CN100500569C - Process for preparing superfine high-purity europium oxide by using europium riched material - Google Patents
Process for preparing superfine high-purity europium oxide by using europium riched material Download PDFInfo
- Publication number
- CN100500569C CN100500569C CNB2007100199532A CN200710019953A CN100500569C CN 100500569 C CN100500569 C CN 100500569C CN B2007100199532 A CNB2007100199532 A CN B2007100199532A CN 200710019953 A CN200710019953 A CN 200710019953A CN 100500569 C CN100500569 C CN 100500569C
- Authority
- CN
- China
- Prior art keywords
- europium
- ultrasonic
- liquid
- extraction
- eucl
- 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
Images
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
- Physical Or Chemical Processes And Apparatus (AREA)
Abstract
The invention relates to a method to make europium oxide that includes the following steps: mixing raw material, taking solid-liquid separation to gain enriched liquid containing europium acid rare earth, taking electrochemistry reaction to gain EuCl2 solution, taking ultrasonic to gain refined liquid of EuCl2, taking electrochemistry reaction to gain refined liquid of EuCl3, taking adsorption and trash extraction, taking ultrasonic crystal deposition to gain Eu2(CO3)3 crystal deposit, taking solid-liquid separation, drying and burning to gain the superfine high purity europium oxide product that has content over 99.99%, and the particle diameter is 0.01-10.0um. The advantages of the invention are that it improves leaching and extracting speed, and the particle diameter is small, and particle size distribution equal.
Description
Technical field
The present invention relates to a kind of method for preparing europium sesquioxide, particularly a kind of is the method for the ultra-fine high-purity europium oxide of feedstock production with rich europium salt acid rare earth, belongs to the hydrometallurgy field.
Background technology
Ultra-fine high-purity europium oxide (Eu
2O
3) product is meant europium sesquioxide content 〉=99.99%, the europium sesquioxide product of grain diameter≤10.0 μ m.Europium sesquioxide is the activator of red fluorescence powder, uses in a large number in fields such as colour television set picture tube and three-color fluorescent lamps.Simultaneously, along with opening up out of electricity-saving lamp market, lamp also will constantly enlarge with the demand of fluorescent RE powder, and this just will drive the consumption cumulative year after year of fluorescence europium oxide.But the general red fluorescence powder of producing can only satisfy the needs of common picture tube, display screen, along with color monitor develops to giant-screen, high definition, high resolving power direction, need have high-purity level of special luminescent properties, the small-particle new phosphors.Therefore, the purity of europium sesquioxide and particle diameter etc. are had higher requirement, also need better preparation method and prepare ultra-fine high-purity europium oxide (Eu
2O
3) product.At present, the main preparation methods of enrichment europium is zinc powder reduction-europous sulfate-barium sulfate coprecipitation method from contain the lower earth solution of europium, can enrichment more than tens times through primary sedimentation operation europium, the rate of recovery of europium is greater than 98%, Eu (II) ion is the most stable in the ion on divalence is rare, character is similar to alkaline-earth metal ions, and is special similar to Ba (II) ion, energy and SO
4 2-Generate white precipitate, easily oxidized etc.This preparation method is mainly decomposed steps such as the inferior europium of hydrochloric acid, europium hydroxide precipitation and forms by zinc powder reduction, europous sulfate-barium sulfate co-precipitation, nitric acid.
(1) zinc powder reduction: in re chloride, zinc can be with Eu
3+Be reduced to Eu
3+, its reaction formula is:
Easily by the oxidation of hydrogen ion institute, in the reduction ratio reaction process of europium, the side reaction of existence is divalent europium in the reductive process:
Reaction formula [2] and [3] influence the transformation efficiency of the reduction ratio reaction process of europium.For fear of and reduce the generation of [2] and [3] reaction, in preparation process, adopt following measure usually: 1. reduce the acidity of earth solution, it is controlled between PH=3～4 with the oxygenizement of minimizing hydrogen ion to divalent europium; 2. reduction process is carried out under the condition of air-isolations such as inert atmosphere or encloses container, prevents that oxygen from participating in the oxidizing reaction of divalent europium; Inert solvent protections such as required kerosene, dimethylbenzene when 3. reduced liquid filters, secluding air.
(2) europous sulfate precipitation: divalent europium has the character of alkaline-earth metal, and in acidic solution, its vitriol is the indissoluble material.According to this character, containing certain SO
4 2-Add zinc powder, with Eu
3+Reductive is Eu simultaneously
2+With SO
4 2-Effect generates the europous sulfate precipitation.SO
4 2-Introducing adopt dual mode: when 1. being raw material, press Eu in the raw material with the rare earth oxide
2O
3Cubage vitriolic requirement, and be made into mixed acid solution with sulfuric acid, the dissolving rare earth oxide prepares solution; 2. raw material be extraction process produce solution the time, for the acidity that makes solution is stable, press Eu in the raw material
2O
3Content add sal epsom or ammonium sulfate.Eu in the solution
2+When concentration is high, EuSO
4Sedimentation speed is fast, Eu
2+Concentration is low, EuSO
4Sedimentation speed is very slow, and precipitation not exclusively.
(3) the sedimentary processing of europous sulfate: contain BaSO in the europous sulfate throw out
4, MgSO
4And non-europium rare earth element, adopt the nitric acid of 5mol/L concentration under greater than 80 ℃ of conditions, to handle Eu usually
2+By nitric acid oxidation is Eu
3+Dissolving becomes solution, and solution is removed BaSO through filtering
4Eu
3+The molten employing ammonia of filtrate is regulated pH 〉=11, generates Eu (OH)
3Precipitation; Filtration, filter cake are done Eu (OH)
3Wash with water, adopt dissolving with hydrochloric acid then, oxalic acid precipitation, filtration washing, dry, calcination obtains the europium sesquioxide primary products, and the europium sesquioxide primary products are produced ultra-fine high-purity europium oxide product by further separating, making with extra care.
The subject matter that above-mentioned zinc powder reduction-europous sulfate-barium sulfate coprecipitation method exists is: (1) preparation technology's problem: step is various in the preparation process of ultra-fine high-purity europium oxide product, time is long, speed is slow, efficient is low, throughput is difficult to improve, the preparation cost height, reagent consumption is big, yield is low; (2) oxalic acid europium crystalline deposit problem: to add oxalic acid in the purified europium nitrate solution is that to generate that oxalic acid europium crystalline deposit separates out be the method for crystallizing and sedimenting of the rare earth element that generally adopts of present industrial production to precipitation agent.Oxalic acid is that precipitation agent uses, the production cost height, and also oxalic acid toxicity is big, contaminate environment.(3) product quality problem: the oxalic acid europium product that adopts traditional crystalline deposit method to obtain, the quality instability of the europium sesquioxide product that the separation of process solid-liquid, drying, calcination obtain generally is difficult to obtain Eu
2O
3Content bigger up to the particle diameter of 99.99% purity, particularly product, and size-grade distribution is inhomogeneous, is difficult to reach the requirement that product uses in high-tech sector.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, provide that a kind of segregation rate and separation efficiency height, product particle particle diameter are little, the method for even particle size distribution, preparing superfine high-purity europium oxide by using europium riched material that purity is high.
The technical scheme that realizes above-mentioned purpose is: a kind of method of preparing superfine high-purity europium oxide by using europium riched material is to be raw material with rich europium salt acid rare earth, and described method steps is as follows:
(1) batch mixes: rich europium salt acid rare earth, hydrochloric acid, water are carried out mix;
(2) solid-liquid separates: separate through solid-liquid, remove insoluble impurities, obtain rich europium hydrochloric acid earth solution feed liquid, the concentration of feed liquid middle-weight rare earths is 0.1-1.2mol/L; Solid phase is recyclable through washing;
(3) electrochemical reduction: the rich europium hydrochloric acid earth solution that previous step is obtained at the negative electrode of electrochemical reactor with trivalent europium Eu
3+Be reduced to divalent europium Eu
2+, obtain EuCl
2Solution;
(4) ultrasonic fractionation extraction: in ultrasonic extraction equipment, add EuCl
2Solution, extraction liquid, washing lotion, the volume ratio of three kinds of proportioning materials are 1:0.5-5.0:0.1-2.0, and operational condition is ultrasonic frequency 19-80kHz, ultrasonication intensity 0.2-20.0W/cm
2, service temperature is 5-60 ℃, carries out ultrasonic fractionation extraction, extracting phase is non-europium rare earth nitrate solution, can remove further separation and purification, reclaims other rare earth element; The also recyclable utilization of organic phase; Central exit liquid is EuCl
2Refined liquid enters next step;
(5) electrochemical oxidation: previous step is obtained EuCl
2Refined liquid is put into electrochemical reactor, at the anode of electrochemical reactor, with divalent europium Eu
2+Be oxidized to trivalent europium Eu
3+, generate EuCl
3Refined liquid;
(6) adsorption-edulcoration: the EuCl that obtains in previous step
3In the refined liquid, add the adsorption-edulcoration agent, carry out further degree of depth adsorption-edulcoration, separate, remove impurity, make purified EuCl through solid-liquid
3Refined liquid enters next step;
(7) ultrasonic crystalline deposit: in ultrasonic crystallizer, add purified hydrochloric acid europium refined liquid, crystalline deposit agent bicarbonate of ammonia or volatile salt, the mol ratio of hydrochloric acid europium refined liquid and crystalline deposit agent batching is 1:1.1-1.6, operational condition is ultrasonic frequency 19-80kHz, ultrasonication intensity 0.2-20.0W/cm
2, service temperature is 5-60 ℃, carries out ultrasonic crystalline deposit, generates europium carbonate Eu
2(CO
3)
3The crystalline deposit thing enters next step;
(8) solid-liquid separates: separate through solid-liquid, obtaining solid phase is europium carbonate Eu
2(CO
3)
3The crystalline deposit thing enters next step; Liquid phase can remove to reclaim ammonium nitrate;
(9) dry, calcination:, obtain europium carbonate Eu 25-800 ℃ of drying
2(CO
3)
3800-900 ℃ of following calcination, obtain Eu
2O
3Content 〉=99.99%, grain diameter are the ultra-fine high-purity europium oxide product of 0.01-10.0 μ m.
Prioritization scheme of the present invention is that the operational condition in ultrasonic fractionation extraction and the ultrasonic crystalline deposit is ultrasonic frequency 25kHz, ultrasonication intensity 2.0W/cm
2, the service temperature of ultrasonic fractionation extraction is 40 ℃, the service temperature of ultrasonic crystalline deposit is 10 ℃.The best results of ultrasonic fractionation extraction and ultrasonic crystalline deposit under this operational condition.Described ultrasonic extraction equipment includes extraction plant and ultrasonic generating unit, extraction plant is the still formula, slot type, any extraction plant in the tubular type, ultrasonic generating unit is a sonde-type, vibrator type, in the ultrasonic generating unit of vibration plate formula any, ultrasonic extraction equipment can be the still formula, slot type, a kind of extraction plant and sonde-type in the tubular type, vibrator type, a kind of combination in the ultrasonic generating unit of vibration plate formula also can be the still formula, slot type, a kind of extraction plant and sonde-type in the tubular type, vibrator type, any two or three combination in the ultrasonic generating unit of vibration plate formula.The extraction kettle that has the probe type ultrasonic generating unit is to be provided with the probe type ultrasonic producer in extraction kettle; The extraction tank that has the probe type ultrasonic generating unit is provided with the probe type ultrasonic producer in extraction tank; The extracting tube that has the probe type ultrasonic generating unit is to be provided with the probe type ultrasonic producer in extracting tube; The extraction kettle that has the ultrasonic generating unit of vibrator type, be that wall at extraction kettle is outside equipped with the vibrator type ultra-sonic generator, wall is meant sidewall and diapire outward, and the vibrator type ultra-sonic generator is set can be only in the sidewall setting, also can only on diapire, be provided with, also can on sidewall and diapire, be provided with simultaneously; The extraction tank that has the ultrasonic generating unit of vibrator type, its structure is identical with the extraction kettle that has the ultrasonic generating unit of vibrator type, just the extraction kettle formula is replaced to extraction tank; The extracting tube that has the ultrasonic generating unit of vibrator type, its structure is identical with the extraction kettle that has the ultrasonic generating unit of vibrator type, just extraction kettle is replaced to extracting tube; The extraction kettle that has the ultrasonic generating unit of vibration plate formula is to be provided with vibration plate formula ultra-sonic generator in extraction kettle; The extraction tank that has the ultrasonic generating unit of vibration plate formula is to be provided with vibration plate formula ultra-sonic generator in extraction tank; The extracting tube that has the ultrasonic generating unit of vibration plate formula is to be provided with vibration plate formula ultra-sonic generator in extracting tube.Described ultrasonic crystallizer includes crystallization apparatus and ultrasonic generating unit, crystallization apparatus is the still formula, slot type, any crystallization apparatus in the tubular type, ultrasonic generating unit is a sonde-type, vibrator type, in the ultrasonic generating unit of vibration plate formula any, ultrasonic crystallizer can be the still formula, slot type, a kind of crystallization apparatus and sonde-type in the tubular type, vibrator type, a kind of combination in the ultrasonic generating unit of vibration plate formula also can be the still formula, slot type, a kind of crystallization apparatus and sonde-type in the tubular type, vibrator type, any two or three combination in the ultrasonic generating unit of vibration plate formula.Its combining form is identical with the combining form of above-mentioned ultrasonic extraction equipment, just extraction plant is replaced to crystallization apparatus and gets final product.Electrochemical reactor among the present invention adopts three-diemsnional electrode barrier film electrochemical reactor oxidation-reduction best results.
The present invention mainly adopts electrochemistry to appraise at the current rate-ultrasonic extraction-ultrasonic crystalline separation method.(1) adopt electrochemistry to appraise at the current rate, utilize the characteristic of appraising at the current rate of europium: europium is one of rare element in the rare earth, and Eu (III) ion and its be element ion Sm (III) on every side, and Gd (III) character and similar is difficult to directly they be separated with ion exchange method with extraction process.But Eu (II) ion is the most stable in the ion on divalence is rare, and character is similar to alkaline-earth metal ions, and is special similar to Ba (II) ion, energy and SO
4 2-Generate white precipitate, easily by NO
3 -Oxidation etc.And the redox potential of europium is lower, Eu
3++ e → Eu
2+The reaction normal electropotential be-0.35V that the rate controlling step of reaction is the transfer transport step.The present invention can adopt Zn, C, and the electrode materials that hydrogen overpotentials such as Ti are high is reduced to divalent europium at negative electrode with the trivalent europium, the Eu of the negative electrode of flowing through like this
3+With electrode bigger contact area is arranged, make it be produced EuSO simultaneously by the reduction of fast quantification ground
4Generate white precipitate; (2) application of three-diemsnional electrode barrier film electrochemical reactor: three-diemsnional electrode barrier film electrochemical reactor is existing the introduction in " chemical industry metallurgical ", (see " chemical industry metallurgical " nineteen ninety-five the 16th volume the 3rd phase 263-270 page or leaf for details, author Xu Wenlin, Wang Yaqiong, document name " fixed bed electrochemical reactor progress "; The anode material of electrochemical reactor is titanium base Ti/Sb
2O
3-SnO
2/ PbO
2Insoluble oxide electrode, its preparation method see " Journal of Inorganic Materials " 2003 the 18th volumes the 5th phase 1033-1038 page or leaf for details, and author Wang Yaqiong, child carry forward, permitted galaxy of literary talent, the document name " Ti/SnO of thermal decomposition method preparation
2+ Sb
2O
3/ PbO
2Electrode property research "; Barrier film is a perfluorinated sulfonic acid enhancement type cationic exchange membrane from material), perfluorinated sulfonic acid enhancement type cationic exchange membrane is done isolated material.The three-diemsnional electrode electrochemical reactor mainly is fixed bed electrochemical reactor and fluidized bed electrochemical reactor, and it has specific surface area big (volume of electrode surface area/electrochemical reactor), rate of mass transfer height, is adapted to the little reactive system of limit transfer rate especially; (3) ultrasound-enhanced sepn process: ultrasonic isolating strengthening effect is derived from ultrasonic cavitation.Ultrasonic cavitation is meant that the small complex in the liquid phase is activated under the high intense ultrasonic wave effect of low frequency, it shows as a series of dynamic processes such as vibration, growth, contraction and collapse of microvesicle.Around cavitation bubble, produce High Temperature High Pressure in the utmost point short period of time of cavitation bubble collapse, and the microjet that is exceedingly fast with intensive shockwave and speed, ultrasonic cavitation produces various additive effects in microenvironment, as turbulence effect, perturbation effect, interfacial effect and cavity effect etc.Wherein turbulence effect can make the frictional belt attenuate, increases rate of mass transfer; That the perturbation effect has been strengthened is liquid-solid, the mixing of liquid-liquid with separate; It is long-pending that interfacial effect has increased mass transfer surfaces.Therefore, ultrasonic cavitation can be strengthened the rate of mass transfer and the efficient of sepn process on the whole.Ultrasonic strengthening effect to sepn process also has heat effect and mechanical effect except cavatition.Heat effect is that molecule produces high vibration because medium absorbs ultrasonic wave and internal friction consumption, and ultransonic mechanical energy is converted into the interior energy of medium, causes that medium temperature raises.Hyperacoustic intensity is bigger, and the heat effect of generation is stronger.The control ultrasound intensity can make the temperature moment rising of solid-liquid organization internal, quickens the stripping of effective constituent, and does not change the character of composition.The propagation of ultra sonic machinery vibrational energy can form in liquid and effectively stir with mobile, destroys the structure of medium, pulverizes the particle in the liquid, can reach the inaccessible effect of common mechanical agitation; (4) crystallization of europium carbonate and precipitation: bicarbonate of ammonia or volatile salt are commodity cheap and easy to get, use bicarbonate of ammonia or volatile salt instead and replace oxalic acid to make precipitation agent, have reduced the cost of producing europium sesquioxide; The solubleness of carbonated rare earth in water is 10 simultaneously
-3-10
-4In the grams per liter scope, the solubleness of rare earth oxalate fluctuates in 0.41-3.3 grams per liter scope, and is more much lower than the solubleness of rare earth oxalate.From the angle of deposition rate and yield, it is more favourable than adopting the rare earth oxalate precipitation to adopt the sedimentary way of carbonated rare earth.Bicarbonate of ammonia is nontoxic, replaces oxalic acid to do the rare-earth precipitation agent with its, can also overcome that oxalic acid toxicity is big, the disadvantage of contaminate environment; (5) quality product and granularity problem: rare earth elements europium is difficult to form crystal form carbonate, and the europium carbonate that makes usually is unformed flocks, and precipitation volume is big, wherein comprise a large amount of water and impurity, washing, filtration difficulty, and the loss of poor product quality, rare earth is big, produces to be difficult to carry out, adopt bicarbonate of ammonia or the ultrasonic crystalline deposit technology of volatile salt, can improve process, the product crystallization perfection of Huo Deing simultaneously, purity height, grain diameter is little, even particle size distribution.
Adopt the benefit of technique scheme to be: (1) electrochemical oxidation-reduction technique: to utilize the characteristic of appraising at the current rate of europium, carry out conversion between trivalent europium and the divalent europium by electrochemical oxidation-reduction.Adopt electrochemical process to carry out appraising at the current rate of europium, not only process is controlled easily, and is easy and simple to handle, and can reduce the consumption of chemical reagent and the treatment capacity of the follow-up three wastes, is a kind of green production technology; If adopting the three-dimensional electrochemical reactor (as fixed bed electrochemical reactor, fluidized bed electrochemical reactor) of three-diemsnional electrode finishes, its effect is better, because it has the advantages that specific surface area is big, rate of mass transfer is high, be specially adapted to the little reactive system of limit transfer rate; (2) three-dimensional electrochemical reactor: in same electrochemical reactor, realize the electrochemical oxidation-reduction of europium, in original electrochemical oxidation process, only used the negative electrode of electrochemical reactor, and anode is not well utilized, and electrochemical reduction of the present invention is to carry out on negative electrode, and oxidation is to carry out on anode, therefore improved the utilising efficiency of electrochemical reactor, reduced the consumption of energy, simultaneously, in the electrochemical reaction process, do not have the generation of electrolysis by product, protected environment yet; (3) the bicarbonate of ammonia crystalline deposit of europium nitrate: the crystalline deposit agent of adopting bicarbonate of ammonia or volatile salt to prepare europium carbonate as europium nitrate solution, not only can reduce production costs, improve settling rate and yield, improve quality product and production environment, reduce the disadvantage of contaminate environment.And, can reclaim by product ammonium nitrate, greatly reduce the consumption of chemical reagent, can reduce production costs significantly; Simultaneously, because in europium carbonate crystalline deposit precipitation process, the employing ultrasonic technique is strengthened, further improved the speed and the efficient of crystallization precipitation process, improved europium carbonate crystalline granularity and size-grade distribution, the europium sesquioxide product particle particle diameter of preparing is little, even particle size distribution, the purity height reaches ultra-fine, high-purity, its europium sesquioxide product E u
2O
3Content 〉=99.99%, grain diameter is 0.01-10.0 μ m, is ultra-fine high-purity europium oxide product, its purity and fineness are much higher than the index that prior art can reach, and suit especially at the high grade product of high-tech sector service requirements; (4) adsorption-edulcoration: before the europium carbonate crystalline deposit, adopt the adsorption-edulcoration method, further degree of depth adsorption-edulcoration, the purity of raising product; (5) adopt ultrasonic fractionation extraction technology, improve the dispersiveness of liquid-liquid extraction process, clarifying process after improving the extraction rate of mass transfer and improving extraction, the Applied Physics technology fundamentally solves the mixing that exists in the rare earth extraction process and the contradiction of clarifying process, improve extracting and separating speed and separation efficiency greatly, improve 20 to 60 times than traditional extraction method, this makes production cost descend, throughput improves, and technology is simple; Under the condition of same turnout, can reduce the investment of equipment and reagent, and production process is continuous, easy and simple to handle, easily and other production line supporting, improve the performance of product.The inventive method has solved does not have the technical barrier that solves for a long time, no matter aspect segregation rate and separation efficiency, still on product cut size and size-grade distribution, also all haveing breakthrough aspect electrochemical oxidation-reduction, and process safety, reliable.
Description of drawings
Fig. 1 is a process flow diagram of the present invention;
Fig. 2-5 is several structural representations of ultrasonic extraction equipment, ultrasonic crystallizer;
Fig. 2 is the extraction kettle that has the probe type ultrasonic generating unit, the structural representation that has the crystallization kettle of probe type ultrasonic generating unit;
Fig. 3 is the extraction tank that has the ultrasonic generating unit of vibrator type, the structural representation that has the crystallizer tank of the ultrasonic generating unit of vibrator type;
Fig. 4 is the extraction tank that has the ultrasonic generating unit of vibration plate formula, the structural representation that has the crystallizer tank of the ultrasonic generating unit of vibration plate formula;
Fig. 5 is the extracting tube that has the ultrasonic generating unit of vibration plate formula, the structural representation that has the crystallizer of the ultrasonic generating unit of vibration plate formula;
Among the figure: 1, probe type ultrasonic producer, 2, the vibrator type ultra-sonic generator, 3, vibration plate formula ultra-sonic generator, 4, extraction kettle or crystallization kettle, 5, extraction tank or crystallizer tank, 6, extracting tube or crystallizer.
Embodiment
The present invention is further detailed explanation below in conjunction with drawings and Examples.
Embodiment one
Major equipment: have the extraction kettle of probe type ultrasonic generating unit, the crystallization kettle that has the probe type ultrasonic generating unit, fixed bed electrochemical reactor.
Main raw material: rich europium salt acid rare earth, HCl, P204 extraction agent, kerosene, NH
4HCO
3
As depicted in figs. 1 and 2, a kind of method of preparing superfine high-purity europium oxide by using europium riched material is to be raw material with rich europium salt acid rare earth, and described method steps is as follows:
(1) batch mixes: rich europium salt acid rare earth, hydrochloric acid, water are carried out mix;
(2) solid-liquid separates: separate through solid-liquid, remove insoluble impurities, obtain rich europium hydrochloric acid earth solution feed liquid, the concentration of feed liquid middle-weight rare earths is 0.1-1.2mol/L; Solid phase is through the washing and recycling recycle;
(3) electrochemical reduction: the rich europium hydrochloric acid earth solution that previous step is obtained at the negative electrode of electrochemical reactor with trivalent europium Eu
3+Be reduced to divalent europium Eu
2+, obtain EuCl
2Solution; Its operational condition is that electrolysis temperature is 50 ℃, and current density is 1000A/m
2, feed temperature 45-50 ℃, feed acidity pH1～2, a reduction ratio of electrolytic reduction europium reaches more than 96%;
(4) ultrasonic fractionation extraction: in ultrasonic extraction equipment, add EuCl
2Solution, extraction liquid, washing lotion, the volume ratio of three kinds of proportioning materials is 1:0.5:0.1, extracted organic phase consist of the P204-kerosene of (0.12-0.68mol) P204 ammonium salt-(0.64-1.5mol), operational condition is ultrasonic frequency 19kHz, ultrasonication intensity 0.2W/cm
2, service temperature is 5 ℃, carries out ultrasonic fractionation extraction, and extracting phase is non-europium rare earth nitrate solution, and further separation and purification reclaims other rare earth element; Organic phase is recycled; Central exit liquid is EuCl
2Refined liquid enters next step;
(5) electrochemical oxidation: previous step is obtained EuCl
2Refined liquid is put into the anode of electrochemical reactor, with divalent europium Eu
2+Be oxidized to trivalent europium Eu
3+, generate EuCl
3Refined liquid; Its operational condition is that electrolysis temperature is 50 ℃, and current density is 1000A/m
2, feed temperature 45-50 ℃, feed acidity pH1～2;
(6) adsorption-edulcoration: the EuCl that obtains in previous step
3In the refined liquid, add activated carbon and do the adsorption-edulcoration agent, carry out further degree of depth adsorption-edulcoration, separate through solid-liquid, remove impurity, solid phase is further recycled, and liquid phase is for making purified EuCl
3Refined liquid enters next step;
(7) ultrasonic crystalline deposit: in ultrasonic crystallizer, add purified hydrochloric acid europium refined liquid, crystalline deposit agent bicarbonate of ammonia or volatile salt, the mol ratio of hydrochloric acid europium refined liquid and crystalline deposit agent batching is 1:1.1, and operational condition is ultrasonic frequency 19kHz, ultrasonication intensity 0.2W/cm
2, service temperature is 5 ℃, carries out ultrasonic crystalline deposit, generates europium carbonate Eu
2(CO
3)
3The crystalline deposit thing enters next step;
(8) solid-liquid separates: separate through solid-liquid, obtaining solid phase is europium carbonate Eu
2(CO
3)
3The crystalline deposit thing enters next step; Liquid phase reclaims ammonium nitrate;
(9) dry, calcination:, obtain europium carbonate Eu 25-800 ℃ of drying
2(CO
3)
3800-900 ℃ of following calcination, obtain Eu
2O
3Content 〉=99.99%, grain diameter are the ultra-fine high-purity europium oxide product of 9.0-10.0 μ m.
Embodiment two
Major equipment: have the extraction tank of the ultrasonic generating unit of vibrator type, the crystallizer tank that has the ultrasonic generating unit of vibrator type, fluidized bed electrochemical reactor.
Main raw material: rich europium salt acid rare earth, HCl, P204 extraction agent, sulfonated kerosene, (NH
4)
2CO
3
As shown in figures 1 and 3, a kind of method of preparing superfine high-purity europium oxide by using europium riched material is to be raw material with rich europium salt acid rare earth, and described method steps is as follows:
(1) batch mixes: rich europium salt acid rare earth, hydrochloric acid, water are carried out mix;
(2) solid-liquid separates: separate through solid-liquid, remove insoluble impurities, obtain rich europium hydrochloric acid earth solution feed liquid, the concentration of feed liquid middle-weight rare earths is 0.1-1.2mol/L; Solid phase is through the washing and recycling recycle;
(3) electrochemical reduction: in the fluidized bed electrochemical reactor, the rich europium hydrochloric acid earth solution that previous step is obtained at the negative electrode of electrochemical reactor with trivalent europium Eu
3+Be reduced to divalent europium Eu
2+, obtain EuCl
2Solution; Its operational condition is that electrolysis temperature is 50 ℃, and current density is 1000A/m
2, feed temperature 45-50 ℃, feed acidity pH 1～2, a reduction ratio of electrolytic reduction europium reaches more than 96%;
(4) ultrasonic fractionation extraction: in the extraction tank that has the ultrasonic generating unit of vibrator type, add EuCl
2Solution, extraction liquid, washing lotion, the volume ratio of three kinds of proportioning materials is 1:5.0:2.0, extracted organic phase consist of the P204-sulfonated kerosene of (0.12-0.68mol) P204 ammonium salt-(0.64-1.5mol), operational condition is ultrasonic frequency 80kHz, ultrasonication intensity 20.0W/cm
2, service temperature is 60 ℃, carries out ultrasonic fractionation extraction, and extracting phase is non-europium hydrochloric acid earth solution, and further separation and purification reclaims other rare earth element; Organic phase is recycled; Central exit liquid is EuCl
2Refined liquid enters next step;
(5) electrochemical oxidation: in the fluidized bed electrochemical reactor, previous step is obtained the anode that the EuCl2 refined liquid is put into electrochemical reactor, with divalent europium Eu
2+Be oxidized to trivalent europium Eu
3+, generate EuCl
3Refined liquid; Its operational condition is that electrolysis temperature is 50 ℃, and current density is 1000A/m
2, feed temperature 45-50 ℃, feed acidity pH1～2;
(6) adsorption-edulcoration: the EuCl that obtains in previous step
3In the refined liquid, add activated carbon and do the adsorption-edulcoration agent, carry out further degree of depth adsorption-edulcoration, separate through solid-liquid, remove impurity, solid phase is further recycled, and liquid phase is for making purified EuCl
3Refined liquid enters next step;
(7) ultrasonic crystalline deposit: in the crystallizer tank that has the ultrasonic generating unit of vibrator type, add purified hydrochloric acid europium refined liquid, crystalline deposit agent volatile salt (NH
4)
2CO
3, the mol ratio of hydrochloric acid europium refined liquid and crystalline deposit agent batching is 1:1.6, operational condition is ultrasonic frequency 80kHz, ultrasonication intensity 20.0W/cm
2, service temperature is 60 ℃, carries out ultrasonic crystalline deposit, generates europium carbonate Eu
2(CO
3)
3The crystalline deposit thing enters next step;
(8) solid-liquid separates: separate through solid-liquid, obtaining solid phase is europium carbonate Eu
2(CO
3)
3The crystalline deposit thing enters next step; Liquid phase reclaims ammonium nitrate;
(9) dry, calcination:, obtain europium carbonate Eu 25-800 ℃ of drying
2(CO
3)
3800-900 ℃ of following calcination, obtain Eu
2O
3Content 〉=99.99%, grain diameter are the ultra-fine high-purity europium oxide product of 1.0-2.0 μ m.
Embodiment three
Major equipment: have the extracting tube of the ultrasonic generating unit of vibration plate formula, the crystallizer that has the ultrasonic generating unit of vibration plate formula, fixed bed electrochemical reactor.
Main raw material: rich europium salt acid rare earth, HCl, P204 extraction agent, No. 200 gasoline, NH
4HCO
3
As Fig. 1 and shown in Figure 5, a kind of method of preparing superfine high-purity europium oxide by using europium riched material is to be raw material with rich europium salt acid rare earth, and described method steps is as follows:
(1) batch mixes: rich europium salt acid rare earth, hydrochloric acid, water are carried out mix;
(2) solid-liquid separates: separate through solid-liquid, remove insoluble impurities, obtain rich europium hydrochloric acid earth solution feed liquid, the concentration of feed liquid middle-weight rare earths is 0.1-1.2mol/L; Solid phase is through the washing and recycling recycle;
(3) electrochemical reduction: the rich europium hydrochloric acid earth solution that previous step is obtained at the negative electrode of electrochemical reactor with trivalent europium Eu
3+Be reduced to divalent europium Eu
2+, obtain EuCl
2Solution; Its operational condition is that electrolysis temperature is 50 ℃, and current density is 1000A/m
2, feed temperature 45-50 ℃, feed acidity pH1～2, a reduction ratio of electrolytic reduction europium reaches more than 96%;
(4) ultrasonic fractionation extraction: in the extracting tube that has the ultrasonic generating unit of vibration plate formula, add EuCl
2Solution, extraction liquid, washing lotion, the volume ratio of three kinds of proportioning materials is 1:2.5:1.0, extracted organic phase consist of the P204-200 gasoline of (0.12-0.68mol) P204 ammonium salt-(0.64-1.5mol), operational condition is ultrasonic frequency 25kHz, ultrasonication intensity 2.0W/cm
2, service temperature is 40 ℃, carries out ultrasonic fractionation extraction, and extracting phase is non-europium hydrochloric acid earth solution, and further separation and purification reclaims other rare earth element; Organic phase is recycled; Central exit liquid is EuCl
2Refined liquid enters next step;
(5) electrochemical oxidation: previous step is obtained EuCl
2Refined liquid is put into the anode of electrochemical reactor, with divalent europium Eu
2+Be oxidized to trivalent europium Eu
3+, generate EuCl
3Refined liquid; Its operational condition is that electrolysis temperature is 50 ℃, and current density is 1000A/m
2, feed temperature 45-50 ℃, feed acidity pH1～2;
(6) adsorption-edulcoration: the EuCl that obtains in previous step
3In the refined liquid, add activated carbon and do the adsorption-edulcoration agent, carry out further degree of depth adsorption-edulcoration, separate through solid-liquid, remove impurity, solid phase is further recycled, and liquid phase is for making purified EuCl
3Refined liquid enters next step;
(7) ultrasonic crystalline deposit: in the crystallizer that has the ultrasonic generating unit of vibration plate formula, add purified hydrochloric acid europium refined liquid, crystalline deposit agent bicarbonate of ammonia or volatile salt, the mol ratio of hydrochloric acid europium refined liquid and crystalline deposit agent batching is 1:1.3, operational condition is ultrasonic frequency 25kHz, ultrasonication intensity 2.0W/cm
2, service temperature is 10 ℃, carries out ultrasonic crystalline deposit, generates europium carbonate Eu
2(CO
3)
3The crystalline deposit thing enters next step;
(8) solid-liquid separates: separate through solid-liquid, obtaining solid phase is europium carbonate Eu
2(CO
3)
3The crystalline deposit thing enters next step; Liquid phase reclaims ammonium nitrate;
(9) dry, calcination:, obtain europium carbonate Eu 25-800 ℃ of drying
2(CO
3)
3800-900 ℃ of following calcination, obtain Eu
2O
3Content 〉=99.99%, grain diameter are the ultra-fine high-purity europium oxide product of 0.01-0.05 μ m.
Remove the various embodiments described above, used equipment also can be selected the ultrasonic extraction equipment and the ultrasonic crystallizer of other mentioned in technical solution of the present invention structure formation for use, all can satisfy requirement of the present invention, all within protection scope of the present invention.Extraction agent is except that selecting P204 for use, also can select P204 etc. for use is the cation extractant of representative with the acid phosphoric acid ester, also can select N1923 etc. for use is the anionresin extraction agent of representative with amine, also can select for use with neutral phosphate extraction agents such as TBP, P350, the present invention selects for use P204 to do the extraction agent ratio to select for use other extraction agent effect better.Optimum operation ultrasonic frequency range in ultrasonic fractionation extraction of the present invention and the ultrasonic crystalline deposit process is 19-25kHz, and optimum point is 25kHz, and optimum operation ultrasonication strength range is 2.0-5.0W/cm
2, optimum point is 2.0W/cm
2, the optimum operating temperature of ultrasonic fractionation extraction is 35-45 ℃, and optimum point is 40 ℃, and the optimum operating temperature of ultrasonic crystalline deposit is 5-25 ℃, and optimum point is 10 ℃.
Claims (5)
1, a kind of method of preparing superfine high-purity europium oxide by using europium riched material is to be raw material with rich europium salt acid rare earth, it is characterized in that described method steps is as follows:
(1) batch mixes: rich europium salt acid rare earth, hydrochloric acid, water are carried out mix;
(2) solid-liquid separates: separate through solid-liquid, remove insoluble impurities, obtain rich europium hydrochloric acid earth solution feed liquid, the concentration of feed liquid middle-weight rare earths is 0.1-1.2mol/L;
(3) electrochemical reduction: the rich europium hydrochloric acid earth solution that previous step is obtained at the negative electrode of electrochemical reactor with trivalent europium Eu
3+Be reduced to divalent europium Eu
2+, obtain EuCl
2Solution;
(4) ultrasonic fractionation extraction: in ultrasonic extraction equipment, add EuCl
2Solution, extraction liquid, washing lotion, the volume ratio of three kinds of proportioning materials are 1:0.5-5.0:0.1-2.0, and operational condition is ultrasonic frequency 19-80kHz, ultrasonication intensity 0.2-20.0W/cm
2, service temperature is 5-60 ℃, carries out ultrasonic fractionation extraction, central exit liquid is EuCl
2Refined liquid enters next step;
(5) electrochemical oxidation: previous step is obtained EuCl
2Refined liquid enters in the electrochemical reactor, at the anode of electrochemical reactor, with divalent europium Eu
2+Be oxidized to trivalent europium Eu
3+, generate EuCl
3Refined liquid;
(6) adsorption-edulcoration: the EuCl that obtains in previous step
3In the refined liquid, add the adsorption-edulcoration agent, carry out further degree of depth adsorption-edulcoration, separate, remove impurity, make purified EuCl through solid-liquid
3Refined liquid enters next step;
(7) ultrasonic crystalline deposit: in ultrasonic crystallizer, add purified hydrochloric acid europium refined liquid, crystalline deposit agent bicarbonate of ammonia or volatile salt, the mol ratio of hydrochloric acid europium refined liquid and crystalline deposit agent batching is 1:1.1-1.6, operational condition is ultrasonic frequency 19-80kHz, ultrasonication intensity 0.2-20.0W/cm
2, service temperature is 5-60 ℃, carries out ultrasonic crystalline deposit, generates europium carbonate Eu
2(CO
3)
3The crystalline deposit thing enters next step;
(8) solid-liquid separates: separate through solid-liquid, obtaining solid phase is europium carbonate Eu
2(CO
3)
3The crystalline deposit thing enters next step;
(9) dry, calcination:, obtain europium carbonate Eu 25-800 ℃ of drying
2(CO
3)
3800-900 ℃ of following calcination, obtain Eu
2O
3Content 〉=99.99%, grain diameter are the ultra-fine high-purity europium oxide product of 0.01-10.0 μ m.
2, the method for preparing superfine high-purity europium oxide by using europium riched material according to claim 1 is characterized in that: the operational condition in ultrasonic fractionation extraction and the ultrasonic crystalline deposit is ultrasonic frequency 25kHz, ultrasonication intensity 2.0W/cm
2, the service temperature of ultrasonic fractionation extraction is 40 ℃, the service temperature of ultrasonic crystalline deposit is 10 ℃.
3, the method for preparing superfine high-purity europium oxide by using europium riched material according to claim 1 is characterized in that: ultrasonic extraction equipment includes extraction plant and ultrasonic generating unit, and ultrasonic crystallizer includes crystallization apparatus and ultrasonic generating unit.
4, the method for preparing superfine high-purity europium oxide by using europium riched material according to claim 3 is characterized in that: described extraction plant is a still formula extraction plant, perhaps is the slot type extraction plant, perhaps is the tubular type extraction plant; Described crystallization apparatus is the kettle type crystallization device, perhaps is the tank crystallization device, perhaps is the tubular type crystallization apparatus; Described ultrasonic generating unit is the probe type ultrasonic generating unit, perhaps is the ultrasonic generating unit of vibrator type, perhaps is the ultrasonic generating unit of vibration plate formula.
5, the method for preparing superfine high-purity europium oxide by using europium riched material according to claim 1 is characterized in that: described electrochemical reactor is a three-diemsnional electrode barrier film electrochemical reactor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100199532A CN100500569C (en) | 2007-02-05 | 2007-02-05 | Process for preparing superfine high-purity europium oxide by using europium riched material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100199532A CN100500569C (en) | 2007-02-05 | 2007-02-05 | Process for preparing superfine high-purity europium oxide by using europium riched material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101024507A CN101024507A (en) | 2007-08-29 |
| CN100500569C true CN100500569C (en) | 2009-06-17 |
Family
ID=38743218
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2007100199532A Expired - Fee Related CN100500569C (en) | 2007-02-05 | 2007-02-05 | Process for preparing superfine high-purity europium oxide by using europium riched material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100500569C (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102115822B (en) * | 2010-11-18 | 2015-06-10 | 吴泉锦 | Method for recovering rare earth oxide from fluorescent powder and polishing powder waste |
| CN102634812A (en) * | 2012-04-26 | 2012-08-15 | 广州有色金属研究院 | Method for carrying out oxidation reduction on europium by electrolytic |
| CN103014761B (en) * | 2012-12-22 | 2015-07-01 | 广州有色金属研究院 | Method for electrolytically reducing europium |
| CN107487779A (en) * | 2017-08-30 | 2017-12-19 | 赣州齐畅新材料有限公司 | A kind of extracting method of high-purity europium oxide |
| CN110745857A (en) * | 2018-07-04 | 2020-02-04 | 乐山东承新材料有限公司 | Preparation method and product of high-purity clean cerium nitrate |
| CN114314636A (en) * | 2022-01-06 | 2022-04-12 | 江西离子型稀土工程技术研究有限公司 | Preparation method of rare earth carbonate ultrafine powder |
-
2007
- 2007-02-05 CN CNB2007100199532A patent/CN100500569C/en not_active Expired - Fee Related
Non-Patent Citations (2)
| Title |
|---|
| 铕的电化学还原-萃取分离及其工业试验的探讨. 侯庆烈等.中国稀土学会第四届学术年会论文集. 2000 |
| 铕的电化学还原-萃取分离及其工业试验的探讨. 侯庆烈等.中国稀土学会第四届学术年会论文集. 2000 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101024507A (en) | 2007-08-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100584967C (en) | Method for separating highly-pure rare-earth oxide from rare earth mine for reinforced baking by sulfuric acid | |
| CN100500569C (en) | Process for preparing superfine high-purity europium oxide by using europium riched material | |
| CN100451138C (en) | Method for preparing ultra-thin highly-pure europium oxide by europium-rich sulfuric acid rare earth | |
| CN100575508C (en) | A kind of method of from the yttrium-rich RE ore deposit, separating high purity rare earth oxides entirely | |
| CN102502720B (en) | Process for producing battery-grade lithium carbonate through processing carbonate type lithium concentrate by deep carbonation method | |
| EP2874152B1 (en) | Treatment method and use of a treatment device for waste water containing radioactive strontium | |
| CN100500568C (en) | Method for preparing superfine high-purity cerium oxide by using rear earth ore sulfuric acid calcination products | |
| CN101864525A (en) | Method for extracting gallium from fly ash | |
| CN108516588A (en) | A method of preparing tungsten product from coarse sodium tungstate | |
| CN108423695B (en) | Preparation method of lithium carbonate | |
| CN104310456A (en) | Production method and device of fine-grained low-chloride rare earth carbonate | |
| CN104762474B (en) | Method for preparing ammonium molybdate through molybdenite | |
| CN112110466B (en) | Method for removing iron impurities in fly ash and intermediate product thereof | |
| CN101824537B (en) | Ultra-pure gadolinium oxide and electrochemical reduction fully-closed type extracting production process thereof | |
| CN107376399A (en) | A kind of method for crystallising of sodium vanadate crystal system and sodium vanadate | |
| CN101318689A (en) | Method for preparing monoclinic system crystalline state cupric oxide and uses thereof | |
| CN103224248A (en) | Method of preparing rare earth carbonate and recycling materials thereof | |
| CN100424197C (en) | Method for preparing ultra-thin highly-pure lanthanum oxide by beneficiated lanthanum | |
| CN110282651A (en) | A method of high-purity rare earth oxide is prepared using compound precipitants | |
| CN110127765A (en) | A kind of method of manganese sulfate solution deeply removing molybdenum | |
| US4525254A (en) | Process and apparatus for purifying effluents and liquors | |
| CN104150570A (en) | Method for extracting chromium from chromium-containing waste liquor | |
| CN103708525A (en) | Production method of high-bulk density fine-grain low-chlorine rare earth carbonate and its oxide | |
| CN100424198C (en) | Method for preparing ultra-thin highly-pure dysprosium oxide by beneficiated terbium-dysprosium | |
| CN1312040C (en) | Purification production technique for producing high pure and high clear lithium hydroxide from lithium hydroxide in industrial grade |
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 | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20090617 Termination date: 20140205 |