained by an electrode method. Specifically, 5-10 ml of the test solution can be taken from the second digestion solution for the measurement of calcium fluoride, and then the remaining second digestion solution can be dry-filtered through a U-type filter, and the rapid filtration is controlled to be completed within 5-10 seconds, and the filtered second digestion solution is analyzed and measured for elements such as calcium, magnesium, aluminum, silicon, iron, manganese, titanium, chromium, potassium, and sodium using ICP spectral analysis technology.

[0061] Optionally, the fluorine element detection reagent includes the following components: trisodium citrate, potassium nitrate and neutralizing base. Specifically, the neutralizing base can be sodium hydroxide or potassium hydroxide, and the mass fraction ratio of trisodium citrate and potassium nitrate can be 13.7:18. The neutralizing base is used to neutralize the nitric acid in the second digestion solution, and its added amount is adapted to the amount of nitric acid in the second digestion solution in the fluorine element detection reagent. Therefore, the amount of the neutralizing base added can be adjusted according to the amount of nitric acid added in the second digestion solution and the actual amount of the second digestion solution mixed with the fluorine element detection reagent. By using the fluorine element detection reagent, complex chemical reactions and volume operations are avoided, and simple and fast connection between processes is achieved.

[0062] The present invention detects the fluorine element alone by the electrode method, and completes the measurement of all components to be measured by two or more detection methods. After the slag sample is dissolved by acid and the silicate is precipitated, the adsorbed ions are condensed and the concentration is made consistent by ultrasonic vibration, eliminating the adsorption effect of silicate on other elements, which is conducive to the accurate measurement of the fluorine element.

[0063] In the prior art, only acid is generally used to digest the slag sample. However, when the acid is used alone to digest the slag sample, the main component of the slag, calcium silicate, is prone to condensation reaction, and then aggregates into a mass and adheres to the bottom of the beaker, so that the digestion reaction cannot be continued, and thus the rapid digestion of the slag sample cannot be achieved. The polar organic solvent used in the present invention does not directly participate in the digestion reaction. The polar functional groups in the polar organic solvent have extremely strong hydrophilicity and can destroy the hydrogen bonds between water molecules. The hydroxyl groups of the water molecules are tightly bound by the polar functional groups of the organic solvent to form a more stable hydrogen bond relationship. Because the calcium silicate in the slag needs to rob the water molecules bound by the polar organic solvent before the hydrolysis reaction can occur. Therefore, due to the presence of the polar organic solvent, the speed at which calcium silicate reacts with water is significantly slowed down, thereby preventing the slag sample particles from condensing into large particles, which is conducive to the continued digestion reaction.

[0064] In addition, polar organic solvents can also protect the slag sample, so that the slag sample particles can maintain their original shape and specifications (usually 80 mesh) as much as possible. This can also avoid the coagulation between sample particles, so that the sample particles react with the acid in an extremely small state, thereby achieving acid dissolution and greatly shortening the digestion time of the sample. Ultrasonic waves can make the sample particles "suspended" in the acid solution, so that the subsequent sample particles can always be in close contact with the acid, dissolving reaction, and under the vibration of ultrasound, the dissolution reaction becomes faster, and the sample can be stably digested completely within 1-2 minutes.

[0065] For two samples without clear specific masses, two groups of mass concentration data of the elements to be measured are obtained according to different digestion processes and different detection methods. One group includes mass concentration data of calcium, magnesium, aluminum, silicon, iron, manganese, titanium, chromium, potassium, and sodium, and the other group includes mass concentration data of the above-mentioned elements to be measured and fluorine. In some specific embodiments, the other group may also include mass concentration data of some of the above-mentioned elements to be measured and fluorine. Then, the proportional relationship between fluorine and elements such as calcium, magnesium, aluminum, silicon, iron, and manganese is unified, and the mass proportional relationship between calcium oxide, calcium fluoride, magnesium oxide, aluminum oxide, silicon dioxide, iron, manganese, and other components in the slag sample is further obtained by chemical formula conversion.

[0066] In some optional embodiments, if two samples are set based on the same substance to be tested, the normalization calculation in the above step S6 specifically includes the following steps:

[0067] S61: Calculate the magnitude proportional relationship coefficient K1 based on a first summation value of mass concentration measurement values ​​of the selected element to be measured in the first digestion solution and a second summation value of mass concentration measurement values ​​of the selected element to be measured in the second digestion solution.

[0068] The selected element to be measured can be several of calcium, magnesium, aluminum, silicon, iron, manganese, titanium, chromium, potassium, and sodium, and preferably, can be three elements of calcium, magnesium, and aluminum. The magnitude proportional relationship coefficient K1 is calculated by the mass concentration measurement values ​​of the same selected elements to be measured in the first digestion solution and the second digestion solution, so as to normalize the two groups of mass concentration measurement values.

[0069] S62: Based on the quantity proportional relationship coefficient K1, the weighted value of the mass concentration of each element to be measured in the first digestion solution and the weighted average value of the mass concentration of the selected element to be measured are calculated.

[0070] Specifically, the weighted value of the mass concentration of each element to be measured in the first digestion solution is calculated as follows: the product of the mass concentration measurement value of each element to be measured in the first digestion solution and the quantity ratio coefficient K1. The weighted average value of the mass concentration of the selected element to be measured is calculated as follows: the average value of the mass concentration weighted value of the selected element to be measured in the first digestion solution and the mass concentration measurement value of the selected element to be measured in the second digestion solution.

[0071] S63: Calculate a third summation value based on the weighted average value of the mass concentration of the selected element to be measured and the weighted values ​​of the mass concentration of other elements to be measured. The third summation value is the sum of the weighted average value of the mass concentration of the selected element to be measured and the weighted values ​​of the mass concentration of other elements to be measured. It should be noted that when fluorine is also detected in the second digestion solution, the third summation value should be the sum of the weighted average value of the mass concentration of the selected element to be measured, the weighted values ​​of the mass concentration of other elements to be measured, and the mass concentration measurement value of fluorine.

[0072] S64: Calculate a weighting coefficient based on the third summation value and the mass concentration standard value of each element to be measured. Specifically, first calculate a fourth summation value of the mass concentration standard value of each element to be measured, and then calculate a weighting coefficient K2 based on the third summation value and the fourth summation value, the weighting coefficient K2 being the ratio of the fourth summation value to the third summation value.

[0073] The standard value of mass concentration of each element to be measured is the average value obtained by statistical analysis of multiple batches of slag samples from multiple different smelting processes.

[0074] S65: Calculate the mass concentration report value of each element to be measured based on the weighting coefficient, the mass concentration weighted value of each element to be measured, and the weighted average value of the mass concentration of the selected element to be measured.

[0075] The mass concentration reported value of each element to be measured is calculated as follows: the product of the weighted value of the mass concentration of each element to be measured and the weighting coefficient K2, or the product of the weighted average value of the mass concentration of each selected element to be measured and the weighting coefficient K2. When fluorine is also detected in the second digestion solution, the mass concentration reported value of fluorine is the product of the mass concentration measurement value of fluorine and the weighting coefficient K2.

[0076] In the embodiment of the present invention, by normalizing the mass concentration measurement values ​​of the elements to be measured in the first digestion solution and the second digestion solution, it is helpful to eliminate the differences between the data caused by different digestion processes, and the test results can be quantitatively reported without accurately weighing the respective samples. Based on the mathematical operation model, it is helpful to realize the automatic detection of slag samples.

[0077] In another embodiment of the present invention, a computer-readable storage medium stores a computer program, and when the program is executed by a processor, the processor executes the above-mentioned chemical quantitative analysis method without sample weighing.

[0078] A computer device according to another embodiment of the present invention includes a memory, a processor, and a computer program stored in the memory and executable on the processor. When the processor executes the computer program, the above-mentioned chemical quantitative analysis method without sample weighing is implemented. Based on the theoretical model of the quantitative analysis method for metallurgical slag of the present invention and the corresponding computer device, a mechanical arm and a sensor are further provided to realize the digestion and transfer process of the sample, so as to realize the automatic detection and analysis of the metallurgical slag.

[0079] The present invention is further described below in conjunction with specific embodiments and comparative examples:

[0080] Example 1

[0081] Reference Figure 1 and Figure 2 As shown, this embodiment performs quantitative analysis on metallurgical slag, and the quantitative analysis process specifically includes the following contents:

[0082] 1. Overall process flow

[0083] (1) Two samples of the same slag sample with a mass of 0.15-0.25 g were placed in beakers respectively, and 10 ml of 50% ethanol solution was added to each beaker. The beakers were shaken to evenly disperse the two samples in the ethanol solution. Then, 100 ml of 65% nitric acid was quantitatively added to each beaker, and ultrasonic vibration was performed for 2 min to obtain the first digestion solution and the second digestion solution.

[0084] (2) 10 ml of hydrofluoric acid with a concentration of 0.15% was added to the first digestion solution, and ultrasonic vibration was continued for 10 seconds. After adding 130 ml of distilled water, electromagnetic stirring was performed, and then the spectral intensity of calcium, magnesium, aluminum, silicon, iron, manganese, titanium, chromium, potassium, and sodium was detected by ICP-AES spectrometer, and the mass concentration measurement value of each element to be measured was further calculated based on the spectral intensity measurement value.

[0085] (3) 140 ml of distilled water was quantitatively added to the second digestion solution, and electromagnetic stirring was performed. 5 ml of the second digestion solution was quantitatively transferred to another 100 ml beaker, and 95 ml of fluorine element detection reagent was added and mixed evenly to obtain a fluorine detection solution. The mass concentration of fluorine element in the fluorine detection solution was obtained by electrode method. Among them, in the fluorine element detection reagent, the concentration of trisodium citrate was 0.0685 g / mL, the concentration of potassium nitrate was 0.09 g / mL, and the concentration of sodium hydroxide was 0.0304 g / mL.

[0086] (4) The remaining second digestion solution is dry-filtered, and the spectral intensity of the three elements of calcium, magnesium, and aluminum in the second digestion solution after filtration is detected by ICP-AES spectrometer, and the mass concentration measurement values ​​of the three elements are further calculated based on the spectral intensity measurement values ​​using a dynamic working curve.

[0087] (5) The test results in (2) and (4) are normalized by the normalized weight method to obtain the mass concentration reported value of each element to be tested.

[0088] 2. Establishment and verification of dynamic working curve

[0089] In order to verify the results of the dynamic curve method, three samples of 0.1500g, 0.2000g and 0.2500g were accurately weighed and named Y1, Y2 and Y3 respectively. Then, chemical digestion was performed according to the steps in the above steps (1) and (2), and calcium, magnesium, aluminum, silicon, iron, manganese, titanium, chromium, potassium and sodium were detected by ICP-AES spectrometer to obtain the spectral intensity measurement values ​​of each element to be tested. The establishment process of the dynamic working curve in this embodiment is described below using calcium as an example:

[0090] First, a mass concentration information database is established based on 10 groups of standard mass concentration points of calcium and their corresponding standard spectral intensity points. The mass concentration information database is specifically shown in Table 1:

[0091] Table 1 Mass concentration information database

[0092]

[0093] Then, based on the spectral intensity measurement values ​​of calcium in the first chemical digestion solution of the three samples Y1, Y2 and Y3, the standard mass concentration point closest to the spectral intensity measurement value of calcium in Table 1 is selected as the central mass concentration point, and two points are selected above and below the central mass concentration point as the first extended mass concentration point and the second extended mass concentration point, and the dynamic working curve of calcium is generated after weighting. Among them, in the dynamic working curve, the central mass concentration point is read 3 times, each first extended mass concentration point is read 2 times, and each second extended mass concentration point is read 1 time. Then the spectral intensity measurement value of calcium is substituted into the dynamic working curve to calculate the mass concentration measurement value. The specific point selection and dynamic working curve drawing process are shown in Table 2:

[0094] Table 2 Specific point selection and dynamic working curve drawing process of sample Y1

[0095]

[0096] Similarly, the specific point selection and dynamic working curve drawing process of samples Y2 and Y3 are the same as that of sample Y1. In summary, the spectral intensity measurement values ​​of samples Y1, Y2 and Y3 and the corresponding dynamic working curve equations are shown in Table 3:

[0097] Table 3 Dynamic working curves of samples Y1, Y2 and Y3

[0098]

[0099] Furthermore, the measured values ​​of the calcium concentration of the above three samples Y1, Y2 and Y3 were converted into reported values ​​under the standard weighing mass of 0.2g, and the calculation formula is:

[0100] The reported value under standard weighing mass = measured value × 0.2 ÷ G (actual weighing mass), where the actual weighing weights of Y1, Y2 and Y3 are 0.15g, 0.2g and 0.25g respectively.

[0101] Finally, according to the above dynamic working curve drawing method and the calculation formula of the reported value under the standard weighing mass, the mass concentration measurement values ​​and the reported values ​​under the standard weighing mass of elements such as Mg, Al, Si, Fe, Mn, etc. are obtained in turn. The results are shown in Table 4 and Table 5:

[0102] Table 4 Mass concentration measurements of each element obtained using the dynamic working curve

[0103]

[0104] Table 5 The reported values ​​under standard weighing mass converted from the measured values ​​of mass concentration of each element

[0105]

[0106] It can be seen from Table 5 that the dynamic working curve in the embodiment of the present invention is not affected by the change of the weighing mass. The mass concentration of the element to be measured can be accurately reported through the dynamic working curve, and the relative error between the mass concentration reported value converted from samples of different weighing masses and the standard value is within 3%.

[0107] Furthermore, according to the above-mentioned method for drawing the dynamic working curve, the mass concentration measurement values ​​of each element to be measured in step (2) and step (4) in (I) are obtained.

[0108] 3. Verification of Normalized Weight Method

[0109] This process occurs in step (5) in (a), specifically, refer to Figure 2 As shown, the mass concentration measurement values ​​of each element to be measured in the first digestion solution and the second digestion solution in Table 6 are normalized. Among them, by statistically analyzing 251 batches of slag samples from 6 different smelting processes, the sum of the mass concentration standard values ​​of each element to be measured is 96.85, that is, the fourth sum value is 96.85. The calculation process and results of the mass concentration reported values ​​of the first digestion solution and the second digestion solution are shown in Table 6:

[0110] Table 6 Calculation process and results of mass concentration reported values ​​of the first digestion solution and the second digestion solution

[0111]

[0112]

[0113] As can be seen from Table 6, the slag sample in this embodiment does not contain fluorine, so the content of fluorine in the second digestion solution is 0%. The mass concentration reported values ​​of each element to be measured calculated by the normalized weight method are within 3% compared with the standard value of its mass concentration. This shows that by normalizing the mass concentration measurement values ​​of each element to be measured in two groups of samples with unknown mass, a more accurate mass concentration reported value can be obtained.

[0114] Comparative Example 1

[0115] The difference between this comparative example and the embodiment is that in step (2) and step (4) of the comparative example, the mass concentration measurement value of each element to be measured is calculated using the standard working curve method.

[0116] Specifically, taking calcium as an example, a standard working curve is established according to the sample mass of 0.2000g and the calcium mass concentration from 10% to 80%. Then the sample is accurately weighed, and 0.1500g, 0.2500g and 0.2000g of the sample are accurately weighed respectively. Based on the spectral intensity measurement value of the calcium element in the digestion solution of each sample, the result is calculated using the above standard working curve to obtain the mass concentration measurement value of the calcium element in each sample.

[0117] Then the mass concentration measurement value is converted to the mass concentration reported value when the standard weighing mass is 0.2g. The conversion formula is: Ca measurement value × 0.2 ÷ G (weighing mass). The mass concentration reported values ​​of calcium in the three samples are shown in Table 7:

[0118] Table 7 Reported values ​​of calcium concentration of three samples in the comparative example under standard weighing mass

[0119]

[0120] It can be seen from Table 7 that for samples with large differences in weighed masses, the reported values ​​of mass concentration of each element calculated using the same standard working curve are quite different and the test results cannot be reported correctly.

[0121] Although the present invention is disclosed as above, the protection scope of the present invention is not limited thereto. Those skilled in the art may make various changes and modifications without departing from the spirit and scope of the present invention, and these changes and modifications will fall within the protection scope of the present invention.

Claims

1. A chemical quantitative analysis method without sample weighing, characterized in that: include: Based on m groups of standard mass concentration points of each element to be measured in the substance to be measured and their corresponding standard spectral intensity points, a mass concentration information database of each element to be measured in the substance to be measured is obtained; Based on at least two samples within a set mass range of the substance to be tested, obtaining a spectral intensity measurement value of each element to be tested in each sample; Based on the mass concentration information database and the spectral intensity measurement value, a central mass concentration point and an extended mass concentration point in the mass concentration information database are obtained; wherein the central mass concentration point is a standard mass concentration point corresponding to a standard spectral intensity point in the mass concentration information database that is closest to the spectral intensity measurement value; and the extended mass concentration point is a standard mass concentration point in the mass concentration information database that extends 1 to n spans above and below the central mass concentration point, respectively, wherein n and m are both positive integers, n>1 and 2n+1 <m; Based on the central mass concentration point and its corresponding standard spectral intensity point, and the extended mass concentration point and its corresponding standard spectral intensity point, a dynamic working curve of spectral intensity and mass concentration of each element to be measured is obtained; wherein, in the dynamic working curve, the weight of the central mass concentration point is not less than 30%; Calculate the mass concentration measurement value of each element to be measured in each sample based on the dynamic working curve and the spectral intensity measurement value of each element to be measured in each sample; The mass concentration measurement values ​​of each element to be measured in at least two samples are normalized and calculated using a normalized weight method to obtain the mass concentration reported values ​​of each element to be measured in the substance to be measured.

2. The chemical quantitative analysis method without sample weighing according to claim 1, characterized in that: The value of n is 2, and the extended mass concentration points include a first extended mass concentration point extending 1 span above and below the central mass concentration point, and a second extended mass concentration point extending 2 spans above and below the central mass concentration point.

3. The chemical quantitative analysis method without sample weighing according to claim 2, characterized in that: In the dynamic working curve, the central mass concentration point and its corresponding standard spectral intensity point are read 3 times, the first extended mass concentration point and its corresponding standard spectral intensity point are read 2 times, and the second extended mass concentration point and its corresponding standard spectral intensity point are read once.

4. The chemical quantitative analysis method without sample weighing according to claim 1, characterized in that: The step of obtaining a spectral intensity measurement value of each element to be detected in each of the at least two samples within a set mass range of the substance to be detected comprises: The substance to be tested is metallurgical slag. At least two samples of the metallurgical slag are chemically digested using different digestion processes to obtain corresponding chemical digestion solutions, and then the spectral intensity measurement value of the element to be tested in each chemical digestion solution is obtained.

5. The chemical quantitative analysis method without sample weighing according to claim 4, characterized in that: The at least two samples are chemically digested using different digestion processes to obtain corresponding chemical digestion solutions, including: At least one portion of the sample is chemically digested using a polar organic solvent, nitric acid, and hydrofluoric acid in sequence to obtain a first digestion solution, and then a spectral intensity measurement value of the element to be measured in the first digestion solution is obtained; At least one portion of the sample is chemically digested using a polar organic solvent and nitric acid in sequence to obtain a second digestion solution, and then a spectral intensity measurement value of the element to be measured in the second digestion solution is obtained.

6. The chemical quantitative analysis method without sample weighing according to claim 5, characterized in that: At least one of the samples is chemically digested with a polar organic solvent and nitric acid in sequence to obtain a second digestion solution, and the method further comprises: After a portion of the second digestion solution is mixed with a fluorine element detection reagent, an electrode method is used to obtain a mass concentration measurement value of the fluorine element in the second digestion solution.

7. The chemical quantitative analysis method without sample weighing according to claim 6, characterized in that: The fluorine element detection reagent comprises the following components: trisodium citrate, potassium nitrate and a neutralizing base.

8. The chemical quantitative analysis method without sample weighing according to claim 1, characterized in that: The method of normalizing the mass concentration measurement values ​​of each element to be measured in at least two samples by using a normalized weight method to obtain the mass concentration reported value of each element to be measured in the substance to be measured includes: Calculating a quantitative proportionality coefficient based on a first sum of mass concentration measurements of a selected element to be measured in one of the samples and a second sum of mass concentration measurements of the selected element to be measured in another sample; Based on the quantitative proportional relationship coefficient, calculate the weighted value of the mass concentration of each element to be measured in one of the samples, and the weighted average value of the mass concentration of the selected element to be measured; Calculating a third summation value based on the weighted average value of the mass concentration of the selected element to be measured and the weighted values ​​of the mass concentrations of other elements to be measured; Calculating a weighting coefficient based on the third summation value and the mass concentration standard value of each element to be measured; Based on the weighting coefficient, the mass concentration reported value of each element to be measured of the substance to be measured is calculated.

9. A computer-readable storage medium, characterized in that: The computer-readable storage medium stores a computer program, and when the computer program is executed by a processor, the processor executes the chemical quantitative analysis method without sample weighing as described in any one of claims 1-8.

10. A computer device, characterized in that: The method comprises a memory, a processor and a computer program stored in the memory and executable on the processor. When the processor executes the computer program, the method for chemical quantitative analysis without sample weighing as described in any one of claims 1 to 8 is implemented.

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