CN116676479A - Method for recovering rare earth and aluminum from ion type rare earth leaching liquid - Google Patents

Method for recovering rare earth and aluminum from ion type rare earth leaching liquid Download PDF

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CN116676479A
CN116676479A CN202310623010.XA CN202310623010A CN116676479A CN 116676479 A CN116676479 A CN 116676479A CN 202310623010 A CN202310623010 A CN 202310623010A CN 116676479 A CN116676479 A CN 116676479A
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rare earth
aluminum
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肖燕飞
陈昕
黄莉
高梦兰
谭传满
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Jiangxi University of Science and Technology
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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
    • 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
    • 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
    • C22B21/00—Obtaining aluminium
    • C22B21/0015—Obtaining aluminium by wet processes
    • 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
    • C22B59/00—Obtaining rare earth metals
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Abstract

The application provides a method for recycling rare earth and aluminum from an ionic rare earth leaching solution, which takes the ionic rare earth leaching solution as a raw material, adopts a way of rubbing and precipitating magnesium oxide and magnesium bicarbonate step by step to precipitate all the rare earth and aluminum, and most of silicon is left in the solution, so that the content of magnesium oxide and silicon dioxide in rare earth enrichment is well controlled. And then, carrying out sodium hydroxide stirring washing on the enriched matters, changing aluminum hydroxide into sodium aluminate, and then, entering the sodium aluminate into a solution, changing basic rare earth sulfate into rare earth hydroxide, and releasing sulfate radical, thus finally obtaining the rare earth hydroxide. The mother solution after impurity removal is carbonized and precipitated by carbon dioxide to obtain aluminum hydroxide, and the aluminum hydroxide is roasted to obtain aluminum oxide with the purity of more than 98wt.% and the average median particle diameter of more than 50 mu m. The application does not undergo the neutralization aluminum removal process, thereby effectively improving the recovery rate of rare earth; meanwhile, the magnesium salt is precipitated step by step, ammonia nitrogen pollution is eliminated, and the contents of magnesium oxide and silicon dioxide in the mixed rare earth oxide are effectively reduced.

Description

Method for recovering rare earth and aluminum from ion type rare earth leaching liquid
Technical Field
The application relates to the field of rare earth separation and recovery, in particular to a method for recovering rare earth and aluminum from ion type rare earth leaching liquid.
Background
The proportion of medium and heavy rare earth elements such as terbium, dysprosium, europium and the like in the ionic rare earth ore is tens times, even tens times higher than that of the light rare earth ore, and has extremely high effectHigh economic value and is a valuable strategic mineral resource in China. In general, the full-phase rare earth grade of the ionic rare earth ore is 0.05% -0.3%, wherein more than 80% of the rare earth exists in the form of ionic phase, and when the ionic phase rare earth encounters chemically active cations (such as Na + 、Mg 2+ 、Ca 2+ 、NH 4 + Etc.) can be desorbed by its exchange into the leachate. According to the characteristics, the scientific workers in China successively develop leaching agents such as sodium chloride, ammonium sulfate, magnesium sulfate and the like and leaching processes such as barrel leaching, pond leaching, heap leaching, in-situ leaching and the like [3-4] . However, in the leaching process of the ionic rare earth ore, whether ammonium sulfate or magnesium sulfate is adopted as a leaching agent, the leaching selectivity of the ionic rare earth ore to rare earth and aluminum is not high, water-soluble aluminum and ion-exchange aluminum in ore bodies can be carried out along with leaching of the ammonium sulfate leaching agent and enter the leaching agent, and the existence of the ionic rare earth ore leaching agent can cause difficulty in subsequent rare earth enrichment.
The ion type rare earth leaching solution has the characteristics of large daily treatment capacity, low rare earth concentration, higher aluminum concentration and the like, is industrially neutralized and dealuminized by adopting ammonium bicarbonate, is precipitated and enriched to obtain rare earth carbonate, and finally is roasted at 1000 ℃ to obtain REO>92％，Al 2 O 3 <1.5％，SO 4 2- <1.5% of mixed rare earth oxide. With the wide development and utilization of ionic rare earth resources in recent years, the related problems caused by the enrichment process of the leaching solution ammonium bicarbonate are increasingly prominent: (1) In the neutralization aluminum removal process, the aluminum removal process can cause more than 8 percent of rare earth loss due to the adsorption of aluminum hydroxide and the co-precipitation of rare earth ions; and the higher the concentration of aluminum ions in the leaching solution is, the higher the rare earth loss is. (2) The use of ammonium salt can cause the excessive standard ammonia nitrogen of the water system in the mining area, the eutrophication of the water body and the great threat to the ecological safety. Therefore, how to effectively solve the problems, realize the efficient separation of rare earth and aluminum in the leaching solution and the green enrichment of rare earth, is a problem to be solved in the ion type rare earth industry, and the characteristics of large leaching solution treatment capacity, low rare earth concentration and the like bring greater challenges to the green efficient enrichment of rare earth in the leaching solution.
In the field of efficient separation of rare earth and aluminum in leaching solution, technological workers take ion type rare earth leaching solution as a research object, and according to the chemical property difference of rare earth or aluminum, various methods such as precipitation (precipitants such as inorganic alkali, carbonate, oxalic acid, sodium sulfate, sodium fluoride, benzoate, 8-hydroxyquinoline and the like), extraction (extractants such as naphthenic acid, chloronaphthenic acid, octylphenoxy isopropyl acid, N1923, P507 and the like), adsorption (PVA cation exchange fiber, D290 resin, CB-ACT resin, porous polyethylene benzene resin, adsorbent of functionalized modified silicon-based/carbon-based material and the like) and the like are proposed to separate rare earth and aluminum in solution, so that rare earth feed liquid or solid rare earth compound with low aluminum content is obtained. However, the method still has the problems of large rare earth loss, large organic loss, low treatment efficiency, large environmental impact, high medicament cost and the like, and is difficult to implement efficiently.
In the field of ammonia-free green enrichment of rare earths, novel ammonia-free precipitation methods and non-precipitation enrichment methods are beginning to be widely focused and studied. (1) ammonia-free precipitation method: the sodium salt precipitant has the problems of high production cost, poor crystallization performance of precipitated products, difficult filtration, fine control of operation and the like; the magnesium-calcium alkaline compound precipitant improves the rare earth precipitation rate, can realize no ammoniation in the whole process of leaching and enriching the ionic rare earth ore, but generates basic rare earth sulfate in the precipitation process, the sulfate radical content in the mixed rare earth oxide obtained after roasting exceeds 15 percent, and the follow-up impurity removal treatment steps such as enriching sodium hydroxide or sodium malonate are needed to obtain the mixed rare earth oxide product meeting national standards, thereby increasing the process flow. In addition, all silicon in the leaching solution can enter into a precipitation product, so that the silicon content exceeds the standard. (2) non-precipitation enrichment method: ion exchange (732 strong acid cation exchange resin, 732 strong acid styrene cation exchange resin, HD325 resin, 001×7 cation exchange resin, chelation resin of phosphinic acid carboxylic acid, etc.), liquid film method (using EM-301, LMA-1, medium amine 185, LMS-2, etc. as surfactant, P507, cyanex272, P204, etc. as carrier), extraction method (using P507, P204, etc. as extractant, adopting centrifugal extraction, bubbling extraction, precipitation extraction, etc. modes) and the like are used for treating rare earth leaching solution with low concentration and large flow, and the problems of insufficient treatment capacity, high cost, organic pollution, etc. exist, and the problems of industrial popularization and application are not reached yet, and many key technical problems are yet to be broken through.
In summary, how to separate rare earth and aluminum from leaching solution and efficiently enrich rare earth, and simultaneously remove ammonia nitrogen pollution, and obtain mixed rare earth oxide meeting requirements, thereby reducing cost has become a common technical problem to be solved urgently.
Disclosure of Invention
The application mainly aims to provide a method for recycling rare earth and aluminum from an ionic rare earth leaching solution, which has the advantages of lower cost, no ammonia nitrogen pollution, reduced rare earth loss in the impurity removal process, realization of high-efficiency recycling of rare earth and aluminum and capability of obtaining mixed rare earth oxide meeting the requirements.
In order to achieve the above purpose, the application provides a method for recycling rare earth and aluminum from ion type rare earth leaching solution, which specifically comprises the following steps: (1) precipitation enrichment: slowly adjusting the pH value of the ion type rare earth leaching solution to 7.0-7.5 by adopting magnesium oxide slurry; adding magnesium bicarbonate solution to precipitate rare earth in the leaching solution; solid-liquid separation is carried out on the slurry after precipitation to obtain rare earth enrichment and liquid after precipitation; (2) stirring, washing and impurity removal: stirring, washing and removing impurities from the rare earth enrichment in a sodium hydroxide solution, wherein the concentration of sodium hydroxide is 4.0-8.0mol/L, the reaction temperature is 40-90 ℃, the liquid-solid ratio is more than or equal to 1.5, and the rare earth hydroxide and the impurity-removing mother liquor are obtained through solid-liquid separation; (3) carbonization recovery: adding aluminum hydroxide seed crystal into the impurity-removed mother liquor, wherein the seed crystal coefficient is controlled to be 0.5-1.5; then introducing carbon dioxide, controlling the carbonization temperature to be 5-40 ℃ and controlling the pH of the carbonization end point to be 11.5-13.0; and after carbonization, stirring and aging for 6-12 hours, and carrying out solid-liquid separation to obtain aluminum hydroxide and filtrate.
Further, in the precipitation enrichment step, the magnesium oxide content of the obtained rare earth enrichment roasted product is less than 2.0wt.%.
Further, in the precipitation enrichment step, the obtained precipitation liquid can be recycled for leaching of the ionic rare earth ore.
Further, in the stirring, washing and impurity removing step, the rare earth purity in the mixed rare earth oxide obtained after the roasting of the rare earth hydroxide is more than 90 wt%, the magnesium oxide content is less than 3.0 wt%, the sulfate radical content is less than 0.5 wt%, the aluminum oxide content is less than 2.0 wt%, and the silicon dioxide content is less than 1.0 wt%.
In the stirring, washing and impurity removing step, the obtained impurity removing mother liquor can be circularly used for stirring, washing and impurity removing of rare earth enrichment after being added with sodium hydroxide for blending.
Further, in the carbonization recovery step, aluminum hydroxide is washed at the time of solid-liquid separation until the pH of the washing water is less than 9.0.
Further, in the carbonization recovery step, the obtained aluminum hydroxide is calcined to obtain aluminum oxide with a purity of 98wt.% or more, the silica content of which is less than 0.02wt.%, na 2 The O content is less than 0.5wt.%, and the average median particle diameter is greater than 50. Mu.m.
The application takes ion type rare earth leaching solution as a research object, firstly, magnesium oxide slurry is used for slowly adjusting the pH value of the rare earth leaching solution to 7.0-7.5, at the moment, aluminum is completely precipitated, a part of rare earth is also precipitated, then magnesium bicarbonate is used for completely precipitating the rest rare earth, the pH value in the process is between 7.0 and 8.0, and silicon in the leaching solution is not completely precipitated; meanwhile, the method of fractional precipitation is adopted, so that the problems of weak alkalinity and slow solid-liquid precipitation reaction of magnesium oxide can be effectively solved, and finally the content of magnesium oxide in the enriched matters can be well controlled. And (3) performing sodium hydroxide stirring and washing on the obtained rare earth enrichment, changing aluminum hydroxide into sodium aluminate, and then, entering the solution, changing basic rare earth sulfate into rare earth hydroxide, and releasing sulfate radical, so as to finally obtain the rare earth hydroxide. Carbon dioxide carbonization precipitation of the mother solution after impurity removal can obtain aluminum hydroxide, aluminum oxide with the purity of more than 98wt.% can be obtained by roasting, the silicon dioxide content is less than 0.02wt.%, and Na is contained 2 The O content is less than 0.5wt.%, and the average median particle diameter is greater than 50. Mu.m. The method does not undergo the neutralization aluminum removal process, and effectively improves the rare earth recovery rate. Meanwhile, the magnesium salt is precipitated step by step, ammonia nitrogen pollution is eliminated, and the contents of magnesium oxide and silicon dioxide in the mixed rare earth oxide are effectively reduced. Finally, the rare earth purity is more than 90wt.% after roasting, the magnesium oxide content is less than 3.0wt.%, the sulfate radical content is less than 0.5wt.%, the aluminum oxide content is less than 2.0wt.%, and the silicon dioxide is obtainedMixed rare earth oxide in an amount less than 1.0wt.%.
Detailed Description
It should be noted that, without conflict, the embodiments of the present application and features of the embodiments may be combined with each other. The present application will be described in detail with reference to examples.
The existing technology for removing aluminum and enriching rare earth in leaching solution by ammonium bicarbonate precipitation method in industry has the problems of low rare earth yield, high energy consumption, ammonia nitrogen pollution and the like, and how to realize the separation of rare earth and aluminum in leaching solution and the efficient enrichment of rare earth, simultaneously remove ammonia nitrogen pollution, obtain mixed rare earth oxide meeting the requirements, reduce the cost and become the common technical problem to be solved urgently at present.
The application provides a method for recycling rare earth and aluminum from ion type rare earth leaching liquid, which specifically comprises the following steps:
(1) And (3) precipitation enrichment: slowly adjusting the pH value of the ion type rare earth leaching solution to 7.0-7.5 by adopting magnesium oxide slurry; adding magnesium bicarbonate solution to precipitate rare earth in the leaching solution; and (3) carrying out solid-liquid separation on the slurry after precipitation to obtain rare earth enriched matters and liquid after precipitation. The pH value of the leaching solution is slowly regulated to 7.0-7.5 by adopting magnesium oxide slurry, all aluminum ions in the leaching solution are precipitated into aluminum hydroxide, part of rare earth is precipitated into rare earth hydroxide and basic rare earth sulfate, then magnesium bicarbonate solution is continuously added to completely precipitate the rare earth of the leaching solution, and the pH value of a system is not more than 8.0 due to limited concentration and alkalinity of magnesium bicarbonate in the process, so that most of silicon in the leaching solution is left in the solution. The magnesium oxide and magnesium bicarbonate step-by-step precipitation of rare earth leaching solution can eliminate ammonia nitrogen pollution, effectively solve the problems of weak alkalinity and slow solid-liquid precipitation reaction of magnesium oxide, simultaneously reduce the introduction of silicon by controlling pH, and finally well control the content of magnesium oxide and silicon dioxide in the enriched substance. The magnesium oxide content of the obtained rare earth enriched product after roasting is less than 2.0wt.%. Meanwhile, the obtained precipitated liquid can be circularly used for leaching the ionic rare earth ore.
(2) Stirring, washing and removing impurities: the rare earth enrichment is put into sodium hydroxide solution for stirring and washing to remove impurities, the concentration of sodium hydroxide is 4.0-8.0mol/L, the reaction temperature is 40-90 ℃, the liquid-solid ratio is more than or equal to 1.5, and the rare earth hydroxide and the impurity-removing mother solution are obtained through solid-liquid separation. The rare earth enrichment is composed of aluminum hydroxide, rare earth hydroxide, basic rare earth sulfate, rare earth carbonate and the like, the aluminum hydroxide can be converted into aluminate under the strong alkaline condition, the basic rare earth sulfate and the rare earth carbonate can be both converted into the rare earth hydroxide, so that the sodium hydroxide solution is adopted for stirring and washing to remove impurities, and the impurities such as aluminum, sulfate radical and the like can be converted into the solution through control and adjustment. However, in the process, proper conditions are found to optimize the thermodynamics and dynamics of the related conversion reaction, so that the conditions of 4.0-8.0mol/L sodium hydroxide concentration, 40-90 ℃ of reaction temperature, more than or equal to 1.5 of liquid-solid ratio and the like are controlled. The rare earth loss in the process of neutralizing and removing aluminum in the leaching solution can be avoided through stirring and washing, the impurity elements in the rare earth enrichment can be effectively removed, the rare earth purity in the mixed rare earth oxide obtained after final roasting of the rare earth hydroxide is more than 90 wt%, the magnesium oxide content is less than 3.0 wt%, the sulfate radical content is less than 0.5 wt%, the aluminum oxide content is less than 2.0 wt%, and the silicon dioxide content is less than 1.0 wt%. In addition, the obtained impurity-removing mother liquor can be circularly used for stirring, washing and impurity removal of rare earth enrichment after being added with sodium hydroxide for preparation.
(3) Carbonization recovery: adding aluminum hydroxide seed crystal into the impurity-removed mother liquor, wherein the seed crystal coefficient is controlled to be 0.5-1.5; then introducing carbon dioxide, controlling the carbonization temperature to be 5-40 ℃ and controlling the pH of the carbonization end point to be 11.5-13.0; and after carbonization, stirring and aging for 6-12 hours, and carrying out solid-liquid separation to obtain aluminum hydroxide and filtrate. The impurity-removing mother liquor is mainly sodium aluminate, sodium hydroxide and sodium sulfate, and part of hydroxide radicals in the solution are changed into carbonate radicals by introducing carbon dioxide into the solution, so that the alkalinity is reduced, and the sodium aluminate is converted into aluminum hydroxide. In order to control the precipitation rate of sodium aluminate, the carbonization temperature is controlled to be 5-40 ℃, the carbonization end point is controlled to be 11.5-13.0, the lower the temperature is, the higher the dissolution efficiency of carbon dioxide is, the lower the solubility of sodium aluminate is, the precipitation rate of aluminum is effectively improved, and finally the precipitation rate of aluminum is over 98%. Meanwhile, seed crystals are added in the precipitation process, and the seed crystal coefficient is controlled to be 0.5-1.5; meanwhile, stirring and ageing are needed for 6-12 hours after carbonization is finished, and the operations can effectively improve the granularity of aluminum hydroxide; more, theMainly, a large amount of sodium carbonate is generated in the carbonization process, and the sodium carbonate is easy to crystallize under the condition of a certain concentration, so that the product is required to be sufficiently washed in the solid-liquid separation process until the pH value of washing water is less than 9.0, and the aluminum hydroxide obtained at the moment can be roasted to obtain aluminum oxide with the purity of more than 98 wt%, the silicon dioxide content is less than 0.02 wt%, and Na 2 The O content is less than 0.5wt.%, and the average median particle diameter is greater than 50. Mu.m.
The leaching agent for leaching ionic rare earth ores and the leaching method thereof provided by the application are further described below with reference to examples.
Comparative example 1
The pH value of the ionic rare earth leaching solution (the rare earth concentration is 0.27g/L, the aluminum ion concentration is 50mg/L, and the silicate ion concentration is 45 mg/L) is slowly regulated to 9.1 by adopting magnesium oxide slurry, at this time, the rare earth is completely precipitated, the precipitated slurry is subjected to solid-liquid separation to obtain rare earth enriched matters and precipitated liquid, the magnesium oxide content in the roasted product of the obtained rare earth enriched matters is 9.8wt.%, and the precipitated liquid can be recycled for leaching the ionic rare earth ore. Stirring, washing and removing impurities from the rare earth enrichment in a sodium hydroxide solution, wherein the concentration of sodium hydroxide is 7.0mol/L, the reaction temperature is 80 ℃, the liquid-solid ratio is 2.0, and the rare earth hydroxide and the impurity-removing mother solution are obtained through solid-liquid separation; the rare earth purity in the mixed rare earth oxide obtained after the roasting of the rare earth hydroxide is 70.6wt.%, the magnesium oxide content is 11.6wt.%, the sulfate radical content is 0.24wt.%, the aluminum oxide content is 9.7wt.%, and the silicon dioxide content is 8.5wt.%. Adding aluminum hydroxide seed crystal into the impurity-removed mother liquor, wherein the seed crystal coefficient is controlled to be 0.5; then introducing carbon dioxide, controlling the carbonization temperature to 25 ℃ and controlling the pH of the carbonization end point to be 12.0; after carbonization, stirring and aging for 7.0 hours, and then carrying out solid-liquid separation to obtain aluminum hydroxide and filtrate, wherein the aluminum hydroxide is washed in the separation process until the pH value of washing water is less than 9.0; the aluminum hydroxide obtained was calcined to give alumina having a purity of 98.2wt.%, a silica content of 0.015wt.%, na 2 O content 0.44wt.%, average median particle diameter 52 μm.
Comparative example 2
Slowly adjusting ions by adopting magnesium oxide slurryThe pH value of the rare earth leaching solution (the rare earth concentration is 0.27g/L, the aluminum ion concentration is 50mg/L, and the silicate ion concentration is 45 mg/L) is 7.0, then the rare earth in the leaching solution is completely precipitated by slowly adding the magnesium bicarbonate solution, the precipitated slurry is subjected to solid-liquid separation to obtain rare earth enrichment and precipitated liquid, the magnesium oxide content in the roasted product of the obtained rare earth enrichment is 1.8wt.%, and the precipitated liquid can be recycled for leaching the ionic rare earth ore. Stirring, washing and removing impurities from the rare earth enrichment in a sodium hydroxide solution, wherein the concentration of sodium hydroxide is 7.0mol/L, the reaction temperature is 80 ℃, the liquid-solid ratio is 2.0, and the rare earth hydroxide and the impurity-removing mother solution are obtained through solid-liquid separation; the rare earth purity in the mixed rare earth oxide obtained after the roasting of the rare earth hydroxide is 91.2wt.%, the magnesium oxide content is 2.8wt.%, the sulfate radical content is 0.33wt.%, the aluminum oxide content is 1.5wt.%, and the silicon dioxide content is 0.8wt.%. Adding aluminum hydroxide seed crystal into the impurity-removed mother liquor, wherein the seed crystal coefficient is controlled to be 0.5; then introducing carbon dioxide, controlling the carbonization temperature to 25 ℃ and controlling the pH of the carbonization end point to be 11.0; after carbonization, stirring and aging for 7.0 hours, and then carrying out solid-liquid separation to obtain aluminum hydroxide and filtrate, wherein the aluminum hydroxide is washed in the separation process until the pH value of washing water is less than 9.0; the aluminum hydroxide thus obtained was calcined to obtain alumina having a purity of 97.4wt.% and a silica content of 0.014wt.%, na 2 O content 1.53wt.%, average median particle diameter 46 μm.
Example 1
The pH value of an ionic rare earth leaching solution (the rare earth concentration is 0.27g/L, the aluminum ion concentration is 50mg/L, and the silicate ion concentration is 45 mg/L) is slowly regulated to 7.0 by adopting magnesium oxide slurry, then the rare earth in the leaching solution is completely precipitated by slowly adding magnesium bicarbonate solution, the precipitated slurry is subjected to solid-liquid separation to obtain rare earth enrichment and post-precipitation liquid, the magnesium oxide content in the roasted product of the obtained rare earth enrichment is 1.8wt.%, and the post-precipitation liquid can be recycled for leaching the ionic rare earth ore. Stirring, washing and removing impurities from the rare earth enrichment in a sodium hydroxide solution, wherein the concentration of sodium hydroxide is 7.0mol/L, the reaction temperature is 80 ℃, the liquid-solid ratio is 2.0, and the rare earth hydroxide and the impurity-removing mother solution are obtained through solid-liquid separation; the purity of rare earth in the mixed rare earth oxide obtained after roasting the rare earth hydroxide is 91.2wt.%, and the content of magnesium oxide is 2.8 wt.%.The sulfate content was 0.33wt.%, the alumina content was 1.5wt.%, and the silica content was 0.8wt.%. Adding aluminum hydroxide seed crystal into the impurity-removed mother liquor, wherein the seed crystal coefficient is controlled to be 0.5; then introducing carbon dioxide, controlling the carbonization temperature to 25 ℃ and controlling the pH of the carbonization end point to be 12.0; after carbonization, stirring and aging for 7.0 hours, and then carrying out solid-liquid separation to obtain aluminum hydroxide and filtrate, wherein the aluminum hydroxide is washed in the separation process until the pH value of washing water is less than 9.0; the aluminum hydroxide thus obtained was calcined to obtain alumina having a purity of 98.5wt.% and a silica content of 0.014wt.%, na 2 O content 0.36wt.%, average median particle diameter 52 μm.
Example 2
The pH value of an ionic rare earth leaching solution (the rare earth concentration is 0.78g/L, the aluminum ion concentration is 120mg/L, and the silicate ion concentration is 52 mg/L) is slowly regulated to 7.2 by adopting magnesium oxide slurry, then the rare earth in the leaching solution is completely precipitated by slowly adding magnesium bicarbonate solution, the precipitated slurry is subjected to solid-liquid separation to obtain rare earth enrichment and post-precipitation liquid, the magnesium oxide content in the roasted product of the obtained rare earth enrichment is 1.6wt.%, and the post-precipitation liquid can be recycled for leaching the ionic rare earth ore. Stirring, washing and removing impurities from the rare earth enrichment in a sodium hydroxide solution, wherein the concentration of sodium hydroxide is 4.0mol/L, the reaction temperature is 90 ℃, the liquid-solid ratio is 1.5, and the rare earth hydroxide and the impurity-removing mother solution are obtained through solid-liquid separation; the rare earth purity in the mixed rare earth oxide obtained after the roasting of the rare earth hydroxide is 92.3wt.%, the magnesium oxide content is 2.4wt.%, the sulfate radical content is 0.38wt.%, the aluminum oxide content is 1.4wt.%, and the silicon dioxide content is 0.6wt.%. Adding aluminum hydroxide seed crystal into the impurity-removed mother liquor, wherein the seed crystal coefficient is controlled to be 1.0; then introducing carbon dioxide, controlling the carbonization temperature to be 5 ℃ and controlling the pH of the carbonization end point to be 11.5; after carbonization, stirring and aging for 6.0h, and then carrying out solid-liquid separation to obtain aluminum hydroxide and filtrate, wherein the aluminum hydroxide is washed in the separation process until the pH value of washing water is less than 9.0; the aluminum hydroxide obtained was calcined to give alumina having a purity of 98.4wt.%, a silica content of 0.012wt.%, na 2 0.45wt.% O, with an average median particle diameter of 56 μm.
Example 3
Using magnesium oxide slurryThe pH value of the ionic rare earth leaching solution (the rare earth concentration is 0.57g/L, the aluminum ion concentration is 89mg/L, and the silicate ion concentration is 68 mg/L) is slowly regulated to 7.5, then the rare earth in the leaching solution is completely precipitated by slowly adding the magnesium bicarbonate solution, the precipitated slurry is subjected to solid-liquid separation to obtain rare earth enrichment and precipitated liquid, the magnesium oxide content in the roasted product of the obtained rare earth enrichment is 1.9wt.%, and the precipitated liquid can be recycled for leaching the ionic rare earth ore. Stirring, washing and removing impurities from the rare earth enrichment in a sodium hydroxide solution, wherein the concentration of sodium hydroxide is 6.0mol/L, the reaction temperature is 40 ℃, the liquid-solid ratio is 2.5, and the rare earth hydroxide and the impurity-removing mother solution are obtained through solid-liquid separation; the rare earth purity in the mixed rare earth oxide obtained after the roasting of the rare earth hydroxide is 91.5wt.%, the magnesium oxide content is 2.6wt.%, the sulfate radical content is 0.35wt.%, the aluminum oxide content is 1.4wt.%, and the silicon dioxide content is 0.7wt.%. Adding aluminum hydroxide seed crystal into the impurity-removed mother liquor, wherein the seed crystal coefficient is controlled to be 1.5; then introducing carbon dioxide, controlling the carbonization temperature to 40 ℃ and controlling the pH of the carbonization end point to be 13.0; after carbonization, stirring and aging for 6.0h, and then carrying out solid-liquid separation to obtain aluminum hydroxide and filtrate, wherein the aluminum hydroxide is washed in the separation process until the pH value of washing water is less than 9.0; the obtained aluminum hydroxide was calcined to obtain alumina having a purity of 99.1wt.%, a silica content of 0.011wt.%, na 2 O content 0.35wt.%, average median particle diameter 61 μm.
Example 4
The pH value of an ionic rare earth leaching solution (the rare earth concentration is 1.23g/L, the aluminum ion concentration is 150mg/L, and the silicate ion concentration is 77 mg/L) is slowly regulated to 7.3 by adopting magnesium oxide slurry, then the rare earth in the leaching solution is completely precipitated by slowly adding magnesium bicarbonate solution, the precipitated slurry is subjected to solid-liquid separation to obtain rare earth enrichment and post-precipitation liquid, the magnesium oxide content in the roasted product of the obtained rare earth enrichment is 1.5wt.%, and the post-precipitation liquid can be recycled for leaching the ionic rare earth ore. Stirring, washing and removing impurities from the rare earth enrichment in a sodium hydroxide solution, wherein the concentration of sodium hydroxide is 8.0mol/L, the reaction temperature is 60 ℃, the liquid-solid ratio is 3.0, and the rare earth hydroxide and the impurity-removing mother solution are obtained through solid-liquid separation; the purity of the rare earth in the mixed rare earth oxide obtained after roasting the rare earth hydroxide is 92.6wt%The magnesium oxide content was 2.2wt.%, the sulfate content was 0.26wt.%, the alumina content was 1.3wt.%, and the silica content was 0.6wt.%. Adding aluminum hydroxide seed crystal into the impurity-removed mother liquor, wherein the seed crystal coefficient is controlled to be 0.8; then introducing carbon dioxide, controlling the carbonization temperature to be 30 ℃ and controlling the pH of the carbonization end point to be 12.5; after carbonization, stirring and aging for 10.0 hours, and then carrying out solid-liquid separation to obtain aluminum hydroxide and filtrate, wherein the aluminum hydroxide is washed in the separation process until the pH value of washing water is less than 9.0; the obtained aluminum hydroxide was calcined to obtain alumina having a purity of 98.4wt.%, a silica content of 0.011wt.%, na 2 0.40wt.% O, with an average median particle diameter of 55. Mu.m.
Example 5
The pH value of an ionic rare earth leaching solution (the rare earth concentration is 0.36g/L, the aluminum ion concentration is 72mg/L, and the silicate ion concentration is 43 mg/L) is slowly regulated to 7.4 by adopting magnesium oxide slurry, then the rare earth in the leaching solution is completely precipitated by slowly adding magnesium bicarbonate solution, the precipitated slurry is subjected to solid-liquid separation to obtain rare earth enrichment and post-precipitation liquid, the magnesium oxide content in the roasted product of the obtained rare earth enrichment is 1.7wt.%, and the post-precipitation liquid can be recycled for leaching the ionic rare earth ore. Stirring, washing and removing impurities from the rare earth enrichment in a sodium hydroxide solution, wherein the concentration of sodium hydroxide is 5.0mol/L, the reaction temperature is 50 ℃, the liquid-solid ratio is 4.0, and the rare earth hydroxide and the impurity-removing mother solution are obtained through solid-liquid separation; the rare earth purity in the mixed rare earth oxide obtained after the roasting of the rare earth hydroxide is 91.8wt.%, the magnesium oxide content is 2.4wt.%, the sulfate radical content is 0.33wt.%, the alumina content is 1.8wt.%, and the silicon dioxide content is 0.7wt.%. Adding aluminum hydroxide seed crystal into the impurity-removed mother liquor, wherein the seed crystal coefficient is controlled to be 1.2; then introducing carbon dioxide, controlling the carbonization temperature to be 10 ℃ and controlling the pH value of the carbonization end point to be 12.0; after carbonization, stirring and aging for 10.0 hours, and then carrying out solid-liquid separation to obtain aluminum hydroxide and filtrate, wherein the aluminum hydroxide is washed in the separation process until the pH value of washing water is less than 9.0; the aluminum hydroxide thus obtained was calcined to obtain alumina having a purity of 98.6wt.% and a silica content of 0.014wt.%, na 2 O content 0.45wt.%, average median particle diameter 58 μm.

Claims (7)

1. The method for recycling rare earth and aluminum from the ion type rare earth leaching solution is characterized by comprising the following steps of: and (3) precipitation enrichment: slowly adjusting the pH value of the ion type rare earth leaching solution to 7.0-7.5 by adopting magnesium oxide slurry; adding magnesium bicarbonate solution to precipitate rare earth in the leaching solution; solid-liquid separation is carried out on the slurry after precipitation to obtain rare earth enrichment and liquid after precipitation;
stirring, washing and removing impurities: stirring, washing and removing impurities from the rare earth enrichment in a sodium hydroxide solution, wherein the concentration of sodium hydroxide is 4.0-8.0mol/L, the reaction temperature is 40-90 ℃, the liquid-solid ratio is more than or equal to 1.5, and the rare earth hydroxide and the impurity-removing mother liquor are obtained through solid-liquid separation;
carbonization recovery: adding aluminum hydroxide seed crystal into the impurity-removed mother liquor, wherein the seed crystal coefficient is controlled to be 0.5-1.5; then introducing carbon dioxide, controlling the carbonization temperature to be 5-40 ℃ and controlling the pH of the carbonization end point to be 11.5-13.0; and after carbonization, stirring and aging for 6-12 hours, and carrying out solid-liquid separation to obtain aluminum hydroxide and filtrate.
2. The method of claim 1, wherein in the precipitation enrichment step, the resulting rare earth enriched calcined product has a magnesium oxide content of less than 2.0wt.%.
3. The method according to claim 1, wherein in the precipitation enrichment step, the resulting post-precipitation liquor may be recycled for leaching of the ionic rare earth ore.
4. The method according to claim 1, wherein in the stirring, washing and impurity removing step, the rare earth purity in the mixed rare earth oxide obtained after the roasting of the rare earth hydroxide is more than 90wt.%, the magnesium oxide content is less than 3.0wt.%, the sulfate content is less than 0.5wt.%, the aluminum oxide content is less than 2.0wt.%, and the silicon dioxide content is less than 1.0wt.%.
5. The method according to claim 1, wherein in the stirring, washing and impurity removing step, the obtained impurity removing mother liquor can be recycled for stirring, washing and impurity removing of rare earth enriched matters after being mixed with sodium hydroxide.
6. The method according to claim 1, wherein in the carbonization recovery step, aluminum hydroxide is washed at the time of solid-liquid separation until the pH of the washing water is less than 9.0.
7. The method according to claim 1, wherein in the carbonization recovery step, the obtained aluminum hydroxide is calcined to obtain aluminum oxide having a purity of 98wt.% or more, a silica content of less than 0.02wt.%, and Na 2 The O content is less than 0.5wt.%, and the average median particle diameter is greater than 50. Mu.m.
CN202310623010.XA 2023-05-30 2023-05-30 Method for recovering rare earth and aluminum from ion type rare earth leaching liquid Pending CN116676479A (en)

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