A method for fluorescent detection of TiO2 content in ores

Abstract

The present application relates to a kind of fluorescence detection methods of TiO2 content in ore, belong to detection field.A kind of fluorescence detection methods of TiO2 content in ore, comprising the following process steps: S1, preparation is drawn work curve standard sample;S2, preparation molten sample piece;S3, the setting of instrument working condition: using fusion fluorescence spectrometry detects TiO2 content in ore, set X light tube's working current is 50mA, voltage is 50KV, the best analysis line selected is K α , carries out standard sample intensity scanning, registration;S4, the drawing of work curve;S5, sample analysis step: unknown TiO2 content sample to be measured is handled according to the steps of S2 and S3, obtains TiO2 content in ore using the standard work curve obtained.Use the method provided in the present application to detect TiO2 element in ore, short cycle, use less chemical medicine, small environmental pollution, guide steelmaking iron production.

Description

Technical Field

[0001] This invention relates to a fluorescence detection method for TiO2 content in ores, belonging to the field of detection. Background Technology

[0002] Iron ore is a raw material used in the steel industry. The main economic benefits of TiO2 in the ore are as follows: In the steel industry, adding an appropriate amount of titanium-containing iron ore to the raw materials will improve the wear resistance, strength, hardness, and ductility of the steel, and reduce costs by 8-10%.

[0003] The TiO2 content in iron ore is typically around 1%, and detection methods include photometry or titration in chemical analysis. Wet methods are time-consuming and cumbersome. To achieve instrumental testing, this study focuses on developing the functionality of an X-ray fluorescence analyzer and has developed a method for analyzing TiO2 in iron ore using fluorescence. Sample preparation for fluorescence spectroscopy includes pellet pressing and fused pellet methods. When using the pellet pressing method, it is crucial to prevent cracks from forming during the pressing process, which could affect the X-ray fluorescence analysis results. Furthermore, mineral and particle effects can influence the TiO2 measurement results; the fused pellet method eliminates these matrix effects.

[0004] To address the above requirements, a highly accurate and precise method for detecting TiO2 was developed. The method employs a fluorescence fusion plate assay to detect TiO2, accumulating standard samples with varying concentrations. Based on the principle that elemental content is proportional to intensity, a working curve is established. The detection range can be expanded by adjusting the standard sample concentration. This method is well-suited for detecting a certain amount of TiO2 in ores. Summary of the Invention

[0005] This invention provides a method for fluorescence detection of TiO2 in iron ore.

[0006] A fluorescence detection method for TiO2 content in ore, comprising the following process steps:

[0007] S1, Prepare standard samples for plotting the working curve: Select iron ore samples with TiO2 element content of a certain gradient;

[0008] S2, Preparation of molten sample: The sample is melted under the following conditions: a certain mass of sample is poured into a platinum crucible containing anhydrous lithium tetraborate flux and cobalt trioxide internal standard reagent, stirred evenly, and then lithium bromide solution and lithium nitrate solution are added as release agents. The platinum crucible is placed in a melting furnace, and the melting temperature is set to 1050℃ and the melting time is 16 minutes.

[0009] S3, Setting the operating conditions of the detection instrument: Using fusion fluorescence spectroscopy to detect the TiO2 content in the ore, the X-ray tube operating current is set to 50mA, the voltage to 50KV, and the optimal analytical line is selected as K. αPerform standard sample intensity scanning and registration;

[0010] S4. Plotting the working curve: The working curve is plotted by corresponding the net intensity of the titanium element analysis line and the standard content (%) in the selected standard sample. During the plotting process, one sample is selected as the standard sample, the measurement conditions are set, and the working curve is automatically generated using Simultix software. During the sample analysis, the intensity value of the sample to be tested is measured using an X-ray fluorescence spectrometer. The intensity value measured by the sample to be tested is converted into the standard content value by using the established working curve of standard content and net intensity.

[0011] S5, Sample analysis steps: Process the sample with unknown TiO2 content according to steps S2 and S3, and use the obtained standard working curve to obtain the TiO2 content in the ore.

[0012] Preferably, in step S1, the iron ore sample is selected from national grade II or above standard samples of iron ore / iron concentrate with a TiO2 content ranging from 0.10% to 0.50%.

[0013] Preferably, in step S2, the concentration of the lithium bromide solution is 400 g / L; the concentration of the lithium nitrate solution is 300 g / L.

[0014] Preferably, in step S2, the volume ratio of lithium bromide solution to lithium nitrate solution is 2 to 5:5.

[0015] Preferably, in step S2, the mass ratio of the sample to the total amount of anhydrous lithium tetraborate is 0.35:5.

[0016] Preferably, in step S2, 0.3500g ± 0.0002g of the dried sample is weighed and placed in a porcelain crucible, and 5.000g ± 0.0002g of anhydrous lithium tetraborate is weighed and placed in another porcelain crucible; 1g of anhydrous lithium tetraborate is first poured into the bottom of the platinum crucible and spread evenly, and 3g of anhydrous lithium tetraborate is poured into the crucible containing the sample and mixed well and poured into the platinum crucible. The remaining material in the crucible containing the sample is washed away with the remaining anhydrous lithium tetraborate, and then added to the platinum crucible. 5 drops of lithium nitrate solution with a concentration of 300g / L and 2-5 drops of lithium bromide solution with a concentration of 400g / L are added, and the crucible is placed in a high-frequency melting furnace.

[0017] Preferably, in step S2, the sample melting mode is as follows: first heating time 60 seconds, first heating temperature 800℃; second heating time 120 seconds, second heating temperature 1050℃; melting time 240 seconds, melting temperature 1050℃; self-cooling time 120 seconds; air cooling time 120 seconds; and oscillation speed at level 8.

[0018] Preferably, in step S3, the detection instrument is a Simultix14 single-channel sequential scanning X-ray fluorescence spectrometer with an Rh target X-ray tube as the excitation source and Simultix as the analysis software.

[0019] A preferred technical solution of the present invention is as follows:

[0020] A fluorescence detection method for TiO2 content in ore, comprising the following process steps:

[0021] S1, Prepare standard samples for plotting the working curve: Select iron ore samples with a certain gradient in TiO2 element content;

[0022] S2, Preparation of molten sample: The sample is melted under the following conditions: a certain mass of sample is poured into a platinum crucible containing anhydrous lithium tetraborate flux and cobalt trioxide internal standard reagent, stirred evenly, and then lithium bromide solution and lithium nitrate solution are added as release agents. The platinum crucible is placed in a melting furnace and the melting temperature is set to 1050℃ and the melting time is 16 minutes.

[0023] S3, Setting the operating conditions of the detection instrument: Using fusion fluorescence spectroscopy to detect the TiO2 content in the ore, the X-ray tube operating current is set to 50mA and the voltage to 50KV. The optimal analytical line is selected as K. α Perform standard sample intensity scanning and register.

[0024] S4. Plotting the working curve: The working curve is plotted by corresponding the net intensity of the titanium element analysis line and the standard content (%) in the selected standard sample. During the plotting process, one sample is selected as the standard sample, the measurement conditions are set, and the working curve is automatically generated using Simultix software. During sample analysis, the intensity value of the sample to be tested is measured using the X-ray fluorescence spectrometer. The intensity value measured by the sample to be tested is converted into the standard content value by using the established working curve of standard content and net intensity.

[0025] S5 Extending the Standard Working Curve: If the TiO2 content in the actual produced ore is higher than the upper limit of the curve, in order to extend the linear range of the curve, expand the element detection range, and improve the accuracy zone, the following method is adopted when standard samples are unavailable: Use high-content vanadium-titanium iron ore, add pure iron powder as the matrix, the amount of pure iron added is 0.1000g~1300g, satisfying the Fe content of 60%~68%, and the sample weighing amount is 0.1000g~0.2500g. By reducing the weighing amount of vanadium-titanium iron ore standard sample, the TiO2 content is changed. Adjust the amount of pure iron and the weighing amount according to the actual situation, repeat steps S2 and S3, and use the obtained data to extend the standard working curve.

[0026] S6, Sample analysis steps: Process the sample with unknown TiO2 content according to steps S2 and S3, and use the obtained standard working curve to obtain the TiO2 content in the ore.

[0027] Preferably, in step S2, the volume ratio of the lithium bromide solution with a concentration of 400 g / L to the lithium nitrate solution with a concentration of 300 g / L is 2 to 5:5.

[0028] The beneficial effects of this invention are as follows: This invention provides a method for fluorescence detection of TiO2 in iron ore, including instrument operating conditions, melting temperature, reagent usage, preparation of analytical samples, plotting of a standard working curve, sample testing procedures, and curve extension methods. Using the method provided by this invention to detect TiO2 in ore results in a short cycle time, less use of chemicals, and less environmental pollution, providing guidance for steelmaking and ironmaking production. Furthermore, the invention provides a method for plotting fluorescence working curves, reducing the sample weight of high-content standards, adding a pure iron matrix, extending the working curve range, ensuring that the content of unknown samples remains within the curve range, and resulting in accurate results. Attached Figure Description

[0029] Figure 1 The working curve includes the sample name and content;

[0030] Figure 2 To fit the working curve for low content;

[0031] Figure 3 The working curve is designed to expand the detection range.

[0032] Figure 4 for Figure 3 The curve linear coefficient graph. Detailed Implementation

[0033] The following non-limiting embodiments are intended to enable those skilled in the art to more fully understand the invention, but do not limit the invention in any way.

[0034] Unless otherwise specified, the experimental methods described in the following examples are conventional methods; the reagents and materials described are commercially available unless otherwise specified.

[0035] Example 1

[0036] A fluorescent detection element for TiO2 content in an ore, comprising the following process steps:

[0037] S1. Prepare standard samples for plotting the working curve: Select iron ore samples with a certain gradient of TiO2 content; the procurement standard is TiO2% ≤ 0.40%, and select 10 national grade II or above standard samples of iron ore / iron concentrate with a content in the range of 0.010% to 0.50% from the standard sample library.

[0038] S2, Preparation of fused sample: The sample is melted under the following conditions: A certain mass of sample is poured into a platinum crucible containing anhydrous lithium tetraborate flux and cobalt trioxide as the internal standard reagent, stirred evenly, and 2-5 drops of lithium bromide solution with a release agent concentration of 400 g / L and 5 drops of lithium nitrate solution with a concentration of 300 g / L are added. The platinum crucible is placed in a melting furnace, and the melting temperature is set to 1050℃ and the melting time is 16 minutes. The flux used is anhydrous lithium tetraborate, the release agent is a solution of lithium bromide and lithium nitrate, and the internal standard reagent is cobalt trioxide. An ideal fused sample is prepared, wherein cobalt trioxide and anhydrous lithium tetraborate are mixed and melted in a 1:10 ratio, ground into a fine powder, dried and stored for later use.

[0039] The specific operation is as follows: Weigh 0.3500g±0.0002g of the dried standard sample and place it in a porcelain crucible. Then weigh 5.000g±0.0002g of anhydrous lithium tetraborate into another porcelain crucible. First, pour 1g of anhydrous lithium tetraborate into the bottom of the platinum crucible and spread it evenly. Then, pour 3g of anhydrous lithium tetraborate into the crucible containing the sample and mix it well. Pour the mixture into the platinum crucible. Use the remaining anhydrous lithium tetraborate to wash the residual material in the crucible containing the sample. Add the sample to the platinum crucible, add lithium nitrate and lithium bromide solutions, and place it in a high-frequency melting furnace.

[0040] Sample melting mode: First heating time 60 seconds, first heating temperature 800℃; second heating time 120 seconds, second heating temperature 1050℃; melting time 240 seconds, melting temperature 1050℃; self-cooling time 120 seconds; air cooling time 120 seconds; swing speed 8 levels.

[0041] S3, Setting the operating conditions of the detection instrument: Using fusion fluorescence spectroscopy to detect the TiO2 content in the ore, the X-ray tube operating current is set to 50mA and the voltage to 50KV. The optimal analytical line is selected as K. α The standard sample intensity was scanned and recorded. The detection instrument was a Simultix14 single-channel sequential scanning X-ray fluorescence spectrometer with an Rh target X-ray tube as the excitation source and Simultix as the analysis software.

[0042] S4. Plotting the working curve: The working curve is plotted by corresponding the net intensity of the titanium element analysis line and the standard content (%) in the selected standard sample. During the plotting process, one sample is selected as the standard sample, the measurement conditions are set, and the working curve is automatically generated using Simultix software. During sample analysis, the intensity value of the sample to be tested is measured using the X-ray fluorescence spectrometer. The intensity value measured by the sample to be tested is converted into the standard content value by using the established working curve of standard content and net intensity.

[0043] S5 Extending the Standard Working Curve: For ores with TiO2 content exceeding the upper limit of the curve in actual production, to extend the linear range of the curve, broaden the elemental detection range, and improve the accuracy zone, the following method is used when standard samples are unavailable: High-content vanadium-titanium iron ore is used, with pure iron powder added as a matrix. The amount of pure iron added is 0.1000g–0.1300g, ensuring an Fe content of 60%–68%, resulting in standard samples with different contents between 1.0% and 3.0%. The obtained data are used to extend the standard working curve. For sample weighing within the range of 0.1000g–0.2500g, by reducing the amount of vanadium-titanium iron ore standard samples to change the TiO2 content, steps S2 and S3 are repeated, and the obtained data are used to extend the standard working curve. Four standard samples with contents of 0.697%, 0.709%, 0.949%, and 2.75% are obtained. The working curve is extended to 2.75%. The required points are adjusted as needed based on the content.

[0044] S6, Sample analysis steps: Process the sample with unknown TiO2 content according to steps S2 and S3, and use the obtained standard working curve to obtain the TiO2 content in the ore.

[0045] Precision and accuracy test

[0046]

[0047] Using the plotted working curve, the linear correlation coefficient R > 0.999 was used to conduct experiments, and the results met the precision and accuracy requirements.

Claims

1. A fluorescence detection method for TiO2 content in ore, comprising the following process steps: S1, Prepare standard samples for plotting the working curve: Select iron ore samples with TiO2 element content of a certain gradient; S2, Preparation of molten sample: The sample is melted under the following conditions: a certain mass of sample is poured into a platinum crucible containing anhydrous lithium tetraborate flux and cobalt trioxide internal standard reagent, stirred evenly, and then lithium bromide solution and lithium nitrate solution are added as release agents. The platinum crucible is placed in a melting furnace, and the melting temperature is set to 1050℃ and the melting time is 16 minutes. S3, Setting the operating conditions of the detection instrument: Using fusion fluorescence spectroscopy to detect the TiO2 content in the ore, the X-ray tube operating current is set to 50mA, the voltage to 50KV, and the optimal analytical line is selected as K. α Perform standard sample intensity scanning and registration; S4. Plotting the working curve: The working curve is plotted by corresponding the net intensity of the titanium element analysis line and the standard content (%) in the selected standard sample. During the plotting process, one sample is selected as the standard sample, the measurement conditions are set, and the working curve is automatically generated using Simultix software. During the sample analysis, the intensity value of the sample to be tested is measured using an X-ray fluorescence spectrometer. The intensity value measured by the sample to be tested is converted into the standard content value by using the established working curve of standard content and net intensity. S5, Extending the Standard Working Curve: If the TiO2 content in the actual produced ore is higher than the upper limit of the curve, in order to extend the linear range of the curve, expand the element detection range, and improve the accuracy zone, the following method is adopted when standard samples are lacking: Use high-content vanadium-titanium iron ore, add pure iron powder as the matrix, the amount of pure iron added is 0.1000g~0.1300g, satisfying the Fe content of 60%~68%, and the sample weighing amount is 0.1000g~0.2500g. By reducing the weighing amount of vanadium-titanium iron ore standard sample, the TiO2 content is changed. Adjust the amount of pure iron and the weighing amount according to the actual situation, repeat steps S2 and S3, and use the obtained data to extend the standard working curve; S6, Sample analysis steps: Process the sample with unknown TiO2 content according to steps S2 and S3, and use the obtained standard working curve to obtain the TiO2 content in the ore.

2. The method according to claim 1, characterized in that: In step S1, the iron ore sample is selected from national grade II or above standard samples of iron ore / iron concentrate with a TiO2 content ranging from 0.10% to 0.50%.

3. The method according to claim 1, characterized in that: In step S2, weigh 0.3500g ± 0.0002g of the dried sample and place it in a porcelain crucible. Then weigh 5.000g ± 0.0002g of anhydrous lithium tetraborate into another porcelain crucible. First, pour 1g of anhydrous lithium tetraborate into the bottom of the platinum crucible and spread it evenly. Then, pour 3g of anhydrous lithium tetraborate into the crucible containing the sample and mix it well. Pour the mixture into the platinum crucible. Use the remaining anhydrous lithium tetraborate to wash away the residual material in the crucible containing the sample. Add the sample to the platinum crucible, add 5 drops of lithium nitrate solution with a concentration of 300g / L and 2-5 drops of lithium bromide solution with a concentration of 400g / L, and place it in a high-frequency melting furnace.

4. The method according to claim 1 or 3, characterized in that: In step S2, the sample melting mode is as follows: first heating time 60 seconds, first heating temperature 800℃; second heating time 120 seconds, second heating temperature 1050℃; melting time 240 seconds, melting temperature 1050℃; self-cooling time 120 seconds; air cooling time 120 seconds; and oscillation speed at level 8.

5. The method according to claim 1, characterized in that: In step S3, the detection instrument is a Simultix14 single-channel sequential scanning X-ray fluorescence spectrometer with an Rh target X-ray tube as the excitation source and Simultix as the analysis software.

6. The method according to claim 1, characterized in that: In step S2, the volume ratio of the lithium bromide solution with a concentration of 400 g / L to the lithium nitrate solution with a concentration of 300 g / L is 2~5:5.

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