CN103952554B - Precipitate the carbothiolic acid dissolubility method containing cerium carbonated rare earth - Google Patents
Precipitate the carbothiolic acid dissolubility method containing cerium carbonated rare earth Download PDFInfo
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- CN103952554B CN103952554B CN201410210983.1A CN201410210983A CN103952554B CN 103952554 B CN103952554 B CN 103952554B CN 201410210983 A CN201410210983 A CN 201410210983A CN 103952554 B CN103952554 B CN 103952554B
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Abstract
The invention belongs to the production technical field of carbonated rare earth, be specifically related to and a kind of precipitate the carbothiolic acid dissolubility method containing cerium carbonated rare earth。Adopt ultrasonic degassed or vacuum outgas elimination containing the gas dissolved in cerium mischmetal feed liquid, precipitant solution and feed liquid dilution water；Stirring when, make degassed after precipitant solution and containing cerium mischmetal feed liquid react, terminal pH is 6.5-7.5, makes rare earth precipitate completely；Precipitating through dehydration, washing obtains containing cerium carbonated rare earth。The acid-soluble effect containing cerium carbonated rare earth obtained through present invention precipitation is obviously improved, and solution is limpid bright, and its turbidity is all at below 5.0NTU, very nearly the same with the acid-soluble effect of the product adopting tradition ammonium bicarbonate precipitation gained。Invention achieves the acid soluble effect improved containing cerium carbonated rare earth, operate relatively easy, have certain commercial introduction meaning。
Description
Technical field
The invention belongs to the production technical field of carbonated rare earth, be specifically related to and a kind of precipitate the carbothiolic acid dissolubility method containing cerium carbonated rare earth。
Background technology
Carbonated rare earth containing cerium mainly includes cerous carbonate, lanthanum carbonate cerium, carbonic acid La-Ce-Pr, few cerium carbonated rare earth, they are the important source material preparing the series of products such as cerous nitrate, ammonium ceric nitrate, cerous sulfate, catalyst and polishing material, generally cerous carbonate or lanthanum carbonate cerium further being used after acid-soluble, therefore theirs is acid-soluble most important。In carbonated rare earth preparation, conventional precipitant is ammonium hydrogen carbonate, and the cerous carbonate or the lanthanum carbonate cerium granule that are settled out are big, it is easy to precipitation and washing, and acid-soluble very good。And now under the pressure of ambient pressure, it is to avoid the pollution of ammonia nitrogen, and consider entreprise cost benefit, in the production process of cerous carbonate, begin with sodium carbonate as precipitant。But the aqueous solution of sodium carbonate, pH is higher, when its with containing cerium rare earth chloride liquid in conjunction with time, very easily form Ce (OH)3With Ce (OH)4, causing the acid-soluble bad of cerous carbonate or lanthanum carbonate cerium, generally require the excessive acid of addition for making this type of salt thoroughly dissolve or add the reducing agent hydrotropies such as hydrogen peroxide, this just brings obstacle to the application of this series products, competitiveness of product in market deficiency。
Patent " a kind of method that can significantly reduce carbonated rare earth crystallization process chlorine root entrainment " (application number: 201210532105.2) utilizes hyperacoustic cavitation effect aids precipitation carbonated rare earth, only relate to the entrainment problem of chloride ion, the solubility property containing cerium carbonated rare earth is not studied。
At present, when preparation is containing cerium carbonated rare earth, report is had no at present for the acid-soluble bad research of the carbonated rare earth containing cerium, for adopting ultrasonic degassed and vacuum outgas to solve the feasible way of this problem and also have no report。
Summary of the invention
It is an object of the invention to provide and a kind of precipitate the carbothiolic acid dissolubility method containing cerium carbonated rare earth, improve the acid soluble effect containing cerium carbonated rare earth, scientific and reasonable, simple to operate。
The precipitation of the present invention carbothiolic acid dissolubility method containing cerium carbonated rare earth, step is as follows:
(1) adopt ultrasonic degassed or vacuum outgas elimination containing the gas dissolved in cerium mischmetal feed liquid, precipitant solution and feed liquid dilution water；
(2) stirring when, make degassed after precipitant solution and containing cerium mischmetal feed liquid react, terminal pH is 6.5-7.5, makes rare earth precipitate completely；
(3) precipitation is through dehydration, and washing obtains containing cerium carbonated rare earth。
Ultrasonic degassed supersonic frequency described in step (1) is 25-130kHz, and ultrasonic time is 1-60min。Ultrasonic degassed be that ultrasonic head is inserted in solution or in the tank wall of each solution, ultrasonic 1-60min。
The vacuum of the vacuum outgas described in step (1) is-1KPa-0.1MPa, and degassing time is 1-60min。Vacuum outgas is that vacuum pump is connected with the storage tank pipeline of each solution, opens vacuum pump, controls vacuum and reaches-1KPa-0.1MPa, degassed 1-60min。
The feed liquid containing cerium mischmetal described in step (1) be cerium chloride feed liquid, cerous nitrate feed liquid, lanthanum-cerium chloride feed liquid, Lanthanum (III) nitrate cerium feed liquid, lanthanum-cerium chloride praseodymium feed liquid, nitric acid La-Ce-Pr feed liquid, containing cerium rare earth chloride liquid or containing the one in cerium nitric rare earth feed liquid。
Precipitant solution described in step (1) is one or both in sodium carbonate liquor or sodium bicarbonate 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。
Reaction temperature described in step (2) is 5-40 DEG C。
Wash time described in step (3) is 5-30min。
Washing described in step (3) adopts pure water, it is preferred to use wash through sloughing the pure water dissolving gas。
In order to improve acid-soluble containing cerium carbonated rare earth such as cerous carbonate, lanthanum carbonate cerium, improve acid-soluble after yield, improve the competitiveness of product in market, the present invention is by preparing the process containing cerium carbonated rare earth, ultrasonic degassed and vacuum outgas method is adopted to remove preparation containing the dissolving gas in the rare earth feed liquid used in cerium carbonated rare earth, precipitant solution, dilution water, greatly reduce the amount generating cerium hydroxide in precipitation process, the product obtained is with after acid-soluble solution, very as clear as crystal, performance is greatly improved。
The present invention compared with prior art, has the advantages that
The acid-soluble effect containing cerium carbonated rare earth obtained through present invention precipitation is obviously improved, and solution is limpid bright, and its turbidity is all at below 5.0NTU, very nearly the same with the acid-soluble effect of the product adopting tradition ammonium bicarbonate precipitation gained。Invention achieves the acid soluble effect improved containing cerium carbonated rare earth, operate relatively easy, have certain commercial introduction meaning。
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described further。
Embodiment 1
Take the cerium chloride feed liquid of Zibo Baogang Ganoderma rare earth extraction Workshop Production, precipitate according to the following steps successively:
(1) in the beaker of 1000ml, add the cerium chloride feed liquid 400mL that concentration is 1.35mol/L, be diluted to 1000mL with pure water, another beaker adds the sodium carbonate liquor that concentration is 12% dissolved。Adopt ultrasonic degassed method degassed, supersonic frequency 40kHz, degassed 40min。
(2) 30 DEG C, stirring when, sodium carbonate liquor is slowly added in cerium chloride feed liquid, is 7 to supernatant pH。
(3) precipitation and centrifugal separation, drip washing 15min, obtain cerium carbonate product。
The cerous carbonate of preparation is dissolved in nitric acid, records its turbidity 3.2NTU。
Embodiment 2
Take the cerous nitrate feed liquid of Zibo Baogang Ganoderma Rare earth sealing Workshop Production, precipitate according to the following steps successively:
(1) adding 1000mL concentration in the bottle,suction of 5000ml is 0.45mol/L cerous nitrate feed liquid, adds the sodium carbonate liquor that concentration is 10% dissolved in another bottle,suction。The mode adopting evacuation degassed carries out degassed, controls vacuum at-60KPa, degassed 15min。
(2) 28 DEG C, stirring when, control sodium carbonate and cerous nitrate material feed liquid parallel-flow precipitation, reaction terminate after pH value be 6.8。
(3) precipitation and centrifugal separation, drip washing 10min, obtain cerium carbonate product。
The cerous carbonate of preparation is dissolved in nitric acid, records its turbidity 0.9NTU。
Embodiment 3
Take Lanthanum (III) nitrate cerium feed liquid prepared by Ganoderma rare earth research and development centre of Zibo Baogang, precipitate according to the following steps successively:
(1) in the bottle,suction of 5000ml, the 2000mL Lanthanum (III) nitrate cerium feed liquid that concentration is 0.86mol/L is added, another bottle,suction adds the sodium carbonate that concentration is 12.5% dissolved and sodium bicarbonate mixed solution, the 3rd bottle,suction adds 4000mL pure water。The mode adopting evacuation degassed carries out degassed, controls vacuum at-1KPa, degassed 20min。
(2) 5 DEG C, stirring when, sodium carbonate and sodium bicarbonate mixed solution are slowly added in Lanthanum (III) nitrate cerium feed liquid, are 7 to supernatant pH。
(3) precipitation and centrifugal separation, with the pure water drip washing 15min after degassed, lanthanum carbonate cerium product is obtained。
The lanthanum carbonate cerium of preparation is dissolved in nitric acid, records its turbidity 0.85NTU。
Embodiment 4
Take Zibo Baogang Ganoderma rare earth extraction Workshop Production lanthanum-cerium chloride feed liquid, precipitate according to the following steps successively:
(1) in the bottle,suction of 5000ml, add the 1000mL lanthanum-cerium chloride feed liquid that concentration is 0.37mol/L, another bottle,suction adds the sodium bicarbonate solution that concentration is 15.1% dissolved, the 3rd bottle,suction adds 3000mL pure water。The mode adopting evacuation degassed carries out degassed, controls vacuum at-100KPa, degassed 5min。
(2) 40 DEG C, stirring when, sodium bicarbonate solution is slowly added in lanthanum-cerium chloride feed liquid, is 7.5 to supernatant pH。
(3) precipitation and centrifugal separation, with the pure water drip washing 10min after degassed, lanthanum carbonate cerium product is obtained。
The lanthanum carbonate cerium of preparation is dissolved in nitric acid, records its turbidity 1.5NTU。
Embodiment 5
Take Zibo Baogang Ganoderma rare earth extraction Workshop Production lanthanum-cerium chloride praseodymium feed liquid, precipitate according to the following steps successively:
(1) in the bottle,suction of 1000ml, add the 500mL lanthanum-cerium chloride praseodymium feed liquid that concentration is 0.43mol/L, another bottle,suction adds the sodium carbonate liquor that concentration is 6.7% dissolved, the 3rd bottle,suction adds 1000mL pure water。The mode adopting evacuation degassed carries out degassed, controls vacuum at-10KPa, degassed 60min。
(2) 30 DEG C, stirring when, sodium carbonate liquor is slowly added in lanthanum-cerium chloride praseodymium feed liquid, is 7.0 to supernatant pH。
(3) precipitation and centrifugal separation, with the pure water drip washing 11min after degassed, carbonic acid La-Ce-Pr product is obtained。
The carbonic acid La-Ce-Pr of preparation is dissolved in nitric acid, records its turbidity 1.7NTU。
Embodiment 6
Take nitric acid La-Ce-Pr feed liquid prepared by Ganoderma rare earth research and development centre of Zibo Baogang, precipitate according to the following steps successively:
(1) in the beaker of 1000ml, add the nitric acid La-Ce-Pr feed liquid 300mL that concentration is 1.45mol/L, be diluted to 1000mL with pure water, another beaker adds the sodium carbonate liquor that concentration is 12% dissolved。Adopt ultrasonic degassed method degassed, supersonic frequency 25kHz, degassed 60min。
(2) 20 DEG C, stirring when, sodium carbonate liquor is slowly added in nitric acid La-Ce-Pr feed liquid, is 6.5 to supernatant pH。
(3) precipitation and centrifugal separation, drip washing 5min, obtain carbonic acid La-Ce-Pr product。
The carbonic acid La-Ce-Pr of preparation is dissolved in nitric acid, records its turbidity 2.2NTU。
Embodiment 7
Take Zibo Baogang Ganoderma rare-earth chlorination rare earth Workshop Production containing cerium rare earth chloride liquid, successively according to the following steps precipitation:
(1) add in the beaker of 1000ml concentration be 1.85mol/L containing cerium rare earth chloride liquid 250mL, be diluted to 1000mL with pure water, another beaker add the sodium carbonate liquor that concentration is 12% that dissolved。Adopt ultrasonic degassed method degassed, supersonic frequency 130kHz, degassed 1min。
(2) 25 DEG C, stirring when, sodium carbonate liquor is slowly added into containing in cerium rare earth chloride liquid, is 7.1 to supernatant pH。
(3) precipitation and centrifugal separation, drip washing 18min, obtain containing cerium carbonated rare earth product。
The carbonated rare earth containing cerium of preparation is dissolved in nitric acid, records its turbidity 2.7NTU。
Embodiment 8
Take prepared by 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) add in the bottle,suction of 1000ml concentration be 1.35mol/L containing cerium nitric rare earth feed liquid 350mL, be diluted to 1000mL with pure water, another bottle,suction add the sodium carbonate liquor that concentration is 12% that dissolved。The mode adopting evacuation degassed carries out degassed, controls vacuum at-100KPa, degassed 1min。
(2) 20 DEG C, stirring when, sodium carbonate liquor is slowly added into containing in cerium nitric rare earth feed liquid, is 7 to supernatant pH。
(3) precipitation and centrifugal separation, drip washing 30min, obtain containing cerium carbonated rare earth product。
The carbonated rare earth containing cerium of preparation is dissolved in nitric acid, records its turbidity 2.7NTU。
Claims (8)
1. a precipitation carbothiolic acid dissolubility method containing cerium carbonated rare earth, it is characterised in that step is as follows:
(1) adopt ultrasonic degassed or vacuum outgas elimination containing the gas dissolved in cerium mischmetal feed liquid, precipitant solution and feed liquid dilution water；
(2) stirring when, make degassed after precipitant solution and containing cerium mischmetal feed liquid react, terminal pH is 6.5-7.5, makes rare earth precipitate completely；
(3) precipitation is through dehydration, and washing obtains containing cerium carbonated rare earth；
Precipitant solution described in step (1) is one or both in sodium carbonate liquor or sodium bicarbonate solution。
2. the precipitation according to claim 1 carbothiolic acid dissolubility method containing cerium carbonated rare earth, it is characterised in that the ultrasonic degassed supersonic frequency described in step (1) is 25-130kHz, and ultrasonic time is 1-60min。
3. the precipitation according to claim 1 carbothiolic acid dissolubility method containing cerium carbonated rare earth, it is characterised in that the vacuum of the vacuum outgas described in step (1) is-1kPa-0.1MPa, and degassing time is 1-60min。
4. the precipitation according to claim 1 carbothiolic acid dissolubility method containing cerium carbonated rare earth, it is characterised in that the feed liquid containing cerium mischmetal described in step (1) is containing cerium rare earth chloride liquid or containing cerium nitric rare earth feed liquid。
5. the precipitation according to claim 1 carbothiolic acid dissolubility method containing cerium carbonated rare earth, it is characterised in that the mass percentage concentration of the precipitant solution described in step (2) is 1-20%。
6. the precipitation according to claim 1 carbothiolic acid dissolubility method containing cerium carbonated rare earth, it is characterised in that the concentration containing cerium mischmetal feed liquid described in step (2) is 0.1-2.0mol/L。
7. the precipitation according to claim 1 carbothiolic acid dissolubility method containing cerium carbonated rare earth, it is characterised in that the reaction temperature described in step (2) is 5-40 DEG C。
8. the precipitation according to claim 1 carbothiolic acid dissolubility method containing cerium carbonated rare earth, it is characterised in that the wash time described in step (3) is 5-30min。
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1323908A (en) * | 2001-03-20 | 2001-11-28 | 北京方正稀土科技研究所有限公司 | Optimal dissolving method of preparing rare earth fluorochloride material liquid from bastnasite concentrate |
| 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 |
| CN102978398A (en) * | 2012-12-12 | 2013-03-20 | 南昌大学 | Method for obviously lowering chlorine content in process of carbonic acid rare earth crystallization |
| 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 |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1323908A (en) * | 2001-03-20 | 2001-11-28 | 北京方正稀土科技研究所有限公司 | Optimal dissolving method of preparing rare earth fluorochloride material liquid from bastnasite concentrate |
| 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 |
| CN102978398A (en) * | 2012-12-12 | 2013-03-20 | 南昌大学 | Method for obviously lowering chlorine content in process of carbonic acid rare earth crystallization |
| 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 |
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Denomination of invention: Method for precipitating acid soluble rare earth carbonate containing cerium Effective date of registration: 20211122 Granted publication date: 20160622 Pledgee: Zibo Linzi sub branch of Bank of Qingdao Co.,Ltd. Pledgor: Zibo Baogang Lingzhi Rare Earth High-Tech Co.,Ltd. Registration number: Y2021980012895 |
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Date of cancellation: 20221026 Granted publication date: 20160622 Pledgee: Zibo Linzi sub branch of Bank of Qingdao Co.,Ltd. Pledgor: Zibo Baogang Lingzhi Rare Earth High-Tech Co.,Ltd. Registration number: Y2021980012895 |