A method for promoting leaching of ionic rare earth ores

Abstract

The application provides a method for promoting ion type rare earth ore leaching, and relates to the technical field of ore dressing. The method comprises the following steps: firstly, uniformly loading ion type rare earth ore into a column leaching device; secondly, compounding, dissolving and stirring a leaching agent and an immersion aid; finally, preparing the leaching agent solution through a peristaltic pump to control the speed of ion type rare earth ore in the column leaching device for leaching and collecting the leaching solution. The leaching agent is at least one of ammonium sulfate, magnesium sulfate and sodium sulfate, and the immersion aid is prepared by taking coconut amide propyl betaine and fatty alcohol polyoxyethylene ether carboxylic acid sodium as raw materials. The immersion aid improves the seepage effect and mass transfer efficiency in the dissolution and leaching process, solves the problems of poor wettability of the leaching agent on the surface of clay minerals, long rare earth extraction period, low leaching recovery rate, high leaching agent unit consumption, large rare earth residue and easy environmental pollution, and is beneficial to the ecological restoration and environmental protection of the rare earth mine.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of mineral processing, in particular to a method for promoting ion-type rare earth ore leaching. BACKGROUND

[0002] Rare earth elements are essential strategic mineral resources for modern industry and technological development. Almost all heavy rare earth raw materials in the world come from ion-type rare earth ore. Since the rare earth elements in ion-type rare earth ore exist in the form of ion adsorption phase, chemical extraction is carried out by ion exchange. Essentially, it is an ion exchange reaction between the cations in the leaching agent and the hydrated rare earth ions or hydroxyl hydrated rare earth ions adsorbed on clay minerals. The main way to extract ion-type rare earth in the industry is through in-situ leaching process by using ammonium sulfate, magnesium sulfate, etc. However, the leaching effect of a single leaching agent is not good, and there is a lot of rare earth residue in the soil, resulting in serious waste of resources.

[0003] Ion-type rare earth ore bodies are mainly composed of clay minerals, with high fine-grained mineral content, small ore body porosity and dense structure. The surface-bound water of the mineral particles has a viscous and absorbing effect on the leaching agent solution, and can reduce the pore volume, etc. These all lead to poor penetration effect of the leaching agent in the ore body during in-situ leaching, slow penetration speed, low rare earth leaching recovery efficiency, and long cycle, especially for the increasingly common complex geological conditions and high weathering degree of ore bodies.

[0004] During the leaching process, the seepage pore channel is blocked due to the migration of fine and loose particles. The leaching agent and rare earth ions cannot seep through in this area, and are left in the ore body. This causes insufficient ion exchange reaction in the in-situ leaching system, the outer seepage diffusion of the leaching agent on the surface of the clay mineral is affected by the interlayer free water and surface-bound water, and the slope stability is poor, resulting in low rare earth leaching recovery rate and great environmental threat.

[0005] Although the currently widely used in-situ leaching process is mature, as the mining continues, the easily leached ores are preferentially used, and the structure of most ore bodies is increasingly complex, making the leaching more difficult, which leads to the problems of high extraction difficulty of rare earth, low utilization rate of rare earth, and so on. SUMMARY

[0006] In order to solve the technical problems of ion-type rare earth ore extraction cycle lengthening, leaching recovery rate reduction, leaching agent unit consumption increasing, and large amount of ore body reagent and rare earth residue in the prior art, the present application provides a method for promoting ion-type rare earth ore leaching. The technical solution is as follows:

[0007] A method for promoting ion-type rare earth ore leaching, the method comprising:

[0008] S1, the heavy yttrium type ion type rare earth ore is evenly loaded into the column leaching device;

[0009] S2, the sulfate leaching agent is compounded, dissolved, stirred and mixed with the leaching aid to obtain a mixed reagent;

[0010] S3, the prepared mixed reagent is leached into the ion type rare earth ore in the column leaching device of step S1 by controlling the speed of the peristaltic pump, and the leaching liquid is collected.

[0011] In the step S1, the heavy yttrium type ion type rare earth ore is evenly loaded into the column leaching device;

[0012] The leaching agent in the step S2 is at least one of ammonium sulfate, magnesium sulfate and sodium sulfate.

[0013] The leaching aid in the step S2 is prepared by mixing cocamide propyl betaine and sodium fatty alcohol polyoxyethylene ether carboxylate at a mass ratio of 1.0: (3.4~6.8).

[0014] The cocamide propyl betaine and sodium fatty alcohol polyoxyethylene ether carboxylate are dissolved and stirred at room temperature for 1~2min to prepare the leaching aid.

[0015] In the step S2, the leaching aid is first dissolved and stirred at room temperature, and then the leaching agent is added and dissolved and stirred, wherein the compounding ratio of the leaching agent to the leaching aid is (60~70):1.

[0016] In the step S3, the leaching is carried out by controlling the flow rate of the reagent in the peristaltic pump to be 0.3~0.8mL / min.

[0017] In the step S3, the leaching liquid is collected according to the solid-liquid ratio of 15~25.

[0018] In the step S3, the concentration of the leaching agent in the mixed reagent is 22~42g / L, and the concentration of the leaching aid is 0.2~0.8g / L.

[0019] In the technical solution, the ion type rare earth ore has the characteristics of high content of fine ore, small ore body porosity, and dense structure, and the surface water of the mineral particles has the characteristics of adhesion and absorption to the leaching agent solution, etc., which leads to the problem of poor penetration effect of the leaching agent in the ore body during in-situ leaching. The leaching agent is added in the leaching process, and the ether bond of the ether of the sodium fatty alcohol polyoxyethylene ether carboxylate in the leaching agent and the hydrogen atom and oxygen atom on the carbon chain have strong hydrogen bond interaction and electrostatic attraction with the hydrogen atom and oxygen atom on the surface of the clay mineral, so that the sodium fatty alcohol polyoxyethylene ether carboxylate ionized anion is firmly adsorbed on the surface of the clay particles. The coconut amido propyl betaine and the sodium fatty alcohol polyoxyethylene ether carboxylate have good surface wetting, which enhances the wettability of the surface of the clay mineral, so that the leaching agent solution is more easily spread on the surface of the clay mineral, resulting in that the outer layer seepage diffusion of the leaching agent on the surface of the clay mineral is not affected by the interlayer free water and the surface bound water, the liquid phase adhesion and drag resistance are reduced, the water layer thickness on the surface of the rare earth ore particles is reduced, the hydration is weakened, and the penetration of the leaching solution in the ore body is facilitated. In addition, this can also enhance the concentration gradient in the leaching mass transfer process, and the liquid phase flowability is improved, thereby promoting the exchange and desorption of rare earth ions.

[0020] The traditional ion type rare earth leaching process usually only adds a single ammonium sulfate leaching agent, which is prone to problems such as fine particle migration during leaching, resulting in pore blockage, and because part of the cations of the leaching agent are associated and adsorbed by the anions on the surface of the clay mineral, the concentration of the cations for exchange reaction with the rare earth ions is reduced, the seepage effect is poor, the exchange reaction is insufficient, and the leaching rate is low. In order to solve this problem, a large amount of leaching agent needs to be added, resulting in increased production cost. When the leaching agent solution is used for leaching of rare earth in the ion type rare earth ore, the anions dissociated from the sodium fatty alcohol polyoxyethylene ether carboxylate are used to complex with the hydrated rare earth ions or hydroxyl hydrated rare earth ions on the surface of the clay mineral, promote the exchange and dissociation of the cations in the leaching agent with the hydrated rare earth ions or hydroxyl hydrated rare earth ions on the surface of the clay mineral, and the exchanged rare earth ions are complexed with organic acid roots to inhibit the re-adsorption of rare earth ions on the clay mineral, improve the leaching efficiency of rare earth, and reduce the amount of leaching agent, thereby avoiding the waste of ion phase rare earth resources in the traditional rare earth leaching method, and realizing the saving of rare earth resources.

[0021] The organic active agent remaining in the rare earth mine can be decomposed by indigenous microorganisms to realize the rapid ecological restoration of the mined mine, avoiding or reducing the ecological damage caused by the chemical leaching agent in the leaching of rare earth. Moreover, the types of chemical leaching agents in the high molecular surfactant complex leaching solution can be selected according to the ion type rare earth ore conditions and element content of the use site, for example, the water-soluble sodium salt, water-soluble magnesium salt and water-soluble potassium salt can supplement soil nutrients while leaching the ion type rare earth ore. The ion type rare earth resource is realized green, efficient and ecological friendly.

[0022] The technical scheme provided by the embodiment of the present application brings at least the following beneficial effects:

[0023] First, the efficient leaching aid is invented, which solves the technical problems of the interlayer seepage resistance of the leaching agent in the clay mineral and the insufficient ion exchange reaction, significantly improves the mass transfer efficiency and seepage effect of the ion type rare earth ore leaching process;

[0024] Second, the leaching aid cooperates with the leaching agent to co-dissolve the ion type rare earth ore, which solves the technical problems of poor wettability of the leaching agent on the surface of the clay mineral, long rare earth extraction period, low leaching recovery rate, high leaching agent consumption, large amount of rare earth residue and easy environmental pollution, and significantly improves and strengthens the green chemical extraction of the ion type rare earth ore;

[0025] Third, the invented leaching aid is a high molecular surfactant, which has high efficient surface wetting capacity and excellent biodegradability, can provide nutrients for the reproduction of microorganisms and soil repair, and is beneficial to the ecological restoration and environmental protection of the rare earth mine. BRIEF DESCRIPTION OF DRAWINGS

[0026] In order to more clearly illustrate the technical scheme in the embodiments of the present application, the drawings needed in the embodiment description will be briefly introduced. Obviously, the drawings in the following description are only some embodiments of the present application, and other drawings can be obtained by those skilled in the art without creative labor.

[0027] Figure 1 It is a method flow chart for promoting the leaching of ion type rare earth ore provided by the embodiment of the present application. DETAILED DESCRIPTION

[0028] The technical scheme in the present application will be described below with reference to the drawings.

[0029] In the embodiments of the present application, the words such as "example", "for example" and the like are used to represent an example, illustration or description. Any embodiment or design scheme described as "example" in the present application should not be interpreted as more preferred or more advantageous than other embodiments or design schemes. Rather, the word "example" is intended to present the concept in a specific manner. In addition, in the embodiments of the present application, the meaning expressed by "and / or" can be both, or can be one of the two.

[0030] In the embodiments of the present application, sometimes the subscript such as W1 may be written in the form of non-subscript such as W1, and the meanings expressed thereby are consistent when the difference is not emphasized.

[0031] In order to make the technical problems, technical schemes and advantages to be solved by the present application more clear, the following will be described in detail in combination with the drawings and specific embodiments.

[0032] The embodiments of the present application provide a method for promoting leaching of ionic rare earth ore. Figure 1 As shown in the method for promoting leaching of ionic rare earth ore, the method can include the following steps:

[0033] S1, uniformly loading heavy yttrium type ionic rare earth ore into a column leaching device;

[0034] S2, compounding, dissolving and stirring a sulfide leaching agent and a leaching aid to obtain a mixed reagent;

[0035] S3, controlling the speed of the prepared mixed reagent through a peristaltic pump to perform leaching on the ionic rare earth ore in the column leaching device of step S1 and collect the leaching solution.

[0036] The following will be described in combination with specific embodiments.

[0037] Embodiment 1

[0038] First, 500ml of a mixed reagent is prepared, the leaching agent is selected as magnesium sulfate, the mass fraction of cocamidopropyl betaine and sodium fatty alcohol polyoxyethylene ether carboxylate in the leaching aid is 0.008% and 0.032% respectively, and the mixed reagent is obtained by mixing and stirring under normal temperature and pressure for 1-2min.

[0039] The selected sample A is taken from an ionic rare earth mine in Yunnan, which is severely weathered and has high mud content. The sample contains a total amount of rare earth REO of 0.059%, and is mainly composed of SiO2 and Al2O3, followed by Fe2O3, K2O, MgO and the like. The rare earth ions are mainly present in clay minerals such as kaolinite, halloysite and illite, and the rare earth elements are in ionic phase form. The ionic rare earth ore is leached and recovered by using the traditional leaching process, and the best rare earth leaching rate obtained is 88.49%.

[0040] Referring to Figure 1The leaching method is used for leaching and recovering of rare earth, and mixed reagents are added in the leaching process, which are prepared by compounding, dissolving and stirring of the leaching agent MgSO4 and the leaching aid of cocamide propyl betaine and sodium fatty alcohol polyoxyethylene ether carboxylate.

[0041] (1) 500g of ion-type rare earth ore A is uniformly loaded into a column leaching device;

[0042] (2) the leaching agent MgSO4 and the leaching aid of cocamide propyl betaine and sodium fatty alcohol polyoxyethylene ether carboxylate are compounded, dissolved, stirred and mixed;

[0043] (3) the prepared mixed reagents are used to leach the ion-type rare earth ore in the column leaching device through a peristaltic pump, and the leaching solution is collected.

[0044] In the leaching process, the concentration of the leaching agent in the mixed reagents is 22-42g / L, and the concentration of the leaching aid is 0.2-0.8g / L.

[0045] The prepared leaching agent solution is used for leaching at a flow rate of 0.5mL / min, and the leaching solution is collected at a solid-liquid ratio of 30.

[0046] The rare earth leaching rate obtained in the embodiment is 95.48%.

[0047] Example 2

[0048] Firstly, 500ml of mixed reagents are prepared, the leaching agent is magnesium sulfate, the mass fraction of cocamide propyl betaine and sodium fatty alcohol polyoxyethylene ether carboxylate in the leaching aid is 0.01% and 0.028% respectively, and the mixed reagents are obtained by mixing and stirring at normal temperature and pressure for 1-2min.

[0049] The selected sample B is taken from an ion-type rare earth mine in Yunnan, which is seriously weathered and has high mud content. The total content of rare earth REO in the sample is 0.038%, the ore is mainly composed of SiO2 and Al2O3, followed by Fe2O3, K2O, MgO and the like, and the rare earth ions are mainly present in clay minerals such as kaolinite, halloysite and illite, and the rare earth elements are in ionic phase form. The ion-type rare earth ore is leached and recovered by using the traditional leaching process, and the best rare earth leaching rate obtained is 87.58%.

[0050] Reference Figure 1 The leaching method is used for leaching and recovering of rare earth, and mixed reagents are added in the leaching process, which are prepared by compounding, dissolving and stirring of the leaching agent MgSO4 and the leaching aid of cocamide propyl betaine and sodium fatty alcohol polyoxyethylene ether carboxylate.

[0051] (1) 500g of ion-type rare earth ore B is uniformly loaded into a column leaching device;

[0052] (2) The leaching agent MgSO4 is compounded, dissolved, stirred and mixed with the assistant leaching agent sodium cocoamphopropyl betaine and fatty alcohol polyoxyethylene ether carboxylic acid sodium;

[0053] (3) The prepared mixed reagent is used for leaching the ion type rare earth ore in the column leaching device through the peristaltic pump control speed, and the leaching liquid is collected.

[0054] In the leaching process, the concentration of the leaching agent in the mixed reagent is 22-42 g / L, and the concentration of the assistant leaching agent is 0.2-0.8 g / L.

[0055] The prepared leaching agent solution is used for leaching at a flow rate of 0.5 mL / min, and the leaching liquid is collected according to the solid-liquid ratio of 30.

[0056] The rare earth leaching rate obtained in the embodiment is 94.12%.

[0057] Example 3

[0058] Firstly, 500 ml of the mixed reagent is prepared, the leaching agent is magnesium sulfate, the mass fraction of the assistant leaching agent sodium cocoamphopropyl betaine and fatty alcohol polyoxyethylene ether carboxylic acid sodium is 0.006% and 0.042% respectively, and the mixed reagent is obtained through mixing and stirring at normal temperature and pressure for 1-2 min.

[0059] The selected sample C is taken from an ion type rare earth mine in Yunnan, has serious weathering and high mud content. The sample contains 0.072% of total rare earth REO, and is mainly composed of SiO2 and Al2O3, followed by Fe2O3, K2O, MgO and the like. The rare earth ions are mainly present in clay minerals such as kaolinite, halloysite and illite, and the rare earth elements are in the form of ion phase. The ion type rare earth ore is leached and beneficiated by using the traditional leaching process, and the best rare earth leaching rate obtained is 88.92%.

[0060] Referring to Figure 1 , the leaching method provided by the present application is used for leaching and recovering rare earth, the leaching process is carried out by adding the mixed reagent, which is prepared by compounding the leaching agent MgSO4 and the assistant leaching agent sodium cocoamphopropyl betaine and fatty alcohol polyoxyethylene ether carboxylic acid sodium, and the selected steps are as follows:

[0061] (1) 500 g of the ion type rare earth ore C is uniformly loaded into the column leaching device;

[0062] (2) The leaching agent MgSO4 is compounded, dissolved, stirred and mixed with the assistant leaching agent sodium cocoamphopropyl betaine and fatty alcohol polyoxyethylene ether carboxylic acid sodium;

[0063] (3) The prepared mixed reagent is used for leaching the ion type rare earth ore in the column leaching device through the peristaltic pump control speed, and the leaching liquid is collected.

[0064] In the leaching process, the concentration of the leaching agent in the mixed solution is 22-42 g / L, and the concentration of the leaching aid is 0.2-0.8 g / L.

[0065] The prepared leaching agent solution is leached at a flow rate of 0.5 mL / min, and the leaching solution is collected at a solid-liquid ratio of 30.

[0066] The rare earth leaching rate obtained in the example is 96.62%.

[0067] The above is only a specific embodiment of the present application, but the protection scope of the present application is not limited thereto, any person skilled in the art can easily think of changes or replacements within the technical range disclosed by the present application, which should be covered within the protection scope of the present application. Therefore, the protection scope of the present application should be subject to the protection scope of the claims.

Claims

1. A method for promoting the leaching of ion-adsorption rare earth minerals, characterized in that, The method includes: S1. The heavy yttrium ion-adsorption rare earth ore is uniformly loaded into the column leaching device; S2. The sulfate leaching agent and the leaching aid are compounded, dissolved, and stirred to obtain a mixed agent; S3. The prepared mixed reagent is leached into the ion-type rare earth ore in the column leaching device of step S1 by a peristaltic pump at a controlled speed and the leachate is collected. The impregnation aid in step S2 is prepared by mixing cocamidopropyl betaine and sodium fatty alcohol polyoxyethylene ether carboxylate at a mass ratio of 1.0:(3.4~6.8). The cocamidopropyl betaine and sodium fatty alcohol polyoxyethylene ether carboxylate were dissolved and stirred at room temperature for 1-2 minutes to prepare the impregnation aid.

2. The method for promoting the leaching of ion-adsorption rare earth minerals according to claim 1, characterized in that, In step S1, particles smaller than 0.15 mm account for 20%-30% of the yttrium ion-adsorption rare earth ore.

3. The method for promoting the leaching of ion-adsorption rare earth minerals according to claim 1, characterized in that, The leaching agent in step S2 is at least one of ammonium sulfate, magnesium sulfate, and sodium sulfate.

4. The method for promoting the leaching of ion-adsorption rare earth minerals according to claim 1, characterized in that, In step S2, the leaching aid is first stirred and dissolved at room temperature, and then the leaching agent is added and stirred and dissolved. The ratio of the leaching agent to the leaching aid is (60~70):

1.

5. The method for promoting the leaching of ion-adsorption rare earth minerals according to claim 1, characterized in that, In step S3, the flow rate of the agent in the peristaltic pump is controlled to be 0.3~0.8 mL / min for leaching.

6. The method for promoting the leaching of ion-adsorption rare earth minerals according to claim 1, characterized in that, In step S3, the leachate is collected at a solid-liquid ratio of 15-25.

7. The method for promoting the leaching of ion-adsorption rare earth minerals according to claim 1, characterized in that, In step S3, the rare earth leaching rate in the leachate is not less than 94%.

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