CN1071706A - The technology of cerium oxide purifying - Google Patents
The technology of cerium oxide purifying Download PDFInfo
- Publication number
- CN1071706A CN1071706A CN91109808A CN91109808A CN1071706A CN 1071706 A CN1071706 A CN 1071706A CN 91109808 A CN91109808 A CN 91109808A CN 91109808 A CN91109808 A CN 91109808A CN 1071706 A CN1071706 A CN 1071706A
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- CN
- China
- Prior art keywords
- oxidation
- technology
- cerium oxide
- cerium
- prepares
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F17/00—Compounds of rare earth metals
- C01F17/20—Compounds containing only rare earth metals as the metal element
- C01F17/206—Compounds containing only rare earth metals as the metal element oxide or hydroxide being the only anion
- C01F17/224—Oxides or hydroxides of lanthanides
- C01F17/235—Cerium oxides or hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F17/00—Compounds of rare earth metals
- C01F17/10—Preparation or treatment, e.g. separation or purification
- C01F17/17—Preparation or treatment, e.g. separation or purification involving a liquid-liquid extraction
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention belongs to a kind of technology of hydrometallurgy separation of rare earth elements cerium, make raw material, under low acidity situation, make oxygenant, carry out fractionation extraction, prepare purity and be 98～99.99% CeO with potassium permanganate with mixed chlorinated rare earth
2, cerium content drops to below 0.5% in the surplus liquid.Can directly be connected with existing separating technology, be suitable for large-scale industrial production.The production efficiency height, high yield, cost is low.
Description
The invention belongs to the hydrometallurgy category, in order to separate the preparation cerium oxide.
The production technique of preparation cerium oxide is mostly directly used liquid-liquid extraction.Therefore because cerium has the character that becomes high price, it is a lot of to utilize this character to separate the method for purification, as: ceric ammonium nitrate recrystallization method, the TBP extracting and separating in nitric acid system, and some other chemical processes.Acidity is very high on the one hand makes troubles to operation for these methods, on the other hand, the cost height, production efficiency is low.In with the ceric process of trivalent cerium oxidation, spendable method for oxidation is a lot, as air oxidation process, and hydrogen peroxide oxidation method.Oxidation rate is too slow in the air oxidation process, and service temperature is very high again, and the dioxygen oxidation rule needs just can carry out under the very low acidity.Be unsuitable for and being connected of liquid-liquid extraction method.
Purpose of the present invention is exactly the shortcoming that will overcome in above-mentioned each method, utilize quadrivalent cerium and other trivalent rare earths that but big separation factor and liquid-liquid extraction operate continuously are arranged, can prepare advantages such as high purity product, oxidation, extraction combines, and prepares cerium oxide by fractionation extraction.Another object of the present invention is exactly to overcome the variety of issue that sulfuric acid system carries out appearance in the oxidation-extraction separation.Rare earth concentration is too low, can only be between 20～50g/l, and concentration is high again crystallization will to occur, thereby causes emulsion, contains a small amount of SO in strip liquor
2- 4Ion brings difficulty for the preparation high-purity cerium dioxide.
The present invention to achieve these goals, the measure of being adopted is: do not adopt sulfuric acid system to adopt hydrochloric acid system, use lower acidity so that be connected with existing extracting and separating, and do not adopt high acidity system.Use high manganese to carry out the classification oxidation, improve purity, high-level efficiency, high yield, low cost as oxygenant.
The objective of the invention is to realize as follows:
Re chloride with 0.1M～1.3M is made raw material, wherein contains cerium more than 8%, under the low acidity situation of 0.1～1.0M, makes oxygenant with the potassium permanganate solution of 1%～25% percent by weight, with 1.0～1.5MP
2O
4-kerosene is made organic phase, through 5～15 grades of extractions, and 7～35 grades of washings, 3～10 grades of back extractions prepare cerium oxide, and wherein the acidity of washing acid is the hydrochloric acid soln of 0.5～3.0M, and strip liquor is the H of 1.0～5.0MHCL and 1%～10%
2O
2Mixed solution.The stream of feed liquid, washing lotion, strip liquor ratio: 2～5: 1～3: 1～15, organic phase is 10～100: 1～15 with the stream ratio of strip liquor, potassium permanganate oxidation liquid adds in extraction section, with solid-liquid ratio be feed liquid: potassium permanganate=1～100: 1～15.Carry out the classification oxidation.Add organic phase in the first step, the 5th～15 grade adds feed liquid, and the 13rd grade～50 grades are the washing lotion inlet, and the 16th～51 grade is anti-liquid inlet.1～15 grade adds potassium permanganate oxidation liquid by example respectively.It is below 0.5% that few cerium mischmetal of first step water outlet contains cerium.Containing cerium in the strip liquor is 98～99.99%.This anti-liquid is heavy by grass, drying, calcination, must cerium oxide.
Combined process flow process of the present invention, details are as follows:
1. at first select organic phase, with kerosene dilution P
2O
4To P
2O
4Concentration is 1.0～1.5M, handles according to a conventional method then, uses to utilize.
2. selection stock liquid, making the rare earth total concn is the re chloride of 0.1～1.2M, and wherein containing cerium is more than 8%, and regulating acidity is between 0.1～1.0M.
3. selective oxidation liquid is mixed with 1～25% solution with potassium permanganate.
4. selection strip liquor: the hydrochloric acid soln of making acidity and be 1.0～5.0M wherein contains 1%～15% H
2O
4
5. selection washings: the hydrochloric acid soln of preparation 0.5M-3.0M is made washings.
6. carry out the fractionation extraction experiment, the first step is the 1st～15 grade of feeding liquid of inlet of organic phase, and adds potassium permanganate oxidation liquid by the feed liquid composition, and the 13rd～50 grade is washing lotion inlet, the 16th grade～51 grades, strip liquor inlet.The surplus liquid outlet of the first step is few cerium mischmetal solution, and containing cerium is below 0.5%, and anti-liquid outlet is for containing the pure cerium solution of cerium 98～99.99%.The stream ratio of each liquid is: feed liquid: washing lotion: organic phase=2～5: 1～3: 1～15, organic phase and anti-liquid be in a ratio of 10～100: 1: 15.
The technology of oxidation-extraction legal system preparing cerium oxide of the present invention, embodiment is as follows: but the garden that is not subjected to this enforcement.
[1] stock liquid: rare earth oxide solution: ∑ RxOy=0.86M,
∑ CexOy=0.44M, acidity=0.47M.
[2] organic phase: 1.5MP
2O
4-kerosin.
[3] washing lotion: 1.5MHCL washing lotion.
[4] anti-liquid: 3.0NHCL+2%H
2O
2Solution.
[5] oxidation liquid: 5%KMnO
4Press 0.3ml, 0.5ml, 1.5ml, 2ml, 2.5ml, 3ml, 7ml adding in 1～7 grade of extraction section of solution respectively.
[6] washing section is 15 grades, and stripping section is 5 grades.
[7] extraction phase ratio: feed liquid: washing lotion: organic=30: 18: 120.
[8] organic phase is compared with strip liquor: 24: 5.
[9] identical duration of contact in the extracting stage: 5 minutes so that its abundant balance.
[10] cerium content 0.3%, acidity 0.35N in the surplus liquid of the first step.
[11] Ce content 99.95% in the strip liquor, yield 99.0%.
[12] organic phase is washed with pure water, recycles.
Claims (7)
1, oxidation--extracting and separating prepares the technology of cerium oxide, it is characterized in that: the re chloride with 0.1M～1.2M is made raw material, wherein contains cerium more than 8%.Under the low acidity situation of 0.1～1.0M, make oxygenant with the potassium permanganate of 1%～25% percent by weight, with 1.0～1.5MP
2O
4--kerosene is made organic phase, through 5～15 grades of extractions, and 7～35 grades of washings, 98～99.99% cerium oxide is prepared purity and is in 3～10 grades of back extractions.
2, oxidation-extraction according to claim 1 separates the technology of preparation cerium oxide, and it is characterized in that: the acidity of washing acid is the hydrochloric acid soln of 0.5M～3.0M.
3, oxidation-extraction according to claim 1 prepares the technology of cerium oxide, it is characterized in that: strip liquor is the HCL of 1.0～5.0M and 1%～15% H
2O
4Mixed solution.
4, oxidation-extraction according to claim 1 prepares the technology of cerium oxide, it is characterized in that: the first step is the inlet of organic phase, and the 5th～15 grade is the feed liquid inlet, and the 13rd grade～50 grades are the washing lotion inlet, the 16th～51 grade of strip liquor inlet.
5, oxidation-extraction according to claim 1 prepares the technology of cerium oxide, it is characterized in that: feed liquid, washing lotion, being in a ratio of of organic phase: feed liquid: washing lotion: organic phase=(2～5: 1～3: 1～15) being in a ratio of of organic phase and strip liquor: 10～100: 1～5.
6, oxidation-extraction according to claim 1 prepares the technology of cerium oxide, it is characterized in that: 17～61 grades of outlets are the solution of cerium chloride by oxidation of purity 98～99.99%, and first step outlet extracts surplus liquid for the mixed chlorinated rare earth that contains 0.5% following cerium.
7, oxidation-extraction according to claim 1 prepares cerium oxide technology, it is characterized in that: mode of oxidizing is the classification oxidation, and feed liquid and oxidation liquor ratio are: 1～100: 1～15.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN91109808A CN1071706A (en) | 1991-10-19 | 1991-10-19 | The technology of cerium oxide purifying |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN91109808A CN1071706A (en) | 1991-10-19 | 1991-10-19 | The technology of cerium oxide purifying |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1071706A true CN1071706A (en) | 1993-05-05 |
Family
ID=4909994
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN91109808A Pending CN1071706A (en) | 1991-10-19 | 1991-10-19 | The technology of cerium oxide purifying |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1071706A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100386452C (en) * | 2006-09-22 | 2008-05-07 | 中国科学院长春应用化学研究所 | Method of dynamic continuous oxidation extracting cerium under potassium hypermanganate preferential extraction condition |
| CN101225469A (en) * | 2008-02-02 | 2008-07-23 | 谢光 | Active additive for improving leaching ratio of hydrometallurgy |
| CN101898779B (en) * | 2009-05-25 | 2013-05-01 | 甘肃稀土新材料股份有限公司 | Method for co-producing high-purity solution of cerous nitrate and high-purity solution of cerium chloride by oxidation-reduction extraction method |
| CN106048264A (en) * | 2016-07-13 | 2016-10-26 | 华东理工大学 | Method for recovering cerium from integral catalyst of waste vehicle tail gas purifier |
| CN110745857A (en) * | 2018-07-04 | 2020-02-04 | 乐山东承新材料有限公司 | Preparation method and product of high-purity clean cerium nitrate |
-
1991
- 1991-10-19 CN CN91109808A patent/CN1071706A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100386452C (en) * | 2006-09-22 | 2008-05-07 | 中国科学院长春应用化学研究所 | Method of dynamic continuous oxidation extracting cerium under potassium hypermanganate preferential extraction condition |
| CN101225469A (en) * | 2008-02-02 | 2008-07-23 | 谢光 | Active additive for improving leaching ratio of hydrometallurgy |
| CN101898779B (en) * | 2009-05-25 | 2013-05-01 | 甘肃稀土新材料股份有限公司 | Method for co-producing high-purity solution of cerous nitrate and high-purity solution of cerium chloride by oxidation-reduction extraction method |
| CN106048264A (en) * | 2016-07-13 | 2016-10-26 | 华东理工大学 | Method for recovering cerium from integral catalyst of waste vehicle tail gas purifier |
| CN106048264B (en) * | 2016-07-13 | 2018-04-17 | 华东理工大学 | The method that cerium is recycled from the integral catalyzer of junked-auto exhaust purifier |
| CN110745857A (en) * | 2018-07-04 | 2020-02-04 | 乐山东承新材料有限公司 | Preparation method and product of high-purity clean cerium nitrate |
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