X-ray fluorescence analysis method of KR desulfurizer
Through the X-ray fluorescence analysis method, combined with standard sample preparation and melt sample preparation technology, the accuracy of multi-element content analysis in KR desulfurizer was solved, and the high accuracy determination of SiO2, TCa, and CaF2 content was achieved, providing a simple and efficient analysis method.
Patent Information
- Application Number
- CN202411466954.1
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-10-21
- Publication Date
- 2025-03-28
AI Technical Summary
The prior art is difficult to accurately analyze the content of multiple elements in KR desulfurization agents, which affects the control of sulfur content during steelmaking.
Using X-ray fluorescence analysis method, the preparation of standard samples of limestone and fluorite, combined with a mixed solvent of lithium tetraborate and lithium metaborate, the sample was prepared by melting, and the analysis was performed using an X-ray fluorescence spectrometer. Appropriate analysis parameters and calibration formulas were set to achieve accurate determination of the SiO2, TCa, and CaF2 content in the KR desulfurizer.
It improves the accuracy and stability of KR desulfurizer analysis, provides a feasible detection method that can replace chemical analysis methods, simplify operations, shorten analysis cycles, and improve the accuracy and reliability of analysis results.
Smart Images
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Abstract
Description
Technical Field
[0001] The invention relates to the technical field of KR desulfurizing agent detection, and in particular to an X-ray fluorescence analysis method of a KR desulfurizing agent. Background Art
[0002] KR desulfurizer is one of the important auxiliary raw materials in the steelmaking process. With the increasing steel production of various steel mills, the demand for it has also increased accordingly. With the reduction of high-grade, low-impurity iron ores such as low-phosphorus and low-sulfur iron ores worldwide, high-phosphorus and high-sulfur iron ores will inevitably enter a large-scale use stage, and the requirements for sulfur content in steel are becoming more and more stringent. Therefore, how to achieve effective desulfurization and produce safe low-sulfur steel has become one of the major issues facing steel workers. KR desulfurizers are all lime-based desulfurizers, and their main components are made of a large amount of metallurgical lime and a certain amount of fluorite. They are mixed materials, and accurate analysis of multiple elements in KR desulfurizers is crucial.
[0003] The sample preparation methods commonly used for X-ray fluorescence analysis are the melting method and the powder pressing method. The melting method makes the element distribution in the sample very uniform, which can eliminate the unevenness of composition, density and particle size, completely eliminate the mineral effect and particle size effect, and the standard sample is stable and easy to preserve. Summary of the invention
[0004] The technical problem to be solved by the present invention is to provide an X-ray fluorescence analysis method for KR desulfurizer in view of the deficiencies of the prior art. The analysis method has high accuracy and provides a feasible detection method for the research and analysis of KR desulfurizer.
[0005] The technical solution adopted by the present invention to solve the above-mentioned problems is:
[0006] An X-ray fluorescence analysis method for a KR desulfurizer comprises the following steps:
[0007] (1) Preparation of standard samples: Place a limestone standard sample in a porcelain crucible and burn it in a muffle furnace at 1050° C. for more than 2 h; Mix the burned limestone with a fluorite standard sample in different mass ratios to prepare at least 5 series of standard samples with a mass of 0.3000 g; Mix the series of standard samples with 6.0000 g of a mixed solvent of lithium tetraborate and lithium metaborate, place them in a yellow-platinum crucible, add 30 mg of a release agent, potassium iodide, and melt them at 980-1000° C. for 150-180 seconds and a tilting time of 500-540 seconds to prepare glass sheets for analysis;
[0008] (2) Treatment of the sample to be tested: accurately weigh 0.3000 g of the sample to be tested and 6.0000 g of a mixed solvent of lithium tetraborate and lithium metaborate; mix the weighed sample to be tested and the mixed solvent of lithium tetraborate and lithium metaborate evenly, place in a yellow-platinum crucible, add 30 mg of a release agent, potassium iodide, and melt at 980-1000° C. for 150-180 seconds and a tilting time of 500-540 seconds to prepare a glass sheet for analysis;
[0009] (3) Preparation of standard curve: placing the glass pieces of the series of standard samples obtained in step (1) in an X-ray fluorescence spectrometer for analysis and testing, obtaining the fluorescence intensity of the series of standard samples, and preparing standard curves for each element;
[0010] (4) Determination of the sample to be tested: The glass piece of the sample to be tested obtained in step (2) is placed in an X-ray fluorescence spectrometer for analysis and testing to obtain the fluorescence intensity of the sample to be tested, which is compared with the standard curve obtained in step (3) to calculate the test result.
[0011] In the above scheme, the mass ratio of lithium tetraborate to lithium metaborate in the mixed solvent of lithium tetraborate and lithium metaborate is 67:33.
[0012] In the above scheme, when using X-ray fluorescence spectrometer for analysis and testing, set SiO 2 、TCa、CaF 2 The corresponding spectral lines are SiKa1,2, CaKa1,2, and FKa1,2.
[0013] In the above scheme, when using X-ray fluorescence spectrometer for analysis and testing, set SiO 2 、TCa、CaF 2 The corresponding crystals are PET, LiF200, and AXO3 respectively.
[0014] In the above scheme, when using X-ray fluorescence spectrometer for analysis and testing, set SiO 2 、TCa、CaF 2 The corresponding collimators are 0.15°, 0.40°, and 0.25° respectively.
[0015] In the above scheme, when using X-ray fluorescence spectrometer for analysis and testing, set SiO 2 、TCa、CaF 2 The corresponding peak values are 109.028, 113.086, and 73.441 respectively.
[0016] In the above scheme, when using X-ray fluorescence spectrometer for analysis and testing, set SiO 2 、TCa、CaF 2The corresponding voltages are 30kV, 50kV, and 30kV respectively.
[0017] In the above scheme, when using X-ray fluorescence spectrometer for analysis and testing, set SiO 2 、TCa、CaF 2 The corresponding currents are 80mA, 50mA, and 80mA respectively.
[0018] In the above scheme, when using X-ray fluorescence spectrometer for analysis and testing, set SiO 2 、TCa、CaF 2 The corresponding counting times are 24s, 24s, and 40s respectively.
[0019] In the above scheme, when using X-ray fluorescence spectrometer for analysis and testing, the TL+ equation provided by OXSAS software is used to perform spectral line overlap interference correction and matrix effect correction at the same time. The correction formula is: Among them C i is the concentration of the element to be measured after correction; α 0 , α 1 , α 2 is the coefficient of the basic curve; I i is the intensity of the element to be measured; C j is the concentration of matrix interfering elements; C k is the concentration of the spectral interfering element; α 1k is the spectral line interference coefficient; α 2j is the matrix interference coefficient.
[0020] In the present invention, by setting the instrument analysis parameters, the determination analysis parameters of the light element F, low voltage and high current are selected, the voltage is 30KV, and the current is 80mA; according to the principle that the finer the collimator, the lower the intensity, and the higher the resolution, a 0.25° collimator is comprehensively selected, so that the accurate analysis of the F element is achieved, and the difficult problem of the accuracy and stability of the fluorescence analysis of calcium fluoride is solved. By correcting the interference of spectral line overlap, the simultaneous determination of SiO in KR desulfurizer by X-ray fluorescence method is achieved. 2 、TCa、CaF 2 content.
[0021] The method of the present invention optimizes the sample processing process by setting the melting conditions, the sample-to-flux ratio of 1:20, the melting temperature of 980-1000° C., the standing time of 150-180 seconds, and the tilting time of 500-540 seconds, without the risk of corrosion of the platinum crucible, and ensuring that the accuracy and precision of the measurement result meet the requirements.
[0022] Compared with the prior art, the present invention has the following beneficial effects:
[0023] (1) The X-ray fluorescence analysis method of a KR desulfurizer provided by the present invention has high accuracy and provides a feasible detection method for the research and analysis of KR desulfurizer.
[0024] (2) The X-ray fluorescence analysis method of KR desulfurizer provided by the present invention can replace the currently commonly used chemical analysis method, and has the advantages of simple operation, short analysis cycle, few operation steps, accurate and reliable analysis results, etc., and can be promoted and applied to the acceptance of KR desulfurizers of all steel companies in the metallurgical industry.
[0025] (3) The X-ray fluorescence analysis method of KR desulfurizer provided by the present invention prepares a series of standard samples by using limestone standard samples and fluorite standard samples, thereby ensuring consistency with the background of the KR desulfurizer sample to be tested, and effectively improving the precision and accuracy of the test results. BRIEF DESCRIPTION OF THE DRAWINGS
[0026] Figure 1 A standard curve of silicon prepared by testing a standard sample using an X-ray fluorescence spectrometer in an X-ray fluorescence analysis method of a KR desulfurizer provided in an embodiment of the present application;
[0027] Figure 2 A standard curve of calcium prepared by testing a standard sample using an X-ray fluorescence spectrometer in an X-ray fluorescence analysis method of a KR desulfurizer provided in an embodiment of the present application;
[0028] Figure 3 In an X-ray fluorescence analysis method for a KR desulfurizer provided in an embodiment of the present application, a standard curve of fluorine is prepared by testing a standard sample using an X-ray fluorescence spectrometer. DETAILED DESCRIPTION
[0029] The technical solution of the present invention will be fully and clearly described below in conjunction with specific embodiments, but the described embodiments are only some embodiments of the present invention. Based on the embodiments in the present invention, all other embodiments obtained by ordinary technicians in the field without making creative work are within the scope of protection of the present invention.
[0030] The present application embodiment provides an X-ray fluorescence analysis method of a KR desulfurizer, comprising the following steps:
[0031] Step (1), preparation of standard sample: put the limestone standard sample (YSBC28704C-2021) into a porcelain crucible and burn it in a muffle furnace at 1050°C for 3h to ensure that the CO 2The gas was exhausted as completely as possible. The burned limestone was mixed with the fluorite standard sample (YSBC28733-2014) in different mass ratios to prepare 7 series of standard samples with a mass of 0.3000g; the series of standard samples were mixed with 6.0000g of lithium tetraborate and lithium metaborate mixed solvent, and then placed in a yellow-platinum crucible, and 30mg of potassium iodide, a release agent, was added, and the glass sheets were melted at 980-1000℃, standing time 150-180S, tilting time 500-540S, and prepared for analysis; Table 1 shows the values of the limestone standard sample and the fluorite standard sample, and Table 2 shows the specific components and chemical composition of the series of standard samples.
[0032] Table 1 Indications of limestone standard samples and fluorite standard samples
[0033]
[0034] Table 2 Specific components and chemical composition of a series of standard samples
[0035]
[0036] Where TCa=TCa 石灰石 +TCa 萤石
[0037] Step (2), treatment of the sample to be tested: accurately weigh 0.3000 g of the sample to be tested and 6.0000 g of a mixed solvent of lithium tetraborate and lithium metaborate (wherein the mass ratio of lithium tetraborate to lithium metaborate is 67:33); mix the weighed sample to be tested and the mixed solvent of lithium tetraborate and lithium metaborate evenly and place them in a yellow-platinum crucible, add 30 mg of a release agent potassium iodide, and melt the mixture at 980-1000° C., stand for 150-180 seconds, and tilt for 500-540 seconds to prepare a glass sheet for analysis.
[0038] Step (3), preparation of standard curve: Place the glass pieces of the series of standard samples obtained in step (1) in an X-ray fluorescence spectrometer for analysis and testing, obtain the fluorescence intensity of the series of standard samples, and prepare the standard curve of each element. Figure 1 , Figure 2 , Figure 3 These are the standard curves for silicon, calcium and fluorine respectively.
[0039] The optimal determination conditions for each element in the X-ray fluorescence spectrometer are shown in Table 3.
[0040] Table 3 Optimal determination conditions of each element in X-ray fluorescence spectrometer
[0041]
[0042]
[0043] The TL+ equation provided by OXSAS software is used to perform both spectral line overlap interference correction and matrix effect correction. The correction formula is: Among them C i is the concentration of the element to be measured after correction; α 0 , α 1 , α 2 is the coefficient of the basic curve; I i is the intensity of the element to be measured; C j is the concentration of matrix interfering elements; C k is the concentration of the spectral interfering element; α 1k is the spectral line interference coefficient; α 2j is the matrix interference coefficient.
[0044] Step (4), determination of the sample to be tested: placing the glass piece of the sample to be tested obtained in step (2) in an X-ray fluorescence spectrometer for analysis and testing, obtaining the fluorescence intensity of the sample to be tested, comparing it with the standard curve obtained in step (3), and calculating the test result.
[0045] Precision test: Use a KR desulfurizer standard sample and test it 10 times in parallel according to the above steps to check the precision of the method. The test data is shown in Appendix 4. Then select one of the samples to repeat the measurement 10 times to check the precision of the instrument analysis method. The test data is shown in Appendix 5. It can be seen from the test results of Appendix 4 and Appendix 5 that the technical method and analysis data have good reproducibility; at the same time, it can be seen from Appendix 4 that the sample preparation method has good reproducibility.
[0046] Table 4 Validation method precision test
[0047]
[0048] Table 5 Verification instrument precision test
[0049]
[0050]
[0051] In summary, the X-ray fluorescence analysis method of a KR desulfurizer provided by the present invention has high accuracy and provides a feasible detection method for the research and analysis of the KR desulfurizer.
[0052] The above is only a preferred specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Any technician familiar with the technical field can make equivalent replacements or changes according to the technical solution and its improved conception within the technical scope disclosed by the present invention, which should be covered by the protection scope of the present invention.
Claims
1. An X-ray fluorescence analysis method for KR desulfurizer, characterized in that: The following steps are involved: (1) Preparation of standard samples: Place a limestone standard sample in a porcelain crucible and burn it in a muffle furnace at 1050° C. for more than 2 h; Mix the burned limestone with a fluorite standard sample in different mass ratios to prepare at least 5 series of standard samples with a mass of 0.3000 g; Mix the series of standard samples with 6.0000 g of a mixed solvent of lithium tetraborate and lithium metaborate, place them in a yellow-platinum crucible, add 30 mg of a release agent, potassium iodide, and melt them at 980-1000° C. for 150-180 seconds and a tilting time of 500-540 seconds to prepare glass sheets for analysis; (2) Treatment of the sample to be tested: accurately weigh 0.3000 g of the sample to be tested and 6.0000 g of a mixed solvent of lithium tetraborate and lithium metaborate; mix the weighed sample to be tested and the mixed solvent of lithium tetraborate and lithium metaborate evenly, place in a yellow-platinum crucible, add 30 mg of a release agent, potassium iodide, and melt at 980-1000° C. for 150-180 seconds and a tilting time of 500-540 seconds to prepare a glass sheet for analysis; (3) Preparation of standard curve: placing the glass pieces of the series of standard samples obtained in step (1) in an X-ray fluorescence spectrometer for analysis and testing, obtaining the fluorescence intensity of the series of standard samples, and preparing standard curves for each element; (4) Determination of the sample to be tested: The glass piece of the sample to be tested obtained in step (2) is placed in an X-ray fluorescence spectrometer for analysis and testing to obtain the fluorescence intensity of the sample to be tested, which is compared with the standard curve obtained in step (3) to calculate the test result.
2. The X-ray fluorescence analysis method of a KR desulfurizer according to claim 1, characterized in that: The mass ratio of lithium tetraborate to lithium metaborate in the lithium tetraborate and lithium metaborate mixed solvent is 67:
33.
3. The X-ray fluorescence analysis method of a KR desulfurizer according to claim 1, characterized in that: When using an X-ray fluorescence spectrometer for analysis and testing, the corresponding spectral lines of SiO2, TCa, and CaF2 are set to SiKa1,2, CaKa1,2, and FKa1,2 respectively.
4. The X-ray fluorescence analysis method of a KR desulfurizer according to claim 1, characterized in that: When using an X-ray fluorescence spectrometer for analysis and testing, the corresponding crystals of SiO2, TCa, and CaF2 are set to PET, LiF200, and AXO3, respectively.
5. The X-ray fluorescence analysis method of a KR desulfurizer according to claim 1, characterized in that: When using an X-ray fluorescence spectrometer for analysis and testing, the corresponding collimators of SiO2, TCa, and CaF2 are set to 0.15°, 0.40°, and 0.25°, respectively.
6. The X-ray fluorescence analysis method of a KR desulfurizer according to claim 1, characterized in that: When using an X-ray fluorescence spectrometer for analysis and testing, the corresponding peak values of SiO2, TCa, and CaF2 were set to 109.028, 113.086, and 73.441, respectively.
7. The X-ray fluorescence analysis method of a KR desulfurizer according to claim 1, characterized in that: When using an X-ray fluorescence spectrometer for analysis and testing, the corresponding voltages of SiO2, TCa, and CaF2 are set to 30 kV, 50 kV, and 30 kV, respectively.
8. The X-ray fluorescence analysis method of a KR desulfurizer according to claim 1, characterized in that: When using an X-ray fluorescence spectrometer for analysis and testing, the corresponding currents of SiO2, TCa, and CaF2 are set to 80mA, 50mA, and 80mA, respectively.
9. The X-ray fluorescence analysis method of a KR desulfurizer according to claim 1, characterized in that: When using an X-ray fluorescence spectrometer for analysis and testing, the corresponding counting times of SiO2, TCa, and CaF2 are set to 24s, 24s, and 40s, respectively.
10. The X-ray fluorescence analysis method of a KR desulfurizer according to claim 1, characterized in that: When using an X-ray fluorescence spectrometer for analysis and testing, the TL+ equation provided by the OXSAS software is used to perform both spectral line overlap interference correction and matrix effect correction. The correction formula is: Among them C i is the concentration of the element to be measured after correction; α0, α1, α2 are the coefficients of the basic curve; I i is the intensity of the element to be measured; C j is the concentration of matrix interfering elements; C k is the concentration of the spectral interfering element; α 1k is the spectral line interference coefficient; α 2j is the matrix interference coefficient.