CN100424016C - Method for preparing cerium trifluoride using neutral phosphoras (phosphine) extraction system - Google Patents
Method for preparing cerium trifluoride using neutral phosphoras (phosphine) extraction system Download PDFInfo
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- CN100424016C CN100424016C CNB2006100171161A CN200610017116A CN100424016C CN 100424016 C CN100424016 C CN 100424016C CN B2006100171161 A CNB2006100171161 A CN B2006100171161A CN 200610017116 A CN200610017116 A CN 200610017116A CN 100424016 C CN100424016 C CN 100424016C
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- micro mist
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- 238000000034 method Methods 0.000 title claims abstract description 39
- QCCDYNYSHILRDG-UHFFFAOYSA-K cerium(3+);trifluoride Chemical compound [F-].[F-].[F-].[Ce+3] QCCDYNYSHILRDG-UHFFFAOYSA-K 0.000 title claims abstract description 22
- 230000007935 neutral effect Effects 0.000 title claims abstract description 22
- 238000000605 extraction Methods 0.000 title claims description 133
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 title claims description 52
- 229910000073 phosphorus hydride Inorganic materials 0.000 title claims description 26
- 239000000203 mixture Substances 0.000 claims abstract description 178
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 72
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 29
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000002904 solvent Substances 0.000 claims abstract description 21
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims abstract description 18
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims abstract description 14
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims abstract description 14
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000007865 diluting Methods 0.000 claims abstract description 11
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000003350 kerosene Substances 0.000 claims abstract description 7
- -1 noane Chemical compound 0.000 claims abstract description 7
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims abstract description 6
- ZMBHCYHQLYEYDV-UHFFFAOYSA-N trioctylphosphine oxide Chemical compound CCCCCCCCP(=O)(CCCCCCCC)CCCCCCCC ZMBHCYHQLYEYDV-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000463 material Substances 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims description 134
- 239000000284 extract Substances 0.000 claims description 129
- 239000007788 liquid Substances 0.000 claims description 123
- 239000003595 mist Substances 0.000 claims description 48
- 239000003795 chemical substances by application Substances 0.000 claims description 42
- 239000012286 potassium permanganate Substances 0.000 claims description 40
- 239000000243 solution Substances 0.000 claims description 35
- 239000007864 aqueous solution Substances 0.000 claims description 28
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 25
- 239000004327 boric acid Substances 0.000 claims description 25
- 239000002253 acid Substances 0.000 claims description 24
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 21
- 239000011737 fluorine Substances 0.000 claims description 21
- 229910052731 fluorine Inorganic materials 0.000 claims description 21
- 238000002156 mixing Methods 0.000 claims description 16
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 claims description 13
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 claims description 10
- 238000006396 nitration reaction Methods 0.000 claims description 9
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 9
- 229910052684 Cerium Inorganic materials 0.000 claims description 8
- 229920000137 polyphosphoric acid Polymers 0.000 claims description 7
- 150000002910 rare earth metals Chemical class 0.000 claims description 7
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- FPGGTKZVZWFYPV-UHFFFAOYSA-M tetrabutylammonium fluoride Chemical compound [F-].CCCC[N+](CCCC)(CCCC)CCCC FPGGTKZVZWFYPV-UHFFFAOYSA-M 0.000 claims description 6
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 5
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims description 5
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 5
- 150000001338 aliphatic hydrocarbons Chemical group 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 4
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 claims description 4
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- GTDKXDWWMOMSFL-UHFFFAOYSA-M tetramethylazanium;fluoride Chemical compound [F-].C[N+](C)(C)C GTDKXDWWMOMSFL-UHFFFAOYSA-M 0.000 claims description 4
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 claims description 4
- 239000004215 Carbon black (E152) Substances 0.000 claims description 3
- 230000002378 acidificating effect Effects 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- 150000002430 hydrocarbons Chemical class 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 claims description 3
- JPGXOMADPRULAC-UHFFFAOYSA-N 1-[butoxy(butyl)phosphoryl]oxybutane Chemical compound CCCCOP(=O)(CCCC)OCCCC JPGXOMADPRULAC-UHFFFAOYSA-N 0.000 claims description 2
- CYXGBTZYTXLVDN-UHFFFAOYSA-N 1-octoxyphosphonoyloxyoctane Chemical class CCCCCCCCOP(=O)OCCCCCCCC CYXGBTZYTXLVDN-UHFFFAOYSA-N 0.000 claims description 2
- DMFVKCBUVMHQSB-UHFFFAOYSA-N C(CCCCCC)OP(OC)(OC)C Chemical compound C(CCCCCC)OP(OC)(OC)C DMFVKCBUVMHQSB-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 238000003113 dilution method Methods 0.000 claims description 2
- 150000003003 phosphines Chemical class 0.000 claims description 2
- 238000005987 sulfurization reaction Methods 0.000 claims description 2
- DAGQYUCAQQEEJD-UHFFFAOYSA-N tris(2-methylpropyl)phosphane Chemical compound CC(C)CP(CC(C)C)CC(C)C DAGQYUCAQQEEJD-UHFFFAOYSA-N 0.000 claims description 2
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 2
- 239000000843 powder Substances 0.000 abstract 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract 1
- 229910052698 phosphorus Inorganic materials 0.000 abstract 1
- 239000011574 phosphorus Substances 0.000 abstract 1
- 238000011084 recovery Methods 0.000 description 21
- 229910052739 hydrogen Inorganic materials 0.000 description 13
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 12
- 230000001590 oxidative effect Effects 0.000 description 12
- 230000001105 regulatory effect Effects 0.000 description 12
- 238000002386 leaching Methods 0.000 description 8
- 229910002651 NO3 Inorganic materials 0.000 description 7
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 7
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 7
- 229910000029 sodium carbonate Inorganic materials 0.000 description 6
- 239000001117 sulphuric acid Substances 0.000 description 6
- 235000011149 sulphuric acid Nutrition 0.000 description 6
- IKNAJTLCCWPIQD-UHFFFAOYSA-K cerium(3+);lanthanum(3+);neodymium(3+);oxygen(2-);phosphate Chemical compound [O-2].[La+3].[Ce+3].[Nd+3].[O-]P([O-])([O-])=O IKNAJTLCCWPIQD-UHFFFAOYSA-K 0.000 description 5
- 239000000693 micelle Substances 0.000 description 5
- 229910052590 monazite Inorganic materials 0.000 description 5
- ITZXULOAYIAYNU-UHFFFAOYSA-N cerium(4+) Chemical compound [Ce+4] ITZXULOAYIAYNU-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000006286 aqueous extract Substances 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000003682 fluorination reaction Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000011858 nanopowder Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000004530 micro-emulsion Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000009206 nuclear medicine Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Abstract
The process of preparing cerium trifluoride micro powder with neutral phosphorus extracting system adopts the material solution of RE sulfuric acid and/or nitric acid solution containing Ce(IV) and F and with acidity of 0.2-6.0 mol/L; extractant comprising Cyanex923 and one or several of TBP, P350, PBBP, DEHEHP, ODOP, Cyanex921, Cyanex925, Cyanex471 and TOEDPO in arbitrary proportion; diluting solvent of n-hexane, n-heptane, octane, noane, decane or sulfonated kerosene to constitute extracting composition together with the extractant; and the back extracting solution of hydrogen peroxide, hydrazine hydrate, hydroxylamine hydrochloride or their mixture with sulfuric acid and/or nitric acid. The extracted composition is washed and back extracted to obtain the cerium trifluoride micro powder with purity of 90-99.9999 % and granularity of 1-4000 nm.
Description
Technical field
The present invention relates to prepare the method for cerous fluoride micro mist, relate in particular to and utilize neutral phosphonic (phosphine) extraction system to prepare CeF from the rare earth sulfuric acid that contains cerium (IV), fluorine or nitric acid or sulfuric acid and nitric acid mixed acid solution
3The method of micro mist.
Background technology
CeF
3Be the important source material that metallothermics is produced the single rare earth metallic cerium, it has important use at aspects such as high energy physics, nuclear medicine, solid lubricant, opto-electronic devices simultaneously.Present CeF
3Synthetic method commonly used comprise HF (NH
4HF
2) precipitation-vacuum dehydration method, HF (NH
4HF
2) fluorination method, NH
4HCO
3Preparation method makes the transition.HF precipitation-the vacuum dehydration methods that adopt in the industrial production promptly at CeCl more
3Directly feed HF in the solution and be settled out CeF
3, handle through washing, drying, vacuum hydro-extraction again and make product.The main drawback of this method is that the throw out particle diameter is difficult to control, is difficult to make nano level CeF
3The Granularity Distribution inequality; Environmental pollution is serious.Laboratory using microwave phase oxidative reduction synthesis process, the compound CeF of prepared by surface modification organic-inorganic
3Methods such as nanoparticle, polyvalent alcohol method, microemulsion preparation can obtain CeF
3Nano-powder.Chinese patent ZL 2,004 1 0010618.2 discloses a kind of method for preparing high-purity cerous fluoride micro mist, this method extracts hamartite sulfuric acid to leach liquid with Cyanex923, utilize the reverse micelle that forms in the extracts composition as microreactor, by control back extraction condition, obtain monodispersed high-purity CeF
3Nano-powder.Use the extraction agent kind single in the method, do not relate to other neutral phosphonic (phosphine) extraction agent except that Cyanex923, alternative extraction agent scope is narrower.
Summary of the invention
The purpose of this invention is to provide a kind of method of utilizing neutral phosphonic (phosphine) extraction system to prepare the cerous fluoride micro mist.This method can utilize solvent extraction technology to prepare the cerous fluoride micro mist under mild conditions.
This method is carried out with condition as follows:
(1) neutral phosphonic (phosphine) extraction agent with diluting solvent by volume dilution method be mixed with extracts composition, wherein the volume ratio of extraction agent and diluting solvent is 1: 9～8: 2, this ratio is preferably 1: 9～3: 2; Described diluting solvent is selected from: aliphatics, alicyclic or aromatic hydrocarbon solvents;
Ten oxide compounds, fluorine concentration are 0.5～25g/L: the adjusting feed acidity is 0.2～6.0mol/L, preferred 2.0～4.0mol/L; Add potassium permanganate, make that potassium permanganate concentration is 0.1～5.0g/L in the feed liquid; Described acidic aqueous solution is the aqueous solution of sulfuric acid, nitric acid or sulfuric acid and nitric acid nitration mixture; Employed fluorochemical is preferably Neutral ammonium fluoride:
Can also select to add boric acid, improve the extraction of extracts composition to fluorine in the feed liquid, the concentration of feed liquid mesoboric acid is 0.1～10.0g/L, is preferably 1.0～5.0g/L;
(3) with quadrivalent cerium and fluorine in the feed liquid of the extracts composition extraction step (2) in the step (1), extraction progression is 1～50 grade, and preferred 5～20 grades, extracts composition is 1: 5～5: 1 with the material liquid flowing ratio;
(4) strip from extracts composition with strip liquor, extracts composition is 1: 5～5: 1 with the stream ratio of strip liquor, and back extraction progression is 1～10 grade; Obtain back extraction mixture C e
3+Solution and CeF
3Micro mist filters the back extraction mixture and obtains CeF
3Micro mist.Its granularity can reach 10～4000nm.
Strip liquor adopts in reducing substances hydrogen peroxide, hydrazine hydrate and the oxammonium hydrochloride any one or multiple mixture with arbitrary proportion usually; Perhaps in hydrogen peroxide, hydrazine hydrate and the oxammonium hydrochloride any one or multiple with arbitrary proportion mixture again with sulfuric acid blended solution; Perhaps in hydrogen peroxide, hydrazine hydrate and the oxammonium hydrochloride mixture of any one or multiple arbitrary proportion again with nitric acid blended solution; Perhaps any one or multiple mixture with arbitrary proportion carry out blended solution with sulfuric acid and nitric acid nitration mixture again in hydrogen peroxide, hydrazine hydrate and the oxammonium hydrochloride, wherein the concentration of volume percent of hydrogen peroxide, hydrazine hydrate or oxammonium hydrochloride is 0.1～10%, and the concentration of sulfuric acid or nitric acid is 0.1～5.0mol/L.
(5) can also add coating in the back extraction mixture that step (4) obtains, making coating concentration is 1～10g/L, to CeF
3Micro mist carries out the surface and coats, prevent its follow-up close poly-, the CeF that obtains having good monodispersity and good resistance reunion ability
3Micro mist; Coating is Methanaminium, N,N,N-trimethyl-, fluoride, tetrabutyl ammonium fluoride, polyphosphoric acid tetramethyl-ammonium or polyphosphoric acid TBuA;
(6) afterwards in step (3) and step (4), can also wash respectively, washings is preferably: the mixing solutions of sulfuric acid, nitric acid or sulfuric acid and nitric acid nitration mixture and boric acid, wherein sulfuric acid or concentration of nitric acid are 0.1～3.0mol/L, boric acid concentration is 0.1～5.0g/L, extracts composition is 1: 10～10: 1 with the stream ratio of washings, and washing progression is 1～10 grade, and washing can be carried out according to mode known per se; Wash after the step (3) and can further reduce the content of the impurity element in the extracts composition, thereby help to improve the purity of the back extraction product that finally obtains; Wash the extracts composition that can make after the washing after the step (4) and recycle, improve the recovery utilization rate of extraction agent.
Help improve the purity of the back extraction product that finally obtains; Wash the extracts composition that can make after the washing after the step (4) and recycle, improve the recovery utilization rate of extraction agent.
In the step of the present invention (1), extracts composition comprises extraction agent and diluting solvent.
Be applicable to that extraction agent of the present invention is the extractant mixture that straight chain trialkyl phosphine (commodity are called Cyanex923) and following extraction agent constitute, these extraction agents are: tributyl phosphate (commodity are called TBP), methyl-phosphorous acid dimethyl heptyl ester (commodity are called P350), dibutyl butylphosphonate (being abbreviated as DBBP), 2-ethylhexyl phosphonic acid-two (2-ethylhexyl) ester (being abbreviated as DEHEHP), dioctyl phosphonic acids monooctyl ester (being abbreviated as ODOP), trioctyl-phosphine oxide (commodity are called Cyanex921), side chain trialkyl phosphine (commodity are called Cyanex925), one or more mixtures in sulfuration tri isobutyl phosphine (commodity are called Cyanex471) or the inferior second dioxygenization two hot phosphines (being abbreviated as TOEDPO) with arbitrary proportion; Wherein, Cyanex923 content is 0.01～30% of extracts composition volume.They all are commodity extraction agents known in the art.
Diluting solvent of the present invention is an aliphatic hydrocarbon solvent: hexane, heptane, octane, nonane, decane, undecane, dodecane, sulfonated kerosene, solvent oil or whiteruss, preferably adopt normal heptane, octane, nonane, decane or sulfonated kerosene;
Perhaps be the clicyclic hydrocarbon solvent: hexanaphthene or perhydronaphthalene that the pentamethylene that pentamethylene or low alkyl group replace, hexanaphthene or low alkyl group replace;
Perhaps be aromatic hydrocarbon solvents: benzene, toluene, neighbour-,-, right-dimethylbenzene or xylol.
To being used for the raw material of step of the present invention (2) feed liquid, as long as wherein contain fluorine and Ce elements.Certainly, be applicable to that the raw material middle-weight rare earths weight content of the inventive method is at least 1%, without limits to the upper limit of ree content; CeO in the ore
2The weight ratio of/REO is 〉=1%.Be applicable to that raw material of the present invention comprises pure hamartite through oxidizing roasting, the pure solitary stone ore through sodium carbonate roasting, pure southern ion-adsorption type ore, mixing ore deposit, mixing the ore deposit, variously contain cerium (IV) enriched substance, variously contain mixed rare-earth oxide, the oxyhydroxide of cerium (IV) or contain cerium (IV) rare-earth salts (halogenide, nitrate, carbonate or vitriol) through the hamartite of oxidizing roasting and other ore through the hamartite of oxidizing roasting and solitary stone ore.
Sour as leaching among the present invention with sulfuric acid, nitric acid or sulfuric acid and nitric acid nitration mixture.According to the Chinese patent 98122348.6 disclosed methods or the present industrial known method of inventions such as Li Deqian, leach or dissolve aforementioned base materials with sulfuric acid, nitric acid or sulfuric acid and nitric acid nitration mixture and all can obtain being applicable to feed liquid of the present invention.
In the extracts composition that extracts composition that extraction agent, extraction agent and diluting solvent form and load have metal ion, all there is reverse micelle to exist.When carrying out back extraction, nano level CeF
3The micro mist nucleation is carried out in the water nuclear of reverse micelle, and reverse micelle can retrain primary nano level CeF as template
3The growth of micro mist.This method not only utilizes the reverse micelle structure to CeF
3Grain size of micropowder retrains, and in extraction process metal ion has been carried out purifying, can obtain high-purity cerous fluoride micro mist, CeF
3Purity is (with CeO
2/ REO represents) between 90～99.9999%.
The present invention adopts neutral phosphonic (phosphine) extraction agent, contains cerium (IV), fluorine raw material, mineral acid, utilizes solvent extraction technology to prepare the cerous fluoride micro mist.The major advantage of this method is to have made the controlled CeF of size
3Micro mist, granularity can reach 10～4000nm; Granularity Distribution is even; Contrast HF (NH
4HF
2) method such as fluorination method, greatly reduce the pollution of fluorine to environment.Extraction agent that method of the present invention is used also relates to other neutral phosphonic (phosphine) extraction agent except that Cyanex923, alternative extraction agent scope is broadened.The CeF that the inventive method obtains
3Purity is (with CeO
2/ REO represents) between 90～99.9999%,
The rate of recovery of cerium can be up to more than 90%.
Embodiment
Enumerate specific embodiment below and further specify the present invention.
Embodiment 1:
(1) get 300ml Cyanex923,100ml TBP, the 600ml normal heptane mixes, and is mixed with extracts composition;
(2) be feed liquid with the nitrate leaching liquid through the hamartite of oxidizing roasting, wherein [REO] is 100g/L, [CeO
2] be 1g/L, the adjusting feed acidity is 0.2mol/L, adds potassium permanganate, makes that potassium permanganate concentration is 0.1g/L in the feed liquid, adds boric acid, making feed liquid mesoboric acid concentration is 0.1g/L;
(3) use the 30ml separating funnel as reactor, carry out the extraction of 5 stage countercurrents, extracts composition is 1: 5 with the stream ratio of feed liquid;
(4) then carry out 2 stage countercurrent back extractions, strip liquor is that concentration of volume percent is 0.1% H
2O
2The aqueous solution, extracts composition is 1: 5 with the stream ratio of strip liquor, filters resulting back extraction mixture, can obtain CeF
3Micro mist, its median size are 75nm, CeO
2/ REO=99.91%.
Can select: then carry out the washing of 3 stage countercurrents, washings is a water, and extracts composition is 1: 10 with the stream ratio of washings.Extracts composition after the washing can be recycled, and improves the recovery utilization rate of extraction agent.
Embodiment 2:
(1) get 200ml Cyanex923,50ml P350, the 750ml normal hexane mixes, and is mixed with extracts composition;
(2) be feed liquid with the sulfuric acid to leach liquid through the hamartite of oxidizing roasting, wherein [REO] is 120g/L, [CeO
2] be 60g/L, the adjusting feed acidity is 1.3mol/L, adds potassium permanganate, makes that potassium permanganate concentration is 1.8g/L in the feed liquid, adds boric acid, making feed liquid mesoboric acid concentration is 5.0g/L;
(3) use the 30ml separating funnel as reactor, carry out the extraction of 5 stage countercurrents, extracts composition is 5: 3 with the stream ratio of feed liquid;
(4) can select: carry out the washing of 4 stage countercurrents then, washings is the H of 0.5mol/L
2SO
4With 1g/L H
3BO
3Mixed aqueous solution, extracts composition is 1: 10 with the stream ratio of washings;
(5) then carry out 2 stage countercurrent back extractions, strip liquor is that concentration of volume percent is 10.0% H
2O
2The aqueous solution, extracts composition is 5: 1 with the stream ratio of strip liquor, filters resulting back extraction mixture, can obtain CeF
3Micro mist, its median size are 28nm, CeO
2/ REO=99.97%.
Certainly can also select: then carry out the washing of 5 stage countercurrents, washings is a water, and extracts composition is 1: 6 with the stream ratio of washings.Extracts composition after the washing can be recycled, and improves the recovery utilization rate of extraction agent.
Embodiment 3:
(1) get 300ml Cyanex923,10ml DBBP, the 690ml octane mixes, and is mixed with extracts composition;
(2) be feed liquid with the sulfuric acid to leach liquid through the hamartite of oxidizing roasting, wherein [REO] is 40g/L, [CeO
2] be 30g/L, the adjusting feed acidity is 3.0mol/L, adds potassium permanganate, makes that potassium permanganate concentration is 5.0g/L in the feed liquid, adds boric acid, making feed liquid mesoboric acid concentration is 5.0g/L;
(3) use the 30ml separating funnel as reactor, carry out the extraction of 6 stage countercurrents, extracts composition is 2: 1 with the stream ratio of feed liquid;
(4) can select: carry out the washing of 6 stage countercurrents then, washings is the H of 0.1mol/L
2SO
4With 0.1g/L H
3BO
3Mixed aqueous solution, extracts composition is 2: 3 with the stream ratio of washings;
(5) then carry out 2 stage countercurrent back extractions, strip liquor is that concentration of volume percent is 10.0% hydrazine hydrate aqueous solution, and extracts composition is 2: 1 with the stream ratio of strip liquor, filters resulting back extraction mixture, can obtain CeF
3Micro mist, its median size are 48nm, CeO
2/ REO=99.997%.
Certainly can also select: then carry out the washing of 4 stage countercurrents, washings is a sulphuric acid soln, and its concentration is 3.0mol/L.Extracts composition is 10: 1 with the stream ratio of washings.Extracts composition after the washing can be recycled, and improves the recovery utilization rate of extraction agent.
Embodiment 4:
(1) get 300ml Cyanex923,150ml ODOP, the 550ml nonane mixes, and is mixed with extracts composition;
(2) be feed liquid with the nitrate leaching liquid through the hamartite of oxidizing roasting, wherein [REO] is 260g/L, [CeO
2] be 160g/L, the adjusting feed acidity is 1.5mol/L, adds potassium permanganate, makes that potassium permanganate concentration is 3.0g/L in the feed liquid, adds boric acid, making feed liquid mesoboric acid concentration is 10.0g/L;
(3) use the 30ml separating funnel as reactor, carry out the extraction of 8 stage countercurrents, extracts composition is 2: 1 with the stream ratio of feed liquid;
(4) can select: carry out the washing of 8 stage countercurrents then, washings is the HNO of 3.0mol/L
3With 2g/L H
3BO
3Mixed aqueous solution, extracts composition is 10: 1 with the stream ratio of washings;
(5) then carry out 2 stage countercurrent back extractions, strip liquor is that concentration of volume percent is 0.1% hydrazine hydrate aqueous solution, and extracts composition is 1: 1 with the stream ratio of strip liquor, filters resulting back extraction mixture, can obtain CeF
3Micro mist, its median size are 38nm, CeO
2/ REO=99.9995%.
Certainly can also select: then carry out the washing of 3 stage countercurrents, washings is a salpeter solution, and its concentration is 2.0mol/L.Extracts composition is 2: 1 with the stream ratio of washings.Extracts composition after the washing can be recycled, and improves the recovery utilization rate of extraction agent.
Embodiment 5:
(1) get 200ml Cyanex923,5ml Cyanex921, the 795ml pentamethylene mixes, and is mixed with extracts composition;
(2) be feed liquid with the sulfuric acid to leach liquid through the hamartite of oxidizing roasting, wherein [REO] is 80g/L, [CeO
2] be 39g/L, the acidity of regulating feed liquid is 6.0mol/L, adds potassium permanganate, makes that potassium permanganate concentration is 1.2g/L in the feed liquid, adds boric acid, making feed liquid mesoboric acid concentration is 7.0g/L, adds Neutral ammonium fluoride, makes that fluorine concentration is 16g/L in the feed liquid;
(3) use the 30ml separating funnel as reactor, carry out the extraction of 6 stage countercurrents, extracts composition is 5: 1 with the stream ratio of feed liquid;
(4) can select: carry out the washing of 6 stage countercurrents then, washings is the H of 0.5mol/L
2SO
4With 1g/L H
3BO
3Mixed aqueous solution, extracts composition is 8: 5 with the stream ratio of washings;
(5) then carry out 2 stage countercurrent back extractions, strip liquor is that concentration of volume percent is 1.5% H
2O
2With 0.01mol/L H
2SO
4Mixing solutions, extracts composition is 3: 2 with the stream ratio of strip liquor, adds the polyphosphoric acid TBuA in resulting back extraction mixture, making its concentration is 5g/L, adds strong aqua and regulates pH value to 9, can obtain the CeF that median size is 5.8nm
3Micro mist, CeO
2/ REO=99.9992%.
Certainly can also select: then carry out the washing of 5 stage countercurrents, washings is a sulphuric acid soln, and its concentration is 1.0mol/L.Extracts composition is 2: 1 with the stream ratio of washings.Extracts composition after the washing can be recycled, and improves the recovery utilization rate of extraction agent.
Embodiment 6:
(1) get 300ml Cyanex923,10ml Cyanex925, the 690ml decane mixes, and is mixed with extracts composition;
(2) be feed liquid with the nitrate leaching liquid through the mixed ore of the hamartite of sodium carbonate roasting and monazite, wherein [REO] is 158g/L, [CeO
2] be 95g/L, the acidity of regulating feed liquid is 1.6mol/L, adds potassium permanganate, makes that potassium permanganate concentration is 5.0g/L in the feed liquid, adds boric acid, making feed liquid mesoboric acid concentration is 5.0g/L, adds Neutral ammonium fluoride, makes that fluorine concentration is 5g/L in the feed liquid;
(3) use the 30ml separating funnel as reactor, carry out the extraction of 6 stage countercurrents, extracts composition is 2: 1 with the stream ratio of feed liquid;
(4) can select: carry out the washing of 8 stage countercurrents then, washings is the HNO of 0.4mol/L
3With 5g/L H
3BO
3Mixed aqueous solution, extracts composition is 8: 5 with the stream ratio of washings;
(5) then carry out 2 stage countercurrent back extractions, strip liquor is that concentration of volume percent is 0.1% H
2O
2With 0.01mol/L HNO
3Mixing solutions, extracts composition is 3: 2 with the stream ratio of strip liquor, filters resulting back extraction mixture, can obtain CeF
3Micro mist, its median size are 70nm, CeO
2/ REO=99.998%.
Certainly can also select: then carry out the washing of 3 stage countercurrents, washings is a salpeter solution, and its concentration is 1.0mol/L.Extracts composition is 2: 1 with the stream ratio of washings.Extracts composition after the washing can be recycled, and improves the recovery utilization rate of extraction agent.
Embodiment 7:
(1) get 200ml Cyanex923,20ml Cyanex471, the 780ml normal heptane mixes, and is mixed with extracts composition;
(2) be feed liquid with the nitrate leaching liquid through the monazite of sodium carbonate roasting, wherein [REO] is 180g/L, [CeO
2] be 20g/L, the acidity of regulating feed liquid is 1.6mol/L, adds potassium permanganate, makes that potassium permanganate concentration is 1.2g/L in the feed liquid, adds boric acid, making feed liquid mesoboric acid concentration is 7.0g/L, adds Neutral ammonium fluoride, makes that fluorine concentration is 25g/L in the feed liquid;
(3) use the 30ml separating funnel as reactor, carry out the extraction of 6 stage countercurrents, extracts composition is 2: 1 with the stream ratio of feed liquid;
(4) can select: carry out the washing of 6 stage countercurrents then, washings is the HNO of 0.4mol/L
3With 1g/L H
3BO
3Mixed aqueous solution, extracts composition is 8: 5 with the stream ratio of washings;
(5) then carry out 2 stage countercurrent back extractions, strip liquor is that concentration of volume percent is 0.1% oxammonium hydrochloride solution and the HNO of 5.0mol/L
3Mixing solutions, extracts composition is 3: 2 with the stream ratio of strip liquor, filters resulting back extraction mixture, can obtain CeF
3Micro mist, its median size are 72nm, CeO
2/ REO=99.998%.
Certainly can also select: then carry out the washing of 3 stage countercurrents, washings is a salpeter solution, and its concentration is 0.1mol/L.Extracts composition is 2: 1 with the stream ratio of washings.Extracts composition after the washing can be recycled, and improves the recovery utilization rate of extraction agent.
Embodiment 8:
(1) get 200ml Cyanex923,40ml TOEDPO, the 760ml sulfonated kerosene mixes, and is mixed with extracts composition;
(2) be feed liquid with the sulfuric acid to leach liquid through the mixed ore of the hamartite of sodium carbonate roasting and monazite, wherein [REO] is 30g/L, [CeO
2] be 22g/L, the acidity of regulating feed liquid is 1.6mol/L, adds potassium permanganate, makes that potassium permanganate concentration is 0.6g/L in the feed liquid, adds boric acid, making feed liquid mesoboric acid concentration is 4.0g/L, adds Neutral ammonium fluoride, makes that fluorine concentration is 15g/L in the feed liquid;
(3) use the 30ml separating funnel as reactor, carry out the extraction of 6 stage countercurrents, extracts composition is 2: 1 with the stream ratio of feed liquid;
(4) can select: carry out the washing of 6 stage countercurrents then, washings is the H of 0.4mol/L
2SO
4With 1g/L H
3BO
3Mixed aqueous solution, extracts composition is 8: 5 with the stream ratio of washings;
(5) then carry out 2 stage countercurrent back extractions, strip liquor is that concentration of volume percent is 10.0% oxammonium hydrochloride and 2.0mol/L H
2SO
4Mixing solutions, extracts composition is 3: 2 with the stream ratio of strip liquor, filters resulting back extraction mixture, can obtain CeF
3Micro mist, its median size are 69nm, CeO
2/ REO=99.992%.
Certainly can also select: then carry out the washing of 3 stage countercurrents, washings is a sulphuric acid soln, and its concentration is 0.1mol/L.Extracts composition is 2: 1 with the stream ratio of washings.Extracts composition after the washing can be recycled, and improves the recovery utilization rate of extraction agent.
Embodiment 9:
(1) get 200ml Cyanex923,200ml P350, the 600ml hexanaphthene mixes, and is mixed with extracts composition;
(2) be feed liquid with the sulfuric acid to leach liquid through the mixed ore of the hamartite of sodium carbonate roasting and monazite, wherein [REO] is 30g/L, [CeO
2] be 22g/L, the acidity of regulating feed liquid is 6.0mol/L, adds potassium permanganate, makes that potassium permanganate concentration is 1.2g/L in the feed liquid, adds boric acid, making feed liquid mesoboric acid concentration is 7.0g/L, adds Neutral ammonium fluoride, makes that fluorine concentration is 15.5g/L in the feed liquid;
(3) use the 30ml separating funnel as reactor, carry out the extraction of 6 stage countercurrents, extracts composition is 2: 1 with the stream ratio of feed liquid;
(4) can select: carry out the washing of 6 stage countercurrents then, washings is the H of 0.4mol/L
2SO
4With 1g/L H
3BO
3Mixed aqueous solution, extracts composition is 8: 5 with the stream ratio of washings;
(5) then carry out 2 stage countercurrent back extractions, strip liquor is that concentration of volume percent is 1.5% H
2O
2With 0.01mol/L H
2SO
4Mixing solutions, extracts composition is 3: 2 with the stream ratio of strip liquor, adds tetrabutyl ammonium fluoride in resulting back extraction mixture, making its concentration is 5g/L, adds strong aqua and regulates pH value to 9, can obtain the CeF that median size is 3.3nm
3Micro mist, CeO
2/ REO=99.9991%.
Certainly can also select: then carry out the washing of 5 stage countercurrents, washings is a sulphuric acid soln, and its concentration is 1.0mol/L.Extracts composition is 2: 1 with the stream ratio of washings.Extracts composition after the washing can be recycled, and improves the recovery utilization rate of extraction agent.
Embodiment 10:
(1) get 200ml Cyanex923,400ml TBP, the 400ml sulfonated kerosene mixes, and is mixed with extracts composition;
(2) contain the feed liquid that the rare earth mixed oxide of cerium obtains with nitric acid dissolve, wherein [REO] is 100g/L, [CeO
2] be 58g/L, the acidity of regulating feed liquid is 1.6mol/L, adds potassium permanganate, makes that potassium permanganate concentration is 1.2g/L in the feed liquid, adds boric acid, making feed liquid mesoboric acid concentration is 7.0g/L, adds Neutral ammonium fluoride, makes that fluorine concentration is 0.1g/L in the feed liquid;
(3) use the 30ml separating funnel as reactor, carry out the extraction of 6 stage countercurrents, extracts composition is 2: 1 with the stream ratio of feed liquid;
(4) can select: carry out the washing of 6 stage countercurrents then, washings is the HNO of 0.8mol/L
3With 1g/L H
3BO
3Mixed aqueous solution, extracts composition is 8: 5 with the stream ratio of washings;
(5) then carry out 2 stage countercurrent back extractions, strip liquor is that concentration of volume percent is 1.5% H
2O
2With 0.02mol/L HNO
3Mixing solutions, extracts composition is 3: 2 with the stream ratio of strip liquor, adds the polyphosphoric acid tetramethyl-ammonium in resulting back extraction mixture, making its concentration is 1g/L, adds strong aqua and regulates pH value to 11, can obtain the CeF that median size is 6.8nm
3Micro mist, CeO
2/ REO=99.998%.
Certainly can also select: then carry out the washing of 3 stage countercurrents, washings is a salpeter solution, and its concentration is 0.1mol/L.Extracts composition is 2: 1 with the stream ratio of washings.Extracts composition after the washing can be recycled, and improves the recovery utilization rate of extraction agent.
Embodiment 11:
(1) get 200ml Cyanex923,100ml TOEDPO, the 700ml normal heptane mixes, and is mixed with extracts composition;
(2) contain the feed liquid that the rare earth mixed oxide of cerium obtains with nitric acid dissolve, wherein [REO] is 100g/L, [CeO
2] be 58g/L, the acidity of regulating feed liquid is 3.0mol/L, adds potassium permanganate, makes that potassium permanganate concentration is 1.2g/L in the feed liquid, adds boric acid, making feed liquid mesoboric acid concentration is 7.0g/L, adds Neutral ammonium fluoride, makes that fluorine concentration is 25g/L in the feed liquid;
(3) use the 30ml separating funnel as reactor, carry out the extraction of 6 stage countercurrents, extracts composition is 2: 1 with the stream ratio of feed liquid;
(4) can select: carry out the washing of 9 stage countercurrents then, washings is the HNO of 0.4mol/L
3With 1g/L H
3BO
3Mixed aqueous solution, extracts composition is 8: 5 with the stream ratio of washings;
(5) then carry out 2 stage countercurrent back extractions, strip liquor is that concentration of volume percent is 1.5% hydrazine hydrate and 0.01mol/L HNO
3Mixing solutions, extracts composition is 3: 2 with the stream ratio of strip liquor, adds Methanaminium, N,N,N-trimethyl-, fluoride in resulting back extraction mixture, making its concentration is 5g/L, adds strong aqua and regulates pH value to 10, can obtain the CeF that median size is 2.9nm
3Micro mist, CeO
2/ REO=99.9997%.
Certainly can also select: then carry out the washing of 3 stage countercurrents, washings is a salpeter solution, and its concentration is 5.0mol/L.Extracts composition is 2: 1 with the stream ratio of washings.Extracts composition after the washing can be recycled, and improves the recovery utilization rate of extraction agent.
Embodiment 12:
(1) get 300ml Cyanex923,50ml ODOP, 10ml Cyanex471, the 640ml normal heptane mixes, and is mixed with extracts composition;
(2) be feed liquid with the sulfuric acid to leach liquid through the hamartite of oxidizing roasting, wherein [REO] is 80g/L, [CeO
2] be 46g/L, regulating its acidity is 1.5mol/L, adds potassium permanganate, makes that potassium permanganate concentration is 2.5g/L in the feed liquid, adds boric acid, making feed liquid mesoboric acid concentration is 5.0g/L;
(3) use the 30ml separating funnel as reactor, carry out the extraction of 6 stage countercurrents, extracts composition is 2: 1 with the stream ratio of feed liquid;
(4) can select: carry out the washing of 8 stage countercurrents then, washings is the H of 3.0mol/L
2SO
4With 2g/L H
3BO
3Mixed aqueous solution, extracts composition is 8: 5 with the stream ratio of washings;
(5) then carry out 2 stage countercurrent back extractions, strip liquor is that concentration of volume percent is 5.0% H
2O
2The aqueous solution, extracts composition is 2: 1 with the stream ratio of strip liquor, filters resulting back extraction mixture, can obtain CeF
3Micro mist, its median size are 42nm, CeO
2/ REO=99.9992%.
Certainly can also select: then carry out the washing of 3 stage countercurrents, washings is a sulphuric acid soln, and its concentration is 2.0mol/L.Extracts composition is 2: 1 with the stream ratio of washings.Extracts composition after the washing can be recycled, and improves the recovery utilization rate of extraction agent.
Embodiment 13:
(1) get 300ml Cyanex923,100ml P350,5ml Cyanex921, the 595ml normal heptane mixes, and is mixed with extracts composition;
(2) be feed liquid with the sulfuric acid to leach liquid through the mixed ore of the hamartite of sodium carbonate roasting and monazite, wherein [REO] is 68g/L, [CeO
2] be 43g/L, the acidity of regulating feed liquid is 1.6mol/L, adds potassium permanganate, makes that potassium permanganate concentration is 2.0g/L in the feed liquid.Add boric acid, making feed liquid mesoboric acid concentration is 5.0g/L, adds Neutral ammonium fluoride, makes that fluorine concentration is 5g/L in the feed liquid;
(3) use the 30m1 separating funnel as reactor, carry out the extraction of 6 stage countercurrents, extracts composition is 2: 1 with the stream ratio of feed liquid;
(4) can select: carry out the washing of 8 stage countercurrents then, washings is the H of 0.4mol/L
2SO
4With 1g/L H
3BO
3Mixed aqueous solution, extracts composition is 8: 5 with the stream ratio of washings;
(5) then carry out 2 stage countercurrent back extractions, strip liquor is that concentration of volume percent is 0.1% H
2O
2With 0.01mol/L H
2SO
4Mixing solutions, extracts composition is 3: 2 with the stream ratio of strip liquor, filters resulting back extraction mixture, can obtain CeF
3Micro mist, its median size are 55nm, CeO
2/ REO=99.998%.
Certainly can also select: then carry out the washing of 3 stage countercurrents, washings is a sulphuric acid soln, and its concentration is 1.0mol/L.Extracts composition is 2: 1 with the stream ratio of washings.Extracts composition after the washing can be recycled, and improves the recovery utilization rate of extraction agent.
Embodiment 14:
(1) get 100ml Cyanex923,100ml TOEDPO, 200ml TBP, the 600ml normal heptane mixes, and is mixed with extracts composition;
(2) contain the feed liquid that the rare earth mixed oxide of cerium obtains with nitric acid dissolve, wherein [REO] is 200g/L, [CeO
2] be 128g/L, the acidity of regulating feed liquid is 2.0mol/L, adds potassium permanganate, makes that potassium permanganate concentration is 1.2g/L in the feed liquid, adds boric acid, making feed liquid mesoboric acid concentration is 7.0g/L, adds Neutral ammonium fluoride, makes that fluorine concentration is 25g/L in the feed liquid;
(3) use the 30ml separating funnel as reactor, carry out the extraction of 6 stage countercurrents, extracts composition is 2: 1 with the stream ratio of feed liquid;
(4) can select: carry out the washing of 8 stage countercurrents then, washings is the HNO of 0.6mol/L
3With 1g/L H
3BO
3Mixed aqueous solution, extracts composition is 8: 5 with the stream ratio of washings;
(5) then carry out 2 stage countercurrent back extractions, strip liquor is that concentration of volume percent is 1.0% H
2O
2With 0.02mol/L HNO
3Mixing solutions, extracts composition is 3: 2 with the stream ratio of strip liquor, adds Methanaminium, N,N,N-trimethyl-, fluoride in resulting back extraction mixture, making its concentration is 10g/L, adds strong aqua and regulates pH value to 10, can obtain the CeF that median size is 5.6nm
3Micro mist, CeO
2/ REO=99.9992%.
Certainly can also select: then carry out the washing of 3 stage countercurrents, washings is a salpeter solution, and its concentration is 3.0mol/L.Extracts composition is 2: 1 with the stream ratio of washings.Extracts composition after the washing can be recycled, and improves the recovery utilization rate of extraction agent.
Embodiment 15:
(1) get 300ml DEHEHP, the 700ml normal heptane mixes, and is mixed with extracts composition;
(2) be feed liquid with the nitrate leaching liquid through the hamartite of oxidizing roasting, wherein [REO] is 128g/L, [CeO
2] be 60g/L, the adjusting feed acidity is 1.5mol/L, adds potassium permanganate, makes that potassium permanganate concentration is 3.0g/L in the feed liquid, adds boric acid, making feed liquid mesoboric acid concentration is 5.0g/L;
(3) use the 30ml separating funnel as reactor, carry out the extraction of 8 stage countercurrents, extracts composition is 2: 1 with the stream ratio of feed liquid;
(4) can select: carry out the washing of 8 stage countercurrents then, washings is the HNO of 3.0mol/L
3With 2g/L H
3BO
3Mixed aqueous solution, extracts composition is 8: 5 with the stream ratio of washings;
(5) then carry out 2 stage countercurrent back extractions, strip liquor is that concentration of volume percent is 1.0% H
2O
2The aqueous solution, extracts composition is 1: 1 with the stream ratio of strip liquor, filters resulting back extraction mixture, can obtain CeF
3Micro mist, its median size are 48nm, CeO
2/ REO=99.9991%.
Certainly can also select: then carry out the washing of 3 stage countercurrents, washings is a salpeter solution, and its concentration is 2.0mol/L.Extracts composition is 2: 1 with the stream ratio of washings.Extracts composition after the washing can be recycled, and improves the recovery utilization rate of extraction agent.
Embodiment 16:
(1) get 300ml P350, the 700ml normal heptane mixes, and is mixed with extracts composition;
(2) be feed liquid with sulfuric acid and nitric acid nitration mixture leaching liquid through the hamartite of oxidizing roasting, wherein [REO] is 136g/L, [CeO
2] be 72g/L, the adjusting feed acidity is 3.2mol/L, adds potassium permanganate, makes that potassium permanganate concentration is 3.0g/L in the feed liquid, adds boric acid, making feed liquid mesoboric acid concentration is 5.0g/L;
(3) use the 30ml separating funnel as reactor, carry out the extraction of 6 stage countercurrents, extracts composition is 2: 1 with the stream ratio of feed liquid;
(4) can select: carry out the washing of 6 stage countercurrents then, washings is the HNO of 2.0mol/L
3, 0.5mol/L H
2SO
4With 2g/L H
3BO
3Mixed aqueous solution, extracts composition is 8: 5 with the stream ratio of washings;
(5) then carry out 2 stage countercurrent back extractions, strip liquor is that concentration of volume percent is 1.0% H
2O
2With 0.02mol/L HNO
3, 0.02mol/L H
2SO
4Mixing solutions, extracts composition is 1: 1 with the stream ratio of strip liquor, filters resulting back extraction mixture, can obtain CeF
3Micro mist, its median size are 31nm, CeO
2/ REO=99.997%.
Certainly can also select: then carry out the washing of 3 stage countercurrents, washings is sulfuric acid and nitric acid mixed acid solution, and its acidity is 2.0mol/L.Extracts composition is 2: 1 with the stream ratio of washings.Extracts composition after the washing can be recycled, and improves the recovery utilization rate of extraction agent.
Embodiment 17:
(1) get 300ml Cyanex925, the 700ml normal heptane mixes, and is mixed with extracts composition;
(2) contain the feed liquid that the rare earth mixed oxide of cerium obtains with nitric acid dissolve, wherein [REO] is 200g/L, [CeO
2] be 128g/L, the acidity of regulating feed liquid is 2.0mol/L, adds potassium permanganate, makes that potassium permanganate concentration is 1.2g/L in the feed liquid, adds boric acid, making feed liquid mesoboric acid concentration is 5.0g/L, adds Neutral ammonium fluoride, makes that fluorine concentration is 25g/L in the feed liquid;
(3) use the 30ml separating funnel as reactor, carry out the extraction of 6 stage countercurrents, extracts composition is 2: 1 with the stream ratio of feed liquid;
(4) can select: carry out the washing of 8 stage countercurrents then, washings is the HNO of 0.5mol/L
3With 2g/L H
3BO
3Mixed aqueous solution, extracts composition is 8: 5 with the stream ratio of washings;
(5) then carry out 2 stage countercurrent back extractions, strip liquor is that concentration of volume percent is 1.0% H
2O
2With 0.02mol/L HNO
3Mixing solutions, extracts composition is 3: 2 with the stream ratio of strip liquor, adds the polyphosphoric acid TBuA in resulting back extraction mixture, making its concentration is 3g/L, adds strong aqua and regulates pH value to 10, can obtain the CeF that median size is 6.5nm
3Micro mist, CeO
2/ REO=99.9992%.
Certainly can also select: then carry out the washing of 3 stage countercurrents, washings is a salpeter solution, and its concentration is 3.0mol/L.Extracts composition is 2: 1 with the stream ratio of washings.Extracts composition after the washing can be recycled, and improves the recovery utilization rate of extraction agent.
Embodiment 18:
(1) get 100ml Cyanex923,10ml TBP, 10mlTOEDPO, the 880ml decane mixes, and is mixed with extracts composition;
(2) the nitrate leaching liquid with southern ion-adsorption type ore is feed liquid, and wherein [REO] is 100g/L, [CeO
2] be 1g/L, the acidity of regulating feed liquid is 1.6mol/L, adds potassium permanganate, makes that potassium permanganate concentration is 5.0g/L in the feed liquid, adds boric acid, making feed liquid mesoboric acid concentration is 5.0g/L, adds Neutral ammonium fluoride, makes that fluorine concentration is 5g/L in the feed liquid;
(3) use the 30ml separating funnel as reactor, carry out the extraction of 6 stage countercurrents, extracts composition is 2: 1 with the stream ratio of feed liquid;
(4) carry out the washing of 8 stage countercurrents then, washings is the HNO of 0.4mol/L
3And 5g/LH
3BO
3Mixed aqueous solution, extracts composition is 8: 5 with the stream ratio of washings;
(5) can select: then carry out 2 stage countercurrent back extractions, strip liquor is that concentration of volume percent is 0.1% H
2O
2With 0.01mol/L HNO
3Mixing solutions, extracts composition is 3: 2 with the stream ratio of strip liquor, filters resulting back extraction mixture, can obtain CeF
3Micro mist, its median size are 102nm, CeO
2/ REO=99.998%.
Certainly can also select: then carry out the washing of 3 stage countercurrents, washings is a salpeter solution, and its concentration is 1.0mol/L.Extracts composition is 2: 1 with the stream ratio of washings.Extracts composition after the washing can be recycled, and improves the recovery utilization rate of extraction agent.
Claims (12)
1. method of utilizing neutral phosphonic (phosphine) extraction system to prepare the cerous fluoride micro mist is characterized in that step and condition are as follows:
(1) neutral phosphonic (phosphine) extraction agent with diluting solvent by volume dilution method be mixed with extracts composition, wherein the volume ratio of extraction agent and diluting solvent is 1: 9～8: 2;
Described diluting solvent is selected from aliphatic hydrocarbon, clicyclic hydrocarbon or aromatic hydrocarbons; Wherein,
Aliphatic hydrocarbon solvent is: hexane, heptane, octane, nonane, decane, undecane, dodecane, sulfonated kerosene, solvent oil or whiteruss;
The clicyclic hydrocarbon solvent is: the pentamethylene that pentamethylene or low alkyl group replace; Hexanaphthene or perhydronaphthalene that hexanaphthene or low alkyl group replace;
Aromatic hydrocarbon solvents is: benzene, toluene, neighbour-,-, right-dimethylbenzene or xylol;
Described extraction agent is: the straight chain trialkyl phosphine, with the extractant mixture of following extraction agent formation;
These extraction agents are: one or more mixtures with arbitrary proportion in tributyl phosphate, methyl-phosphorous acid dimethyl heptyl ester, dibutyl butylphosphonate, 2-ethylhexyl phosphonic acid-two (2-ethylhexyl) ester, dioctyl phosphonic acids monooctyl ester, trioctyl-phosphine oxide, side chain trialkyl phosphine, sulfuration tri isobutyl phosphine or the inferior second dioxygenization two hot phosphines; Wherein, straight chain trialkyl phosphine content is 0.01～30% of extracts composition volume;
(2) be feed liquid, wherein CeO with the acidic aqueous solution that contains rare earth ion
2/ REO 〉=1%, described REO are the total rare earth (TRE) oxide compound, and fluorine concentration is 0.5～25g/L; The adjusting feed acidity is 0.2～6.0mol/L; Add potassium permanganate, make that potassium permanganate concentration is 0.1～5.0g/L in the feed liquid; Described acidic aqueous solution is the aqueous solution of sulfuric acid, nitric acid or sulfuric acid and nitric acid nitration mixture; Employed fluorochemical is a Neutral ammonium fluoride;
(3) with quadrivalent cerium and fluorine in the feed liquid of the extracts composition extraction step (2) in the step (1), extraction progression is 1～50 grade, and extracts composition is 1: 5～5: 1 with the material liquid flowing ratio;
(4) strip from extracts composition with strip liquor, extracts composition is 1: 5～5: 1 with the stream ratio of strip liquor, and back extraction progression is 1～10 grade; Obtain back extraction mixture C e
3+Solution and CeF
3Micro mist filters the back extraction mixture and obtains CeF
3Micro mist;
Strip liquor adopts in reducing substances hydrogen peroxide, hydrazine hydrate and the oxammonium hydrochloride any one or multiple mixture with arbitrary proportion usually; Wherein the concentration of volume percent of hydrogen peroxide, hydrazine hydrate or oxammonium hydrochloride is 0.1～10%.
2. a kind of method of utilizing neutral phosphonic (phosphine) extraction system to prepare the cerous fluoride micro mist as claimed in claim 1 is characterized in that, adds coating in the back extraction mixture that step (4) obtains, to CeF
3Micro mist carries out the surface and coats, and coating concentration is 1～10g/L, and coating is Methanaminium, N,N,N-trimethyl-, fluoride, tetrabutyl ammonium fluoride, polyphosphoric acid tetramethyl-ammonium or polyphosphoric acid TBuA.
3. a kind of method of utilizing neutral phosphonic (phosphine) extraction system to prepare the cerous fluoride micro mist as claimed in claim 1, it is characterized in that, in step (3) and step (4) afterwards, wash respectively, washings is: the mixing solutions of sulfuric acid, nitric acid or sulfuric acid and nitric acid nitration mixture and boric acid, wherein sulfuric acid or concentration of nitric acid are 0.1～3.0mol/L, boric acid concentration is 0.1～5.0g/L, extracts composition is 1: 10～10: 1 with the stream ratio of washings, washing progression is 1～10 grade, and washing is carried out in known manner.
4. a kind of method of utilizing neutral phosphonic (phosphine) extraction system to prepare the cerous fluoride micro mist as claimed in claim 1 is characterized in that in the step (1), and described aliphatic hydrocarbon solvent adopts normal heptane, octane, nonane, decane or sulfonated kerosene.
5. a kind of method of utilizing neutral phosphonic (phosphine) extraction system to prepare the cerous fluoride micro mist as claimed in claim 1 is characterized in that in the step (1), the volume ratio of described extraction agent and diluting solvent is 1: 9～3: 2.
6. a kind of method of utilizing neutral phosphonic (phosphine) extraction system to prepare the cerous fluoride micro mist as claimed in claim 1 is characterized in that in the step (2) that described adjusting feed acidity is 2.0～4.0mol/L.
7. a kind of method of utilizing neutral phosphonic (phosphine) extraction system to prepare the cerous fluoride micro mist as claimed in claim 1, it is characterized in that described step (2) adds boric acid, improve the extraction of extracts composition to fluorine in the feed liquid, the concentration of feed liquid mesoboric acid is 0.1～10.0g/L.
8. a kind of method of utilizing neutral phosphonic (phosphine) extraction system to prepare the cerous fluoride micro mist as claimed in claim 7 is characterized in that, described step (2) adds boric acid, and the concentration of feed liquid mesoboric acid is 1.0～5.0g/L.
9. a kind of method of utilizing neutral phosphonic (phosphine) extraction system to prepare the cerous fluoride micro mist as claimed in claim 1 is characterized in that step (3), and described extraction progression is 5～20 grades.
10. a kind of method of utilizing neutral phosphonic (phosphine) extraction system to prepare the cerous fluoride micro mist as claimed in claim 1, it is characterized in that step (4), described strip liquor adopt in hydrogen peroxide, hydrazine hydrate and the oxammonium hydrochloride any one or multiple with arbitrary proportion mixture again with sulfuric acid blended solution.
11. a kind of method of utilizing neutral phosphonic (phosphine) extraction system to prepare the cerous fluoride micro mist as claimed in claim 1, it is characterized in that step (4), the mixture that described strip liquor adopts in hydrogen peroxide, hydrazine hydrate and the oxammonium hydrochloride any one or multiple arbitrary proportion again with nitric acid blended solution.
12. a kind of method of utilizing neutral phosphonic (phosphine) extraction system to prepare the cerous fluoride micro mist as claimed in claim 1, it is characterized in that step (4), described strip liquor adopts in hydrogen peroxide, hydrazine hydrate and the oxammonium hydrochloride any one or multiple mixture with arbitrary proportion to carry out blended solution with sulfuric acid and nitric acid nitration mixture again.
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| CN107287409A (en) * | 2017-05-23 | 2017-10-24 | 中国科学院长春应用化学研究所 | A kind of method for preparing cerous fluoride |
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| CN1556038A (en) * | 2004-01-09 | 2004-12-22 | 中国科学院长春应用化学研究所 | Method of preparing high purity cerium trifluoride micro powder |
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| CN1556038A (en) * | 2004-01-09 | 2004-12-22 | 中国科学院长春应用化学研究所 | Method of preparing high purity cerium trifluoride micro powder |
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