CN1236017A - Ammonium chloride process for extracting rare-earth chloride from bastnaesite fine ore - Google Patents
Ammonium chloride process for extracting rare-earth chloride from bastnaesite fine ore Download PDFInfo
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- CN1236017A CN1236017A CN 99109357 CN99109357A CN1236017A CN 1236017 A CN1236017 A CN 1236017A CN 99109357 CN99109357 CN 99109357 CN 99109357 A CN99109357 A CN 99109357A CN 1236017 A CN1236017 A CN 1236017A
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Abstract
Through the processes of grinding bastnaesite ore concentrate, mixing the ore powder with NaCO3 in the ratio of 1 to 0.1-0.4, roasting the mixture at 400-800 deg.c for 1-6 hr, elution of the roasted sand with hot water to obtain NaF, drying filtered drag after eluting NaF and mixing the dried drag with ammonium chloride, roasting the mixture at 300-600 deg.c for 1-3 hr, hot water soaking to obtain rare earth chloride solution, extraction with 20% kerosine solution of naphthenic acid, and hydrochloric acid counter extraction to obtain rare earth chloride product.
Description
The invention relates to a method for extracting rare earth chloride from bastnaesite concentrate by an ammonium chloride method, belonging to the technical field of rare earth mineral smelting.
China is a large rare earth resource country, 80% of the rare earth resource reserves which are discovered in the world are in China at present, and bastnaesite in the whole rare earth minerals is the rare earthmineral with the largest yield and reserve in the world. The bastnaesite is mainly used for extracting light rare earth, and with the gradual popularization and application of technologies such as automobile exhaust purification and rare earth silicon alloy, the demand for light rare earth is more and more large. Therefore, the smelting technology of bastnaesite is increasingly receiving wide attention.
At present, the main methods for extracting rare earth from bastnaesite concentrate in China include an acid method and an alkaline method, wherein the acid method adopts a sulfuric acid reinforced roasting mode to decompose rare earth minerals, and after rare earth is leached out by water, alkali conversion is carried out, hydrochloric acid is adopted for preferential dissolution and conversion into a rare earth chloride solution, and then the rare earth chloride solution can be used for further separating single rare earth products. The alkali method adopts concentrated caustic soda at a temperature of more than 200 ℃ to decompose the bastnaesite concentrate in advance, and after fluoride and soluble impurities are washed out by water, the rare earth chloride is obtained by preferential dissolution of hydrochloric acid. The acid method or the alkali method can generate waste acid, alkali or waste gas to pollute the environment, the process flow is long, the reagent consumption is large, and the requirement of extracting rare earth from the bastnaesite concentrate by the acid method or the alkali method on the corrosion resistance of equipment is high. Therefore, the research on a new method for smelting the more economical and low-pollution bastnaesite concentrate is always the aim of people to pursue.
The applicant has proposed a method for extracting rare earth from bastnaesite or low-grade concentrate by adopting ammonium chloride roasting method, application number is 99106149.7, which provides a new method with low pollution for decomposingand extracting rare earth from bastnaesite, but the method is not applicable to rare earth concentrate, and the recovery rate of rare earth in bastnaesite concentrate decomposed by adopting the method is lower than 30%. The main reason is that the chlorination of rare earth is influenced by the high fluorine content in the concentrate.
The invention aims to provide a method for extracting rare earth chloride from bastnaesite concentrate by an ammonium chloride method, which adopts a sodium carbonate method to defluorinate the bastnaesite concentrate in advance, and then adopts the ammonium chloride method to chlorinate rare earth in the defluorinated bastnaesite concentrate, wherein the chlorination rate of the rare earth reaches more than 80 percent, and the decomposition of bastnaesite by the method can reduce the roasting amount of minerals, thereby achieving the purpose of reducing the cost. Therefore, it is a new method for decomposing and extracting rare earth from bastnaesite concentrate.
The invention discloses a method for extracting rare earth chloride from bastnaesite concentrate by an ammonium chloride method, which comprises the following steps:
(1) the raw fluorine-carbon-cerium concentrate (grade>50%) is ground to below-200 meshes so as to be mixed with sodium carbonate in the defluorination process and ammonium chloride in the chlorination process.
(2) Mixing the ground bastnaesite with NaCO3Mixing, wherein the proportion is that of raw ore: NaCO3And (5) the ratio of the powder to the solid is 1: 0.1-0.4. The materials are ground and mixed by a mortar, and can be mixed by a ball mill in industry.
(3) And (3) putting the uniformly mixed materials into a crucible, and roasting for 1-6 hours in a muffle furnace at 400-800 ℃, wherein the optimal roasting temperature and time are 500 ℃ and 2 hours.
(4) Washing the calcined sand with hot water to remove NaF, and stirring and washing the calcined sand in hot water at the temperature of 60-90 ℃ for 2 times at the liquid-solid ratio of 5-10: 1, wherein the stirring and washing time is 20-40 min each time. The filter residue after washing out the NaF (called defluorinated rare earth concentrate) is dried and used for further chlorination to recover rare earth.
(5) Mixing the defluorinated RE ore concentrate with ammonium chloride. The proportion is defluorination rare earth concentrate: NH (NH)4Cl = 1: 0.5-3, and the materials are ground and mixed by a mortar for further chlorination.
(6) And roasting the mixed material in a muffle furnace at 300-600 ℃ for 1-3 hours, and leaching the roasted product with hot water at 60-90 ℃ to obtain a rare earth chloride solution.
(7) And (3) adopting 20% naphthenic acid coal oil liquid (extractant) to completely salvage the rare earth in the rare earth chloride solution, then adopting 3-6N hydrochloric acid to perform back extraction to obtain a purified solution with the rare earth content of about 100g/l, and evaporating and crystallizing to obtain a rare earth chloride product.
The invention adopts ammonium chloride method to extract rare earth chloride from bastnaesite concentrate, and the main chemical reaction is as follows:
as minerals, bastnaesite concentrate generally contains acertain amount of silicate, iron, calcium, aluminum and other components, and thermodynamic analysis shows that SiO in the minerals is in a temperature range of 300-800 DEG C2,Al2O3And Fe2O3Does not react with HCl. Therefore, the purpose of selective chlorination can be achieved by extracting rare earth from the bastnaesite concentrate by adopting ammonium chloride, thereby being beneficial to further recycling of the rare earth.
The embodiment of the invention comprises the following steps:
in the practice of the invention, the tetrachua bastnaesite concentrate is adopted, and the main components and the rare earth distribution of the mineral are shown in tables 1 and 2.
Table 1 analysis results of major elemental composition of sichuan concentrates Si Al Fe Mg Ca F content (wt.%) 6.400.160.901.405.806.23 elemental composition Ba Ti P Mn Pb TREO content (wt.%) 5.800.120.100.072.3056.10 table 2 analysis results of partition of sichuan concentrates La2O3CeO2Pr6O11Nd2O3Sm2O3Eu2O3Gd2O3Tb4O7Content (wt.%) 17.6028.002.306.500.500.011.000.005 partition (%) 31.3749.914.1011.590.890.0181.780.0089 element Dy2O3Ho2O3Er2O3Tm2O3Yb2O3Lu2O3Y2O3TREO content (mg/l) 0.0010.0010.0030.00010.0010.00010.1856.10 partition (%) 0.00180.00180.00530.00020.00180.00020.321100.00
It can be seen from tables 1 and 2 that the concentrate is a light rare earth partition type rare earth concentrate mainly containing bastnaesite. The invention takes the concentrate as raw material toextract rare earth chloride, and the method is shown in the following embodiment:
example 1: weighing 10 g of tetrakage bastnaesite concentrate sample and 3 g of Na2CO3Grinding and mixing the mixture evenly in a mortar, and putting the mixture into a 50ml crucible to be roasted for 2h at 500 ℃. The calcine is washed with 100ml water each time at 80 deg.C for 30min under stirring, and 3 times according to the above procedures. The analysis of the fluorine content in the minerals results in a concentrate defluorination rate of 92%. The defluorinated rare earth concentrate is ground and mixed with 20 g of ammonium chloride after being dried and roasted for 90min at 480 ℃. The calcine is extracted with 100ml of hot water at 90 deg.C for 20 min. Filtering with 20ml waterAnd (4) washing, namely mixing the washing liquid with the filtrate and analyzing the rare earth content of the filtrate. The leaching recovery rate of the rare earth is 82.25 percent.
Example 2: weighing 50 g of tetrakage bastnaesite concentrate sample and 10 g of Na2CO3Grinding and mixing the mixture evenly in a mortar, and putting the mixture into a 200ml crucible to be roasted for 2h at 500 ℃. The calcine is treated with 500ml of water at 80 deg.CStirring and washing for 30min, and washing for 3 times according to the above operation. The analysis of the fluorine content in the minerals resulted in a concentrate defluorination of 81.52%. The defluorinated rare earth concentrate is ground and mixed with 75 g of ammonium chloride after being dried and roasted for 100min at 480 ℃. The calcine is leached with 300ml of hot water at 90 deg.C for 20 min. The filter residue was washed with 50ml of water, and the rare earth content was analyzed after mixing the washing solution with the filtrate. The rare earth leaching recovery rate is 71.55 percent.
Example 3: weighing 20 g of tetrakaflurocene bastnaesite concentrate sample and 6 g of Na2CO3Grinding and mixing the mixture evenly in a mortar, and putting the mixture into a 100ml crucible to be roasted for 2h at 500 ℃. The calcine is washed with 200ml water each time at 80 ℃ for 30min with stirring, and the above operations are carried out for 3 times. The analysis of the fluorine content in the minerals results in a concentrate defluorination rate of 91.2%. The defluorinated rare earth concentrate is ground and mixed with 50 g of ammonium chloride after being dried and roasted for 120min at the temperature of 450 ℃. The calcine is extracted with 100ml of hot water at 90 deg.C for 20 min. The filter residue was washed with 30ml of water, and the rare earth content was analyzed after mixing the washing solution with the filtrate. The rare earth leaching recovery rate is 91.20%.
The rare earth leachate obtained from the above example was analyzed for its composition and distribution in tables 3 and 4.
TABLE 3 composition of Sichuan concentrate leachate composition TREO Mg Al Fe Mn Ca content (g/l) 6.0980.080.0050.10.132.25
TABLE 4 results of partition analysis of Sichuan concentrate leachate with La element2O3CeO2Pr6O11Nd2O3Sm2O3Eu2O3Gd2O3Tb4O7Content (mg/l) 22503025215535105500.50 partition (%) 36.8949.603.538.770.160.080.820.01 element Dy2O3Ho2O3Er2O3Tm2O3Yb2O3Lu2O3Y2O3TREO content (mg/l) 5.00.500.500.500.500.500.56098.5 partition (%) 0.080.010.010.010.010.010.01100.00 tables 1,2,3 and 4 were each analyzed by Jiangxi analytical test
From tables 3 and4, it can be seen that the main impurities in the leachate are Ca and Mn, while the rare earth composition of the leachate does not change much compared to the original concentrate.
And (3) taking 20% naphthenic acid as an extracting agent to completely salvage the rare earth in the rare earth leaching solution so as to separate out impurities such as Ca, Mn and the like. The purified rare earth chloride solution with the rare earth content of 102.5g/l is obtained by back extraction with 6N hydrochloric acid, and the rare earth chloride solution is evaporated and crystallized at 145 ℃ to obtain a rare earth chloride product with the rare earth content of 45.53 percent of REO.
Claims (1)
1. A method for extracting rare earth chloride from bastnaesite concentrate by an ammonium chloride method is characterized in that
The method comprises the following steps:
(1) grinding the fluorine-carbon cerium raw ore concentrate (the grade is more than 50 percent) to be below-200 meshes so as to be convenient for mixing with sodium carbonate in the defluorination process and ammonium chloride in the chlorination process;
(2) mixing the ground bastnaesite with NaCO3Mixing, wherein the proportion is that of raw ore: NaCO3=1∶0.1～0.4；
(3) Placing the uniformly mixed materials into a crucible, and roasting for 1-6 hours in a muffle furnace at 400-800 ℃;
(4) washing the calcined sand with hot water to remove NaF, stirring and washing the calcined sand in hot water at the temperature of 60-90 ℃ for 2 times at the liquid-solid ratio of 5-10: 1, wherein the stirring and washing time is 20-40 min each time, and drying filter residues obtained after NaF washing is used forfurther chlorination and rare earth recovery;
(5) mixing the defluorinated rare earth concentrate with ammonium chloride, wherein the proportion of the defluorinated rare earth concentrate is as follows: NH (NH)4Cl=1∶0.5～3；
(6) Roasting the mixed material in a muffle furnace at 300-600 ℃ for 1-3 hours, and leaching the roasted product with hot water at 60-90 ℃ to obtain a rare earth chloride solution;
(7) and (3) adopting 20% naphthenic acid coal oil liquid (extractant) to completely salvage the rare earth in the rare earth chloride solution, then adopting 3-6N hydrochloric acid to perform back extraction to obtain a purified solution with the rare earth content of about 100g/l, and evaporating and crystallizing to obtain the rare earth chloride product.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100436611C (en) * | 2007-04-24 | 2008-11-26 | 北京科技大学 | Method of purifying cerium by controlling pH |
| CN102296182A (en) * | 2011-07-28 | 2011-12-28 | 包头市新源稀土高新材料有限公司 | Method for recovering rare earth elements from waste rare earth element grinding materials |
| CN102605198A (en) * | 2012-01-13 | 2012-07-25 | 东北大学 | Decomposition method of bastnaesite |
| CN104843761A (en) * | 2015-03-31 | 2015-08-19 | 福建省长汀金龙稀土有限公司 | Method for recovering rare earth from rare earth fluoride fused salt electrolysis waste with effects of environmental protection and low cost |
| CN104911377A (en) * | 2015-06-26 | 2015-09-16 | 河南理工大学 | Separation method of effective components of rare earth tailings |
| CN104946887A (en) * | 2015-07-22 | 2015-09-30 | 中国恩菲工程技术有限公司 | Method for treating bastnasite concentrate |
| CN105969974A (en) * | 2016-05-20 | 2016-09-28 | 辽宁科技大学 | Method for selectively extracting rare-earth metals from rare-earth ores |
| CN106048265A (en) * | 2016-08-17 | 2016-10-26 | 成都理工大学 | Extraction method of rare-earth elements from bastnaesite |
| CN106191454A (en) * | 2016-07-05 | 2016-12-07 | 江西理工大学 | A kind of method of Extraction of rare earth from calciothermic reduction rare-earth smelting slag |
| CN106636626A (en) * | 2016-12-13 | 2017-05-10 | 江苏省冶金设计院有限公司 | System and method for processing rare earth concentrates |
| CN106925434A (en) * | 2015-12-30 | 2017-07-07 | 核工业北京化工冶金研究院 | One kind ore dressing defluorination process from beryllium ore deposit |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1077546C (en) * | 1998-06-04 | 2002-01-09 | 葛新芳 | Method for producing mixed rare-earth chloride |
-
1999
- 1999-06-25 CN CN99109357A patent/CN1081241C/en not_active Expired - Fee Related
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100436611C (en) * | 2007-04-24 | 2008-11-26 | 北京科技大学 | Method of purifying cerium by controlling pH |
| CN102296182A (en) * | 2011-07-28 | 2011-12-28 | 包头市新源稀土高新材料有限公司 | Method for recovering rare earth elements from waste rare earth element grinding materials |
| CN102605198A (en) * | 2012-01-13 | 2012-07-25 | 东北大学 | Decomposition method of bastnaesite |
| CN102605198B (en) * | 2012-01-13 | 2013-09-25 | 东北大学 | Decomposition method of bastnaesite |
| CN104843761A (en) * | 2015-03-31 | 2015-08-19 | 福建省长汀金龙稀土有限公司 | Method for recovering rare earth from rare earth fluoride fused salt electrolysis waste with effects of environmental protection and low cost |
| 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 |
| CN104911377A (en) * | 2015-06-26 | 2015-09-16 | 河南理工大学 | Separation method of effective components of rare earth tailings |
| CN104946887A (en) * | 2015-07-22 | 2015-09-30 | 中国恩菲工程技术有限公司 | Method for treating bastnasite concentrate |
| CN106925434A (en) * | 2015-12-30 | 2017-07-07 | 核工业北京化工冶金研究院 | One kind ore dressing defluorination process from beryllium ore deposit |
| CN105969974A (en) * | 2016-05-20 | 2016-09-28 | 辽宁科技大学 | Method for selectively extracting rare-earth metals from rare-earth ores |
| CN106191454A (en) * | 2016-07-05 | 2016-12-07 | 江西理工大学 | A kind of method of Extraction of rare earth from calciothermic reduction rare-earth smelting slag |
| CN106191454B (en) * | 2016-07-05 | 2018-06-22 | 江西理工大学 | A kind of method of Extraction of rare earth in rare-earth smelting slag from calciothermic reduction |
| CN106048265A (en) * | 2016-08-17 | 2016-10-26 | 成都理工大学 | Extraction method of rare-earth elements from bastnaesite |
| CN106048265B (en) * | 2016-08-17 | 2018-05-25 | 成都理工大学 | A kind of extracting method of bastnaesite rare earth elements |
| CN106636626A (en) * | 2016-12-13 | 2017-05-10 | 江苏省冶金设计院有限公司 | System and method for processing rare earth concentrates |
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| CN1081241C (en) | 2002-03-20 |
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