CN1048531A - Preparation method of rare earth fluoride - Google Patents
Preparation method of rare earth fluoride Download PDFInfo
- Publication number
- CN1048531A CN1048531A CN89104555A CN89104555A CN1048531A CN 1048531 A CN1048531 A CN 1048531A CN 89104555 A CN89104555 A CN 89104555A CN 89104555 A CN89104555 A CN 89104555A CN 1048531 A CN1048531 A CN 1048531A
- Authority
- CN
- China
- Prior art keywords
- rare earth
- acid
- oxalic acid
- hydrofluoric acid
- earth metal
- 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.)
- Withdrawn
Links
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 123
- -1 rare earth fluoride Chemical class 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Natural products OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 161
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 130
- 239000007788 liquid Substances 0.000 claims abstract description 80
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 80
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 53
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims abstract description 26
- 239000002002 slurry Substances 0.000 claims abstract description 22
- 239000007864 aqueous solution Substances 0.000 claims abstract description 19
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000000926 separation method Methods 0.000 claims abstract description 11
- 239000002253 acid Substances 0.000 claims abstract description 7
- 238000001556 precipitation Methods 0.000 claims abstract description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 6
- 150000003839 salts Chemical class 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 230000002378 acidificating effect Effects 0.000 claims description 18
- 239000013078 crystal Substances 0.000 claims description 12
- 238000013019 agitation Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 229910002651 NO3 Inorganic materials 0.000 claims description 6
- 238000003916 acid precipitation Methods 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 25
- 238000001914 filtration Methods 0.000 abstract description 18
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract description 16
- 239000011737 fluorine Substances 0.000 abstract description 16
- 229910052731 fluorine Inorganic materials 0.000 abstract description 16
- 238000011084 recovery Methods 0.000 abstract description 11
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 7
- 238000012797 qualification Methods 0.000 abstract description 3
- 239000002351 wastewater Substances 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract 1
- 239000000047 product Substances 0.000 description 26
- 150000001875 compounds Chemical class 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 229910052684 Cerium Inorganic materials 0.000 description 8
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 8
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 8
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 8
- 238000003672 processing method Methods 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 6
- CMIHHWBVHJVIGI-UHFFFAOYSA-N gadolinium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Gd+3].[Gd+3] CMIHHWBVHJVIGI-UHFFFAOYSA-N 0.000 description 6
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 6
- 238000000247 postprecipitation Methods 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 230000018044 dehydration Effects 0.000 description 4
- 238000006297 dehydration reaction Methods 0.000 description 4
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 description 4
- 101100215615 Arabidopsis thaliana ADO2 gene Proteins 0.000 description 3
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000000084 colloidal system Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 3
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 3
- FKTOIHSPIPYAPE-UHFFFAOYSA-N samarium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Sm+3].[Sm+3] FKTOIHSPIPYAPE-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 229910003317 GdCl3 Inorganic materials 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 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 description 2
- 238000005352 clarification Methods 0.000 description 2
- 238000004737 colorimetric analysis Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- MEANOSLIBWSCIT-UHFFFAOYSA-K gadolinium trichloride Chemical compound Cl[Gd](Cl)Cl MEANOSLIBWSCIT-UHFFFAOYSA-K 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- ATINCSYRHURBSP-UHFFFAOYSA-K neodymium(iii) chloride Chemical compound Cl[Nd](Cl)Cl ATINCSYRHURBSP-UHFFFAOYSA-K 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- LHBNLZDGIPPZLL-UHFFFAOYSA-K praseodymium(iii) chloride Chemical compound Cl[Pr](Cl)Cl LHBNLZDGIPPZLL-UHFFFAOYSA-K 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229960001866 silicon dioxide Drugs 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 102100024348 Beta-adducin Human genes 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 241000370738 Chlorion Species 0.000 description 1
- KOLOHTSFJKVHEP-UHFFFAOYSA-L EDTA monomagnesium salt Chemical compound [Mg+2].[O-]C(=O)C[NH+](CC([O-])=O)CC[NH+](CC([O-])=O)CC([O-])=O KOLOHTSFJKVHEP-UHFFFAOYSA-L 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 101000689619 Homo sapiens Beta-adducin Proteins 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- QCCDYNYSHILRDG-UHFFFAOYSA-K cerium(3+);trifluoride Chemical compound [F-].[F-].[F-].[Ce+3] QCCDYNYSHILRDG-UHFFFAOYSA-K 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- GEZAXHSNIQTPMM-UHFFFAOYSA-N dysprosium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Dy+3].[Dy+3] GEZAXHSNIQTPMM-UHFFFAOYSA-N 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- AEBZCFFCDTZXHP-UHFFFAOYSA-N europium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Eu+3].[Eu+3] AEBZCFFCDTZXHP-UHFFFAOYSA-N 0.000 description 1
- IMBKASBLAKCLEM-UHFFFAOYSA-L ferrous ammonium sulfate (anhydrous) Chemical compound [NH4+].[NH4+].[Fe+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O IMBKASBLAKCLEM-UHFFFAOYSA-L 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 239000003605 opacifier Substances 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- AMWVZPDSWLOFKA-UHFFFAOYSA-N phosphanylidynemolybdenum Chemical compound [Mo]#P AMWVZPDSWLOFKA-UHFFFAOYSA-N 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- VGBPIHVLVSGJGR-UHFFFAOYSA-N thorium(4+);tetranitrate Chemical compound [Th+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VGBPIHVLVSGJGR-UHFFFAOYSA-N 0.000 description 1
- BYMUNNMMXKDFEZ-UHFFFAOYSA-K trifluorolanthanum Chemical compound F[La](F)F BYMUNNMMXKDFEZ-UHFFFAOYSA-K 0.000 description 1
- 238000004879 turbidimetry Methods 0.000 description 1
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
- C01F17/253—Halides
- C01F17/265—Fluorides
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The present invention relates to the preparation of rare earth metal fluoride, and is characterized by that it uses soluble rare earth salt aqueous solution, rare earth oxide, oxalic acid rare earth salt, sulfuric acid rare earth ammonium complex salt and slurry of acid carbonic acid rare earth salt as raw material liquor, adds oxalic acid and hydrofluoric acid, and makes solid-liquid separation. The process method has strong adaptability, less working procedures, short production period, less used equipment, low energy and various raw material consumption, low product cost, high precipitation and filtration speed, stable product quality, high qualification rate, over 98 percent of recovery rate, no direct discharge of fluorine-containing wastewater, and easy environmental protection and industrialization.
Description
The present invention relates to producing of rare earth compound, more precisely is producing of rare earth metal fluorochemical.
The rare earth metal fluorochemical can be used as the additive of steel, non-ferrous metal alloy, carbon arc rods, can also be as the raw material and the ionogen of re metal electrolyzing, and lanthanum fluoride, cerium fluoride can be used as the opacifier of Ceramic glaze again.
The abundance of cerium accounts for the first place of rare earth element, thereby the fluorochemical of cerium has more wide prospect.
Two kinds of wet method and dry method are arranged in the method for existing production rare earth metal fluorochemical, and (the rare-earth wet method smelting technology is learned, the employee education teaching material editing P329-333 of office of company of China Non-Ferrous Metals Industry), wet method is that the oxyhydroxide with rare earth, carbonate, rare earth chloride, rare earth nitrate, rare earth sulfate and hydrofluoric acid or the Neutral ammonium fluoride reaction of rare earth generate rare earth fluorine, and thermal dehydration forms anhydrous rare earth fluorine.For example: with the rare earth chloride is raw material, rare earth concentration 300 grams per liters are controlled (by rare earth oxide in rare earth chloride dissolving back, in the time of 80 °-90 ℃, under stirring, add 4N dilute sulphuric acid clarification filtration down together), impurity barium and part calcium are removed with the form of slag in the rare earth chloride, the rare-earth chloride solution rare earth concentration is controlled at the 100-130 grams per liter then, dense hydrofluoric acid with 48% is fluoridized, removing chlorion control PH with 70 °-80 ℃ hot wash again is 5-6, clarification obtains containing the rare earth fluorine of crystal water, in order to remove the Silicon dioxide, hydrate that produces owing to hydrolysis in the rare earth fluorine that contains crystal water, therefore before dehydration, admix a certain amount of Neutral ammonium fluoride and dewater and obtain anhydrous rare earth metal fluorochemical.
The dehydration of rare earth fluorine is carried out under vacuum condition, in order to guarantee that vacuum tightness is at the 100-200 mmhg, the speed that heats up should not be too fast, generally be controlled at 20 ℃/hour, most of moisture content of rare earth metal fluorochemical is removed, be controlled at about 45 ℃ and be incubated 6-8 hour, and obtain anhydrous rare earth metal fluorochemical.
It is rare earth oxide is heated in the hydrofluoric acid air-flow and to obtain anhydrous rare earth metal fluorochemical that dry method is produced the rare earth metal fluorochemical.
Wet method is compared with dry method, it is short that dry method has flow process, good product quality, rate of recovery advantages of higher, but the high temperature material of anti-the fluorine, fluorizating apparatus, difficult solution such as security measures, so the application of dry production rare earth metal fluorochemical is less, wet method equipment is simple, easy handling, but long flow path, poor product quality, the rate of recovery is low, the many working strength of workers of industrial chemicals that consume are big, the product cost height, and be precipitation agent when producing the rare earth metal fluorochemical with hydrofluoric acid or Neutral ammonium fluoride, maximum problem is that the rare earth metal fluorochemical that generates is the colloidal precipitation, filtration difficulty, need reach more than 30 hours during a collection of sometimes rare earth metal fluorochemical sedimentation and filtration, and easily wear filter, the production cycle is long, loss is big, is unsuitable for suitability for industrialized production.
Purpose of the present invention just is to work out the processing method that a kind of new wet method is produced the rare earth metal fluorochemical; the rare earth metal fluorochemical that is precipitated out with processing method of the present invention is easy to filter; production cycle is shortened; the rate of recovery increases; cost is low; equipment used is simple, helps environment protection, is easy to industrialization.
The preparation method of a kind of rare earth metal fluorochemical of the present invention, acidic aqueous solution with soluble rare-earth salt, rare earth oxide, rare earth oxalate salt, sulfuric acid rare earth ammonium double salt, wherein a kind of slurries of acid carbonated rare earth salt are stock liquid, stock liquid adds oxalic acid in room temperature to ebullient temperature in stock liquid under stirring, the add-on of oxalic acid make A/B=0-3.0(wherein A be the mole number that contains the oxalic acid of two crystal water in 1 liter of stock liquid, contain the atom number that contains rare earth in the mole number ÷ rare earth oxide molecule of rare earth oxide in every liter of stock liquid of B=, A, the connotation of B is following all with last same), be that room temperature to ebullient temperature under agitation adds hydrofluoric acid and carries out solid-liquid separation at stock liquid then.
The acidic aqueous solution that rare earth chloride is arranged in the acidic aqueous solution of used stock liquid soluble rare-earth salt in the technology of producing the rare earth metal fluorochemical, the acidic aqueous solution of rare earth sulfuric acid, the acidic aqueous solution of rare earth nitrate, the acidity of the acidic aqueous solution of rare earth chloride is PH2-0.64N, its rare earth concentration is 0.12-1.35M, but the acidic aqueous solution acidity with rare earth chloride is 0.3-0.5N, and its rare earth concentration is that 0.4-0.6 is good; The acidity of the acidic aqueous solution of rare earth nitrate is 0.44-3.11N, and its rare earth concentration is 0.29-1.26M, but is 0.4-0.6N with the acidic aqueous solution acidity of rare earth nitrate, and its rare earth concentration is that 0.4-0.6M is advisable; The acidity of the acidic aqueous solution of rare earth sulfate is 0.44-0.64N, and its rare earth concentration is 0.12-0.41M, but is 0.4-0.5N with the acidity of the acidic aqueous solution of rare earth sulfate, and its concentrations of rare-earth is that 0.3-0.4M is good.
If wherein a kind of mixed with the slurries of rare earth oxalate salt, sulfuric acid rare earth ammonium double salt, acid carbonated rare earth salt is stock liquid mutually, the rare-earth salts concentration of its suspension is 0.55-1.36M, but is good with 1.2-1.3M.
If the liquid with the slurries of rare earth oxide is stock liquid, the concentration of the rare earth oxide of its suspension is 0.20-4.5M, but is good with 2.0-2.5M.
With rare earth oxalate salt, rare earth oxide, sulfuric acid rare earth ammonium double salt, a kind of slurries wherein of acid carbonated rare earth salt are that stock liquid is produced the rare earth metal fluorochemical and can not added oxalic acid, under agitation, at stock liquid is that (said room temperature is generally 15 °-35 ℃ under room temperature-ebullient temperature, as follows) directly add hydrofluoric acid, it is the mole number that contains hydrofluoric acid in every liter of stock liquid that the amount of the hydrofluoric acid that is added makes C/B=3-5(C, the connotation of C is following in this together), but with C/B=3.0-3.4 is good, and the temperature of stock liquid is controlled at 48 °-62 ℃ and is advisable when adding hydrofluoric acid.The concentration that joins the used hydrofluoric acid in the stock liquid generally contains hydrofluoric acid 30-40%(weight percentage), with the hydrofluoric acid that adds hydrofluoric acid containing 35-40% for well.Continuing insulated and stirred 3-180 minute after adding hydrofluoric acid, 20-30 minute was good to continue insulated and stirred again.The rare earth metal fluorochemical that is generated is functional, is easy to filter.
When the slurries with rare earth oxide are stock liquid, after generating the rare earth metal fluorochemical, in the sedimentary supernatant liquor of rare earth metal fluorochemical, still have a small amount of colloid rare earth metal fluorochemical precipitation, so when being stock liquid with the rare-earth oxide slurries, before being preferably in adding hydrofluoric acid, under agitation add oxalic acid in room temperature-ebullient stock liquid, the amount that adds oxalic acid makes A/B=0.01-2.50, but so that A/B=0.1-0.7 for well.The temperature of stock liquid is to be controlled at 48 °-62 ℃ for good when adding oxalic acid.Continued again insulated and stirred 3-80 minute after adding oxalic acid, and then adding hydrofluoric acid, the amount of the hydrofluoric acid that is added makes C/B=3-5, the sedimentary particle of rare earth metal fluorochemical that is generated like this is thick, be easy to filter, also do not occur colloid rare earth metal fluorochemical precipitation in the sedimentary supernatant liquor of rare earth metal fluorochemical.
At acidic aqueous solution with rare earth chloride, the acidic aqueous solution of rare earth nitrate, when the acidic aqueous solution of rare earth sulfate is stock liquid, formed rare earth fluorine is colloidal state after directly adding hydrofluoric acid, these colloidal solution even place and be still stable colloid in three months are very easily worn filter, so be difficult to filter, sometimes a collection of product filters and reaches more than 30 hours, and the rate of recovery is reduced greatly.But before adding hydrofluoric acid, add oxalic acid earlier, add hydrofluoric acid again, the rare earth metal fluorochemical deposit seeds of Xing Chenging is big like this, be easy to filter, the oxalic acid that is added normally has the oxalic acid of two crystal water, because it is easy to buy on market, the oxalic acid that adds anhydrous oxalic acid certainly or have an indefinite crystal water all can, the do not fix a number oxalic acid of crystal water of the oxalic acid of no crystal water or band needs prepare especially.The amount of the oxalic acid that is added makes A/B=1.5-3.0, is good with A/B=1.6-2.2 again.When adding oxalic acid, under agitation the temperature of stock liquid remains under room temperature-boiling state and carries out.But the temperature of stock liquid is controlled at 48 °-62 ℃ better when adding oxalic acid.The temperature of stock liquid still remains on room temperature-boiling behind the adding oxalic acid, but better is controlled at 48 °-62 ℃, continues insulated and stirred 3-80 minute, adds hydrofluoric acid again.The amount that adds hydrofluoric acid makes C/B=3-5, better make C/B=3.0-3.4, adding hydrofluoric acid preferably under agitation carries out, the concentration that joins hydrofluoric acid used in the stock liquid is generally and contains hydrofluoric acid 30-40%(weight percentage) commercially available hydrofluoric acid, but be advisable for 35-40% hydrofluoric acid with the hydrofluoric acid containing.Continuing insulated and stirred 3-180 minute after adding hydrofluoric acid, 20-30 minute was good to continue insulated and stirred again, made the deposit seeds of the rare earth metal fluorochemical that is generated thick, was easy to filter.
Add hydrofluoric acid and continue to stir after 3-180 minute, preferably water (for example deionization, distilled water) pulp washing rare earth metal fluorochemical precipitation is 1-3 time, behind the pulp washing, carries out solid-liquid separation.
In order further to reduce the consumption of oxalic acid and hydrofluoric acid, avoided simultaneously the discharging of hydrofluoric acid containing waste water again, isolate the liquid (filtrate when for example filtering separation rare earth metal fluorochemical precipitates) of rare earth metal fluorochemical post precipitation, can be used for the oxalic acid precipitation of next batch feed liquid because of the whole oxalic acid that wherein contain remaining hydrofluoric acid and cement out.When the rare earth oxide total mole number in the feed liquid during with preceding a collection of equating, add oxalic acid, the additional amount of oxalic acid is A/B=0.1-0.5, added the follow-up continuation of insurance temperature of oxalic acid 3-80 minute, add and to contain hydrofluoric acid 30-40%(weight percentage) commercially available hydrofluoric acid, continued again insulated and stirred 3-180 minute, be good with 60-80 minute, after the solid-liquid separation, product is sent to oven dry; Liquid after the solid-liquid separation continues to enter as stated above the oxalic acid precipitation operation; so recycle; can make consumption of oxalic acid be reduced to A/B=0.1-0.5; for successional industrial production; only need the container of this liquid of deposit to get final product; solve the emission problem of fluoride waste simultaneously, helped environment protection.
The rare earth metal fluorochemical that the various stock liquids of above-mentioned usefulness prepare should be dried 1.5-12.5 hour at 150 ° of-350 ℃ of following drying and dewaterings, be preferably in 200 ° of-350 ℃ of following drying and dewatering 3-4 hours.
Used analytical procedure is each component emission spectrographic determination of stock liquid middle-weight rare earths in above-mentioned technology, product middle-weight rare earths (in rare earth oxide) is used the oxalate gravimetric determination, cerium dioxide volumetric determination ferrous ammonium sulfate in the product, fluorine in product thorium nitrate 99.99004323A8urity volumetric determination, phosphorus is measured with phosphorus molybdenum blue colorimetric method in the product.Iron phenanthroline colorimetric method for determining in the product, sulfate radical turbidimetry for Determination in the product, calcium and magnesium EDTA volumetric determination in the product.
The method of used solid-liquid separation can be used methods such as filter paper filtering, centrifugation, press filtration.
Advantage of the present invention just is:
1. technical process operation of the present invention is few, with short production cycle, and the energy and various raw materials consumption are descended significantly, product cost is low, and the economic benefit height only carries out solid-liquid separation one time, filtration velocity is fast, for example every batch of product volume filters and has only used 30 minutes when the 50-200 kilogram, makes the production cycle shorten 10-60 doubly, processing method output of the present invention is big, be easy to industrialization, dehydration temperaturre gets final product more than 200 ℃, has improved labor condition.
2. processing method adaptability of the present invention is strong, can prepare multiple rare earth metal fluorochemical product, constant product quality.
3. processing method equipment used of the present invention is simple, and quantity is few, and easy handling is convenient to maintenance.
4. processing method product first-time qualification rate height of the present invention does not need middle control analysis, and rate of recovery Gao Keda is more than 98%.
5. fluorine and oxalic acid content are very low in the processing method waste liquid of the present invention, non-environmental-pollution.
More specifically describe the present invention with following non-limiting examples, protection scope of the present invention is not subjected to the qualification of these embodiment.
Embodiment 1
Get 1 liter of cerous compounds solution after extracting and separating, place and have the polyvinyl chloride tube (the tetrafluoroethylene tube is better) of making agitator (agitator with polyfluortetraethylene plate system is better) by polyvinyl chloride panel, the concentration of cerous compounds is 0.1434M, and hydrogen ion concentration is 0.6027N.The composition of stock liquid middle-weight rare earths (weight percentage of each rare earth oxide in the total rare earth (TRE) oxide compound) is:
Lanthanum sesquioxide 0.031% 11 oxidation six praseodymiums 0.022%
Neodymium sesquioxide 0.1% samarium sesquioxide 0.032%
Yttrium oxide＜0.0026% cerium dioxide 99.77%
Under agitation add the oxalic acid (technical grade) that has two crystal water in room temperature (24 ℃) and make A/B=2.66, continue insulated and stirred after 20 minutes, contain hydrofluoric acid 35.27%(weight percentage in 96 ℃ of addings) hydrofluoric acid (technical grade), the amount of the hydrofluoric acid that is added makes C/B=4.67, continued insulated and stirred 20 minutes, deionized water (60 ℃) pulp washing with heat precipitates 2 times, use filter paper filtering, filtration time has only been used 3 minutes, dried 1.5 hours at the AD02 drying baker in 200 ℃, the rate of recovery is 98.83%, and the content of cerium in the product (in cerium dioxide) is 83.02%, the content of fluorine is 26.01%, and the content of phosphorus is less than 0.05%.
Embodiment 2
Equipment used is with embodiment 1, Sedemesis (the trivalent cerium that will have 10 crystal water, the method of all knowing by the one of ordinary skill in the art, promptly in cerous compounds solution, add the oxalic acid synthetic) place 1 premium on currency furnishing slurries, as stock liquid, making the concentration of Sedemesis in stock liquid that has 10 crystal water is 0.96M, the temperature of the slurries of stock liquid remains on 60 ℃, in stirring, in the slurries of stock liquid, add and contain hydrofluoric acid 40%(weight percentage) hydrofluoric acid (technical grade), the amount of the hydrofluoric acid that is added makes C/B=4.02, continues insulated and stirred 30 minutes.Precipitate 2 times with 60 ℃ deionized water pulp washings, use filter paper filtering, filtration time has only been used 3 minutes, dried 3.5 hours in the ADD2 drying baker in 200 ℃, the rate of recovery 98.12% contains rare earth (in rare earth oxide) 81.05% in the product, contain cerium (in cerium dioxide) 80.87%, fluorine-containing 26.85%, phosphorous less than 0.02%, moisture and other compounds 2.60%.
Embodiment 3
Equipment used is with embodiment 1, with Ce2(SO4) 3.(NH4) 2SO4.8H2O places 1 premium on currency furnishing slurries as stock liquid, make Ce2(SO4) 3.(NH4) concentration of 2SO4.8H2O in the slurries of stock liquid is 0.56M, the temperature of the slurries of stock liquid keeps 70 ℃, under agitation in the slurries of stock liquid, add and contain hydrofluoric acid 40%(weight percentage) hydrofluoric acid (technical grade), the amount of the hydrofluoric acid that is added makes C/B=3.4, continued insulated and stirred 40 minutes, deionized water pulp washing with 50 ℃ of heat precipitates 2 times, use filter paper filtering, filtration time is only used 3 minutes, dries 2 hours in the ADO2 drying baker in 250 ℃, the rate of recovery 98.15%, contain rare earth (in rare earth oxide) 80.58% in the product, contain cerium (in cerium dioxide) 80.40%, fluorine-containing 22.23%, sulfur-bearing acid group 4.93%, water content is less than 1%.
Embodiment 4
Equipment used is with embodiment 1, with Ce(HCO3) 3 place 1 premium on currency furnishing slurries as stock liquid, making Ce(HCO3) 3 concentration in the slurries of stock liquid are 1.0M, the temperature of the slurries of stock liquid keeps 90 ℃, under agitation in the slurries of stock liquid, add and contain hydrofluoric acid 40%(weight percentage) hydrofluoric acid (technical grade), the amount of the hydrofluoric acid that is added makes C/B=3.2, continued insulated and stirred 40 minutes, deionized water pulp washing with 65 ℃ of heat precipitates 2 times, use filter paper filtering, filtration time is only used 11 minutes, dries 2 hours in the ADO2 drying baker in 260 ℃, the rate of recovery 98.10%.Contain rare earth (in rare earth oxide) 81.00% in the product, contain cerium (in cerium dioxide) 80.81%, fluorine-containing 26.03%, phosphorous 0.01%, moisture and other compound 5.86%.
Embodiment 5
Place 1 premium on currency furnishing slurries as stock liquid 40 gram cerium dioxides, the composition of equipment used and rare earth is with embodiment 1, under agitation add the oxalic acid (technical grade) that has two crystal water in 22 ℃, make A/B=0.546, continue insulated and stirred after 4 minutes, contain hydrofluoric acid 40%(weight percentage in 73 ℃ of addings) the amount of the hydrofluoric acid that added of hydrofluoric acid (technical grade) make C/B=3.0, continued insulated and stirred 20 minutes, deionized water pulp washing with 73 ℃ of heat precipitates 2 times, use filter paper filtering, filtration time is only used 3 minutes, dries 1.5 hours the rate of recovery 98.83% in the ADO2 drying baker in 220 ℃, contain rare earth (in rare earth oxide) 84.97% in the product, contain cerium (in cerium dioxide) 84.81%, fluorine-containing 26.47%, phosphorous＜0.019%.
Embodiment 6,7,8,9,10,11.
Its working method and condition and equipment used have a little operational condition differences only with embodiment 5, and operational condition and product analysis that they are different the results are shown in table 1 and the table 2.
The operational condition of table 1 embodiment 6-embodiment 11
The product analysis result of table 2 embodiment 6-embodiment 11
Embodiment 12,13,14,15,16.
Its working method and condition and equipment used have a little operational condition differences only with embodiment 1, and used stock liquid is 0.5 liter of lanthanum trichloride solution, and the concentration of lanthanum trichloride is 0.6833M, and hydrogen ion concentration is 0.44N.The composition of stock liquid middle-weight rare earths (weight percentage of each rare earth oxide in the total rare earth (TRE) oxide compound is:
Cerium dioxide＜0.1% 11 oxidation six praseodymiums＜0.1%
Neodymium sesquioxide＜0.1% samarium sesquioxide＜0.03%
Yttrium oxide＜0.03% ferric oxide＜50ppm
Silicon-dioxide 62PPM lanthanum sesquioxide 99.5%
Its different operational condition is tabulated in 3
The operational condition of table 3 embodiment 12-embodiment 16
Embodiment 17,18,19,20,21.
Its working method and condition and equipment used have a little operational condition differences only with embodiment 1, and used stock liquid is 2 liters of lanthanum trichloride solution, and the concentration of lanthanum trichloride is 0.4179M, and hydrogen ion concentration is 0.0218N.The stock liquid middle-weight rare earths is formed lanthanum sesquioxide/rare earth oxide 〉=99.9%, after embodiment 17 added hydrofluoric acid and transform, isolate the filtrate of rare earth metal fluorochemical post precipitation, join and carry out oxalic acid precipitation after adding oxalic acid again in the stock liquid of embodiment 18, embodiment 19,20,21 is with embodiment 18.Embodiment 18-21 is that the filtrate of isolating rare earth metal fluorochemical post precipitation of previous embodiment is added in the back embodiment stock liquid and adds oxalic acid again, adds the oxalic acid amount and is respectively A/B=0.18,0.13,0.23,0.49.
Embodiment 22-27
Its working method and condition and equipment used have a little operational condition differences only with embodiment 17-21, and used stock liquid is a praseodymium trichloride, and the concentration of praseodymium trichloride is 0.5020M, and the PH of solution is 0.64, and the hydrofluoric acid that is added is to contain 39% hydrofluoric acid.Its different operational condition tabulate in 5 (be that the filtrate of isolating rare earth metal fluorochemical post precipitation of previous embodiment is added in the back embodiment stock liquid and adds oxalic acid again among the embodiment 23-27, adding the oxalic acid amount is A/B=0.16).
The operation of table 5 embodiment 19-embodiment 24
Embodiment 28-35
Its working method and condition and equipment used have a little operational condition differences only with embodiment 17-22, and raw materials used is neodymium trichloride, and the concentration of neodymium trichloride is 0.7931M, and hydrogen ion concentration is 0.436N, contains 38.2% hydrofluoric acid.Operational condition that they are different and product analysis the results are shown in (embodiment 29-32 in table 6 and the table 7, be that filtrate that previous embodiment isolates rare earth metal fluorochemical post precipitation is added in the back embodiment stock liquid and adds oxalic acid again among the 34-35, adding into the oxalic acid amount is that A/B is respectively 0.25 and 0.50).
(continued on next page)
The operational condition of table 6 embodiment 28-35
The product analysis result of table 7 embodiment 29,30,35
Embodiment 36-43.
Its working method and condition and equipment used have a little operational condition differences only with embodiment 5, do not add oxalic acid, and raw materials used is the solid Gadolinium trioxide, and the composition of Gadolinium trioxide middle-weight rare earths (weight percentage of various oxide compounds in the total rare earth (TRE) oxide compound) is:
Samarium sesquioxide 0.016% europiumsesquioxide 0.057%
Terbium peroxide 0.015% yttrium oxide＜0.005%
Gadolinium trioxide 99.90% Dysprosium trioxide＜0.005%
Its different operational condition is listed in the table 8.
The operational condition of table 8 embodiment 36-43
Embodiment 44,45,46.
Its working method and condition and equipment used are with embodiment 17-22, have a little operational condition differences only, used stock liquid is 1 liter of gadolinium trichloride solution, the concentration of gadolinium trichloride is 0.8386M, hydrogen ion concentration is 0.01N, the stock liquid middle-weight rare earths is formed with embodiment 36, adds and contains 37.6% hydrofluoric acid, and its different operational condition is listed in the table 9.
(embodiment 45-46 is the filtrate that previous embodiment isolates rare earth metal fluorochemical post precipitation, is added to add oxalic acid again in the back embodiment stock liquid and make A/B=0.50.）
The operational condition of table 9 embodiment 41-43
Claims (7)
1, a kind of preparation method of rare earth metal fluorochemical, acidic aqueous solution with soluble rare-earth salt, rare earth oxide, rare earth oxalate salt, sulfuric acid rare earth ammonium double salt, wherein a kind of slurries of acid carbonated rare earth salt are stock liquid, feature of the present invention is, in stirring, in stock liquid, add oxalic acid in room temperature to ebullient temperature, the add-on of oxalic acid makes A/B=0-3.0, and (wherein A is the mole number that contains the oxalic acid of two crystal water in 1 liter of stock liquid, contain the atomicity that contains rare earth in the mole number ÷ rare earth oxide molecule of rare earth oxide in every liter of stock liquid of B=, A, all same therewith below the connotation of B), be that room temperature to ebullient temperature under agitation adds hydrofluoric acid at stock liquid then, carry out solid-liquid separation.
2, according to the preparation method of a kind of rare earth metal fluorochemical of claim 1, it is characterized in that, with rare earth oxalate salt, rare earth oxide, sulfuric acid rare earth ammonium double salt, acid carbonated rare earth salt a kind of slurries wherein is stock liquid, make A/B=0, directly add hydrofluoric acid, it is the mole number that contains hydrofluoric acid in every liter of stock liquid that the amount of adding hydrofluoric acid makes C/B=3-5(C), add the follow-up continuation of insurance temperature of hydrofluoric acid and stirred 3-180 minute.
3, according to the preparation method of a kind of rare earth metal fluorochemical of claim 2, it is characterized in that, is stock liquid with the slurries of rare-earth oxide, before adding hydrofluoric acid, add oxalic acid, the amount that adds oxalic acid makes A/B=0.01-2.50, adds the follow-up continuation of insurance temperature of oxalic acid and stirs 3-80 minute.
4, according to the preparation method of a kind of rare earth metal fluorochemical of claim 1, it is characterized in that, with the acidic aqueous solution of rare earth chloride, the acidic aqueous solution of rare earth nitrate, the acidic aqueous solution of rare earth sulfate is a stock liquid, the amount that adds oxalic acid makes A/B=1.5-3.0, adds the follow-up continuation of insurance temperature of oxalic acid and stirs after 3-80 minute, adds hydrofluoric acid, the amount that adds hydrofluoric acid makes C/B=3-5, continues to stir 3-180 minute again.
5, according to the preparation method of a kind of rare earth metal fluorochemical of claim 1, it is characterized in that, isolate the liquid behind the rare earth metal fluorochemical, the oxalic acid precipitation that is used for the next batch feed liquid, when the rare earth oxide total mole number in the feed liquid during with preceding a collection of equating, add oxalic acid, the additional amount of oxalic acid is A/B=0.1-0.5.
6, according to the preparation method of claim 1,2,3,4, a kind of rare earth metal fluorochemical of 5, it is characterized in that, add hydrofluoric acid and continue to stir after 3-180 minute, after water pulp washing rare earth metal fluorochemical precipitation 1-3 time, carry out solid-liquid separation.
7, according to the preparation method of a kind of rare earth metal fluorochemical of claim 6, it is characterized in that, carry out solid-liquid separation after, directly with the solid rare earth metal fluoride at 150 ° of-360 ℃ of following drying and dewaterings, dried 1.5-12.5 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN89104555A CN1017985B (en) | 1989-07-07 | 1989-07-07 | Preparation method of rare earth fluoride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN89104555A CN1017985B (en) | 1989-07-07 | 1989-07-07 | Preparation method of rare earth fluoride |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1048531A true CN1048531A (en) | 1991-01-16 |
| CN1017985B CN1017985B (en) | 1992-08-26 |
Family
ID=4855597
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN89104555A Expired CN1017985B (en) | 1989-07-07 | 1989-07-07 | Preparation method of rare earth fluoride |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1017985B (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1321897C (en) * | 2005-10-19 | 2007-06-20 | 清华大学 | Method for preparing monodisperse rare-earth fluoride nano particles |
| CN100387524C (en) * | 2005-08-03 | 2008-05-14 | 北京有色金属研究总院 | Method of preparing rare earth fluoride from rare earth oxide |
| CN101805008A (en) * | 2010-04-26 | 2010-08-18 | 赣州虔东稀土集团股份有限公司 | Anhydrous high-purity rare earth fluoride and preparation method thereof |
| CN101628729B (en) * | 2009-08-17 | 2011-05-25 | 浙江理工大学 | Method for preparing ball cactus shape terbium fluorination green luminescent material |
| CN101400607B (en) * | 2006-03-13 | 2012-03-21 | 昭和电工株式会社 | Method of recovering rare earth element from composition containing rare earth fluoride |
| CN104419839A (en) * | 2013-08-19 | 2015-03-18 | 中铝稀土（常州）有限公司 | Method for preparing rare earth oxalate precipitation |
| CN110372026A (en) * | 2019-07-18 | 2019-10-25 | 赣州湛海新材料科技有限公司 | A kind of rare earth fluoride preparation method applied to crystalline material |
| CN111170352A (en) * | 2020-01-21 | 2020-05-19 | 包头稀土研究院 | Method for preparing rare earth fluoride particles by using fluorine-containing waste acid |
| CN111252798A (en) * | 2020-01-21 | 2020-06-09 | 包头稀土研究院 | Method for preparing rare earth fluoride particles under alkaline condition and application of alkaline substance |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100417752C (en) * | 2005-12-20 | 2008-09-10 | 中国科学院兰州化学物理研究所 | Chemical process for preparing one-dimensional nano lanthanum fluoride material |
-
1989
- 1989-07-07 CN CN89104555A patent/CN1017985B/en not_active Expired
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100387524C (en) * | 2005-08-03 | 2008-05-14 | 北京有色金属研究总院 | Method of preparing rare earth fluoride from rare earth oxide |
| CN1321897C (en) * | 2005-10-19 | 2007-06-20 | 清华大学 | Method for preparing monodisperse rare-earth fluoride nano particles |
| CN101400607B (en) * | 2006-03-13 | 2012-03-21 | 昭和电工株式会社 | Method of recovering rare earth element from composition containing rare earth fluoride |
| CN101628729B (en) * | 2009-08-17 | 2011-05-25 | 浙江理工大学 | Method for preparing ball cactus shape terbium fluorination green luminescent material |
| CN101805008A (en) * | 2010-04-26 | 2010-08-18 | 赣州虔东稀土集团股份有限公司 | Anhydrous high-purity rare earth fluoride and preparation method thereof |
| CN101805008B (en) * | 2010-04-26 | 2011-11-16 | 赣州虔东稀土集团股份有限公司 | Anhydrous high-purity rare earth fluoride and preparation method thereof |
| CN104419839A (en) * | 2013-08-19 | 2015-03-18 | 中铝稀土（常州）有限公司 | Method for preparing rare earth oxalate precipitation |
| CN110372026A (en) * | 2019-07-18 | 2019-10-25 | 赣州湛海新材料科技有限公司 | A kind of rare earth fluoride preparation method applied to crystalline material |
| CN110372026B (en) * | 2019-07-18 | 2022-02-11 | 赣州湛海新材料科技有限公司 | Preparation method of rare earth fluoride applied to crystal material |
| CN111170352A (en) * | 2020-01-21 | 2020-05-19 | 包头稀土研究院 | Method for preparing rare earth fluoride particles by using fluorine-containing waste acid |
| CN111252798A (en) * | 2020-01-21 | 2020-06-09 | 包头稀土研究院 | Method for preparing rare earth fluoride particles under alkaline condition and application of alkaline substance |
| CN111252798B (en) * | 2020-01-21 | 2022-05-24 | 包头稀土研究院 | Method for preparing rare earth fluoride particles under alkaline condition and use of alkaline substance |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1017985B (en) | 1992-08-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1027890C (en) | Process for preparing rare earth ammonium double oxalate and use for preparing rare earth oxidate | |
| CN1240858C (en) | Carbon reducting roast process of producing RE chloride with mixed RE concentrate | |
| CN109290060A (en) | A kind of process for subsequent treatment and phosphate ore floatation method of phosphate ore flotation tailings | |
| CN85101989A (en) | Processing method with preparation of Li 2 CO 3 by treating lithium-loaded mica with K 2 SO 4 | |
| CN1048531A (en) | Preparation method of rare earth fluoride | |
| CN1415665A (en) | Method for producing the red pigment of ferric oxide from ferrous sulphate of byproduct abolished by titanium white | |
| CN109320117A (en) | Modified ardealite and preparation method thereof as cement retarder | |
| CN102849764B (en) | Method for preparing pseudo-boehmite by pulverized fuel ash | |
| CN1618998A (en) | Method for preparing high-purity magnesite by taking bischofite in salt lake as raw material | |
| CN1024565C (en) | Comprechensive utilization of serpentine tailings | |
| CN1103111A (en) | Making rare-earth material liquid from bastnae site | |
| CN1415666A (en) | Method for producing the yellow pigment of ferric oxide from ferrous sulphate of byproduct abolished by titanium white | |
| CN1036548A (en) | Make the method for zirconia hydrate from the zirconium white of granular crystal | |
| CN117247092A (en) | Fluorine removing agent for fluorine-containing wastewater treatment and preparation method thereof | |
| CN111847518A (en) | Efficient recycling method of silicomanganese slag | |
| CN1907859A (en) | Method of preparing rare earth fluoride from rare earth oxide | |
| CN87104013A (en) | The combination medicament of froth flotation zircon | |
| CN110407241B (en) | Preparation method of high-activity calcium oxide | |
| CN1147501A (en) | Producing process for rare earth oxide | |
| CN1022558C (en) | Method for separating ultrafine iron oxide from waste mother liquor from rutile production by dilute hydrochloric acid | |
| CN1095045A (en) | The Retreatment method of the residue that is used for removing waste water dissolved fluorine and produces | |
| CN1031687A (en) | A kind of is the novel method of raw material production Magnesium Carbonate Light 41-45 with the rhombspar | |
| CN1043685A (en) | Ion type rareearth ore sulfuric acid ore leachate ammonia precipitation rare earth extraction process | |
| CN1218113A (en) | Method for treating and recovering emulsion phase in extracting separation of raw rare earth materials | |
| CN107043118B (en) | A method of preparing calcium sulfate crystal whiskers using aluminium polychloride production waste residue |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C13 | Decision | ||
| GR02 | Examined patent application | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |