Beryllium ore analysis test solution and preparation method thereof

Abstract

The application discloses a beryllium ore analysis test solution and a preparation method thereof, and belongs to the technical field of mineral analysis, and is used for solving the technical problems of a traditional beryllium ore analysis system process being complicated, equipment cost being high, and batch detection efficiency being insufficient. The method comprises the following steps: adding ammonium hydrogen fluoride, trihydrogen fluorine acid triethylamine and dichloromethane into beryllium ore test materials in sequence to obtain a first mixed solution; sequentially performing first heating, cooling and adding dichloromethane on the first mixed solution to obtain a second mixed solution; sequentially performing second heating and cooling on the second mixed solution to obtain a third mixed solution; adding hydrofluoric acid into the third mixed solution, sequentially performing third heating, cooling, water dilution and mixing to obtain a fourth mixed solution; and adding hydrofluoric acid into the fourth mixed solution, then diluting with water and mixing uniformly. The beryllium ore analysis test solution can realize rapid and synchronous quantitative analysis of multiple elements / components in beryllium ore raw ore and concentrate.

Description

Technical Field

[0001] This invention belongs to the field of mineral analysis technology, and particularly relates to a beryllium ore analysis solution and its preparation method. Background Technology

[0002] Beryllium is a rare light metal with numerous excellent physical properties, making it irreplaceable in fields such as nuclear industry, weapons systems, aerospace, and cutting-edge defense technologies. In a changing global environment and increasingly competitive landscape, the importance of beryllium resource supply is becoming increasingly apparent. Under the current demands of industrial development, it is imperative to ensure the accuracy and timeliness of beryllium ore composition analysis data to meet the requirements of domestic beryllium resource development.

[0003] The current standard method for ICP-OES of beryllium ore, YS / T 254.8-2023 "Chemical Analysis Methods for Beryllium Concentrate and Beryl - Part 8: Determination of Beryllium Oxide, Ferric Oxide, Calcium Oxide and Phosphorus Content by Inductively Coupled Plasma Atomic Emission Spectrometry", has requirements for the preparation of analytical solutions. These requirements include a "slow decomposition" process for the ore pretreatment, a long operation procedure, and, especially when operating with multiple samples, the slow decomposition of individual samples, resulting in a very long smoke emission time, which seriously affects work efficiency. Summary of the Invention

[0004] One of the objectives of this invention is to provide a method for preparing a beryllium ore analytical solution. The beryllium ore analytical solution prepared by this method has the characteristics of complete dissolution, high transparency and low viscosity, and is highly efficient and has a short cycle time. Under the premise of ensuring analytical accuracy, the experimental process is greatly optimized.

[0005] The second objective of this invention is to provide an analytical solution for beryllium ore.

[0006] To achieve one of the above objectives, the present invention employs the following technical solution: A method for preparing a beryllium ore analytical solution, the method comprising the following steps: Step S1: Ammonium bifluoride, triethylamine trihydrofluoride, and dichloromethane are added sequentially to the beryllium ore sample to obtain the first mixed solution; Step S2: After heating and cooling the first mixed solution in sequence, dichloromethane is added to obtain the second mixed solution; Step S3: The second mixed solution is heated and cooled for a second time to obtain a third mixed solution; Step S4: After adding hydrofluoric acid to the third mixed solution, heat and cool it for the third time in sequence, then dilute it with water and mix it evenly to obtain the fourth mixed solution; Step S5: After adding hydrofluoric acid to the fourth mixed solution, dilute with water and mix evenly to obtain a beryllium ore analysis solution.

[0007] Furthermore, in step S1, the 12-24 mL first mixed solution contains 0.10-0.20 g of beryllium ore sample, 2-4 g of ammonium bifluoride, 2-4 mL of triethylamine trihydrofluoride, and 10-20 mL of dichloromethane.

[0008] Furthermore, in step S2, the volume ratio of the first mixed solution to dichloromethane is 12~24:10~15.

[0009] Furthermore, in step S2, the temperature of the first heating is 200-220°C, and the time is 25-30 minutes.

[0010] Furthermore, in step S3, the temperature of the second heating is 300-320°C, and the time is 10-20 minutes.

[0011] Furthermore, in step S4, the volume ratio of the third mixed solution, hydrofluoric acid, and water is 0.1–4:5–10:86–94.9.

[0012] Furthermore, in step S4, the temperature of the third heating is 300-320°C, and the time is 3-5 minutes.

[0013] Furthermore, in step S4, each 1L of the fourth mixed solution contains 1.13 to 2.26 mol of hydrofluoric acid.

[0014] Furthermore, in step S5, the volume ratio of the fourth mixed solution, hydrofluoric acid, and water is 5~10:5~10:80~90; In step S5, each 1L of beryllium ore analytical solution contains 1.19~2.49mol of hydrofluoric acid.

[0015] To achieve the second objective mentioned above, the present invention employs the following technical solution: A beryllium ore analysis solution, characterized in that the beryllium ore analysis solution is prepared using the preparation method described above.

[0016] In summary, the solution proposed in this invention has the following technical effects: The present invention utilizes a mixed system (i.e., the first mixed solution) formed by triethylamine trihydrofluoride, dichloromethane, and ammonium bifluoride, which has both good thermal conductivity and fluidity. This system not only provides an anhydrous dissolution environment for beryllium ore, preventing hydrolysis, but also accelerates the reaction rate and increases the reaction speed, enabling efficient decomposition of beryllium ore and effectively solving the problem of insufficient decomposition motive force.

[0017] This invention employs a multi-stage temperature-controlled heating process (i.e., first heating, second heating, and third heating and cooling) to control the reaction to achieve stratification of the organic and inorganic reaction phases. The ore decomposition liquid is in a high-density solution state, covered by a low-density organic layer, which improves the reaction kinetics and efficiency.

[0018] The beryllium ore analytical solution prepared by this invention is clear and exhibits low levels of interference. It is analyzed using an ICP-OES-HF resistant system. The analytical solution preparation time is reduced by more than 50%.

[0019] The beryllium ore analysis solution prepared by this invention features complete solubility, high transparency, and low viscosity, making it highly suitable for high-efficiency instrumental analysis techniques such as ICP-OES and ICP-MS for beryllium ore analysis. Furthermore, due to its simple matrix and minimal interference, it can determine most metallic and non-metallic elements that can be analyzed by wet methods. This enables the efficient construction of a comprehensive synchronous analysis system for beryllium ore, facilitating rapid and simultaneous quantitative analysis of multiple elements / components (including but not limited to BeO, Fe2O3, CaO, Li2O, P, as well as MgO, Al2O3, MnO, NiO, ZnO, Cr2O3, TiO2, Na2O, K2O, etc.) in beryllium ore (including raw ore and concentrate). This is of great significance in improving the quality and efficiency of beryllium chemical analysis, and its innovative achievements are of great value in ensuring the advancement and autonomy of my country's beryllium industry.

[0020] This invention avoids the redundancy caused by the separate preparation of multiple reagents in the traditional method, significantly shortens the operation cycle, and improves the overall analytical efficiency. This invention greatly optimizes the experimental procedure while ensuring analytical accuracy.

[0021] The entire analysis process for a single sample using this invention can be completed within one hour, and batch processing can be finished within two hours, demonstrating good accuracy and practicality. This technical solution plays a positive role in establishing an efficient and accurate beryllium ore testing system, helps to improve the methodological system for testing related beryllium raw materials, and further enhances the industry's testing efficiency and technical level. Detailed Implementation

[0022] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0023] The chemical principle of the beryllium ore digestion reaction in this embodiment is as follows: Main decomposition reaction of beryllium ore: BeO + 2NH4HF2→ (NH4)2BeF4+ H2O; Be2SiO4+ 7NH4HF2→ 2(NH4)2BeF4+ (NH4)2SiF6+ 4H2O + NH3.

[0024] (NH4)2SiF6 will undergo further reactions upon heating: .

[0025] SiF4 reacts with water Meanwhile, the fluoride / silicate system Ca in the ore 2+ F - SO4 2- They readily interact to form CaSO4 colloids / suspensions, CaF2 precipitates, etc., which prevents the sample from completely decomposing and leads to lower analytical results.

[0026] Based on the above principles, this embodiment provides a method for preparing a beryllium ore analytical solution, which includes the following steps: Step S1: Ammonium bifluoride, triethylamine trihydrofluoride, and dichloromethane are added sequentially to the beryllium ore sample to obtain the first mixed solution.

[0027] This embodiment controls the content of each raw material in the mixed reaction system (i.e., the first mixed solution). Specifically, 12-24 mL of the first mixed solution contains 0.10-0.20 g of beryllium ore sample, 2-4 g of ammonium bifluoride, 2-4 mL of triethylamine trifluoride, and 10-20 mL of dichloromethane. This not only provides an anhydrous and stable dissolution environment for the beryllium ore, preventing the hydrolysis and precipitation of fluorosilicone compounds, but also, through the reaction of excess fluoride ions and calcium ions, forms a soluble tetrafluorocalcium complex ion, significantly reducing free calcium ions and inhibiting the precipitation of CaSO4 and CaF2. By controlling the proportions of each raw material in the first mixed solution, complete decomposition of the beryllium ore is ensured, and the analysis cycle is short.

[0028] Step S2: After heating and cooling the first mixed solution in sequence, dichloromethane is added to the reaction vessel to obtain the second mixed solution.

[0029] In this embodiment, the beryllium ore gradually decomposes into a high-density solution state and is covered by a low-density dichloromethane organic layer, which improves the reaction kinetics and efficiency. Simultaneously, the continued addition of dichloromethane provides a consistently anhydrous and high-concentration fluoride ion reaction environment, preventing hydrolysis and precipitation, reducing the volatilization rate of fluorine in the reaction system, maintaining reaction stability, and promoting ore decomposition. To ensure a complete decomposition reaction, the volume ratio of the first mixed solution to dichloromethane in this embodiment is controlled at 12-24:10-15.

[0030] In this embodiment, by controlling the temperature of the first heating to 200-220°C and the time to 25-30 minutes, it is beneficial to the formation of the reaction solution. At the same time, it controls the evaporation rate of the reactant mixture solution, maintains the stability of the reaction environment, and makes the decomposition reaction of beryllium ore stable and efficient.

[0031] The reaction in this embodiment is typically carried out in a reaction vessel, such as a PTFE cup, which has a large volume, is easy to operate, and allows for quantification of reaction time and temperature. This avoids analytical errors caused by operator misjudgment of experimental phenomena, reducing the analytical difficulty and the skill requirements for personnel. The reaction solution is ultimately controlled to achieve the desired FT. - The concentration is optimized to suppress turbidity and precipitation caused by hydrolysis of CaF2, etc. Sulfuric acid and hydrochloric acid are not used in the reaction process, thus avoiding CaSO4 colloidal precipitation and Be loss due to evaporation / sublimation of BeCl2 at high temperatures. Simultaneously, it ensures that components such as BeO, Fe2O3, CaO, Li2O, P, MgO, Al2O3, MnO, NiO, ZnO, Cr2O3, TiO2, Na2O, and K2O, as analyzed according to YS / T 254 standards, can be analyzed using a single set of analytical solutions. This eliminates the need for additional steps in preparing analytical solutions for other analytes, significantly improving work efficiency.

[0032] Step S3: The second mixed solution is heated and cooled for a second time to obtain a third mixed solution.

[0033] In order to achieve complete stratification between the ore decomposition liquid and the organic phase, this embodiment controls the temperature of the second heating to be 300-320°C and the time to be 10-20 minutes, so that the high-density ore decomposition liquid is located in the lower layer and covered by the low-density dichloromethane organic phase, which effectively improves the reaction kinetics and overall reaction efficiency.

[0034] Step S4: After adding hydrofluoric acid to the third mixed solution, heat and cool it for the third time, then dilute it with water and mix it evenly to obtain the fourth mixed solution.

[0035] In this embodiment, by controlling the volume ratio of the third mixed solution, hydrofluoric acid, and water to 0.1–4:5–10:86–95.9, and with each liter of the fourth mixed solution containing 1.13–2.26 mol of hydrofluoric acid, excess fluoride ions are generated. Through coordination, the formation of calcium fluoride and silicon fluoride precipitates is inhibited, thus preventing turbidity of the solution. This avoids the problem of excessively low amounts or molar concentrations of hydrofluoric acid causing turbidity, while excessively high amounts or molar concentrations of hydrofluoric acid leading to excessively high acidity in the reaction system interfere with subsequent analysis and detection, resulting in inaccurate results.

[0036] To provide a stable and efficient molten salt dissolution reaction environment, this embodiment controls the temperature of the third heating to be 300–320°C and the time to be 3–5 minutes.

[0037] Step S5: After adding hydrofluoric acid to the fourth mixed solution, dilute with water and mix evenly to obtain a beryllium ore analysis solution.

[0038] To avoid interfering with subsequent analysis and to ensure the accuracy of the results, the volume ratio of the fourth mixed solution, hydrofluoric acid, and water in this embodiment is 5~10:5~10:80~90. Each liter of beryllium ore analysis solution contains 1.19~2.49 mol of hydrofluoric acid, which generates excess fluoride ions, inhibits the formation of calcium fluoride and silicon fluoride precipitates, and avoids turbidity in the solution.

[0039] In this embodiment, the mass fraction of hydrofluoric acid is preferably 40%.

[0040] Another embodiment provides a beryllium ore analysis solution prepared using the preparation method described in the above embodiments.

[0041] The technical solution of the present invention will be described below with reference to specific embodiments: Example 1: Step S1: According to the first mixed solution containing 0.10g of beryllium ore sample, 2g of ammonium bifluoride, 2mL of triethylamine trihydrofluoride and 10mL of dichloromethane, ammonium bifluoride, triethylamine trihydrofluoride and dichloromethane are added sequentially to a polytetrafluoroethylene beaker containing beryllium ore sample to obtain the first mixed solution.

[0042] Step S2: Place the polytetrafluoroethylene beaker containing the first mixed solution on a 200°C hot plate and heat for 25 minutes. After cooling, add dichloromethane to the polytetrafluoroethylene beaker to obtain the second mixed solution. The volume ratio of the first mixed solution to dichloromethane is 12:10.0.

[0043] Step S3: Place the polytetrafluoroethylene beaker containing the second mixed solution on a 300°C hot plate and heat for 10 minutes to completely evaporate the organic phase and exhaust the large amount of white smoke from the ore decomposition liquid. Remove and cool to obtain the third mixed solution.

[0044] Step S4: After adding hydrofluoric acid to the PTFE beaker containing the third mixed solution, rinse the beaker walls with water, place it on a 300℃ hot plate, heat for 3 minutes, remove and cool, transfer to a polyethylene volumetric flask, dilute with water, and mix thoroughly to obtain the fourth mixed solution. The volume ratio of the third mixed solution, hydrofluoric acid, and water is 0.01:5:94.9. Each liter of the fourth mixed solution contains 1.13 mol of hydrofluoric acid.

[0045] Step S5: After adding hydrofluoric acid to the polyethylene volumetric flask containing the fourth mixed solution, dilute with water and mix thoroughly to obtain the beryllium ore analysis solution. The volume ratio of the fourth mixed solution, hydrofluoric acid, and water is 5:5:90. Each liter of the beryllium ore analysis solution contains 1.19 mol of hydrofluoric acid.

[0046] The beryllium ore analysis solution in this embodiment was used for analysis in ICP-OES (hydrofluoric acid resistant system), and the results were compared with the analysis solution prepared by the YS / T 254.8-2023 method to verify the accuracy of the method. The results are shown in Table 1.

[0047] Table 1. Analysis results of beryllium ore in Example 1

[0048] As shown in Table 1, the measured values ​​of the beryllium concentrate sample treated with the beryllium ore analysis solution of Example 1 are in good agreement with the standard method, indicating good method accuracy.

[0049] Example 2: Step S1: According to the first mixed solution containing 0.20g of beryllium ore sample, 4g of ammonium bifluoride, 4mL of triethylamine trihydrofluoride and 20mL of dichloromethane, ammonium bifluoride, triethylamine trihydrofluoride and dichloromethane are added sequentially to a polytetrafluoroethylene beaker containing beryllium ore sample to obtain the first mixed solution.

[0050] Step S2: Place the polytetrafluoroethylene beaker containing the first mixed solution on a 220°C hot plate and heat for 30 minutes. After cooling, add dichloromethane to the polytetrafluoroethylene beaker to obtain the second mixed solution. The volume ratio of the first mixed solution to dichloromethane is 24:15.

[0051] Step S3: Place the polytetrafluoroethylene beaker containing the second mixed solution on a 320°C hot plate and heat for 20 minutes to completely evaporate the organic phase and exhaust the large amount of white smoke from the ore decomposition liquid. Remove and cool to obtain the third mixed solution.

[0052] Step S4: After adding hydrofluoric acid to the PTFE beaker containing the third mixed solution, rinse the beaker walls with water, place it on a 320℃ hot plate, heat for 5 minutes, remove and cool, transfer to a polyethylene volumetric flask, dilute with water, and mix thoroughly to obtain the fourth mixed solution. The volume ratio of the third mixed solution, hydrofluoric acid, and water is 4:10:86. Each liter of the fourth mixed solution contains 2.26 mol of hydrofluoric acid.

[0053] Step S5: After adding hydrofluoric acid to the polyethylene volumetric flask containing the fourth mixed solution, dilute with water and mix thoroughly to obtain the beryllium ore analysis solution. The volume ratio of the fourth mixed solution, hydrofluoric acid, and water is 10:10:80. Each liter of the beryllium ore analysis solution contains 2.49 mol of hydrofluoric acid.

[0054] The beryllium ore analysis solution in this embodiment was used for analysis in ICP-OES (hydrofluoric acid resistant system), and the results were compared with the analysis solution prepared by the YS / T 254.8-2023 method to verify the accuracy of the method. The results are shown in Table 2.

[0055] Table 2. Analysis results of beryllium ore in Example 2

[0056] As shown in Table 2, the measured values ​​of the beryllium concentrate sample treated with the beryllium ore analysis solution of Example 2 are consistent with the standard method, indicating good method accuracy.

[0057] Example 3: Step S1: According to the first mixed solution containing 0.15g of beryllium ore sample, 3g of ammonium bifluoride, 3mL of triethylamine trihydrofluoride and 15mL of dichloromethane, ammonium bifluoride, triethylamine trihydrofluoride and dichloromethane are added sequentially to a polytetrafluoroethylene beaker containing beryllium ore sample to obtain the first mixed solution.

[0058] Step S2: Place the polytetrafluoroethylene beaker containing the first mixed solution on a 210°C hot plate and heat for 28 minutes. After cooling, add dichloromethane to the polytetrafluoroethylene beaker to obtain the second mixed solution. The volume ratio of the first mixed solution to dichloromethane is 20:12.

[0059] Step S3: Place the polytetrafluoroethylene beaker containing the second mixed solution on a 310°C hot plate and heat for 15 minutes to completely evaporate the organic phase and exhaust the large amount of white smoke from the ore decomposition liquid. Remove and cool to obtain the third mixed solution.

[0060] Step S4: After adding hydrofluoric acid to the PTFE beaker containing the third mixed solution, rinse the beaker walls with water, place it on a 310℃ hot plate, heat for 4 minutes, remove and cool, transfer to a polyethylene volumetric flask, dilute with water, and mix thoroughly to obtain the fourth mixed solution. The volume ratio of the third mixed solution, hydrofluoric acid, and water is 2:8:90. Each liter of the fourth mixed solution contains 1.808 mol of hydrofluoric acid.

[0061] Step S5: After adding hydrofluoric acid to the polyethylene volumetric flask containing the fourth mixed solution, dilute with water and mix thoroughly to obtain the beryllium ore analysis solution. The volume ratio of the fourth mixed solution, hydrofluoric acid, and water is 6:8:86. Each liter of the beryllium ore analysis solution contains 1.916 mol of hydrofluoric acid.

[0062] The beryllium ore analysis solution in this embodiment was used for analysis in ICP-OES (hydrofluoric acid resistant system). The accuracy of the method was verified by the standard value of the beryllium ore composition analysis standard material (GBW07151). The results are shown in Table 3.

[0063] Table 3. Analysis results of beryllium ore in Example 3

[0064] As shown in Table 3, the measured values ​​of the beryllium ore composition analysis standard material (GBW07151) treated with the beryllium ore analysis test solution of Example 3 are in good agreement with the standard values, indicating good method accuracy.

[0065] The above embodiments merely illustrate several implementation methods of this application, and while the descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the invention patent. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of this application, and these all fall within the protection scope of this application. Therefore, the protection scope of this patent application should be determined by the appended claims.

Claims

1. A method for preparing an analytical solution for beryllium ore, characterized in that, The preparation method includes the following steps: Step S1: Ammonium bifluoride, triethylamine trihydrofluoride, and dichloromethane are added sequentially to the beryllium ore sample to obtain the first mixed solution; Step S2: After heating and cooling the first mixed solution in sequence, dichloromethane is added to obtain the second mixed solution; Step S3: The second mixed solution is heated and cooled for a second time to obtain a third mixed solution; Step S4: After adding hydrofluoric acid to the third mixed solution, heat and cool it for the third time in sequence, then dilute it with water and mix it evenly to obtain the fourth mixed solution; Step S5: After adding hydrofluoric acid to the fourth mixed solution, dilute with water and mix evenly to obtain a beryllium ore analysis solution.

2. The preparation method according to claim 1, characterized in that, In step S1, each 12-24 mL of the first mixed solution contains 0.10-0.20 g of beryllium ore sample, 2-4 g of ammonium bifluoride, 2-4 mL of triethylamine trihydrofluoride, and 10-20 mL of dichloromethane.

3. The preparation method according to claim 2, characterized in that, In step S2, the volume ratio of the first mixed solution to dichloromethane is 12~24:10~15.

4. The preparation method according to claim 3, characterized in that, In step S2, the temperature of the first heating is 200-220°C, and the time is 25-30 minutes.

5. The preparation method according to claim 4, characterized in that, In step S3, the temperature of the second heating is 300-320°C, and the time is 10-20 minutes.

6. The preparation method according to claim 5, characterized in that, In step S4, the volume ratio of the third mixed solution, hydrofluoric acid, and water is 0.1–4:5–10:86–94.

9.

7. The preparation method according to claim 6, characterized in that, In step S4, the temperature of the third heating is 300-320°C, and the time is 3-5 minutes.

8. The preparation method according to claim 7, characterized in that, In step S4, each 1L of the fourth mixed solution contains 1.13 to 2.26 mol of hydrofluoric acid.

9. The preparation method according to claim 8, characterized in that, In step S5, the volume ratio of the fourth mixed solution, hydrofluoric acid, and water is 5~10:5~10:80~90; In step S5, each 1L of beryllium ore analytical solution contains 1.19~2.49 mol of hydrofluoric acid.

10. A beryllium ore analytical solution, characterized in that, The beryllium ore analytical solution is prepared using the preparation method described in any one of claims 1 to 9.

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