CN109207717B - Method for preparing high-purity mixed rare earth chloride by neutralizing, impurity removing and circulating rare earth sulfate water extract - Google Patents
Method for preparing high-purity mixed rare earth chloride by neutralizing, impurity removing and circulating rare earth sulfate water extract Download PDFInfo
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- CN109207717B CN109207717B CN201811024910.8A CN201811024910A CN109207717B CN 109207717 B CN109207717 B CN 109207717B CN 201811024910 A CN201811024910 A CN 201811024910A CN 109207717 B CN109207717 B CN 109207717B
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
- C22B1/06—Sulfating roasting
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- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
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- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
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- C22B59/00—Obtaining rare earth metals
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Abstract
The invention discloses a method for preparing high-purity mixed rare earth chloride by neutralizing, impurity removing and circulating rare earth sulfate water extract, which comprises the following steps: roasting the mixed rare earth concentrate at high temperature by concentrated sulfuric acid, and leaching by water to obtain water leaching slag and clear pulp liquid, wherein the temperature of the clear pulp liquid is less than or equal to 40 ℃; neutralizing the clear liquid of the ore pulp with a neutralizing agent until the pH value is 3.8-4.5, and separating to obtain a water leaching solution and neutralizing slag; the water leaching solution is prepared into a mixed alkaline rare earth compound through cocurrent flow precipitation of an ammonia precipitator, so that ammonium sulfate wastewater and the mixed alkaline rare earth compound are obtained; the mixed rare earth carbonate in the mixed alkaline rare earth compound is dissolved and transformed into high-purity mixed rare earth chloride suitable for extraction and separation by hydrochloric acid. The invention solves the problems of sulfate crystallization in the processes of neutralization and calcium and magnesium removal of the clear liquid of the rare earth sulfate ore pulp and concentration of sulfate wastewater, and the problem of ammonium double salt precipitation of rare earth sulfate in the processes of ammonia neutralization and precipitation.
Description
Technical Field
The invention relates to a hydrometallurgy technology, in particular to a method for preparing high-purity mixed rare earth chloride by neutralizing, impurity removing and circulating rare earth sulfate water extract.
Background
The mixed rare earth concentrate in Baotou areas is mainly treated by adopting a concentrated sulfuric acid high-temperature roasting process, and the process comprises the steps of mixing the rare earth concentrate with the concentrated sulfuric acid, roasting at high temperature, soaking in water, neutralizing with magnesium to remove impurities, transforming (carbon precipitation or extraction) and the like. Although the process flow is simple and has strong applicability to mineral grade, the problem of great difficulty in treating three wastes is also existed, and the problem of waste water is particularly prominent in the three wastes.
In the existing production process, during the process of extracting rare earth minerals into rare earth sulfate and converting the rare earth sulfate into rare earth chloride, industrial magnesium oxide neutralization and impurity removal (iron, phosphorus, aluminum, zinc and the like) are required, ammonium bicarbonate precipitation-hydrochloric acid dissolution transformation or P507 magnesium soap extraction transformation is carried out, and thus ammonium magnesium sulfate mixed wastewater or magnesium sulfate wastewater is formed. The main problems of impurity removal and saponification by adopting magnesium neutralization are two aspects, in the rare earth smelting and extraction process, a large amount of calcium oxide is carried in industrial magnesium oxide, and calcium sulfate crystals are formed in the neutralization process and wrapped on the surface of minerals, so that the rare earth sulfate extraction efficiency is greatly reduced; calcium sulfate crystals formed in the saponification process cause crystallization at multiple positions such as an extraction tank body and an organic-water phase interface, so that the extraction process is seriously hindered, the organic loss is increased, and the working condition is extremely poor. From the aspect of wastewater treatment, on one hand, the mixed wastewater of magnesium ammonium sulfate is formed, the application field of the magnesium ammonium sulfate mixture is narrow, and the market value is low. On the other hand, in the concentration process of the waste water, the crystallization process is seriously hindered by the crystallization problem of calcium sulfate and magnesium sulfate.
It is well known that rare earth sulfates tend to K in solution systems+、Na+、NH4 +A double salt precipitate is formed, the precipitation order being K+＞Na+＞NH4 +. Therefore, the purification process of rare earth sulfate solution has been avoiding the use of the above-mentioned alkaline compound of monovalent ion. If the solution is directly neutralized and saponified by ammonia water and sodium hydroxide solution, the impurity ions of calcium, magnesium and the like can be avoidedIntroduction of, but NH4 +、Na+Too high a local concentration increases the risk of double salt formation.
Disclosure of Invention
The invention aims to solve the technical problems of providing a method for preparing high-purity mixed rare earth chloride by neutralizing, impurity removing and circulating rare earth sulfate water extract, solving the problems of sulfate crystallization in the processes of neutralizing, calcium and magnesium removing of clear rare earth sulfate pulp, sulfate wastewater concentration and ammonium double salt precipitation of rare earth sulfate in the processes of ammonia neutralization and precipitation.
The technical scheme is as follows:
a method for preparing high-purity mixed rare earth chloride by neutralizing, impurity removing and circulating rare earth sulfate water leaching solution comprises the following steps:
roasting the mixed rare earth concentrate at high temperature by concentrated sulfuric acid, and leaching by water to obtain water leaching slag and clear pulp liquid, wherein the temperature of the clear pulp liquid is less than or equal to 40 ℃;
neutralizing the clear pulp liquid by using a prepared neutralizer until the pH value is 3.8-4.5, separating to obtain a water extract and neutralizing slag, and performing size mixing on the neutralizing slag by using water and returning to the roasting ore leaching process;
the water extract is prepared into a mixed alkaline rare earth compound through cocurrent flow precipitation of an ammonia precipitator, and pure ammonium sulfate wastewater is obtained through separation; the mixed alkaline rare earth compound and ammonia precipitator are respectively taken and blended into neutralizer which is then continuously used for neutralizing clear liquid of ore pulp, and the rest mixed rare earth carbonate is dissolved into mixed rare earth chloride by hydrochloric acid.
Further: the neutralizer is an alkaline mixture prepared from a mixed alkaline rare earth compound or a mixed alkaline rare earth compound and one or more of ammonia water, ammonium bicarbonate and ammonium carbonate; mixing the alkaline rare earth compound and NH according to the mixing ratio4 +The molar ratio is 99: 1-1: 99.
Further: the pH value of the end point of the parallel flow precipitation is 6.2-6.8, the molar ratio of ammonia water to ammonium bicarbonate is less than or equal to 2:1, and the molar ratio of ammonia water to ammonium carbonate is less than or equal to 1: 1.
Further: the mixed alkaline rare earth compound is one or more of mixed rare earth carbonate and mixed alkaline rare earth compound.
Further: in the ammonium sulfate wastewater, the concentration of MgO is less than 0.5g/L, and the concentration of CaO is less than 0.5g/L, and ammonium sulfate by-products and reuse water are obtained through concentration and crystallization.
Further: in the high-purity mixed rare earth chloride, the mass percentage of MgO/REO is less than 0.01 percent, and the mass percentage of CaO/REO is less than 0.05 percent.
The invention has the technical effects that:
the mixed alkaline rare earth compound or the mixture of the mixed alkaline rare earth compound and the ammonia precipitator is used as a clear liquid neutralizer of the rare earth sulfate ore pulp, and the mixed alkaline rare earth compound is used as a neutralization transfer medium of the alkaline ammonia compound, so that the contact of ammonium ions and the rare earth sulfate is greatly reduced or avoided, and the generation of ammonium double salts of the rare earth sulfate is prevented. The single pure ammonium sulfate wastewater is formed, the introduction of calcium and magnesium ions is avoided, the wastewater treatment difficulty is reduced, and the economic value of byproducts is improved. Meanwhile, in the process of precipitation transformation, a parallel-flow precipitation mode is adopted, so that instantaneous high-concentration contact between ammonium ions and rare earth ions in a sulfate system can be controlled, and the problem of complex salt formation is solved. Effectively controlling the pH value of the neutralization impurity removal and transformation precipitation end point, further adjusting and controlling the mixed precipitation of impurity ions such as calcium, magnesium and the like, and purifying the rare earth chloride solution.
Drawings
FIG. 1 is a flow chart of the method for preparing high-purity mixed rare earth chloride by neutralizing, impurity removing and circulating rare earth sulfate water extract.
Detailed Description
In order to better understand the present invention, the following examples are further provided to illustrate the content of the present invention, but the content of the present invention is not limited to the following examples.
Example 1:
(1) blending a neutralizing agent: mixed rare earth carbonate: ammonia water 10:1 (molar ratio);
(2) neutralizing: neutralizing the clear liquid of the ore pulp at 30 ℃ by using a prepared neutralizing agent until the pH value is 4.0, and separating to obtain water extract and neutralized slag. The neutralized slag is mixed with water to be slurry and then returns to the roasting ore leaching process;
(3) precipitation transformation: the water extract and ammonium bicarbonate precipitator are precipitated in parallel until the pH value is 6.8, rare earth carbonate is prepared, pure ammonium sulfate wastewater is obtained by separation, the MgO concentration is 0.21g/L, the CaO concentration is 0.26g/L, and ammonium sulfate by-products and reuse water are obtained by concentration and crystallization;
(4) and (3) recycling: the mixed rare earth carbonate compound is divided according to the requirement, and is continuously used for neutralizing clear liquid of ore pulp after being prepared, the rest mixed rare earth carbonate is dissolved and transformed into high-purity mixed rare earth chloride suitable for P507 extraction and separation by hydrochloric acid, and the MgO/REO mass percentage content is less than 0.01 percent, and the CaO/REO mass percentage content is 0.03 percent.
Example 2:
(1) blending a neutralizing agent: mixed alkaline rare earth compound: ammonium bicarbonate: ammonia water is 1:5:10 (molar ratio of effective substances);
(2) neutralizing: neutralizing the clear liquid of the ore pulp at 20 ℃ by using a prepared neutralizing agent until the pH value is 4.2, and separating to obtain a water extract and neutralized slag. The neutralized slag is mixed with water to be slurry and then returns to the roasting ore leaching process;
(3) precipitation transformation: preparing ammonia water and ammonium bicarbonate into a mixed precipitant according to a molar ratio of 2:1, performing cocurrent precipitation on a water extract and the mixed precipitant until the final pH value is 6.2 to prepare a mixed alkaline rare earth compound, separating to obtain pure ammonium sulfate wastewater, wherein the MgO concentration of the ammonium sulfate wastewater is 0.23g/L, the CaO concentration of the ammonium sulfate wastewater is 0.32g/L, and performing concentration crystallization to obtain an ammonium sulfate byproduct and reuse water;
(4) and (3) recycling: the mixed alkaline rare earth compound is divided according to the requirement, the mixed alkaline rare earth compound is continuously used for neutralizing clear liquid of ore pulp after being prepared, the rest mixed alkaline rare earth compound is dissolved and transformed into high-purity mixed rare earth chloride suitable for P507 extraction and separation, and the MgO/REO mass percentage content is less than 0.01 percent, and the CaO/REO mass percentage content is 0.04 percent.
Example 3:
(1) blending a neutralizing agent: mixed rare earth carbonate: ammonium carbonate 99:1 (molar ratio).
(2) Neutralizing: neutralizing the clear liquid of the ore pulp at 40 ℃ by using a prepared neutralizing agent until the pH value is 3.8, and separating to obtain a water extract and neutralized slag. And (4) pulping the neutralized slag by using water and returning to the roasting ore leaching process.
(3) Precipitation transformation: ammonia water and ammonium bicarbonate are prepared into a mixed precipitant according to the molar ratio of 1:1, a water extract and the mixed precipitant are subjected to cocurrent precipitation reaction until the final pH value is 6.5, mixed rare earth carbonate is prepared, pure ammonium sulfate wastewater is obtained through separation, the concentration of MgO is 0.1g/L, the concentration of CaO is 0.2g/L, and ammonium sulfate byproducts and reuse water are obtained through concentration and crystallization.
(4) And (3) recycling: the mixed rare earth carbonate is divided according to the requirement, the mixed rare earth carbonate is blended and then continuously used for neutralizing clear liquid of ore pulp, the rest mixed rare earth hydroxide is dissolved and transformed by hydrochloric acid into high-purity mixed rare earth chloride suitable for P507 extraction and separation, and the MgO/REO mass percentage content is less than 0.01 percent, and the CaO/REO mass percentage content is 0.03 percent.
Example 4:
(1) blending a neutralizing agent: mixed rare earth carbonate: ammonia water: ammonium bicarbonate 1: 49: 49 (molar ratio).
(2) Neutralizing: neutralizing the clear liquid of the ore pulp at 32 ℃ with a prepared neutralizing agent until the pH value is 4.5, and separating to obtain water extract and neutralized slag. And (4) pulping the neutralized slag by using water and returning to the roasting ore leaching process.
(3) Precipitation transformation: and (3) carrying out cocurrent precipitation on the water extract and an ammonium carbonate precipitator until the final pH value is 6.8, preparing mixed rare earth carbonate, separating to obtain pure ammonium sulfate wastewater, wherein the MgO concentration is 0.17g/L and the CaO concentration is 0.28g/L, and concentrating and crystallizing to obtain an ammonium sulfate byproduct and reuse water.
(4) And (3) recycling: and (3) dividing part of the mixed rare earth carbonate according to the requirement, blending, continuously using the mixed rare earth carbonate for neutralizing clear liquid of ore pulp, dissolving and transforming the rest mixture by hydrochloric acid into high-purity mixed rare earth chloride suitable for P507 extraction and separation, wherein the MgO/REO mass percentage content is less than 0.01%, and the CaO/REO mass percentage content is 0.027%.
Example 5:
(1) blending a neutralizing agent: mixing basic rare earth carbonate: ammonium bicarbonate at a molar ratio of 1: 10.
(2) Neutralizing: neutralizing the clear liquid of the ore pulp at 32 ℃ by using a prepared neutralizing agent until the pH value is 4.2, and separating to obtain water extract and neutralized slag. And (4) pulping the neutralized slag by using water and returning to the roasting ore leaching process.
(3) Precipitation transformation: ammonia water and ammonium carbonate are mixed according to the molar ratio of 1:1 to prepare a mixed precipitant, the water extract and the mixed precipitant are subjected to cocurrent precipitation until the final pH value is 6.5, mixed rare earth carbonate is prepared, pure ammonium sulfate wastewater is obtained through separation, the concentration of MgO is 0.23g/L, the concentration of CaO is 0.27g/L, and ammonium sulfate byproducts and reuse water are obtained through concentration and crystallization.
(4) And (3) recycling: and (3) dividing part of the mixed basic rare earth carbonate according to the requirement, blending, continuously using the obtained mixture for neutralizing clear liquid of ore pulp, dissolving and transforming the rest of the mixture by hydrochloric acid into high-purity mixed rare earth chloride suitable for P507 extraction and separation, wherein the MgO/REO mass percentage content is less than 0.01%, and the CaO/REO mass percentage content is 0.03%.
It should be understood that the above description is only an embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of changes or substitutions within the technical scope of the present invention, and the present invention should be covered thereby. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.
Claims (2)
1. A method for preparing high-purity mixed rare earth chloride by neutralizing, impurity removing and circulating rare earth sulfate water leaching solution is characterized by comprising the following steps:
roasting the mixed rare earth concentrate at high temperature by concentrated sulfuric acid, and leaching by water to obtain water leaching slag and clear pulp liquid, wherein the temperature of the clear pulp liquid is less than or equal to 40 ℃;
neutralizing the clear pulp liquid by using a prepared neutralizer until the pH value is 3.8-4.5, separating to obtain a water extract and neutralization slag, and performing size mixing on the neutralization slag by using water and returning to the roasting ore leaching process; wherein the neutralizer is an alkaline mixture prepared by mixing rare earth carbonate with one or more of ammonia water, ammonium bicarbonate and ammonium carbonate; mixing rare earth carbonate with NH4 +The molar ratio of (A) to (B) is 99: 1-1: 99;
the water extract is prepared into mixed rare earth carbonate through cocurrent flow precipitation of ammonia precipitator, and pure ammonium sulfate wastewater is obtained through separation; mixing the mixed rare earth carbonate and an ammonia precipitator to prepare a neutralizer, continuously neutralizing the clear liquid of the ore pulp, and dissolving the rest of the mixed rare earth carbonate into high-purity mixed rare earth chloride by hydrochloric acid;
wherein, in the ammonium sulfate wastewater, the concentration of MgO is less than 0.5g/L, the concentration of CaO is less than 0.5g/L, and ammonium sulfate by-products and reuse water are obtained through concentration and crystallization;
wherein, in the high-purity mixed rare earth chloride, the weight percentage of MgO/REO is less than 0.01 percent, and the weight percentage of CaO/REO is less than 0.05 percent.
2. The method for preparing high-purity mixed rare earth chloride by neutralizing, impurity removing and circulating rare earth sulfate water extract according to claim 1, wherein the pH value of the precipitation end point of the cocurrent precipitation is 6.2-6.8.
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| CN111235411A (en) * | 2020-03-02 | 2020-06-05 | 包头稀土研究院 | Process for removing calcium-containing minerals in rare earth concentrate and application of sulfuric acid solution |
| CN112301220B (en) * | 2020-10-30 | 2022-10-18 | 内蒙古包钢和发稀土有限公司 | Method for reducing iron content in rare earth sulfate water leaching solution |
| CN112410589A (en) * | 2020-11-30 | 2021-02-26 | 包头稀土研究院 | Treatment method of rare earth sulfate roasted ore |
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| CN1240858C (en) * | 2001-04-29 | 2006-02-08 | 路远 | Carbon reducting roast process of producing RE chloride with mixed RE concentrate |
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