CN109055783B - Method for recovering rare earth oxide from waste containing rare earth oxide - Google Patents
Method for recovering rare earth oxide from waste containing rare earth oxide Download PDFInfo
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- 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
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
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Abstract
The application relates to a method for recovering rare earth oxide in rare earth oxide-containing waste, which comprises the following steps: mixing the waste containing the rare earth oxide, strong base and an auxiliary agent for roasting to obtain a roasted product; washing the roasted product by hot water in a multi-stage countercurrent manner until the pH value of an eluate is 7-9, so as to obtain washing slag containing rare earth oxide; leaching washing slag by adopting strong acid multistage countercurrent, and filtering to obtain leaching solution containing rare earth ions; separating and purifying the leaching solution, and precipitating and burning the leaching solution by using oxalic acid to obtain the high-purity rare earth oxide.
Description
Technical Field
The invention relates to the technical field of rare earth resource recycling, in particular to a method for recycling rare earth oxide in waste materials containing rare earth oxide.
Background
The rare earth polishing powder mainly comprises cerium oxide, has uniform granularity, moderate hardness, high polishing efficiency, good polishing quality, long service life, cleanness and environmental protection, and is widely used for polishing optical glass, liquid crystal glass substrates and touch screen glass cover plates. In recent years, with the rise of industries such as mobile phone touch screens, vehicle-mounted displays, large-screen liquid crystal televisions and the like, high-performance cerium-based rare earth polishing powder is rapidly developed, the domestic dosage is over 3 ten thousand tons, and the derived rare earth polishing powder contains 15 ten thousand tons of waste cement per year. In the future 3-5 years, the application market of the rare earth polishing powder will still rapidly increase at a speed of 20-30%, and the formed rare earth polishing powder waste will also continuously increase.
Rare earth resources are not renewable and are unevenly distributed in the crust, resulting in high processing costs, and have been classified as scarce resources in the european union, the united states and japan. Although the rare earth resource in China is in the forefront of the world, the rare earth resource is more and more valued by people as an important strategic resource and irreplaceability.
Realizes the recycling of the rare earth polishing powder waste, can provide raw materials for nickel-metal hydride batteries, rare earth energy storage materials and rare earth polishing powder, and has great significance for sustainable development and environmental protection.
The prior art discloses a method for recovering rare earth oxide from rare earth polishing powder waste, which adopts firing pretreatment, then adopts mixed solution of sulfuric acid, glacial acetic acid and cosolvent to dissolve the rare earth polishing powder waste, filtrate enters a multistage extraction tank to carry out rare earth extraction and separation, and zinc powder is adopted to reduce Eu3+The method of (1) can obtain high-purity europium oxide. However, the method does not separate impurities in the polishing powder waste, and introduces new impurity Zn, so that the method is difficult to actually prepare high-purity rare earth oxide.
In addition, the prior art discloses a method for preparing rare earth oxide finished products by carrying out alkali roasting, washing and impurity removal on rare earth polishing powder waste, acidifying by hydrochloric acid, adjusting the pH value by NaOH, precipitating acidified filtrate by oxalic acid to obtain rare earth oxide finished products, and washing and drying acidified slag by pure water. However, the rare earth oxide prepared by the method has lower purity.
Disclosure of Invention
Based on this, there is a need for a method for recovering rare earth oxides from rare earth oxide-containing waste materials that can obtain high-purity rare earth oxides.
A method for recovering rare earth oxide from rare earth oxide-containing waste materials comprises the following steps:
mixing the waste containing the rare earth oxide, strong base and an auxiliary agent for roasting to obtain a roasted product;
washing the roasted product by hot water in a multi-stage countercurrent manner until the pH value of an eluate is 7-9, so as to obtain washing slag containing rare earth oxides;
carrying out multistage countercurrent leaching on the washing slag containing the rare earth oxide by adopting strong acid, and filtering to obtain leaching solution containing rare earth ions;
and separating and purifying the leaching solution containing the rare earth ions, and precipitating and burning the leaching solution by using oxalic acid to obtain rare earth oxide.
In one embodiment, the rare earth oxide in the rare earth oxide-containing waste material is cerium oxide and lanthanum oxyfluoride; the waste material containing rare earth oxide also contains impurities, and the impurities are at least one of aluminum oxide, silicon oxide and fluorine-containing compounds.
In one embodiment, the strong base is sodium hydroxide or potassium hydroxide, and the molar ratio of the impurities to the strong base is 1 (1.2-4).
In one embodiment, the auxiliary agent is carbon powder, ammonium chloride or ammonium bicarbonate, and the mass ratio of the waste material containing the rare earth oxide to the auxiliary agent is (10-5): 1.
In one embodiment, the roasting temperature is 550-800 ℃, and the roasting time is 1-4 hours.
In one embodiment, the number of stages of the multistage countercurrent washing is 2-5 stages.
In one embodiment, the strong acid is hydrochloric acid, sulfuric acid, or nitric acid.
In one embodiment, the multistage countercurrent leaching is performed in 2-4 stages.
In one embodiment, the method for separation and purification comprises the following steps: extracting agent is adopted for multi-stage countercurrent extraction, washing and back extraction.
In one embodiment, the extracting agent is a combination of di (2-ethylhexyl) phosphate or 2-ethylhexyl phosphate mono 2-ethylhexyl and kerosene, the concentration of di (2-ethylhexyl) phosphate or 2-ethylhexyl phosphate mono 2-ethylhexyl phosphate in the extracting agent is 1mol/L to 2mol/L, and the saponification rate of the extracting agent is 30% to 50%.
According to the method for recovering the rare earth oxide in the rare earth oxide-containing waste, impurities in the waste are converted into soluble salts through strong alkali and auxiliary agent roasting, then hot water is adopted for multi-stage countercurrent washing, the impurity removal effect is greatly improved, then strong acid is used for multi-stage countercurrent leaching, the rare earth oxide in the waste is converted into rare earth ions as far as possible to be dissolved in a leaching solution, a purified rare earth ion solution is obtained through separation and purification, and finally the purified rare earth ion solution is precipitated and burned by oxalic acid, so that the high-purity rare earth oxide can be obtained.
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FIG. 1 is a process flow diagram of a method for recovering rare earth oxides from rare earth oxide-containing waste material in accordance with one embodiment.
Detailed Description
In order that the invention may be more fully understood, a more particular description of the invention will now be rendered by reference to specific embodiments thereof that are illustrated in the appended drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
Referring to fig. 1, one embodiment of the method for recovering rare earth oxide from rare earth oxide-containing waste includes the following steps S110 to S160:
and S110, providing the waste material containing the rare earth oxide.
In this embodiment, the rare earth oxide in the rare earth oxide-containing scrap is cerium oxide (CeO)2) And lanthanum oxide (La)2O3)。
Further, the rare earth oxide-containing scrap may further contain an impurity, which is alumina (Al)2O3) Silicon oxide (SiO)2) And a fluorine-containing compound (F).
S120, mixing the waste containing the rare earth oxide, strong base and an auxiliary agent, and roasting to obtain a roasted product.
In this embodiment, the strong base is sodium hydroxide or potassium hydroxide.
Furthermore, the molar ratio of the impurities in the waste material containing the rare earth oxide to the strong base is 1 (1.2-4), and the waste material containing the rare earth oxide is used for converting all the impurities in the waste material into soluble salts.
In the present embodiment, the auxiliary agent is carbon powder, ammonium chloride or ammonium bicarbonate.
Furthermore, the mass ratio of the waste material containing the rare earth oxide to the auxiliary agent is (10-5): 1, and the waste material containing the rare earth oxide is used for promoting the reaction of impurities and strong base so that the impurities in the waste material are quickly and effectively converted into soluble salts.
Furthermore, the roasting temperature is 550-800 ℃, and the roasting time is 1-4 hours.
The waste material, the strong base and the auxiliary agent are mixed and roasted, and the impurities in the waste material can be quickly and effectively converted into soluble salts by controlling the molar ratio of the impurities to the strong base in the waste material and the mass ratio of the waste material to the auxiliary agent.
In the present embodiment, the above-mentioned calcined product contains cerium oxide, lanthanum oxide, meta-aluminate, silicate and fluoride salt.
S130, performing multi-stage countercurrent washing on the roasted product by using hot water until the pH value of an eluate is 7-9, and obtaining the washing slag containing the rare earth oxide.
In the present embodiment, the number of stages of the multistage countercurrent washing is 2 to 5 stages.
It is to be understood that the number of stages of the above-mentioned multistage countercurrent washing is not limited as long as soluble salts, remaining strong base and auxiliaries in the roasted product can be removed.
And (3) performing multistage countercurrent washing on the roasted product by using hot water, wherein impurities converted into soluble salts in the step S120 can be dissolved in the hot water for removal, and the rare earth oxides are remained in the washing slag.
The roasted product is washed by hot water in a multistage countercurrent manner, so that the amount of washing wastewater can be reduced, the environmental pollution is reduced, the impurity removal effect can be greatly improved, and the difficulty of subsequent separation and purification is reduced.
In the present embodiment, the washing slag contains cerium oxide and lanthanum oxide.
S140, performing multistage countercurrent leaching on the washing slag containing the rare earth oxide by adopting strong acid, and filtering to obtain a leaching solution containing rare earth ions.
In this embodiment, the strong acid is hydrochloric acid, sulfuric acid, or nitric acid.
Furthermore, the stage number of the multistage countercurrent leaching is 2-4.
It can be understood that the number of stages of the multistage countercurrent leaching is not limited as long as the rare earth oxides in the washing slag can be completely converted into rare earth ions.
The washing slag containing rare earth oxide is leached by multistage countercurrent of strong acid, so that the acid consumption can be greatly reduced.
In the present embodiment, the leachate contains cerium ions and lanthanum ions, and the pH of the leachate is 1 to 3.
S150, separating and purifying the leaching solution containing the rare earth ions to obtain a purified rare earth ion solution.
In this embodiment, the method for separation and purification is: extracting agent is adopted for multi-stage countercurrent extraction, washing and back extraction.
Further, the extractant is a combination of di (2-ethylhexyl) phosphate (P204) or 2-ethylhexyl phosphate mono 2-ethylhexyl ester (P507) and kerosene, the concentration of di (2-ethylhexyl) phosphate or 2-ethylhexyl phosphate mono 2-ethylhexyl ester in the extractant is 1mol/L to 2mol/L, and the saponification rate of the extractant is 30% to 50%.
The extractant combines the P204 or P507 with the kerosene, and can effectively extract cerium ions in the leachate by controlling the concentration of the P204 or P507 in the extractant and the saponification rate of the extractant.
In this embodiment, the acidity of the leachate containing rare earth ions prepared in step S140 is just suitable for an extraction system, and the extraction process can be directly performed without adjusting the acidity, thereby reducing the number of operation steps.
It can be understood that after the leachate containing cerium ions and lanthanum ions is subjected to multistage countercurrent extraction by using an extractant, cerium ions are extracted into the extractant stage by stage, and then a back-extraction solution containing cerium ions is obtained by washing (three-stage washing with 1.3mol/L hydrochloric acid) and back-extraction (two-stage back-extraction with 3mol/L hydrochloric acid), and lanthanum ions stay in the leachate.
It should be noted that, the above-mentioned separation and purification method is not limited, as long as different rare earth ions in the leaching solution can be separated through separation and purification, so as to obtain a plurality of purified rare earth ion solutions.
And S160, precipitating and burning the purified rare earth ion solution by using oxalic acid to obtain rare earth oxide.
Wherein the burning temperature is 800 ℃.
Step S160, the rare earth ion solutions after being purified are respectively precipitated and burned by oxalic acid, and then the corresponding rare earth oxide with high purity can be obtained.
In this embodiment, the leaching solution containing lanthanum ions is precipitated with oxalic acid and burned to obtain lanthanum oxide with a purity of 99.5% or higher. The back extraction liquid containing cerium ions is precipitated and burned by oxalic acid to obtain cerium oxide with the purity of more than 99.5 percent.
According to the method for recovering the rare earth oxide in the rare earth oxide-containing waste, impurities in the waste are converted into soluble salts through roasting of strong base and auxiliaries, then hot water is adopted for multi-stage countercurrent washing, the impurities in the waste can be eluted by more than 90%, the impurity removal effect is greatly improved, then the rare earth oxide in the waste is converted into rare earth ions as far as possible through multi-stage countercurrent leaching of strong acid and dissolved in a leaching solution, different rare earth ions in the leaching solution are separated through separation and purification, a plurality of purified rare earth ion solutions are obtained, finally the plurality of purified rare earth ion solutions are respectively precipitated and burned by oxalic acid, and the corresponding high-purity rare earth oxide can be obtained, and the recovery rate of the rare earth oxide is more than 85%.
In addition, the alkaline washing water generated by the multistage countercurrent washing can be neutralized with the acidic wastewater after oxalic acid precipitation, no excess wastewater is generated in the whole process, and the method is environment-friendly and pollution-free.
The method for recovering the rare earth oxide in the waste material containing the rare earth oxide is suitable for the waste material containing the rare earth oxide, wherein any impurities can be converted into soluble salt through alkali roasting.
The following are specific examples.
In examples 1 to 4, the waste containing rare earth oxide and impurities was a rare earth polishing powder waste, and the chemical composition thereof is shown in table 1:
TABLE 1
Example 1
(1) Weighing 500g of rare earth polishing powder waste, 168g of sodium hydroxide and 50g of carbon powder, and uniformly mixing in a mixer to obtain a mixture; wherein, according to the mol ratio, the (Al) in the rare earth polishing powder waste2O3+SiO2+ F): strong base (1: 1.2); according to the mass ratio, the rare earth polishing powder waste material: carbon powder (10: 1);
(2) placing the mixture in a crucible, placing the crucible in a muffle furnace, and roasting at 550 ℃ for 4h to obtain a roasted product;
(3) and cooling the roasted product, and carrying out four-stage countercurrent washing by using hot water until the pH value is close to 7 to obtain washing slag.
(4) Leaching the washing residue with hydrochloric acid in a two-stage countercurrent manner, and filtering to obtain a leaching solution with the pH value of 1 and filter residue;
(5) and (3) performing ten-stage countercurrent extraction on the leachate by using a 1.5mol/LP507+ kerosene extraction system, performing three-stage washing by using 1.3mol/L hydrochloric acid, performing two-stage back extraction by using 3mol/L hydrochloric acid, respectively precipitating raffinate and back extraction liquid by using oxalic acid, and burning the obtained filter cakes at 800 ℃ to respectively obtain high-purity lanthanum oxide and cerium oxide products. The analysis results are shown in Table 2
TABLE 2
| Composition (I) | La2O3 | CeO2 | Al2O3 | CaO | MgO | SiO2 | F | Others |
| Product La2O3Mass content/%) | 99.65 | 0.08 | 0.015 | 0.05 | 0.03 | 0.016 | 0.013 | 0.146 |
| Product CeO2Mass content/%) | 0.05 | 99.51 | 0.017 | 0.03 | 0.07 | 0.016 | 0.013 | 0.294 |
Comparative example 1
Comparative example 1 is substantially the same as example 1 except that comparative example 1 employs direct water washing instead of hot water multistage counter current washing, and the purity of the obtained product is close to that of example 1, but the amount of water consumed is more than 3 times that of example 1, and the amount of waste water generated is more than 3 times that of example 1.
Comparative example 2
Comparative example 2 is basically the same as example 1, except that comparative example 2 adopts a mode of directly adding strong acid instead of adopting the strong acid multistage countercurrent leaching, and the purity of the obtained product is close to that of example 1, but the leaching rate is reduced by about 5 percent compared with that of example 1.
Example 2
(1) Weighing 500g of rare earth polishing powder waste, 391g of potassium hydroxide and 50g of ammonium chloride, and uniformly mixing in a mixer to obtain a mixture; wherein, according to the mol ratio, the (Al) in the rare earth polishing powder waste2O3+SiO2+ F): potassium hydroxide ═ 1: 2; according to the mass ratio, the rare earth polishing powder waste material: ammonium chloride ═ 10: 1;
(2) placing the mixture in a crucible, placing the crucible in a muffle furnace, and roasting at 800 ℃ for 1h to obtain a roasted product;
(3) and cooling the roasted product, and performing two-stage countercurrent washing by using hot water to reach the pH value of 9 to obtain washing slag.
(4) Leaching the washing slag by four stages of sulfuric acid in a counter-current manner, and filtering to obtain leachate with the pH value of 3 and filter residue;
(5) and extracting and separating the leachate to obtain high-purity lanthanum oxide and cerium oxide finished products respectively. The analysis results are shown in Table 3. Other conditions in this example were the same as in example 1.
TABLE 3
Example 3
(1) Weighing 500g of rare earth polishing powder waste, 588g of potassium hydroxide and 62.5g of ammonium bicarbonate, and uniformly mixing in a mixer to obtain a mixture; wherein, according to the mol ratio, the (Al) in the rare earth polishing powder waste2O3+SiO2+ F): potassium hydroxide ═ 1: 3; according to the mass ratio, the rare earth polishing powder waste material: ammonium bicarbonate (8: 1);
(2) placing the mixture in a crucible, placing the crucible in a muffle furnace, and roasting at 600 ℃ for 3h to obtain a roasted product;
(3) and cooling the roasted product, and carrying out three-stage countercurrent washing by using hot water to reach the pH value of 9 to obtain washing slag.
(4) Carrying out three-stage countercurrent leaching on the washing slag by using nitric acid, and filtering to obtain a leaching solution with the pH value of 2 and filter residues;
(5) and extracting and separating the leachate to obtain high-purity lanthanum oxide and cerium oxide finished products respectively. The analysis results are shown in Table 4. Other conditions in this example were the same as in example 1.
TABLE 4
Example 4
(1) Weighing 500g of rare earth polishing powder waste, 558g of sodium hydroxide and 100g of carbon powder, and uniformly mixing in a mixer to obtain a mixture; wherein, according to the mol ratio, the (Al) in the rare earth polishing powder waste2O3+SiO2+ F): sodium hydroxide ═ 1: 4; according to the mass ratio, the rare earth polishing powder waste material: carbon powder (5: 1);
(2) placing the mixture in a crucible, placing the crucible in a muffle furnace, and roasting at 800 ℃ for 4h to obtain a roasted product;
(3) and cooling the roasted product, and carrying out five-stage countercurrent washing by using hot water to reach the pH value of 8 to obtain washing slag.
(4) Carrying out three-stage countercurrent leaching on the washing residues by using sulfuric acid, and filtering to obtain leachate with the pH value of 2 and filter residues;
(5) and extracting and separating the leachate to obtain high-purity lanthanum oxide and cerium oxide finished products respectively. The analysis results are shown in Table 5. Other conditions in this example were the same as in example 1.
TABLE 5
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (6)
1. A method for recovering rare earth oxide from rare earth oxide-containing waste materials is characterized by comprising the following steps:
mixing the waste containing the rare earth oxide, strong base and an auxiliary agent for roasting to obtain a roasted product; the roasting temperature is 550-800 ℃, and the roasting time is 1-4 hours;
washing the roasted product by hot water in a multi-stage countercurrent manner until the pH value of an eluate is 7-9, so as to obtain washing slag containing rare earth oxides;
carrying out multistage countercurrent leaching on the washing slag containing the rare earth oxide by adopting strong acid, and filtering to obtain leaching solution containing rare earth ions;
separating and purifying the leaching solution containing the rare earth ions, and precipitating and firing the leaching solution by using oxalic acid to obtain rare earth oxide;
the separation and purification method comprises the following steps: extracting by adopting an extractant in a multi-stage countercurrent manner, washing and back extracting; the extracting agent is the combination of di (2-ethylhexyl) phosphate or 2-ethylhexyl phosphate mono 2-ethylhexyl and kerosene, the concentration of the di (2-ethylhexyl) phosphate or 2-ethylhexyl phosphate mono 2-ethylhexyl and the saponification rate of the extracting agent is 30-50%;
wherein the auxiliary agent is carbon powder, ammonium chloride or ammonium bicarbonate, and the mass ratio of the waste material containing rare earth oxide to the auxiliary agent is (10-5): 1; the rare earth oxide in the waste material containing the rare earth oxide is cerium oxide and lanthanum oxide; the waste material containing rare earth oxide also contains impurities, wherein the impurities are at least one of aluminum oxide, silicon oxide and fluorine-containing compounds; the strong acid is hydrochloric acid.
2. The method for recovering rare earth oxide from rare earth oxide-containing waste according to claim 1, wherein the pH of the leachate containing rare earth ions is 1 to 3.
3. The method for recovering the rare earth oxide in the rare earth oxide-containing waste material as claimed in claim 2, wherein the strong base is sodium hydroxide or potassium hydroxide, and the molar ratio of the impurities to the strong base is 1 (1.2-4).
4. The method for recovering rare earth oxide from rare earth oxide-containing waste according to claim 1, wherein the number of stages of the multistage countercurrent washing is 2 to 5.
5. The method for recovering rare earth oxides from rare earth oxide-containing waste according to claim 1, wherein the multistage countercurrent leaching is performed in 2 to 4 stages.
6. The method according to claim 1, wherein the mass ratio of the rare earth oxide-containing waste to the auxiliary is 10: 1.
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| CN112725622B (en) * | 2020-12-02 | 2022-09-09 | 北京工业大学 | Method for recovering rare earth in waste cerium-based rare earth polishing powder by two-step acid leaching gradient separation |
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