CN108707753B - Process for recovering rare earth-containing waste material by solvent extraction - Google Patents
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Abstract
The invention relates to a process for recovering rare earth-containing waste materials by solvent extraction, which comprises the steps of sintering the rare earth-containing waste materials containing Ce, Pr, Dy, Er and Tm at high temperature, acid-leaching by hydrochloric acid, adjusting the pH value, forming a mixed organic phase by a novel extractant P227 and a traditional extractant P507, performing saponification-free extraction by matching with a resin phase, and controlling the separation sequence of each rare earth element by utilizing the extraction back-extraction activity of different rare earth elements. The invention has the advantages of high purity and high yield of Tm products, suitability for large-scale production, small consumption of the whole chemical reagent in the whole process, easy automation, simple and convenient operation, low production cost and the like.
Description
Technical Field
The invention relates to the field of valuable metal recovery, in particular to a process for recovering rare earth-containing waste materials by solvent extraction.
Background
Rare earth elements play an important role in the global modern industrial construction of the 21 st century, and are closely related to excellent magnetic, optical, electric and other characteristics. As such, rare earth metals are critical to some rapidly developing industries in the world, such as catalysts, magnetic materials, glass, metallurgy, electronics, and phosphors, as key elements and important non-renewable strategic resources essential to upgrade the traditional industry, develop the national defense science and technology industry, and create emerging industries. With the use of rare earths in catalysts, magnets, rare earth alloys, the worldwide demand for rare earths will grow at 6% per year before 2020. The rare earth ore is leached by a leaching agent, and then is precipitated by ammonium carbonate and roasted to obtain a rare earth oxide primary product. Dissolving by HCl, and separating by chemical precipitation, ion exchange, organic solvent extraction, extraction chromatography, and liquid membrane method. The solvent extraction method has the advantages of high extraction and separation efficiency, large treatment capacity, high reaction speed and the like, and is a rare earth separation method widely adopted by rare earth hydrometallurgy enterprises at home and abroad at present.
The extractant can selectively lead metal ions to enter an organic phase from an aqueous phase through a complexation reaction, and can also realize the conversion of the metal ions from the organic phase to the aqueous phase through another complexation reaction, thereby achieving the enrichment and separation of metals. The extractant needs to have both a reactive group that complexes with the metal ion and a hydrophobic group that increases oil solubility. The extraction system can be divided into a phosphorus type extraction system, an amine phosphorus type extraction system, a chelate type extraction system and the like according to the types of the extracting agents. The classification method is particularly suitable for systems with uncertain extraction mechanism; according to the difference of the acidity of the water phase to be extracted, the extraction system can be divided into an acidic extraction system and a neutral extraction system; the extraction system can be divided into a sulfuric acid extraction system, a hydrochloric acid extraction system and a nitric acid system according to different extraction media; the extraction systems commonly used are classified according to the extraction mechanism or the nature of the extraction compounds formed during the extraction process, and can be classified into the following types: a simple molecular extraction system, a neutral complex extraction system, an acidic complex extraction system, an ion association extraction system, a synergistic extraction system and a high-temperature extraction system.
At present, alkaline substances such as ammonia water and the like are mainly used in industrial production to saponify P507 and P204 extracting agents for extracting and separating rare earth elements, and high-concentration NH is generated in the extraction and separation process4+、Na+Or Ca2+The saponified wastewater seriously harms the environment, the ammonia nitrogen wastewater problem is the most difficult environmental problem to solve in the rare earth separation factory in recent years, and the traditional process for extracting and separating the rare earth elements also has the problems of long flow, variable components, lag in mass transfer, large organic cancellation consumption, potential safety hazard and the like
Disclosure of Invention
In order to solve the technical problems, the invention provides a process for recovering rare earth-containing waste materials by solvent extraction, which can efficiently recover rare earth elements in the rare earth-containing waste materials, belongs to a new extraction and separation technology which is urgently needed by the rare earth extraction industry, and can really reduce the consumption of an extracting agent, increase the extraction efficiency, reduce the reaction time, reduce the solvent consumption and reduce the cost.
The process comprises the following steps:
1) uniformly mixing the pretreated rare earth-containing waste material with caustic soda and calcium chloride according to the mass ratio of 1: 0.75-0.85: 0.4-0.5, heating to 350-450 ℃, preserving heat for 1-2 hours, and continuing to heat to 700-800 ℃, preserving heat for 2-3 hours to obtain a sintered material; reacting the sintered material with excessive hydrochloric acid solution, and filtering after reaction to obtain feed liquid containing Ce, Pr, Dy, Er and Tm and insoluble substances;
2) sequentially adding a sulfonated kerosene mixed organic phase of P227 and P507 into a reactor, a feed liquid containing Ce, Pr, Dy, Er and Tm and an N-methylimidazole anion exchange resin phase; stirring and reacting for 0.5-1 h at 25-35 ℃, and standing for about 30 min; obtaining a DyErTm loaded organic phase from an upper organic phase, and obtaining a CePr feed liquid from a water phase;
3) adding conventional saponified P507 organic phase into the CePr feed liquid, extracting and separating to obtain an aqueous phase product Ce and a loaded Pr organic phase, back-extracting the loaded Pr organic phase by adopting hydrochloric acid with the concentration of 3-5 mol/L, and separating from the aqueous phase to obtain a product Pr;
4) adding 1.0-1.5 mol/L hydrochloric acid into the DyErTm loaded organic phase for back extraction, separating to obtain a product Dy and an ErTm loaded organic phase, performing secondary back extraction on the ErTm loaded organic phase by adopting 3-5 mol/L hydrochloric acid, and separating from a water phase to obtain an ErTm material liquid;
5) adding the ErTm material liquid into a P507 organic phase and an N-methylimidazole anion exchange resin phase, extracting and separating to obtain an aqueous phase product Er and a Tm loaded organic phase, performing secondary back extraction on the Tm loaded organic phase by adopting hydrochloric acid with the concentration of 4-5 mol/L, and separating from the aqueous phase to obtain a product Tm.
And 2) in the mixed organic phase, the concentration of P507 is 1-1.5 mol/L, and the concentration of P227 is 0.25-0.50 mol/L.
And 2), the average particle size of the N-methylimidazole anion exchange resin is 0.2-0.4 mm, and the effective exchange capacity relative to chloride ions is 3.5-5.0 mol/kg.
And 2) the molar ratio of the rare earth in the feed liquid containing Ce, Pr, Dy, Er and Tm to the mixed organic phase is 0.2-0.3: 1.
The concentration of rare earth elements in the feed liquid containing Ce, Pr, Dy, Er and Tm is 0.6-0.8 mol/L, and the pH value range is 2-3.
And 4) controlling the mole ratio of the hydrochloric acid for the secondary back extraction to the rare earth in the ErTm organic phase to be 3.7-3.9: 1.
And 5) controlling the mole ratio of hydrochloric acid for secondary stripping to rare earth in the Tm loaded organic phase to be 3.7-3.9: 1.
The Tm purity of the product is more than 99.9995%, and the yield is 93.8-95.2%.
The pretreatment is to carry out crushing, grinding and washing pretreatment on the waste containing the rare earth.
The waste material containing rare earth is one or more of slag in the production process of the rare earth molecular sieve, FCC waste catalyst, automobile exhaust waste catalyst and special ceramic waste material containing rare earth.
The invention has the advantages that: the method comprises the steps of sintering rare earth waste containing Ce, Pr, Dy, Er and Tm at high temperature, acid-leaching with hydrochloric acid, adjusting the pH value, forming a mixed organic phase by a novel extracting agent P227 and a traditional extracting agent P507, performing saponification-free extraction by matching with a resin phase, and controlling the separation order of various rare earth elements by utilizing the extraction back-extraction activity of different rare earth elements. The invention has the advantages of high purity and high yield of Tm products, suitability for large-scale production, small consumption of the whole chemical reagent in the whole process, easy automation, simple and convenient operation, low production cost and the like.
Detailed Description
Solvent extraction is a process that uses the solubility difference between two immiscible liquid phases of a solute to achieve separation and enrichment of the solute, and may be referred to as liquid-liquid extraction. At present, the extracting agents mainly adopted by the rare earth industry in China are acidic phosphine extracting agents such as P204, P507 and the like, and the extracting systems comprise a P507-HCl system and a P507-HNO system3System and P204-H2SO4Systems, and the like. These extraction systems are sensitive to the change of acidity, and when the acidity is high, the rare earth extraction performance is liable to be reduced, so that the saponification process is often required to be added.
In order to realize the aim of simultaneous realization of industrial production and environmental protection, the problems of ammonia nitrogen and high-salt wastewater in the rare earth extraction saponification link and environmental pollution are solved from the source, and the development of a more green and clean solvent extraction process for separating rare earth elements is urgent. In recent years, the broad researchers have diverged the thinking, and put forward a new direction of extraction and separation of rare earth without saponification, namely a process for directly extracting and separating rare earth without saponification of an extracting agent.
In addition, compared with other separation technologies, the extraction resin technology has the advantages of high selectivity of a solvent extraction method and simplicity and high efficiency of equipment of an ion exchange method, and can be used as an effective method for separating and preparing a single high-purity rare earth product, and is called as a second-generation extraction system.
The patent is further described in detail below with reference to examples and comparative examples.
Example 1:
crushing, grinding and washing the rare earth-containing waste materials containing the slag of the rare earth molecular sieve production process, the FCC waste catalyst and the automobile exhaust waste catalyst. Uniformly mixing the pretreated rare earth-containing waste material, caustic soda and calcium chloride according to the mass ratio of 1: 0.75: 0.4, heating to 450 ℃, preserving heat for 2h, and continuing to heat to 700 ℃, preserving heat for 2h to obtain a sintering material.
The method comprises the steps of reacting the sintering material with excessive hydrochloric acid solution, filtering after reaction to obtain feed liquid containing Ce, Pr, Dy, Er, Tm and insoluble substances, sequentially adding a sulfonated kerosene mixed organic phase containing P227 and P507 into a reactor, wherein the feed liquid containing Ce, Pr, Dy, Er, Tm and an N-methylimidazole anion exchange resin phase, the concentration of P507 in the mixed organic phase is 1 mol/L, the concentration of P227 is 0.25 mol/L, the average particle size of the N-methylimidazole anion exchange resin is 0.2mm, the effective exchange capacity relative to chloride ions is 5.0 mol/kg., the molar ratio of rare earth elements in the feed liquid containing Ce, Pr, Dy, Er and Tm to the mixed organic phase is 0.3: 1, the concentration of rare earth elements in the feed liquid containing Ce, Pr, Dy, Er and Tm is 0.6 mol/L, the pH value is 2, stirring and reacting for 1 hour at 25 ℃, standing for about 30min, and the loaded organic phase is obtained from the upper organic phase and the CePr, Tm and the aqueous phase is obtained from the loaded organic phase.
Adding conventional saponified P507 organic phase into the CePr feed liquid, extracting and separating to obtain a water-phase product Ce and a loaded Pr organic phase, back-extracting the loaded Pr organic phase by adopting hydrochloric acid with the concentration of 3 mol/L, and separating from the water phase to obtain the product Pr.
Adding 1.0 mol/L hydrochloric acid into the DyErTm loaded organic phase for back extraction, separating to obtain a Dy product and an ErTm loaded organic phase, performing secondary back extraction on the ErTm loaded organic phase by adopting 3 mol/L hydrochloric acid, and controlling the mole ratio of the hydrochloric acid subjected to secondary back extraction to the rare earth in the ErTm loaded organic phase to be 3.7: 1.
Adding the ErTm feed liquid into a P507 organic phase and an N-methylimidazole anion exchange resin phase, extracting and separating to obtain an aqueous phase product Er and a Tm loaded organic phase, performing secondary back extraction on the Tm loaded organic phase by using hydrochloric acid with the concentration of 4 mol/L, and controlling the mole ratio of the hydrochloric acid subjected to the secondary back extraction to the rare earth in the Tm loaded organic phase to be 3.7: 1, so as to obtain a Tm product from aqueous phase separation, wherein the Tm purity of the product is 99.9995%, and the yield is 93.8%.
Example 2:
crushing, grinding and washing the rare earth-containing waste materials including the slag of the rare earth molecular sieve production process, the FCC waste catalyst and the rare earth-containing special ceramic waste materials. Uniformly mixing the pretreated waste material containing rare earth with caustic soda and calcium chloride according to the mass ratio of 1: 0.85: 0.5, heating to 450 ℃, preserving heat for 1h, and continuing to heat to 800 ℃, preserving heat for 2h to obtain a sintering material.
The method comprises the steps of reacting the sintering material with excessive hydrochloric acid solution, filtering after reaction to obtain feed liquid containing Ce, Pr, Dy, Er, Tm and insoluble substances, sequentially adding a sulfonated kerosene mixed organic phase containing P227 and P507 into a reactor, wherein the feed liquid containing Ce, Pr, Dy, Er, Tm and an N-methylimidazole anion exchange resin phase, the concentration of P507 in the mixed organic phase is 1 mol/L, the concentration of P227 is 0.50 mol/L, the average particle size of the N-methylimidazole anion exchange resin is 0.4mm, the effective exchange capacity relative to chloride ions is 4.0 mol/kg., the molar ratio of rare earth elements in the feed liquid containing Ce, Pr, Dy, Er and Tm to the mixed organic phase is 0.3: 1, the concentration of rare earth elements in the feed liquid containing Ce, Pr, Dy, Er and Tm is 0.7 mol/L, the pH value is 2, stirring and reacting for 1 hour at 35 ℃, standing for about 30min, and loading the Dy, Tm feed liquid containing Ce, the loaded aqueous phase and the Erer phase is obtained from the upper organic phase.
Adding conventional saponified P507 organic phase into the CePr feed liquid, extracting and separating to obtain a water-phase product Ce and a loaded Pr organic phase, back-extracting the loaded Pr organic phase by adopting hydrochloric acid with the concentration of 5 mol/L, and separating from the water phase to obtain the product Pr.
Adding 1.5 mol/L hydrochloric acid into the DyErTm loaded organic phase for back extraction, separating to obtain a Dy product and an ErTm loaded organic phase, performing secondary back extraction on the ErTm loaded organic phase by adopting 5 mol/L hydrochloric acid, and controlling the mole ratio of the hydrochloric acid subjected to secondary back extraction to the rare earth in the ErTm loaded organic phase to be 3.9: 1.
Adding the ErTm feed liquid into a P507 organic phase and an N-methylimidazole anion exchange resin phase, extracting and separating to obtain an aqueous phase product Er and a Tm loaded organic phase, performing secondary back extraction on the Tm loaded organic phase by using hydrochloric acid with the concentration of 5 mol/L, and controlling the mole ratio of the hydrochloric acid subjected to the secondary back extraction to the rare earth in the Tm loaded organic phase to be 3.9: 1, so as to obtain a product Tm from aqueous phase separation, wherein the Tm purity of the product is 99.9999%, and the yield is 95.2%.
Example 3:
the method comprises the steps of crushing, grinding and washing the rare earth-containing waste materials containing the FCC waste catalyst, the automobile exhaust waste catalyst and the rare earth-containing special ceramic waste materials. Uniformly mixing the pretreated rare earth-containing waste material, caustic soda and calcium chloride according to the mass ratio of 1: 0.80: 0.45, heating to 400 ℃, preserving heat for 1h, and continuously heating to 750 ℃, preserving heat for 3h to obtain a sintering material.
The sintering material is reacted with excessive hydrochloric acid solution, and after reaction, the reaction product is filtered to obtain feed liquid containing Ce, Pr, Dy, Er and Tm and insoluble substances, a sulfonated kerosene mixed organic phase containing P227 and P507 is sequentially added into a reactor, the feed liquid containing Ce, Pr, Dy, Er and Tm and an N-methylimidazole anion exchange resin phase are added, in the mixed organic phase, the concentration of P507 is 1.2 mol/L, the concentration of P227 is 0.40 mol/L, the average particle size of the N-methylimidazole anion exchange resin is 0.3mm, the effective exchange capacity relative to chloride ions is 4.0 mol/kg., the molar ratio of rare earth in the feed liquid containing Ce, Pr, Dy, Er and Tm and the mixed organic phase is 0.25: 1, the concentration of rare earth elements in the feed liquid containing Ce, Pr, Dy, Er and Tm is 0.6 mol/L, the pH value is 3, the mixture liquid is stirred and reacts for 0.5h at 35 min, the load aqueous phase is obtained from the organic phase, and the ErTm is stood to obtain an ErTm aqueous phase.
Adding conventional saponified P507 organic phase into the CePr feed liquid, extracting and separating to obtain a water-phase product Ce and a loaded Pr organic phase, back-extracting the loaded Pr organic phase by adopting hydrochloric acid with the concentration of 4 mol/L, and separating from the water phase to obtain the product Pr.
Adding 1.0 mol/L hydrochloric acid into the DyErTm loaded organic phase for back extraction, separating to obtain a Dy product and an ErTm loaded organic phase, performing secondary back extraction on the ErTm loaded organic phase by adopting 4 mol/L hydrochloric acid, and controlling the mole ratio of the hydrochloric acid subjected to secondary back extraction to the rare earth in the ErTm loaded organic phase to be 3.8: 1.
Adding the ErTm feed liquid into a P507 organic phase and an N-methylimidazole anion exchange resin phase, extracting and separating to obtain an aqueous phase product Er and a Tm loaded organic phase, performing secondary back extraction on the Tm loaded organic phase by using hydrochloric acid with the concentration of 4 mol/L, and controlling the mole ratio of the hydrochloric acid subjected to the secondary back extraction to the rare earth in the Tm loaded organic phase to be 3.8: 1, so as to obtain a Tm product from aqueous phase separation, wherein the Tm purity of the product is 99.9995%, and the yield is 94.6%.
Comparative example 1:
in the recovery process, when the components and the proportion of an extraction system are changed, particularly the content of organic phase and resin phase is excessive or insufficient, the extraction reaction efficiency of rare earth elements and the extraction sequence of different rare earth elements are influenced, and the recovery rate and the purity of rare earth are reduced.
Comparative example 2:
when the sintering and acid leaching steps or parameters after pretreatment are changed, especially the addition amount of different sintering raw materials and the pH value control of acid leaching after sintering result in excessive impurities contained in rare earth feed liquid or loss of rare earth elements, thereby reducing the efficiency and yield of the subsequent extraction and separation steps.
As can be seen from examples 1-3 and comparative examples 1 and 2, the invention carries out high-temperature sintering on the waste material containing rare earth, acid leaching with hydrochloric acid and pH value adjustment, then forms a mixed organic phase by a novel extractant P227 and a traditional extractant, carries out non-saponification extraction by matching with a resin phase, and controls the separation order of each rare earth element by utilizing the extraction back-extraction activity of different rare earth elements. The invention has the advantages of high purity and high yield of Tm products, suitability for large-scale production, small consumption of the whole chemical reagent in the whole process, easy automation, simple and convenient operation, low production cost and the like.
While embodiments of the present patent have been shown and described, it will be understood by those of ordinary skill in the art that: various changes, modifications, substitutions and alterations can be made to the embodiments without departing from the principles and spirit of this patent, the scope of which is defined by the claims and their equivalents.
Claims (7)
1. A process for recovering rare earth-containing waste materials by solvent extraction is characterized in that: the process comprises the following specific steps:
1) uniformly mixing the pretreated rare earth-containing waste material with caustic soda and calcium chloride according to the mass ratio of 1: 0.75-0.85: 0.4-0.5, heating to 350-450 ℃, preserving heat for 1-2 hours, and continuing to heat to 700-800 ℃, preserving heat for 2-3 hours to obtain a sintered material; reacting the sintered material with excessive hydrochloric acid solution, and filtering after reaction to obtain feed liquid containing Ce, Pr, Dy, Er and Tm and insoluble substances;
2) sequentially adding a sulfonated kerosene mixed organic phase of P227 and P507 into a reactor, a feed liquid containing Ce, Pr, Dy, Er and Tm and an N-methylimidazole anion exchange resin phase; stirring and reacting for 0.5-1 h at 25-35 ℃, and standing for 30 min; obtaining a DyErTm loaded organic phase from an upper organic phase, and obtaining a CePr feed liquid from a water phase;
3) adding conventional saponified P507 organic phase into the CePr feed liquid, extracting and separating to obtain an aqueous phase product Ce and a loaded Pr organic phase, back-extracting the loaded Pr organic phase by adopting hydrochloric acid with the concentration of 3-5 mol/L, and separating from the aqueous phase to obtain a product Pr;
4) adding 1.0-1.5 mol/L hydrochloric acid into the DyErTm loaded organic phase for back extraction, separating to obtain a product Dy and an ErTm loaded organic phase, performing secondary back extraction on the ErTm loaded organic phase by adopting 3-5 mol/L hydrochloric acid, and separating from a water phase to obtain an ErTm material liquid;
5) adding the ErTm material liquid into a P507 organic phase and an N-methylimidazole anion exchange resin phase, extracting and separating to obtain an aqueous phase product Er and a Tm loaded organic phase, performing secondary back extraction on the Tm loaded organic phase by adopting hydrochloric acid with the concentration of 4-5 mol/L, and separating from the aqueous phase to obtain a product Tm;
step 2), the average particle size of the N-methylimidazole anion exchange resin is 0.2-0.4 mm, and the effective exchange capacity relative to chloride ions is 3.5-5.0 mol/kg;
step 2), the molar ratio of the rare earth in the feed liquid containing Ce, Pr, Dy, Er and Tm to the mixed organic phase is 0.2-0.3: 1;
the Tm purity of the product is more than 99.9995%, and the yield is 93.8-95.2%.
2. The process as set forth in claim 1, wherein in the step 2), the concentration of P507 is 1 to 1.5 mol/L, and the concentration of P227 is 0.25 to 0.50 mol/L.
3. The process as claimed in claim 1, wherein the rare earth element concentration in the feed liquid containing Ce, Pr, Dy, Er and Tm is 0.6-0.8 mol/L, and the pH value is 2-3.
4. The process as claimed in claim 1, wherein: and 4) controlling the mole ratio of the hydrochloric acid for the secondary back extraction to the rare earth in the ErTm organic phase to be 3.7-3.9: 1.
5. The process as claimed in claim 1, wherein: and 5) controlling the mole ratio of hydrochloric acid for secondary stripping to rare earth in the Tm loaded organic phase to be 3.7-3.9: 1.
6. The process as claimed in claim 1, wherein: the pretreatment is to carry out crushing, grinding and washing pretreatment on the waste containing the rare earth.
7. The process as claimed in claim 1, wherein: the waste material containing rare earth is one or more of slag in the production process of the rare earth molecular sieve, FCC waste catalyst, automobile exhaust waste catalyst and special ceramic waste material containing rare earth.
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| CN111961856B (en) * | 2020-07-06 | 2022-01-07 | 廖乐 | Device for separating vanadium and rare earth elements from waste FCC catalyst |
| CN113337739B (en) * | 2021-06-03 | 2023-03-21 | 赣州有色冶金研究所有限公司 | Desorption method of rare earth loaded resin and recovery method of rare earth |
| CN114890450B (en) * | 2022-05-11 | 2024-03-26 | 湖南东方钪业股份有限公司 | Method for preparing scandium oxide |
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