Method for deeply separating uranium and beryllium from beryllium-iron-uranium coexisting solution based on ultrasonic waves
Based on ultrasonic -based methods, oxidative treatment and pH adjustment of tancin cohabitation solutions, combined with ultrasound treatment, the efficient and depth separation of uranium and cymbal is achieved, solving the problem of incomplete separation and complex process in existing technologies, simplified The craftsmanship and reduced costs.
Patent Information
- Application Number
- CN202411485706.1
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-10-23
- Publication Date
- 2025-01-24
AI Technical Summary
In the prior art, there are few deep separation technologies for uranium and beryllium in uranium beryllium symbiotic ore. In the existing technology, uranium and beryllium are not completely separated and require multiple leaching, which makes the process complex.
An ultrasonic-based method is used to deeply separate uranium and beryllium from beryllium iron uranium coexistence solution. Through oxidation pretreatment, pH adjustment and ultrasonic treatment, highly selective separation of uranium and beryllium is achieved.
The efficient separation of uranium and cymbals has been achieved, and the separation rate reaches more than 99.99 %. It simplifies the wet metallurgical technology of uranium ore ore and reduces costs.
Smart Images
Figure CN119351785A_ABST
Abstract
Description
Technical Field
[0001] The invention relates to a method for separating a beryllium-iron-uranium coexisting solution, in particular to a method for deeply separating uranium and beryllium from the beryllium-iron-uranium coexisting solution based on ultrasound, and belongs to the technical field of hydrometallurgy. Background Art
[0002] Metallic beryllium has the advantages of high melting point, low density, high specific strength, low oxidation resistance at room temperature, small expansion coefficient, good deformation stability, and small neutron absorption cross section. It is widely used as structural materials, reactor protection materials, and neutron source preparation in the aviation and aerospace industries. The excellent properties of beryllium make it have key applications in many fields such as electronics, aerospace, and national defense.
[0003] Natural uranium resources are national strategic resources and are called the "food" for the development of national nuclear energy. In recent years, with the rapid development of nuclear power, single uranium ore resources have been sharply reduced, and the development and utilization of natural uranium resources have gradually shifted to polymetallic uranium ore resources. At present, there are a lot of reports on the technology of comprehensive recovery of valuable metals from associated / symbiotic ores such as uranium-molybdenum, uranium-molybdenum-vanadium, etc., but the development of technology for recovering uranium and beryllium from uranium-beryllium symbiotic ores is still in its infancy. In uranium-beryllium symbiotic ores, the grades of uranium and beryllium are not low, both have a good market, and have high economic development value. However, there are few reports on the relevant technology for deep separation of uranium and beryllium in the prior art. In the existing leaching process of uranium-beryllium symbiotic ore, uranium is first leached into the solution with dilute sulfuric acid, and beryllium remains in the leaching residue to achieve the initial separation of uranium and beryllium. The disadvantage is that a small amount of beryllium is still leached during the leaching of uranium, and the separation of uranium and beryllium is incomplete, and it needs to be leached twice. A large amount of iron impurities will also be generated during the secondary leaching of beryllium, and the impurity removal process is complicated. Therefore, if a process for deep separation of uranium and beryllium from a solution system is developed, it will be of great significance to simplify the hydrometallurgical process of uranium and beryllium ores. Summary of the invention
[0004] Aiming at the technical problem that it is difficult to deeply separate uranium and beryllium in the existing iron-beryllium-uranium leaching solution, the purpose of the present invention is to provide a method for deeply separating uranium and beryllium from a beryllium-iron-uranium coexisting solution based on ultrasound. The method can completely separate uranium and beryllium from the leaching solution containing iron, beryllium and uranium, and obtain products such as beryllium hydroxide, sodium uranyl tricarbonate, iron hydroxide and the like with high purity. Compared with the existing beryllium-uranium separation process, the method can reduce the two leaching processes in the original uranium-first-then-beryllium leaching process, simplify the process and reduce the cost.
[0005] In order to achieve the above technical purpose, the present invention provides a method for deeply separating uranium and beryllium from a beryllium-iron-uranium coexisting solution based on ultrasound. The method comprises the following steps: subjecting the beryllium-iron-uranium coexisting solution to an oxidation pretreatment to obtain a pretreated solution; adjusting the pH of the pretreated solution to above 12, subjecting the pretreated solution to an ultrasonic treatment, and filtering the pretreated solution to obtain a beryllium-containing solution and a uranium-iron coprecipitation slag; and dissolving the uranium-iron coprecipitation slag with a sodium carbonate solution to obtain a sodium uranyl tricarbonate solution and an iron hydroxide slag phase.
[0006] The method for deeply separating uranium and beryllium from a beryllium-iron-uranium coexisting solution based on ultrasound is as follows: first, the beryllium-iron-uranium coexisting solution is subjected to an oxidation treatment so that ferrous ions in the solution are converted into ferric ions. The main reason is that during the sedimentation process, ferric ions can better form uranium-iron coprecipitates than ferrous ions, and the sedimentation is complete and the filtration performance is good. On this basis, alkaline precipitation is performed. In the alkaline precipitation process, the hydrolysis characteristics of ferric ions, uranium ions and beryllium ions at different pH values are utilized to achieve high-selective separation of beryllium. Ferric ions and uranium ions are easy to form coprecipitates under weak alkaline conditions, and can exist stably in a high pH environment. However, beryllium ions are different. They are precipitated in the form of Be(OH)2 under weak alkaline conditions of about pH=8. When the pH reaches 11, Be(OH)2 begins to dissolve, and beryllium is redissolved in the solution. When the pH reaches above 12, the solubility of Be(OH)2 is relatively high, and the solubility is mainly in the form of [Be(OH)4] 2- In the form of uranium, Be(OH)2 enters the solution, especially under the synergistic effect of pH and ultrasound, which can promote the complete dissolution of Be(OH)2 in the uranium-iron co-precipitation slag, so that the deep separation of beryllium can be achieved through simple solid-liquid separation, and the remaining uranium-iron co-precipitation slag can use sodium carbonate solution to selectively convert the uranium phase into water-soluble sodium uranyl tricarbonate, so as to achieve the selective separation of uranium in the uranium-iron co-precipitation slag, and the remaining slag is iron hydroxide slag.
[0007] As a preferred solution, in the beryllium-iron-uranium coexistence solution, the beryllium content is 3-15 g / L, the iron content is 5-30 g / L, and the uranium content is 0.1-3 g / L.
[0008] As a preferred solution, during the oxidation pretreatment, hydrogen peroxide is used as an oxidant, and the oxidation potential is adjusted to between -400 and -550 mV. The preferred use of hydrogen peroxide as an oxidant can avoid the introduction of other impurities. Strictly controlling the oxidation potential can ensure that divalent iron is highly selectively converted into trivalent iron.
[0009] As a preferred solution, the conditions of the ultrasonic treatment are: frequency of 20kHz to 50kHz, and time of 1 to 3h. Ultrasonic treatment can promote the dissolution of beryllium hydroxide in the uranium-iron coprecipitation slag, thereby achieving the purpose of deep separation of beryllium. If the ultrasonic frequency is too low or the time is too short, a small amount of beryllium hydroxide will not be fully dissolved and will remain, and the purpose of deep separation cannot be achieved. If the ultrasonic frequency is too high or the time is too long, the dissolution of beryllium hydroxide will not be further promoted, and the power consumption will be significantly increased.
[0010] As a preferred solution, the beryllium-containing solution is adjusted to a pH of 7 to 9 and boiled to obtain a Be(OH)2 precipitate. Under preferred conditions, beryllium forms a stable Be(OH)2 precipitate.
[0011] As a preferred solution, the concentration of the sodium carbonate solution is 200-300 g / L.
[0012] The present invention provides a method for deep separation of uranium and beryllium from a beryllium iron uranium coexisting solution based on ultrasound, comprising the following specific steps:
[0013] (1) Adjust the solution potential. Add an appropriate amount of hydrogen peroxide to the beryllium iron uranium coexistence solution and adjust the solution potential to between -400 and -550 mV to convert the ferrous ions in the solution into ferric ions.
[0014] (2) Alkali precipitation. Add solid NaOH to the solution after oxidation pretreatment and stir continuously until the pH reaches above 12. During this period, uranium and iron are precipitated first, and then beryllium is precipitated as Be(OH)2. When the pH reaches 11, Be(OH)2 begins to dissolve, and beryllium redissolves in the solution. When the pH reaches 12, Be dissolves in the solution.
[0015] (4) Ultrasonic deep dissolution of beryllium. Ultrasonic waves are added during the stirring of the solid-liquid mixture, with an ultrasonic frequency of 20kHz to 50kHz and a reaction time of 1 to 3 hours to accelerate the complete dissolution of beryllium.
[0016] (5) Vacuum filtration. A vacuum filtration system is used to separate the solid and liquid. The filtrate is a beryllium-containing solution, and the filter residue is a uranium-containing residue.
[0017] (6) Hydrolysis of the filtrate. Add water to the filtrate until the pH reaches 7-9 and boil it to obtain Be(OH)2 precipitate. The radioactivity in the beryllium product can be less than 100 Bq / g.
[0018] (7) Dissolving the filter residue. Add 200-300 g / L of sodium carbonate solution to the filter residue to dissolve the uranium. After filtering, sodium uranyl tricarbonate filtrate is obtained. The filter residue is ferric hydroxide, and the uranium and iron are separated.
[0019] Compared with the prior art, the technical solution of the present invention has the following beneficial technical effects:
[0020] Compared with the prior art which uses a step-by-step leaching method to separate uranium and beryllium from uranium-beryllium ore, the technical solution of the present invention can achieve efficient separation of uranium and beryllium from a solution containing iron, beryllium and uranium, and the efficient separation rate of uranium and beryllium can reach more than 99.99%, and a sodium uranyl tricarbonate product with extremely low beryllium content and a beryllium hydroxide product with extremely low uranium content can be obtained, while iron hydroxide is produced as a by-product, so that a one-step leaching method can be used to achieve efficient leaching of useful metals in uranium-beryllium ore, and the separation method of the present invention greatly simplifies the hydrometallurgical process of uranium-beryllium ore. BRIEF DESCRIPTION OF THE DRAWINGS
[0021] Figure 1 The figure is a process flow chart for deep separation of uranium and beryllium from beryllium-iron-uranium coexisting solution based on ultrasound. DETAILED DESCRIPTION
[0022] The following specific embodiments are intended to further illustrate the content of the present invention in detail, rather than to limit the protection scope of the claims of the present invention.
[0023] Example 1
[0024] Take 200mL of iron, uranium and beryllium solution, of which the uranium content is 1g / L, the beryllium content is 10g / L, and the iron content is 30g / L. Adjust the potential to 500mV by adding hydrogen peroxide and stir until no bubbles are generated. Add NaOH solid to the pretreated solution and stir continuously until the pH reaches 12. Add ultrasound during the stirring of the solid-liquid mixture at a power of 30Hz and react for 3h to accelerate the complete dissolution of beryllium. Use a vacuum filtration system to separate the solid and liquid. The filtrate is a beryllium-containing solution, and the filter residue is a uranium-containing residue. Add water to the filtrate until the pH reaches 9 and boil it to obtain Be(OH)2 precipitate. The radioactivity in the beryllium product is only 30Bq / g, and the beryllium recovery rate is 99%. Sodium carbonate solution was added to the filter residue to dissolve the uranium, and the sodium uranyl tricarbonate filtrate was obtained after filtration. The uranium recovery rate was 99.5%, the beryllium content was 5 μg / L, and the filter residue was ferric hydroxide, and the beryllium and uranium residues were both less than 0.5 mg / g.
[0025] Comparative Example 1
[0026] Take 200mL of iron, uranium and beryllium solution, in which the uranium content is 1g / L, the beryllium content is 10g / L, and the iron content is 30g / L. Adjust the potential to 550mV by adding hydrogen peroxide, and stir until no bubbles are generated. Add NaOH solid to the pretreated solution and stir continuously until the pH reaches 12. Do not add ultrasound during the stirring of the solid-liquid mixture. Use a vacuum filtration system to separate the solid and liquid. The filtrate is a beryllium-containing solution, and the filter residue is a uranium-containing residue. Add water to the filtrate to a pH of 9, boil it, and you can get Be(OH)2 precipitate. The radioactivity in the beryllium product is 45Bq / g, and the recovery rate is 98%. Add sodium carbonate solution to the filter residue to dissolve the uranium, and filter to obtain sodium uranyl tricarbonate filtrate, the uranium recovery rate is 98.5%, the beryllium content is 280mg / L, and the filter residue is iron hydroxide, and the beryllium uranium residue is less than 0.5mg / g.
[0027] Example 2
[0028] Take 200mL of uranium-beryllium solution, in which the uranium content is 0.1g / L, the beryllium content is 3g / L, and the iron content is 10g / L. Adjust the potential to 450mV by adding hydrogen peroxide, and stir until no bubbles are generated. Add NaOH solid to the pretreated solution and stir continuously until the pH reaches 13. Add ultrasound during the stirring of the solid-liquid mixture at a power of 30Hz and react for 2h to accelerate the complete dissolution of beryllium. Use a vacuum filtration system to separate the solid and liquid. The filtrate is a beryllium-containing solution, and the filter residue is a uranium-containing residue. Add water to the filtrate until the pH reaches 8 and boil it to obtain Be(OH)2 precipitate. The radioactivity in the beryllium product is only 25Bq / g, and the recovery rate is 99%. Sodium carbonate solution was added to the filter residue to dissolve the uranium, and the sodium uranyl tricarbonate filtrate was obtained after filtration. The uranium recovery rate was 99%, and the beryllium content was 21 μg / L. The filter residue was ferric hydroxide. The uranium and iron were separated, and the residual beryllium and uranium were less than 0.5 mg / g.
[0029] Example 3
[0030] Take 200mL of a solution containing iron, uranium and beryllium, of which the uranium content is 1g / L, the beryllium content is 3g / L, and the iron content is 5g / L. Adjust the potential to 550mV by adding hydrogen peroxide and stir until no bubbles are generated. Add solid NaOH to the pretreated solution and stir continuously until the pH reaches 13.5. Add ultrasound during the stirring of the solid-liquid mixture at a power of 50Hz and react for 1h to accelerate the complete dissolution of beryllium. Use a vacuum filtration system to separate the solid and liquid. The filtrate is a beryllium-containing solution, and the filter residue is a uranium-containing residue. Add water to the filtrate until the pH reaches 7 and boil it to obtain Be(OH)2 precipitate. The radioactivity in the beryllium product is only 44Bq / g, and the recovery rate is 99%. Sodium carbonate solution was added to the filter residue to dissolve the uranium, and the sodium uranyl tricarbonate filtrate was obtained after filtration. The uranium recovery rate was 99.2%, the beryllium content was 12 μg / L, and the filter residue was ferric hydroxide, and the residual beryllium and uranium content was less than 0.5 mg / g.
Claims
1. A method for deep separation of uranium and beryllium from a beryllium iron uranium coexisting solution based on ultrasound, characterized in that: The beryllium iron uranium coexisting solution is subjected to oxidation pretreatment to obtain a pretreated solution; The pretreatment solution is adjusted to a pH value of above 12, subjected to ultrasonic treatment, and then filtered to obtain a beryllium-containing solution and uranium-iron co-precipitation slag; the uranium-iron co-precipitation slag is dissolved with a sodium carbonate solution to obtain a sodium uranyl tricarbonate solution and an iron hydroxide slag phase.
2. The method for deep separation of uranium and beryllium from a beryllium-iron-uranium coexisting solution based on ultrasound according to claim 1, characterized in that: In the beryllium-iron-uranium coexistence solution, the beryllium content is 3-15 g / L, the iron content is 5-30 g / L, and the uranium content is 0.1-3 g / L.
3. A method for deep separation of uranium and beryllium from a beryllium-iron-uranium coexisting solution based on ultrasound according to claim 1 or 2, characterized in that: During the oxidation pretreatment, hydrogen peroxide is used as an oxidant, and the oxidation potential is adjusted to between -400 and -550 mV.
4. The method for deep separation of uranium and beryllium from a beryllium-iron-uranium coexisting solution based on ultrasound according to claim 1, characterized in that: The conditions of the ultrasonic treatment are: frequency of 20kHz to 50kHz, and time of 1 to 3h.
5. The method for deep separation of uranium and beryllium from a beryllium-iron-uranium coexisting solution based on ultrasound according to claim 1, characterized in that: The beryllium-containing solution is adjusted to a pH of 7 to 9 and boiled to obtain Be(OH)2 precipitation.
6. The method for deep separation of uranium and beryllium from a beryllium-iron-uranium coexisting solution based on ultrasound according to claim 1, characterized in that: The concentration of the sodium carbonate solution is 200-300 g / L.