CN102816930A - Method for gas phase precipitation of rare earth - Google Patents
Method for gas phase precipitation of rare earth Download PDFInfo
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- CN102816930A CN102816930A CN2012102861468A CN201210286146A CN102816930A CN 102816930 A CN102816930 A CN 102816930A CN 2012102861468 A CN2012102861468 A CN 2012102861468A CN 201210286146 A CN201210286146 A CN 201210286146A CN 102816930 A CN102816930 A CN 102816930A
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Abstract
The invention relates to a method for gas phase precipitation of rare earth, and belongs to the field of rare earth hydrometallurgy. According to the method, ammonium bicarbonate is heated and decomposed into carbon dioxide and ammonia gas; under a stirring condition, the carbon dioxide and the ammonia are introduced to a rare earth material liquid with a certain temperature and a certain concentration, and precipitation is performed to generate rare earth carbonate; the precipitate slurry is filtered and dried to obtain the rare earth carbonate, or the precipitate slurry is calcined into the rare earth oxide. The method of the present invention has characteristics of simple process, sealing, pollution lower than the original method, low cost, and the like, and is applicable for industrial scale production.
Description
Technical field
The invention belongs to the rare-earth wet method field of metallurgy, relate to the sedimentary method of carbonated rare earth.
Background technology
REE is owing to the singularity of its structure has characteristics such as the not available light of many other elements, electricity, magnetic; Thereby become an indispensable group element in the high-tech area; Being claimed " industrial monosodium glutamate ", is the indispensable raw material of preparation new and high technology novel material.China has in the world the abundantest rare earth Mineral resources, is again Rare Earth Production and big export country, mainly with rare earth oxide, carbonated rare earth as rare-earth products.Carbonated rare earth is sometimes as the intermediates that are sintered into rare earth oxide; Carbonated rare earth is increasing as the proportion of intermediates or end product, and owing to sodium hydrogencarbonate, yellow soda ash precipitation agent cost costliness, bicarbonate of ammonia is cheap; Therefore; On rare earth primary raw materials and separating prod, generally adopt bicarbonate of ammonia as the rare-earth precipitation agent, but major part is the not too high rare-earth products of elementary purity, seldom uses bicarbonate of ammonia as the rare-earth precipitation agent for high pure rare earth product.
Along with rare-earth industry is fast-developing, the environmental protection problem in the Rare Earth Production has caused the attention of country, and country has issued " rare-earth industry pollutant emission standard "; And carried out the implementation phase, wherein the discharging of rare-earth precipitation mother liquor is one of subject matter, and this also is that the problem that will solve is badly in need of in Rare Earth Production enterprise; Existing Rare Earth Production enterprise comes precipitating rare earth with bicarbonate of ammonia wiring solution-forming and heavy peace and quietization; The process water amount is big, and water displacement is also big, and this also is to influence a Rare Earth Production environmental protection of enterprise major obstacle up to standard; Therefore, reducing deposition that waste liquid amount and bicarbonate of ammonia in the Rare Earth Production be used for high purity product becomes one of Rare Earth Production and studies new problem.
Summary of the invention
The objective of the invention is to reduce waste liquid amount in the Rare Earth Production; Provide bicarbonate of ammonia to be used for the deposition of high pure rare earth product; Improve the content of rare-earth precipitation mother liquor ammonium chloride, prepare, fundamentally solve the problem of environmental pollution in the Rare Earth Production for the comprehensive recovery of post precipitation mother liquor performs raw material.
The technical scheme that the present invention adopts is: utilize bicarbonate of ammonia to be heated to be prone to resolve into the characteristics of carbonic acid gas and ammonia, carbonic acid gas and ammonia generate carbonated rare earth with the rare earth feed liquid deposition, the warp filtration, dry and obtain the carbonated rare earth product, or be sintered into rare earth oxide.
The present invention realizes through following steps.
(1) be raw material with single or mixed rare earth solution, the concentration of earth solution is 0.3～2.0mol/L.Under condition of stirring, the earth solution in the precipitation reactor is heated to 40 ℃～95 ℃, and is maintained to the precipitin reaction end.
(2) in decomposition reactor, add solid ammonium bicarbonate, its add-on is not less than 1.2 times of theoretical consumption.
(3) connect precipitation reactor and decomposition reactor, and make the reactive system sealing, keep the decomposition temperature that temperature in the reaction process is not less than bicarbonate of ammonia.
(4) under precipitation reactor stirring and constant temperature; The thermal degradation reactor drum makes the decomposition reaction actuator temperature be controlled at 40 ℃～100 ℃, and the bicarbonate of ammonia in the decomposition reactor begins to decompose; Beginning rare-earth precipitation reaction in the precipitation reactor, the pressure in the reactive system is controlled at 1Kpa～100KPa.
(5) when the material pH in the precipitation reactor 6.8～7.0 the time, stop thermal precipitation reactor drum and decomposition reactor, precipitation reactor continues to stir 10～20 minutes.
(6) from precipitation reactor, emit the carbonated rare earth slurry, filter, wash, filter and do; 80 ℃～150 ℃ dryings 2～4 hours obtain carbonated rare earth; Or 800 ℃～1000 ℃ the calcining 2 hours, obtain rare earth oxide.
Among the present invention,, in step (1), can in the earth solution of precipitation reactor, add the crystalline carbon acid rare earth and make crystal seed in order to help forming the carbonated rare earth crystalline precipitate.
Earth solution described in the step of the present invention (1) comprises rare earth chloride, rare earth nitrate, sulfuric acid rare earth, perchloric acid rare earth and acetic acid earth solution.
Filter described in the step of the present invention (6) comprises plate and frame(type)filter press, vacuum filter, whizzer; Washing lotion can be selected tap water, filtered water, zero(ppm) water or deionized water for use according to product gas purity in the step 6.
Adopt the carbonated rare earth of the present invention's preparation to have good strainability, be easy to washing; Can reduce preparation a large amount of mother liquor of precipitation of ammonium that precipitation agent brought, for the mother liquor of precipitation of ammonium post-processed provides favourable condition; The bicarbonate of ammonia decomposition itself is the purification process of a precipitation agent, can be used for the deposition of high-purity rare-earth, avoids bringing expensive with high-purity precipitation agent.
The present invention has characteristics such as technology is simple, airtight, pollution is lower than former method, and cost is low, is adapted to commercial scale prodn.
Description of drawings
The technological line figure that Fig. 1 adopts for the present invention.
Fig. 2 is Phosbloc SEM figure of the present invention.
Fig. 3 is cerous carbonate SEM figure of the present invention.
Fig. 4 is neodymium carbonate SEM figure of the present invention.
Embodiment
The present invention will be described further through following examples.
Embodiment
Embodiment 1.Method with the gaseous phase deposition lanthanum.
In the reactor drum of heating unit is arranged, adding concentration is 1.0mol/L lanthanum chloride solution 1500 mL, under condition of stirring, with lanthanum chloride solution heat to 80～85 ℃.Have at another to add the bicarbonate of ammonia solid in reactor drum of heating unit, connect two reactor drums, the decomposition reactor to 45 ℃ of bicarbonate of ammonia is equipped with in heating, makes its bicarbonate of ammonia begin to decompose the blow-off valve emptying in 1 minute of opening the reactor drum that lanthanum chloride solution is housed; The temperature of control decomposition reactor is reacted the air pressure in its system about 5KPa, when reaction mass pH 6.8 the time, stop thermal precipitation reactor drum and bicarbonate of ammonia decomposition reactor, precipitation reactor continues stirring 20 minutes; The carbonated rare earth slurry is put into the vacuum filter suction filtration, with distilled water wash 2～4 times, drains, 105 ℃ of dryings 2 hours.The carbonated rare earth slurry was emitted natural subsidence 30 minutes, and precipitation volume is 0.77mL/ gLa
2O
3, belong to precipitation volume Xiao Yi and filter slurry; Deposition oven dry calcining back burn decrement rate is 26.2%.
Embodiment 2.Method with the gaseous phase deposition cerium.
In the reactor drum of heating unit is arranged, adding concentration is 0.8mol/L lanthanum chloride solution 1500 mL, under condition of stirring, with lanthanum chloride solution heat to 75～75 ℃.Have at another to add the bicarbonate of ammonia solid in reactor drum of heating unit, connect two reactor drums, heating is equipped with more than the reactor drum to 45 ℃ of bicarbonate of ammonia, makes its bicarbonate of ammonia begin to decompose the blow-off valve emptying in 1 minute of opening the reactor drum that lanthanum chloride solution is housed; The temperature of control decomposition reactor is reacted the air pressure in its system about 10KPa, when reaction mass pH 7.0 the time, stop thermal precipitation reactor drum and bicarbonate of ammonia decomposition reactor, precipitation reactor continues stirring 20 minutes; The carbonated rare earth slurry is put into the vacuum filter suction filtration, with distilled water wash 2～4 times, drains, 105 ℃ of dryings 2 hours.It is fast that the carbonated rare earth slurry is emitted natural subsidence speed, and draining volume is 0.85mL/ gLa
2O
3, belong to precipitation volume Xiao Yi and filter slurry; Deposition oven dry calcining back burn decrement rate is 25.0%.
Embodiment 3.Method with the gaseous phase deposition neodymium.
In the reactor drum of heating unit is arranged, adding concentration is 0.5mol/L lanthanum chloride solution 1500 mL, under condition of stirring, with lanthanum chloride solution heat to 90～95 ℃.Have at another to add the bicarbonate of ammonia solid in reactor drum of heating unit, connect two reactor drums, heating is equipped with more than the reactor drum to 45 ℃ of bicarbonate of ammonia, makes its bicarbonate of ammonia begin to decompose the blow-off valve emptying in 1 minute of opening the reactor drum that lanthanum chloride solution is housed; The temperature of control decomposition reactor is reacted the air pressure in its system about 25KPa, when reaction mass pH 7.0 the time, stop thermal precipitation reactor drum and bicarbonate of ammonia decomposition reactor, precipitation reactor continues stirring 20 minutes; The carbonated rare earth slurry is put into the vacuum filter suction filtration, with distilled water wash 4 times, drains, 105 ℃ of dryings 2 hours.The carbonated rare earth slurry is emitted the natural subsidence rapid speed, and draining precipitation volume is 1.1mL/ gNd
2O
3, belong to the less easy filtration slurry of precipitation volume; Deposition oven dry calcining back burn decrement rate is 27.8%.
Embodiment 4.Method with the gaseous phase deposition yttrium.
In the reactor drum of heating unit is arranged, adding concentration is 1.0mol/L Lanthanum trichloride (cerium) solution 1600 mL, under condition of stirring, with lanthanum chloride solution heat to 60～65 ℃.Have at another to add the bicarbonate of ammonia solid in reactor drum of heating unit, connect two reactor drums, heating is equipped with more than the reactor drum to 45 ℃ of bicarbonate of ammonia, makes its bicarbonate of ammonia begin to decompose the blow-off valve emptying in 1 minute of opening the reactor drum that lanthanum chloride solution is housed; The temperature of control decomposition reactor is reacted the air pressure in its system about 20KPa, when reaction mass pH 6.9 the time, stop thermal precipitation reactor drum and bicarbonate of ammonia decomposition reactor, precipitation reactor continues stirring 20 minutes; The carbonated rare earth slurry is put into the vacuum filter suction filtration, with distilled water wash 4 times, drains, 105 ℃ of dryings 2 hours.It is slower that the carbonated rare earth slurry is emitted natural subsidence speed, and draining precipitation volume is 2.10mL/ gY
2O
3, it is bigger to belong to precipitation volume, is prone to filtering slurry; Deposition oven dry calcining back burn decrement rate is 41.3%.
Embodiment 5.Method with gaseous phase deposition lanthanum cerium mixture.
In the reactor drum of heating unit is arranged, adding concentration is 1.0mol/L lanthanum chloride solution 1500 mL, under condition of stirring, with lanthanum chloride solution heat to 75 ℃.Have at another to add the bicarbonate of ammonia solid in reactor drum of heating unit, connect two reactor drums, heating is equipped with more than the reactor drum to 45 ℃ of bicarbonate of ammonia, makes its bicarbonate of ammonia begin to decompose the blow-off valve emptying in 1 minute of opening the reactor drum that lanthanum chloride solution is housed; The temperature of control decomposition reactor is reacted the air pressure in its system about 10KPa, when reaction mass pH 7.0 the time, stop thermal precipitation reactor drum and bicarbonate of ammonia decomposition reactor, precipitation reactor continues stirring 20 minutes; The carbonated rare earth slurry is put into the vacuum filter suction filtration, with distilled water wash 3 times, drains, 105 ℃ of dryings 2 hours.It is fast that the carbonated rare earth slurry is emitted natural subsidence speed, and draining precipitation volume is 0.80mL/ g (LaCe)
2O
3, belong to precipitation volume Xiao Yi and filter slurry; Deposition oven dry calcining back burn decrement rate is 29.0%.
Above-described embodiment is the typical specific embodiments of several lab scale of the present invention, and those skilled in the art can make pilot scale and industrial production within the scope of the appended claims, and can make any modification in the claim scope.
Claims (2)
1. the method for a gaseous phase deposition rare earth is characterized in that according to the following steps:
(1) be raw material with single or mixed rare earth solution, the concentration of earth solution is 0.3～2.0mol/L, under condition of stirring, the earth solution in the precipitation reactor is heated to 40 ℃～95 ℃, and is maintained to the precipitin reaction end;
(2) in decomposition reactor, add solid ammonium bicarbonate, its add-on is not less than 1.2 times of theoretical consumption;
(3) connect precipitation reactor and decomposition reactor, and make the reactive system sealing, keep the decomposition temperature that temperature in the reaction process is not less than bicarbonate of ammonia;
(4) under precipitation reactor stirring and constant temperature; The thermal degradation reactor drum makes the decomposition reaction actuator temperature be controlled at 40 ℃～100 ℃, and the bicarbonate of ammonia in the decomposition reactor begins to decompose; Beginning rare-earth precipitation reaction in the precipitation reactor, the pressure in the reactive system is controlled at 1Kpa～100KPa;
(5) when the material pH in the precipitation reactor 6.8～7.0 the time, stop thermal precipitation reactor drum and decomposition reactor, precipitation reactor continues to stir 10～20 minutes;
(6) from precipitation reactor, emit the carbonated rare earth slurry, filter, wash, filter and do; 80 ℃～150 ℃ dryings 2～4 hours obtain carbonated rare earth; Or 800 ℃～1000 ℃ the calcining 2 hours, obtain rare earth oxide.
2. the method for gaseous phase deposition rare earth according to claim 1 is characterized in that in the described step (1), in the earth solution of precipitation reactor, adds the crystalline carbon acid rare earth.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103276440A (en) * | 2013-06-15 | 2013-09-04 | 清远市嘉禾稀有金属有限公司 | Processing method for rare earth carbonate with low chlorine ions |
| CN103351017A (en) * | 2013-07-01 | 2013-10-16 | 南昌大学 | Preparation method of fine-grained, high-bulk-density, ball-shaped, rare earth carbonate and oxide thereof |
| CN104117682A (en) * | 2013-04-27 | 2014-10-29 | 北京有色金属研究总院 | Method for preparing narrow range rare earth oxide with controllable particle size |
| CN106517200A (en) * | 2015-09-09 | 2017-03-22 | 有研稀土新材料股份有限公司 | Method for preparing metal carbonate |
| WO2017114312A1 (en) * | 2015-12-31 | 2017-07-06 | 安集微电子科技(上海)有限公司 | Method for preparing cerium oxide and application thereof in chemical-mechanical polishing (cmp) |
| CN107298457A (en) * | 2017-06-30 | 2017-10-27 | 中铝广西有色金源稀土有限公司 | A kind of method that utilization carbon dioxide prepares rare earth carbonate |
| WO2020063989A1 (en) * | 2018-09-28 | 2020-04-02 | 中国恩菲工程技术有限公司 | Rare earth precipitation device and rare earth precipitation method |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1093059A (en) * | 1993-03-29 | 1994-10-05 | 中国科学院长春应用化学研究所 | Preparation of rare-earth oxide ultramicro powder by carbonate precipitation method |
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2012
- 2012-08-13 CN CN2012102861468A patent/CN102816930A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1093059A (en) * | 1993-03-29 | 1994-10-05 | 中国科学院长春应用化学研究所 | Preparation of rare-earth oxide ultramicro powder by carbonate precipitation method |
Non-Patent Citations (2)
| Title |
|---|
| 肖楚民等: "碳酸氢铵沉淀法制备二氧化铈超细粉体", 《矿冶工程》 * |
| 韩旗英等: "晶型重稀土碳酸盐沉淀工艺技术", 《湖南有色金属》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104117682A (en) * | 2013-04-27 | 2014-10-29 | 北京有色金属研究总院 | Method for preparing narrow range rare earth oxide with controllable particle size |
| CN104117682B (en) * | 2013-04-27 | 2016-12-28 | 北京有色金属研究总院 | A kind of method of prepared sizes controllable narrow distribution rare earth oxide |
| CN103276440A (en) * | 2013-06-15 | 2013-09-04 | 清远市嘉禾稀有金属有限公司 | Processing method for rare earth carbonate with low chlorine ions |
| CN103276440B (en) * | 2013-06-15 | 2015-09-02 | 清远市嘉禾稀有金属有限公司 | A kind of low chlorine root rare earth carbonate working method |
| CN103351017A (en) * | 2013-07-01 | 2013-10-16 | 南昌大学 | Preparation method of fine-grained, high-bulk-density, ball-shaped, rare earth carbonate and oxide thereof |
| CN106517200A (en) * | 2015-09-09 | 2017-03-22 | 有研稀土新材料股份有限公司 | Method for preparing metal carbonate |
| WO2017114312A1 (en) * | 2015-12-31 | 2017-07-06 | 安集微电子科技(上海)有限公司 | Method for preparing cerium oxide and application thereof in chemical-mechanical polishing (cmp) |
| CN107298457A (en) * | 2017-06-30 | 2017-10-27 | 中铝广西有色金源稀土有限公司 | A kind of method that utilization carbon dioxide prepares rare earth carbonate |
| WO2020063989A1 (en) * | 2018-09-28 | 2020-04-02 | 中国恩菲工程技术有限公司 | Rare earth precipitation device and rare earth precipitation method |
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Application publication date: 20121212 |