CN112858361A - Detection method for measuring slag pressing agent by melting method sample preparation X-ray fluorescence spectrometry - Google Patents
Detection method for measuring slag pressing agent by melting method sample preparation X-ray fluorescence spectrometry Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 54
- 238000001514 detection method Methods 0.000 title claims abstract description 52
- 238000002844 melting Methods 0.000 title claims abstract description 45
- 230000008018 melting Effects 0.000 title claims abstract description 45
- 239000002893 slag Substances 0.000 title claims abstract description 38
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 25
- 238000003825 pressing Methods 0.000 title claims abstract description 25
- 238000004846 x-ray emission Methods 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000012360 testing method Methods 0.000 claims abstract description 34
- 238000004876 x-ray fluorescence Methods 0.000 claims abstract description 18
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 62
- 239000011521 glass Substances 0.000 claims description 50
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 42
- PSHMSSXLYVAENJ-UHFFFAOYSA-N dilithium;[oxido(oxoboranyloxy)boranyl]oxy-oxoboranyloxyborinate Chemical compound [Li+].[Li+].O=BOB([O-])OB([O-])OB=O PSHMSSXLYVAENJ-UHFFFAOYSA-N 0.000 claims description 36
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 32
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 31
- 229910052742 iron Inorganic materials 0.000 claims description 31
- 229910052698 phosphorus Inorganic materials 0.000 claims description 31
- 239000011574 phosphorus Substances 0.000 claims description 31
- 229910052717 sulfur Inorganic materials 0.000 claims description 31
- 239000011593 sulfur Substances 0.000 claims description 31
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 24
- 235000010344 sodium nitrate Nutrition 0.000 claims description 21
- 239000004317 sodium nitrate Substances 0.000 claims description 21
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 20
- 239000010703 silicon Substances 0.000 claims description 20
- 229910052710 silicon Inorganic materials 0.000 claims description 20
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 claims description 18
- 238000012937 correction Methods 0.000 claims description 16
- 239000000377 silicon dioxide Substances 0.000 claims description 16
- 238000005259 measurement Methods 0.000 claims description 10
- 230000001680 brushing effect Effects 0.000 claims description 8
- 239000011159 matrix material Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 230000003647 oxidation Effects 0.000 claims description 8
- 238000007254 oxidation reaction Methods 0.000 claims description 8
- 238000001304 sample melting Methods 0.000 claims description 8
- 238000011088 calibration curve Methods 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 5
- 229910001570 bauxite Inorganic materials 0.000 claims description 4
- 238000007670 refining Methods 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 3
- 239000000156 glass melt Substances 0.000 claims 1
- 238000005070 sampling Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 11
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 abstract description 9
- 229910052500 inorganic mineral Inorganic materials 0.000 abstract description 5
- 239000011707 mineral Substances 0.000 abstract description 5
- 239000006060 molten glass Substances 0.000 abstract description 5
- 229910052697 platinum Inorganic materials 0.000 abstract description 4
- 239000002245 particle Substances 0.000 abstract description 3
- 238000009827 uniform distribution Methods 0.000 abstract description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 6
- 238000011084 recovery Methods 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 3
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- 238000004737 colorimetric analysis Methods 0.000 description 2
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- 238000002474 experimental method Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 2
- 238000009628 steelmaking Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 229910001260 Pt alloy Inorganic materials 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
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- 239000012491 analyte Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000009614 chemical analysis method Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- -1 ferric trioxide Chemical compound 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
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- 238000002156 mixing Methods 0.000 description 1
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- 238000012986 modification Methods 0.000 description 1
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- 239000002994 raw material Substances 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
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Classifications
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
- G01N23/22—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material
- G01N23/223—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material by irradiating the sample with X-rays or gamma-rays and by measuring X-ray fluorescence
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
- G01N23/22—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material
- G01N23/2202—Preparing specimens therefor
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Abstract
The invention relates to a detection method for detecting a slag pressing agent by a melting method sample preparation X-ray fluorescence spectrometry, which comprises the steps of determining a test condition, drawing a standard curve and preparing and detecting a sample. The invention adopts a melting method to prepare samples, and solves the influence of mineral effect and particle effect on the detection result. By selecting proper sample preparation conditions, a molten glass sample with a smooth surface, uniform distribution, compactness and no bubbles is prepared; the problem that the platinum dish is directly contacted with a sample and possibly corroded is solved; the influence of sample splashing on the detection result is solved; the problem that part of elements are likely to volatilize due to high temperature is solved; according to the invention, the molten glass sample is detected by an X-ray fluorescence spectrometer, and the stability and accuracy of the detection result meet the relevant requirements.
Description
Technical Field
The invention relates to the technical field of detection, in particular to a detection method for determining a slag pressing agent by a melting method sample preparation X-ray fluorescence spectrometry.
Background
The slag pressing agent is an important auxiliary material for steelmaking, and the content of silicon dioxide, sulfur, phosphorus, total iron and other components in the slag pressing agent has obvious influence on the ironmaking process, so that the content of silicon dioxide, sulfur, phosphorus and iron needs to be accurately measured, the quality of reaction raw materials can be fairly adjusted, and the steelmaking fine ingredient smelting can be scientifically guided, so that the production cost is controlled. The existing detection method for chemical components of silicon dioxide, sulfur, phosphorus and iron in the slag pressing agent is commonly used for wet chemical analysis detection, wherein the sulfur content is determined by a combustion iodometry method or an infrared absorption spectrometry method, the silicon dioxide is determined by a silicomolybdenum blue colorimetry or a perchloric acid dehydration gravimetric method, the phosphorus is determined by total iron by a potassium dichromate volumetric method, the content of the silicon dioxide, the sulfur, the phosphorus and the total iron in the slag pressing agent is determined by a wet method, only single element determination can be performed, the method is time-consuming and tedious in operation, a large amount of chemical reagents are needed, the environment is polluted by acid gas and waste liquid generated in the detection process, the requirement for batch rapid detection is difficult to meet, and the requirement for green environmental protection of steel enterprises is not met. At present, the content of silicon dioxide, sulfur, phosphorus, total iron and other components in the slag pressing agent is not measured by using an X-ray fluorescence spectrometry method. In addition, the slag pressing agent is measured by adopting the X-ray fluorescence spectrometry, when a sample suitable for X-ray fluorescence spectrometry is prepared, metal iron in the slag pressing agent directly contacts with a platinum dish to corrode the platinum dish, and the analysis result is possibly influenced by a splashing phenomenon due to improper temperature control in the sample preparation process. Therefore, how to overcome various defects of the existing X-ray fluorescence spectrometry is to establish a detection method which is suitable for silicon dioxide, sulfur, phosphorus and iron in the slag pressing agent, and the detection speed is accelerated to become the slag pressing agent.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a detection method for measuring the slag pressing agent by a melting method sample preparation X-ray fluorescence spectrometry, which comprises the steps of adopting a lithium tetraborate bottoming protective crucible, mixing a sample and lithium tetraborate, preparing a glass sheet after sectional calcination and melting in an electric heating melting furnace, and measuring the intensity on an X-ray fluorescence spectrometer; the content of the analyte in the sample was determined from a calibration curve prepared using the standard sample. The operation is convenient and controllable, and the detection efficiency is high.
The technical purpose of the invention is realized by the following technical scheme:
the detection method for measuring the slag pressing agent by using a melting method sample preparation X-ray fluorescence spectrometry comprises the steps of determining a test condition, drawing a standard curve and preparing and detecting a sample;
determining test conditions, respectively selecting standard glass fuse pieces with highest element content of phosphorus, iron, sulfur and silicon, respectively placing the standard glass fuse pieces into an X-ray fluorescence spectrometer, and determining the test conditions of the elements of phosphorus, iron, silicon and sulfur;
drawing a standard curve, taking a plurality of standard samples, preparing each sample according to the following method, laying anhydrous lithium tetraborate on the bottom of a crucible, adding the standard samples and sodium nitrate, stirring with a stirring wire to uniformly mix the anhydrous lithium tetraborate, the sodium nitrate and the standard samples, brushing the stirring wire clean, covering the anhydrous lithium tetraborate on the uniformly mixed standard samples, adding a plurality of drops of lithium bromide solution, covering a crucible cover, placing the crucible in a sample melting furnace for pre-oxidation and melting treatment, after the melting time is over, after the crucible is naturally cooled, the molten liquid forms a glass fuse piece in the crucible, the glass fuse piece is poured out from the crucible, after the glass fuse piece is cooled to the room temperature, measuring the prepared glass fuse piece of the standard sample on an X-ray fluorescence instrument under the determined test conditions to obtain the detection results of the elements of silicon, iron, sulfur and phosphorus in the standard sample, and establishing a standard curve according to the detection results;
preparing and detecting a sample, paving anhydrous lithium tetraborate at the bottom of a crucible, adding the sample and sodium nitrate, stirring with a stirring wire to uniformly mix the anhydrous lithium tetraborate, the sodium nitrate and the sample, brushing the stirring wire clean, covering the uniformly mixed sample with the anhydrous lithium tetraborate, adding a plurality of drops of lithium bromide solution, covering a crucible cover, placing the crucible in a sample melting furnace for pre-oxidation and melting treatment, naturally cooling the crucible after the melting time is over, forming a glass fuse piece in the crucible by the molten liquid, pouring the glass fuse piece out of the crucible, measuring the glass fuse piece of the prepared sample on an X-ray fluorescence instrument under the determined test conditions after the glass fuse piece is cooled to room temperature to obtain the detection results of silicon, iron, sulfur and phosphorus elements in the sample, and comparing the detection results with a standard curve to determine the content of the silicon, iron, sulfur and phosphorus elements in the sample.
In one embodiment, in the step of determining the test conditions, the test conditions are voltage, current, spectroscopic crystal, filter, 2 θ angle, and measurement time.
In one embodiment, in the step of determining the test condition, the measurement time is set to 20s to ensure the count rate and detection limit of each element.
In one embodiment, the standard samples include blast furnace slag, refining slag, silica, converter slag, and bauxite.
In one embodiment, in the step of drawing the standard curve, an empirical coefficient method and a theoretical alpha coefficient method are used for matrix correction and spectral line superposition interference correction on the standard curve, and although the sample by a melting method can eliminate the granularity and the mineral effect of the sample, the matrix effect correction is still needed due to the inconsistent content of the components in the calibration sample.
In one embodiment, in the steps of drawing the standard curve and preparing and detecting the sample, the melting conditions are that the melting time is 20-30min and the temperature is 1100-1200 ℃.
In one embodiment, in the step of drawing the standard curve, the standard sample is burned in sections and then melted, bubbles are removed manually in the melting process, and a glass fuse piece of the standard sample is prepared, so that the influence of the splashing of the standard sample on the detection result is solved; the problem that part of elements are likely to volatilize due to high temperature is solved, and the glass fuse piece of the prepared standard sample is flat in surface, uniform in distribution, compact and free of bubbles.
In one embodiment, in the step of preparing and detecting the sample, the sample is burned in sections and then melted, bubbles are removed manually in the melting process, and a glass fuse piece of the sample is prepared, so that the influence of sample splashing on the detection result is avoided; the problem that part of elements are likely to volatilize due to high temperature is solved, and the prepared glass fuse piece of the sample is flat in surface, uniform in distribution, compact and free of bubbles.
In one embodiment, in the steps of drawing the standard curve and preparing and testing the sample, the mass of anhydrous lithium tetraborate is taken for the first time and is 1.5000-2.5000g, the mass of the standard sample or the sample is 0.1500-0.2500g, the mass of sodium nitrate is 0.4500-0.5500g, and the mass of anhydrous lithium tetraborate is taken for the second time and is 4.5000-5.5000 g.
In one embodiment, in the steps of drawing the standard curve and preparing and detecting the sample, the mass ratio of the anhydrous lithium tetraborate taken for the first time, the standard sample or sample, the sodium nitrate and the anhydrous lithium tetraborate taken for the second time is 20:2:5: 50.
The invention has the following beneficial effects:
the invention adopts a melting method to prepare samples, and solves the influence of mineral effect and particle effect on the detection result. By selecting proper sample preparation conditions, a molten glass sample with a smooth surface, uniform distribution, compactness and no bubbles is prepared; the problem that the platinum dish is directly contacted with a sample and possibly corroded is solved; the influence of sample splashing on the detection result is solved; the problem that part of elements are likely to volatilize due to high temperature is solved; according to the invention, the molten glass sample is detected by an X-ray fluorescence spectrometer, and the stability and accuracy of the detection result meet the relevant requirements.
Detailed Description
The present invention will be described in detail with reference to examples.
The contents of silica, sulfur, phosphorus and iron in the slag pressing agent are shown in table 1.
TABLE 1 physicochemical indices of silica, Sulfur, phosphorus, and iron in the slag depressants
| Name (R) | SiO2 | TFe | P | S | H2O |
| Slag pressing agent | ≥35 | ≥10 | ≤0.2 | ≤1.2 | ≤3 |
The detection method for detecting the slag pressing agent by using a melting method sample preparation X-ray fluorescence spectrometry comprises the steps of determining a test condition, drawing a standard curve, preparing and detecting a sample,
determining test conditions, respectively selecting standard glass fuse pieces with highest element content of phosphorus, iron, sulfur and silicon, respectively placing the standard glass fuse pieces into an X-ray fluorescence spectrometer, and determining the test conditions of the elements of phosphorus, iron, silicon and sulfur;
drawing a standard curve, taking a plurality of standard samples, preparing each sample according to the following method, laying anhydrous lithium tetraborate on the bottom of a crucible, adding the standard samples and sodium nitrate, stirring with a stirring wire to uniformly mix the anhydrous lithium tetraborate, the sodium nitrate and the standard samples, brushing the stirring wire clean, covering the anhydrous lithium tetraborate on the uniformly mixed standard samples, adding a plurality of drops of lithium bromide solution, covering a crucible cover, placing the crucible in a sample melting furnace for pre-oxidation and melting treatment, after the melting time is over, after the crucible is naturally cooled, the molten liquid forms a glass fuse piece in the crucible, the glass fuse piece is poured out from the crucible, after the glass fuse piece is cooled to the room temperature, measuring the prepared glass fuse piece of the standard sample on an X-ray fluorescence instrument under the determined test conditions to obtain the detection results of the elements of silicon, iron, sulfur and phosphorus in the standard sample, and establishing a standard curve according to the detection results;
preparing and detecting a sample, paving anhydrous lithium tetraborate at the bottom of a crucible, adding the sample and sodium nitrate, stirring with a stirring wire to uniformly mix the anhydrous lithium tetraborate, the sodium nitrate and the sample, brushing the stirring wire clean, covering the uniformly mixed sample with the anhydrous lithium tetraborate, adding a plurality of drops of lithium bromide solution, covering a crucible cover, placing the crucible in a sample melting furnace for pre-oxidation and melting treatment, naturally cooling the crucible after the melting time is over, forming a glass fuse piece in the crucible by the molten liquid, pouring the glass fuse piece out of the crucible, measuring the glass fuse piece of the prepared sample on an X-ray fluorescence instrument under the determined test conditions after the glass fuse piece is cooled to room temperature to obtain the detection results of silicon, iron, sulfur and phosphorus elements in the sample, and comparing the detection results with a standard curve to determine the content of the silicon, iron, sulfur and phosphorus elements in the sample.
In the present embodiment, in the step of determining the test conditions, the test conditions are a voltage, a current, a spectroscopic crystal, a filter, a 2 θ angle, and a measurement time, wherein the measurement time is set to 20s to secure a count rate and a detection limit of each element.
In the embodiment, the standard samples comprise a series of standard samples containing silicon dioxide, sulfur, iron and phosphorus in a gradient manner, such as blast furnace slag, refining slag, silica, converter slag and bauxite, and the problem of no standard sample of the existing slag pressing agent is solved.
In one embodiment, in the steps of preparing the standard curve and preparing and detecting the sample, the melting conditions are a melting time of 20-30min, such as 25min, a temperature of 1100-.
In combination with the above, in the present embodiment,
determining test conditions, respectively selecting standard glass fuse pieces with highest element content of phosphorus, iron, sulfur and silicon, respectively placing the standard glass fuse pieces into an X-ray fluorescence spectrometer, and determining the test conditions of the elements of phosphorus, iron, silicon and sulfur;
drawing a standard curve, taking a plurality of standard samples, preparing each sample according to the following method, paving 2.0000g of anhydrous lithium tetraborate at the bottom of a crucible, adding 0.2000g of standard sample and 0.5000g of sodium nitrate, stirring with a stirring wire to uniformly mix the anhydrous lithium tetraborate, the sodium nitrate and the standard sample, brushing the stirring wire, covering 5.0000g of anhydrous lithium tetraborate on the uniformly mixed standard sample, adding a plurality of drops of lithium bromide solution, covering a crucible cover, placing the crucible in a melting furnace for pre-oxidation and melting treatment, wherein the melting time is 25min, the temperature is 1150 ℃, after the melting time is over, naturally cooling the crucible, forming a glass fuse piece in the crucible, pouring the glass fuse piece out of the crucible, measuring the glass fuse piece of the prepared standard sample on an X-ray fluorescence instrument under the determined test condition to obtain silicon in the standard sample, measuring the glass fuse piece of the standard sample on the X-ray fluorescence instrument, and measuring the glass fuse piece of the standard sample by using the test condition, Detecting the iron, sulfur and phosphorus elements, and establishing a standard curve according to the detection result;
preparing and detecting a sample, paving 2.0000g of anhydrous lithium tetraborate at the bottom of a crucible, adding 0.2000g of the sample and 0.5000g of sodium nitrate, stirring with a stirring wire to uniformly mix the anhydrous lithium tetraborate, the sodium nitrate and the sample, brushing the stirring wire, covering 5.0000g of the anhydrous lithium tetraborate on the uniformly mixed sample, adding 2 drops of a lithium bromide solution, covering a crucible cover, placing the crucible in a sample melting furnace for pre-oxidation and melting treatment, wherein the melting time is 25min, the temperature is 1150 ℃, after the melting time is finished, naturally cooling the crucible to form a glass fuse piece in the crucible, pouring the glass fuse piece out of the crucible, measuring the glass fuse piece of the prepared sample on an X-ray fluorescence instrument under the determined test conditions after the glass fuse piece is cooled to the room temperature to obtain the detection results of silicon, iron, sulfur and phosphorus elements in the sample, and comparing the detection results with a standard curve, and determining the contents of silicon, iron, sulfur and phosphorus elements in the sample.
In the embodiment, in the step of drawing the standard curve, an empirical coefficient method and a theoretical alpha coefficient method are adopted to perform matrix correction and spectral line superposition interference correction on the standard curve, although the sample prepared by a melting method can eliminate the granularity and the mineral effect of the sample, the matrix effect correction is still required due to the inconsistent content of components in the calibration sample, and the specific correction steps are as follows, Super Q software carried by the instrument is utilized to perform matrix correction and spectral line superposition interference correction on the curve. The relevant parameters of the calibration curve are shown in the table 2 and the table 3. It can be seen from table 2 that the RMS (mean square root deviation) of each element of the correction is small. The K value range satisfies that the K value of the metal product is between 0.01 and 0.10, and the K value of the oxide is between 0.02 and 0.07. The method establishment requirements are met.
TABLE 2 regression equations and ranges for calibration curves
The formula for calculating the detection limit is,
in the formula: m is the count rate per unit content, kcps/%; i isbBackground count rate, kcps; t is tbTime was measured for background.
TABLE 3 Curve correction coefficients
Wherein,
wherein the RMS value is the root mean square deviation; ccalcIs the calculated value of the calibration curve,%; cchemIs the standard value of the standard sample,%; c0Is a weight factor; k is a quality factor, and n is the number of standard samples participating in calculation; k is the regression curve calculation coefficient.
The formula used for the correction of the matrix effect is,
in the formula, CiAnalyzing the content of the element i in an unknown sample; diCalibrating the intercept of the curve for analysis element i; l isijA line overlap interference correction factor for interference element k to analysis element i; zkIs the content or count rate of the interfering element k; eiCalibrating the slope of the curve for analysis element i; riTo analyze the count rate of element i; n is the number of coexistence elements j; alpha is alphaijA matrix correction factor; i. j and k are respectively an analysis element, a coexistence element and an interference element; zj is the content of the coexisting element j.
A wet-process-valued slag pressing agent sample is selected, 11 glass melting sheets are prepared according to the method of the invention under the same condition, measurement is carried out on X-ray fluorescence, the coefficient of variation is calculated, and the result is shown in Table 5.
TABLE 5 precision test results (n-11)
As can be seen from Table 5: the laboratory coefficient of variation CV of the method meets the requirement of table F.2 in GB/T27404-2008, see table 6.
TABLE 6 GB/T27404-2008 TABLE F.2 in-laboratory coefficient of variation
| Content of the measured component | Coefficient of Variation (CV)/% in laboratory |
| 0.1g/kg | 43 |
| 1.0g/kg | 30 |
| 10g/kg | 21 |
| 100g/kg | 15 |
| 1mg/kg | 11 |
| 10mg/kg(0.001％) | 7.5 |
| 100mg/kg(0.01％) | 5.3 |
| 1000mg/kg(0.1％) | 3.8 |
| 1％ | 2.7 |
| 10％ | 2.0 |
| 100％ | 1.3 |
Five samples of the slag pressing agent are randomly extracted and detected by the method of the invention, and are compared with the chemical analysis method and the ICP-AES (inductively coupled plasma-atomic emission Spectrometry) measurement, and the results are shown in Table 7.
TABLE 7 accuracy data
As can be seen from Table 7: the comparison result shows that the detection result of the detection method has better consistency with the detection result of the wet method.
A sample is selected, YSBC13840-96 converter slag standard samples with different contents are respectively added, a recovery rate experiment is carried out, the experimental result is shown in table 8, and the recovery rate of the method can meet the requirement of the recovery rate required by table F.1 in GB/T27404-2008 is shown in table 9.
TABLE 8 recovery test (%)
Table 9 GB/T27404-2008 Table F.1 requires the requirement for recovery
| Content of the component to be measured (mg/kg) | Extent of recovery% |
| ＞100 | 95-105 |
| 1-100 | 90-110 |
| 0.1-1 | 80-110 |
| ＜0.1 | 60-120 |
The main instruments and parameters used in the present invention,
an Axios type X-ray fluorescence spectrometer (4 kW, end window, rhodium target X-ray tube, manufactured by Pasacaceae, the Netherlands), an RYL-05 type automatic sample melting furnace (Luoyang spectrum Ruoka equipment, Inc.), a platinum alloy crucible (Pt 95% -Au 5%), and measurement conditions of each element, which are shown in Table 10.
TABLE 10 conditions of instrumental measurements
The main reagents of the invention, anhydrous lithium tetraborate (solid), sodium nitrate (solid), lithium bromide (1000 g/L). The reagents used are analytically pure if not noted, and the experimental water meets the third-grade water specified in GB/T6682. The standard samples used in the tests are shown in Table 11.
TABLE 11 Standard samples for the experiments
The technical scheme of the invention has reasonable process, safety, reliability, easy implementation, practicability and high efficiency, and concretely comprises the following steps,
the method uses national standard samples such as blast furnace slag, refining slag, silica, converter slag, bauxite and the like, prepares a series of standard samples and wet-method fixed-value samples, and solves the problem that no standard sample of the existing slag pressing agent exists.
The method uses the lithium tetraborate substrate for protection, and reduces the problem that the crucible is in direct contact with the sample and can be corroded.
The glass fuse piece is prepared by adding a crucible cover, burning a sample in a segmented mode, melting and manually removing bubbles in the melting process, and the problem that the detection result is influenced by sample splashing is solved; the problem that part of elements are likely to volatilize due to high temperature is solved. The prepared molten glass sample has smooth surface, uniform distribution, compactness and no bubbles.
And a melting method is adopted for sample preparation, so that the influence of mineral effect and particle effect on a detection result is solved.
The variety and the dosage of the reagent are reduced, so that the occupational health adverse factors can be reduced; the sample is a solid glass fuse after being processed, is easy to recycle and can reduce the harm to the environment.
Compared with the existing gravimetric method, colorimetric method and ICP-AES method, the X-ray fluorescence spectrometry method can be used for detecting the target in batches quickly, and has the advantages of high accuracy of detection results, high efficiency and short period.
The skill requirement on operators can be reduced, and the standard operation level of detection operation can be improved.
The X-ray fluorescence spectrometry is adopted for detection, so that the detection level of instrumentation, automation and intelligence can be improved.
The universality is high, and the detection method has certain reference significance for detecting components such as silicon dioxide, sulfur, ferric trioxide, phosphorus and the like in other refractory materials.
The above description is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above embodiments, and all technical solutions belonging to the idea of the present invention belong to the protection scope of the present invention. It should be noted that modifications and embellishments within the scope of the invention may occur to those skilled in the art without departing from the principle of the invention, and are considered to be within the scope of the invention.
Claims (10)
1. The detection method for measuring the slag pressing agent by using the melting method sample preparation X-ray fluorescence spectrometry is characterized by comprising the steps of determining a test condition, drawing a standard curve, preparing and detecting a sample,
determining test conditions, respectively selecting standard glass fuse pieces with highest element content of phosphorus, iron, sulfur and silicon, respectively placing the standard glass fuse pieces into an X-ray fluorescence spectrometer, and determining the test conditions of the elements of phosphorus, iron, silicon and sulfur;
drawing a standard curve, taking a plurality of standard samples, preparing each sample according to the following method, laying anhydrous lithium tetraborate on the bottom of a crucible, adding the standard samples and sodium nitrate, stirring with a stirring wire to uniformly mix the anhydrous lithium tetraborate, the sodium nitrate and the standard samples, brushing the stirring wire clean, covering the anhydrous lithium tetraborate on the uniformly mixed standard samples, adding a plurality of drops of lithium bromide solution, covering a crucible cover, placing the crucible in a sample melting furnace for pre-oxidation and melting treatment, after the melting time is over, after the crucible is naturally cooled, the molten liquid forms a glass fuse piece in the crucible, the glass fuse piece is poured out from the crucible, after the glass fuse piece is cooled to the room temperature, measuring the prepared glass fuse piece of the standard sample on an X-ray fluorescence instrument under the determined test conditions to obtain the detection results of the elements of silicon, iron, sulfur and phosphorus in the standard sample, and establishing a standard curve according to the detection results;
preparing and detecting a sample, paving anhydrous lithium tetraborate at the bottom of a crucible, adding the sample and sodium nitrate, stirring with a stirring wire to uniformly mix the anhydrous lithium tetraborate, the sodium nitrate and the sample, brushing the stirring wire clean, covering the uniformly mixed sample with the anhydrous lithium tetraborate, adding a plurality of drops of lithium bromide solution, covering a crucible cover, placing the crucible in a sample melting furnace for pre-oxidation and melting treatment, naturally cooling the crucible after the melting time is over, forming a glass fuse piece in the crucible by the molten liquid, pouring the glass fuse piece out of the crucible, measuring the glass fuse piece of the prepared sample on an X-ray fluorescence instrument under the determined test conditions after the glass fuse piece is cooled to room temperature to obtain the detection results of silicon, iron, sulfur and phosphorus elements in the sample, and comparing the detection results with a standard curve to determine the content of the silicon, iron, sulfur and phosphorus elements in the sample.
2. The method of claim 1, wherein in the step of determining the test conditions, the test conditions are voltage, current, spectroscopic crystal, filter, 2 θ angle, and measurement time.
3. The method of claim 2, wherein the measurement time is set to 20s in the step of determining the test condition.
4. The method of claim 1, wherein the standard samples comprise blast furnace slag, refining slag, silica, converter slag, and bauxite.
5. The method for detecting a slag pressing agent by fusion-sampling X-ray fluorescence spectrometry according to claim 4, wherein in the step of drawing a standard curve, a matrix correction and a line overlap interference correction are performed on the standard curve by an empirical coefficient method and a theoretical alpha coefficient method.
6. The method as claimed in claim 1, wherein the melting conditions in the steps of drawing the calibration curve and preparing and detecting the sample include a melting time of 20-30min and a temperature of 1100 ℃ to 1200 ℃.
7. The method for detecting slag pressing agent according to claim 1, wherein in the step of drawing the standard curve, the standard sample is burned in stages and melted, and bubbles are manually removed during melting to obtain the glass fuse piece of the standard sample.
8. The method of claim 7, wherein the step of preparing and detecting the sample comprises burning the sample in stages, melting, and manually removing bubbles during melting to obtain the glass melt sheet.
9. The method of claim 1, wherein in the steps of drawing a calibration curve and preparing and testing a sample, the mass of the anhydrous lithium tetraborate is 1.5000-2.5000g for the first time, the mass of the standard sample or the sample is 0.1500-0.2500g, the mass of the sodium nitrate is 0.4500-0.5500g, and the mass of the anhydrous lithium tetraborate is 4.5000-5.5000g for the second time.
10. The method of claim 9, wherein the step of drawing a calibration curve and preparing and detecting a sample comprises the step of taking anhydrous lithium tetraborate, the calibration sample or sample, the sodium nitrate, and the second step of taking anhydrous lithium tetraborate at a mass ratio of 20:2:5: 50.
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