CN1202465A - Process for extracting cerium oxide from bastnaesite - Google Patents
Process for extracting cerium oxide from bastnaesite Download PDFInfo
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- CN1202465A CN1202465A CN 98112057 CN98112057A CN1202465A CN 1202465 A CN1202465 A CN 1202465A CN 98112057 CN98112057 CN 98112057 CN 98112057 A CN98112057 A CN 98112057A CN 1202465 A CN1202465 A CN 1202465A
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- cerium
- add
- alkali
- double salt
- rare earth
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Links
- 238000000034 method Methods 0.000 title claims description 15
- 229910000420 cerium oxide Inorganic materials 0.000 title claims description 13
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 title claims description 13
- 239000007788 liquid Substances 0.000 claims abstract description 61
- 239000003513 alkali Substances 0.000 claims abstract description 58
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 56
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 45
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 37
- 238000001556 precipitation Methods 0.000 claims abstract description 29
- 238000005406 washing Methods 0.000 claims abstract description 27
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 22
- 239000012286 potassium permanganate Substances 0.000 claims abstract description 18
- 239000002253 acid Substances 0.000 claims abstract description 16
- 238000001354 calcination Methods 0.000 claims abstract description 13
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 13
- 238000003916 acid precipitation Methods 0.000 claims abstract description 7
- 238000004090 dissolution Methods 0.000 claims abstract description 3
- 230000009466 transformation Effects 0.000 claims abstract description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 79
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 79
- 150000003839 salts Chemical class 0.000 claims description 56
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 46
- 239000012065 filter cake Substances 0.000 claims description 22
- 239000012452 mother liquor Substances 0.000 claims description 21
- 229940056729 sodium sulfate anhydrous Drugs 0.000 claims description 18
- -1 rare earth fluoride Chemical class 0.000 claims description 17
- 239000000706 filtrate Substances 0.000 claims description 16
- 230000003647 oxidation Effects 0.000 claims description 16
- 238000007254 oxidation reaction Methods 0.000 claims description 16
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 16
- JJEJDZONIFQNHG-UHFFFAOYSA-N [C+4].N Chemical compound [C+4].N JJEJDZONIFQNHG-UHFFFAOYSA-N 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 13
- 238000002386 leaching Methods 0.000 claims description 11
- 239000000047 product Substances 0.000 claims description 11
- GHLITDDQOMIBFS-UHFFFAOYSA-H cerium(3+);tricarbonate Chemical compound [Ce+3].[Ce+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O GHLITDDQOMIBFS-UHFFFAOYSA-H 0.000 claims description 10
- 239000003085 diluting agent Substances 0.000 claims description 10
- 238000009825 accumulation Methods 0.000 claims description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 9
- 238000004062 sedimentation Methods 0.000 claims description 9
- 238000002791 soaking Methods 0.000 claims description 8
- 239000002689 soil Substances 0.000 claims description 8
- 238000010792 warming Methods 0.000 claims description 8
- 238000005352 clarification Methods 0.000 claims description 7
- 239000012530 fluid Substances 0.000 claims description 7
- 229910052746 lanthanum Inorganic materials 0.000 claims description 7
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- ZMZNLKYXLARXFY-UHFFFAOYSA-H cerium(3+);oxalate Chemical compound [Ce+3].[Ce+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O ZMZNLKYXLARXFY-UHFFFAOYSA-H 0.000 claims description 6
- 239000012141 concentrate Substances 0.000 claims description 6
- 238000007599 discharging Methods 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 238000006386 neutralization reaction Methods 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 claims description 5
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 4
- 238000005554 pickling Methods 0.000 claims description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 4
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 239000011737 fluorine Substances 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 3
- 239000006210 lotion Substances 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- 241000370738 Chlorion Species 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 241001274216 Naso Species 0.000 claims 1
- 238000000605 extraction Methods 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 25
- 238000004458 analytical method Methods 0.000 description 14
- 238000003756 stirring Methods 0.000 description 12
- 238000007654 immersion Methods 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 10
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 9
- 238000005189 flocculation Methods 0.000 description 8
- 230000016615 flocculation Effects 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 6
- 229910052801 chlorine Inorganic materials 0.000 description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000001117 sulphuric acid Substances 0.000 description 4
- 235000011149 sulphuric acid Nutrition 0.000 description 4
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 3
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 3
- 239000001099 ammonium carbonate Substances 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000002893 slag Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 210000005056 cell body Anatomy 0.000 description 2
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000010413 mother solution Substances 0.000 description 2
- 238000004451 qualitative analysis Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 229960003010 sodium sulfate Drugs 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- GXDMSPJKVWIJRG-UHFFFAOYSA-N O(O)O.[Th] Chemical compound O(O)O.[Th] GXDMSPJKVWIJRG-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 238000005188 flotation Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- GJEZFXDASHZTRO-UHFFFAOYSA-N iron thorium Chemical compound [Fe].[Fe].[Fe].[Fe].[Fe].[Th] GJEZFXDASHZTRO-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000001698 pyrogenic effect Effects 0.000 description 1
Landscapes
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The extraction process includes the steps of calcination, lixiviation, twice precipitation, alkali transformation,acid dissolution, oxalic acid precipitation and burning. After calcination, the bastnaesite ore is first soaked in dilute hydrochloric acid, and the riched bastnaesite is then neutralized and boiled with alkali. After washing, the material liquid is added with potassium permanganate to become red and then added with concentrated sulfuric acid to dissolve its rare earth into solution.
Description
The present invention with from hamartite or relevant based on the technology of extracting cerium oxide the mixing ore deposit of hamartite, especially to extract the technology of cerium oxide from hamartite relevant with utilizing roasting to decompose---dilute sulphuric acid leaching---double salt precipitation method.
The processing step of existing chemical process separation of oxygenated cerium is as follows:
1, roasting:
At a certain temperature, make hamartite resolve into rare earth oxide and oxyfluoride, and emit carbon dioxide, meanwhile, cerium wherein is oxidized to tetravalence by airborne oxygen.
2, leach:
With the dissolving of the rare earth in the product of roasting, quadrivalent cerium can stably exist in solution with dilute sulphuric acid.
3, primary sedimentation:
In leach liquor, add Sodium sulfate anhydrous.min(99), can be with wherein non-Ce rare earth precipitation, and the quadrivalent cerium that will be difficult to form double salt precipitation is stayed in the solution, thus reached cerium and the isolating purpose of non-Ce rare earth.
4, secondary sedimentation:
The primary sedimentation mother liquor adds ferrous sulfate, and quadrivalent cerium is reduced into trivalent cerium, trivalent cerium and superfluous sodium sulfate generation cerium double salt precipitation.
5, alkali transforms:
Cerium or non-Ce rare earth double salt, available caustic soda is converted into cerous hydroxide or rare earth hydrate.
6, in the alkali conversion process, except that generating rare-earth hydroxide, also generate a large amount of sodium sulfate, in addition, also have part to remain alkali.Adopt washing with the soluble impurity eccysis.
7, excellent molten:
Washing product (rare earth hydrate) is used dissolving with hydrochloric acid, generate rare earth chloride, and in the rare earth hydrate, a small amount of quadrivalent cerium oxyhydroxide and iron, the thorium oxyhydroxide carried secretly is stayed then in the excellent molten cake.
8, acid is molten:
The cerous hydroxide dissolving with hydrochloric acid generates Cerium II Chloride.
9, oxalic acid precipitation:
In the solution of cerium chloride by oxidation, add oxalic acid, then cerium wherein forms the Sedemesis precipitation.
10, calcination:
Sedemesis at high temperature decomposes, and generates cerium oxide.
Existing technical process is longer, and the solid-liquid conversion times is many, and the leaching yield and the oxidation ratio of hamartite are low, and alkali commentaries on classics alkali consumption is bigger, and the rare earth yield is low, and production cost is higher.
It is low to the purpose of this invention is to provide a kind of production cost, yield height of cerium, overall process yield height, the method that proposes cerium oxide from hamartite that facility investment is few.
The present invention is achieved in that
The present invention includes roasting, leach, primary sedimentation, secondary sedimentation, alkali transforms, the acid dissolving, oxalic acid precipitation, the calcination step is characterized in that behind the hamartite calcination steps, and is earlier that product of roasting is excellent molten with dilute hydrochloric acid, give earlier from going out a large amount of trivalent rare earths and Ce (IV), rich cerium ore deposit after excellent the soaking is boiled with the alkali neutralization, transform the excellent rare earth fluoride that soaks generation, and with chlorine rare earth and the hydrochloric acid neutralization precipitation carried secretly in the rich cerium ore deposit, after washing, in feed liquid, add potassium permanganate feed liquid is taken on a red color, add the vitriol oil again, quadrivalent cerium is leached in solution the dissolving of the rare earth in the rich cerium ore deposit.
In the primary sedimentation step of the present invention, Sodium sulfate anhydrous.min(99) adopts secondary to add, and promptly adds in the acidleach diluent for the first time, gets the cerium mother liquor after the filtration, adds into Sodium sulfate anhydrous.min(99) in the cerium mother liquor for the second time, avoids the cerium mother liquor to be reduced into secondary double salt and produces rare earth fluoride.
In the alkali step of converting of the present invention, secondary double salt transforms and adopts the carbon ammonium to transform, and the adding mode adopts counter adding, and is about to secondary double salt and adds in the carbon ammonium.
Its processing step of the present invention is as follows:
(1) roasting: with hamartite oxidizing roasting, temperature is 500-550 ℃,
(2) roasted ore leaching: roasted ore is added in the dilute hydrochloric acid that acidity is 1.0-1.5N, trivalent rare earth oxide amount=0.9-11 in hydrochloric acid consumption/roasted ore, temperature≤60 ℃, leaching time 〉=2 hour, with pickling liquor filter clear liquid and rich cerium ore deposit,
(3) the complete molten rich cerium of sulfuric acid ore deposit: in rich cerium ore deposit, add alkali lye and boil, chlorion and small amount of fluorine are removed in washing, till adding potassium permanganate takes on a red color feed liquid, slowly add the vitriol oil, acidity of sulfuric acid 〉=6N, the vitriol oil (〉=98%) consumption are 0.6 times of roasted ore weight, temperature is more than 90 ℃, time 〉=1 hour, after the roasted ore dissolving, thin up is to rare earth concentration TCeO
250-60g/L is warming up to 75-80 ℃,
(4) double salt precipitations:
Adding Sodium sulfate anhydrous.min(99) or alkali in the sulfuric acid dissolution diluent changes liquid separation trivalent rare earth and Ce (IV), and the Sodium sulfate anhydrous.min(99) add-on is CeO in the diluent
2The 1.3-1.5 of weight doubly makes Ce in the diluent
4+/ TCeO
2〉=99%, it is CeO in the diluent that alkali changes the liquid add-on
2Weight * (0.21-0.24)/alkali commentaries on classics liquid [Na
+] (liter), filter at once after the insulated and stirred, get a double salt filter cake, with the Na of 0.05mol/L
2SO
4Hot solution washing leaching cake, washing lotion incorporate in the filtrate the cerium mother liquor,
(5) secondary double salt precipitation:, add into Sodium sulfate anhydrous.min(99) amount 〉=TCeO with cerium mother liquor heat temperature raising 〉=80 ℃
2* volume * (0.5-0.8), add green vitriol or SO
2Gas or S-WAT make Ce in the solution
4+=0, insulated and stirred is filtered, and gets secondary double salt filter cake, removes filtrate,
(6) alkali changes a double salt filter cake: a double salt filter cake is added NaOH solution transform, to free alkalinity＜0.5N, washing alkali changes filter cake, and making pH is 7-8, filters to such an extent that rich lanthanum alkali changes cake,
(7) alkali changes secondary double salt filter cake, according to the processing condition alkali of (6) change cerous hydroxide or transform with the carbon ammonium, the processing condition of carbon ammonium conversion are as follows:
The carbon ammonium is dissolved as 200～300g/L concentration, adds ammoniacal liquor or NaOH and transfer pH8-9, be warming up to 40-60 ℃, press the carbon ammonium: double salt CeO
2=1.7-2.2: 1, slowly add secondary double salt filter cake in ammonium fluid, reaction times 〉=2 hour, transformation efficiency 〉=98%, washing transforms filter cake, makes SO
4 2-(solution)＜0.05g/l, the washing solid: liquid=1: 15～20, filter, dewater cerous carbonate.
(8) excellent molten, the rich lanthanum alkali of preorder step gained cake is added potassium permanganate (or add hydrogen peroxide to precipitation be yellow) till redness just occurred, slowly adding step 2) the salt pickling liquor (or adding hydrochloric acid) of gained is stabilized in 3.0～3.5 to PH, stirred 0.5-1 hour, add ammoniacal liquor and transfer pH to 4.0-4.5, add potassium permanganate (or H
2O
2+ NH
4OH) oxidation removes cerium and makes solution C eO
2/ TREO＜5% adds BaCl
2Make SO
4 2-/ TREO＜0.15% boils, and clarification is filtered, and gets lanthanum concentrate rare earth chloride liquid and accumulation of salt in the surface soil cake.
(9) acid is molten: accumulation of salt in the surface soil cake is added Na
2OH makes pH 〉=10, boils, and washes and makes pH to 7-8 1-2 time, adds potassium permanganate feed liquid is taken on a red color, and slowly adds sulfuric acid, the sulfuric acid consumption: filter cake REO: H
2SO
4〉=1: 1.1-1.2, filter ℃ time 〉=1, temperature 〉=90 hour, keeps filtrate, the discharging filter residue, filtrate is gone step (4).
(10) calcination: the cerous carbonate calcination that step (7) is produced gets cerium oxide product.
(11) with the cerous hydroxide of step (7) gained or cerous carbonate with the filtrate of gained in the dissolving with hydrochloric acid and after the removal of impurities with alkali or oxalic acid or carbon ammonium precipitation, filter, go filtrate, with the cerous hydroxide filter cake dry cerium oxide, Sedemesis, cerous carbonate calcination are got cerium oxide product.
The present invention has following advantage:
1, the present invention with the hamartite roasting after, earlier excellent molten through dilute hydrochloric acid, give and separate a large amount of trivalent rare earths and Ce (IV) earlier, the excellent rate REO that soaks can reach 45%, the excellent rate of soaking of trivalent rare earth can reach 85%, CeO in the excellent immersion liquid
2/ TREO can reach≤and 5%, boil with the alkali neutralization in the excellent rich cerium ore deposit, back of soaking, and has both transformed the excellent rare earth fluoride that soaks generation, again with rare earth chloride and the hydrochloric acid neutralization precipitation carried secretly in the rich cerium ore deposit, can remove CI through washing
-And NaF, for the complete molten raising leaching yield of dilute sulphuric acid has been created condition, before adding sulfuric acid, add a small amount of potassium permanganate simultaneously sulfuric acid immersion liquid cerium oxidation ratio is improved, so that improve the double salt separating effect.Therefore, this technology is remarkable to leaching yield and the cerium oxidation ratio effect that improves and improve the less-than-ideal hamartite of roasting.
2,, thereby make CeO in the sulfuric acid immersion liquid in rich cerium ore deposit because a large amount of trivalent rare earth directly forms rare earth chloride when soaking in that dilute hydrochloric acid is excellent
2/ TREO can reach 85%, separates to double salt and has created good condition, makes Sodium sulfate anhydrous.min(99), and sulfuric acid and double salt alkali transform required NaOH consumption and significantly descends, and the accumulation rate of Ce (IV) in the cerium mother liquor significantly improves, and can reach 65-80%, and one time the double salt amount significantly reduces.
3, Sodium sulfate anhydrous.min(99) adding of the present invention adopts secondary to add, and adds Sodium sulfate anhydrous.min(99) for the first time and makes cerium mother liquor purity 〉=99%, adds for the second time and avoids the cerium mother liquor to be reduced into secondary double salt generation rare earth fluoride, can improve the separating effect of cerium.
4, secondary double salt of the present invention transforms and adopts the carbon ammonium to transform, and the adding mode adopts counter adding, and has both reduced production cost, can reduce SO again
4 2-
5, the present invention lumps together precipitation with double salt and sulphur acid leaching residue, has both changed and has soaked the slag strainability, can make simultaneously to soak the rare earth that does not leach in the slag and form oxyhydroxide after alkali changes, and helps improving the rare earth yield.
6, the present invention gives to roasted ore that first hydrochloric acid is excellent to soak processing, add alkali again and transform after washing to pH7-8, alkali consumption: NaOH: roasted ore REO=0.40-0.80: 1 (weight ratio), temperature＞90 ℃, time 〉=2 hour, can remove a large amount of iron, fluorine, after adding potassium permanganate,, can in filtrate, directly extract Ce (IV) with extraction agent if at the complete molten after-filtration of sulfuric acid, can reduce and eliminate collection, carry cerium for undoubtedly the hamartite extraction process new way is provided except that getting agent poisoning emulsion.
In a word: the present invention is than traditional chemical method process for extracting cerium, and it is low to have a production cost, yield height of cerium, and overall process yield height, facility investment waits significant advantage less.
Following is embodiments of the invention: first part: pyrogenic process one, concentrate oxidizing roasting: ingredient requirement: TREO 〉=60%, and gravity treatment, magnetic concentration, (flotation ore deposit) raw material is a Sichuan Mianning hamartite, chemical formula: REF
3RE
2(CO
3)
3Or REFCO
3Processing condition: maturing temperature: 500～550 ℃ of temperature of charge
Roasting time: 500～550 ℃ of technical requirementss in following 1 hour: cerium oxidation ratio 〉=95% middle control analysis project: 1. concentrate TREO TCeO
22. roasted ore TCeO
2Ce
4+Two, calcination: raw material: Sedemesis, cerous carbonate processing condition: temperature: 850～900 ℃ (output product TREO 〉=98.5%)
900～950 ℃ (output product TREO 〉=99%)
Time: technical requirements in 1 hour: product TREO 〉=98.5% (or 99%)
CeO
2/ TREO 〉=98.5% (or 99%) middle control analysis project: cerium oxide TREO, TCeO
2
Second section cerium extraction one, the excellent soaking technology condition of roasted ore: dilute hydrochloric acid acidity＜1.5N
Add hydrochloric acid: hydrochloric acid o'clock is added in pH 〉=1.5, time 〉=30 minute
Temperature: 45-55 ℃
Time: 2h
The technical hydrochloric acid consumption: the 1.0-1.1 of roasted ore trivalent rare earth theoretical amount doubly, i.e. roasted ore REO (total amount): technical hydrochloric acid=1 ton: 1.0-1.1m
3Technical requirements: excellent immersion liquid: TREO 〉=70g/l, TCeO
2/ TREO≤10%.Operation: 1/2 technical hydrochloric acid of calculated amount is put into reactive tank, and thin up is to concentration≤1.5N simultaneously.Start stirring system, drop into quantitative roasted ore, heat temperature raising to 45 ℃ stops heating, surveys pH 〉=1.5 and o'clock begins slowly to add spent acid, mends the acid time to be not less than 30 minutes, reacts to 2h.Add DA-III flocculation agent 5-10 liter, stop to stir clarification immediately.Record feed liquid cumulative volume V, TREO, TCeO are surveyed in sampling (clear liquid)
2The excellent soaking pit of hydrochloric acid (being as the criterion not siphon away precipitation and to exhaust as far as possible) is gone in careful siphon, clear liquid.In precipitation (being rich cerium ore deposit), add adjusting PH with base 11-13, heated and boiled 0.5h.(if press extraction process, the NaOH consumption is roasted ore REO * 0.4-0.8, alkali concn 50%, heated and boiled 2-4h), thin up adds PHP-III flocculation agent 5-10 liter to certain volume, stops to stir, and clarifies siphon discharging clear liquid 1-2 hour.Wash 1-2 time, pH7-8 drains clear liquid.
The middle control analysis project:
1. excellent immersion liquid TREO, TCeO
2, H
+
2. the excellent material liquid volume V that soaks:
3. the excellent leaching yield of soaking:
Two, the molten rich cerium of auric sulfate ore deposit:
Processing condition: acidity: 6N (H
2SO
4)
Temperature: more than 90 ℃
Time: 1 hour
Gu: liquid=1: 4～4.2
Sulfuric acid (〉=98%) consumption=666.7 (the excellent molten solubility rate of 1-)
(liter)/ton oxidized ore
Promptly=roasted ore * 0.6
Operate: start and stir, add the industrial sulphuric acid that potassium permanganate makes the slow adding of cerium oxidation ratio 〉=95% calculated amount in rich cerium ore deposit, heating rises to more than 90 ℃ temperature, insulated and stirred 1 hour, and thin up is to rare earth concentration TOeO
250～60g/l, record material liquid volume V, sampling (clear liquid) is TREO, TCeO then
2, be warming up to 75～80 ℃.
Middle control analysis project: sulfuric acid solubility rate TREO TCeO
2
Three, double salt precipitation:
Processing condition: temperature: 70～80 ℃
Time: 1 hour
TCeO in Sodium sulfate anhydrous.min(99) add-on=immersion liquid
2Concentration * immersion fluid
Long-pending * 1.3～1.5
Alkali changes TCeO in liquid add-on=immersion liquid
2Concentration * immersion fluid
Long-pending * 0.21～0.24/ alkali changes liquid [Na
+] (liter)
Technical requirements: cerium mother liquor TCeO
2/ REO 〉=99% (or Ce
4+/ TCeO
2〉=99%)
Operation: under 75～80 ℃, added Sodium sulfate anhydrous.min(99) (or alkali commentaries on classics liquid) insulated and stirred 1 hour by calculated amount, filter at once, filtrate is gone into the cerium mother liquid tank.Precipitation can 0.05mol/LNa
2SO
4Hot solution washing 1 time, washing lotion is incorporated the cerium mother liquor into.
The middle control analysis project:
1. alkali changes liquid [Na
+]
2. cerium mother liquor TCeO
2Ce
4+
Four, the complete molten accumulation of salt in the surface soil cake of sulfuric acid
Processing condition: acidity: 5～6N (H
2SO
4)
Temperature: more than 90 ℃
Time: 1 hour
The sulfuric acid consumption:
H
2SO
4: accumulation of salt in the surface soil cake (weight in wet base)=1M
3: 4 tons
Operation: accumulation of salt in the surface soil cake is metered into reactive tank, adds water and stir, add bicarbonate of ammonia (or liquid caustic soda) and transfer pH7 (PH10), wash 2～3 times, add the DA-III clarification, the siphon clear liquid.Start and stir (add a little potassium permanganate and make cerium oxidation ratio 〉=95%), quantitatively carefully slowly add sulfuric acid, be warming up to more than 90 ℃, insulated and stirred 1 hour, clarified 2～4 hours, siphon clear liquid desulfuration acid solution storage tank (going a double salt to separate), pulp water is washed filtration (or press filtration) discharging, and filtrate is incorporated storage tank into.
Five, secondary double salt precipitation:
Processing condition: temperature 〉=90 ℃
Time: 1 hour Sodium sulfate anhydrous.min(99) additional amount=cerium mother solution C e
4+* volume * 0.5～0.8
Green vitriol add-on: quadrivalent cerium concentration * volume * 1.6 in the cerium mother liquor
SO
2Gas usage: till no longer generation precipitation of feeding
S-WAT consumption: quadrivalent cerium concentration * volume * 0.5 in the cerium mother liquor
H251S consumption: tetravalence concentration * volume * 0.056～0.05 in the cerium mother liquor
Technical requirements: Ce in the clear liquid
4+=0
Operation: cerium mother liquor in the reactive tank is heated to 80～90 ℃, adds Sodium sulfate anhydrous.min(99), add green vitriol again and (or feed SO by calculated amount
2Gas, or add S-WAT or H251S) to Ce
4+=0, insulated and stirred 1 hour is promptly filtered.
The middle control analysis project:
1. cerium mother solution C e
4+
2. precipitate clear liquid Ce
4+(but qualitative analysis)
Six, double salt transforms:
(1) alkali transforms
Processing condition: temperature 〉=90 ℃
Time: 1～1.5 hour
Caustic soda consumption: REO (CeO
2): NaOH=1: 0.9-1.0
Technical requirements: alkali rate of rotation 〉=98%, free alkalinity＜0.5N
Operate: add a certain amount of liquid caustic soda earlier in the alkali turn trough, add once then or secondary double salt filter cake, control pH＞13 transform 1～1.5 hour, sample presentation survey alkali rate of rotation 〉=more than 98%, pump into the washing bath washing.
Middle control analysis project: the alkali rate of rotation [OH that dissociates
-]
(2) bicarbonate of ammonia transforms (only being applicable to secondary double salt)
Processing condition: temperature: 40～60 ℃
Time: 1～2 hour
Bicarbonate of ammonia consumption: secondary double salt (weight in wet base): NH
4HCO
3
=1: 0.5～0.6 (weight ratio)
Washing: Gu: liquid=1: 15-20, washing terminal point SO
4 2-＜0.5g/l
Operation: in the alkali turn trough, add a certain amount of NH earlier
4HCO
3Add the solution that water is made into concentration 200～300g/l, add liquid caustic soda or ammoniacal liquor and make pH8～9, be warming up to 40～60 ℃, start and stir, slowly add secondary double salt filter cake by calculated amount then, insulated and stirred reaction 1～2h is till reacting completely.Dilute with water adds PAM-II flocculation agent clarification 2 hours, and clear liquid is discharged in siphon, and water at normal temperature is washed 7～10 times repeatedly, makes SO
4 2-＜0.05g/l filters, dehydration.
Seven, washing (alkali that alkali transforms is starched):
Processing condition: temperature: 60～70 ℃
Middle control analysis project: SO
4 2-
Eight, the complete molten cerous hydroxide of hydrochloric acid:
Processing condition: temperature:＞80 ℃
Time: 2-3 hour
Final pH: 4.0-4.5
BaCl
2Consumption: SO
4 2-: BaCl
2=1: 2.5 (to producing chlorine
Adopt when changing cerium)
Technical requirements: SO
4 2-/ TCeO
2≤ 0.15% (adopting when producing Cerium II Chloride)
Operation: technical hydrochloric acid is put into sour fluid bowl, volume surpass cell body long-pending 1/2, start exhaust blower and stirrer, heat simultaneously, slowly add cerous hydroxide, after material finishes, pH is stabilized in about 1.0～1.5, under temperature＜60 ℃, add a small amount of industrial hydrogen peroxide, just cerous hydroxide dissolves fully.Be warming up to 80 ℃, add ammoniacal liquor, adjust pH 4～4.5 makes iron thorium hydrolytic precipitation.If when producing Cerium II Chloride, should get solution and survey SO
4 2-, add BaCl
2Make SO
4 2-/ TCeO
2＜0.15%, boiled 15～20 minutes.Add 5～10 liters of DA-III flocculation agents, the siphon clear liquid filters (if slag CeO
2More, it is complete molten and need not to filter to continue next time hydrochloric acid).
Middle control analysis project: SO
4 2-, TCeO
2(requiring when producing Cerium II Chloride)
Nine, oxalic acid precipitation (or ammonium bicarbonate precipitation)
(1) oxalic acid precipitation:
Processing condition: temperature: more than 70 ℃
Time: 1 hour
CeO in oxalic acid add-on=acid solution
2Concentration * volume * 1.25
Technical requirements: moisture content in the Sedemesis≤40%
Operation: earlier acid solution is sent into settling bath, the amount volume is also measured CeO
2Concentration, be heated to more than 70 ℃ after, add oxalic acid by calculated amount, stirred 1 hour, the qualitative oxalic acid precipitation of use of take a sample is if can also produce precipitation, till then adding oxalic acid extremely no longer generation precipitating.Clarified 1 hour, and filtered centrifuge dehydration at once.
Middle control analysis project: acid solution CeO
2
Whether qualitative split pole precipitates fully
(2) ammonium bicarbonate precipitation
Processing condition: temperature: 80 ℃
Time: 〉=2h
Final pH value: 7-8
Ammonium bicarbonate solution: 200-300g/l adds ammoniacal liquor and transfers pH8-9
CeO in bicarbonate of ammonia consumption=acid solution
2Concentration * volume * 1.5-1.7
Technical requirements: CeO in the cerous carbonate
2〉=42%～45%
Operation: earlier acid solution is sent into settling bath, volume is no more than its volumetrical 2/3, and the amount volume is also measured CeO
2Concentration is heated to 80 ℃, the careful 200-300g/l that slowly adds, and the bicarbonate of ammonia acid solution of pH8～9 makes the pH7-8 clarification, adds about PAM-II flocculation agent 5L and clarifies, and clear liquid is drained in siphon, washes 1 time, filters centrifuge dehydration.
Middle control analysis project: solution of cerium chloride by oxidation CeO
2
Whether qualitative analysis precipitates fully
The third part lanthanum concentrate rare earth chloride
One, a double salt alkali changes (changeing with secondary double salt alkali)
Two, the alkali cake is excellent molten:
Processing condition: temperature: normal temperature, (50～60 ℃ of the excellent solubility temperatures of chlorine oxidation)
Time: 3～4 hours (excellent 5～6 hours molten time of chlorine oxidation)
Finally: pH4.0～4.5
Technical requirements: CeO in the excellent solution
2/ TREO≤5%TREO 〉=150g/l
Operate one: will wash a good double salt alkali changes cake, pumps into excellent fluid bowl, starts and stirs, and adds potassium permanganate and extremely just occurs till the redness, or add H
2O
2Make cerium oxidation ratio 〉=95%, add the excellent immersion liquid of hydrochloric acid and be stabilized in 3.0-3.5 or 4.0-4.5 (if the excellent immersion liquid deficiency of hydrochloric acid can carefully slowly add small amount of hydrochloric acid), stirring at normal temperature 1.0-1.5 hour to pH, add less ammonia (or bicarbonate of ammonia) and transfer pH4.0-4.5, add potassium permanganate (or H
2O
2+ NH
4OH) oxidation removes cerium, makes CeO
2/ TREO＜5%.Add DA-III flocculation agent 5-10 liter, stop to stir, clarified 2 hours, the siphon clear liquid removes rich cerium rare earth chloride solution storage tank, and slagging (being accumulation of salt in the surface soil cake) is filtered (or press filtration) filtrate and incorporated storage tank into.
Operation two: the oxyhydroxide after will wash is earlier sent into excellent fluid bowl, adds the water control REO concentration 100g/l that sizes mixing, and is heated to 50～60 ℃, and under agitation logical chlorine carries out oxidation, and chlorine flowrate is approximately greater than 4kg/h, and behind the 5-6h, pH value 3-3.5 gets solution survey TREO, CeO
2, if CeO
2/ TREO 〉=5% adds ammoniacal liquor and H
2O
2Remove cerium in pH 〉=4.5 oxidations, make CeO
2/ TREO≤5%.(or add potassium permanganate to only taking on a red color, add ammoniacal liquor simultaneously and transfer pH4.0-4.5).Boil, add DA-III flocculation agent 5-10 liter, clarified 2 hours, the siphon clear liquid goes to concentrate, and filters at once.
Middle control analysis project: excellent solution TREO, CeO
2
Three, condensing crystal:
Processing condition: 110 ℃ of temperature
Vacuum tightness 600mmHg
Vapor pressure 4-5Kg/cm
2
Technical requirements: TREO 〉=45.0-45.5%
Middle control analysis project: TREO TCeO
2
The 4th part cerous hydroxide
Processing condition: temperature 80-90 ℃
Time: 2h
Final pH 〉=10
Washing terminal point pH7
Technical requirements: press customer requirements and carry out
Operation: add in the alkali deep gouge a certain amount of sig water (volume be no more than cell body long-pending 1/2), be heated to 80 ℃, start stirring, slowly add the Cerium II Chloride feed liquid to pH 〉=10, boil, add PHP-III flocculation agent 5-10 liter, stop immediately stirring, clarified 1-2 hour, siphon discharging clear liquid is washed to pH7, clarification discharging clear liquid, precipitation is dewatered to technical requirements, packing.
Middle control analysis project: TREO TCeO
2W SO
4 2-
Claims (4)
1, a kind of method of extracting cerium oxide from hamartite, comprise roasting, leach primary sedimentation, secondary sedimentation, alkali transforms, the acid dissolving, oxalic acid precipitation, calcination step, it is characterized in that behind the hamartite calcination steps, earlier product of roasting is soaked with dilute hydrochloric acid is excellent, give and isolate a large amount of trivalent rare earths and Ce (IV) earlier, the rich cerium ore deposit after excellent the soaking is boiled with the alkali neutralization, transform the excellent rare earth fluoride that soaks generation, and, after washing, in feed liquid, add potassium permanganate feed liquid is taken on a red color rare earth chloride and the hydrochloric acid neutralization precipitation carried secretly in the rich cerium ore deposit, add the vitriol oil again with the dissolving of the rare earth in the rich cerium ore deposit, quadrivalent cerium is leached in solution.
2, method according to claim 1, it is characterized in that in the primary sedimentation step, Sodium sulfate anhydrous.min(99) adopts secondary to add, promptly in the acidleach diluent, add for the first time, get the cerium mother liquor after the filtration, in the cerium mother liquor, add for the second time, avoid the cerium mother liquor to be reduced into secondary double salt and produce rare earth fluoride into Sodium sulfate anhydrous.min(99).
3, method according to claim 1 and 2, in the alkali step of converting, secondary double salt transforms and adopts the carbon ammonium to transform, and the adding mode adopts counter adding, and is about to secondary double salt and adds in the carbon ammonium.
4, method according to claim 3 is characterized in that its processing step is as follows:
(1) roasting: with hamartite oxidizing roasting, temperature is 500-550 ℃,
(2) roasted ore leaching: roasted ore is added in the dilute hydrochloric acid that acidity is 1.0-1.5N trivalent rare earth oxide amount=0.9-1 in hydrochloric acid consumption/roasted ore: 1, temperature≤60 ℃, leaching time 〉=2 hour, with pickling liquor filter clear liquid and rich cerium ore deposit,
(3) the complete molten rich cerium of sulfuric acid ore deposit: in rich cerium ore deposit, add alkali lye and boil, chlorion and small amount of fluorine are removed in washing, till adding potassium permanganate takes on a red color feed liquid, slowly add the vitriol oil, acidity of sulfuric acid 〉=6N, the vitriol oil (〉=98%) consumption are 0.6 times of roasted ore weight, temperature is more than 90 ℃, time 〉=1 hour, after the roasted ore dissolving, thin up is to rare earth concentration TCeO
250-60g/L is warming up to 75-80 ℃,
(4) double salt precipitations:
Adding Sodium sulfate anhydrous.min(99) or alkali in the sulfuric acid dissolution diluent changes liquid separation trivalent rare earth and Ce (IV), and the Sodium sulfate anhydrous.min(99) add-on is CeO in the diluent
2The 1.3-1.5 of weight doubly makes Ce in the diluent
4+/ TCeO
2〉=99%, alkali changes CeO in liquid add-on=diluent
2Weight * (0.21-0.24)/alkali commentaries on classics liquid [Na
+] (liter), filter at once after the insulated and stirred, get a double salt filter cake, with the NaSO of 0.05mol/L
4Hot solution washing leaching cake, washing lotion incorporate in the filtrate the cerium mother liquor,
(5) secondary double salt precipitation:, add into Sodium sulfate anhydrous.min(99) amount 〉=TCeO with cerium mother liquor heat temperature raising 〉=80 ℃
2* volume * (0.5-0.8), add green vitriol or SO
2Gas or S-WAT make Ce in the solution
4+=0, insulated and stirred is filtered, and gets secondary double salt filter cake, removes filtrate,
(6) alkali changes a double salt filter cake: a double salt filter cake is added NaOH solution transform, to free alkalinity＜0.5N, washing alkali changes filter cake, and making pH is 7-8, filters to such an extent that rich lanthanum alkali changes cake,
(7) alkali changes secondary double salt filter cake, according to the processing condition alkali of (6) change cerous hydroxide or transform with the carbon ammonium, the processing condition of carbon ammonium conversion are as follows:
The carbon ammonium is dissolved as 200～300g/L concentration, adds ammoniacal liquor or NaOH and transfer pH8-9, be warming up to 40-60 ℃, press the carbon ammonium: double salt CeO
2=1.7-2.2: 1, slowly add secondary double salt filter cake in ammonium fluid, reaction times 〉=2 hour, transformation efficiency 〉=98%, washing transforms filter cake, makes SO
4 2-(solution)＜0.05g/l, the washing solid: liquid=1: 15～20, filter, dewater cerous carbonate.
(8) excellent molten, the rich lanthanum alkali of preorder step gained cake is added potassium permanganate (or add hydrogen peroxide to precipitation be yellow) till redness just occurred, the salt pickling liquor (or adding hydrochloric acid) that slowly adds step (2) gained is stabilized in 3.0～3.5 to PH, stirred 0.5-1 hour, add ammoniacal liquor and transfer pH to 4.0-4.5, add potassium permanganate (or H
2O
2+ NH
4OH) oxidation removes cerium and makes solution C eO
2/ TREO＜5% adds BaCl
2Make SO
4 2-/ TREO＜0.15% boils, and clarification is filtered, and gets lanthanum concentrate rare earth chloride liquid and accumulation of salt in the surface soil cake.
(9) acid is molten: accumulation of salt in the surface soil cake is added NaOH make pH 〉=10, boil, wash and make pH to 7-8 1-2 time, add potassium permanganate feed liquid is taken on a red color, slowly add sulfuric acid, the sulfuric acid consumption: filter cake REO: H
2SO
4〉=1: 1.1-1.2, temperature 〉=90 ℃, filter time 〉=1 hour, keeps filtrate, the discharging filter residue, filtrate is gone step (4).
(10) calcination: the cerous carbonate calcination that step (7) is produced gets cerium oxide product
(11) with the cerous hydroxide of step (7) gained or cerous carbonate with the filtrate of gained in the dissolving with hydrochloric acid and after the removal of impurities with alkali or oxalic acid or carbon ammonium precipitation, filter, go filtrate, with the cerous hydroxide filter cake dry cerous hydroxide, with Sedemesis, the scorching hot cerium oxide product that gets of cerous carbonate.
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|---|---|---|---|
| CN98112057A CN1077547C (en) | 1998-06-08 | 1998-06-08 | Process for extracting cerium oxide from bastnaesite |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98112057A CN1077547C (en) | 1998-06-08 | 1998-06-08 | Process for extracting cerium oxide from bastnaesite |
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| CN1202465A true CN1202465A (en) | 1998-12-23 |
| CN1077547C CN1077547C (en) | 2002-01-09 |
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ID=5221936
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|---|---|---|---|
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102146512A (en) * | 2010-02-08 | 2011-08-10 | 北京有色金属研究总院 | Hamartite smelting separation process |
| CN102399983A (en) * | 2010-09-10 | 2012-04-04 | 周毅 | Bastnaesite (bastnasite) pyrrole separation method |
| CN102899486A (en) * | 2012-11-05 | 2013-01-30 | 内蒙古科技大学 | Method for leaching bastnaesite-containing rare-earth ore concentrates in complexing mode and preparing kryocide |
| CN103395820A (en) * | 2013-08-09 | 2013-11-20 | 连云港市镧溪新材料有限公司 | Process of extraction of high-purity soluble cerium hydroxide from fluorine-carbon-cerium mixed rare earth carbonate |
| CN106119577A (en) * | 2016-07-29 | 2016-11-16 | 乐山东承新材料有限公司 | A kind of method that rare earth chloride is prepared in low-grade bastnaesite decomposition |
| CN108118166A (en) * | 2017-12-20 | 2018-06-05 | 宁波市鄞州智伴信息科技有限公司 | A kind of technique for being separated from Rare Earth Mine and extracting fluorine carbon cerium mischmetal |
| CN108928845A (en) * | 2018-08-01 | 2018-12-04 | 连云港高品再生资源有限公司 | The preparation method of high-purity cerium oxide for compact fluorescent lamp |
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Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1038261C (en) * | 1994-03-25 | 1998-05-06 | 颜克昌 | Impregnation process for separation of cerium oxide and mixed low-cerium rare earth elements |
| CN1114365A (en) * | 1994-06-30 | 1996-01-03 | 郭西林 | Process for extracting high-valence cerium from ore leachate directly |
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1998
- 1998-06-08 CN CN98112057A patent/CN1077547C/en not_active Expired - Fee Related
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102146512A (en) * | 2010-02-08 | 2011-08-10 | 北京有色金属研究总院 | Hamartite smelting separation process |
| CN102399983A (en) * | 2010-09-10 | 2012-04-04 | 周毅 | Bastnaesite (bastnasite) pyrrole separation method |
| CN102899486A (en) * | 2012-11-05 | 2013-01-30 | 内蒙古科技大学 | Method for leaching bastnaesite-containing rare-earth ore concentrates in complexing mode and preparing kryocide |
| CN102899486B (en) * | 2012-11-05 | 2014-04-02 | 内蒙古科技大学 | Method for leaching bastnaesite-containing rare-earth ore concentrates in complexing mode and preparing kryocide |
| CN103395820A (en) * | 2013-08-09 | 2013-11-20 | 连云港市镧溪新材料有限公司 | Process of extraction of high-purity soluble cerium hydroxide from fluorine-carbon-cerium mixed rare earth carbonate |
| CN103395820B (en) * | 2013-08-09 | 2015-10-28 | 连云港市镧溪新材料有限公司 | A kind of fluorine carbon cerium mixed rare earth carbonate extracts high purity solubility cerous hydroxide technique |
| CN106119577A (en) * | 2016-07-29 | 2016-11-16 | 乐山东承新材料有限公司 | A kind of method that rare earth chloride is prepared in low-grade bastnaesite decomposition |
| CN108118166A (en) * | 2017-12-20 | 2018-06-05 | 宁波市鄞州智伴信息科技有限公司 | A kind of technique for being separated from Rare Earth Mine and extracting fluorine carbon cerium mischmetal |
| CN108928845A (en) * | 2018-08-01 | 2018-12-04 | 连云港高品再生资源有限公司 | The preparation method of high-purity cerium oxide for compact fluorescent lamp |
| CN112410588A (en) * | 2020-11-18 | 2021-02-26 | 东北大学 | A kind of roasting process of bastnaesite |
| CN117186777A (en) * | 2023-11-07 | 2023-12-08 | 琥崧科技集团股份有限公司 | Polishing liquid used in semiconductor industry and preparation method thereof |
| CN117186777B (en) * | 2023-11-07 | 2024-01-26 | 琥崧科技集团股份有限公司 | Polishing liquid used in semiconductor industry and preparation method thereof |
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