Preparation method of drift correction sample for X fluorescence analysis of free acid-containing product in copper smelting

Abstract

The invention discloses a preparation method of a drift correction sample for X fluorescence analysis of a free acid-containing product in copper smelting, and belongs to the technical field of drift correction of an X fluorescence analyzer. The method comprises the following steps: (1) selecting a free acid-containing product generated in a copper smelting process, and adding the free acid-containing product into high-purity water to prepare slurry; (2) adding a saturated solution of alkali metal hydroxide or alkaline earth metal hydroxide into the slurry until the pH value is 6.8-7.2 to obtain a liquid mixture; (3) filtering the liquid mixture to obtain a solid substance; (4) drying, crushing and uniformly mixing the solid substance to obtain uniform powder; and (5) pressing the uniform powder into a circular sheet to obtain the drift correction sample. According to the method, the free acid is neutralized, so that the negative effects of corrosion of the free acid on the X fluorescence analyzer, aggravation of fracture damage, chemical component change and the like of the drift correction sample are avoided, and the drift correction accuracy and the drift correction sample stability are improved.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of X fluorescence analyzer drift correction, and relates to a preparation method of a drift correction sample for X fluorescence analysis of a copper smelting free acid-containing product. BACKGROUND

[0002] Each process in the copper smelting process basically produces free acid-containing materials, such as free acid-containing flue dust generated in the pyrometallurgical process, free acid-containing copper and copper removal sludge generated in the copper electrolysis process, free acid-containing acid sludge generated in the industrial sulfuric acid production process, and free acid-containing sludge generated in the water treatment process. The detection of the element content and composition of the free acid-containing product can provide guidance for the copper smelting production process, thereby ensuring product quality and providing a basis for harmless disposal of smelting by-products.

[0003] The X fluorescence analyzer is a non-destructive detection equipment based on the principle of X-ray fluorescence, mainly used for determining the element content and composition of solid, liquid, powder and other samples, widely applied in the fields of industrial detection, RoHS harmful substance screening, food heavy metal analysis and archaeological identification, and has the characteristics of rapid, efficient, high-precision detection and analysis, and is often used in the copper smelting process for the detection and analysis of the element content and composition of the free acid-containing product.

[0004] With the increase of the use time, the X fluorescence analyzer will appear drift phenomenon, once the drift appears, the detection and analysis results of the X fluorescence analyzer will appear large deviation, which leads to the decrease of the accuracy and reliability of the results, and large deviation of the component analysis of the free acid-containing product, and the detection and analysis results lose availability, therefore, it is necessary to regularly correct the drift of the X fluorescence analyzer to ensure the accuracy of the detection and analysis results of the X fluorescence analyzer.

[0005] X-ray fluorescence (XRF) analyzer drift calibration typically requires a drift calibration sample. The elemental content and composition of the drift calibration sample must be as close as possible to the analyte detected by the XRF analyzer (the drift calibration sample needs to contain all elements of the analyte, and the content of each element in the drift calibration sample should be as close as possible to the content of each element in the analyte). Therefore, drift calibration samples used for detecting and analyzing products containing free acid are generally products produced in the same process. However, while using products produced in the same process as drift calibration samples achieves a higher degree of similarity between the drift calibration sample and the analyte, there are several drawbacks. First, the free acid in the product can escape after X-ray irradiation, corroding the components of the XRF analyzer and potentially damaging the expensive analyzer (typically costing 2 million RMB per unit). Second, the free acid in the drift calibration sample can absorb moisture from the air, leading to sample breakage and damage. Furthermore, the free acids contained in the drift correction sample can easily react chemically with other components in the drift correction sample, causing changes in the composition of the drift correction sample, resulting in poor stability and increased component differences between the drift correction sample and the target for analysis. This further increases the drift correction deviation and leads to low accuracy of the analysis results.

[0006] Therefore, it is necessary to provide a method for preparing drift-corrected samples for X-ray fluorescence analysis of copper smelting products containing free acid, so as to eliminate the negative impact of free acid in drift samples. Summary of the Invention

[0007] To overcome the problems in the prior art, this invention uses alkali metals or alkaline earth metals with strong neutralizing ability to neutralize the free acid in the product, thereby eliminating the free acid in the product, obtaining a drift-corrected sample, avoiding corrosion of the X-ray fluorescence analyzer by the free acid during the drift correction process, extending the service life of the X-ray fluorescence analyzer, reducing the operating cost of the X-ray fluorescence analyzer, and effectively avoiding sample breakage and damage caused by the absorption of moisture by the free acid, as well as poor sample stability caused by chemical reactions between the free acid and other components in the sample, thereby improving the component stability of the drift-corrected sample and improving the accuracy of drift correction.

[0008] To achieve the above objectives, the present invention is implemented through the following technical solution: This invention proposes a method for preparing drift-corrected samples for X-ray fluorescence analysis of copper smelting products containing free acid. The preparation method includes the following steps: (1) Select the free acid-containing product generated during copper smelting and add it to high-purity water to prepare a slurry. The high-purity water can be in excess, just enough to ensure that the free acid-containing product is completely dispersed in the high-purity water.

[0009] (2) Add a saturated solution of alkali metal hydroxide or alkaline earth metal hydroxide to the slurry in step (1) and monitor the pH value of the liquid in real time. When the pH value reaches 6.8~7.2, stop adding the saturated solution of alkali metal hydroxide or alkaline earth metal hydroxide to obtain a liquid mixture.

[0010] (3) Filter the liquid mixture in step (2) to obtain a solid substance.

[0011] (4) After drying the solid material in step (3), the dried solid material is crushed to a particle size of no more than 150 mesh, and then the crushed powder is mixed to obtain a uniform powder.

[0012] (5) Press the uniform powder from step (4) into a circular sheet to obtain a drift correction sample.

[0013] Preferably, in step (2), a saturated Ca(OH)2 solution is added to the slurry from step (1).

[0014] Preferably, the free acid-containing product contains 0.5% calcium oxide by mass fraction.

[0015] Preferably, in step (4), the drying temperature is 105°C.

[0016] Preferably, in step (5), the inner diameter of the pressing mold is 34 mm and the thickness is ≥3 mm.

[0017] Preferably, in step (5), the pressing pressure is 40 tons.

[0018] The beneficial effects of this invention are: 2. This invention reduces the water absorption of drift-corrected samples by neutralizing free acid with alkali metal or alkaline earth metal hydroxides, effectively extending the service life of drift-corrected samples and reducing drift correction costs.

[0019] 3. This invention uses alkali metal or alkaline earth metal hydroxides to neutralize free acid, thereby reducing the degree of change in the chemical composition of drift-corrected samples, effectively improving the stability of drift-corrected samples, and enhancing the accuracy of drift correction.

[0020] 4. This invention uses Ca(OH)2 to neutralize free acids. On the one hand, it utilizes the extremely strong neutralizing ability of Ca(OH)2 to reduce the amount of Ca(OH)2 used, thereby reducing the amount of element introduced and minimizing the degree of change in the chemical composition of the drift correction sample, thus maintaining a high degree of similarity between the drift correction sample and the analyte. On the other hand, it introduces the Ca element that is already present in the product containing free acids, avoiding the direct introduction of new elements not present in the product containing free acids. This helps to maintain a high degree of similarity between the drift correction sample and the analyte while minimizing other side reactions that could alter the chemical composition of the drift correction sample.

[0021] 5. In the copper smelting process, the calcium oxide content in the free acid products is typically around 4.5%. This means that under normal circumstances, the highest spectral intensity of calcium oxide detected by an X-ray fluorescence spectrometer corresponds to 4.5%. This invention selects free acid products with a specific calcium oxide content and leverages the strong neutralizing ability of Ca(OH)2 to ensure that the calcium oxide content in the drift-corrected sample after neutralization is approximately 60% of the highest calcium oxide content in the free acid products. At this point, during the drift correction process, the oxidation spectral intensity of the drift-corrected sample is also around 60% of the highest spectral intensity, which helps to keep the drift correction within an optimal intensity range and improves the drift correction effect.

[0022] 6. This invention increases the service life of drift-corrected samples from 3 months to more than 10 months by neutralizing free acid with alkali metal or alkaline earth metal hydroxides, effectively reducing the cost of setting drift-corrected samples (usually 10 samples, each sample requires setting 13 elements, each element costs 200 yuan, totaling 26,000 yuan each time, and each time a drift-corrected sample is replaced, the setting needs to be repeated). Attached Figure Description

[0023] Figure 1 This describes the usage time of the drift correction sample in this invention; Figure 2 The appearance of the drift correction sample of this invention to date; Figure 3 This is a schematic diagram of the neutralization process of the present invention; Figure 4 This is a physical image of the drift correction sample prepared according to the present invention. Detailed Implementation

[0024] The present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments, but the scope of protection of the present invention is not limited to the content described.

[0025] Example In this embodiment, a drift-corrected sample is prepared using the following method: (1) Select a product containing free acid with a calcium oxide mass fraction of 0.5% during copper smelting, add it to high-purity water, and make a slurry.

[0026] (2) Add the prepared Ca(OH)2 saturated solution to the slurry and monitor the pH value of the slurry in real time. Stop adding the Ca(OH)2 saturated solution when the pH value is between 6.8 and 7.2 to obtain a liquid mixture.

[0027] (3) Use qualitative filter paper to filter the liquid mixture to obtain solid substances.

[0028] (4) Place the solid material in an oven and dry it at 105°C for 120 minutes. Then take out the solid material and grind it to a particle size of no more than 150 mesh by grinding or mechanical crushing. Then mix the crushed powder by mechanical mixing or stirring.

[0029] (5) Add the uniform powder into a plastic ring pressing mold with an inner diameter of 34 mm, an outer diameter of 40 mm, and a thickness of 5 mm, and fill the mold completely. Press the uniform powder into a circular sheet under a pressure of 40 tons, which is the drift correction sample (e.g. Figure 4 (As shown).

[0030] pass Figure 1 , Figure 2 As can be seen, the drift correction sample prepared by this invention has been used stably since October 2024, and no water absorption or cracking has occurred. The drift correction sample remains stable for a long period of time and can be used continuously for a long time.

Claims

1. A method for preparing drift-corrected samples for X-ray fluorescence analysis of copper smelting products containing free acid, characterized in that: The preparation method includes the following steps: (1) Select products containing free acid generated during copper smelting, and add the products containing free acid to high-purity water to prepare a slurry; (2) Add a saturated solution of alkali metal hydroxide or alkaline earth metal hydroxide to the slurry in step (1) and monitor the pH value of the liquid in real time. When the pH value reaches 6.8~7.2, stop adding the saturated solution of alkali metal hydroxide or alkaline earth metal hydroxide to obtain a liquid mixture. (3) Filter the liquid mixture in step (2) to obtain a solid substance; (4) After drying the solid material in step (3), the dried solid material is crushed to a particle size of no more than 150 mesh, and then the crushed powder is mixed to obtain a uniform powder. (5) Press the uniform powder from step (4) into a circular sheet to obtain a drift correction sample.

2. The preparation method according to claim 1, characterized in that: In step (2), a saturated Ca(OH)2 solution is added to the slurry from step (1).

3. The preparation method according to claim 2, characterized in that: The free acid-containing product contains 0.5% calcium oxide by mass fraction.

4. The preparation method according to claim 1, characterized in that: In step (4), the drying temperature is 105°C.

5. The preparation method according to claim 1, characterized in that: In step (5), the inner diameter of the pressing mold is 34mm and the thickness is ≥3mm.

6. The preparation method according to claim 1, characterized in that: In step (5), the pressing pressure is 40 tons.

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