CN1635169A - Process for preparing cerous hydroxide - Google Patents
Process for preparing cerous hydroxide Download PDFInfo
- Publication number
- CN1635169A CN1635169A CNA2003101103295A CN200310110329A CN1635169A CN 1635169 A CN1635169 A CN 1635169A CN A2003101103295 A CNA2003101103295 A CN A2003101103295A CN 200310110329 A CN200310110329 A CN 200310110329A CN 1635169 A CN1635169 A CN 1635169A
- Authority
- CN
- China
- Prior art keywords
- cerium
- cerous
- hydroxide
- described step
- ion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 title claims description 41
- 238000004519 manufacturing process Methods 0.000 title abstract description 10
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 27
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000007788 liquid Substances 0.000 claims abstract description 15
- 239000003513 alkali Substances 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 11
- -1 cerium ion Chemical class 0.000 claims abstract description 10
- 238000002360 preparation method Methods 0.000 claims abstract description 9
- 239000007787 solid Substances 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 6
- 150000002500 ions Chemical class 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 238000007254 oxidation reaction Methods 0.000 claims description 16
- 230000003647 oxidation Effects 0.000 claims description 14
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 12
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 8
- XMPZTFVPEKAKFH-UHFFFAOYSA-P ceric ammonium nitrate Chemical compound [NH4+].[NH4+].[Ce+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O XMPZTFVPEKAKFH-UHFFFAOYSA-P 0.000 claims description 8
- 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 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 229910000333 cerium(III) sulfate Inorganic materials 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 239000012286 potassium permanganate Substances 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- 238000013019 agitation Methods 0.000 claims description 4
- GHLITDDQOMIBFS-UHFFFAOYSA-H cerium(3+);tricarbonate Chemical compound [Ce+3].[Ce+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O GHLITDDQOMIBFS-UHFFFAOYSA-H 0.000 claims description 4
- 239000000460 chlorine Substances 0.000 claims description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 238000000354 decomposition reaction Methods 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 230000015556 catabolic process Effects 0.000 claims 1
- 238000006731 degradation reaction Methods 0.000 claims 1
- 229910052761 rare earth metal Inorganic materials 0.000 abstract description 26
- 150000002910 rare earth metals Chemical class 0.000 abstract description 20
- 239000000047 product Substances 0.000 abstract description 14
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 abstract description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 abstract description 2
- 239000002244 precipitate Substances 0.000 abstract description 2
- UNJPQTDTZAKTFK-UHFFFAOYSA-K cerium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Ce+3] UNJPQTDTZAKTFK-UHFFFAOYSA-K 0.000 abstract 3
- DPUCLPLBKVSJIB-UHFFFAOYSA-N cerium;tetrahydrate Chemical compound O.O.O.O.[Ce] DPUCLPLBKVSJIB-UHFFFAOYSA-N 0.000 abstract 2
- 239000007800 oxidant agent Substances 0.000 abstract 2
- 239000000463 material Substances 0.000 abstract 1
- 238000005272 metallurgy Methods 0.000 abstract 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 11
- 238000001556 precipitation Methods 0.000 description 10
- 229910000420 cerium oxide Inorganic materials 0.000 description 7
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 7
- 239000012535 impurity Substances 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 235000001018 Hibiscus sabdariffa Nutrition 0.000 description 3
- 235000005291 Rumex acetosa Nutrition 0.000 description 3
- 240000007001 Rumex acetosella Species 0.000 description 3
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 235000003513 sheep sorrel Nutrition 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 description 2
- 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
- WMOHXRDWCVHXGS-UHFFFAOYSA-N [La].[Ce] Chemical compound [La].[Ce] WMOHXRDWCVHXGS-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- ITZXULOAYIAYNU-UHFFFAOYSA-N cerium(4+) Chemical compound [Ce+4] ITZXULOAYIAYNU-UHFFFAOYSA-N 0.000 description 1
- VZDYWEUILIUIDF-UHFFFAOYSA-J cerium(4+);disulfate Chemical compound [Ce+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VZDYWEUILIUIDF-UHFFFAOYSA-J 0.000 description 1
- 229910000355 cerium(IV) sulfate Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- FGHSTPNOXKDLKU-UHFFFAOYSA-N nitric acid;hydrate Chemical compound O.O[N+]([O-])=O FGHSTPNOXKDLKU-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-O oxonium Chemical compound [OH3+] XLYOFNOQVPJJNP-UHFFFAOYSA-O 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 238000005502 peroxidation Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention belongs to wet method metallurgy field of rare earth production, especially relates to a preparation method for cerium hydroxide. The method comprises: (1) adding raw cerium material into alkali liquor with stirring for creating precipitate Ce(OH)3 ensuring that the mol ratio of OH ion and cerium ion is 0.5-4:1; (2) adding oxidizing agent with stirring under normal temperature with mol ratio of oxidizing agent and Ce(OH)3 as 0.1-4:1 for creating Ce(OH)4 or Ce(OH)3OOH; (3) washing the Ce(OH)4 obtained in step (2), separating the solid from liquid, airing, and obtaining the cerium hydroxide product. The invention has a wide range of application. According to different purposes, cerium hydroxide products with different purities (80~99.9999%(CeO2/sigma RE2O3)) depending to the raw material.
Description
Technical field
The invention belongs to the hydrometallurgy field of Rare Earth Production, particularly the preparation method of cerous hydroxide.
Background technology
Cerous hydroxide is a kind of important industrial raw material, is used as toughness, intensity and other optical property that the colour television flourescent screen additive can change fluorescent glass, also can be used for preparing ceric ammonium nitrate, and boundless development prospect is arranged.
Producing cerous hydroxide has many kinds of methods, mainly contains following four kinds at present:
(1) Chinese patent literature CN 87100620A has proposed a kind of method of producing cerous hydroxide, the acidic aqueous solution separated into two parts that contains cerium and cerium rare earth element in addition, alkali metal hydroxide or ammonia are added in the first part, separate the rare-earth hydroxide solid that is generated, again this solid is added generation cerous hydroxide solid in the second section in company with oxygenant.The advantage of this method is that technical process is short, and the impurity of introducing is less, but the product purity that obtains is low, and wherein cerium oxide only can account for 83.6% of total rare earth content.
(2) method of the production cerous hydroxide of Chinese patent literature CN 1075171A proposition is to add precipitation agent to generate carbonated rare earth in the mishmetal feed liquid, add oxygenant again and generate high cerium double salt and peroxidation cerium, the hydrogen ion that hydrolysis generates in this process can be with non-cerium carbonated rare earth dissolving, generate ceric sulfate after reacting by heating is complete, prepare cerous hydroxide.This method technology is simple, the foreign ion of introducing is less, but oxygenant directly adds in the carbonated rare earth, oxidation rate is slower, the full hydrogen ion that generates by hydrolysis dissolves also limited value very of trivalent rare earth speed, must strict control condition just trivalent rare earth can be removed, the purity of cerous hydroxide just can improve.
(3) method of the production cerous hydroxide that proposes of Chinese patent literature CN 1269327A is to be raw material with the mishmetal feed liquid, and alkali changes makes RE
3-Be precipitated as RE (OH)
3Add the Ce (OH) in the oxygenant oxidation mixing rare earth hydrate
3Be Ce (OH)
4Adding acid dissolves rare-earth precipitation fully, at this moment contained cerium is to coexist as in the solution with the form of tetravalence attitude and other trivalent rare earth, then through adding precipitation agent or heating, destroy the stability of cerium (IV) in the acidic solution, it is separated out with the form of cerous hydroxide particulate, obtain to contain the suspension of cerous hydroxide; Filtering separation, filtrate are few cerium lanthanum concentrate rare earth chloride solution, and filter cake obtains cerous hydroxide after washing.But the cerous hydroxide purity that this method is produced is not high, can carry a large amount of rare earth impurities secretly, be difficult to washing and cause the wasting of resources, and separating out of cerous hydroxide will control pH value of solution and remains on 1～2 just passablely, needs control pH value of solution with weak base the difficult control of actually operating.
(4) method of the production cerous hydroxide that proposes of Chinese patent literature CN 1048239A is to use potassium permanganate to produce cerous hydroxide in the acidic aqueous solution that contains rare earth beyond cerium and the cerium.This technology is oxidized to quadrivalent cerium with potassium permanganate with trivalent cerium earlier, generates hydronium(ion) oxidation cerium and manganous hydroxide (IV) precipitation, realizes that cerium separates with other non-Ce rare earth, and the gained precipitation adds sulphite reduction quadrivalent cerium and tetravalence manganese is Ce
2(SO
4)
3And bivalent manganese, add an alkali metal salt and generate cerous sulfate (III) sodium double salt precipitation, reach cerium, manganese separation, finally again double salt alkali is changed into cerous hydroxide.The cerous hydroxide that this method is produced easily filters, oxidation ratio height and speed of response are very fast, but still has wretched insufficiency: technology is loaded down with trivial details, and flow process is oversize; Used supplementary material is more, and it is more to introduce non-rare earth impurity, makes that cerous hydroxide purity is lower; Solid-liquid separation repeatedly, washing times is many, reduces yield.
The preparation method of above-mentioned cerous hydroxide is from the mishmetal feed liquid, the cerous hydroxide product that is obtained be difficult to filter and product purity lower, can carry parcel Na secretly
+, Mn
2+, SO
4 2-With other rare earth impurities etc., make that the cerous hydroxide purity that these methods obtained is on the low side, in the fields of much having relatively high expectations, for example make automobile exhaust purifier, produce ceric ammonium nitrate etc. for product impurity, be restricted during application.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of cerous hydroxide,, high oxidation rate, high total amount high-purity, be soluble in the cerous hydroxide of nitric acid realize to obtain, and the method easy handling, stable and reliable product quality, with short production cycle.
Preparation method's step of cerous hydroxide of the present invention comprises:
(1) under agitation add alkali lye in cerium raw material (when the cerium raw material is solid, need adds water and size mixing), the throw out of generation is Ce (OH)
3, contained OH in the alkali lye
-The mol ratio of cerium ion is 0.5～4: 1 in ion and the cerium feed liquid, contained OH in the alkali lye
-Concentration is 3wt～50wt%.
(2) add oxygenant under the stirring at normal temperature, the oxygenant of adding and Ce (OH)
3Mol ratio be 0.1～4: 1; Ce (OH)
3Oxidation products is Ce (OH)
4Or Ce (OH)
3OOH;
As Ce (OH)
3The oxidation products therefrom is Ce (OH)
3During OOH, need be heated to 50～130 ℃, make its decomposition obtain Ce (OH)
4
(3) washing step (2) gained Ce (OH)
4, solid-liquid separation is dried, and obtains the product cerous hydroxide.
Cerium feed liquid described in the step (1) is selected from one or more in cerous nitrate, Cerium II Chloride, cerous sulfate, cerous carbonate or the ceric ammonium nitrate.
Alkali described in the step (1) is selected from one or more in sodium hydroxide, potassium hydroxide, the ammoniacal liquor.
Oxygenant described in the step (2) is selected from one or more in air, oxygen, ozone, hydrogen peroxide, potassium permanganate, chlorine or the perchloric acid.When selecting air, calculate with oxygenous amount.
The inventive method was compared with former other technology, had following obvious advantage:
1) the method scope of application of the present invention is very wide.Can produce cerous hydroxide purity according to the different purposes of cerous hydroxide is 80～99.999% (CeO
2/ ∑ RE
2O
3) variant production, purity is determined by raw material.
2) the cerous hydroxide particle of being produced is thick, is easy to filter, and be the best of raw material with the cerous carbonate especially wherein, filtration velocity is the fastest.
3) the oxidation ratio height of the cerous hydroxide of being produced is generally at 98～99.9% (Ce
4+/ ∑ Ce).
4) the cerous hydroxide total amount height of being produced, cerium dioxide account for gross weight 70～90% between.
5) has good nitric acid dissolve.The prepared product solvability of the present invention is better than cerous hydroxide nitric acid dissolve conventional criteria: under 90～100 ℃ condition, the 50g cerous hydroxide dissolves in the nitric acid of 88ml 67%, and solution is as clear as crystal, no residue.
6) the reaction conditions gentleness, the reaction times is short, productive rate is high, the raw material cheapness, environmental pollution is minimum.The method according to this invention just can be produced cerous hydroxide in the simple mode of industrial usefulness.
Below, the present invention will be described in more detail with reference to example.But the present invention is not subjected to the restriction of these specific examples.
Embodiment
Embodiment 1:
With purity is that 99% cerous carbonate adds water and sizes mixing, and is mixed with to contain CeO
2The feed liquid of 170g/L.
1) under agitation add the sodium hydroxide solution of 10wt%, the sodium hydroxide of adding and the mol ratio of rare earth ion are 0.6: 1, generate canescence Ce (OH)
3Precipitation.
2) add hydrogen peroxide, the mol ratio of hydrogen peroxide and rare earth ion is 1: 1,65 ℃ of oxidations 1 hour, Ce (OH)
3Be oxidized to the sorrel superoxide.
3) be warming up to 100 ℃, heated 2 hours, the sorrel superoxide fades to yellow Ce (OH)
4
4) hot wash is 7 to pH, and normal temperature dries.
5) the cerous hydroxide sample oxidation ratio that is obtained by step 4) is 98.8%, is soluble in nitric acid, CeO
2Content is 77%, and the glassy yellow powder is mobile good, wherein Cl
-Content is 0.048%, Na
+Content 0.0072% is not introduced other metal and nonmetallic impurity.
Embodiment 2:
The direct CeCl that comes out with extraction tank
3Preparation, cerium oxide content 1.3mol/L wherein, cerium oxide accounts for 99% of total amount of rare earth, pH value of solution 2～3, all the other processing condition are with embodiment 1.
The cerium partition is 99.9% in the gained cerous hydroxide, oxidation ratio 99.3%, CeO
2Content is 42%, and mobile poor, solvability is good; Through the ethanol rinse in 110 ℃ the oven dry 1 hour after, good fluidity, CeO
2Content can reach 77%, and solvability is still up to standard, Cl
-Content is 0.050%, Na
+Content 0.0063%.
Embodiment 3:
With cerous sulfate solution is raw material, wherein cerium ion concentration is 1.1mol/L, pH value of solution 2～3, adding weight at normal temperatures in solution is the ammoniacal liquor of 1.3ReO, generates gray precipitate, the mol ratio that adds potassium permanganate and rare earth ion is 0.5: 1, precipitation becomes the sorrel superoxide, is heated to 100 ℃ and decomposes 2 hours yellowly cerous hydroxide precipitations, wash to pH be 7, the ethanol rinse was dried 1 hour for 110 ℃.Products obtained therefrom oxidation ratio 98.4%, CeO
2Content is 73%, and solvability is good, good fluidity.
Embodiment 4:
Because the method production that a lot of rare earth producers are usefulness forms double salt, purification cerium oxide for simplicity, can be the feedstock production cerous hydroxide with cerous sulfate sodium directly.
2n cerous sulfate sodium is added water size mixing, be mixed with and contain CeO
2The feed liquid of 150g/L, other processing condition are with embodiment 1.
Products obtained therefrom oxidation ratio 97.8%, CeO
2Content is 69%, and solvability is good, good fluidity.But reaction finishes back waste water contains more SO
4 2-, just can discharge after must handling.
Embodiment 5:
By CeCl
3Preparation, cerium oxide content 170g/L wherein, cerium oxide accounts for 95% of total amount of rare earth, and pH value of solution 2～3 under agitation adds 30% industrial liquid caustic soda, and liquid caustic soda weight is 1.7ReO, generates canescence Ce (OH)
3Precipitation is simultaneously with 100m
3/ hour speed blast air, stirred at normal temperatures then 6 hours, hot wash is 7 to pH, normal temperature dries.
Products obtained therefrom oxidation ratio 96.5%, CeO
2Content is 53%, and cerium oxide accounts for 95% of total amount of rare earth.
Claims (7)
1. the preparation method of a cerous hydroxide, it is characterized in that: described method steps comprises:
(1). under agitation add alkali lye in the cerium raw material, the throw out of generation is Ce (OH)
3, contained OH in the alkali lye
-The mol ratio of cerium ion is 0.5～4: 1 in ion and the cerium feed liquid;
(2). add oxygenant under the stirring at normal temperature, the oxygenant of adding and Ce (OH)
3Mol ratio be 0.1～4: 1, Ce (OH)
3Oxidation products is Ce (OH)
4Or Ce (OH)
3OOH;
As Ce (OH)
3The oxidation products therefrom is Ce (OH)
3During OOH, need heating to make its decomposition obtain Ce (OH)
4
(3). washing step (2) gained Ce (OH)
4, solid-liquid separation obtains the product cerous hydroxide.
2. the method for claim 1 is characterized in that: when the cerium raw material in the described step (1) is solid, need adds water and size mixing.
3. the method for claim 1 is characterized in that: contained OH in described step (1) alkali lye
-Concentration is 3wt～50wt%.
4. the method for claim 1, it is characterized in that: the cerium feed liquid in the described step (1) is selected from one or more in cerous nitrate, Cerium II Chloride, cerous sulfate, cerous carbonate or the ceric ammonium nitrate.
5. the method for claim 1, it is characterized in that: the alkali in the described step (1) is selected from one or more in sodium hydroxide, potassium hydroxide, the ammoniacal liquor.
6. the method for claim 1, it is characterized in that: the oxygenant in the described step (2) is selected from one or more in air, oxygen, ozone, hydrogen peroxide, potassium permanganate, chlorine or the perchloric acid.
7. the method for claim 1, it is characterized in that: the temperature of the need thermal degradation in the described step (2) is 50～130 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2003101103295A CN1289699C (en) | 2003-12-30 | 2003-12-30 | Process for preparing cerous hydroxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2003101103295A CN1289699C (en) | 2003-12-30 | 2003-12-30 | Process for preparing cerous hydroxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1635169A true CN1635169A (en) | 2005-07-06 |
| CN1289699C CN1289699C (en) | 2006-12-13 |
Family
ID=34843197
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2003101103295A Expired - Fee Related CN1289699C (en) | 2003-12-30 | 2003-12-30 | Process for preparing cerous hydroxide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1289699C (en) |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101891235A (en) * | 2010-07-17 | 2010-11-24 | 天津市化学试剂研究所 | Method for preparing high-grade pure ceric sulfate |
| CN102775635A (en) * | 2012-08-16 | 2012-11-14 | 上海华明高纳稀土新材料有限公司 | Cerium hydroxide heat stabilizer and preparation method thereof |
| CN102992380A (en) * | 2012-09-22 | 2013-03-27 | 包头市京瑞新材料有限公司 | Method for preparing macrogranular europium oxide |
| CN103058724A (en) * | 2012-09-22 | 2013-04-24 | 包头市京瑞新材料有限公司 | Preparation method of large-particle gadolinium oxide |
| CN103073045A (en) * | 2012-09-22 | 2013-05-01 | 包头市京瑞新材料有限公司 | Preparation method of peroxycarbonate gadolinium |
| CN103482673A (en) * | 2013-10-12 | 2014-01-01 | 瑞科稀土冶金及功能材料国家工程研究中心有限公司 | Preparation method of rare earth hydroxide |
| CN103526056A (en) * | 2013-10-09 | 2014-01-22 | 中国科学院长春应用化学研究所 | Wet-method atmospheric oxidation method of cerium in rare earth hydroxides |
| CN103910373A (en) * | 2014-04-04 | 2014-07-09 | 江西稀有金属钨业控股集团有限公司 | Method and system for preparing cerium hydroxide |
| CN106186036A (en) * | 2016-07-10 | 2016-12-07 | 九江学院 | A kind of preparation method of hexagon cerium dioxide nano sheet material |
| CN107973331A (en) * | 2018-01-19 | 2018-05-01 | 常州市卓群纳米新材料有限公司 | A kind of pollution-free preparation method of ceric sulfate |
| CN109761259A (en) * | 2019-03-27 | 2019-05-17 | 淄博加华新材料资源有限公司 | A kind of high preparation method at colloidality cerium glue |
| CN111060501A (en) * | 2019-12-06 | 2020-04-24 | 山东理工大学 | Nano cerium peroxide catalyst and method for catalyzing TMB color development by using same |
| CN112074619A (en) * | 2018-05-03 | 2020-12-11 | 阿拉弗拉资源有限公司 | Treatment of rare earth sulphate solutions |
| CN112919524A (en) * | 2021-03-08 | 2021-06-08 | 益阳鸿源稀土有限责任公司 | Preparation method of high-purity ceric sulfate tetrahydrate |
| 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 |
| CN113023763A (en) * | 2021-03-08 | 2021-06-25 | 益阳鸿源稀土有限责任公司 | Preparation method of high-purity cerium ammonium sulfate |
-
2003
- 2003-12-30 CN CNB2003101103295A patent/CN1289699C/en not_active Expired - Fee Related
Cited By (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101891235A (en) * | 2010-07-17 | 2010-11-24 | 天津市化学试剂研究所 | Method for preparing high-grade pure ceric sulfate |
| CN102775635A (en) * | 2012-08-16 | 2012-11-14 | 上海华明高纳稀土新材料有限公司 | Cerium hydroxide heat stabilizer and preparation method thereof |
| CN102992380A (en) * | 2012-09-22 | 2013-03-27 | 包头市京瑞新材料有限公司 | Method for preparing macrogranular europium oxide |
| CN103058724A (en) * | 2012-09-22 | 2013-04-24 | 包头市京瑞新材料有限公司 | Preparation method of large-particle gadolinium oxide |
| CN103073045A (en) * | 2012-09-22 | 2013-05-01 | 包头市京瑞新材料有限公司 | Preparation method of peroxycarbonate gadolinium |
| CN103058724B (en) * | 2012-09-22 | 2014-12-03 | 包头市京瑞新材料有限公司 | Preparation method of large-particle gadolinium oxide |
| CN103073045B (en) * | 2012-09-22 | 2015-03-25 | 包头市京瑞新材料有限公司 | Preparation method of peroxycarbonate gadolinium |
| CN102992380B (en) * | 2012-09-22 | 2015-06-03 | 包头市京瑞新材料有限公司 | Method for preparing macrogranular europium oxide |
| CN103526056B (en) * | 2013-10-09 | 2015-07-22 | 中国科学院长春应用化学研究所 | Wet-method atmospheric oxidation method of cerium in rare earth hydroxides |
| CN103526056A (en) * | 2013-10-09 | 2014-01-22 | 中国科学院长春应用化学研究所 | Wet-method atmospheric oxidation method of cerium in rare earth hydroxides |
| CN103482673A (en) * | 2013-10-12 | 2014-01-01 | 瑞科稀土冶金及功能材料国家工程研究中心有限公司 | Preparation method of rare earth hydroxide |
| CN103910373B (en) * | 2014-04-04 | 2016-05-18 | 江西稀有金属钨业控股集团有限公司 | A kind of preparation method of cerium hydroxide and system |
| CN103910373A (en) * | 2014-04-04 | 2014-07-09 | 江西稀有金属钨业控股集团有限公司 | Method and system for preparing cerium hydroxide |
| CN106186036A (en) * | 2016-07-10 | 2016-12-07 | 九江学院 | A kind of preparation method of hexagon cerium dioxide nano sheet material |
| CN106186036B (en) * | 2016-07-10 | 2017-10-24 | 九江学院 | A kind of preparation method of hexagon cerium dioxide nano sheet material |
| CN107973331A (en) * | 2018-01-19 | 2018-05-01 | 常州市卓群纳米新材料有限公司 | A kind of pollution-free preparation method of ceric sulfate |
| CN112074619A (en) * | 2018-05-03 | 2020-12-11 | 阿拉弗拉资源有限公司 | Treatment of rare earth sulphate solutions |
| US11767228B2 (en) | 2018-05-03 | 2023-09-26 | Arafura Resources Limited | Processing rare earth sulphate solutions |
| CN109761259A (en) * | 2019-03-27 | 2019-05-17 | 淄博加华新材料资源有限公司 | A kind of high preparation method at colloidality cerium glue |
| CN109761259B (en) * | 2019-03-27 | 2021-04-02 | 淄博加华新材料有限公司 | Preparation method of cerium glue with high gelling property |
| CN111060501A (en) * | 2019-12-06 | 2020-04-24 | 山东理工大学 | Nano cerium peroxide catalyst and method for catalyzing TMB color development by using same |
| 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 |
| CN112919524A (en) * | 2021-03-08 | 2021-06-08 | 益阳鸿源稀土有限责任公司 | Preparation method of high-purity ceric sulfate tetrahydrate |
| CN113023763A (en) * | 2021-03-08 | 2021-06-25 | 益阳鸿源稀土有限责任公司 | Preparation method of high-purity cerium ammonium sulfate |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1289699C (en) | 2006-12-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1289699C (en) | Process for preparing cerous hydroxide | |
| US8808660B2 (en) | Method of precipitation of metal ions | |
| CN101549882B (en) | Method for preparing high-purity cupric oxide powder from acid cupriferous waste liquid | |
| CN1114564C (en) | Technological process of preparing pure cerium hydroxide | |
| CN105803199B (en) | A kind of method that hydroxide precipitation method prepares low-sulfur rare earth oxide | |
| CN102786095B (en) | Method for preparing manganous manganic oxide | |
| CN101269831A (en) | Method for producing high purity strontium carbonate with double decomposition reaction-dissolution-abstraction | |
| CN102502722A (en) | Preparation method of high-purity magnesium oxide | |
| CN113371757A (en) | Method for preparing sodium pyroantimonate and regenerating and recycling mother liquor | |
| CN115582105A (en) | Method for preparing CO by modifying titanium-containing blast furnace slag 2 Method for coupling mineralization of capture material | |
| 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 | |
| CN1194060C (en) | Preparation method of rare-earth polishing powder | |
| CN101786644B (en) | Sandy alumina preparation method | |
| CN1683248A (en) | Process for preparing nano cerium dioxide | |
| CN111847518A (en) | Efficient recycling method of silicomanganese slag | |
| CN112662866B (en) | Method for reducing sulfate radical content in rare earth oxide by carbonization roasting | |
| CN1765750A (en) | Blanc fixe preparation method | |
| CN112939094B (en) | Method for preparing nano cobalt tungstate and recovering crude titanium slag | |
| CN114560486A (en) | CO with recyclable leaching aid2Indirect mineralization method | |
| CN1034744C (en) | Method of extracting cerium-rich solution | |
| CN1048239A (en) | Produce the processing method of pure cerous hydroxide | |
| CN111186851A (en) | Method for preparing modified aluminum-based catalyst by recycling electric dust collection powder of fluidized bed roaster | |
| CN1119424C (en) | Process for extracting cerium by oxydol oxidation method | |
| CN1475443A (en) | Method of producing neutral high quality anhydrous sodium sulfate using natucal salt lake sodium sulfate decahydrate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20061213 Termination date: 20191230 |