X-ray fluorescence analysis correction method and on-line ore composition analysis method

Abstract

The present application belongs to the technical field of component analysis, and relates to an X-ray fluorescence analysis correction method and an online ore component analysis method. The correction method adopts a Monte Carlo method to simulate the attenuation degree of X-rays in air, and obtains the reaction of X-rays in air. The energy of X-rays is taken as the horizontal coordinate, and the number of remaining X-rays after passing through a distance d of air is taken as the vertical coordinate. A curve is fitted to obtain the attenuation curve of X-rays in air. The Eval() function in the TGraph class is used for difference to obtain the transmittance of different incident energies. The obtained transmittance is used to correct the real yield of each element in the measured sample. The correction method and the online ore component analysis method are applied to the ore component analysis process, and can make the component analysis equipment be used directly in air without a vacuum pump.

Description

Technical Field

[0001] This invention belongs to the field of component analysis technology, and relates to X-ray fluorescence analysis technology. Specifically, it relates to a correction method for X-ray fluorescence analysis in air and an online ore component analysis method. Background Technology

[0002] Compositional analysis technology is mainly used to analyze unknown substances and unknown components of minerals. Through compositional analysis technology, various constituent elements in a target sample can be quickly identified, and the sample can be quickly qualitatively and quantitatively analyzed.

[0003] In recent years, energy-dispersive X-ray fluorescence (EDXRF) has gained increasingly widespread application in fields such as mineral exploration, aerospace, geological exploration, and petrochemicals due to its advantages of being non-destructive to samples, providing high-precision analytical results, and providing reliable data. However, commercially available equipment of this type is primarily used for laboratory data analysis, is complex to maintain, and has cumbersome operating procedures, making it unsuitable for direct application on production lines and hindering large-scale and intelligent industrial production. Summary of the Invention

[0004] To address the aforementioned problems in existing methods, this invention provides a correction method for X-ray fluorescence analysis in air and an online ore composition analysis method. When applied to the ore composition analysis process, this method enables the composition analysis equipment to be used directly in air without a vacuum pump.

[0005] To achieve the above objectives, the present invention provides a correction method for X-ray fluorescence analysis in air, comprising the following steps:

[0006] S1. The Monte Carlo method is used to simulate the attenuation of X-rays in air, and the reaction of X-rays in air is obtained.

[0007] S2. Using the energy of X-rays as the x-axis and the number of remaining X-rays after passing through air at a distance d, d≥1cm as the y-axis, fit the curve to obtain the attenuation curve of X-rays in air, and use the Eval() function in the TGraph class to obtain the transmittance of different incident energies.

[0008] S3. Correct the X-ray count using the transmittance obtained in step S2. The correction formula is: y = x / ε, where y is the corrected X-ray count, x is the X-ray count after penetrating a distance d in air, and ε is the transmittance of the X-rays after penetrating a distance d in air.

[0009] Preferably, in step S1, the specific method for simulating the attenuation of X-rays in air using the Monte Carlo method is as follows: the environment is a vacuum, the X-ray excitation source is placed at a distance d from the detector, the medium between the X-ray excitation source and the detector is air, the X-ray excitation source emits X-rays of different energies at a distance 2π from the air, and the detector records the reaction of the X-rays in the air.

[0010] Preferably, the detector is configured as a cuboid with a side length of 800 mm and a thickness of 10 mm.

[0011] To achieve the above objectives, the present invention also provides an online ore composition analysis method, comprising the following steps:

[0012] S1. Emit continuously adjustable X-rays to the ore sample to be tested. X-rays of different energies interact with the ore sample to generate secondary X-rays of different energies.

[0013] S2. Detect secondary X-rays, amplify and shape the detected secondary X-rays, perform analog-to-digital conversion and classification, and obtain the count and energy of secondary X-rays with different energies.

[0014] S3. Match the secondary X-ray energy with the X-ray energy corresponding to the known elements, and obtain the probability of secondary X-ray occurrence and its corresponding element based on the matched X-ray energy.

[0015] S4. Correct the count of secondary X-rays using the above-mentioned X-ray fluorescence analysis correction method, find the peaks in the corrected secondary X-ray energy spectrum, and calculate the peak area of ​​each peak.

[0016] S5. Calculate the elemental content P in the ore sample based on the peak area and the probability of occurrence of secondary X-rays of the element. i Element content P i Represented as: In the formula, I i Let A be the intensity of element i. i Let ε be the peak area of ​​element i. i Let ε be the probability of secondary X-rays occurring from element i. j To determine the intrinsic detection efficiency of the X-ray detection device for secondary X-rays of element i, the content of each element is calculated according to the above formula.

[0017] Furthermore, following step S5, the following steps are also included:

[0018] The matrix effect correction is applied to the calculated elemental content using the measurement results of standard ore samples to obtain the final elemental content of each element in the ore sample.

[0019] Preferably, the specific steps for matrix effect correction are as follows: assuming the concentration of element i in the standard ore sample is A%, the concentration of element i calculated by the calculation module is B%, B is B / A times A, and the final concentration of element i is the element concentration B% calculated by the calculation module divided by B / A.

[0020] Compared with the prior art, the advantages and positive effects of the present invention are as follows:

[0021] (1) The X-ray fluorescence analysis correction method of the present invention performs Monte Carlo simulation on the attenuation of X-rays in air to correct the attenuation of X-rays. When applied to the process of ore composition analysis, it enables the composition analysis equipment to be used directly in the air without a vacuum pump.

[0022] (2) The online ore composition analysis method of the present invention corrects the count of secondary X-rays based on the attenuation efficiency of X-rays in air and applies it to the ore composition analysis process, which enables the composition analysis equipment to be used directly in the air without a vacuum pump.

[0023] (3) The online ore composition analysis method of the present invention uses the measurement results of standard ore samples to correct the matrix effect of the calculated element content, which can make the measurement results more accurate when measuring non-standard samples. Attached Figure Description

[0024] Figure 1 This is a schematic diagram of the simulation state for simulating the attenuation of X-rays in air using the Monte Carlo method as described in an embodiment of the present invention.

[0025] Figure 2 This is a schematic diagram of the simulation results of the Monte Carlo method used in an embodiment of the present invention to simulate the attenuation of X-rays of different energies in air;

[0026] Figure 3 for Figure 2 A magnified view of a portion of the image;

[0027] Figure 4 This is a schematic diagram showing known elements and their corresponding X-ray energies. Detailed Implementation

[0028] The present invention will now be described in detail through exemplary embodiments. However, it should be understood that, without further description, elements, structures, and features in one embodiment may be advantageously incorporated into other embodiments.

[0029] This invention provides a correction method for X-ray fluorescence analysis in air, comprising the following steps:

[0030] S1. The Monte Carlo method is used to simulate the attenuation of X-rays in air, and the reaction of X-rays in air is obtained.

[0031] Specifically, the method for simulating the attenuation of X-rays in air using the Monte Carlo method is as follows: the environment is a vacuum, the X-ray excitation source is placed at a distance d from the detector, d≥1cm, the medium between the X-ray excitation source and the detector is air, the X-ray excitation source emits X-rays of different energies at a distance 2π from the air, and the detector records the reaction of the X-rays in the air.

[0032] S2. Using the energy of X-rays as the x-axis and the number of remaining X-rays after passing through air at a distance d, d≥1cm as the y-axis, fit the curve to obtain the attenuation curve of X-rays in air, and use the Eval() function in the TGraph class to obtain the transmittance of different incident energies.

[0033] S3. Correct the X-ray count using the transmittance obtained in step S2. The correction formula is: y = x / ε, where y is the corrected X-ray count, x is the X-ray count after penetrating a distance d in air, and ε is the transmittance of the X-rays after penetrating a distance d in air.

[0034] The X-ray fluorescence analysis correction method of the present invention performs Monte Carlo simulation on the attenuation of X-rays in air to correct the attenuation of X-rays. When applied to the process of ore composition analysis, it enables the composition analysis equipment to be used directly in air without a vacuum pump.

[0035] This invention also provides an online ore composition analysis method, comprising the following steps:

[0036] S1. X-rays with continuously adjustable energy are emitted to the ore sample to be tested. X-rays of different energies interact with the ore sample to generate secondary X-rays of different energies.

[0037] S2. Detect secondary X-rays, amplify and shape the detected secondary X-rays, and then perform analog-to-digital conversion and classification to obtain the count and energy of secondary X-rays with different energies.

[0038] S3. Compare the secondary X-ray energy with the X-ray energy corresponding to the known elements (see...). Figure 4 The matching is performed, and the probability of secondary X-ray occurrence and its corresponding element are obtained based on the matched X-ray energy.

[0039] S4. Correct the count of secondary X-rays using the above-mentioned X-ray fluorescence analysis correction method, find the peaks in the corrected secondary X-ray energy spectrum, and calculate the peak area of ​​each peak.

[0040] Specifically, in this embodiment, after finding the peaks on the energy spectrum, the peak area of ​​each peak is calculated by integration. Since calculating the peak area on the energy spectrum by integration is a known existing technique, the specific process of calculating the peak area by integration will not be described in detail here.

[0041] S5. Calculate the elemental content P in the ore sample based on the peak area and the probability of occurrence of secondary X-rays of the element. i Element content P i Represented as: In the formula, I i Let A be the intensity of element i. i Let ε be the peak area of ​​element i. i Let ε be the probability of secondary X-rays occurring from element i. j To determine the intrinsic detection efficiency of the X-ray detector for secondary X-rays of element i, the content of each element is calculated using the formula above. It should be noted that the intrinsic detection efficiency of the detector is a known parameter of the detector.

[0042] In one specific embodiment of the invention, after step S5, the following step is further included:

[0043] The final elemental content of each element in the ore sample is obtained by correcting the calculated elemental content for matrix effects using the measurement results of a standard ore sample. The specific steps for matrix effect correction are as follows: Assuming the concentration of element i in the standard ore sample is A%, the concentration of element i calculated by the calculation module is B%, and B is B / A times A. The final concentration of element i is the elemental concentration B% calculated by the calculation module divided by B / A. For example, if the concentration of potassium in the standard ore sample is 10%, and the concentration of potassium calculated by the calculation module is 15%, which is 1.5 times the true concentration, then when measuring non-standard samples, the calculated concentration should be divided by 1.5. Similarly, if the concentration of calcium in the standard ore sample is 10%, and the concentration of calcium calculated by the calculation module is 13%, which is 1.3 times the true concentration, then when measuring non-standard samples, the calculated concentration should be divided by 1.3.

[0044] In one specific embodiment of the present invention, the X-ray excitation source and the detector for detecting secondary X-rays are positioned above the mineral sample to be tested at an angle of 45°-135°. This ensures that the mineral sample can be effectively excited by X-rays, and that the generated secondary X-rays can be fully absorbed by the detector. It should be noted that the angle between the detector (e.g., a semiconductor detector) and the excitation source (e.g., a controllable X-ray excitation source) can be selected according to actual needs. It can be 45°, 135°, 60°, 90°, 120°, etc.

[0045] In one specific embodiment of the present invention, multi-angle measurement (i.e., multi-point measurement) of the ore sample can also be achieved by changing the angle of the ore sample to be tested. Specifically, by rotating the sample container holding the ore sample, the ore sample rotates with the sample container, enabling multi-point measurement and averaging of the ore sample. This solves the measurement deviation caused by the uneven distribution of various elements within the sample, making the measurement results more accurate. When rotating the sample container, the rotation of the sample container can be automatically controlled by driving the sample container to rotate by a set angle α at set time intervals T, saving labor costs. For example, if the set time T = 60s and the set angle α = 180 degrees, the sample container can be driven to rotate 180 degrees according to the set time of 60s, realizing automatic multi-point measurement control of the sample. It should be noted that the set time T and the set angle α can be set according to actual needs, and are not limited to a set time of 60s and a set angle of 180 degrees.

[0046] The above-mentioned online ore composition analysis method of the present invention corrects the count of secondary X-rays based on the attenuation efficiency of X-rays in air. At the same time, it uses the measurement results of standard ore samples to correct the matrix effect of the calculated element content, so that the analysis equipment can be used directly in air without the control of a vacuum pump. This allows it to be directly applied to the production line, simplifies the ore composition analysis operation process, saves manpower and time costs, and greatly improves production efficiency.

[0047] The above-mentioned X-ray fluorescence analysis correction method and online ore composition analysis method are further explained below with reference to specific embodiments.

[0048] Example 1: A correction method for X-ray fluorescence analysis, comprising the following steps:

[0049] S1. The Monte Carlo method is used to simulate the attenuation of X-rays in air, and the reaction of X-rays in air is obtained.

[0050] Specifically, the Monte Carlo method for simulating the attenuation of X-rays in air is as follows: the environment is a vacuum, the X-ray excitation source is placed 1 cm away from the detector, and the medium between the X-ray excitation source and the detector is air. The X-ray excitation source emits X-rays of different energies at a distance of 2π from the air, and the detector records the reaction of the X-rays in the air. The detector is set as a cuboid with a side length of 800 mm and a thickness of 10 mm.

[0051] The simulated X-ray energies were 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.2, 1.4, 1.6, 1.8, 2.0, 2.2, 2.4, 2.6, 2.8, 3.0, 3.2, 3.4, 3.6, 3.8, 4.0, 4.2, 4.4, 4.6, 4.8, 5.0, 5.2, 5.4, 5.6, 5.8, 6.0, 6.2, 6.4, 6.6, 6.8, and 7. Energy points of 0, 7.2, 7.4, 7.6, 7.8, 8.0, 8.2, 8.4, 8.6, 8.8, 9.0, 9.2, 9.4, 9.6, 9.8, 10.0, 11.0, 12.0, 13.0, 14.0, 15.0, 16.0, 17.0, 18.0, 19.0, 20.0, 25.0, 30.0, 35.0, 40.0, 45.0, and 50.0 keV. Each energy point simulates 1,000,000 X-ray emissions (see...). Figure 1 (In the diagram, the gray area represents the air).

[0052] S2. Plotting the X-ray energy on the x-axis and the number of X-rays remaining after passing through 1 cm of air on the y-axis, fit a curve to obtain the attenuation curve of X-rays in air (see...). Figure 2 , Figure 3 The transmittance for different incident energies is obtained by using the difference in the Eval() function of the TGraph class;

[0053] S3. Correct the X-ray count using the transmittance obtained in step S2. The correction formula is: y = x / ε, where y is the corrected X-ray count, x is the X-ray count after penetrating a distance d in air, and ε is the transmittance of the X-rays after penetrating a distance d in air.

[0054] It should be noted that in this embodiment, the detector is not limited to a cuboid with a side length of 800mm and a thickness of 10, but can also be other shapes. The distance between the detector and the X-ray excitation source is not limited to 1cm, but can be adjusted according to the actual situation, such as 2cm, 3cm, 4cm, etc.

[0055] Example 2: An online ore composition analysis method, comprising the following steps:

[0056] S1. X-rays with continuously adjustable energy are emitted to the ore sample to be tested. X-rays of different energies interact with the ore sample to generate secondary X-rays of different energies.

[0057] S2. Detect secondary X-rays, amplify and shape the detected secondary X-rays, perform analog-to-digital conversion and classification, and obtain the count and energy of secondary X-rays with different energies. The detector for detecting secondary X-rays is 1 cm away from the ore sample to be tested.

[0058] S3. Compare the secondary X-ray energy with the X-ray energy corresponding to the known elements (see...). Figure 4 The matching is performed, and the probability of secondary X-ray occurrence and its corresponding element are obtained based on the matched X-ray energy.

[0059] S4. The secondary X-ray count is corrected using the X-ray fluorescence analysis correction method described in Example 1. Peaks are searched on the corrected secondary X-ray energy spectrum, and the peak area of ​​each peak is obtained by integration.

[0060] S5. Calculate the elemental content P in the ore sample based on the peak area and the probability of occurrence of secondary X-rays of the element. i Element content P i Represented as: In the formula, I i Let A be the intensity of element i. i Let ε be the peak area of ​​element i. i Let ε be the probability of secondary X-rays occurring from element i. j To determine the intrinsic detection efficiency of the X-ray detection device for secondary X-rays of element i, the content of each element is calculated according to the above formula.

[0061] In this embodiment, the X-ray excitation source and the detector for detecting secondary X-rays are positioned at a 60° angle above the mineral sample to be tested.

[0062] In this embodiment, a semiconductor detector is used.

[0063] Example 3: An online ore composition analysis method, comprising the following steps:

[0064] S1. X-rays with continuously adjustable energy are emitted to the ore sample to be tested. X-rays of different energies interact with the ore sample to generate secondary X-rays of different energies.

[0065] S2. Detect secondary X-rays, amplify and shape the detected secondary X-rays, perform analog-to-digital conversion and classification, and obtain the count and energy of secondary X-rays with different energies. The detector for detecting secondary X-rays is 1 cm away from the ore sample to be tested.

[0066] S3. Compare the secondary X-ray energy with the X-ray energy corresponding to the known elements (see...). Figure 4 The matching is performed, and the probability of secondary X-ray occurrence and its corresponding element are obtained based on the matched X-ray energy.

[0067] S4. The secondary X-ray count is corrected using the X-ray fluorescence analysis correction method described in Example 1. Peaks are searched on the corrected secondary X-ray energy spectrum, and the peak area of ​​each peak is obtained by integration.

[0068] S5. Calculate the elemental content P in the ore sample based on the peak area and the probability of occurrence of secondary X-rays of the element. i Element content P i Represented as: In the formula, I i Let A be the intensity of element i. i Let ε be the peak area of ​​element i. i Let ε be the probability of secondary X-rays occurring from element i. j To determine the intrinsic detection efficiency of the X-ray detection device for secondary X-rays of element i, the content of each element is calculated according to the above formula.

[0069] S6. Using the measurement results of the standard ore sample, the calculated elemental content is corrected for matrix effects to obtain the final elemental content of each element in the ore sample. The specific steps for matrix effect correction are as follows: Assume the concentration of element i in the standard ore sample is A%, and the concentration of element i calculated by the calculation module is B%, where B is B / A times A. The final concentration of element i is the elemental concentration B% calculated by the calculation module divided by B / A. For example, if the concentration of potassium in the standard ore sample is 10%, and the concentration of potassium calculated by the calculation module is 15%, which is 1.5 times the true concentration, then when measuring non-standard samples, the calculated concentration should be divided by 1.5. If the concentration of calcium in the standard ore sample is 10%, and the concentration of calcium calculated by the calculation module is 13%, which is 1.3 times the true concentration, then when measuring non-standard samples, the calculated concentration should be divided by 1.3.

[0070] In this embodiment, the X-ray excitation source and the detector for detecting secondary X-rays are positioned at a 90° angle above the mineral sample to be tested.

[0071] In this embodiment, a semiconductor detector is used.

[0072] The above embodiments are used to explain the present invention, but not to limit the present invention. Any modifications and changes made to the present invention within the spirit and scope of the claims shall fall within the protection scope of the present invention.

Claims

1. An online ore composition analysis method, characterized in that, Includes the following steps: S1. Emit continuously adjustable X-rays to the ore sample to be tested. X-rays of different energies interact with the ore sample to generate secondary X-rays of different energies. S2. Detect secondary X-rays, amplify and shape the detected secondary X-rays, perform analog-to-digital conversion and classification, and obtain the count and energy of secondary X-rays with different energies. S3. Match the secondary X-ray energy with the X-ray energy corresponding to the known elements, and obtain the probability of secondary X-ray occurrence and its corresponding element based on the matched X-ray energy. S4. Correct the secondary X-ray count using X-ray fluorescence analysis correction method, locate peaks in the corrected secondary X-ray energy spectrum, and calculate the peak area of ​​each peak; the X-ray fluorescence analysis correction method includes the following steps: S41. The Monte Carlo method is used to simulate the attenuation of X-rays in air, and the reaction of X-rays in air is obtained. S42. Using the energy of X-rays as the x-axis and the number of remaining X-rays after passing through air at a distance d, d≥1cm as the y-axis, fit a curve to obtain the attenuation curve of X-rays in air, and use the Eval() function in the TGraph class to obtain the transmittance of different incident energies. S43. The X-ray count is corrected using the transmittance obtained in step S42. The correction formula is expressed as: y=x / ε, where y is the corrected X-ray count, x is the X-ray count after penetrating a distance d in air, and ε is the transmittance of X-rays after penetrating a distance d in air. S5. Calculate the elemental content in the ore sample based on the peak area and the probability of occurrence of secondary X-rays of the elements. P i Element content P i Represented as: In the formula, I i For elements i The strength, A i For elements i peak area, ε i For elements i Probability of secondary X-ray occurrence ε j Devices for detecting X-rays and elements i Intrinsic detection efficiency of secondary X-rays; calculate the content of each element according to the above formula; S6. Using the measurement results of the standard ore sample, the calculated elemental content is corrected for matrix effects to obtain the final elemental content of each element in the ore sample; the specific steps for matrix effect correction are as follows: assuming that the elements in the standard ore sample... i The concentration is A%, and the element is calculated. i The concentration is B%, and B is B / A times that of A. i The final concentration is the calculated elemental concentration B% divided by B / A.

2. The online ore composition analysis method as described in claim 1, characterized in that, Step S41, the specific method for simulating the attenuation of X-rays in air using the Monte Carlo method is as follows: the environment is a vacuum, the X-ray excitation source is set at a distance d from the detector, the medium between the X-ray excitation source and the detector is air, the X-ray excitation source emits X-rays of different energies at a distance of 2π from the air, and the detector records the reaction of X-rays in the air.

3. The online ore composition analysis method as described in claim 1 or 2, characterized in that, The detector is designed as a cuboid with a side length of 800 mm and a thickness of 10 mm.

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