CN101638731B - Method for separating rare earth oxides from rare earth ore by using ammonium chloride-potassium chloride gas phase transmission - Google Patents
Method for separating rare earth oxides from rare earth ore by using ammonium chloride-potassium chloride gas phase transmission Download PDFInfo
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- CN101638731B CN101638731B CN200910012454XA CN200910012454A CN101638731B CN 101638731 B CN101638731 B CN 101638731B CN 200910012454X A CN200910012454X A CN 200910012454XA CN 200910012454 A CN200910012454 A CN 200910012454A CN 101638731 B CN101638731 B CN 101638731B
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- repone
- oxalate
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Abstract
The invention provides a method for separating rare earth oxides from rare earth ore by using ammonium chloride-potassium chloride gas phase transmission. The main technical characteristic of the method is as follows: mixing rare earth ore and sodium carbonate to roast; dissolving the decomposition product obtained by roasting in water, drying and grinding insoluble substance to mix with ammoniumchloride and perform chlorination reaction; dissolving the chlorinate to obtain filtrate, adding BaCl2 and H2SO4 in the filtrate to separate precipitates such as ThO2, Fe2O3, U2O3 and the like; treating the filtrate through evaporating, oxidizing and calcining, chlorhydric acid leaching and drying in turn, then adding NH4Cl and KCl to perform chemical gas phase transmission for 20-25 times; dissolving the obtained product with water, adding oxalic acid to obtain lanthanum oxalate, praseodymium oxalate, neodymium oxalate and other rare earth oxalates except for cerium oxalate; then igniting the oxalates above 800 DEG C to obtain corresponding rare earth oxides. The method has the advantages that the problem of separating radioactive elements can be effectively solved, the use of chlorine gas and the emission of wastewater and effluent gas can be reduced in the production process, and the discharged gas can be recyled for reproduction.
Description
Technical field:
The present invention relates to a kind of Metal smelting middle-weight rare earths separating technology, particularly a kind of method of utilizing ammonium chloride-potassium chloride gas phase transmission rare-earth separating oxide compound from rare-earth mineral.
Background technology:
Rare earth element separates the method for purifying and mainly contains fractionation, ion exchange method, solvent extration, also has chromes, liquid membrane separation method in addition, and above method respectively has relative merits.The pyrogenic process of development in recent years is a chemical vapor transport method, and the achievement in research of rare-earth separating is the continuity of pyrocarbon thermal chlorination.Since 1991, follow-up stories such as Adachi employing chemical vapor transport method (CVT) by forming gaseous state title complex separation of rare earth elements, and think that this method is well worth doing, might replace wet processing in advance.In CVT technology, be raw material with mixed rare-earth oxide or rare earth ore concentrate, adding alkali metal chloride with AlCl3 or AlCl3 is chlorizating agent and part, according to the difference of rare earth gaseous state complexes stability, control certain thermograde, realize Rare Earth Separation by the gas phase transmission.But this method reaction times reaches tens of hours, still has the pollution of radioelement to exist in the product.Professor Wang Zhichang proposes branch one-step chlorination chemical vapor transport method (SC-CVT) separation of rare earth elements; Adopt the method for substep selective chlorination-chemical gas phase transmission reaction (SC-CVT) rare-earth separating, the cryogenic selective chlorination of mixed rare-earth oxide is transmitted combining with the pyrochemistry gas phase of mixed rare earth chlorides; The carburizing chlorination technology of being created has solved in the mineral alkaline-earth metal and radioelement can not effective isolating problem, but adopts poisonous and hazardous chlorine to cook chlorizating agent; Can allow to contain 0.001 milligram in chlorine in the 1L air at most, this amount of surpassing will cause that human body is poisoned even sudden death; If liquid chlorine cylinder overcharge, misloading occur, load in mixture, or meet to be exposed to the sun physics or chemical blast can take place, thereby chlorine is had relatively high expectations to equipment and production management in accumulating and production process.
Summary of the invention:
The objective of the invention is the deficiency that exists in the above-mentioned technology, a kind of method of utilizing ammonium chloride-potassium chloride gas phase transmission rare-earth separating oxide compound from rare-earth mineral is provided.It is an extraction separation rare earth single oxide from the rare earth hamartite, and purpose is the separation that effectively solves radioelement, reduces the use of chlorine in the production process and the discharging of waste gas and waste water, and will discharge gas and recycle in producing again.
The object of the present invention is achieved like this: it is characterized in that this method comprises the following steps:
(1) the mishmetal ore deposit mixed with yellow soda ash, grind evenly, its ratio is mishmetal ore deposit 70%, yellow soda ash 30% (by weight);
(2) material that mixes is put into the high alumina ceramic reactor, be warming up to 300 ℃, be incubated 1 hour, in 1 hour, continue to be warming up to 500～600 ℃ again, be incubated 2～3 hours, remove CO
2Deng volatile matter, get the rare-earth mineral degradation production;
(3) the rare-earth mineral degradation production after will coming out of the stove mixes by solid-to-liquid ratio with water at 1: 5, and 80～90 ℃ of temperature stirred 1～2 hour, heavy clear, filtration, drip washing, fluorine-containing filtered liquid and contain the filter cake that mixes rare earth oxide;
(4) in the oxide compound that contains rare earth in step (3) by the oxide compound that contains rare earth: ammonia chloride=1: 1.5 mixes (weight ratio) and grinds, be warming up to 350 ℃, be incubated 1 hour, carry out chlorination reaction, the ammonia chloride gas of discharging in the reaction process is through the cooling recycling; Chlorizate is water-soluble, heavy clear, filtration, drip washing are with insolubles SiO
2, Al
2O
3, ThO
2, Fe
2O
3, U
2O
3Deng separating away, contain the mixing rare earth chloride in the filtrate;
(5) add BaCl in the filtrate in step (4)
2And H
2SO
4, the limit edged stirs, and adds the back that finishes and continues to stir 30 minutes, heavy clear, filtration, drip washing, insolubles CaSO
4, BaSO
4, RaSO
4With mixed rare earth chlorides filtrate, the filtrate evaporation oxidation is calcined;
(6) add the dilute hydrochloric acid acidleach in step (5) gained oxidizing roasting product, stirred 30 minutes, heavy clear, filtration, drip washing must insolubles CeO
2With non-cerium mixed rare earth chlorides filtrate, the filtrate evaporative crystallization gets non-cerium mishmetal oxychloride;
(7) in the non-cerium mishmetal of step (6) gained oxychloride, add NH
4Cl and KCI, and by non-cerium mishmetal oxychloride: NH
4Cl: KCI=1: 1.5: 1.5 (weight ratio) mixed and ground, the material that mixes is put into the high alumina ceramic reactor and insert the transmission Reaktionsofen, be warming up to 350 ℃, be incubated 1 hour, carry out chlorination reaction, continue to be warming up to and carry out chemical gas phase transmission reaction when reactant end temperature is 800 ℃, to transmit in the Reaktionsofen between 800 ℃ to 600 ℃ at resultant end product and after product is collected respectively below 600 ℃, press said process and continue 20～25 chemical gas phase transmission reactions, get Lanthanum trichloride+Repone K respectively, praseodymium chloride+Repone K, Neodymium trichloride+Repone K and other rare earth chloride+Repone K, the ammonia chloride gas of discharging in the reaction process is through the cooling recycling;
(8) Lanthanum trichloride+Repone K, praseodymium chloride+Repone K, Neodymium trichloride+Repone K and other non-Ce rare earth muriate+Repone K of step (7) gained are added after water-soluble respectively while stirring oxalic acid to precipitation fully, heavy clear, filtration, drip washing, get single rare earth lanthanum oxalate, praseodymium oxalate, neodymium oxalate and other non-Ce rare earth oxalate precipitation, filtrate is through evaporation, crystallization, dry that Repone K can be recycled;
(9) calcination under greater than 800 ℃ of temperature of step (8) gained single rare earth lanthanum oxalate, praseodymium oxalate, neodymium oxalate and other non-Ce rare earth oxalate precipitation is got lanthanum trioxide, Praseodymium trioxide, Neodymium trioxide and other non-Ce rare earth oxide compound.Advantage of the present invention is, effectively solves the separation of radioelement, reduce chlorine in the production process use and
The discharging of waste gas and waste water, and will discharge gas and recycle in producing again.
Description of drawings:
Accompanying drawing is a process flow sheet of the present invention;
Embodiment:
The present invention will be further described below in conjunction with embodiment:
Fluorine carbon cerium raw ore, main chemical compositions (%): REO (16.8), Al
2O
3(10.7), Fe
2O
3(3.7), CaO (6.4), BaO (11.2), MgO (1.7), MnO
2(0.6), PbO (0.6), SiO
2(41.6), F (2.8), ThO
2(0.2), P (0.4).CeO in the rare-earth mineral
2Content accounts for 46.5%, and non-Ce rare earth oxide compound lanthanum trioxide, Praseodymium trioxide and Neodymium trioxide account for 51%.
Above-mentioned fluorine carbon cerium raw ore through being ground to less than 50 μ m, is got 70g, add yellow soda ash 30g, put into the high alumina ceramic reactor after mixing, be warming up to 300 ℃, be incubated to continue at after 1 hour and continue to be warming up to 500～600 ℃ in 1 hour, be incubated 2～3 hours; To decompose the back solid product mixes by solid-to-liquid ratio with water at 1: 5,80～90 ℃ of temperature, stirred 1～2 hour, heavy clear, filtration, drip washing must contain the solids that mixes rare earth oxide and by the oxide compound that contains rare earth: ammonia chloride=mix (weight ratio) grinding insert in Reaktionsofen at 1: 1.5, be warming up to 350 ℃, be incubated 1 hour, carry out chlorination reaction, chlorizate is water-soluble, heavy clear, filtration, drip washing, insolubles is SiO
2, Al
2O
3, ThO
2, Fe
2O
3, U
2O
3Go out etc. separable; In filtrate, add BaCl
2And H
2SO
4, add the back that finishes and continue to stir 30 minutes, heavy clear, filtration, drip washing, insolubles CaSO
4, BaSO
4, RaSO
4With mixed rare earth chlorides filtrate, filtrate evaporation oxidation calcining back is added the dilute hydrochloric acid acidleach, to stir 30 minutes, heavy clear, filtration, drip washing get insolubles CeO
2(purity＞96%, yield＞90%) and non-cerium mixed rare earth chlorides filtrate, the filtrate evaporative crystallization gets non-cerium mixed rare earth chlorides and rare earth oxychloride; And by non-cerium mixed rare earth chlorides and rare earth oxychloride: NH
4Cl: KCl=1: 1.5: 1.5 (weight ratio) mixed and ground, the material that mixes is put into the high alumina ceramic reactor and insert the transmission Reaktionsofen, be warming up to 350 ℃, be incubated 1 hour, carry out chlorination reaction, continue to be warming up to and carry out chemical gas phase transmission reaction when reactant end temperature is 800 ℃, to transmit in the Reaktionsofen between 800 ℃ to 600 ℃ at resultant end product and after product is collected respectively below 600 ℃, press said process and continue 20～25 chemical gas phase transmission reactions, get Lanthanum trichloride+Repone K respectively, praseodymium chloride+Repone K, Neodymium trichloride+Repone K and other rare earth chloride+Repone K, it is complete to precipitation to add oxalic acid after water-soluble respectively while stirring, heavy clear, filter, drip washing, get the single rare earth lanthanum oxalate, praseodymium oxalate, neodymium oxalate and other non-Ce rare earth oxalate precipitation, respectively the calcination under greater than 800 ℃ of temperature of single rare earth oxalate precipitation is got lanthanum trioxide, Praseodymium trioxide, Neodymium trioxide (purity＞90%, yield＞85%) and other non-Ce rare earth oxide compound.
The ammonia chloride gas of discharging in the reaction process is through the cooling recycling; Containing Repone K filtrate can be recycled after evaporation, crystallization, drying.
Claims (1)
1. a method of utilizing ammonium chloride-potassium chloride gas phase transmission rare-earth separating oxide compound from rare-earth mineral is characterized in that this method comprises the following steps:
(1) the mishmetal ore deposit mixed with yellow soda ash, grind evenly, its ratio is mishmetal ore deposit 70%, yellow soda ash 30% weight ratio;
(2) material that mixes is put into the high alumina ceramic reactor, be warming up to 300 ℃, be incubated 1 hour, in 1 hour, continue to be warming up to 500～600 ℃ again, be incubated 2～3 hours, remove CO
2Volatile matter gets the rare-earth mineral degradation production;
(3) the rare-earth mineral degradation production that step (2) is obtained mixes by solid-to-liquid ratio with water at 1: 5, and 80～90 ℃ of temperature stirred 1～2 hour, heavy clear, filtration, drip washing, fluorine-containing filtered liquid and contain the filter cake that mixes rare earth oxide;
(4) containing in the filter cake that mixes rare earth oxide by containing the oxide compound that mixes rare earth in step (3): ammonia chloride=weight ratio was mixed in 1: 1.5, be warming up to 350 ℃, be incubated 1 hour, carry out chlorination reaction, the ammonia chloride gas of discharging in the reaction process is through the cooling recycling; Chlorizate is water-soluble, heavy clear, filtration, drip washing are with insolubles SiO
2, Al
2O
3, ThO
2, Fe
2O
3, U
2O
3Separate, contain rare earth chloride in the filtrate;
(5) add BaCl in the filtrate in step (4)
2And H
2SO
4, the limit edged stirs, and adds the back that finishes and continues to stir 30 minutes, heavy clear, filtration, drip washing, insolubles CaSO
4, BaSO
4, RaSO
4With mixed rare earth chlorides filtrate, the filtrate evaporation oxidation is calcined;
(6) add the dilute hydrochloric acid acidleach in step (5) gained oxidizing roasting product, stirred 30 minutes, heavy clear, filtration, drip washing must insolubles CeO
2With non-cerium mixed rare earth chlorides filtrate, the filtrate evaporative crystallization gets non-cerium mishmetal oxychloride;
(7) in the non-cerium mishmetal of step (6) gained oxychloride, add NH
4Cl and KCl, and by non-cerium mishmetal oxychloride: NH
4Cl: KCl=1: 1.5: 1.5 (weight ratio) mixed and ground, the material that mixes is put into the high alumina ceramic reactor and insert the transmission Reaktionsofen, be warming up to 350 ℃, be incubated 1 hour, carry out chlorination reaction, continue to be warming up to and carry out chemical gas phase transmission reaction when reactant end temperature is 800 ℃, after will transmitting in the Reaktionsofen between 800 ℃ to 600 ℃ at resultant end product and collecting respectively less than 600 ℃ of products, press said process and continue 20～25 chemical gas phase transmission reactions, get Lanthanum trichloride+Repone K respectively, praseodymium chloride+Repone K, Neodymium trichloride+Repone K and other non-Ce rare earth muriate+Repone K, the ammonia chloride gas of discharging in the reaction process is through the cooling recycling;
(8) Lanthanum trichloride+Repone K, praseodymium chloride+Repone K, Neodymium trichloride+Repone K and other non-Ce rare earth muriate+Repone K of step (7) gained are added after water-soluble respectively while stirring oxalic acid to precipitation fully, heavy clear, filtration, drip washing, get single rare earth lanthanum oxalate, praseodymium oxalate, neodymium oxalate and other non-Ce rare earth oxalate precipitation, filtrate recycles through the Repone K that evaporation, crystallization, drying obtain.
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|---|---|---|---|
| CN200910012454XA CN101638731B (en) | 2009-07-10 | 2009-07-10 | Method for separating rare earth oxides from rare earth ore by using ammonium chloride-potassium chloride gas phase transmission |
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|---|---|---|---|
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| CN101638731B true CN101638731B (en) | 2011-05-11 |
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| CN102952948B (en) * | 2011-08-26 | 2016-03-30 | 格林美股份有限公司 | The separating and purifying method of fluorescent material middle-weight rare earths metal |
| CN104053801B (en) * | 2012-01-06 | 2016-10-26 | 日立金属株式会社 | The separation and recovery method of rare earth element |
| JP5967210B2 (en) * | 2012-10-10 | 2016-08-10 | 日立金属株式会社 | Rare earth element separation method and separation apparatus |
| CN103570054B (en) * | 2013-11-05 | 2016-03-09 | 江西稀有金属钨业控股集团有限公司 | The preparation method of ultralow radioactivity rare earth oxide and preparation system |
| CN104911377B (en) * | 2015-06-26 | 2018-06-22 | 河南理工大学 | A kind of separation method of rare-earth tailing active principle |
| CN105481679A (en) * | 2015-11-20 | 2016-04-13 | 天津工业大学 | Preparation method for rare earth oxalic acid complex |
| CN105969974B (en) * | 2016-05-20 | 2018-03-30 | 辽宁科技大学 | A kind of method of the selective extraction rare earth metal from rare earth ore |
| CN109811135B (en) * | 2019-03-20 | 2023-12-15 | 中国恩菲工程技术有限公司 | Method and device for selectively extracting rare earth oxide from red mud |
| CN109811122B (en) * | 2019-03-20 | 2020-11-10 | 中国恩菲工程技术有限公司 | Extraction method of rare earth oxide |
| EP4107298A4 (en) * | 2020-02-21 | 2024-04-03 | The Saskatchewan Research Council | Process of rare earth recovery from ores containing bastnaesite |
| CN115092953A (en) * | 2022-05-05 | 2022-09-23 | 龙南京利有色金属有限责任公司 | Method for extracting rare earth oxide from rare earth fluorescent powder waste |
| CN115418505A (en) * | 2022-08-25 | 2022-12-02 | 萍乡泽昊新材料有限责任公司 | Method for removing cerium and non-rare earth impurities from rare earth feed liquid |
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