CN1047110A - The novel method of from mishmetal, separating cerium dioxide - Google Patents
The novel method of from mishmetal, separating cerium dioxide Download PDFInfo
- Publication number
- CN1047110A CN1047110A CN89103042A CN89103042A CN1047110A CN 1047110 A CN1047110 A CN 1047110A CN 89103042 A CN89103042 A CN 89103042A CN 89103042 A CN89103042 A CN 89103042A CN 1047110 A CN1047110 A CN 1047110A
- Authority
- CN
- China
- Prior art keywords
- cerium
- mishmetal
- feed liquid
- rare earth
- cerium dioxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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
- C01F17/282—Sulfates
-
- 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
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
- C22B1/06—Sulfating roasting
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B59/00—Obtaining rare earth metals
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Geology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Geochemistry & Mineralogy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
With oxidation by ozone gas sulfuric acid of rare-earth concentrate roasting infusion, oxidation can make cerium ion become higher valence state and hydrolytic precipitation, thereby separate with other rare earth ion, gained precipitation after filtration, just can to obtain purity behind 900 ℃ of high temperature sinterings be cerium dioxide more than 95% for washing, dry back, yield is higher than 99%, Ce/Re<0.5% in few cerium mischmetal.
Description
The invention belongs to technical field of wet metallurgy.
As everyone knows, metallic cerium and oxide compound thereof have important purposes in industrial production.But, because rare earth element is present among the raw mineral materials with the form of mishmetal, the oxide compound that will therefrom obtain higher cerium of purity or cerium must be through complicated separation purification means, do not separate a small amount of completely cerium often as a kind of impurity element, have a strong impact on the purity and the use range of all the other rare earth compounds.Before the present invention, the method that is used for separating purifying cerium both at home and abroad can find from following document:
1, Liu Zezheng etc., rare earth (1), 1,1983.
2, Luo Zhenhua etc., the 4th national rare earth chemistry and the academic meeting paper summary of hydrometallurgy compilation, first volume 2-18-1
3, archive office of Gansu Rare Earth Co., low-grade cerium oxide production technology
4, rare earth is write group, rare earth, (on) (metallurgical industry press) 315-328,522-533(1978)
5、Campbell,D.O.J.Inory????????and????????Nucl????????Chem.35.(1)3911-19,1973.
From the existing production technology that above-mentioned document provided, mainly contain solvent (P
507Deng) extraction separation method and potassium permanganate oxidation oxalic acid reduction partition method is actually used in industrial production, the former costs an arm and a leg owing to organic solvent, industrial implementation equipment is complicated and make product cost too high, and reagent prices such as potassium permanganate that uses in latter's method and oxalic acid are still higher.Aftertreatment complexity and separating effect are undesirable, make the yield of cerium on the low side.Purity is not high.The objective of the invention is for industrial production provides a kind of cost lower, easy and simple to handle, the yield of cerium higher with product purity and separate the back cerium the little separation method of residual quantity.
The present invention directly uses the sulfuric acid baking infusion of rare earth ore concentrate as raw material, carries out ozone oxidation and separates, and controls the pH value of solution with adding rare earth hydrate solid way art in the sepn process.99% cerium can effectively be separated.Products obtained therefrom cerium dioxide purity is more than 95%, cerium content is less than 0.5% in the back cerium mischmetal less of separation, its effect is better than institute's reported method in any prior art, and the agents useful for same cost is lower, treating processes is simple, can not introduce new impurity, equipment used is simple, and the ozone oxidation device can be made arbitrary specification.Thereby, use method of the present invention from mishmetal, to separate cerium dioxide, outstanding characteristics are: method is easy, separates thoroughly, and raw material is easy to get, and cost is lower, remarkable in economical benefits.
Implementation process of the present invention is as follows:
1, feed liquid treating processes:
Rare earth ore concentrate is added infusion behind the concentrated sulfuric acid roasting, and (as representing rare earth ion with Re, then the hydroxide solids of mishmetal consists of: Re(OH) to add the hydroxide solids of mishmetal
3NH
2O), the pH value that makes feed liquid is between the 4-6, adds suitable vitriol and (can be K
2SO
4, Na
2SO
4, (NH
4)
2SO
4, MgSO
4Deng) make the sulfate concentration in the feed liquid and the concentration ratio of rare earth ion be: [SO
2-
4]/[Re
3+] greater than 1.6, the rare earth metal content in the solution is with Re
2O
3Count in every liter of 50g.
2, ozone oxidation process:
Above-mentioned feed liquid is placed a sizeable container, under constantly stirring, feeds ozone gas, have cerium ion in the feed liquid only following reaction takes place:
After reacting completely, solution is filtered, be precipitated as Ce(OH)
2SO
4, filtrate can be used raw material as other rare earth ion separation, in this ozone oxidation process, needs heating so that feed temperature is 40-90 ℃.
3, with Ce(OH)
2SO
4Be converted into products C eO
2
With gained Ce(OH after the above-mentioned filtration)
2SO
4Behind washing and drying,, promptly get products C eO being higher than 850 ℃ of following calcinations
2
The present invention has an embodiment as follows:
Measure sulfuric acid of rare-earth concentrate roasting infusion 1000ml(and contain Re
2O
332 grams), adjusting makes SO
2-
4Concentration and Re
3+Concentration ratio is greater than 1.6, and the pH value that adds in the mixed rare earth hydroxide control reaction process is 4-6, heated solution, under agitation feed oxidation by ozone gas, the oxidation reaction solution that takes a morsel after seven hours is centrifugal, when cerium ion has been can not check in inspection in the clear liquid, with reacting liquid filtering, precipitation is behind washing and drying, place High Temperature Furnaces Heating Apparatus in 900 ℃ of calcinations one hour, get final product to such an extent that cerium dioxide 23.1 restrains purity 〉=95%, the rate of recovery of cerium is 99%, cerium content<0.5% in few cerium mischmetal.
Claims (2)
1, a kind of method of from mishmetal, separating cerium dioxide, the infusion that adds behind the sulfuric acid baking with rare earth ore concentrate is a raw material, it is characterized in that: the pH value of regulating feed liquid with the hydroxide solids of mishmetal is 4-6, with SO in the vitriol adjusting feed liquid
4 2-The concentration ratio of concentration and mixed rare earth ions was greater than 1.6: 1, and the heating feed liquid is isolated precipitation to feeding ozone in the feed liquid to cerium is oxidized fully after 40-90 ℃, and precipitation is through washing, drying and promptly get cerium dioxide after calcination under the temperature more than 850 ℃.
2, according to the said a kind of method of from mishmetal, separating cerium dioxide of claim 1, it is characterized in that: be used for regulating feed liquid SO
2-
4The vitriol of concentration can be MgSO
4, (NH
4)
2SO
4Na
2SO
4, K
2SO
4, etc. in any material.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN89103042A CN1021579C (en) | 1989-05-09 | 1989-05-09 | Process for separating cerium dioxicde from mixed rare earth |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN89103042A CN1021579C (en) | 1989-05-09 | 1989-05-09 | Process for separating cerium dioxicde from mixed rare earth |
Publications (2)
Publication Number | Publication Date |
---|---|
CN1047110A true CN1047110A (en) | 1990-11-21 |
CN1021579C CN1021579C (en) | 1993-07-14 |
Family
ID=4854958
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN89103042A Expired - Fee Related CN1021579C (en) | 1989-05-09 | 1989-05-09 | Process for separating cerium dioxicde from mixed rare earth |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN1021579C (en) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0541158A1 (en) * | 1991-11-06 | 1993-05-12 | SOLVAY (Société Anonyme) | Process for extracting cerium from an aqueous solution containing a mixture of rare earth elements |
CN104278164A (en) * | 2014-09-29 | 2015-01-14 | 乐山盛和稀土股份有限公司 | Treatment technique of rare earth fluorocarbonate ores with grade of 62-72% |
CN105907959A (en) * | 2016-05-16 | 2016-08-31 | 龙南县锦易矿业有限公司 | Ammonia-free mining method for rare earth ore in south China |
CN108977675A (en) * | 2018-08-03 | 2018-12-11 | 江西理工大学 | A kind of method that anti-charging precipitating-baking inphases prepare low sulfur content rare earth oxide |
CN112981148A (en) * | 2021-02-08 | 2021-06-18 | 江西理工大学 | Method for separating cerium, calcium and magnesium by oxidizing, hydrolyzing and precipitating |
-
1989
- 1989-05-09 CN CN89103042A patent/CN1021579C/en not_active Expired - Fee Related
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0541158A1 (en) * | 1991-11-06 | 1993-05-12 | SOLVAY (Société Anonyme) | Process for extracting cerium from an aqueous solution containing a mixture of rare earth elements |
CN104278164A (en) * | 2014-09-29 | 2015-01-14 | 乐山盛和稀土股份有限公司 | Treatment technique of rare earth fluorocarbonate ores with grade of 62-72% |
CN104278164B (en) * | 2014-09-29 | 2016-05-18 | 乐山盛和稀土股份有限公司 | Grade is at the fluorine carbonated rare earth ore deposit of 62%-72% treatment process |
CN105907959A (en) * | 2016-05-16 | 2016-08-31 | 龙南县锦易矿业有限公司 | Ammonia-free mining method for rare earth ore in south China |
CN108977675A (en) * | 2018-08-03 | 2018-12-11 | 江西理工大学 | A kind of method that anti-charging precipitating-baking inphases prepare low sulfur content rare earth oxide |
CN108977675B (en) * | 2018-08-03 | 2021-03-02 | 江西理工大学 | Method for preparing low-sulfur-content rare earth oxide by reverse feeding precipitation-staged roasting |
CN112981148A (en) * | 2021-02-08 | 2021-06-18 | 江西理工大学 | Method for separating cerium, calcium and magnesium by oxidizing, hydrolyzing and precipitating |
Also Published As
Publication number | Publication date |
---|---|
CN1021579C (en) | 1993-07-14 |
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