Method for simultaneously determining beryllium, tungsten and tin contents in polymetallic ore based on ICP-MS (Inductively Coupled Plasma Mass Spectrometry)

Abstract

The invention relates to the technical field of ore analysis and detection, in particular to a method for simultaneously determining beryllium, tungsten and tin contents in polymetallic ore based on ICP-MS. Comprising the following steps: S1, crushing and grinding to-be-detected ore to obtain polymetallic ore powder; s2, adding the polymetallic ore powder into a mixed flux containing sodium peroxide and sodium hydroxide, melting at a high temperature, cooling, adding a hydrochloric acid solution of citric acid, carrying out heat extraction, and adding water to a constant volume, so as to obtain a sample solution to be detected; and S3, detecting the sample to be detected by adopting ICP-MS (Inductively Coupled Plasma Mass Spectrometry The method for simultaneously measuring the beryllium content, the tungsten content and the tin content in the polymetallic ore based on the ICP-MS. The method has the characteristics of simplicity, convenience, rapidness, accuracy and the like, and can be used for simultaneously measuring the beryllium content, the tungsten content and the tin content in the polymetallic ore.

Description

Technical Field

[0001] The present invention relates to the technical field of ore analysis and detection, and particularly to a method for simultaneously determining the contents of beryllium, tungsten, and tin in polymetallic ores based on ICP-MS. Background Art

[0002] Due to the limited reserves and inherent scarcity of metals, with the continuous progress of modern industry and manufacturing, their consumption has been increasing year by year, making it difficult for existing resources to meet the growing development needs. With the rapid progress of mineral exploration technology and modern ore dressing technology, the importance of effectively exploiting and efficiently utilizing ore resources has become increasingly prominent. In the ore dressing process, quickly and accurately quantitatively analyzing samples can provide crucial data support for engineers, thus helping to optimize the production process, improve operation efficiency, and product quality. In this process, chemical analysis technology plays a role in real-time monitoring. It can measure key indicators such as the acid-base balance and ion concentration of pulp, and accordingly quickly adjust the dosage of reagents and process parameters, thereby enhancing the ore dressing efficiency and recovery rate. At the same time, this technology is also applied to detect the quality of concentrates and tailings to ensure that the final products meet both market demands and environmental protection standards. Therefore, quickly and accurately detecting the target components in the mined ores or the ore dressing process has become a core concern in the field of rock and mineral analysis. Given the rapid progress of the times and the continuous upgrading of geological sample detection standards, it is imperative to optimize detection technologies and introduce more advanced analysis methods. In geological sample analysis, instrumental analysis methods, with their ability to quickly determine multiple elements, have significantly improved the detection efficiency and the accuracy of results.

[0003] As an amphoteric element, the form of beryllium changes with the pH value, and incomplete decomposition may occur during acid decomposition. Therefore, the alkali fusion method has become the most commonly used and effective method. Tin is extremely stable in chemical properties and difficult to dissolve in acid. Tin salts are prone to hydrolysis in aqueous solutions. Therefore, the alkali fusion method is generally considered the best solution for dissolving tin. After the decomposition of the sample, tungsten mainly remains in the form of tungstic acid or tungstate, and reacting with citric acid and tartaric acid can form stable W(VI) complexes, which can effectively prevent the precipitation of tungstic acid under acidic conditions.

[0004] Due to the significant differences in chemical properties among these three elements, the current standards have limitations in simultaneously detecting beryllium, tungsten, and tin in polymetallic ores. There is no method in the existing technology for simultaneously determining these three elements in polymetallic ores. For example, the industry standard YS / T 254.8-2023 stipulates the determination method of beryllium oxide in beryllium concentrate and beryl, DZ / T0453.2-2023 stipulates the determination method of beryllium in niobium-tantalum ore, and DZ / T 0452.3-2023 stipulates the determination method of beryllium in rare earth ores; DZ / T 0453.2-2023 stipulates the determination method of tungsten content in niobium-tantalum ore chemistry, DZ / T0452.3-2023 stipulates the determination method of tungsten in rare earth ores, and DZ / T 0279.2-2016 stipulates the determination of tungsten for regional geochemical sample analysis methods; the national standard GB / T 6150.2-2022 stipulates the determination method of tin content in tungsten concentrate, and GB / T 14506.30-2010 stipulates the determination method of tin content in silicate rocks.

[0005] Therefore, there is an urgent need for a method that can simultaneously detect these three elements using spectroscopic or mass spectrometric methods in the same system to simplify the analysis process, improve the detection efficiency, and promote the accelerated progress of detection technology. Summary of the Invention

[0006] The purpose of the present invention is to overcome the deficiencies of the existing technology and provide a method for simultaneously determining the contents of beryllium, tungsten, and tin in polymetallic ores based on ICP-MS, so as to achieve at least the effects of simultaneous determination, simple operation, and accurate detection results.

[0007] The purpose of the present invention is achieved through the following technical solutions:

[0008] A method for simultaneously determining the contents of beryllium, tungsten, and tin in polymetallic ores based on ICP-MS includes the following steps:

[0009] S1: Crush and grind the ore to be tested to obtain polymetallic ore powder;

[0010] S2: Add the polymetallic ore powder to a mixed flux containing sodium peroxide and sodium hydroxide, melt it at high temperature, after cooling, add a hydrochloric acid solution of citric acid for hot extraction, and then add water to make up the volume to obtain a sample solution to be tested;

[0011] S3: Detect the sample to be tested using ICP-MS.

[0012] Further, in step S2, in the mixed flux, the weight ratio of sodium peroxide to sodium hydroxide is 7:3.

[0013] Further, in step S2, the addition amount of the mixed flux is 4 to 6 times the weight of the polymetallic ore powder; preferably, the addition amount of the mixed flux is 5 times the weight of the polymetallic ore powder.

[0014] Further, in step S2, the melting temperature is 700 to 800 °C; preferably, the melting temperature is 750 °C.

[0015] Further, in step S2, the melting time is 8 to 12 min; preferably, the melting time is 10 min.

[0016] Further, in step S2, 50 mL of the hydrochloric acid solution of citric acid is added per 0.2 g of the polymetallic ore powder.

[0017] Further, in step S2, the content of citric acid in the hydrochloric acid solution of citric acid is 80 to 120 g / L; preferably, the content of citric acid in the hydrochloric acid solution of citric acid is 100 g / L.

[0018] Further, in step S2, the hydrochloric acid concentration in the hydrochloric acid solution of citric acid is 450 to 550 mL / L; preferably, the hydrochloric acid concentration in the hydrochloric acid solution of citric acid is 500 mL / L.

[0019] Further, in step S3, the detection method specifically includes:

[0020] S4: Select In and Re as internal standard substances, and dilute with nitric acid solution to overcome baseline drift and matrix interference;

[0021] S5: Prepare a standard mixed solution containing beryllium, tungsten, and tin, and draw a standard curve;

[0022] S6: Prepare a blank sample solution, and simultaneously detect beryllium, tungsten, and tin in the test sample solution and the blank sample solution by ICP-MS, and obtain the concentration values of each element according to the standard curve.

[0023] Preferably, in step S4, the concentration of the nitric acid solution is 3 to 5%, and the concentration of the mixed internal standard solution is 50 ng / mL.

[0024] Preferably, in step S5, the standard mixed solution is obtained by diluting the corresponding standard stock solutions of beryllium, tungsten, and tin with 3 to 5% dilute nitric acid.

[0025] Preferably, the standard curve adopts a series of concentrations of 50, 100, 200, 500, 1000 μg / mL.

[0026] The beneficial effects of the present invention are:

[0027] The present invention has developed and established a method for simultaneously determining the contents of beryllium, tungsten, and tin in polymetallic ores based on ICP-MS. This method is simple, rapid, and accurate, and can be used for the simultaneous determination of the contents of beryllium, tungsten, and tin in polymetallic ores. Description of the Drawings

[0028] Figure 1 It is the test result of the influence of different flux ratios on the determination results in Comparative Example 4;

[0029] Figure 2 It is the test result of the influence of the dosage of complexing acid on the determination results in Comparative Example 5. Detailed Description of the Invention

[0030] The technical solution of the present invention will be further described in detail below with reference to the drawings, but the protection scope of the present invention is not limited to the following.

[0031] Experimental materials and reagents:

[0032] Hydrochloric acid (HCl), nitric acid (HNO 3 ), hydrofluoric acid (HF), perchloric acid (HClO 4 ), sulfuric acid (H 2 SO 4 ), citric acid (C 6 H 8 O 7 ), tartaric acid (C 4 H 6 O 6 ) are all of analytical grade. Sodium peroxide (Na 2 O 2 ), anhydrous sodium carbonate (Na 2 CO 3 ) are all of analytical grade. High-purity argon (Ar) has a purity greater than 99.99%.

[0033] Be, Sn, WO 3 Single-element standard stock solutions (100 mg / L, National Nonferrous Metals and Electronic Materials Analysis and Testing Center); for Be, Sn, WO 3 The mass concentration of each element in the mixed standard solution is 1000 μg / L, and the medium is 5% aqua regia (v, v); In and Re single-element standard stock solutions (100 mg / L, National Research Center for Certified Reference Materials); the mass concentrations of In and Re in the internal standard mixed solution are both 50 ng / mL, and the medium is 2% nitric acid (v, v). GBW07240, GBW07241, GBW07281, GBW07282, GBW07150 are all from the Standard Sample Information Center of Standard Substances.

[0034] Instrument and working conditions: Inductively coupled plasma mass spectrometer (NexION350X, PerkinElmer);

[0035] Table 1 ICP-MS detection working conditions

[0036] Item Parameter Item Parameter Output power / W 1400 Measurement method Peak jumping Cooling air flow rate / (L / min) 16.0 Number of scans / times 10 Auxiliary air flow rate / (L / min) 1.2 Residence time / (ms / point) 10

[0037] Example 1

[0038] Simultaneous determination of beryllium, tungsten, and tin contents in polymetallic ores based on ICP-MS. The specific method is as follows:

[0039] 1) Sample preparation: Take polymetallic ore samples (from the Limu polymetallic ore, a total of 3 samples were taken during the ore dressing process and denoted as I, II, and III respectively), and grind the samples until the particle size is less than 0.075 mm. Dry them at 100 - 105 °C for 1 h, then place them in a desiccator and cool to room temperature.

[0040] 2) Sample pretreatment to prepare the solution to be measured: Accurately weigh 0.2000 g of polymetallic ore powder A using an analytical balance and place it in a corundum crucible. Add 1 g of sodium peroxide + sodium hydroxide flux (7:3, w / w), and perform high-temperature ore melting in a high-temperature muffle furnace at 750 °C for 10 min. Take it out and cool. Add 50 mL of a hot hydrochloric acid solution (50%, v / v) of citric acid (10%, w / v) for extraction, and after cooling, make up the volume to 100 mL in a volumetric flask. Take 10 mL of the solution and dilute it to 100 mL in a volumetric flask, shake well to obtain the solution to be measured.

[0041] 3) Preparation of the mixed internal standard solution: Select In and Re as internal standard substances, and dilute them with a 3 - 5% nitric acid aqueous solution to prepare a mixed internal standard solution with a mass concentration of 50 ng / mL to overcome baseline drift and matrix interference.

[0042] 4) Preparation of the mixed standard solution: Take an appropriate amount of the standard stock solution, add 3 - 5% HNO 3 Dilute it to prepare a series of mixed standard working solutions with concentrations of 50, 100, 200, 500, 1000 μg / L containing Be, W, and Sn;

[0043] 5) Sample determination: Use an inductively coupled plasma mass spectrometer to measure the prepared standard solutions of each trace element to obtain a standard curve, and then inject the blank sample solution and the sample solution to be measured into the ICP-MS respectively, and obtain the concentration values of each element according to the standard curve.

[0044] Among them, the preparation method of the blank sample solution is that in step 2), no metal ore powder is added, and all other steps are the same.

[0045] Comparative Example 1

[0046] This comparative example is used to compare the effects of water extraction and acidification on the determination results after high-temperature smelting of ore in a muffle furnace, as follows:

[0047] For the three elements of beryllium, tungsten, and tin in the national first-class standard substances GBW07240, GBW07241, GBW07281, GBW07282, and GBW07150, sub-determinations were carried out. For each standard substance, two samples of 0.2000 g were accurately weighed into corundum crucibles, 1 g of sodium peroxide flux was added, and the ore was smelted at 750 °C in a high-temperature muffle furnace for 10 min until the temperature reached. After taking out and cooling, they were extracted with 50 mL of hot water / hot hydrochloric acid (50%, v / v) acidification, and collected with a 100 mL volumetric flask. After cooling, they were made up to the mark. 10 mL of the solution was taken and diluted to 100 mL in a volumetric flask, shaken well and ready for measurement, and a blank experiment was carried out with the sample.

[0048] The test results are shown in Table 2:

[0049] Table 2

[0050]

[0051] Judging from the test results, some of the tin and beryllium extracted with hot water precipitated in the water and were not dissolved. The water extraction method would lead to a lower determination result; while the elements in the solution extracted with hydrochloric acid acidification were dissolved better, and the determination result was close to the true value.

[0052] Comparative Example 2

[0053] This comparative example is used to compare the effects of different complexing acids on the determination results after high-temperature smelting of ore in a muffle furnace, as follows:

[0054] For the three elements of beryllium, tungsten, and tin in the national first-class standard substances GBW07240, GBW07241, GBW07281, GBW07282, and GBW07150, sub-determinations were carried out. Two samples of 0.2000 g were accurately weighed into corundum crucibles respectively, 1 g of sodium peroxide flux was added, and the ore was smelted at 750 °C in a high-temperature muffle furnace for 10 min until the temperature reached. After taking out and cooling, 50 mL of a hot hydrochloric acid (50%, v / v) solution of tartaric acid / citric acid (10%, w / v) was added for extraction, and after cooling, it was made up to the mark in a 100 mL volumetric flask. 10 mL of the solution was taken and diluted to 100 mL in a volumetric flask, shaken well and ready for measurement, and a blank experiment was carried out with the sample.

[0055] The results are shown in Table 3:

[0056] Table 3

[0057]

[0058] The results show that adding a complexing acid has a certain effect. However, when tartaric acid is added, the instrument blank is relatively high, and tartaric acid has a great impact on the instrument and is not stable. When citric acid is added as the complexing acid, the values of each element are within the allowable error, and it has a good effect on the standard sample. It can overcome the hydrolysis of tungsten under acidic conditions and meet the simultaneous determination of beryllium, tungsten, and tin in this type of ore.

[0059] Comparative Example 3

[0060] This comparative example is used to compare the influence of different fluxes on the determination results as follows:

[0061] For the three elements of beryllium, tungsten, and tin in the national first-class standard reference materials GBW07240, GBW07241, GBW07281, GBW07282, and GBW07150, this determination was carried out. Precisely weigh two portions of 0.2000 g of the sample into corundum crucibles. Add 1 g of sodium hydroxide as the flux to one portion, and add sodium peroxide + sodium hydroxide (7:3, w / w) as the flux to the other portion. Place them in a high-temperature muffle furnace at 750 °C and melt the ore for 10 min when it reaches the temperature. Take it out and cool it. Add 50 mL of a hot hydrochloric acid (50%, v / v) solution of citric acid (10%, w / v) for extraction, and make up the volume to 100 mL in a volumetric flask after cooling. Take 10 mL of the solution and dilute it to 100 mL in a volumetric flask, shake well and wait for measurement, and conduct a blank experiment with the sample.

[0062] The results are shown in Table 4:

[0063] Table 4

[0064]

[0065] The results show that when melting the ore with sodium hydroxide, the results of beryllium and tungsten are better, but the tin sample is not easily decomposed and the results are on the low side. The mixed flux has a better effect. Adding a small amount of sodium hydroxide can lower the melting point of sodium peroxide. When there is a large amount of sulfur present, the reaction can proceed more gently.

[0066] Comparative Example 4

[0067] This comparative example is used to compare the influence of different flux dilution ratios on the determination results as follows:

[0068] The beryllium, tungsten, and tin in the national primary reference materials GBW07241, GBW07282, and GBW07150 were determined multiple times. The method selected the melting and decomposition with a mixed flux of sodium peroxide and sodium hydroxide as the sample decomposition method. Inevitably, a large amount of sodium salt matrix would be introduced into the solution. ICP-MS is a precision instrument with high sensitivity and low salt tolerance. A large amount of salts would not only cause matrix interference to the results but also easily lead to the blockage of the nebulizer. To reduce the salt content in the determination system and ensure that the detection limit of the method meets the requirements as much as possible, it is necessary to reduce the dosage of the mixed flux while not affecting the melting effect. The results are shown in Figure 1 .

[0069] When the ratio of the sample to the flux reaches 1:4 or more, the determination of the results is within the allowable error; to avoid the influence caused by the error in the addition of the flux, the final selected flux ratio is 1:5, which minimizes the dosage of the flux and improves the negative factors on the instrument measurement.

[0070] Comparative Example 5

[0071] This comparative example is used to compare the influence of the dosage of the complexing acid on the determination results as follows:

[0072] Since tungsten will hydrolyze to form "tungstic acid" precipitate in an acid solution, the extraction solution of tungsten needs to have a complexing acid present, and the complexing acid forms a stable complex ion with tungsten and exists in the solution. We used the standard sample GBW07241 to do the hydrolysis test. Finally, the amount of citric acid in the diluted solution was ensured to be 0, 0.05%, 0.1%, 0.5%, and 1.0%. ICP-MS was used to determine tungsten to determine the optimal citric acid concentration. The results are shown in Figure 2 .

[0073] The concentration of citric acid has a great influence on the results of tungsten in the sample. When the citric acid in the solution reaches 0.5% or more, the results of tungsten meet the allowable error. To ensure its complete extraction and not introduce too many salts to affect the instrument determination, the selected concentration of citric acid is 0.5% (this concentration is the concentration in the diluted sample solution).

[0074] Example 2

[0075] To verify the accuracy of the determination results of this method, as follows:

[0076] By repeatedly measuring the contents of Be, W, and Sn in the national primary reference materials GBW07240, GBW07282, GBW07150 and the beneficiation process samples I, II, and III many times, it can be seen that the detection precision of the detection method provided by this application is reliable and is applicable to the simultaneous determination of the contents of beryllium, tungsten, and tin in polymetallic ores by ICP-MS method, as shown in Table 5.

[0077] Table 5

[0078]

[0079] The above are only the preferred embodiments of the present invention. It should be understood that the present invention is not limited to the forms disclosed herein, and should not be regarded as excluding other embodiments, but can be used in various other combinations, modifications and environments, and can be changed within the scope of the concept described herein through the above teachings or the technology or knowledge in the relevant field. And any changes and modifications made by those skilled in the art without departing from the spirit and scope of the present invention shall fall within the protection scope of the appended claims of the present invention.

Claims

1. A method for simultaneously determining the contents of beryllium, tungsten and tin in polymetallic ores based on ICP-MS, characterized in that: The following steps are involved: S1: crushing and grinding the ore to be tested to obtain polymetallic ore powder; S2: adding the polymetallic ore powder to a mixed flux containing sodium peroxide and sodium hydroxide, melting it at a high temperature, adding a hydrochloric acid solution of citric acid to perform heat extraction after cooling, and then adding water to make up the volume to obtain a sample solution to be tested; S3: Using ICP-MS to detect the sample to be tested.

2. The method according to claim 1, characterized in that: In step S2, in the mixed flux, the weight ratio of the sodium peroxide to the sodium hydroxide is 7:

3.

3. The method according to claim 1, characterized in that: In step S2, the amount of the mixed flux added is 4 to 6 times the weight of the polymetallic ore powder.

4. The method according to claim 1, characterized in that: In step S2, the melting temperature is 700-800°C.

5. The method according to claim 1, characterized in that: In step S2, the melting time is 8 to 12 minutes.

6. The method according to claim 1, characterized in that: In step S2, 50 mL of the citric acid hydrochloric acid solution is added for every 0.2 g of the multi-metallic ore powder.

7. The method according to claim 1, characterized in that: In step S2, the content of citric acid in the citric acid hydrochloric acid solution is 80-120 g / L.

8. The method according to claim 1, characterized in that: In step S2, the hydrochloric acid concentration in the citric acid hydrochloric acid solution is 450-550 mL / L.

9. The method according to claim 1, characterized in that: In step S3, the detection method specifically includes: S4: In and Re are selected as internal standard substances, diluted with nitric acid solution to prepare a mixed internal standard solution to overcome baseline drift and matrix interference; S5: prepare a standard mixed solution containing beryllium, tungsten and tin, and draw a standard curve; S6: prepare a blank sample solution, and put the sample solution to be tested and the blank sample solution into ICP-MS to detect beryllium, tungsten and tin at the same time, and obtain the concentration value of each element according to the standard curve.

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