CN1048239A - Process for preparing pure cerium hydroxide - Google Patents
Process for preparing pure cerium hydroxide Download PDFInfo
- Publication number
- CN1048239A CN1048239A CN89103858A CN89103858A CN1048239A CN 1048239 A CN1048239 A CN 1048239A CN 89103858 A CN89103858 A CN 89103858A CN 89103858 A CN89103858 A CN 89103858A CN 1048239 A CN1048239 A CN 1048239A
- Authority
- CN
- China
- Prior art keywords
- cerium
- cerous
- hydroxide
- feed liquid
- rare earth
- 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- Withdrawn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
- 238000004519 manufacturing process Methods 0.000 title abstract description 7
- UNJPQTDTZAKTFK-UHFFFAOYSA-K cerium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Ce+3] UNJPQTDTZAKTFK-UHFFFAOYSA-K 0.000 title abstract 6
- 239000007788 liquid Substances 0.000 claims abstract description 80
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 79
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract description 79
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 50
- 239000007864 aqueous solution Substances 0.000 claims abstract description 31
- 239000012286 potassium permanganate Substances 0.000 claims abstract description 24
- 150000003839 salts Chemical class 0.000 claims abstract description 22
- 230000002378 acidificating effect Effects 0.000 claims abstract description 21
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims abstract description 19
- 230000001590 oxidative effect Effects 0.000 claims abstract description 7
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 6
- 239000003513 alkali Substances 0.000 claims abstract description 6
- 239000007800 oxidant agent Substances 0.000 claims abstract description 6
- 229910052938 sodium sulfate Inorganic materials 0.000 claims abstract description 6
- 235000011152 sodium sulphate Nutrition 0.000 claims abstract description 6
- 239000002253 acid Substances 0.000 claims abstract description 5
- 239000002244 precipitate Substances 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 64
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 39
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 34
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical group O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 31
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 31
- 238000001556 precipitation Methods 0.000 claims description 27
- 150000002910 rare earth metals Chemical class 0.000 claims description 24
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 20
- 238000003672 processing method Methods 0.000 claims description 17
- 238000000926 separation method Methods 0.000 claims description 16
- 229910000333 cerium(III) sulfate Inorganic materials 0.000 claims description 15
- 229910052708 sodium Inorganic materials 0.000 claims description 15
- 239000011734 sodium Substances 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 15
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 13
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 claims description 13
- -1 hydrogen cerium oxide Chemical class 0.000 claims description 13
- 239000003153 chemical reaction reagent Substances 0.000 claims description 12
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 claims description 12
- 239000001117 sulphuric acid Substances 0.000 claims description 12
- 235000011149 sulphuric acid Nutrition 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 8
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- 238000013019 agitation Methods 0.000 claims description 6
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 5
- 239000005695 Ammonium acetate Substances 0.000 claims description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 5
- 229940043376 ammonium acetate Drugs 0.000 claims description 5
- 235000019257 ammonium acetate Nutrition 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 5
- 235000015320 potassium carbonate Nutrition 0.000 claims description 5
- 235000017550 sodium carbonate Nutrition 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 4
- ZNRSXPDDVNZGEN-UHFFFAOYSA-K trisodium;chloride;sulfate Chemical compound [Na+].[Na+].[Na+].[Cl-].[O-]S([O-])(=O)=O ZNRSXPDDVNZGEN-UHFFFAOYSA-K 0.000 claims description 3
- 238000004513 sizing Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 22
- 235000002639 sodium chloride Nutrition 0.000 abstract description 19
- 238000001914 filtration Methods 0.000 abstract description 13
- 230000003647 oxidation Effects 0.000 abstract description 12
- 238000007254 oxidation reaction Methods 0.000 abstract description 12
- 239000000047 product Substances 0.000 abstract description 11
- 230000008569 process Effects 0.000 abstract description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 abstract description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 abstract 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 abstract 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 abstract 1
- 229910052783 alkali metal Inorganic materials 0.000 abstract 1
- 150000001340 alkali metals Chemical class 0.000 abstract 1
- 230000001376 precipitating effect Effects 0.000 abstract 1
- VAFIMBGPHIITSF-UHFFFAOYSA-J sodium cerium(3+) disulfate Chemical compound [Na+].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VAFIMBGPHIITSF-UHFFFAOYSA-J 0.000 abstract 1
- 239000011780 sodium chloride Substances 0.000 abstract 1
- 235000010265 sodium sulphite Nutrition 0.000 abstract 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 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 14
- 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 13
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 10
- 239000000292 calcium oxide Substances 0.000 description 10
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 10
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 10
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 10
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- 229910052746 lanthanum Inorganic materials 0.000 description 6
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 6
- 238000011084 recovery Methods 0.000 description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 5
- 239000000706 filtrate Substances 0.000 description 5
- 239000008399 tap water Substances 0.000 description 5
- 235000020679 tap water Nutrition 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- CMIHHWBVHJVIGI-UHFFFAOYSA-N gadolinium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Gd+3].[Gd+3] CMIHHWBVHJVIGI-UHFFFAOYSA-N 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- FKTOIHSPIPYAPE-UHFFFAOYSA-N samarium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Sm+3].[Sm+3] FKTOIHSPIPYAPE-UHFFFAOYSA-N 0.000 description 4
- 239000006228 supernatant Substances 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 229910052777 Praseodymium Inorganic materials 0.000 description 3
- 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 3
- 238000007689 inspection Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004737 colorimetric analysis Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- 229910052694 Berkelium Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- WMOHXRDWCVHXGS-UHFFFAOYSA-N [La].[Ce] Chemical compound [La].[Ce] WMOHXRDWCVHXGS-UHFFFAOYSA-N 0.000 description 1
- WCYXDPQRKFQCSQ-UHFFFAOYSA-N [Nd].[Sm] Chemical compound [Nd].[Sm] WCYXDPQRKFQCSQ-UHFFFAOYSA-N 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- PWVKJRSRVJTHTR-UHFFFAOYSA-N berkelium atom Chemical compound [Bk] PWVKJRSRVJTHTR-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- MBZLJHHVUVLDSX-UHFFFAOYSA-N cerium hydrochloride Chemical compound Cl.[Ce] MBZLJHHVUVLDSX-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- MFSVDLVJNJLACW-UHFFFAOYSA-N periodic acid;potassium Chemical compound [K].OI(=O)(=O)=O MFSVDLVJNJLACW-UHFFFAOYSA-N 0.000 description 1
- 238000000247 postprecipitation Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 239000000126 substance Substances 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
- C01F17/30—Compounds containing rare earth metals and at least one element other than a rare earth metal, oxygen or hydrogen, e.g. La4S3Br6
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F17/00—Compounds of rare earth metals
- C01F17/20—Compounds containing only rare earth metals as the metal element
- C01F17/206—Compounds containing only rare earth metals as the metal element oxide or hydroxide being the only anion
- C01F17/224—Oxides or hydroxides of lanthanides
- C01F17/235—Cerium oxides or hydroxides
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)
Abstract
The invention relates to a process for preparing cerium hydroxide, which comprises using acidic aqueous solution containing cerium and rare earth elements except cerium as feed liquid, potassium permanganate as oxidant, adding carbonate of alkali metal or ammonium or one of bicarbonate thereof to make pH of the feed liquid 1-6, precipitating cerium, dissolving cerium hydroxide with acid, adding sodium sulfite and sodium chloride or sodium sulfate to generate sodium cerium sulfate double salt, and converting alkali into cerium hydroxide. The technological process of the present invention has high oxidation rate, large cerium hydroxide precipitate grain, easy filtering, simple apparatus, stable and reliable product quality and low cost, and may be used in preparing cerium hydroxide of 85-99.8% purity.
Description
The present invention relates to a kind of producing and manufacturing technique of cerous hydroxide, produce the processing method of cerous hydroxide more precisely the acidic aqueous solution of the rare earth element beyond containing cerium and cerium.
Cerium oxide is a kind of good glass decolouring finings, and late nineteen seventies is widespread use abroad, and it can be used as polishing powder again, therefore a lot of to the producing and manufacturing technique report of producing cerous hydroxide, cerium oxide both at home and abroad.
SU952742 and Zhujiang Smeltery (potassium permanganate TBP-P204 sulfonated kerosene extraction cerium oxide 1979) etc. propose to use potassium permanganate oxidation, P204 extraction process to prepare cerium oxide, are a kind of processing methodes of sophisticated production cerium oxide, but the cost height, complicated operation.
Chinese patent literature CN87100620A has proposed a kind of production method of cerous hydroxide, this method is that the acidic aqueous solution that contains cerium and cerium rare earth element in addition is divided into two batches, alkali metal hydroxide or ammonia are joined in first solution (1), isolate the solid that is generated, this solid is added in the second batch of solution (2) in company with oxygenant, to generate the solid hydrogen cerium oxide.The pH value of feed liquid that contains the acidic aqueous solution of the rare earth element beyond cerium and the cerium is 6 to the maximum, and the add-on of alkali metal hydroxide or ammonia should make the PH that adds after the mentioned reagent be at least 10.This processing method flow process of producing cerous hydroxide is more brief, but the cerous hydroxide purity of producing is not high, and the content of cerium oxide in rare earth oxide only reaches 83.6%, and the ability of daily output cerous hydroxide is low.
Purpose of the present invention just is to work out a kind of processing method that can produce also can the production purity lower cerous hydroxide of the high cerous hydroxide of purity, and makes the processing method easy handling, the stable and reliable product quality of producing, and day output is big.
A kind of processing method of producing cerous hydroxide of the present invention, the acidic aqueous solution of rare earth element is a feed liquid beyond cerium and the cerium to contain, with potassium permanganate is oxygenant, trivalent cerium is oxidized to quadrivalent cerium, add ammonium acetate, volatile salt, yellow soda ash, salt of wormwood, sodium bicarbonate, saleratus, bicarbonate of ammonia a kind of reagent wherein, the PH that makes feed liquid is that 1-6 makes the cerium precipitation, separate the solid hydrogen cerium oxide precipitation that is generated, cerium is separated with other rare earth elements, add sour dissolved hydrogen cerium oxide, the hydrogen ion concentration that makes feed liquid is the 0.1-3 mol, add sodium-chlor, sodium sulfate a kind of reagent wherein makes cerium generate cerous sulfate sodium double salt precipitation, carries out solid-liquid separation, with alkali metal hydroxide cerous sulfate sodium double salt is changed into cerous hydroxide, carry out solid-liquid separation.
Producing the used feed liquid of cerous hydroxide is the acidic aqueous solution that contains cerium and cerium rare earth element in addition.Its hydrogen ion concentration is 1-10
-6Mol, (hydrochloric acid or sulfuric acid or nitric acid) but feed acidity is good with PH2-4.Contain 1.5-5.0 grams per liter calcium oxide and 0.007-0.05 grams per liter ferric oxide in this feed liquid.The feed liquid that contains the acidic aqueous solution of other rare earth elements beyond cerium and the cerium is meant the sulfuric acid aqueous solution that contains other rare earth elements beyond cerium and the cerium, contain the nitric acid acidic aqueous solution of the rare earth element beyond the cerium and contain cerium and cerium beyond the hydrochloric acid acidic aqueous solution of other rare earth elements, but with contain the rare earth element sulfuric acid aqueous solution beyond cerium and the cerium and contain cerium and cerium beyond rare earth element hydrochloric acid acidic aqueous solution as feed liquid for well.Because it is strong to equipment corrosion to contain the nitric acid acidic aqueous solution of other rare earth elements beyond cerium and the cerium, contaminate environment, cost height.
Usually the amount that contains rare earth in the feed liquid of the sulfuric acid aqueous solution of other rare earth elements beyond containing cerium and cerium is that the 5-50 grams per liter is (in rare earth oxide, as follows), but to contain rare earth content 20-35 grams per liter is good, this its rare earth of feed liquid that contains the sulfuric acid aqueous solution of cerium and cerium other rare earth elements is in addition formed (with the ratio of total amount of rare earth) and is lanthanum sesquioxide 25-34%, about cerium dioxide 49-66%, 11 oxidations, six praseodymium 0.83-5.5%, neodymium sesquioxide 15-17%, about samarium sesquioxide 1.2%, about europiumsesquioxide 0.2%, about Gadolinium trioxide 0.4%, other rare earth oxide 1-3%.
In the feed liquid of the hydrochloric acid acidic aqueous solution that contains other rare earth elements beyond cerium and the cerium, contain rare earth content 5-255 grams per liter, but be good to contain rare earth content 50-120 grams per liter.In the feed liquid of this hydrochloric acid acidic aqueous solution that contains other rare earth elements beyond cerium and the cerium, based on light rare earths, it is lanthanum sesquioxide 20-50% that its rare earth is formed (with the ratio of total amount of rare earth), cerium dioxide 45-65%, 11 oxidations, six praseodymium 0.03-7%, neodymium sesquioxide 0.03-25%, samarium sesquioxide 0.03-5, europiumsesquioxide 0.03-1.5%.
In the feed liquid of the hydrochloric acid acidic aqueous solution that contains cerium and lanthanum, contain rare earth content 5-255 grams per liter but be good to contain rare earth content 50-120 grams per liter, its rare earth is formed (with the ratio of total amount of rare earth) and is lanthanum oxide 25-55% in the feed liquid of this hydrochloric acid acidic aqueous solution that contains cerium and lanthanum, cerium dioxide 45-75%, 11 oxidations, six praseodymiums less than 1%, three Neodymium trioxide less than 0.8%.
The temperature of feed liquid should remain between 50 °-100 ℃ when under agitation adding oxidant potassium permanganate, but with the sulfuric acid aqueous solution that contains cerium and cerium other rare earth element in addition is feed liquid, when adding oxidant potassium permanganate, the temperature of feed liquid remains on 40 °-60 ℃ for good, with the hydrochloric acid acidic aqueous solution that contains other rare earth elements beyond cerium and the cerium or with the hydrochloric acid acidic aqueous solution that contains the cerium lanthanum is feed liquid, and the temperature of feed liquid remains on 40 °-70 ℃ for well when adding oxidant potassium permanganate.The amount that adds oxidant potassium permanganate cans be compared to the amount of reacting the potassium permanganate of needed equivalent with cerium most and surpasses more than 10% for well.But adding also is fine with the potassium permanganate that cerium reacts needed equivalent.
In the oxidising process of potassium permanganate, under stirring, in 5 minutes-480 minutes time range, add ammonium acetate, volatile salt, yellow soda ash, salt of wormwood, sodium bicarbonate, saleratus, bicarbonate of ammonia a kind of reagent wherein lentamente, but to add bicarbonate of ammonia is good, since the bicarbonate of ammonia low price, reacting balance.The ammonium acetate that is added, volatile salt, yellow soda ash, salt of wormwood, the light sodium of carbonic acid, saleratus, bicarbonate of ammonia wherein a kind of amount of reagent make the PH1-6 of feed liquid, make the cerium precipitation fully, if PH can not precipitate fully less than 1 cerium, PH greater than 6 other rare earth elements also with the cerium coprecipitation.Making the pH value of feed liquid as if the amount that with the sulfuric acid aqueous solution that contains cerium and cerium other rare earth elements in addition is feed liquid adding bicarbonate of ammonia is that 2.5-3.5 is advisable; If with the hydrochloric acid acidic aqueous solution that contains other rare earth elements beyond cerium and the cerium or to contain cerium, when the hydrochloric acid acidic aqueous solution of lanthanum is feed liquid, it is 2-4.5 that the amount of adding bicarbonate of ammonia makes the pH value of feed liquid, the cerous hydroxide post precipitation (is checked the sedimentary supernatant liquor of cerous hydroxide, whether observe cerium precipitates fully, the method of checking be red-brown do not appear with the hydrogen peroxide inspection and till), carry out solid-liquid separation, solid-liquid separation can be used filter paper filtering, press filtration, methods such as centrifugation (method of following solid-liquid separation is with same herein), the cerous hydroxide water of separating (tap water or deionized water or distilled water) is sized mixing, under agitation add sulfuric acid or hydrochloric acid, but be good to add the vitriol oil.Heating is dissolved cerous hydroxide fully, and making the solution hydrogen ion concentration is the 0.1-3 mol.
For the cerous hydroxide that generates behind the adding bicarbonate of ammonia is dissolved better, Manganse Dioxide is easier to reduction of dissolved, after the cerous hydroxide water sized mixing under agitation the temperature of feed liquid remain on 5 °-70 ℃, be preferably under the condition of room temperature (15 °-30 ℃) and add S-WAT, feed temperature is too high to be surpassed 70 ℃ and makes the sulfurous acid accelerate decomposition, the amount that adds S-WAT is a cerium dioxide: S-WAT=1: the 0.30-3.0(weight ratio), but the amount that adds S-WAT is so that cerium dioxide: S-WAT=1: be good the 1.2-2.0(weight ratio), add sulfuric acid therebetween at this, preferably adding the vitriol oil, to make feed acidity keep PH be 0.5-5, preferably PH is 2.5-3.5, after the yellowish-white for the treatment of that material becomes, adding the vitriol oil again, to make the feed liquid hydrogen ion concentration be the 0.1-3 mol.
Remain under the 15 ℃-ebullient condition at feed temperature, and under constantly stirring, add sodium-chlor, sodium sulfate a kind of reagent wherein, make cerium generate cerous sulfate sodium double salt precipitation, but to add sodium-chlor is good, the sodium-chlor low price, the sodium-chlor that is added, sodium sulfate a kind of reagent wherein measure to cerium precipitation fully till (get supernatant liquor do not have a precipitation till) with the sodium sulfate inspection, restir 20-200 minute, carry out solid-liquid separation.
In order to improve the purity of product cerous hydroxide, with potassium permanganate trivalent cerium is oxidizing to tetravalence, use ammonium acetate, volatile salt, yellow soda ash, salt of wormwood, sodium bicarbonate, saleratus, bicarbonate of ammonia a kind of reagent wherein is settled out (to be good with bicarbonate of ammonia) behind the cerous hydroxide from contain the acid rare earth feed liquid beyond cerium and the cerium, at first use sulfuric acid or the hydrochloric acid soln pulp washing several of PH1-3.5, with sulphuric acid soln is good, pulp washing 1-4 time is for well, carry out then the solid-liquid separation water with cerous hydroxide size mixing the back add S-WAT more as stated above step carry out double salt precipitation.
The cerous sulfate sodium double salt of separating adds alkali metal hydroxide aqueous solution and carries out the alkali commentaries on classics by one of ordinary skill in the art's method in common knowledge, and cerous sulfate sodium double salt is changed into cerous hydroxide.Said alkali metal hydroxide is sodium hydroxide, potassium hydroxide, its method normally under agitation adds the sodium hydroxide of 5-14N in the container that fills cerous sulfate sodium double salt precipitation, making the free alkali in the solution is 0.1-0.6N sodium hydroxide, be heated to boiling, boil reaction 20-60 minute, make cerous sulfate double salt be converted into cerous hydroxide fully, add tap water, boil, make the cerous hydroxide sedimentation, take out supernatant liquor, with the alkaline aqueous solution washing for several times, general washing 1-2 time is filtered, and cerous hydroxide is dried under 400 ℃ temperature.Cerous hydroxide through oven dry becomes cerium dioxide by the method known to those of ordinary skills with the cerous hydroxide roasting.
Change the purity of the cerous hydroxide be precipitated out with containing the 0.2-0.8%(weight percentage in order to improve alkali) the sulphuric acid soln washing of the PH1-2.5 of S-WAT for several times, be advisable for 1-4 time with washing.Carry out solid-liquid separation after the washing.
Analysis determining method used in technological process of the present invention is, the mixed rare-earth oxide total amount is measured with the molten amount method of EDTA, cerium dioxide is measured with the ferrous sulfate reduction method, the neodymium sesquioxide spectrophotometry, calcium oxide EDTA volumetric determination, Manganse Dioxide periodic acid potassium oxidation colorimetry, the ferric oxide colorimetry.
The invention has the advantages that:
1. processing method of the present invention is an oxygenant with potassium permanganate, is settled out cerous hydroxide with alkaline carbonate, volatile salt, basic metal acid carbonate, bicarbonate of ammonia a kind of reagent wherein.With potassium permanganate is that oxygenant oxidation speed is fast, oxidation ratio can reach more than 99%, because it is big that potassium permanganate and S-WAT are used in combination the cerous hydroxide deposit seeds that makes generation, performance is good, filtration velocity is fast, and equipment is simple, and the building ring mirror is good, be suitable for large-scale industrial production, stable and reliable product quality.
2. make oxygenant with potassium permanganate, compare as oxygenant with air, hydrogen peroxide, ozone, chlorine, oxidation rate can improve 3-10 doubly, has particularly overcome the cerous hydroxide colloidal compound and has been difficult to filtering shortcoming.Cerous hydroxide does not need to handle again, can calcine out the powdery cerium oxide, has saved fragmentation operation such as sieve, and productive rate can improve more than 5 times, and atmospheric operation safety, the rate of recovery height of cerium.
3. processing method of the present invention is compared with the P204 solvent extration, and technical process is brief, the chemical materials cheapness, and the rate of recovery height of cerium, cost is low, has got rid of the many shortcomings of consumption acid, has reduced environmental pollution.
4. select ammonium bicarbonate precipitation cerous hydroxide reacting balance even, overcome local generation non-Ce rare earth element hydrogen oxide precipitation and influence the shortcoming of product purity.
5. select S-WAT to make Manganse Dioxide become the solubility bivalent manganese and removed impurity manganese as reductive agent, and the reduction quadrivalent cerium becomes trivalent cerium, inferior sulfate radical is oxidized to sulfate radical, precipitated cerium again, so S-WAT has played reduction and sedimentary two kinds of functions, save precipitation agent, reduced product cost.
6. processing method adaptability of the present invention is strong, can produce the ratio that contains cerium dioxide 85-99.8%(cerium dioxide and total amount of the rare earth oxide according to the different purposes of cerous hydroxide, cerium oxide) the cerium dioxide product.
The cerium dioxide that processing method of the present invention is produced can be used as the various cerium dioxides that glass polishing, painted, glass decolouring, carbon dioxide process carbon electrode and alloy addition are used, and can also produce the Ce(OH that contains cerium dioxide 63 ± 1% of crt glass shell decolouring usefulness) 4.From byproduct lanthanum rich rare earth solution, can make the lanthanum rich rare earth oxide compound of market in urgent need again.The content of cerium dioxide is less than 5% of the standard laid down by the ministries or commissions of the Central Government in the rich lanthanum-oxides.
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
Used feed liquid is the water logging sulfuric acid mishmetal aqueous solution of the vitriol intensified roasting in Baotou rare earth ore deposit in the present embodiment, contain 25 grams per liter rare earth oxides in the feed liquid, contain 12.5 grams per liter cerium dioxides, contain 0.09 grams per liter ferric oxide, contain 2.52 grams per liter calcium oxide, hydrogen ion concentration is 0.2 mol.The composition of feed liquid middle-weight rare earths element (with the ratio of total amount of rare earth) lanthanum sesquioxide 25.4%, cerium dioxide 50.1%, ten one oxidation six praseodymiums 4.5%, neodymium sesquioxide 15.6%, samarium sesquioxide 1.2%, europiumsesquioxide 0.2%, Gadolinium trioxide 0.4%, its rare earth oxide 2.6%.With 7 cubic metres feed liquids in 60 ℃, in stirring, add 29.2 kilograms in potassium permanganate, add bicarbonate of ammonia in time mixing of 40 minutes adding potassium permanganate, the PH that makes feed liquid is 3, and the precipitation cerium is after cerium precipitates fully in the sedimentary upper clear supernate of inspection cerous hydroxide, press filtration, cerous hydroxide is separated from solution, and the filtrate middle-weight rare earths consists of and contains 0.79% cerium dioxide in the total rare earth (TRE) oxide compound, contains other rare earth oxides of 99.21%.With the cerous hydroxide separated precipitation with the sulphuric acid soln pulp washing of PH2 2 times, each sulphuric acid soln 400 liters with PH2, press filtration, carry out solid-liquid separation, the cerous hydroxide precipitation of separating is sized mixing with 300 liters of tap water, feed temperature is 25 ℃, in stirring, add 87.5 kilograms of S-WATs, adding the vitriol oil during this period, to make feed liquid keep PH be 2, treat that material becomes white after, adding the acidity that the vitriol oil makes feed liquid again is PH0.5, in 95 ℃ of feed liquids, and under constantly stirring, add 105 kg sodium-chlor, and continue to stir after 30 minutes and carry out press filtration, isolate cerous sulfate sodium double salt precipitation.The sodium hydroxide solution that in stirring, in the container that fills cerous sulfate sodium double salt precipitation, adds 8N, the free alkali that makes feed liquid is a 0.5N sodium hydroxide, be heated to and boil, boil reaction 40 minutes, make cerous sulfate sodium double salt be converted into cerous hydroxide fully, add tap water, boil, make the cerous hydroxide sedimentation, take out supernatant liquor, wash with water 2 times, filter, in 400 ℃ of oven dry, berkelium burns till cerium dioxide with cerous hydroxide, and products obtained therefrom contains 95.7% cerium dioxide, contain 4.3% other rare earth oxides, contain 0.04% ferric oxide, contain Manganse Dioxide, contain calcium oxide less than 0.05% less than 0.2%.The rate of recovery of cerium is greater than 98%.
Embodiment 2
Its working method and condition are substantially with embodiment 1, only different is that used feed liquid is the acid aqueous solution of mixed light rare earth salt after P204 neodymium-samarium grouping, contain 250.6 grams per liter rare earth oxides in the feed liquid, contain 130.1 gram liter cerium dioxides, contain 0.007 grams per liter ferric oxide, contain 1.7 grams per liter calcium oxide, hydrogen ion concentration is 0.5 mol, the composition of feed liquid middle-weight rare earths element (with the ratio of total amount of rare earth) lanthanum sesquioxide 26.3%, cerium dioxide 51.9%, ten one oxidation six praseodymiums 5.2%, neodymium sesquioxide 16.1%, samarium sesquioxide 0.1%, other rare earth oxide are 0.4%.With 6 cubic metres of feed liquids under 15 ℃, add 278 kilograms in potassium permanganate, add bicarbonate of ammonia in time mixing of 80 minutes adding potassium permanganate, the PH that makes feed liquid is 5, isolate filtrate middle-weight rare earths behind the cerous hydroxide and consist of and contain 0.25% cerium dioxide in the total rare earth (TRE) oxide compound, contain 99.75% other rare earth oxides.The cerous hydroxide separated precipitation with the sulphuric acid soln pulp washing of PH3.5 2 times, is used PH3.5 sulphuric acid soln 800 liters at every turn, and press filtration is sized mixing with 800 liter tap water, is 15 ℃ at feed temperature, adds 1355 kilograms of S-WATs.Adding the vitriol oil during this period, to make feed liquid PH be 3.5, treat material become faint yellow after, adding the vitriol oil again, to make the hydrogen ion concentration of feed liquid be 1.5 mol, 20 ℃ of feed liquids, adds 603 kilograms of sodium-chlor, continues to stir after 20 minutes solid-liquid separation.The products obtained therefrom cerium dioxide contains 90.5% cerium dioxide, contains other rare earth oxides of 9.5%, contains 0.028% ferric oxide, contains less than 0.2% Manganse Dioxide, contains less than 0.05% calcium oxide, and the rate of recovery of cerium is greater than 95%.
Embodiment 3
Its working method and condition are substantially with embodiment 1, only different is that used feed liquid is lanthanum, the cerium hydrochloric acid acidic aqueous solution after P507 carries out cerium, praseodymium grouping, contain 85.6 grams per liter rare earth oxides in the feed liquid, contain 56 grams per liter cerium dioxides, contain 0.08 grams per liter ferric oxide, contain 2.7 grams per liter calcium oxide, hydrogen ion concentration is 0.4 mol, the composition of feed liquid middle-weight rare earths element (with the ratio of total amount of rare earth) lanthanum sesquioxide 32.9%, cerium dioxide 65.4%, 11 oxidations, six praseodymiums 0.83%, neodymium sesquioxide 0.7%, other rare earth oxides are 0.17%.With 6 cubic metres feed liquids under 40 ℃, add 102.8 kilograms in potassium permanganate, adding bicarbonate of ammonia in time mixing of 50 minutes adding potassium permanganate makes feed liquid PH remain 2, isolate filtrate middle-weight rare earths behind the cerous hydroxide and consist of and contain 1.59% cerium dioxide in the total rare earth (TRE) oxide compound, contain 98.4% other rare earth oxides.Is 1 sulphuric acid soln pulp washing 3 times with the cerous hydroxide separated precipitation with PH, each sulphuric acid soln 600 liters with PH1.5, press filtration, size mixing with 500 premium on currency, add 180 kilograms of S-WATs, adding the vitriol oil during this period, to keep feed liquid PH be 1.5, treat that material becomes white after, adding the vitriol oil again, to make hydrogen ion concentration be 2 mol, add sodium sulfate, continue to stir after 40 minutes solid-liquid separation, products obtained therefrom contains 99.8% cerium dioxide, contain other rare earth oxides of 0.20%, contain 0.038% ferric oxide, contain Manganse Dioxide less than 0.2%, contain 0.08% calcium oxide, the rate of recovery of cerium is greater than 98%.
Embodiment 4
Its working method and condition be substantially with embodiment 2, and only different is to add bicarbonate of ammonia to make the PH of feed liquid remain 3, isolates cerous hydroxide rear filtrate middle-weight rare earths and consist of and contain 0.86% cerium dioxide in the total rare earth (TRE) oxide compound, contains other rare earth oxides of 99.14%.The cerous hydroxide separated precipitation is behind the sulphuric acid soln pulp washing of PH2 2 times, press filtration, the cerous hydroxide of separating is deposited under 95 ℃ the temperature with concentrated sulfuric acid dissolution cerous hydroxide precipitation (not adding S-WAT), the acidity of control feed liquid is 2 mol, under boiling, add sodium-chlor, continue to boil and stirred 2 hours, solid-liquid separation, cerous sulfate sodium double salt is changed into cerous hydroxide, with the sulphuric acid soln pulp washing of the PH2 of 0.5% S-WAT 2 times, each with 500 liters of the PH2 sulphuric acid solns that contains 0.5% S-WAT (weight percentage), press filtration.Products obtained therefrom (cerium dioxide) contains 88.7% cerium dioxide, contains 17.3% other rare earth oxides, contains 0.05% ferric oxide, contains less than 0.2% Manganse Dioxide, contains 0.07% calcium oxide.
Embodiment 5
Its working method and condition are substantially with embodiment 2, only different is adds bicarbonate of ammonia to make feed liquid keep its PH is 3, isolating cerous hydroxide rear filtrate middle-weight rare earths consists of and contains 1.05% cerium dioxide in the total rare earth (TRE) oxide compound, contain other rare earth oxides of 98.95%, behind the hydrochloric acid soln pulp washing of PH2 2 times, solid-liquid separation, it is 70 ℃ that the cerous hydroxide of separating is deposited in feed temperature, add 376 kilograms of S-WATs, add concentrated hydrochloric acid during this period and make feed liquid PH 1 treat that material becomes white, adding concentrated hydrochloric acid again, to make the hydrogen ion concentration of feed liquid be 1.0 mol, when 40 ℃ of feed temperatures, adding sodium sulfate does not have the precipitation appearance in sedimentary upper clear supernate, continue to stir press filtration 30 minutes, contain 93.2% cerium dioxide in the gained cerium dioxide, contain 6.8% other rare earth oxides, contain 0.04% ferric oxide.Contain less than 0.2% Manganse Dioxide, contain 0.05% calcium oxide.The rate of recovery of cerium is greater than 99%.
Claims (6)
1, a kind of processing method of producing cerous hydroxide is a feed liquid with the acidic aqueous solution that contains cerium and cerium rare earth element in addition, and feature of the present invention is:
(1) with potassium permanganate be oxygenant, it is 1-6 that adding ammonium acetate, volatile salt, yellow soda ash, salt of wormwood, sodium bicarbonate, saleratus, bicarbonate of ammonia a kind of reagent wherein make the PH of feed liquid, separates the solid hydrogen cerium oxide precipitation that is generated,
(2) add sour dissolved hydrogen cerium oxide, the hydrogen ion concentration that makes feed liquid is the 0.1-3 mol, adds sodium-chlor, sodium sulfate a kind of reagent wherein, generates cerous sulfate sodium double salt precipitation, carries out solid-liquid separation,
(3) with alkali metal hydroxide cerous sulfate sodium double salt is changed into cerous hydroxide, carry out solid-liquid separation.
According to a kind of processing method of producing cerous hydroxide of claim 1, it is characterized in that 2, the temperature of feed liquid remains on 5 °-100 ℃ when under agitation adding oxidant potassium permanganate.
3, according to a kind of processing method of producing cerous hydroxide of claim 1, it is characterized in that, with add the cerous hydroxide water that generates behind the bicarbonate of ammonia size mixing after under agitation the temperature of feed liquid remain on 50 °-70 ℃ and add S-WATs, the amount that adds S-WAT is a cerium dioxide: S-WAT=1: the 0.30-3.0(weight ratio), adding sulfuric acid during this period makes feed acidity protect PH0.5-5, after the yellowish-white for the treatment of that material becomes, adding the vitriol oil again, to make the feed liquid hydrogen ion concentration be the 0.1-3 mol.
4, according to a kind of processing method of producing cerous hydroxide of claim 1, it is characterized in that, remain under the 15 ℃-ebullient condition at feed temperature, add sodium-chlor in stirring, sodium sulfate a kind of reagent wherein makes cerium generate cerous sulfate sodium and precipitates again, the amount that is added, complete to the cerium precipitation, restir 20-200 minute, carry out solid-liquid separation.
5, according to a kind of processing method of producing cerous hydroxide of claim 1, it is characterized in that, after being settled out cerous hydroxide the acid rare earth feed liquid of bicarbonate of ammonia beyond containing cerium and cerium, sulfuric acid, hydrochloric acid a kind of solution pulp washing cerous hydroxide precipitation several wherein with PH1-3.5, the water adding S-WAT of sizing mixing carries out cerous sulfate sodium double salt precipitation then.
According to a kind of processing method of producing cerous hydroxide of claim 1, it is characterized in that 6, alkali changes the cerous hydroxide be precipitated out with containing the 0.2-0.8%(weight percentage) the sulphuric acid soln washing of the PH1-2.5 of S-WAT is for several times.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN89103858A CN1017984B (en) | 1989-06-19 | 1989-06-19 | Process for preparing pure cerium hydroxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN89103858A CN1017984B (en) | 1989-06-19 | 1989-06-19 | Process for preparing pure cerium hydroxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1048239A true CN1048239A (en) | 1991-01-02 |
| CN1017984B CN1017984B (en) | 1992-08-26 |
Family
ID=4855324
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN89103858A Expired CN1017984B (en) | 1989-06-19 | 1989-06-19 | Process for preparing pure cerium hydroxide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1017984B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1114564C (en) * | 1999-04-01 | 2003-07-16 | 张其春 | Technological process of preparing pure cerium hydroxide |
| CN101955218A (en) * | 2010-05-31 | 2011-01-26 | 北京颖新泰康国际贸易有限公司 | Method for preparing ceric compound by using cerous salt-containing aqueous solution |
| CN103917672A (en) * | 2011-11-14 | 2014-07-09 | 住友金属矿山株式会社 | Method for recovering rare earth element |
| CN109167006A (en) * | 2018-04-27 | 2019-01-08 | 华东交通大学 | A kind of lithium ion battery separator and preparation method thereof |
| CN109628768A (en) * | 2018-12-17 | 2019-04-16 | 中铝广西国盛稀土开发有限公司 | A kind of method that conventional ion adsorption method prepares high-purity rare-earth |
| CN112981148A (en) * | 2021-02-08 | 2021-06-18 | 江西理工大学 | Method for separating cerium, calcium and magnesium by oxidizing, hydrolyzing and precipitating |
-
1989
- 1989-06-19 CN CN89103858A patent/CN1017984B/en not_active Expired
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1114564C (en) * | 1999-04-01 | 2003-07-16 | 张其春 | Technological process of preparing pure cerium hydroxide |
| CN101955218A (en) * | 2010-05-31 | 2011-01-26 | 北京颖新泰康国际贸易有限公司 | Method for preparing ceric compound by using cerous salt-containing aqueous solution |
| CN101955218B (en) * | 2010-05-31 | 2012-07-04 | 北京颖新泰康国际贸易有限公司 | Method for preparing ceric compound by using cerous salt-containing aqueous solution |
| CN103917672A (en) * | 2011-11-14 | 2014-07-09 | 住友金属矿山株式会社 | Method for recovering rare earth element |
| CN103917672B (en) * | 2011-11-14 | 2016-06-22 | 住友金属矿山株式会社 | The recovery method of rare earth element |
| CN109167006A (en) * | 2018-04-27 | 2019-01-08 | 华东交通大学 | A kind of lithium ion battery separator and preparation method thereof |
| CN109167006B (en) * | 2018-04-27 | 2021-08-20 | 华东交通大学 | Lithium ion battery diaphragm and preparation method thereof |
| CN109628768A (en) * | 2018-12-17 | 2019-04-16 | 中铝广西国盛稀土开发有限公司 | A kind of method that conventional ion adsorption method prepares high-purity rare-earth |
| CN112981148A (en) * | 2021-02-08 | 2021-06-18 | 江西理工大学 | Method for separating cerium, calcium and magnesium by oxidizing, hydrolyzing and precipitating |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1017984B (en) | 1992-08-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA2833281A1 (en) | A method for recovering indium, silver, gold and other rare, precious and base metals from complex oxide and sulfide ores | |
| Morais et al. | Recovery of europium by chemical reduction of a commercial solution of europium and gadolinium chlorides | |
| CN1114564C (en) | Technological process of preparing pure cerium hydroxide | |
| CN1289699C (en) | Process for preparing cerous hydroxide | |
| CN114684801A (en) | Method for preparing high-purity iron phosphate by using pyrite cinder | |
| CN1048239A (en) | Process for preparing pure cerium hydroxide | |
| CN111235392A (en) | Method for deep oxidation and harmless comprehensive recovery of valuable metals from zinc sulfite slag | |
| CN117327930B (en) | Method for recovering vanadium from primary shale stone coal | |
| US20030150818A1 (en) | Processes for treating iron-containing waste streams | |
| CN114275815A (en) | Method for preparing high-purity vanadium pentoxide by reducing and precipitating sodium vanadium solution | |
| CN112981148A (en) | Method for separating cerium, calcium and magnesium by oxidizing, hydrolyzing and precipitating | |
| CN108977675A (en) | A kind of method that anti-charging precipitating-baking inphases prepare low sulfur content rare earth oxide | |
| WO2020138137A1 (en) | Method for purifying vanadium oxide | |
| GB2194941A (en) | Process for recovering vanadium values | |
| CN1683568A (en) | Sulfuric acid process for treating bastnaesite and separating and purifying cerium | |
| CN1009079B (en) | Method of production of titanium dioxide | |
| CN1028769C (en) | Process for cerium oxide | |
| US2462499A (en) | Process for recovering manganese values from manganese ores | |
| CA1077176A (en) | Process for neutralizing waste sulfuric acids | |
| CN1021579C (en) | Process for separating cerium dioxicde from mixed rare earth | |
| CN102050495A (en) | Process for preparing tetrahydrate manganese chloride by leaching out rhodochrosite with waste acid | |
| CN1102175C (en) | Method for recovering copper and zinc oxide from copper-zinc waste catalyst | |
| CN1119424C (en) | Process for extracting cerium by oxydol oxidation method | |
| CN1034744C (en) | Method of extracting cerium-rich solution | |
| CN1053412A (en) | The bicarbonate of ammonia neutralisation is produced zinc oxide |
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 | ||
| C15 | Extension of patent right duration from 15 to 20 years for appl. with date before 31.12.1992 and still valid on 11.12.2001 (patent law change 1993) | ||
| OR01 | Other related matters | ||
| 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 |