Preparation process of high-concentration single bastnaesite acid-soluble feed liquid
By introducing the excellent solution as the bottom water of the optimal immersion step in the rare earth smelting separation process and using the first washing water as the bottom water of the optimal dissolving step, a virtuous cycle is formed, which solves the existing process's large resource consumption, high energy consumption and water consumption. The problem of resource consumption has achieved efficient rare earth separation and concentration, reducing production costs.
Patent Information
- Application Number
- CN202411644005.8
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-11-18
- Publication Date
- 2025-02-18
AI Technical Summary
The existing rare earth smelting and separation process has a long flow, high resource consumption, high energy consumption, and requires a large amount of clean water as bottom water, resulting in increased difficulty and energy consumption of water resource consumption and subsequent concentration stages.
By introducing the best solution as bottom water in the best leach step, the cooked ore reacts with the best solution first, and then slowly adds hydrochloric acid to carry out the acid leach reaction, obtaining the best leach solution and the best leach residue, and the best leach residue is washed. Next, a wash water is used as the bottom water in the optimum dissolution step, and the optimum solution is recovered and put into the optimum dipping step to form a virtuous cycle, thereby increasing the concentration of the chloride rare earth liquid.
It reduces water resources consumption, reduces energy consumption, optimizes the concentration stage, improves process production efficiency, reduces production costs, and enables the acid solution to be directly used for subsequent extraction, separation and purification, and is used to produce rare earth products.
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Figure CN119464777A_ABST
Abstract
Description
Technical Field
[0001] The present application relates to the technical field of rare earth smelting and separation, and in particular to a preparation process of a high-concentration single bastnaesite acid-soluble solution. Background Art
[0002] In the existing traditional rare earth ore production and processing technology, the rare earth ore is usually calcined, and then the calcined ore is acid-leached to obtain a superior leaching solution and superior leaching residue; the superior leaching residue is alkali-converted and acid-dissolved to obtain a superior solution; the superior solution and the superior leaching solution are then mixed, and after impurity removal and concentration, extraction, separation and purification are carried out.
[0003] The above conventional process methods have long procedures, large resource consumption and high energy consumption. In addition, in the existing process, the optimal leaching and optimal dissolution stages usually require the addition of a large amount of clean water as bottom water for reaction, which will consume a large amount of water resources on the one hand, and increase the difficulty and energy consumption of the subsequent concentration stage on the other hand. Summary of the invention
[0004] The purpose of this application is to provide a preparation process for a high-concentration single bastnaesite acid-soluble feed solution, which can reduce the consumption of water resources, and has mild process conditions and low energy consumption. At the same time, it can optimize the concentration section, which helps to further improve the process production efficiency and reduce production costs. The acid-soluble feed solution produced by the scheme can be directly used for subsequent extraction, separation and commission for the production of rare earth products.
[0005] The technical solution of this application is as follows:
[0006] On the one hand, the present application embodiment provides a preparation process of a high-concentration single bastnaesite acid solution, which comprises the following steps:
[0007] Pre-leaching: bastnaesite is roasted to obtain cooked ore; a pre-leaching solution is added to the cooked ore as the bottom water for the pre-leaching operation, and then hydrochloric acid is added to carry out acid leaching reaction to obtain a pre-leaching solution and a pre-leaching residue, and the pre-leaching residue is washed to obtain primary washing water;
[0008] Pre-dissolving: the washed leaching residue is successively alkali-converted and water-washed to obtain water-washed residue, and the first washing water is added to the water-washed residue as bottom water, and then hydrochloric acid is added to perform a pre-dissolving operation to obtain a pre-solution and a pre-dissolving residue; wherein the pre-dissolving residue is dried to obtain a cerium-enriched product, and the pre-solution is returned to the above-mentioned pre-leaching step and used as the bottom water of the pre-leaching operation;
[0009] Impurity removal: The above-mentioned superior leaching solution is tempered and defluorinated, and the lead and barium are removed from the feed solution to obtain a rare earth cerium-containing feed solution, that is, the above-mentioned acid-soluble feed solution, which is used for subsequent extraction and separation to prepare rare earth products.
[0010] Furthermore, in some embodiments of the present application, in the above-mentioned optimal leaching step, when the mature ore is optimally leached, the process temperature condition is 45-55°C.
[0011] Furthermore, in some embodiments of the present application, in the above-mentioned optimal leaching step, the solid-to-liquid ratio of the added cooked ore to the optimal solution is 1:2.
[0012] Furthermore, in some embodiments of the present application, in the above-mentioned optimal leaching step, the volume ratio of the added hydrochloric acid to the optimal solution is (0.20-0.24):1.
[0013] Furthermore, in some embodiments of the present application, in the above-mentioned optimal leaching step, the optimal solution is added to the cooked ore as the bottom water of the optimal leaching operation, the reaction is carried out for 30 minutes, and then hydrochloric acid is added at a uniform rate to carry out acid leaching reaction. After the acid addition is completed, the stirring reaction is continued for 30 minutes.
[0014] Furthermore, in some embodiments of the present application, in the above-mentioned leaching step, the total time consumed for uniformly adding hydrochloric acid is 1 to 10 hours.
[0015] The embodiment of the present application also provides a high-concentration single fluorocarbon cerium ore acid-soluble solution, which is prepared by the above-mentioned preparation process.
[0016] On the other hand, an embodiment of the present application also provides an application of the above-mentioned high-concentration single fluorocarbon cerium ore acid solution in the preparation of rare earth products.
[0017] Compared with the prior art, the embodiments of the present application have at least the following advantages or beneficial effects:
[0018] In view of the above aspects, the embodiment of the present application provides a preparation process of a high-concentration single fluorocarbon cerium ore acid-soluble feed solution. In the process, a preferred solution is first introduced into the preferred leaching step as the bottom water of the preferred leaching operation, so that the cooked ore first reacts with the preferred solution, and then hydrochloric acid is slowly and uniformly added for acid leaching reaction to obtain a preferred leaching solution and a preferred leaching residue, and then the preferred leaching residue is washed to obtain a primary wash water. Then the preferred dissolution step is performed: the preferred leaching residue is subjected to alkali conversion and water washing to obtain a water-washed residue, and then the previously obtained primary wash water is added to the water-washed residue, and the primary wash water is used as the reaction bottom water, and hydrochloric acid is added thereto for a preferred dissolution operation to obtain a preferred solution and a preferred soluble slag, wherein the preferred soluble slag is a cerium-enriched product, and the preferred solution is recovered and returned to the preferred leaching step, and the preferred solution is used as the bottom water of the preferred leaching operation. As for the optimal leaching solution obtained in the optimal leaching step, it is directly subjected to impurity removal work to remove impurities such as fluorine, lead, and barium, thereby obtaining a rare earth cerium-fewer solution, that is, the acid-soluble solution provided in the present application; the obtained acid-soluble solution can be directly used for subsequent extraction, separation, and purification operations for the production of rare earth products.
[0019] In the production process, the optimal solution is used as the bottom water of the optimal leaching process, so as to increase the concentration of the rare earth chloride feed liquid in the optimal leaching solution produced in the optimal leaching step; the primary washing water is used as the bottom water of the optimal dissolution process to increase the concentration of the rare earth chloride in the optimal solution produced in the optimal dissolution step, and the optimal solution is recycled and put into the optimal leaching step to form a virtuous cycle, which can eventually effectively increase the concentration of the rare earth chloride in the optimal leaching solution produced in the optimal leaching step, thereby optimizing the traditional concentration section. Even without concentration, the optimal leaching solution has a sufficiently high concentration, so that subsequent tempering, defluorination, lead removal, barium removal and other work can be directly carried out, and the entire process flow is optimized. The acid-soluble feed liquid finally obtained can be directly used for extraction, separation and purification of rare earth production; in addition, by recycling the optimal solution and the primary washing water, water resource consumption can be further saved, and the process conditions are mild, which can effectively save energy consumption, thereby further reducing process production costs and improving production efficiency. BRIEF DESCRIPTION OF THE DRAWINGS
[0020] In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings required for use in the embodiments will be briefly introduced below. It should be understood that the following drawings only show certain embodiments of the present application and therefore should not be regarded as limiting the scope. For ordinary technicians in this field, other related drawings can be obtained based on these drawings without paying creative work.
[0021] Figure 1 A process flow chart of a preparation process of a high-concentration single fluorocarbon cerium ore acid-soluble solution provided in an embodiment of the present application. DETAILED DESCRIPTION
[0022] In order to make the purpose, technical scheme and advantages of the embodiments of the present application clearer, the technical scheme in the embodiments of the present application will be described clearly and completely below. If the specific conditions are not specified in the embodiments, they are carried out according to the conventional conditions or the conditions recommended by the manufacturer. If the manufacturer is not specified for the reagents or instruments used, they are all conventional products that can be purchased commercially.
[0023] It should be noted that the term "include" or any other variation thereof is intended to cover non-exclusive inclusion, so that a process, method, article or device including a series of elements includes not only those elements, but also other elements not explicitly listed, or also includes elements inherent to such process, method, article or device. In the absence of further restrictions, the elements defined by the sentence "include..." do not exclude the existence of other identical elements in the process, method, article or device including its elements.
[0024] It should be noted that, in the absence of conflict, the embodiments and features in the embodiments of the present application may be combined with each other.
[0025] The features and performance of the present application are further described in detail below in conjunction with the embodiments.
[0026] Example
[0027] The present application example provides a preparation process for a single bastnaesite acid solution, and the process flow is as follows: Figure 1 As shown; it includes the following steps:
[0028] Pre-leaching: bastnaesite is roasted to obtain cooked ore; under the condition of maintaining 45-55°C throughout the process, a pre-leaching solution is added to the cooked ore at a solid-liquid ratio of 1:2 as the bottom water for the pre-leaching operation, and the reaction is carried out for 30 minutes, and then hydrochloric acid is added (the volume ratio of the added hydrochloric acid to the pre-leaching solution is (0.20-0.24):1; the hydrochloric acid is added at a uniform rate, and the total time consumed for adding the hydrochloric acid is 1-10 hours). After all the hydrochloric acid is added, the reaction is continued by stirring for 30 minutes to obtain a pre-leaching solution and a pre-leaching residue; the pre-leaching residue is washed to obtain a wash water;
[0029] Pre-dissolving: the washed leaching residue is successively alkali-converted and water-washed to obtain water-washed residue, and the first washing water is added to the water-washed residue as bottom water, and then hydrochloric acid is added to perform a pre-dissolving operation to obtain a pre-solution and a pre-dissolving residue; wherein the pre-dissolving residue is dried to obtain a cerium-enriched product, and the pre-solution is returned to the above-mentioned pre-leaching step and used as the bottom water of the pre-leaching operation;
[0030] Impurity removal: The above-mentioned superior leaching solution is tempered and defluorinated, and the lead and barium are removed from the solution to obtain a rare earth cerium-less solution, namely the above-mentioned acid-soluble solution.
[0031] Experimental verification of this application scheme:
[0032] 1: Adjustments are made based on the process steps of the embodiment: In the above-mentioned optimal leaching step, after adding bottom water (optimal solution) to the cooked ore, hydrochloric acid is directly added to react without waiting for the reaction, and the whole process is under room temperature conditions.
[0033] According to the above method, the amount of hydrochloric acid added was adjusted to obtain multiple groups of excellent leaching solutions, and the rare earth oxide concentration (REO), the ratio of rare earth cerium in rare earth oxide (C / R), and the hydrogen ion concentration (H + ).
[0034] The results of each group are shown in Table 1:
[0035] The bottom water (optimal solution) used was tested to have the following parameters: REO = 157.95 g / L; C / R = 5.04%; H + =0.23mol / L.
[0036] Table 1
[0037]
[0038] Based on the above experiment 1, the acid addition time was further adjusted, as shown in Table 2:
[0039] Table 2
[0040]
[0041] It can be seen from the results that, under the same other reaction conditions, extending the acid addition time can reduce the cerium distribution in the superior leaching product by about 3%.
[0042] 2. Adjustments were made based on the process steps of the embodiment: In the above-mentioned optimal leaching step, bottom water was added to the cooked ore at room temperature, and hydrochloric acid was added after a period of reaction. After all the hydrochloric acid was added, the temperature was adjusted and the stirring reaction was continued for 30 minutes.
[0043] According to the above method, the relevant process conditions were adjusted to obtain multiple groups of excellent leaching solutions, and the rare earth oxide concentration (REO), the ratio of rare earth cerium in rare earth oxide (C / R), and the hydrogen ion concentration (H + ).
[0044] The results of each group are shown in Table 3:
[0045] The relevant parameters of the bottom water (optimal solution) used are: REO = 157.95 g / L; C / R = 5.04%; H + =0.23mol / L.
[0046] Table 3
[0047]
[0048] It can be seen from the results that it is of little significance to react the cooked ore with bottom water at room temperature first; heating to 50°C after the acid is added, stopping heating and stirring the reaction for 30 minutes can reduce the cerium distribution in the optimal leaching product by about 6%.
[0049] Based on the above experiment 2, the effect of temperature conditions on the reaction was further verified. The results are shown in Table 4:
[0050] Table 4
[0051]
[0052] It can be seen from the results that increasing the temperature is beneficial to improving the REO concentration in the leaching solution product and can effectively inhibit the dissolution of cerium.
[0053] Based on the above experimental conclusions, it can be concluded that in the optimal leaching step, the best process is to maintain a temperature of about 50°C throughout the process, the cooked ore first reacts with bottom water, and then hydrochloric acid is added to react, thereby obtaining the preparation process provided in the embodiment of the present application; wherein, each principle ratio is a more suitable ratio range obtained through theoretical calculation when the amount of cooked ore is determined.
[0054] 3. According to the process steps of the embodiment, the relevant process conditions are changed to obtain multiple groups of optimized leaching solutions, and the rare earth oxide concentration (REO), the ratio of rare earth cerium in rare earth oxide (C / R), and the hydrogen ion concentration (H + ). The results are shown in Table 5:
[0055] The relevant parameters of the bottom water (optimal solution) used are: REO = 157.95 g / L; C / R = 5.04%; H + =0.23mol / L.
[0056] Table 5
[0057]
[0058] Another batch of cooked ore was taken, and bottom water (optimal solution) was added to carry out relevant processes. The results are shown in Table 6:
[0059] The relevant parameters of the bottom water (optimal solution) used are: REO = 145.16 g / L; C / R = 1.05%; H + =0.048mol / L.
[0060] Table 6
[0061]
[0062]
[0063] Take a new batch of cooked ore, add bottom water (optimal solution) to carry out relevant processes, the results are shown in Table 7:
[0064] The relevant parameters of the bottom water (optimal solution) used are: REO = 124.86 g / L; C / R = 11.51%; H + =0.24mol / L.
[0065] Table 7
[0066]
[0067] Take a new batch of cooked ore, add bottom water (optimal solution) to carry out relevant processes, the results are shown in Table 8:
[0068] The relevant parameters of the bottom water (optimal solution) used are: REO = 121.10 g / L; C / R = 13.57%; H + =0.17mol / L.
[0069] Table 8
[0070]
[0071] Based on the above results, it can be concluded that maintaining a certain temperature (around 50°C) throughout the process is beneficial to reducing the dissolution of cerium components, and 50°C is the optimal temperature.
[0072] In summary, the embodiment of the present application provides a preparation process for a high-concentration single fluorocarbon cerium ore acid-soluble feed solution. In its production process, the optimal solution is used as the bottom water of the optimal leaching process, so as to increase the concentration of the rare earth chloride feed solution in the optimal leaching solution produced in the optimal leaching step; the primary washing water is used as the bottom water of the optimal dissolution process to increase the concentration of rare earth chloride in the optimal solution produced in the optimal dissolution step, and then the optimal solution is recycled and put into the optimal leaching step to form a virtuous cycle, which can ultimately effectively increase the concentration of rare earth chloride in the optimal leaching solution produced in the optimal leaching step, thereby optimizing the traditional concentration section. Even if concentration is not performed, the optimal leaching solution has a sufficiently high concentration, so that subsequent tempering, fluorine removal, lead removal, and barium removal can be directly carried out, and the entire process flow is optimized. The acid-soluble feed solution finally obtained can be directly used for extraction, separation, and purification of rare earth production; in addition, by recycling the optimal solution and the primary washing water, water resource consumption can be further saved, and the process conditions are mild, which can effectively save energy consumption, thereby further reducing the process production cost and improving production efficiency.
[0073] The embodiments described above are part of the embodiments of the present application, rather than all of the embodiments. The detailed description of the embodiments of the present application is not intended to limit the scope of the present application for protection, but merely represents the selected embodiments of the present application. Based on the embodiments in the present application, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present application.
Claims
1. A process for preparing a high-concentration single bastnaesite acid solution, characterized in that: It includes the following steps: Pre-leaching: bastnaesite is roasted to obtain cooked ore; a pre-leaching solution is added to the cooked ore as the bottom water for the pre-leaching operation, and then hydrochloric acid is added to carry out acid leaching reaction to obtain a pre-leaching solution and a pre-leaching residue, and the pre-leaching residue is washed to obtain primary washing water; Pre-dissolving: the washed leaching residue is successively alkali-converted and water-washed to obtain water-washed residue, and the first washing water is added to the water-washed residue as bottom water, and then hydrochloric acid is added to perform a pre-dissolving operation to obtain a pre-solution and a pre-dissolving residue; wherein the pre-dissolving residue is dried to obtain a cerium enrichment, and the pre-solution is returned to the pre-leaching step and used as bottom water for the pre-leaching operation; Impurity removal: the superior leaching solution is subjected to conditioning and defluorination, and the lead and barium are removed from the slurry to obtain a rare earth cerium-less slurry, namely the acid-soluble slurry.
2. The process for preparing a high-concentration single bastnaesite acid-soluble solution according to claim 1, characterized in that: In the preferred leaching step, when the mature ore is subjected to preferred leaching, the process temperature condition is 45-55°C.
3. The process for preparing a high-concentration single bastnaesite acid-soluble solution according to claim 1, characterized in that: In the optimal leaching step, the solid-to-liquid ratio of the added cooked ore to the optimal solution is 1:
2.
4. The process for preparing a high-concentration single bastnaesite acid-soluble solution according to claim 1, characterized in that: In the leaching step, the volume ratio of the added hydrochloric acid to the leaching solution is (0.20-0.24):
1.
5. The process for preparing a high-concentration single bastnaesite acid-soluble solution according to claim 1, characterized in that: In the preferred leaching step, the preferred solution is added to the cooked ore as the bottom water for the preferred leaching operation, and the reaction is carried out for 30 minutes. Then, hydrochloric acid is added at a uniform rate to carry out an acid leaching reaction. After the acid addition is completed, the reaction is continued by stirring for 30 minutes.
6. The process for preparing a high-concentration single bastnaesite acid-soluble solution according to claim 5, characterized in that: In the soaking step, the total time consumed by uniformly adding hydrochloric acid is 1 to 10 hours.
7. A high concentration single bastnaesite acid solution, characterized in that: The method is prepared by the preparation process according to any one of claims 1 to 6.
8. Use of the high-concentration single bastnaesite acid solution as claimed in claim 7 in the preparation of rare earth products.