CN109722532B - Leaching method of weathering crust leaching type rare earth ore and rare earth product - Google Patents
Leaching method of weathering crust leaching type rare earth ore and rare earth product Download PDFInfo
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Abstract
The invention relates to the field of hydrometallurgy, in particular to an ore leaching method of weathering crust elution-deposited rare earth ore and a rare earth product. The invention provides an ore leaching method of weathering crust elution-deposited rare earth ore, which comprises the following steps: leaching weathering crust eluviation type rare earth ore by using a leaching agent, and collecting rare earth leachate flowing out of the bottom of the ore soil by two times; and (3) removing impurities and precipitating rare earth from the rare earth leaching solution collected for the first time, mixing the rare earth leaching solution with the rare earth leaching solution collected for the second time, supplementing a leaching agent, and returning the mixed solution serving as a fresh leaching agent to the rare earth ore for leaching. The ore leaching method provided by the invention is simple and feasible, reduces the hydrometallurgy operation load, and is economic and environment-friendly.
Description
Technical Field
The invention relates to the field of hydrometallurgy, in particular to an ore leaching method of weathering crust elution-deposited rare earth ore and a rare earth product.
Background
The storage amount of the medium-heavy rare earth contained in the weathering crust leaching type rare earth ore accounts for more than 80 percent of the world, the defect of low content of the medium-heavy rare earth in the mineral type rare earth ore is made up, the mineral type rare earth ore is greatly concerned by downstream industries using the medium-heavy rare earth, the mineral type rare earth ore is a valuable mineral resource, and the development and the utilization of the mineral type rare earth ore play important roles in the world rare earth industry.
At present, the leaching process commonly used in weathering crust leaching type rare earth ore is a heap leaching process and an in-situ leaching process, wherein a certain amount of leaching agent solution is firstly injected into ore soil, the leaching agent solution migrates downwards in the ore soil and is subjected to ion exchange with rare earth ions adsorbed on clay minerals, and finally rare earth leachate is collected through a flow guide hole and a liquid collection ditch at the bottom of the ore soil and is completely sent to a hydrometallurgy workshop, and rare earth can be recovered through impurity removal and precipitation.
The traditional method for circularly leaching the rare earth leachate is to mix and collect all the rare earth leachate flowing out from the bottom of the ore soil, then concentrate the leachate to remove impurities by using ammonium bicarbonate, regulate and control the pH value of the solution, and precipitate and recover rare earth. The traditional rare earth leachate circulating leaching method is used for collecting the rare earth leachate flowing out of the bottom of the ore soil at one time, so that the amount of the collected rare earth leachate is large, and the concentration of the rare earth is low and is generally only 0.5-1.5 g/L. A large amount of rare earth leachate needs to be subjected to impurity removal and rare earth precipitation, the hydrometallurgy workload is large, the production period is long, more structures such as an impurity removal pool, a sedimentation pool and the like need to be prepared, and the capital investment is high; the rare earth concentration in the rare earth leaching solution is too low, so that the rare earth loss in the impurity removal process is high, the consumption of the precipitator is increased, and the rare earth recovery rate is low.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The invention aims to provide an ore leaching method for weathering crust leaching type rare earth ore, which reduces the hydrometallurgy workload, reduces the requirements on structures such as an impurity removal tank, a sedimentation tank and the like, and has high rare earth leaching rate.
Another object of the present invention is to provide a rare earth product having high rare earth purity.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
the invention provides an ore leaching method of weathering crust elution-deposited rare earth ore, which comprises the following steps:
leaching weathering crust eluviation type rare earth ore by using a leaching agent, and collecting rare earth leachate flowing out of the bottom of the ore soil by two times;
and (3) removing impurities and precipitating rare earth from the rare earth leaching solution collected for the first time, mixing the rare earth leaching solution with the rare earth leaching solution collected for the second time, supplementing a leaching agent, and returning the mixed solution serving as a fresh leaching agent to the rare earth ore for leaching.
The invention also provides a rare earth product which is obtained by leaching according to the leaching method of the weathering crust elution type rare earth ore.
Compared with the prior art, the invention has the following beneficial effects:
the method has the advantages that the rare earth leaching solution is collected twice, and the operation is simple and feasible; secondly, the method only carries out impurity removal and precipitation operation on the rare earth leaching solution collected for the first time, reduces the hydrometallurgy operation load, shortens the production period, reduces the requirements on structures such as an impurity removal pool, a precipitation pool and the like, and reduces the one-time construction investment; secondly, the concentration of rare earth and impurity ions in the rare earth leachate collected for the second time is lower, the concentration of the rare earth and impurity ions in the rare earth leachate collected for the first time can be improved, the consumption of an impurity removing agent and a precipitating agent is reduced, and the impurity removing rate and the rare earth recovery rate are increased; in addition, the rare earth leachate collected for the second time is directly mixed with the rare earth leachate collected for the first time after impurity removal and precipitation, and the mixture can be returned to a mine for use without adjusting the pH value of the solution after adding a proper amount of leaching agent, so that the production process is simplified, the recycling of the wastewater in a mining area is realized, no wastewater is discharged, and the process is economic and environment-friendly.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, and it is apparent that the drawings in the following description are only some embodiments of the present invention, and therefore should not be considered as limiting the scope of protection, and it is obvious for those skilled in the art that other drawings can be obtained based on these drawings without creative efforts.
FIG. 1 is a flow chart of the weathering crust elution-deposited rare earth ore leaching process of the present invention;
FIG. 2 is a schematic diagram of the outflow curve and secondary collection of the weathering crust elution type rare earth ore leaching process in example 1 of the present invention.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The ore leaching method for the weathering crust elution-deposited rare earth ore provided by the embodiment of the invention is briefly described below.
The invention provides an ore leaching method of weathering crust elution-deposited rare earth ore, which comprises the following steps:
s1 leaching weathering crust eluviation type rare earth ore
Rare earth elements in weathering crust eluviation type rare earth ore are leached by adopting an in-situ leaching process, and then water-jacking operation is carried out by using top water. Specifically, a leaching agent is injected into a naturally buried ore body, and the leaching agent migrates downwards in ore soil and performs ion exchange with rare earth ions adsorbed on clay minerals to make rare earth enter a solution; after all the leaching agent solution is injected into the ore body, the ore body is washed by using top water so as to discharge the solution remained in the ore soil, the recovery rate of the rare earth is improved, and the pollution of the leaching agent to the ore soil is reduced.
Further, during leaching, the clay minerals that adsorb the rare earth ions constitute an ion exchange "resin" that is complex in structure and non-uniform in size. Wherein the clay mineral for adsorbing rare earth ions is a stationary phase, the leaching agent is a mobile phase, and an ion exchange reaction occurs between the clay mineral and the leaching agent. The rare earth ions on the clay mineral are subjected to ion exchange with the cations in the leaching agent, the cations in the leaching agent are adsorbed, and the rare earth ions are desorbed. In addition, the weathering crust leaching type rare earth ore also contains ion phase metal impurities which can also enter the solution through ion exchange reaction with cations in a leaching agent, so that the rare earth ions are leached together in the leaching process, and the subsequent impurity removal and precipitation process is carried out.
Furthermore, the leaching agent is one or a mixture of more of ammonium sulfate, ammonium chloride and ammonium nitrate solution, the mass concentration of the leaching agent is 1-4%, and the volume of the leaching agent added in each 1kg of rare earth ore is 0.2-0.8L. The leaching agent has strong selectivity, can selectively react with rare earth elements in the ore soil, and is difficult to react with other components, so that a good separation effect is achieved, and leaching of impurities is inhibited. In addition, the larger the solid-to-liquid ratio of the leaching agent to the rare earth mineral in a certain range, the more the cations in the leaching agent contact with the rare earth ions adsorbed by the clay mineral, the more the ion exchange reaction is facilitated, the higher the rare earth leaching rate is, however, after the solid-to-liquid ratio is increased to a certain value, if the solid-to-liquid ratio is continuously increased, the rare earth leaching rate is not increased, and due to the fact that the consumption amount of the reagent is large, the production cost is increased and the environmental load is increased, therefore, in the in-situ leaching process, the proper solid-to-liquid ratio is one of the key factors for guaranteeing higher rare earth recovery rate.
Further, the top water is one or a mixture of more of distilled water, tap water, river water and well water, and the volume of the top water added to each 1kg of rare earth ore is 0.8-1.5L.
S2, collecting rare earth leachate twice
As shown in fig. 1, when the rare earth leachate flows out from the bottom of the rare earth ore, the collection is started until the volume of the collected rare earth leachate is the same as that of the leaching agent or when the concentration of the flowing rare earth leachate is reduced to be below 0.5g/L after passing through a maximum value, the collection is stopped, and the collection is the first collection; and stopping collecting the rare earth leachate flowing out after the first collection until no rare earth leachate flows out, wherein the second collection is adopted.
Furthermore, the rare earth leaching solution collected for the first time only accounts for 20-50% of the total liquid yield, so that the hydrometallurgy operation load is reduced, the production period is shortened, the requirements on structures such as an impurity removal pool and a sedimentation pool are reduced during subsequent impurity removal and sedimentation operation, and the one-time construction investment is reduced; meanwhile, the rare earth concentration of the rare earth leachate collected for the second time is lower than 0.5g/L, so that the concentration of rare earth and impurity ions in the rare earth leachate collected for the first time can be improved, the consumption of an impurity removing agent and a precipitating agent is reduced, and the impurity removing rate and the rare earth recovery rate are increased.
S3, impurity removal and precipitation steps
And (3) removing impurities and precipitating rare earth from the rare earth leaching solution collected for the first time, mixing the rare earth leaching solution with the rare earth leaching solution collected for the second time, supplementing a leaching agent, and returning the mixed solution serving as a fresh leaching agent to the rare earth ore for leaching.
Further, removing impurities by using 5-20% by mass of ammonium bicarbonate as an impurity removing agent, adjusting the pH to 4.5-5.0, stirring for 1-3 hours, standing and aging for 1-6 hours, and transferring supernatant into a sedimentation tank to precipitate rare earth. The volume ratio of the impurity removing agent to the rare earth leachate to be removed, which is collected for the first time, is 0.004-0.05: 1, and preferably, sulfuric acid, hydrochloric acid or ammonia water is used for adjusting the pH in the embodiment.
When the ammonium salt is used for leaching rare earth, impurity ions such as aluminum, iron, calcium, potassium and the like are influenced by the physical and chemical properties of minerals, a leaching agent solution and a related leaching process, and the rare earth ions are exchanged by ammonium ions and enter a rare earth leaching solution. The main impurities of the leaching solution of the weathering crust leaching type rare earth ore comprise residual leaching agent and non-rare earth ion impurity ions leached together with rare earth. The impurities must be removed before extracting the rare earth, otherwise, the consumption of raw materials is increased, and the purity of rare earth oxide is influenced or the rare earth carbonate is not easy to form crystal form precipitate. Non-rare earth impurity aluminum and rare earth ions are exchanged into the solution to different degrees, so that subsequent rare earth extraction is not facilitated, and the content of aluminum is also an important standard for inspecting the quality of rare earth products.
Further, when ammonium bicarbonate is used as an impurity removal agent in the impurity removal process, aluminum ions are the main impurities in the rare earth leachate, floccules are formed and precipitated when the ammonium bicarbonate precipitates the rare earth elements, so that the purity of the rare earth product is not high, and the aluminum ions are hydrolyzed to generate colloidal aluminum hydroxide, so that the crystallization active area is reduced, and the crystal form precipitate is not easy to generate. Therefore, the pH value of the solution is adjusted to 4.5-5.0, only the impurity ions such as aluminum and the like can form carbonic acid precipitation, and the rare earth is not precipitated. Thereby achieving the purpose of removing impurities.
Further, precipitating the rare earth by using 5-20% of ammonium bicarbonate as a precipitator, stirring for 1-3 hours, and standing and aging for 1-6 hours; wherein the volume ratio of the precipitator to the rare earth leaching solution subjected to impurity removal is 0.01-0.1: 1. And at the moment, when the ammonium bicarbonate with the amount is added into the leaching solution after impurity removal, the pH is adjusted to 6-7, and rare earth ions can form rare earth carbonate to precipitate to obtain a rare earth carbonate product.
It should be noted that, although ammonium bicarbonate is adopted in both the impurity removal process and the precipitation process, the ammonium bicarbonate plays a completely different role in the two processes, and in the impurity removal process, the ammonium bicarbonate and aluminum ions generate aluminum carbonate precipitation at a pH value of 4.5-5.0 without precipitating rare earth. During the precipitation process, ammonium bicarbonate and rare earth ions form rare earth carbonate precipitates at a pH value of 6-7.
Furthermore, the rare earth leachate collected for the second time is directly mixed with the rare earth leachate collected for the first time after impurity removal and precipitation, and after a proper amount of leaching agent is added, the solution can be returned to a mine for use without adjusting the pH value of the solution, so that the production process is simplified, the recycling of the waste water in a mining area is realized, no waste water is discharged, and the process is economic and environment-friendly.
The features and properties of the present invention are described in further detail below with reference to examples.
Example 1
S1 leaching weathering crust eluviation type rare earth ore
Weighing 250g of dried weathering crust eluviation type rare earth ore sample, slowly and uniformly loading the weathering crust eluviation type rare earth ore sample into a glass column with the diameter of 45mm, paving 2-3 layers of filter paper on the surface of an ore layer, then feeding 100mL of 2% ammonium sulfate solution at the speed of 0.4mL/min by a constant flow pump, wherein the liquid-solid ratio of the volume (L) of the ammonium sulfate solution to the mass (kg) of the rare earth ore is 0.4:1, and feeding the ammonium sulfate solution to the top of the ore sample for leaching operation. After the ammonium sulfate solution is completely injected into the glass column, 200mL of distilled water is used for water-lifting operation, and the liquid-solid ratio of the distilled water (L) to the mass (kg) of the rare earth ore is 0.8: 1.
S2, collecting rare earth leachate twice
And (3) collecting the rare earth leachate at the bottom of the glass column by using a beaker, stopping the first collection after the volume of the effluent liquid reaches 100mL, wherein the instantaneous concentration is 0.32g/L (less than 0.5g/L) and 0.16g/L respectively when the volume of the leachate reaches 100mL, and the concentration of ammonium radicals is higher and is about 0.2 mol/L. The beaker is then replaced and a second collection is performed until no more liquid flows out, stopping the collection.
In the rare earth leaching solution collected for the first time, the concentrations of rare earth and aluminum are respectively 2.15g/L and 0.34g/L, and the concentration of ammonium radicals is 0.089 mol/L. In the leachate collected for the second time, the concentrations of rare earth and aluminum are respectively 0.0062g/L and 0.0075g/L, and the concentration of ammonium radicals is 0.019 mol/L.
S3, impurity removal and precipitation steps
And adding 2.5mL of 10% ammonium bicarbonate solution into 100mL of rare earth leachate collected for the first time, adjusting the pH of the solution to 4.5 by using sulfuric acid and ammonia water, stirring for 1h, standing and aging for 3h, and filtering to obtain the rare earth leachate after impurity removal.
And adding 3.5mL of 10% ammonium bicarbonate solution into the rare earth leachate after impurity removal, stirring for 1h, standing and aging for 3h, and filtering to obtain rare earth carbonate and supernatant, wherein the purity of the rare earth in the rare earth carbonate product is 95.02%, and the recovery rate of the rare earth is 96.33%.
And mixing the supernatant with the leachate collected for the second time, and adding a proper amount of ammonium sulfate solid into the solution to enable the concentration of the ammonium sulfate to be 2% so as to obtain the recyclable leaching agent.
And (3) carrying out a column leaching test on 250g of dried weathering crust elution type rare earth ore sample by using the leaching agent recycled, and repeating the test to obtain the rare earth leaching rate of 98.41%.
Examples 2 to 6
The mineral leaching method for the weathering crust elution type rare earth ore provided in the embodiment 2-6 is basically operated in the same way as the mineral leaching method for the weathering crust elution type rare earth ore provided in the embodiment, and the difference is that the specific operation conditions are changed.
Example 2
S1 leaching weathering crust eluviation type rare earth ore
The leaching agent is 3% ammonium sulfate, and the liquid-solid ratio is 1.2:1 during the operation of top water.
S2, collecting rare earth leachate twice
The rare earth concentration of the rare earth leachate collected for the first time is 3.63g/L, and the concentration of impurity aluminum is 0.41 g/L.
S3, impurity removal and precipitation steps
Adding 5mL of 5% ammonium bicarbonate solution during impurity removal, adjusting the pH to 4.8, stirring for 1.5h, and standing and aging for 4 h.
Adding 10mL of 5% ammonium bicarbonate solution into the leachate after impurity removal, stirring for 2h, standing and aging for 6h, wherein the rare earth purity in the rare earth carbonate product reaches 97.34%, and the rare earth recovery rate is 98.12%.
The above experiment was repeated with addition of ammonium sulfate solids to the supernatant to a concentration of 3% as a circulating leaching agent, and the rare earth leaching rate was found to be 99.16%.
Example 3
S1 leaching weathering crust eluviation type rare earth ore
The leaching agent is 50ml of 2% ammonium chloride, the leaching solution-solid ratio is 0.2:1, and the solution-solid ratio during the top water operation is 1.5: 1.
S2, collecting rare earth leachate twice
And stopping the first collection after the volume of the effluent liquid reaches 50 mL. The rare earth concentration of the rare earth leachate collected for the first time is 1.23g/L, and the concentration of impurity aluminum is 0.11 g/L.
S3, impurity removal and precipitation steps
Adding 0.2mL of 20% ammonium bicarbonate solution in the impurity removal process, adjusting the pH to 5.0, stirring for 1.5h, and standing and aging for 4 h.
Adding 0.5mL of 5% ammonium bicarbonate solution into the leachate after impurity removal, stirring for 2h, standing and aging for 6h, wherein the rare earth purity in the rare earth carbonate product reaches 92.82%, and the rare earth recovery rate is 93.67%.
The ammonium chloride solid was added to the supernatant to give an ammonium chloride concentration of 2% as a circulating leaching agent, and the above experiment was repeated to find that the rare earth leaching rate was 98.02%.
Example 4
S1 leaching weathering crust eluviation type rare earth ore
The leaching agent is 150ml of a mixed solution of 2% ammonium sulfate and 2% ammonium nitrate, the leaching liquid-solid ratio is 0.6:1, and the liquid-solid ratio in the top water operation is 1: 1.
S2, collecting rare earth leachate twice
And stopping the first collection after the volume of the effluent liquid reaches 150 mL. The rare earth concentration of the rare earth leachate collected for the first time is 4.82g/L, and the concentration of impurity aluminum is 0.76 g/L.
S3, impurity removal and precipitation steps
Adding 6mL of 15% ammonium bicarbonate solution in the impurity removal process, adjusting the pH to 4.5, stirring for 1h, standing and aging for 1 h.
Adding 6mL of 15% ammonium bicarbonate solution into the leachate after impurity removal, stirring for 1h, standing and aging for 1h, wherein the rare earth purity in the rare earth carbonate product is 96.41%, and the rare earth recovery rate is 97.10%.
And adding ammonium sulfate and ammonium nitrate solid into the supernatant to make the concentrations of the ammonium sulfate and the ammonium nitrate respectively be 2 percent, and using the ammonium sulfate and the ammonium nitrate as circulating leaching agents, and repeating the test to obtain the rare earth leaching rate of 98.66 percent.
Example 5
S1 leaching weathering crust eluviation type rare earth ore
The leaching agent is 200ml of 1% ammonium chloride solution, the leaching solution-solid ratio is 0.8:1, and the solution-solid ratio during the top water operation is 0.8: 1.
S2, collecting rare earth leachate twice
And stopping the first collection after the volume of the effluent liquid reaches 200 mL. The rare earth concentration of the rare earth leachate collected for the first time is 1.59g/L, and the concentration of impurity aluminum is 0.21 g/L.
S3, impurity removal and precipitation steps
Adding 3mL of 10% ammonium bicarbonate solution in the impurity removal process, adjusting the pH to 4.8, stirring for 3h, standing and aging for 5 h.
Adding 4.5mL of 10% ammonium bicarbonate solution into the leachate after impurity removal, stirring for 2.5h, standing and aging for 5h, wherein the rare earth purity in the rare earth carbonate product is 94.38%, and the rare earth recovery rate is 96.83%.
And adding ammonium chloride solid into the supernatant to make the concentration of ammonium chloride be 1%, and using the ammonium chloride as a circulating leaching agent, and repeating the test to find that the rare earth leaching rate can be up to 96.98%.
Example 6
S1 leaching weathering crust eluviation type rare earth ore
The leaching agent is 150ml of a mixed solution of 2% ammonium sulfate and 1% ammonium chloride, the leaching liquid-solid ratio is 0.6:1, and the liquid-solid ratio in the top water operation is 1: 1.
S2, collecting rare earth leachate twice
And stopping the first collection after the volume of the effluent liquid reaches 150 mL. The rare earth concentration of the rare earth leachate collected for the first time is 5.32g/L, and the concentration of impurity aluminum is 0.81 g/L.
3. Removing impurities and precipitating
Adding 5mL of 20% ammonium bicarbonate solution during impurity removal, adjusting the pH to 4.5, stirring for 1.5h, and standing and aging for 4 h.
Adding 5.5mL of 20% ammonium bicarbonate solution into the leachate after impurity removal, stirring for 1.5h, standing and aging for 5h, wherein the rare earth purity in the rare earth carbonate product is 97.72%, and the rare earth recovery rate is 97.63%.
The above experiment was repeated with the addition of ammonium sulfate and ammonium chloride solids to the supernatant to give ammonium sulfate and ammonium chloride concentrations of 2% and 1%, respectively, as the circulating leaching agents, and the rare earth leaching rate was found to be 98.14%.
Comparative example
The leaching method of the weathering crust elution type rare earth ore provided by the comparative example is basically consistent with the leaching method of the weathering crust elution type rare earth ore provided by the example 1 in operation, and is different in that the leaching solution of the rare earth ore is collected at one time, the leaching liquid amount of the collected rare earth is large and 175mL, the concentration of the rare earth is low and 1.23g/L, the purity of the rare earth in a rare earth product reaches 90.89%, and the recovery rate of the rare earth is 92.13%.
FIG. 2 is a schematic view showing the leaching process outflow curve and secondary collection of the weathering crust elution-deposited rare earth ore in example 1 of the present invention, and it can be seen from FIG. 2 that the concentrations of rare earth, aluminum and ammonium radicals increase to a maximum value and then decrease and finally approach to zero with the increase of the outflow volume. When the volume of the leachate reaches 100mL, i.e. the entire volume of lixiviant solution injected is removed from the ore, the instantaneous concentrations of rare earths and aluminium impurities in the leachate are already low, respectively 0.32g/L and 0.16g/L, while the concentration of ammonium radicals is high, approximately 0.2 mol/L. In the rare earth leaching solution collected for the first time, the concentrations of rare earth and aluminum are respectively 2.15g/L and 0.34g/L, and the concentration of ammonium radicals is 0.089 mol/L. In the leachate collected for the second time, the concentrations of rare earth and aluminum are respectively 0.0062g/L and 0.0075g/L, and the concentration of ammonium radicals is 0.019 mol/L.
And then the leachate is collected for the second time, and because the concentration of rare earth and impurities in the leachate collected for the second time is extremely low, the leachate can be directly recycled without impurity removal and precipitation operation. Only the rare earth leaching solution (100mL) collected for the first time is subjected to impurity removal and precipitation operation, and the part of the solution only accounts for 57 percent of the total liquid yield.
The rare earth purity and rare earth recovery rate of rare earth products obtained by the leaching modes in the examples 1-6 and the comparative example show that collecting the leaching solution twice reduces the hydrometallurgy workload and shortens the production period. The requirements on structures such as an impurity removal tank, a sedimentation tank and the like are reduced, and one-time construction investment is reduced. In addition, the leachate is collected in two steps, so that the concentration of rare earth and impurity ions in the solution collected in the first step can be improved, the consumption of an impurity removing agent and a precipitating agent is reduced, and the impurity removing rate and the rare earth recovery rate are increased.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (9)
1. The mineral leaching method of the weathering crust eluviation type rare earth mineral is characterized by comprising the following steps:
leaching weathering crust eluviation type rare earth ore by using a leaching agent, and collecting rare earth leachate flowing out of the bottom of the ore soil by two times;
after the rare earth leachate collected for the first time is subjected to impurity removal and rare earth precipitation, the rare earth leachate is mixed with the rare earth leachate collected for the second time, the leaching agent is added, and the mixed solution is used as a fresh leaching agent and returned to the rare earth ore for leaching operation, wherein the impurity removal step is as follows: removing impurities by using 5-20% by mass of ammonium bicarbonate as an impurity removing agent, adjusting the pH to 4.5-5.0, stirring for 1-3 h, and standing and aging for 1-6 h; the volume ratio of an impurity removing agent to the rare earth leaching solution to be subjected to impurity removal and collected for the first time is 0.004-0.05: 1, and the precipitation step is as follows: precipitating rare earth by using ammonium bicarbonate with the mass concentration of 5-20% as a precipitator, stirring for 1-3 h, and standing and aging for 1-6 h; the volume ratio of the precipitator to the rare earth leachate after impurity removal is 0.01-0.1: 1, and the first collection is as follows: starting to collect the rare earth leachate from the bottom of the rare earth ore when the rare earth leachate flows out, and stopping collecting until the volume of the collected rare earth leachate is the same as that of the leaching agent or the concentration of the flowing rare earth leachate is reduced to be below 0.5g/L after passing through a maximum value; the second collection is: and collecting the rare earth leachate flowing out after the first collection until no more rare earth leachate flows out, and stopping collection.
2. The method for leaching rare earth ore according to claim 1, wherein the leaching agent is ammonium salt solution.
3. The method for leaching rare earth ore according to claim 2, wherein the leaching agent comprises one or more of ammonium sulfate, ammonium chloride and ammonium nitrate solution.
4. The leaching method for the weathering crust elution type rare earth ore according to claim 2, wherein the mass concentration of the ammonium salt solution is 1-4%.
5. The method for leaching weathering crust elution-deposited rare earth ore according to claim 1, wherein the volume of the leaching agent added to 1kg of rare earth ore is 0.2-0.8L.
6. The method for leaching rare earth ore according to claim 1, wherein the method further comprises injecting top water after the leaching agent is completely injected into the rare earth ore.
7. The method for leaching rare earth ore according to claim 6, wherein the top water is one or more of distilled water, tap water, river water and well water.
8. The leaching method of weathering crust elution-deposited rare earth ore according to claim 6, wherein the volume of the top water added per 1kg of rare earth ore is 0.8-1.5L.
9. A rare earth product obtained by leaching according to the leaching method of the rare earth ore of the weathering crust elution type of any one of claims 1 to 8.
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| CN112011697B (en) * | 2020-09-24 | 2021-05-28 | 中国科学院广州地球化学研究所 | Method for electrically exploiting rare earth ore and leaching agent for electrically exploiting rare earth ore |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101476033A (en) * | 2008-10-28 | 2009-07-08 | 黄日平 | Novel method for leaching, impurity removing and precipitating ion type rare earth ore |
| CN105803226A (en) * | 2016-03-25 | 2016-07-27 | 长沙矿冶研究院有限责任公司 | Method for extracting rare earth and aluminum from ion adsorption type rare earth ores |
| CN104328290B (en) * | 2013-07-22 | 2018-06-01 | 北京有色金属研究总院 | A kind of ion type rareearth concentrate acid leaching process |
| CN108677005A (en) * | 2018-06-08 | 2018-10-19 | 武汉工程大学 | A kind of method of the secondary Situ Leaching recovering rare earth of weathered superficial leaching rare-earth ore |
| CN108728642A (en) * | 2018-06-28 | 2018-11-02 | 武汉工程大学 | A kind of method of weathered superficial leaching rare-earth ore leachate ammonium bicarbonate precipitation rare earth Mother liquor multiplexing recovering rare earth |
| CN109055784A (en) * | 2018-08-17 | 2018-12-21 | 王颖皓 | A kind of ion type rareearth ore leaching mother liquor impurity removal process |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101798627B (en) * | 2009-02-09 | 2013-07-03 | 有研稀土新材料股份有限公司 | Method for precipitating rare earth |
-
2019
- 2019-03-06 CN CN201910169818.9A patent/CN109722532B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101476033A (en) * | 2008-10-28 | 2009-07-08 | 黄日平 | Novel method for leaching, impurity removing and precipitating ion type rare earth ore |
| CN104328290B (en) * | 2013-07-22 | 2018-06-01 | 北京有色金属研究总院 | A kind of ion type rareearth concentrate acid leaching process |
| CN105803226A (en) * | 2016-03-25 | 2016-07-27 | 长沙矿冶研究院有限责任公司 | Method for extracting rare earth and aluminum from ion adsorption type rare earth ores |
| CN108677005A (en) * | 2018-06-08 | 2018-10-19 | 武汉工程大学 | A kind of method of the secondary Situ Leaching recovering rare earth of weathered superficial leaching rare-earth ore |
| CN108728642A (en) * | 2018-06-28 | 2018-11-02 | 武汉工程大学 | A kind of method of weathered superficial leaching rare-earth ore leachate ammonium bicarbonate precipitation rare earth Mother liquor multiplexing recovering rare earth |
| CN109055784A (en) * | 2018-08-17 | 2018-12-21 | 王颖皓 | A kind of ion type rareearth ore leaching mother liquor impurity removal process |
Non-Patent Citations (3)
| Title |
|---|
| 丁嘉榆.对离子型稀土矿原地浸出与堆浸工艺优劣的探讨.《稀土信息》.2017, * |
| 对离子型稀土矿原地浸出与堆浸工艺优劣的探讨;丁嘉榆;《稀土信息》;20171231;第29-30页，图4 * |
| 用碳酸氢铵分离铝和稀土的新工艺研究;池汝安;《湖南化工》;19911231;第35-39页 * |
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