CN103952555A - Method for precipitating cerium-containing rare-earth carbonate - Google Patents
Method for precipitating cerium-containing rare-earth carbonate Download PDFInfo
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- CN103952555A CN103952555A CN201410212256.9A CN201410212256A CN103952555A CN 103952555 A CN103952555 A CN 103952555A CN 201410212256 A CN201410212256 A CN 201410212256A CN 103952555 A CN103952555 A CN 103952555A
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Abstract
The invention belongs to the technical field of production of rare-earth carbonate, and particularly relates to a method for precipitating cerium-containing rare-earth carbonate. The method comprises the following steps: introducing inactive gas into a cerium-containing rare-earth solution to be precipitated, a precipitant solution and dilution water for solutions to expel dissolved oxygen and air in the precipitation reaction kettle; while stirring, reacting the precipitant solution with the cerium-containing rare-earth solution until the pH value is 6.5-7.5 so as to completely precipitate the rare earth; and dehydrating the precipitate, and washing to obtain the cerium-containing rare-earth carbonate. The acid solubility effect of the cerium-containing rare-earth carbonate is obviously improved, the solution is clear and transparent, and the turbidity is less than 5.0NTU, so the acid solubility effect is similar to that of the product precipitated by the traditional ammonium bicarbonate. The method achieves the effect of enhancing the acid solubility of the cerium-containing rare-earth carbonate, is simpler to operate, and has certain industrial popularization meanings.
Description
Technical field
The invention belongs to the production technical field of carbonated rare earth, specifically relate to the method for a kind of precipitation containing cerium carbonated rare earth.
Background technology
Mainly comprise cerous carbonate, Phosbloc cerium, carbonic acid La-Ce-Pr, few cerium carbonated rare earth containing the carbonated rare earth of cerium, they are important source material of preparing the series product such as cerous nitrate, ceric ammonium nitrate, cerous sulfate, catalyzer and polishing material, conventionally cerous carbonate or Phosbloc cerium are further used after acid-soluble again, therefore theirs is acid-soluble most important.In carbonated rare earth preparation, conventional precipitation agent is bicarbonate of ammonia, and the cerous carbonate being settled out or Phosbloc cerium particle are large, is easy to precipitation and washing, and acid-soluble very good.And now under the pressure of environmental stress, avoid the pollution of ammonia nitrogen, and consider enterprise cost benefit, in the production process of cerous carbonate, start to adopt sodium carbonate as precipitation agent.But the aqueous solution of sodium carbonate, pH is higher, when it is in the time being combined containing cerium rare earth chloride liquid, very easily forms Ce (OH)
3and Ce (OH)
4, cause the acid-soluble bad of cerous carbonate or Phosbloc cerium, add excessive acid or add the reductive agent hydrotropies such as hydrogen peroxide for the thorough dissolving of this type of salt is often needed, this brings obstacle, competitiveness of product in market deficiency with regard to the application of giving this series products.
While adopting sodium carbonate to do precipitation agent and prepare content carbonated rare earth, about cause its acid-soluble bad research to have no at present report because of the appearance of tetravalence cerous hydroxide, the way feasible for head it off also has no report.
Summary of the invention
The object of this invention is to provide the method for a kind of precipitation containing cerium carbonated rare earth, improved the acid soluble effect containing cerium carbonated rare earth, scientific and reasonable, simple to operate.
Precipitation of the present invention is containing the method for cerium carbonated rare earth, and step is as follows:
(1) first to treating that precipitation contains cerium mischmetal feed liquid, precipitant solution and feed liquid with passing into inactive gas in dilution water, discharges the air in dissolved oxygen and precipitin reaction still;
(2) under the condition stirring, make precipitant solution and react containing cerium mischmetal feed liquid, terminal pH is 6.5-7.5, and rare earth is precipitated completely;
(3) precipitation is through dehydration, and washing obtains containing cerium carbonated rare earth.
Inactive gas described in step (1) is the one in argon gas, nitrogen or carbonic acid gas.
The time that passes into inactive gas described in step (1) is 1-120min.
In step (1), pass into inactive gas to treating that precipitation contains in cerium mischmetal feed liquid, precipitant solution, discharge the dissolved oxygen in feed liquid, to dissolved oxygen content <5mg/g, preferred dissolution oxygen level <1mg/g, more preferably dissolved oxygen content <0.1mg/g.
Being Cerium II Chloride feed liquid, cerous nitrate feed liquid, lanthanum-cerium chloride feed liquid, lanthanum nitrate cerium feed liquid, lanthanum-cerium chloride praseodymium feed liquid, nitric acid La-Ce-Pr feed liquid, containing cerium rare earth chloride liquid or contain the one in cerium nitric rare earth feed liquid containing cerium mischmetal feed liquid described in step (1).
Precipitant solution described in step (1) is one or both in sodium carbonate solution or sodium hydrogen carbonate solution.
The mass percentage concentration of the precipitant solution described in step (2) is 1-20%.
The concentration containing cerium mischmetal feed liquid described in step (2) is 0.1-2.0mol/L.
Temperature of reaction described in step (2) is 5-40 DEG C.
Washing time described in step (3) is 5-30min.
Contain the acid-soluble of cerium carbonated rare earth in order to improve cerous carbonate, Phosbloc cerium etc., improve the yield after acid-soluble, improve the competitiveness of product in market, the present invention is by containing in the process of cerium rare earth chloride in precipitation, the method that passes into inactive gas has been avoided the appearance of tetravalence cerous hydroxide, and the acid-soluble of product improves greatly.
The present invention compared with prior art, has following beneficial effect:
The acid-soluble successful containing cerium carbonated rare earth obtaining through the present invention precipitation improves, and solution is limpid bright, and its turbidity is all below 5.0NTU, and the acid-soluble effect of product of traditional ammonium bicarbonate precipitation gained is very nearly the same with adopting.The present invention has reached the acid soluble effect improving containing cerium carbonated rare earth, operates relatively simply, has certain industrial dissemination.
Embodiment
Below in conjunction with embodiment, the present invention is described further.
Embodiment 1
Get the Cerium II Chloride feed liquid of Zibo Baogang glossy ganoderma rare earth extraction Workshop Production, precipitate according to the following steps successively:
(1) in the beaker of 5000ml, adding 1000mL concentration is the Cerium II Chloride feed liquid of 0.45mol/L, and in another beaker, adding concentration is 13% sodium carbonate solution.Adopt Bubbling method to pass into respectively nitrogen 5min in Cerium II Chloride feed liquid and sodium carbonate solution, discharge the air in beaker, and discharge the dissolved oxygen in each solution, the concentration that detects dissolved oxygen is in Cerium II Chloride feed liquid: 0.32mg/L; In sodium carbonate solution: 0.16mg/L.
(2) 23 DEG C, stir condition under, sodium carbonate solution is slowly joined in Cerium II Chloride feed liquid, to supernatant liquor pH be 7.
(3), precipitation and centrifugal separation, drip washing 15min, obtains cerium carbonate product.
The cerous carbonate of preparation is dissolved in nitric acid, records its turbidity 1.2NTU.
Embodiment 2
Get the cerous nitrate feed liquid of Zibo Baogang glossy ganoderma Rare earth sealing Workshop Production, precipitate according to the following steps successively:
(1) in the beaker of 5000ml, adding 1000mL concentration is the cerous nitrate feed liquid of 0.54mol/L, and in another beaker, adding concentration is 10% sodium hydrogen carbonate solution.Adopt Bubbling method to pass into respectively argon gas 10min in cerous nitrate feed liquid and sodium hydrogen carbonate solution, discharge the air in beaker, and discharge the dissolved oxygen in each solution.The concentration that detects dissolved oxygen is in cerous nitrate feed liquid: 0.22mg/L; In sodium hydrogen carbonate solution: 0.26mg/L.
(2) under 25 DEG C, the condition that stirs, control sodium bicarbonate and cerous nitrate feed liquid parallel-flow precipitation, the pH value of reacting after finishing is 6.85.
(3), precipitation and centrifugal separation, drip washing 10min, obtains cerium carbonate product.
The cerous carbonate of preparation is dissolved in nitric acid, records its turbidity 1.3NTU.
Embodiment 3
Get Zibo Baogang glossy ganoderma rare earth extraction Workshop Production lanthanum-cerium chloride feed liquid, precipitate according to the following steps successively:
(1) in the beaker of 5000ml, adding 1000mL concentration is the lanthanum-cerium chloride feed liquid of 0.84mol/L, and in another beaker, adding concentration is 8% sodium carbonate solution, in the 3rd beaker, adds 4000mL pure water.Adopt Bubbling method to pass into respectively carbonic acid gas 20min in lanthanum-cerium chloride feed liquid, sodium carbonate solution and pure water, discharge the air in beaker, and discharge the dissolved oxygen in each solution.The concentration that detects dissolved oxygen is in lanthanum-cerium chloride feed liquid: 0.12mg/L; In sodium carbonate solution: <0.1mg/L; In pure water: <0.1mg/L.
(2) 5 DEG C, stir condition under, sodium carbonate solution is slowly joined in lanthanum-cerium chloride feed liquid, to supernatant liquor pH be 7.
(3), precipitation and centrifugal separation, with above-mentioned pure water drip washing 30min, obtain Phosbloc cerium product.
The Phosbloc cerium of preparation is dissolved in nitric acid, records its turbidity 1.1NTU.
Embodiment 4
Get Zibo Baogang glossy ganoderma rare-earth chlorination rare earth Workshop Production containing cerium rare earth chloride liquid, precipitate according to the following steps successively:
(1) in the beaker of 5000ml, add 400mL concentration be 1.81mol/L containing cerium rare earth chloride liquid, in another beaker, adding concentration is 5% sodium carbonate and the mixing solutions of sodium bicarbonate, in the 3rd beaker, adds 4000mL pure water.Adopt Bubbling method to pass into respectively carbonic acid gas 35min in the mixing solutions containing cerium rare earth chloride liquid, sodium carbonate and sodium bicarbonate, pure water, discharge the air in beaker, and discharge the dissolved oxygen in each solution.Detect the concentration of dissolved oxygen for containing in cerium rare earth chloride liquid: 0.21mg/L; In the mixing solutions of sodium carbonate and sodium bicarbonate: <0.1mg/L; In pure water: <0.1mg/L.
(2) 40 DEG C, stir condition under, the mixing solutions of sodium carbonate and sodium bicarbonate is slowly joined containing in cerium rare earth chloride liquid, to supernatant liquor pH be 7.2.
(3), precipitation and centrifugal separation, with above-mentioned pure water drip washing 30min, obtain containing cerium carbonated rare earth product.
By being dissolved in nitric acid containing cerium carbonated rare earth of preparation, record its turbidity 1.9NTU.
Embodiment 5
Get Zibo Baogang glossy ganoderma Rare earth sealing Workshop Production containing cerium nitric rare earth feed liquid, precipitate according to the following steps successively:
(1) at 5m
3reactor in add 1000L concentration be 0.51mol/L containing cerium nitric rare earth feed liquid, at a 5m
3in storage tank, adding concentration is 10% sodium carbonate solution 3m
3, at a 5m
3in pure water storage tank, add 4.5m
3pure water.Adopt Bubbling method to passing into respectively carbonic acid gas 50min containing in cerium nitric rare earth feed liquid, sodium carbonate solution and pure water, discharge the air in reactor, and discharge the dissolved oxygen in each solution.Detect the concentration of dissolved oxygen for containing in cerium nitric rare earth feed liquid: 0.29mg/L; In sodium carbonate solution: 0.15mg/L; In pure water: <0.1mg/L.
(2) 30 DEG C, stir condition under, sodium carbonate solution is slowly joined containing in cerium nitric rare earth feed liquid, to supernatant liquor pH be 7.1.
(3), precipitation and centrifugal separation, with above-mentioned pure water drip washing 25min, obtain containing cerium carbonated rare earth product.
By being dissolved in nitric acid containing cerium carbonated rare earth of preparation, record its turbidity 2.3NTU.
Embodiment 6
Get Zibo Baogang glossy ganoderma rare earth extraction Workshop Production lanthanum-cerium chloride praseodymium feed liquid, precipitate according to the following steps successively:
(1) in the beaker of 5000ml, adding 1000mL concentration is the lanthanum-cerium chloride praseodymium feed liquid of 0.64mol/L, and in another beaker, adding concentration is 11% sodium carbonate solution, in the 3rd beaker, adds 4000mL pure water.Adopt Bubbling method to pass into respectively carbonic acid gas 1min in lanthanum-cerium chloride praseodymium feed liquid, sodium carbonate solution and pure water, discharge the air in beaker, and discharge the dissolved oxygen in each solution.The concentration that detects dissolved oxygen is in lanthanum-cerium chloride praseodymium feed liquid: 0.22mg/L; In sodium carbonate solution: <0.1mg/L; In pure water: <0.1mg/L.
(2) 25 DEG C, stir condition under, sodium carbonate solution is slowly joined in lanthanum-cerium chloride praseodymium feed liquid, to supernatant liquor pH be 7.5.
(3), precipitation and centrifugal separation, with above-mentioned pure water drip washing 15min, obtain containing carbonic acid La-Ce-Pr product.
The carbonic acid La-Ce-Pr of preparation is dissolved in nitric acid, records its turbidity 1.5NTU.
Embodiment 7
Get Zibo Baogang glossy ganoderma Rare earth sealing Workshop Production nitric acid La-Ce-Pr feed liquid, precipitate according to the following steps successively:
(1) in the beaker of 5000ml, adding 1000mL concentration is the nitric acid La-Ce-Pr feed liquid of 0.55mol/L, and in another beaker, adding concentration is 10.5% sodium carbonate solution, in the 3rd beaker, adds 4000mL pure water.Adopt Bubbling method to pass into respectively carbonic acid gas 20min in nitric acid La-Ce-Pr feed liquid, sodium carbonate solution and pure water, discharge the air in beaker, and discharge the dissolved oxygen in each solution.The concentration that detects dissolved oxygen is in nitric acid La-Ce-Pr feed liquid: 0.26mg/L; In sodium carbonate solution: <0.1mg/L; In pure water: <0.1mg/L.
(2) 23 DEG C, stir condition under, sodium carbonate solution is slowly joined in nitric acid La-Ce-Pr feed liquid, to supernatant liquor pH be 6.5.
(3), precipitation and centrifugal separation, with above-mentioned pure water drip washing 5min, obtain containing carbonic acid La-Ce-Pr product.
The carbonic acid La-Ce-Pr of preparation is dissolved in nitric acid, records its turbidity 1.1NTU.
Embodiment 8
Get prepared by glossy ganoderma rare earth research and development centre of Zibo Baogang containing cerium nitric rare earth feed liquid, precipitation according to the following steps successively:
(1) in the beaker of 5000ml, add 1000mL concentration be 0.41mol/L containing cerium nitric rare earth feed liquid, in another beaker, adding concentration is 5.5% sodium carbonate solution, in the 3rd beaker, adds 4000mL pure water.Adopt Bubbling method to passing into respectively carbonic acid gas 120min containing in cerium nitric rare earth feed liquid, sodium carbonate solution and pure water, discharge the air in beaker, and discharge the dissolved oxygen in each solution.Detect the concentration of dissolved oxygen for containing in cerium nitric rare earth feed liquid: 0.26mg/L; In sodium carbonate solution: <0.1mg/L; In pure water: <0.1mg/L.
(2) 28 DEG C, stir condition under, sodium carbonate solution is slowly joined containing in cerium nitric rare earth feed liquid, to supernatant liquor pH be 7.0.
(3), precipitation and centrifugal separation, with above-mentioned pure water drip washing 15min, obtain containing cerium carbonated rare earth product.
By being dissolved in nitric acid containing cerium carbonated rare earth product of preparation, record its turbidity 0.9NTU.
Claims (9)
1. precipitation, containing a method for cerium carbonated rare earth, is characterized in that step is as follows:
(1) first to treating that precipitation contains cerium mischmetal feed liquid, precipitant solution and feed liquid with passing into inactive gas in dilution water, discharges the air in dissolved oxygen and precipitin reaction still;
(2) under the condition stirring, make precipitant solution and react containing cerium mischmetal feed liquid, terminal pH is 6.5-7.5, and rare earth is precipitated completely;
(3) precipitation is through dehydration, and washing obtains containing cerium carbonated rare earth.
2. precipitation according to claim 1, containing the method for cerium carbonated rare earth, is characterized in that the inactive gas described in step (1) is the one in argon gas, nitrogen or carbonic acid gas.
3. precipitation according to claim 1, containing the method for cerium carbonated rare earth, is characterized in that the time that passes into inactive gas described in step (1) is 1-120min.
4. precipitation according to claim 1, containing the method for cerium carbonated rare earth, is characterized in that being Cerium II Chloride feed liquid, cerous nitrate feed liquid, lanthanum-cerium chloride feed liquid, lanthanum nitrate cerium feed liquid, lanthanum-cerium chloride praseodymium feed liquid, nitric acid La-Ce-Pr feed liquid, containing cerium rare earth chloride liquid or contain the one in cerium nitric rare earth feed liquid containing cerium mischmetal feed liquid described in step (1).
5. precipitation according to claim 1, containing the method for cerium carbonated rare earth, is characterized in that the precipitant solution described in step (1) is one or both in sodium carbonate solution or sodium hydrogen carbonate solution.
6. precipitation according to claim 1, containing the method for cerium carbonated rare earth, is characterized in that the mass percentage concentration of the precipitant solution described in step (2) is 1-20%.
7. precipitation according to claim 1, containing the method for cerium carbonated rare earth, is characterized in that the concentration containing cerium mischmetal feed liquid described in step (2) is 0.1-2.0mol/L.
8. precipitation according to claim 1, containing the method for cerium carbonated rare earth, is characterized in that the temperature of reaction described in step (2) is 5-40 DEG C.
9. precipitation according to claim 1, containing the method for cerium carbonated rare earth, is characterized in that the washing time described in step (3) is 5-30min.
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| CN201410212256.9A CN103952555A (en) | 2014-05-19 | 2014-05-19 | Method for precipitating cerium-containing rare-earth carbonate |
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| CN201410212256.9A CN103952555A (en) | 2014-05-19 | 2014-05-19 | Method for precipitating cerium-containing rare-earth carbonate |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113651352A (en) * | 2021-09-02 | 2021-11-16 | 甘肃稀土新材料股份有限公司 | Method for preparing low-calcium cerium lanthanum carbonate from high-calcium cerium lanthanum chloride solution |
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| CN102936029A (en) * | 2012-11-30 | 2013-02-20 | 淄博包钢灵芝稀土高科技股份有限公司 | Method for precipitating rare earth carbonate |
| CN103436697A (en) * | 2013-08-15 | 2013-12-11 | 南昌大学 | Rare-earth carbonate crystallizing and precipitating method for processing aluminum-containing rare-earth feed liquid |
-
2014
- 2014-05-19 CN CN201410212256.9A patent/CN103952555A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102936029A (en) * | 2012-11-30 | 2013-02-20 | 淄博包钢灵芝稀土高科技股份有限公司 | Method for precipitating rare earth carbonate |
| CN103436697A (en) * | 2013-08-15 | 2013-12-11 | 南昌大学 | Rare-earth carbonate crystallizing and precipitating method for processing aluminum-containing rare-earth feed liquid |
Non-Patent Citations (1)
| Title |
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| 冯天泽: "稀土碳酸盐的制法、性质和组成", 《稀土》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113651352A (en) * | 2021-09-02 | 2021-11-16 | 甘肃稀土新材料股份有限公司 | Method for preparing low-calcium cerium lanthanum carbonate from high-calcium cerium lanthanum chloride solution |
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