CN1253374C - Method of preparing high purity cerium trifluoride micro powder - Google Patents
Method of preparing high purity cerium trifluoride micro powder Download PDFInfo
- Publication number
- CN1253374C CN1253374C CNB2004100106182A CN200410010618A CN1253374C CN 1253374 C CN1253374 C CN 1253374C CN B2004100106182 A CNB2004100106182 A CN B2004100106182A CN 200410010618 A CN200410010618 A CN 200410010618A CN 1253374 C CN1253374 C CN 1253374C
- Authority
- CN
- China
- Prior art keywords
- feed liquid
- concentration
- organic phase
- hydrogen peroxide
- hydrazine hydrate
- 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.)
- Expired - Fee Related
Links
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
Landscapes
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Catalysts (AREA)
Abstract
The present invention belongs to a preparation method of high purity cerous fluoride. Rare earth sulfuric acid solution which contains cerium (IV) and fluorine is used as feed solution, the acidity of the feed solution is from 0.1 to 6.0 mol/L, an extracting agent is Cyanex923, diluent solvent comprises hexane, normal heptane, octane, nonane, decane or sulfonic coal oil, the volume ratio of the extracting agent to the diluent solvent is from 1: 10 to 4: 6, an extraction composition is composed of the extracting agent and the diluent solvent, the flow rate of the extraction composition to the feed solution is from 1: 5 to 5: 1, the flow rate of the extraction composition to strip liquor is from 1: 5 to 5: 1, and the strip liquor is mixed solution of hydrogen peroxide, hydrazine hydrate and hydroxylamine hydrochloride, or hydrogen peroxide, hydrazine hydrate, hydroxylamine hydrochloride and sulphuric acid or hydrochloric acid. The extraction composition is washed and backextracted to obtain cerous fluoride micro powder, the purity (measured by CeO2 /REO) of the cerous fluoride micro powder is between 99.9 and 99.999%, and the particle size distribution is between 1 and 4000 nm.
Description
Technical field
The present invention relates to prepare CeF
3Method, more specifically, the present invention relates to prepare high-purity CeF from the rare earth sulfuric acid solution that contains cerium (IV), fluorine
3The method of micro mist.
Background technology
CeF
3Be the important source material that metallothermics prepares the single rare earth metallic cerium, simultaneously owing to its Faraday effect, CeF
3Crystal can be made laser communications modulator and single-pass light valve etc.Nano level CeF
3Be good solid lubricant, also can be used as lubricating grease and lubricating oil additive.
The CeF that industry is commonly used
3Synthetic method comprises HF (NH
4HF
2) precipitation-vacuum dehydration method, HF (NH
4HF
2) fluorination method, NH
4HCO
3Transition, preparation method adopted HF precipitation-vacuum dehydration methods in producing at present, 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 nano level CeF
3Nano-powder.Still have no way of at present directly preparing CeF in the hamartite
3The report of nano-powder.
Microemulsion can be used for preparing nano-powder as microreactor, is characterized in that may command particle volume and product have good monodispersity, have favorable industrial application prospect.Its general step comprises: prepare the respond microemulsion of thing of solubilising respectively in water-oil-surfactant system, mix and stir, centrifuging, washing and drying.There are two shortcomings in this process: surfactant dissolves causes the organic phase change of component in organic phase, and organic phase can not recycle, and excessive tensio-active agent is difficult to reclaim; Reactant must be a pure substance, the production cost height.
Chinese patent 98122348.6 discloses a kind of employing trihydrocarbyl phosphine oxygen compound and the primary amine kind of extractants new separating technology of extracting and separating Ce (IV) and Th from hamartite leachate simultaneously, this process using trihydrocarbyl phosphine oxygen compound TRPO (R is the alkane or the aromatic hydrocarbons of 4～15 carbon atoms) and industrialized extraction agent primary amine RNH2 (R is 11～17 straight-chain paraffin), the rare earth sulfuric acid solution that leaches or obtain with yellow soda ash sintering-sulfuric acid to leach with hamartite oxidizing roasting-sulfuric acid is a raw material, use the solvent extraction method separating cerium, thorium, technical process is simple, the yield height, not producing emissive industrial waste residue and waste water, is a cleaning, the technical process of safety.But this flow process is respectively with CeO
2Reclaim cerium and fluorine in the feed liquid with the form of NaF, need carry out twice back extraction, the soda acid unit consumption is relatively large, complex disposal process.
Summary of the invention
The purpose of this invention is to provide a kind of method for preparing high-purity cerous fluoride micro mist.
Cyanex923 is the trialkylphosphine oxide extraction agent that Cytec Canada Inc. company develops, it is a kind of mixture of trialkyl phosphine of straight chain, has facile hydrolysis not, solubleness is little in water, loading capacity is high, can arbitrary proportion be dissolved in the advantage of common solvent.
When with Cyanex923 hamartite sulfuric acid to leach liquid being extracted, cerium in the feed liquid and fluorine can be with Ce (HF) (HSO
4)
2SO
4The form of 2 (Cyanex923) is extracted into organic phase simultaneously.
Utilize the reverse micelle that forms in the organic phase as microreactor,, can utilize reverse micelle, obtain monodispersed high-purity CeF as template by control back extraction condition
3Nano-powder, purity is (with CeO
2/ REO represents) between 99.9～99.999%, the diameter of the nano-powder that obtains can obtain required size distribution by finishing at 1～4000nm.
The Cyanex923 that the present invention adopts Cytec Canada Inc. company to produce makes extraction agent.
The preparation method has following three kinds according to the feed liquid difference:
1) feed liquid that obtains through the hamartite of oxidizing roasting with sulfuric acid to leach, wherein CeO
2/ REO 〉=5%, Ce (IV) is 10～125g/L, F 〉=0.5g/L
A, be 0.1～6.0mol/L with the acidity adjustment of feed liquid;
B, add potassium permanganate, make that potassium permanganate concentration is 0.1～5.0g/L in the feed liquid;
C, from described feed liquid, extract Ce (IV) and F with extracts composition, extraction progression is 1～50 grade, the extracts composition organic phase is 1: 5～5: 1 with the material liquid flowing ratio, described extracts composition is extraction agent and nonpolar hydrocarbon solvents, and nonpolar hydrocarbon solvents is hexane, heptane, octane, nonane, decane, undecane, dodecane, kerosene, solvent oil or whiteruss;
D, from organic phase, strip, obtain Ce (III) solution and CeF with strip liquor
3Micro mist;
E, in the back extraction mixture that steps d obtains, add coating, to CeF
3Micro mist carries out the surface and coats, and prevents its follow-up reunion, and coating is Methanaminium, N,N,N-trimethyl-, fluoride, tetrabutyl ammonium fluoride, polyphosphoric acid tetramethyl-ammonium or polyphosphoric acid TBuA.
2) feed liquid that obtains through the mixed ore of the hamartite of sodium carbonate roasting and monazite with sulfuric acid to leach, wherein CeO
2/ REO 〉=5%, Ce (IV) is 10～125g/L, F 〉=0.5g/L
A, be 0.1～6.0mol/L with the acidity adjustment of feed liquid;
B, add Neutral ammonium fluoride, make that fluorine concentration is 0.5～25g/L in the feed liquid;
C, add potassium permanganate, make that potassium permanganate concentration is 0.1～5.0g/L in the feed liquid;
D, adding boric acid, making feed liquid mesoboric acid concentration is 0.1～10.0g/L;
E, from described feed liquid, extract Ce (IV) and F with extracts composition, extraction progression is 1～50 grade, the extracts composition organic phase is 1: 5～5: 1 with the material liquid flowing ratio, described extracts composition is extraction agent and nonpolar hydrocarbon solvents, and nonpolar hydrocarbon solvents is hexane, heptane, octane, nonane, decane, undecane, dodecane, kerosene, solvent oil or whiteruss;
F, strip from organic phase with strip liquor, reextraction progression is 1～10 grade, and organic phase and back extraction liquid flowing ratio are 1: 5～5: 1, obtain Ce (III) solution and CeF
3Micro mist;
G, in the back extraction mixture that step f obtains, add coating, to CeF
3Micro mist carries out the surface and coats, and prevents its follow-up reunion, and coating is Methanaminium, N,N,N-trimethyl-, fluoride, tetrabutyl ammonium fluoride, polyphosphoric acid tetramethyl-ammonium or polyphosphoric acid TBuA.
3) contain the feed liquid that the rare earth mixed oxide of cerium obtains, wherein CeO with sulfuric acid dissolution
2/ REO 〉=5%, Ce (IV) is 10～125g/L
A, be 0.1～6.0mol/L with the acidity adjustment of feed liquid;
B, add Neutral ammonium fluoride, make that fluorine concentration is 0.5～25g/L in the feed liquid;
C, add potassium permanganate, make that potassium permanganate concentration is 0.1～5.0g/L in the feed liquid;
D, adding boric acid, making feed liquid mesoboric acid concentration is 0.1～10.0g/L;
E, from described feed liquid, extract Ce (IV) and F with extracts composition, extraction progression is 1～50 grade, the extracts composition organic phase is 1: 5～5: 1 with the material liquid flowing ratio, described extracts composition is extraction agent and nonpolar hydrocarbon solvents, and nonpolar hydrocarbon solvents is hexane, heptane, octane, nonane, decane, undecane, dodecane, kerosene, solvent oil or whiteruss;
F, with washings washing organic extraction phase;
G, from organic phase, strip, obtain Ce (III) solution and CeF with strip liquor
3Micro mist;
H, in the back extraction mixture that step g obtains, add coating, to CeF
3Micro mist carries out the surface and coats, and prevents its follow-up reunion, and coating is Methanaminium, N,N,N-trimethyl-, fluoride, tetrabutyl ammonium fluoride, polyphosphoric acid tetramethyl-ammonium or polyphosphoric acid TBuA.
Though do not wish to be subjected to theoretical constraint, the description of following reaction process will help the understanding of the present invention:
In sulfuric acid medium, Ce and F and HF can form the neutral compound that is dissolved in organic solvent with extraction agent used in the present invention, and reaction formula can be expressed as follows:
B represents extractant molecules in the formula.At this moment, elements such as thorium, iron, trivalent rare earth do not react with extractant molecules, stay water.By separating immiscible water and organic phase, can realize that cerium, fluorine separate with a large amount of impurity elements.
The adding of boric acid can promote the extraction of fluorine in the feed liquid:
Collection is gone into Ce in the organic phase with Ce (HF) (HSO
4)
2SO
4The form of 2 (Cyanex923) exists, when using H
2O
2When the Ce in the organic phase (IV) is reduced to Ce (III), Ce and F simultaneously from load organic phases back extraction get off, and with CeF
3Form at aqueous phase precipitation.This reaction can be expressed as follows:
It is believed that in the extracts composition of Cyanex923 and Cyanex923 and solvent composition all have reverse micelle to exist, its mean diameter is 1～3nm.When carrying out reduction reextraction, these reverse micelles can be used as template, the growth of constraint primary partical, thus obtain mono-dispersed nano level CeF
3Particle, the mean diameter of its particle diameter and reverse micelle is suitable, at 1～3nm.
Because nano level CeF
3Particle has very high surfactivity, is easy to reunite, therefore, to CeF
3The median size of particle and size-grade distribution have under the situation of requirement, can be with the salt that contains organic quaternary ammonium ion, as the polyphosphoric acid tetramethyl-ammonium to CeF
3Nanoparticle carries out the surface and coats.In order to reduce cost, also can not take encapsulation steps.At this moment, CeF
3Nanoparticle will be reunited, and particle diameter increases with the prolongation of the time of reuniting, finally can reach 10～4000nm.
In principle, to being used for raw material of the present invention without limits, as long as wherein contain fluorine and Ce elements.Be applicable to that raw material of the present invention comprises mixing mixing the ore deposit, containing cerium mixed rare-earth oxide and fluorochemical of ore deposit, hamartite and other ore of pure hamartite, hamartite and monazite.Usually, be applicable to that the raw material middle-weight rare earths content of the inventive method should be 10% weight at least, without limits to the upper limit of ree content.CeO in the ore
2/ REO (weight ratio) 〉=5%.
Sour as leaching among the present invention with sulfuric acid.According to the Chinese patent 98122348.6 disclosed methods or the present industrial known method of inventions such as Li Deqian, all can obtain being applicable to feed liquid of the present invention with sulfuric acid to leach or dissolving aforementioned base materials.If desired, the acidity adjustment of the feed liquid that leaching can be obtained is 0.1～6.0mol/L, preferred 2.0～4.0mol/L.The content of fluorine is answered 〉=0.5g/L in the feed liquid, if not enough, should add fluorochemical and supply.Employed fluorochemical is preferably Neutral ammonium fluoride.
Extracts composition of the present invention comprises extraction agent and solvent.Be applicable to that extraction agent Cyanex923 of the present invention is a commodity extraction agent known in the art.
Form the preferably nonpolar hydrocarbon solvent of solvent of extracts composition of the present invention, comprise aliphatics, alicyclic and aromatic hydrocarbon solvents.The example that is applicable to aliphatic hydrocarbon solvent of the present invention includes but not limited to hexane, heptane, octane, nonane, decane, undecane, dodecane, kerosene, solvent oil, whiteruss etc.The example that is applicable to clicyclic hydrocarbon solvent of the present invention include but not limited to pentamethylene that pentamethylene and low alkyl group replace, hexanaphthene as and the hexanaphthene that replaces of low alkyl group, perhydronaphthalene etc.The example that is applicable to aromatic hydrocarbon solvents of the present invention include but not limited to benzene, toluene, neighbour-,-and right-dimethylbenzene, xylol etc.Consider from the accessibility of economy and operation, preferably adopt normal heptane, octane, nonane, decane, sulfonated kerosene as solvent.
The volume ratio of extraction agent and diluting solvent can change in very wide scope, but considers that from the angle of economy and effect of extracting this ratio can be 1: 9～8: 2, and both form the extracts composition organic phase.
Extracting operation can carry out according to mode known per se, and fractionation extraction is 1～50 grade with washing progression, and preferred 5～20 grades, organic phase is 1: 5～5: 1 with the stream ratio of feed liquid.
In extraction process,, can improve the extraction of extracted species to fluorine in the feed liquid by adding boric acid.If adding boric acid, then the concentration of feed liquid mesoboric acid is generally 0.1～10.0g/L, is preferably 1.0～5.0g/L.
Washing can be carried out according to mode known per se.Washing can further reduce the content of the impurity element in the extraction liquid, thereby helps to improve the purity of the back extraction product that finally obtains.Washings is preferably the mixing solutions of sulfuric acid and boric acid, and wherein sulfuric acid concentration is 0.1～3.0mol/L, and boric acid concentration is 0.1～5.0g/L.Organic phase is 1: 10～10: 1 with the stream ratio of washings, and washing progression is 1～10 grade.
Strip liquor can adopt in reducing substances such as hydrogen peroxide, hydrazine hydrate and the oxammonium hydrochloride any one usually, perhaps in hydrogen peroxide, hydrazine hydrate and the oxammonium hydrochloride any one or with the vitriolic mixing solutions, the perhaps mixing solutions of any one and hydrochloric acid in hydrogen peroxide, hydrazine hydrate and the oxammonium hydrochloride, wherein the concentration of hydrogen peroxide or hydrazine hydrate or oxammonium hydrochloride is 0.1～10% (volume ratio), and the concentration of sulfuric acid or hydrochloric acid is 0.1～5.0mol/L.Organic phase is 1: 5～5: 1 with the stream ratio of strip liquor, and back extraction progression is 1～10 grade.
The extraction agent Cyanex923 that the present invention selects has high stability, hypotoxicity, low volatility.Employed extracts composition has higher percentage extraction, good separating effect.The CeF that the inventive method obtains
3Purity is (with CeO
2/ REO represents) between 99.9～99.999%, the rate of recovery of cerium can be up to more than 90%.
Below in conjunction with embodiment the present invention is described clearly further, but it only is for illustrative purposes, and scope of the present invention is not had any restriction.Among all embodiment employed feed liquid all with sulfuric acid to leach through the hamartite of oxidizing roasting or mixing the ore deposit or containing the cerium mixed rare-earth oxide and fluorochemical obtains through the hamartite of sodium carbonate roasting and monazite.
Embodiment 1:
Feed liquid is from the sulfuric acid to leach liquid of hamartite oxidizing roasting, and the acidity of regulating feed liquid is 0.1mol/L, adds potassium permanganate, makes that potassium permanganate concentration is 0.1g/L in the feed liquid.Add boric acid, making feed liquid mesoboric acid concentration is 0.1g/L.Get 300mlCyanex923, the 700ml normal heptane mixes, and is mixed with extracts composition.As reactor, carry out the extraction of 5 stage countercurrents with the 30ml separating funnel, organic phase is 1: 5 with the stream ratio of feed liquid.Then carry out 2 stage countercurrent back extractions, strip liquor is 0.1% H
2O
2The aqueous solution, organic phase is 1: 10 with the stream ratio of strip liquor.Filter resulting back extraction product, can obtain CeF
3Nano-powder, its median size are 70nm, CeO
2/ REO=99.92%.Then carry out the washing of 3 stage countercurrents, washings is a water, and organic phase is 1: 10 with the stream ratio of washings.Organic phase after the washing can be recycled.
Embodiment 2:
From the feed liquid of embodiment 1, regulating its acidity is 1.5mol/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.Get 200mlCyanex923, the 800ml octane mixes, and is mixed with extracts composition.As reactor, carry out the extraction of 5 stage countercurrents with the 30ml separating funnel, organic phase is 3: 2 with the stream ratio of feed liquid.Carry out the washing of 4 stage countercurrents then, washings is the H of 0.5mol/L
2SO
4And 1g/LH
3BO
3Mixed aqueous solution, organic phase is 1: 10 with the stream ratio of washings.Then carry out 2 stage countercurrent back extractions, strip liquor is 10.0% H
2O
2The aqueous solution, organic phase is 1: 10 with the stream ratio of strip liquor.Filter resulting back extraction product, can obtain CeF
3Nano-powder, its median size are 25nm, CeO
2/ REO=99.98%.Then carry out the washing of 5 stage countercurrents, washings is a sulphuric acid soln, and its concentration is 0.1mol/L.Organic phase is 1: 5 with the stream ratio of washings.Organic phase after the washing can be recycled.
Embodiment 3:
From the feed liquid of embodiment 1, regulating its acidity is 3.0mol/L, adds potassium permanganate, makes that potassium permanganate concentration is 5.0g/L in the feed liquid.Add boric acid, making feed liquid mesoboric acid concentration is 5.0g/L.Get 300mlCyanex923, the 700ml normal hexane mixes, and is mixed with extracts composition.As reactor, carry out the extraction of 6 stage countercurrents with the 30ml separating funnel, organic phase is 2: 1 with the stream ratio of feed liquid.Carry out the washing of 6 stage countercurrents then, washings is the H of 0.5mol/L
2SO
4And 1g/LH
3BO
3Mixed aqueous solution, organic phase is 2: 3 with the stream ratio of washings.Then carry out 2 stage countercurrent back extractions, strip liquor is 10.0% hydrazine hydrate aqueous solution, and organic phase is 2: 1 with the stream ratio of strip liquor.Filter resulting back extraction product, can obtain CeF
3Nano-powder, its median size are 42nm, CeO
2/ REO=99.998%.Then carry out the washing of 4 stage countercurrents, washings is a salpeter solution, and its concentration is 4.0mol/L.Organic phase is 4: 1 with the stream ratio of washings.Organic phase after the washing can be recycled.
Embodiment 4:
From the feed liquid of embodiment 1, regulating its acidity is 1.6mol/L, adds potassium permanganate, makes that potassium permanganate concentration is 3.0g/L in the feed liquid.Add boric acid, making feed liquid mesoboric acid concentration is 10.0g/L.Get 300mlCyanex923, the 700ml nonane mixes, and is mixed with extracts composition.As reactor, carry out the extraction of 8 stage countercurrents with the 30ml separating funnel, organic phase is 2: 1 with the stream ratio of feed liquid.Carry out the washing of 8 stage countercurrents then, washings is the H of 5.0mol/L
2SO
4And 2g/LH
3BO
3Mixed aqueous solution, organic phase is 10: 1 with the stream ratio of washings.Then carry out 2 stage countercurrent back extractions, strip liquor is 0.1% hydrazine hydrate aqueous solution, and organic phase is 1: 1 with the stream ratio of strip liquor.Filter resulting back extraction product, can obtain CeF
3Nano-powder, its median size are 32nm, CeO
2/ REO=99.9992%.Then carry out the washing of 3 stage countercurrents, washings is a sulphuric acid soln, and its concentration is 2.0mol/L.Organic phase is 2: 1 with the stream ratio of washings.Organic phase after the washing can be recycled.
Embodiment 5:
Feed liquid is from the mix ore deposit of hamartite with monazite, through yellow soda ash oxidizing roasting, sulfuric acid to leach.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.Add boric acid, making feed liquid mesoboric acid concentration is 5.0g/L.Add Neutral ammonium fluoride, make that fluorine concentration is 5g/L in the feed liquid.Get 300mlCyanex923, the 700ml decane mixes, and is mixed with extracts composition.As reactor, carry out the extraction of 6 stage countercurrents with the 30ml separating funnel, organic phase is 2: 1 with the stream ratio of feed liquid.Carry out the washing of 8 stage countercurrents then, washings is the H of 0.4mol/L
2SO
4And 1g/LH
3BO
3Mixed aqueous solution, organic phase is 8: 5 with the stream ratio of washings.Then carry out 2 stage countercurrent back extractions, strip liquor is 0.1% H
2O
2And 0.01mol/MH
2SO
4Mixing solutions, organic phase is 3: 2 with the stream ratio of strip liquor.Filter resulting back extraction product, can obtain CeF
3Nano-powder, its median size are 65nm, CeO
2/ REO=99.998%.Then carry out the washing of 3 stage countercurrents, washings is a sulphuric acid soln, and its concentration is 1.0mol/L.Organic phase is 2: 1 with the stream ratio of washings.Organic phase after the washing can be recycled.
Embodiment 6:
Feed liquid is from the mix ore deposit of hamartite with monazite, through yellow soda ash oxidizing roasting, sulfuric acid to leach.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.Add boric acid, making feed liquid mesoboric acid concentration is 7.0g/L.Add Neutral ammonium fluoride, make that fluorine concentration is 25g/L in the feed liquid.Get 200mlCyanex923, the 800ml normal heptane mixes, and is mixed with extracts composition.As reactor, carry out the extraction of 6 stage countercurrents with the 30ml separating funnel, organic phase is 2: 1 with the stream ratio of feed liquid.Carry out the washing of 6 stage countercurrents then, washings is the H of 0.4mol/L
2SO
4And 1g/LH
3BO
3Mixed aqueous solution, organic phase is 8: 5 with the stream ratio of washings.Then carry out 2 stage countercurrent back extractions, strip liquor is 0.1% oxammonium hydrochloride solution, and organic phase is 3: 2 with the stream ratio of strip liquor.Filter resulting back extraction product, can obtain CeF
3Nano-powder, its median size are 65nm, CeO
2/ REO=99.998%.Then carry out the washing of 3 stage countercurrents, washings is a salpeter solution, and its concentration is 0.1mol/L.Organic phase is 2: 1 with the stream ratio of washings.Organic phase after the washing can be recycled.
Embodiment 7:
From the feed liquid of embodiment 6, 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.Add boric acid, making feed liquid mesoboric acid concentration is 4.0g/L.Add Neutral ammonium fluoride, make that fluorine concentration is 15g/L in the feed liquid.Get 200ml Cyanex923, the 800ml sulfonated kerosene mixes, and is mixed with extracts composition.As reactor, carry out the extraction of 6 stage countercurrents with the 30ml separating funnel, organic phase is 2: 1 with the stream ratio of feed liquid.Carry out the washing of 6 stage countercurrents then, washings is the H of 0.4mol/L
2SO
4And 1g/LH
3BO
3Mixed aqueous solution, organic phase is 8: 5 with the stream ratio of washings.Then carry out 2 stage countercurrent back extractions, strip liquor is 10.0% oxammonium hydrochloride and the mixing solutions of 5.0mol/LHCl, and organic phase is 3: 2 with the stream ratio of strip liquor.Filter resulting back extraction product, can obtain CeF
3Nano-powder, its median size are 62nm, CeO
2/ REO=99.991%.Then carry out the washing of 3 stage countercurrents, washings is a salpeter solution, and its concentration is 0.1mol/L.Organic phase is 2: 1 with the stream ratio of washings.Organic phase after the washing can be recycled.
Embodiment 8:
Come self-contained cerium mixed rare-earth oxide (CeO wherein
2/ REO=58%), through the feed liquid of sulfuric acid dissolution, 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.Add boric acid, making feed liquid mesoboric acid concentration is 7.0g/L.Add Neutral ammonium fluoride, make that fluorine concentration is 0.1g/L in the feed liquid.Get 200ml Cyanex923, the 800ml sulfonated kerosene mixes, and is mixed with extracts composition.As reactor, carry out the extraction of 6 stage countercurrents with the 30ml separating funnel, organic phase is 2: 1 with the stream ratio of feed liquid.Carry out the washing of 6 stage countercurrents then, washings is the H of 0.4mol/L
2SO
4And 1g/LH
3BO
3Mixed aqueous solution, organic phase is 8: 5 with the stream ratio of washings.Then carry out 2 stage countercurrent back extractions, strip liquor is 1.5% H
2O
2With the mixing solutions of 0.01mol/LHCl, organic phase is 3: 2 with the stream ratio of strip liquor.Add the polyphosphoric acid tetramethyl-ammonium in the back extraction product, making its concentration is 1g/L, adds strong aqua and regulates pH value to 11, can obtain the CeF that median size is 6.2nm
3Nanoparticle, CeO
2/ REO=99.998%.Then carry out the washing of 3 stage countercurrents, washings is a sulphuric acid soln, and its concentration is 0.1mol/L.Organic phase is 2: 1 with the stream ratio of washings.Organic phase after the washing can be recycled.
Embodiment 9:
From the feed liquid of embodiment 8, 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.Add boric acid, making feed liquid mesoboric acid concentration is 7.0g/L.Add Neutral ammonium fluoride, make that fluorine concentration is 25g/L in the feed liquid.Get 200mlCyanex923, the 800ml normal heptane mixes, and is mixed with extracts composition.As reactor, carry out the extraction of 6 stage countercurrents with the 30ml separating funnel, organic phase is 2: 1 with the stream ratio of feed liquid.Carry out the washing of 9 stage countercurrents then, washings is the H of 0.4mol/L
2SO
4And 1g/LH
3BO
3Mixed aqueous solution, organic phase is 8: 5 with the stream ratio of washings.Then carry out 2 stage countercurrent back extractions, strip liquor is 1.5% hydrazine hydrate and the mixing solutions of 0.01mol/LHCl, and organic phase is 3: 2 with the stream ratio of strip liquor.Add Methanaminium, N,N,N-trimethyl-, fluoride in the back extraction product, making its concentration is 5g/L, adds strong aqua and regulates pH value to 10, can obtain the CeF that median size is 2.2nm
3Nanoparticle, CeO
2/ REO=99.9997%.Then carry out the washing of 3 stage countercurrents, washings is a sulphuric acid soln, and its concentration is 5.0mol/L.Organic phase is 2: 1 with the stream ratio of washings.Organic phase after the washing can be recycled.
Embodiment 10:
From the feed liquid of embodiment 1, 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.Add boric acid, making feed liquid mesoboric acid concentration is 7.0g/L.Add Neutral ammonium fluoride, make that fluorine concentration is 15.5g/L in the feed liquid.Get 200ml Cyanex923, the 800ml normal heptane mixes, and is mixed with extracts composition.As reactor, carry out the extraction of 6 stage countercurrents with the 30ml separating funnel, organic phase is 2: 1 with the stream ratio of feed liquid.Carry out the washing of 6 stage countercurrents then, washings is the H of 0.4mol/L
2SO
4And 1g/LH
3BO
3Mixed aqueous solution, organic phase is 8: 5 with the stream ratio of washings.Then carry out 2 stage countercurrent back extractions, strip liquor is 1.5% H
2O
2With the mixing solutions of 0.01mol/LHCl, organic phase is 3: 2 with the stream ratio of strip liquor.Add the polyphosphoric acid TBuA in the back extraction product, making its concentration is 5g/L, adds strong aqua and regulates pH value to 9, can obtain the CeF that median size is 4.8nm
3Nanoparticle, CeO
2/ REO=99.9993%.Then carry out the washing of 5 stage countercurrents, washings is a sulphuric acid soln, and its concentration is 1.0mol/L.Organic phase is 2: 1 with the stream ratio of washings.Organic phase after the washing can be recycled.
Embodiment 11:
From the feed liquid of embodiment 5, 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.Add boric acid, making feed liquid mesoboric acid concentration is 7.0g/L.Add Neutral ammonium fluoride, make that fluorine concentration is 15.5g/L in the feed liquid.Get 200ml Cyanex923, the 800ml normal heptane mixes, and is mixed with extracts composition.As reactor, carry out the extraction of 6 stage countercurrents with the 30ml separating funnel, organic phase is 2: 1 with the stream ratio of feed liquid.Carry out the washing of 6 stage countercurrents then, washings is the H of 0.4mol/L
2SO
4And 1g/LH
3BO
3Mixed aqueous solution, organic phase is 8: 5 with the stream ratio of washings.Then carry out 2 stage countercurrent back extractions, strip liquor is 1.5% H
2O
2With the mixing solutions of 0.01mol/LHCl, organic phase is 3: 2 with the stream ratio of strip liquor.Add tetrabutyl ammonium fluoride in the back extraction product, making its concentration is 5g/L, adds strong aqua and regulates pH value to 9, can obtain the CeF that median size is 2.6nm
3Nanoparticle, CeO
2/ REO=99.9996%.Then carry out the washing of 5 stage countercurrents, washings is a sulphuric acid soln, and its concentration is 1.0mol/L.Organic phase is 2: 1 with the stream ratio of washings.Organic phase after the washing can be recycled.
Claims (3)
1, a kind of method for preparing high-purity cerous fluoride micro mist adopts Cyanex923 to make extraction agent, the feed liquid that obtains through the hamartite of oxidizing roasting with sulfuric acid to leach, wherein CeO
2/ REO 〉=5%, Ce
4+Be 10～125g/L, F 〉=0.5g/L
Preparation process:
A, be 0.1～6.0mol/L with the acidity adjustment of feed liquid;
B, add potassium permanganate, make that potassium permanganate concentration is 0.1～5.0g/L in the feed liquid;
C, from described feed liquid, extract Ce with extracts composition
4+And F, extraction progression is 1～50 grade, the extracts composition organic phase is 1: 5～5: 1 with the material liquid flowing ratio, described extracts composition is extraction agent and nonpolar hydrocarbon solvents, and nonpolar hydrocarbon solvents is hexane, heptane, octane, nonane, decane, undecane, dodecane, kerosene, solvent oil or whiteruss;
D, from organic phase, strip, obtain Ce with strip liquor
3+Solution and CeF
3Micro mist, described strip liquor be in hydrogen peroxide, hydrazine hydrate and the oxammonium hydrochloride any one, perhaps any one and vitriolic mixing solutions in hydrogen peroxide, hydrazine hydrate and the oxammonium hydrochloride, the perhaps mixing solutions of any one and hydrochloric acid in hydrogen peroxide, hydrazine hydrate and the oxammonium hydrochloride, wherein the volume by volume concentration of hydrogen peroxide or hydrazine hydrate or oxammonium hydrochloride is 0.1～10%, and the concentration of sulfuric acid or hydrochloric acid is 0.1～5.0mol/L; Organic phase is 1: 5～5: 1 with the stream ratio of strip liquor, and back extraction progression is 1～10 grade;
E, add coating in the back extraction mixture that steps d obtains, coating is Methanaminium, N,N,N-trimethyl-, fluoride, tetrabutyl ammonium fluoride, polyphosphoric acid tetramethyl-ammonium or polyphosphoric acid TBuA.
2, a kind of method for preparing high-purity cerous fluoride micro mist adopts Cyanex923 to make extraction agent, the feed liquid that obtains through the mixed ore of the hamartite of sodium carbonate roasting and monazite with sulfuric acid to leach, wherein CeO
2/ REO 〉=5%, Ce
4+Be 10～125g/L, F 〉=0.5g/L
Preparation process:
A, be 0.1～6.0mol/L with the acidity adjustment of feed liquid;
B, add Neutral ammonium fluoride, make that fluorine concentration is 0.5～25g/L in the feed liquid;
C, add potassium permanganate, make that potassium permanganate concentration is 0.1～5.0g/L in the feed liquid;
D, adding boric acid, making feed liquid mesoboric acid concentration is 0.1～10.0g/L;
E, from described feed liquid, extract Ce with extracts composition
4+And F, extraction progression is 1～50 grade, the extracts composition organic phase is 1: 5～5: 1 with the material liquid flowing ratio, described extracts composition is extraction agent and nonpolar hydrocarbon solvents, and nonpolar hydrocarbon solvents is hexane, heptane, octane, nonane, decane, undecane, dodecane, kerosene, solvent oil or whiteruss;
F, strip from organic phase with strip liquor, back extraction progression is 1～10 grade, and organic phase is 1: 5～5: 1 with the stream ratio of strip liquor; Obtain Ce
3+Solution and CeF
3Micro mist, described strip liquor be in hydrogen peroxide, hydrazine hydrate and the oxammonium hydrochloride any one, perhaps any one and vitriolic mixing solutions in hydrogen peroxide, hydrazine hydrate and the oxammonium hydrochloride, the perhaps mixing solutions of any one and hydrochloric acid in hydrogen peroxide, hydrazine hydrate and the oxammonium hydrochloride, wherein the concentration volume ratio of hydrogen peroxide or hydrazine hydrate or oxammonium hydrochloride is 0.1～10%, and the concentration of sulfuric acid or hydrochloric acid is 0.1～5.0mol/L;
G, add coating in the back extraction mixture that step f obtains, coating is Methanaminium, N,N,N-trimethyl-, fluoride, tetrabutyl ammonium fluoride, polyphosphoric acid tetramethyl-ammonium or polyphosphoric acid TBuA.
3, a kind of method for preparing high-purity cerous fluoride micro mist adopts Cyanex923 to make extraction agent, contains the feed liquid that the rare earth mixed oxide of cerium obtains, wherein CeO with sulfuric acid dissolution
2/ REO 〉=5%, Ce
4+Be 10～125g/L
Preparation process:
A, be 0.1～6.0mol/L with the acidity adjustment of feed liquid;
B, add Neutral ammonium fluoride, make that fluorine concentration is 0.5～25g/L in the feed liquid;
C, add potassium permanganate, make that potassium permanganate concentration is 0.1～5.0g/L in the feed liquid;
D, adding boric acid, making feed liquid mesoboric acid concentration is 0.1～10.0g/L;
E, from described feed liquid, extract Ce with extracts composition
4+And F, extraction progression is 1～50 grade, the extracts composition organic phase is 1: 5～5: 1 with the material liquid flowing ratio, described extracts composition is extraction agent and nonpolar hydrocarbon solvents, and nonpolar hydrocarbon solvents is hexane, heptane, octane, nonane, decane, undecane, dodecane, kerosene, solvent oil or whiteruss;
F, with washings washing organic extraction phase;
G, from organic phase, strip, obtain Ce with strip liquor
3+Solution and CeF
3Micro mist, described strip liquor be in hydrogen peroxide, hydrazine hydrate and the oxammonium hydrochloride any one, perhaps any one and vitriolic mixing solutions in hydrogen peroxide, hydrazine hydrate and the oxammonium hydrochloride, the perhaps mixing solutions of any one and hydrochloric acid in hydrogen peroxide, hydrazine hydrate and the oxammonium hydrochloride, wherein the concentration volume ratio of hydrogen peroxide or hydrazine hydrate or oxammonium hydrochloride is 0.1～10%, and the concentration of sulfuric acid or hydrochloric acid is 0.1～5.0mol/L; Organic phase is 1: 5～5: 1 with the stream ratio of strip liquor, and back extraction progression is 1～10 grade;
H, add coating in the back extraction mixture that step g obtains, coating is Methanaminium, N,N,N-trimethyl-, fluoride, tetrabutyl ammonium fluoride, polyphosphoric acid tetramethyl-ammonium or polyphosphoric acid TBuA.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100106182A CN1253374C (en) | 2004-01-09 | 2004-01-09 | Method of preparing high purity cerium trifluoride micro powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100106182A CN1253374C (en) | 2004-01-09 | 2004-01-09 | Method of preparing high purity cerium trifluoride micro powder |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1556038A CN1556038A (en) | 2004-12-22 |
| CN1253374C true CN1253374C (en) | 2006-04-26 |
Family
ID=34350910
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004100106182A Expired - Fee Related CN1253374C (en) | 2004-01-09 | 2004-01-09 | Method of preparing high purity cerium trifluoride micro powder |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1253374C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100386452C (en) * | 2006-09-22 | 2008-05-07 | 中国科学院长春应用化学研究所 | Method of dynamic continuous oxidation extracting cerium under potassium hypermanganate preferential extraction condition |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100424016C (en) * | 2006-08-18 | 2008-10-08 | 中国科学院长春应用化学研究所 | Method for preparing cerium trifluoride using neutral phosphoras (phosphine) extraction system |
| CN100418886C (en) * | 2006-10-13 | 2008-09-17 | 河南大学 | Organic dispersion lanthanum trifluoride nanometer particle preparation method |
| CN102618736B (en) | 2012-03-31 | 2013-09-04 | 中国科学院长春应用化学研究所 | Extraction separation method of rare-earth element |
| CN105132682B (en) * | 2015-09-10 | 2017-09-22 | 中国科学院长春应用化学研究所 | Extract and separate cerium, fluorine, the method for phosphorus in a kind of ore deposit sulphuric leachate from Baotou rare earth |
| CN107287419B (en) * | 2016-04-13 | 2018-08-03 | 中国科学院长春应用化学研究所 | Purposes and method of the neutral phosphine extractant for extraction and separation cerium (IV) or thorium (IV) |
| 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 |
| CN112624179B (en) * | 2021-02-03 | 2022-07-01 | 浙江爱科新材料有限公司 | Preparation method of high-purity homogeneous zinc sulfate heptahydrate |
-
2004
- 2004-01-09 CN CNB2004100106182A patent/CN1253374C/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100386452C (en) * | 2006-09-22 | 2008-05-07 | 中国科学院长春应用化学研究所 | Method of dynamic continuous oxidation extracting cerium under potassium hypermanganate preferential extraction condition |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1556038A (en) | 2004-12-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106319218A (en) | Method for recovering rare earth, aluminum and silicon from rare earth-containing aluminum and silicon wastes | |
| CN102312098B (en) | Method for separation and purification of fluorescent grade yttrium oxide and europium oxide from waste phosphor powder | |
| CN103468950B (en) | Method for removing metal ion purity of rare earth aqueous solution extraction | |
| Zhou et al. | Recovery of gold from waste mobile phone circuit boards and synthesis of nanomaterials using emulsion liquid membrane | |
| CN1253374C (en) | Method of preparing high purity cerium trifluoride micro powder | |
| CN107828961B (en) | Extraction method of rare earth element ions and obtained rare earth enrichment liquid | |
| Chen et al. | Extraction of rare earth ions from phosphate leach solution using emulsion liquid membrane in concentrated nitric acid medium | |
| CN104928504B (en) | A kind of recovery method of aluminium scrap silicon middle rare earth | |
| CN102417992A (en) | Purification method of thorium | |
| CN109874342A (en) | The purposes of fluoropolymer resin, preparation method and its extraction (one or more) precious metal that composite extractant enhances | |
| CN112981139B (en) | Hydrophobic eutectic solvent for separating nickel and cobalt ions, preparation method thereof and method for separating nickel and cobalt ions | |
| CN102583486A (en) | Preparation method of nano calcium fluoride for self-lubricating tool material | |
| CN1817403A (en) | Saponification of organic extractant | |
| CN103122408A (en) | Method and device for extracting and separating praseodymium and neodymium | |
| Li et al. | Towards zero-consumption of acid and alkali recycling rare earths from scraps: a precipitation-stripping-saponification extraction strategy using CYANEX® 572 | |
| CN109811149A (en) | A kind of back extraction and regeneration method of extracting and separating rear earth ionic liquid | |
| CN103122410B (en) | Method for extracting and grouping-separating light, middle and heavy rare earth elements in multi-rare earth complex solution | |
| CN100406590C (en) | Process for preparing grain-size-adjustable rare earth fluoride micro-powder in neutral phosphorus (phosphine) extraction system | |
| CN1162558C (en) | Process for extracting and separating thorium and extracting rare earth chloride from sulfuric and phosphoric mixed acid system | |
| CN101164890A (en) | Method for separating cerium, reclaiming fluorin and preparing cerous fluoride ultra-micro powder for mixed extraction system | |
| CN100424016C (en) | Method for preparing cerium trifluoride using neutral phosphoras (phosphine) extraction system | |
| CN101181984B (en) | Process for purifying and reclaiming impurities in phosphoric acid by liquid membrane method | |
| CN1880489A (en) | Non-saponifiable extraction full-separating process for high concentration rare earth solution | |
| AU2016341192B2 (en) | Compositions and methods for separating immiscible liquids | |
| CN1891839A (en) | Extracting agent for metal extraction, and its method and use |
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 | ||
| ASS | Succession or assignment of patent right |
Owner name: CHANGZHOU INSTITUTE OF ENERGY STORAGE MATERIALS + Free format text: FORMER OWNER: CHANGCHUN INSTITUTE OF APPLIED CHEMISTRY HINESE ACADEMY OF SCIENCES Effective date: 20121231 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| COR | Change of bibliographic data |
Free format text: CORRECT: ADDRESS; FROM: 130022 CHANGCHUN, JILIN PROVINCE TO: 213000 CHANGZHOU, JIANGSU PROVINCE |
|
| TR01 | Transfer of patent right |
Effective date of registration: 20121231 Address after: Changzhou City, Jiangsu province Hehai road 213000 No. 9 Patentee after: Changzhou Institute of Energy Storage Materials & Devices Address before: 130022 Changchun people's street, Jilin, No. 5625 Patentee before: Changchun Institue of Applied Chemistry, Chinese Academy of Sciences |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20170204 Address after: 130022 Changchun people's street, Jilin, No. 5625 Patentee after: Changchun Applied Chemistry Inst., Chinese Academy of Sciences Address before: Changzhou City, Jiangsu province Hehai road 213000 No. 9 Patentee before: Changzhou Institute of Energy Storage Materials & Devices |
|
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20060426 Termination date: 20200109 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |