CN112649455A - Fluorescence detection method for steel plant - Google Patents
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- 238000000034 method Methods 0.000 title claims abstract description 32
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 25
- 239000010959 steel Substances 0.000 title claims abstract description 25
- 238000001917 fluorescence detection Methods 0.000 title claims abstract description 24
- 239000000243 solution Substances 0.000 claims abstract description 62
- 230000004907 flux Effects 0.000 claims abstract description 44
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
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- 238000011088 calibration curve Methods 0.000 claims abstract description 9
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- 238000012921 fluorescence analysis Methods 0.000 claims abstract description 8
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- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 claims description 8
- 238000001304 sample melting Methods 0.000 claims description 7
- 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 6
- HZRMTWQRDMYLNW-UHFFFAOYSA-N lithium metaborate Chemical compound [Li+].[O-]B=O HZRMTWQRDMYLNW-UHFFFAOYSA-N 0.000 claims description 6
- 238000002844 melting Methods 0.000 claims description 6
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- 238000004448 titration Methods 0.000 description 31
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- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
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- VYTBPJNGNGMRFH-UHFFFAOYSA-N acetic acid;azane Chemical compound N.N.CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O VYTBPJNGNGMRFH-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
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- HXOLFXRMWWHLMH-UHFFFAOYSA-L disodium boric acid carbonate Chemical compound [Na+].[Na+].OB(O)O.[O-]C([O-])=O HXOLFXRMWWHLMH-UHFFFAOYSA-L 0.000 description 1
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Images
Classifications
-
- 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
Abstract
The invention discloses a fluorescence detection method for a steel plant, which comprises the following steps: weighing a mixed flux and a sample and placing the mixed flux and the sample in a reaction unit; uniformly mixing the mixed flux and the sample to form a mixed flux; dropwise adding a solution into the mixture, wherein the solution and the mixture are placed in a reaction furnace to be melted to form a mixed solution; and detecting the mixed solution by adopting fluorescence analysis equipment, and establishing a calibration curve of the element content and the corrected fluorescence intensity value. The production efficiency can be improved, the inspection time is shortened, the labor cost is reduced, and the labor intensity is reduced.
Description
Technical Field
The invention relates to the technical field of metallurgical analysis, in particular to a fluorescence detection method for a steel plant.
Background
The silicon-magnesium-carbon balls are used as newly purchased materials in a steel plant, and the magnesium-carbon balls have the functions of slag discharge, slag composition adjustment, alkalinity, viscosity and reaction capacity in iron-making and steel-making smelting processes in the plant. The purpose is to produce metal with the required composition and temperature by reacting slag with metal.
About 4 hours is needed for testing a sample, for large-scale test in steel plants, the test quantity of the magnesium-carbon balls is about 20 batches per day, the defects of low efficiency, long time, multiple occupied times and high labor intensity of workers exist in actual test operation, and the rhythm of the conventional test task is also severely restricted and influenced.
It is known that the relevant laboratory test unit uses a new technology of fluorescence analysis after melting at high temperature for magnesium-carbon spheres, but in a specific operation, the magnesium oxide test needs to obtain the calculation result of ignition reduction, and then the fluorescence data is calibrated. The time of about 3 hours is needed, and meanwhile, the influence of the environmental humidity is large during the detection, so that the detection error is easily caused, the calibration coefficient during the fluorescent detection is influenced, and the accuracy of the magnesium-carbon-ball magnesium oxide is reduced.
Disclosure of Invention
The invention aims to provide a fluorescence detection method for a steel plant, which can improve the detection efficiency, shorten the detection time and reduce the labor cost.
In order to solve the technical problems, the invention is realized by the following technical scheme: weighing a mixed flux and a sample and placing the mixed flux and the sample in a reaction unit; uniformly mixing the mixed flux and the sample to form a mixed flux;
dropwise adding a solution into the mixture, wherein the solution and the mixture are placed in a reaction furnace to be melted to form a mixed solution; and detecting and analyzing the mixed solution by adopting a fluorescence analysis device.
In one embodiment, the mixed flux includes lithium metaborate and lithium tetraborate.
In one embodiment, the lithium metaborate is present in an amount of 60-70% of the mixed flux.
In one embodiment, the lithium tetraborate comprises 20-40% of the mixed flux.
In one embodiment, the mixed flux may weigh between 5 and 10 grams.
In one embodiment, the sample comprises a series of magnesium carbon spheres, which may have a gram number of 0.5 to 0.7 grams, placed in a reaction cell.
In one embodiment, the reaction unit includes a crucible for melting the mixed flux and the sample.
In one embodiment, the reaction unit places the mixing agent.
In one embodiment, the reaction furnace comprises a sample melting furnace, the reaction time of the reaction furnace is 15-18min, and the temperature of the reaction furnace is set to be 500-.
In one embodiment, the solution comprises ammonium bromide solution, the ammonium bromide solution is 15-25% and the volume of the ammonium bromide solution is 0.5-0.7 ml.
The invention provides a fluorescence detection method for a steel plant and a method thereof, comprising the steps of weighing a mixed flux and a sample, and placing the mixed flux and the sample in a reaction unit; uniformly mixing the mixed flux and the sample to form a mixed flux; dropwise adding a solution into the mixture, wherein the solution and the mixture are placed in a reaction furnace to be melted to form a mixed solution; and detecting and analyzing the mixed solution by adopting a fluorescence analysis device. The production efficiency can be improved, the inspection time is shortened, the labor cost is reduced, and the labor intensity is reduced.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a schematic flow chart of a fluorescence detection method for steel plants according to the present invention.
FIG. 2 is a graph showing the working curve of magnesium oxide in the fluorescence detection method for steel plants according to the present invention.
FIG. 3 is a silica working curve diagram of the fluorescence detection method for steel plants of the present invention.
FIG. 4 is a PHA map of magnesium oxide in a fluorescence detection method for steel plants according to the present invention.
FIG. 5 is a PHA map of silica in accordance with the fluorescence detection method for steel plants of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It should be noted that the drawings provided in the following embodiments are only for illustrating the basic idea of the present invention, and the components related to the present invention are only shown in the drawings rather than drawn according to the number, shape and size of the components in actual implementation, and the type, quantity and proportion of the components in actual implementation may be changed freely, and the layout of the components may be more complicated.
According to an embodiment of the invention, a fluorescence detection method for steel factories is provided, which at least comprises the following steps: weighing a mixed flux and a sample and placing the mixed flux and the sample in a reaction unit; uniformly mixing the mixed flux and the sample to form a mixed flux; dropwise adding a solution into the mixture, wherein the solution and the mixture are placed in a reaction furnace to be melted to form a mixed solution; and detecting and analyzing the mixed solution by adopting a fluorescence analysis device.
S1: and weighing the mixed flux and the magnesium-carbon spheres, placing the weighed mixed flux and the magnesium-carbon spheres in a reaction unit, and preparing a standard sample wafer.
Weighing part of the calibration sample by weight, setting the temperature of the muffle furnace to be 170-180 ℃, for example, drying the calibration sample in the muffle furnace to constant weight, cooling the calibration sample to room temperature, and placing the calibration sample in a dryer for later use. About 5 g of the sample was taken during compression, and the sample was placed in a die of a tablet press, and boric acid was placed around the die to perform compression.
S2: and uniformly mixing the mixed flux and the sample to form a mixture, and establishing a calibration curve of the element content and the corrected fluorescence intensity value.
The mixed flux in the present invention may be, for example, lithium metaborate and lithium tetraborate, the content of lithium metaborate in the present invention may be, for example, 60 to 70% of the mixed flux, and the content of lithium tetraborate in the present invention may be, for example, 20 to 40% of the mixed flux. Preparing calibration samples for establishing a calibration curve, wherein the calibration samples respectively comprise elements with different types and different contents; wherein the element is one or two of calcium and silicon;
s3: and dropwise adding a solution into the mixture, wherein the solution and the mixture are placed in a reaction furnace to be melted to form a mixed solution. The solution comprises an ammonium bromide solution, which in the present invention may be present in an amount of, for example, 15-25%, and the volume of the ammonium bromide solution in the present invention may be, for example, 0.5-0.7 ml. The addition amount of the release agent is in a required range, and when the addition amount of the release agent is 0.7ml in the test process, the calcium oxide is lower than a standard value of 0.09-0.21%; when the addition amount of the release agent is 0.4ml, the calcium oxide is higher than the standard value by 0.12-0.29%. The reaction furnace in the present invention may be, for example, a sample melting furnace, the reaction time of the reaction furnace in the present invention may be, for example, 15 to 18min, and the temperature of the reaction furnace in the present invention may be, for example, set to 500-. The sample melting furnace has a swinging function. The temperature of the sample melting furnace cannot be lower than 970 ℃ after the furnace cover is opened and the crucible is placed, so that the phenomenon that the temperature is too much reduced to cause the lengthening of the temperature rise time and the inconsistency of the melting time is avoided. In the test process of the method, when the temperature of the sample melting furnace is reduced to 950 ℃, the early-stage heating time is prolonged by about 1min, and the calcium oxide is lower than the standard value by 0.08-0.19%. And in the test process of the method, when the crucible is taken out after 90 seconds after the end of the sample melting furnace, bubbles exist at the bottom of the sample wafer after the sample wafer is molded and cooled, and the crucible cannot be used.
S4: and detecting the mixed solution by adopting a fluorescence analysis device.
Firstly, setting analysis conditions;
in the present invention, first, a curve is selected, and in the present invention, the curve may be, for example, a KA curve. Respectively measuring the fluorescence intensity values of calcium and silicon elements in the prepared calibration sample wafer by using an X-ray fluorescence spectrometer, correcting the elements by using a theoretical alpha coefficient, and establishing a calibration curve of the element content and the corrected fluorescence intensity value; obtaining the slope and intercept of the calibration curve; an angle is defined, which in the present invention may include, for example, 20-30. Setting a background, the background can include 1.5-3 in the invention, setting a power parameter, the power parameter can include time and wattage in the invention, the power time can be 45-60kW in the invention, the power wattage can be 55-75mA in the invention, fixing the analysis time, the analysis time can be 15-30 seconds in the invention.
Referring to fig. 1 and 5, the chemical value of the mg-c sphere is calibrated by at least two consecutive measurements, the sample wafer to be tested is analyzed by an X-ray fluorescence spectrometer to obtain fluorescence intensity values after correction of mg and si elements, and a standard curve is drawn, wherein a working curve (y: 1.7307X-10.2671) of the magnesium oxide and a correlation coefficient 0.995901 are obtained. Silica working curve (y-0.32303 x-90.94948), correlation coefficient 0.997711.
And quickly weighing the sample to be accurate to 0.0001 go to the metallurgical lime sample. A blank test was carried out with the sample. And (3) transferring the silicon dioxide standard solution into a group of volumetric flasks filled with hydrochloric acid in advance, adding absolute ethyl alcohol, diluting with water to a certain volume, mixing the solution uniformly, and measuring the absorbance by taking a reagent blank as a reference. And drawing a standard curve by taking the silica as an abscissa and the absorbance as an ordinate.
Finally, the results were analyzed and the precision was checked.
In formula (1):
ω(SiO2) -mass fraction of silica;
v-volume of stock solution in ml;
V1-dividing the volume of the stock solution in milliliters;
m1-the amount of silica, in micrograms, found on a standard curve;
m is the amount of sample in grams.
And (3) calculating the absolute value of the difference value of the two independent analysis results of the consent sample according to the formula (1), and taking the arithmetic mean value as the analysis result if the absolute value is not more than the repeatability limit r value.
Referring to fig. 1, in an embodiment of the present invention, the sample may also be leached with a sodium carbonate-boric acid mixed flux and diluted hydrochloric acid. Taking part of the test solution, masking iron, aluminum and pickaxe plasma by triethanolamine, taking calcium liquid acid as an indicator in a strong alkali medium, and titrating the calcium oxide amount by using ethylene diamine tetraacetic acid or ethylene glycol diethylacetamide tetraacetic acid standard titration solution. For high-magnesium samples, ethylene diamine tetraacetic acid or ethylene glycol diethyl wake-up diamine tetraacetic acid standard titration solution is preset before the test solution is adjusted to be alkaline, and the content range of the ethylene diamine tetraacetic acid in the invention is 90-95% so as to eliminate the influence of a large amount of magnesium. Taking another part of the test solution, wherein the part of the test solution can comprise triethanolamine to mask iron, aluminum, plasma and the like in the invention, dissolving the part of the test solution in an ammonia buffer solution, setting the pH value of the ammonia buffer solution to be 10 in the invention, wherein the mixed indicator comprises acid Naphthalein K and rabucinol green B, titrating the amount of calcium oxide and magnesium oxide by using a standard titration solution of ethylenediamine tetraacetic acid, or masking calcium by using a slightly excessive standard titration solution of ethylene glycol diethylstilbazamide tetraacetic acid, and titrating the amount of magnesium oxide by using the standard titration solution of cyclohexanediamine tetraacetic acid.
Referring to fig. 1, in the embodiment of the present invention, the sample further includes iron oxide and aluminum oxide, wherein the content of iron oxide and aluminum oxide is greater than 2.0% or the content of ingot oxide is greater than 0.10%, sodium diethyldithiocarbamate is used to precipitate and separate iron, aluminum, manganese and the like, the separated filtrate is titrated with ethylene glycol diethyldiaminotetraacetic acid and cyclohexanediaminetetraacetic acid standard titration solution to titrate the content of calcium oxide and the content of magnesium oxide.
Referring to fig. 1, in an embodiment of the present invention, a sample is placed in a whole range of a pincers containing a mixed flux in advance, mixed, and covered with the mixed flux. And (3) placing the clamp increasing snail temperature in a high-temperature furnace at the furnace temperature, covering a clamp cover, leaving a gap, gradually raising the furnace temperature to 950-1000, melting for 10min, taking out the clamp increasing snail, rotating the clamp collapse into the whole boundless, and cooling the clamp increasing snail.
Referring to fig. 1, in an embodiment of the invention, the whole boundless outer wall of the aluminum is washed with water, the whole boundless tong is covered in a beaker, hydrochloric acid is added, the frit is leached by low-temperature heating, and the whole boundless outer wall is washed out with water. Heating at low temperature until the test solution is clear, and cooling to room temperature. Transferring the test solution into a volumetric flask, diluting the test solution to a scale with water, and uniformly mixing the flux.
Referring to fig. 1, in an embodiment of the present invention, the test solution can be used as stock solutions for measuring the amounts of calcium oxide, magnesium oxide, silicon dioxide, aluminum oxide and iron oxide, and can be used for performing a complex titration method to measure the amounts of calcium oxide and magnesium oxide, a silicon-aluminum blue spectrophotometry method to measure the amount of silicon dioxide, a Mingqing S spectrophotometry method to measure the amount of aluminum oxide, and a phenanthroline spectrophotometry method to measure the amount of iron oxide, respectively. If the contents of these chemical components in a sample are simultaneously measured, only one stock solution of the sample may be prepared and separated and then measured according to each analysis method.
Referring to fig. 1, in one embodiment of the present invention, two portions of the stock solution are separately placed in a conical flask, and a certain ml of water is added to determine the amount of calcium oxide and the amount of magnesium oxide.
Further, when the content of alumina and iron oxide in the sample is more than 2.0% or the content of the oxidized pickaxe is more than 0.10%, separating the sample by adopting a copper reagent: dividing a sample, putting the stock solution into a volumetric flask, adding water, putting a small piece of Congo red test paper into the solution, neutralizing most of acid with a potassium hydroxide solution, washing the bottleneck with water, dropwise adding ammonia water for neutralization until the test paper is just red, adding a copper reagent solution, violently shaking, cooling to room temperature, diluting to a scale with water, uniformly mixing the solvent, standing for a period of time, carrying out dry filtration with medium-speed quantitative filter paper, and discarding the initial filtrate. Two portions of the filtrate were removed and placed in conical flasks, respectively, and the amounts of calcium oxide and magnesium oxide were measured by the following methods. Adding triethanolamine into one part of test solution, mixing the solution uniformly, adding an ethylenediaminetetraacetic acid standard titration solution which is equivalent to 90-95% of calcium oxide in the titration solution, adding a potassium hydroxide solution and about 0.1g of a calcium indicator, and mixing the solution uniformly. And continuously titrating with an ethylene diamine tetraacetic acid standard titration solution until the test solution is changed from red to bright blue. And adding a magnesium oxide standard solution before titration in a blank test, and not presetting a titrant.
Referring to fig. 1, in one embodiment of the present invention, to determine the preset titrant amount, a pre-titration may be performed first. A portion of the test solution is titrated according to the titration method, and the pre-titration volume is determined. Pre-adding a titrant with a certain volume less than the pre-titration volume at the titration time.
Referring to fig. 1, in one embodiment of the present invention, triethanolamine is added to another sample solution, the solution is mixed, an ammoniacal buffer solution is added, at least four to five drops of acidic Namepron K-Sea phenol Green B mixed indicator solution are added, and the solution is titrated with an ethylenediaminetetraacetic acid standard titration solution until the sample solution changes from dark red to blue-green.
Referring to fig. 1, in an embodiment of the present invention, ethylene glycol bis (ethylene diamine tetraacetic acid) and cyclohexane diamine tetraacetic acid are used to titrate calcium oxide and magnesium oxide amounts of titrated limestone and metallurgical lime samples.
Referring to fig. 1, in one embodiment of the present invention, triethanolamine is added to a sample solution, mixed, potassium hydroxide solution and about 0.1g calcium indicator are added, and the solution is mixed. Titrating with ethylene glycol diethylacetamide tetraacetic acid standard titration solution until the end point of the test solution changes from red to bright blue. Blank test and test samples with less than 1.0% magnesium oxide, magnesium oxide standard solution was added before titration with ethylene glycol diethylacetamide tetraacetic acid standard titration solution.
Referring to fig. 1, in an embodiment of the present invention, when the amount of magnesium oxide in the sample is greater than 2.5%, the titration is performed by using a standard titration solution of ethylene glycol diethylacetamide tetraacetic acid according to the preset titration method.
Referring to fig. 1, in one embodiment of the present invention, triethanolamine is added to a sample solution, and the solution is mixed. Added to the solution equivalent to the titration
Ethylene glycol diethylacetamide tetraacetic acid standard titration solution with calcium oxide amount, potassium hydroxide solution and about 0.1g calcium indicator are mixed evenly. And continuously titrating with the ethylene glycol diethylacetamide tetraacetic acid standard titration solution until the end point that the test solution is changed from red to bright blue. And adding a magnesium oxide standard solution before titration in a blank test, and not presetting a titrant.
Referring to fig. 1, in one embodiment of the present invention, triethanolamine is added to another sample solution, the solution is mixed, and ethylene glycol diethylacetamide tetraacetic acid standard titration solution is added, wherein the addition amount of the ethylene glycol diethylacetamide tetraacetic acid standard titration solution is 0.4mL more than the volume of the ethylene glycol diethylacetamide tetraacetic acid standard titration solution consumed in titrating calcium oxide. Adding an ammoniacal buffer solution, adding
Acid stuffing blue K- phenol green B mixed indicator solution, using cyclohexane diamine tetraacetic acid standard titration solution to titrate until the test solution changes from dark red to blue green.
Referring to fig. 1, in one embodiment of the present invention, a sample is uniformly placed in a platinum crucible, the platinum crucible is placed in a high temperature furnace, and a platinum lid is covered, so that a gap is left between the platinum crucible and the platinum lid. And (3) heating the high-temperature furnace to 1000 ℃, keeping the temperature for 30min, taking out the platinum crucible and the platinum cover, and cooling for a period of time until the temperature is reduced to room temperature. The residue in the platinum crucible was transferred to a beaker with a small amount of water and hydrochloric acid, and the platinum crucible and the platinum lid were washed. Covering the vessel, slowly adding hydrochloric acid, heating the test solution to boiling state, cooling for a period of time, washing the vessel and the cup wall with water, evaporating the test solution to about 20ml at low temperature, and adding perchloric acid. Covering the vessel, heating until perchloric acid white smoke is emitted, and keeping smoke backflow
Cooling for a period of time until the temperature drops to room temperature. Adding hydrochloric acid and hot water, restarting the vessel and the cup wall with a small amount of hot water, and stirring to dissolve the salts. Filtering with medium-speed quantitative filter paper and appropriate amount of paper pulp, wiping off the precipitate on the cup wall with glass rod and small piece of filter paper, and combining onto filter paper. By usingThe hot hydrochloric acid washes the beaker and precipitates, wherein the number of washes and precipitates is at least 6. The precipitate was washed with hot water more than 16 times until the solution was no longer acidic. The filtrate and washings were evaporated to about 20mL at low temperature, a metered amount of perchloric acid was added and the procedure repeated.
Referring to fig. 1, in an embodiment of the present invention, if a sample that is not completely decomposed is observed in a sample solution dissolved in hydrochloric acid, the residue needs to be collected. The test solution was filtered while hot, and the filter paper was washed with water, and the filtrate and the washing solution were retained. Putting the filter paper and the residues into a platinum crucible, further carbonizing and ashing, burning for a period of time and temperature, and cooling for a period of time until the temperature is reduced to room temperature. Adding a mixed flux into a platinum crucible, uniformly mixing, placing the platinum crucible in a high-temperature furnace, covering a platinum cover, melting for 10min, taking out the platinum crucible, rotating the platinum crucible, and cooling for a period of time until the temperature is reduced to room temperature. The hydrochloric acid-depleted proximal frit was used in a beaker containing the filtrate and wash solution. Heating is continued until the volume is about 20mL, ethanol is added, evaporation to dryness is carried out at low temperature, hydrochloric acid is added, salts are dissolved by heating, and perchloric acid is added.
Referring to fig. 1 and 5, in an embodiment of the present invention, the present invention further provides a fluorescence detection method for steel factories, including grinding a magnesium-carbon sphere, configuring a calibration sample for establishing a calibration curve, pressing the burned calibration sample into a sample tablet by using a tablet press, respectively measuring fluorescence intensity values of calcium and silicon elements in the prepared calibration sample tablet by using an X-ray fluorescence spectrometer, performing correction between elements by using a theoretical α coefficient, and establishing a calibration curve of element content and the corrected fluorescence intensity values; obtaining the slope and intercept of the calibration curve, preparing a sample wafer of a sample to be detected, and analyzing the sample wafer of the sample to be detected by using an X-ray fluorescence spectrometer to obtain fluorescence intensity values after magnesium and silicon elements are corrected; setting magnesium oxide measuring conditions and silicon dioxide measuring conditions.
Further, the magnesium oxide measurement conditions in the present invention may include, for example, crystal setting, target setting, angle setting, etc., the crystal setting in the present invention may be, for example, RX35 SPC, the target setting in the present invention may be, for example, Rh40kV70mA, and the angle setting in the present invention may be, for example, 2 θ 21.050 degrees, PHA100 to 326, and this condition setting may improve the stability of the inspection results.
Further, the silica measurement conditions in the present invention may include, for example, crystal setting, target setting, angle setting, etc., the crystal setting in the present invention may be, for example, RX35 SPC, the target setting in the present invention may be, for example, Rh40kV70mA, and the angle setting in the present invention may be, for example, 2 θ 144.780 degrees, PHA102 to 319, and this condition setting may improve the stability of the inspection results.
In summary, the present invention provides a fluorescence detection method for steel factories, which includes weighing a mixed flux and a sample, placing the mixed flux and the sample in a reaction unit; uniformly mixing the mixed flux and the sample to form a mixed flux; dropwise adding a solution into the mixture, wherein the solution and the mixture are placed in a reaction furnace to be melted to form a mixed solution; and detecting and analyzing the mixed solution by adopting a fluorescence analysis device. The production efficiency can be improved, the inspection time is shortened, the labor cost is reduced, and the labor intensity is reduced.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The preferred embodiments of the invention disclosed above are intended to be illustrative only. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise embodiments disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best utilize the invention. The invention is limited only by the claims and their full scope and equivalents.
Claims (10)
1. A fluorescence detection method for steel factories is characterized by at least comprising the following steps:
weighing mixed flux and the magnesium carbon spheres and placing the mixed flux and the magnesium carbon spheres in a reaction unit;
uniformly mixing the mixed flux and the sample to form a mixed flux;
dropwise adding a solution into the mixture, wherein the solution and the mixture are placed in a reaction furnace to be melted to form a mixed solution;
and detecting the mixed solution by adopting fluorescence analysis equipment, and establishing a calibration curve of the element content and the corrected fluorescence intensity value.
2. The fluorescence detection method for a steel plant according to claim 1, wherein the mixed flux comprises lithium metaborate and lithium tetraborate.
3. The fluorescence detection method for steel plants according to claim 2, wherein the content of the lithium metaborate is 60-70% of the content of the mixed flux.
4. The fluorescence detection method for steel plants according to claim 2, wherein the content of lithium tetraborate in the mixed flux is in the range of 20-40%.
5. The fluorescence detection method for steel factories according to claim 1, wherein the weight gram number of the mixture is 5-10 g.
6. The fluorescence detection method for steel plants according to claim 1, wherein the mg-c spheres are placed in the reaction unit in a gram number of 0.5-0.7 g.
7. The fluorescence detection method for a steel plant according to claim 6, wherein the reaction unit includes a crucible for melting the mixed flux and the sample.
8. The fluorescence detection method for steel plants according to claim 1, wherein said reaction unit is equipped with said reagent mixture.
9. The fluorescence detection method for steel plant as claimed in claim 1, wherein the reaction furnace comprises a sample melting furnace, the reaction time of the reaction furnace is 15-18min, and the temperature of the reaction furnace is set to 500-.
10. The fluorescence detection method according to claim 1, wherein the solution comprises ammonium bromide solution, the content of the ammonium bromide solution is 15-25%, and the volume of the ammonium bromide solution is 0.5-0.7 ml.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106442073A (en) * | 2016-12-22 | 2017-02-22 | 山东莱钢永锋钢铁有限公司 | Fusion sample preparation method for X-ray fluorescence analysis of element contents of silicon and phosphorus in silicon-manganese ball alloy |
| CN110376232A (en) * | 2019-06-18 | 2019-10-25 | 邯郸钢铁集团有限责任公司 | A kind of method that X-fluorescence fuse piece method measures Main elements in ferrocolumbium |
| CN111855722A (en) * | 2020-07-10 | 2020-10-30 | 南京钢铁股份有限公司 | MgO and SiO in light-burned magnesium and magnesium stone2X-ray fluorescence spectrum analysis method of content |
-
2020
- 2020-12-18 CN CN202011505014.0A patent/CN112649455A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106442073A (en) * | 2016-12-22 | 2017-02-22 | 山东莱钢永锋钢铁有限公司 | Fusion sample preparation method for X-ray fluorescence analysis of element contents of silicon and phosphorus in silicon-manganese ball alloy |
| CN110376232A (en) * | 2019-06-18 | 2019-10-25 | 邯郸钢铁集团有限责任公司 | A kind of method that X-fluorescence fuse piece method measures Main elements in ferrocolumbium |
| CN111855722A (en) * | 2020-07-10 | 2020-10-30 | 南京钢铁股份有限公司 | MgO and SiO in light-burned magnesium and magnesium stone2X-ray fluorescence spectrum analysis method of content |
Non-Patent Citations (2)
| Title |
|---|
| 化学工业部天津化工研究院, 中国建材工业出版社 * |
| 张香荣等: "铝质、硅质和镁质耐火材料的X射线荧光光谱快速分析", 《冶金分析》 * |
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