CN101012505A - Method for preparing ultra-thin highly-pure lanthanum oxide by beneficiated lanthanum - Google Patents
Method for preparing ultra-thin highly-pure lanthanum oxide by beneficiated lanthanum Download PDFInfo
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Abstract
The invention discloses a making method of lanthanum oxide, which comprises the following steps: (1) blending raw material to form enriched lanthanum slurry; (2) fractionating and extracting through ultrasound; obtaining La (NO3) 3 solution and promethium-neodymium enriched liquid; (3) adsorbing impurity; (4) separating solid from liquid; obtaining fined liquid of purified La(NO3)3; (5) crystallizing; sedimenting La2(CO3)3; (6) proceeding solid-liquid separation; (7) drying; sintering; obtaining La2O3 with content not less than 99.99% and grain size at 0.01-10.0um.
Description
Technical field
The present invention relates to a kind of method for preparing lanthanum trioxide, particularly a kind of is the method for the ultra-fine high purity lanthanum oxide of feedstock production with the lanthanum enriched substance, belongs to the hydrometallurgy field.
Background technology
Ultra-fine high purity lanthanum oxide (La
2O
3) product is meant lanthanum trioxide content 〉=99.99%, the lanthanum trioxide product of grain diameter≤10.0 μ m.At present, ultra-fine high purity lanthanum oxide (La
2O
3) method that adopts for preparing of product generally is to be raw material with the lanthanum enriched substance, adopts HNO
3Lanthanum nitrate hexahydrate is made in dissolving, adopt P350 etc. for extraction agent carries out extracting and separating then, obtain the purified lanthanum nitrate hexahydrate, it is that precipitation agent generates the lanthanum oxalate crystalline deposit and separates out that lanthanum nitrate hexahydrate adopts oxalic acid, lanthanum oxalate obtains ultra-fine high purity lanthanum oxide product again through super-dry, calcination.The subject matter of these preparation methods' existence is at present: (1), extracting and separating speed and efficient are low: the equipment that present extraction separating method uses is mixer-settler, centrifugal extractor etc., carry out multi-stage solvent extraction, if improve the purity of product, just must increase progression, existing extraction progression is many, generally will just can finish whole extraction process by the 70-100 level; And rare earth extraction speed and separation efficiency are low, and the extraction time is long, and this has caused the increase of production cost, and throughput is difficult to improve; (2), lanthanum oxalate crystalline deposit poor effect: to add oxalic acid in the purified lanthanum nitrate hexahydrate is that to generate that the lanthanum oxalate crystalline deposit separates out be the method for crystallizing and sedimenting of the rare earth element that generally adopts at present to precipitation agent.Is the production cost height with oxalic acid as the shortcoming of precipitation agent, and oxalic acid toxicity is big, contaminate environment.Rare-earth elements of lanthanum be difficult to form crystal form carbonate, and the Phosbloc that makes usually is unformed flocks, and precipitation volume is big, wherein comprises a large amount of water and impurity, washing, filtration difficulty, and poor product quality, rare earth loss are big, produce to be difficult to carry out; (3), poor product quality: the lanthanum oxalate product that adopts traditional crystallization precipitator method of generally adopting at present to obtain, through solid-liquid separate, dry, calcination and the quality instability of the lanthanum trioxide product prepared generally is difficult to obtain La
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 segregation rate and separation efficiency height, product particle particle diameter are little, the method for even particle size distribution, a kind of preparing ultra-thin highly-pure lanthanum oxide by beneficiated lanthanum that purity is high.
The technical scheme that realizes above-mentioned purpose is: a kind of method of preparing ultra-thin highly-pure lanthanum oxide by beneficiated lanthanum is to be raw material with the lanthanum enriched substance, and described method steps is as follows:
(1) mix: lanthanum enriched substance, nitric acid, water are carried out mix, separate through solid-liquid, remove insoluble impurities, obtain lanthanum enriched substance feed liquid, the concentration of feed liquid middle-weight rare earths is 0.1-2.3mol/L;
(2) ultrasonic fractionation extraction: in ultrasonic extraction equipment, add lanthanum enriched substance feed liquid, extraction liquid, strip liquor, the volume ratio of three kinds of proportioning materials is 1: 0.5-5.0: 0.1-2.0, 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 praseodymium-neodymium Pr-Nd pregnant solution, can go further fractionation extraction refining; Waste water can go further evaporation to recycle, and raffinate is lanthanum nitrate La (NO
3)
3Solution enters next step;
(3) adsorption-edulcoration: the lanthanum nitrate La (NO that obtains in the previous step fractionation extraction
3)
3In the solution, add the adsorption-edulcoration agent, carry out adsorption-edulcoration;
(4) solid-liquid separates: separate through solid-liquid, remove impurity, liquid phase is the pure lanthanum nitrate La (NO that makes
3)
3Refined liquid enters next step; Solid phase is through washing recyclable useful material, and washings can reclaim use after treatment;
(5) ultrasonic crystalline deposit: in ultrasonic crystallizer, add pure lanthanum nitrate La (NO
3)
3Refined liquid, crystalline deposit agent bicarbonate of ammonia or volatile salt, lanthanum nitrate La (NO
3)
3The mol ratio of 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 Phosbloc La
2(CO
3)
3The crystalline deposit thing enters next step;
(6) solid-liquid separates: separate through solid-liquid, obtaining solid phase is Phosbloc La
2(CO
3)
3The crystalline deposit thing enters next step; Liquid phase is through evaporation concentration, recyclable ammonium nitrate;
(7) dry, calcination:, obtain Phosbloc La 25-800 ℃ of drying
2(CO
3)
3800-900 ℃ of following calcination, obtain lanthanum trioxide La
2O
3Content 〉=99.99%, grain diameter are the ultra-fine high purity lanthanum 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.It is identical in conjunction with pattern in conjunction with pattern and above-mentioned ultrasonic extraction equipment, just extraction plant is replaced to crystallization apparatus and gets final product.
What the present invention mainly adopted is ultrasonic fractionation extraction-ultrasonic crystalline deposit-chemical treatment separation method.(1) 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 the vibration of microvesicle, growth, a series of dynamic processes such as contraction and collapse, 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 the turbulence effect, the 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; (2) crystalline deposit of Phosbloc: 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 lanthanum trioxide; 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.But the bicarbonate of ammonia volatile salt 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; (3) quality product and granularity problem: rare-earth elements of lanthanum is difficult to form crystal form carbonate, and the Phosbloc 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 carbon ammonium ultrasound precipitation technology, can improve process.The product crystallization perfection of Huo Deing simultaneously, the purity height, grain diameter is little, even particle size distribution.
Adopt the benefit of technique scheme to be: (1) adopts 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, the progression of extraction reduces greatly, is generally the 15-20 level and just can finishes, and can obtain praseodymium-neodymium Pr-Nd pregnant solution simultaneously; (2) the ultrasonic crystalline deposit of the bicarbonate of ammonia of lanthanum nitrate or volatile salt: the crystalline deposit agent of adopting bicarbonate of ammonia or volatile salt to prepare Phosbloc as lanthanum nitrate hexahydrate, because bicarbonate of ammonia or volatile salt price are more cheap than oxalic acid, nontoxic, can reduce production costs, and can improve settling rate and yield, improve quality product and production environment, reduce contaminate environment, while can reclaim by product ammonium nitrate and other has valence component, rate of recovery height, the raw and auxiliary material consumption is less, greatly reduce the consumption of chemical reagent, moreover, owing in Phosbloc crystalline deposit precipitation process, adopt ultrasonic technique to strengthen, further improved the speed and the efficient of ultrasonic crystalline deposit process, Phosbloc crystalline granularity and size-grade distribution have been improved, the lanthanum trioxide product particle particle diameter of preparing is little, even particle size distribution, purity height, reach ultra-fine, high-purity, its lanthanum trioxide La
2O
3Content 〉=99.99%, the ultra-fine high purity lanthanum oxide product of grain diameter≤10.0 μ m, grain diameter is 0.01-10.0 μ m, and its purity and fineness are much higher than the index that prior art can reach, and suits especially at the high grade product of high-tech sector service requirements; (3) treatment capacity of the follow-up material of the present invention reduces 50% at least than prior art, greatly reduces the energy consumption of subsequent disposal, and the method for its recycling has realized cleaner production veritably.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, all have breakthrough, 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 probe type ultrasonic generating unit extraction kettle, have the crystallization kettle of probe type ultrasonic generating unit.
Main raw material: lanthanum enriched substance, HNO
3, TBP extraction agent, kerosene, NH
4HCO
3
As depicted in figs. 1 and 2, a kind of method of preparing ultra-thin highly-pure lanthanum oxide by beneficiated lanthanum is to be raw material with the lanthanum enriched substance, and described method steps is as follows:
(1) mix: lanthanum enriched substance, nitric acid, water are carried out mix, separate through solid-liquid, remove insoluble impurities, obtain lanthanum enriched substance feed liquid, the concentration of feed liquid middle-weight rare earths is 0.1-2.3mol/L;
(2) ultrasonic fractionation extraction: in the extraction kettle that has the probe type ultrasonic generating unit, add lanthanum enriched substance feed liquid, extraction liquid, strip liquor, the volume ratio of three kinds of proportioning materials is 1: 0.5: 0.1, extracted organic phase consist of 30%TBP-70% kerosene, operational condition is ultrasonic frequency 19kHz, ultrasonication intensity 0.2W/cm
2, service temperature is 5 ℃, carries out ultrasonic fractionation extraction, and central exit liquid is praseodymium-neodymium Pr-Nd pregnant solution, and further fractionation extraction is refining, prepares Praseodymium trioxide and Neodymium trioxide product; Waste water is after evaporation concentration, solid-liquid separation, and its solid phase is recycled, and liquid phase is got back to the first step recycle, and raffinate is lanthanum nitrate La (NO
3)
3Solution enters next step;
(3) adsorption-edulcoration: the lanthanum nitrate La (NO that obtains in the previous step fractionation extraction
3)
3In the solution, add activated carbon and do the adsorption-edulcoration agent, carry out adsorption-edulcoration;
(4) solid-liquid separates: separate through solid-liquid, remove impurity, liquid phase is the pure lanthanum nitrate La (NO that makes
3)
3Refined liquid enters next step; Solid phase is through washing recyclable useful materials, and washings can reclaim use after treatment;
(5) ultrasonic crystalline deposit: in the crystallization kettle that has the probe type ultrasonic generating unit, add pure lanthanum nitrate La (NO
3)
3Refined liquid, crystalline deposit agent bicarbonate of ammonia NH
4HCO
3, lanthanum nitrate La (NO
3)
3The mol ratio of 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 Phosbloc La
2(CO
3)
3The crystalline deposit thing enters next step;
(6) solid-liquid separates: separate through solid-liquid, obtaining solid phase is Phosbloc La
2(CO
3)
3The crystalline deposit thing enters next step; Liquid phase reclaims ammonium nitrate through evaporation concentration;
(7) dry, calcination:, obtain Phosbloc La 25-800 ℃ of drying
2(CO
3)
3800-900 ℃ of following calcination, obtain lanthanum trioxide La
2O
3Content 〉=99.99%, grain diameter are the ultra-fine high purity lanthanum oxide product of 9.0-10.0 μ m.
Embodiment two
Major equipment: have the ultrasonic generating unit of vibrator type extraction tank, have the crystallizer tank of the ultrasonic generating unit of vibrator type.
Main raw material: lanthanum enriched substance, HNO
3, TBP extraction agent, sulfonated kerosene, (NH
4)
2CO
3
As shown in figures 1 and 3, a kind of method of preparing ultra-thin highly-pure lanthanum oxide by beneficiated lanthanum is to be raw material with the lanthanum enriched substance, and described method steps is as follows:
(1) mix: lanthanum enriched substance, nitric acid, water are carried out mix, separate through solid-liquid, remove insoluble impurities, obtain lanthanum enriched substance feed liquid, the concentration of feed liquid middle-weight rare earths is 0.1-2.3mol/L;
(2) ultrasonic fractionation extraction: in the extraction tank that has the ultrasonic generating unit of vibrator type, add lanthanum enriched substance feed liquid, extraction liquid, strip liquor, the volume ratio of three kinds of proportioning materials is 1: 5.0: 2.0, extracted organic phase consist of the 30%TBP-70% sulfonated kerosene, operational condition is ultrasonic frequency 80kHz, ultrasonication intensity 20.0W/cm
2, service temperature is 60 ℃, carries out ultrasonic fractionation extraction, central exit liquid is praseodymium-neodymium Pr-Nd pregnant solution, goes further fractionation extraction refining, prepares Praseodymium trioxide and Neodymium trioxide product; Waste water is after evaporation concentration, solid-liquid separation, and its solid phase is recycled, and liquid phase is got back to the first step recycle, and raffinate is lanthanum nitrate La (NO
3)
3Solution enters next step;
(3) adsorption-edulcoration: the lanthanum nitrate La (NO that obtains in the previous step fractionation extraction
3)
3In the solution, add ion exchange resin and do the adsorption-edulcoration agent, carry out adsorption-edulcoration;
(4) solid-liquid separates: separate through solid-liquid, remove impurity, liquid phase is the pure lanthanum nitrate La (NO that makes
3)
3Refined liquid enters next step; Solid phase is through washing recyclable useful materials, and washings can reclaim use after treatment;
(5) ultrasonic crystalline deposit: in the crystallizer tank that has the ultrasonic generating unit of vibrator type, add pure lanthanum nitrate La (NO
3)
3Refined liquid, crystalline deposit agent volatile salt (NH
4)
2CO
3, lanthanum nitrate La (NO
3)
3The mol ratio of refined liquid and crystalline deposit agent batching is 1: 1.6, and operational condition is ultrasonic frequency 80kHz, ultrasonication intensity 20.0W/cm
2, service temperature is 60 ℃, carries out ultrasonic crystalline deposit, generates Phosbloc La
2(CO
3)
3The crystalline deposit thing enters next step;
(6) solid-liquid separates: separate through solid-liquid, obtaining solid phase is Phosbloc La
2(CO
3)
3The crystalline deposit thing enters next step; Liquid phase reclaims ammonium nitrate through evaporation concentration;
(7) dry, calcination:, obtain Phosbloc La 25-800 ℃ of drying
2(CO
3)
3800-900 ℃ of following calcination, obtain lanthanum trioxide La
2O
3Content 〉=99.99%, grain diameter are the ultra-fine high purity lanthanum oxide product of 1.0-2.0 μ m.
Embodiment three
Major equipment: major equipment: have the ultrasonic generating unit of vibration plate formula extracting tube, have the crystallizer of the ultrasonic generating unit of vibration plate formula.
Main raw material: lanthanum enriched substance, HNO
3, TBP extraction agent, No. 200 gasoline, NH
4HCO
3
As Fig. 1 and shown in Figure 5, a kind of method of preparing ultra-thin highly-pure lanthanum oxide by beneficiated lanthanum is to be raw material with the lanthanum enriched substance, and described method steps is as follows:
(1) mix: lanthanum enriched substance, nitric acid, water are carried out mix, separate through solid-liquid, remove insoluble impurities, obtain lanthanum enriched substance feed liquid, the concentration of feed liquid middle-weight rare earths is 0.1-2.3mol/L;
(2) ultrasonic fractionation extraction: in the extracting tube that has the ultrasonic generating unit of vibration plate formula, add lanthanum enriched substance feed liquid, extraction liquid, strip liquor, the volume ratio of three kinds of proportioning materials is 1: 2.5: 1.0, extracted organic phase consist of 40%TBP-60%200 gasoline, operational condition is ultrasonic frequency 25kHz, ultrasonication intensity 2.0W/cm
2, service temperature is 40 ℃, carries out ultrasonic fractionation extraction, central exit liquid is praseodymium-neodymium Pr-Nd pregnant solution, goes further fractionation extraction refining, prepares Praseodymium trioxide and Neodymium trioxide product; Waste water is after evaporation concentration, solid-liquid separation, and its solid phase is recycled, and liquid phase is got back to the first step recycle, and raffinate is lanthanum nitrate La (NO
3)
3Solution enters next step;
(3) adsorption-edulcoration: the lanthanum nitrate La (NO that obtains in the previous step fractionation extraction
3)
3In the solution, add activated carbon and do the adsorption-edulcoration agent, carry out adsorption-edulcoration;
(4) solid-liquid separates: separate through solid-liquid, remove impurity, liquid phase is the pure lanthanum nitrate La (NO that makes
3)
3Refined liquid enters next step; Solid phase is through washing recyclable useful materials, and washings can reclaim use after treatment;
(5) ultrasonic crystalline deposit: in the crystallizer that has the ultrasonic generating unit of vibration plate formula, add pure lanthanum nitrate La (NO
3)
3Refined liquid, crystalline deposit agent bicarbonate of ammonia NH
4HCO
3, lanthanum nitrate La (NO
3)
3The mol ratio of refined liquid and crystalline deposit agent batching is 1: 1.3, and operational condition is ultrasonic frequency 25kHz, ultrasonication intensity 2.0W/cm
2, service temperature is 10 ℃, carries out ultrasonic crystalline deposit, generates Phosbloc La
2(CO
3)
3The crystalline deposit thing enters next step;
(6) solid-liquid separates: separate through solid-liquid, obtaining solid phase is Phosbloc La
2(CO
3)
3The crystalline deposit thing enters next step; Liquid phase reclaims ammonium nitrate through evaporation concentration;
(7) dry, calcination:, obtain Phosbloc La 25-800 ℃ of drying
2(CO
3)
3800-900 ℃ of following calcination, obtain lanthanum trioxide La
2O
3Content 〉=99.99%, grain diameter are the ultra-fine high purity lanthanum 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 also can be selected neutral phosphate extraction agents such as P350 for use except that selecting TBP for use, also can select P507, P204 etc. for use is the cation extractant of representative with the acid phosphoric acid ester, and also can select N1923 etc. for use is the anionresin extraction agent of representative with amine.The present invention selects for use TBP 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 (4)
1, a kind of method of preparing ultra-thin highly-pure lanthanum oxide by beneficiated lanthanum is to be raw material with the lanthanum enriched substance, it is characterized in that described method steps is as follows:
(1) mix: lanthanum enriched substance, nitric acid, water are carried out mix, separate through solid-liquid, remove insoluble impurities, obtain lanthanum enriched substance feed liquid, the concentration of feed liquid middle-weight rare earths is 0.1-2.3mol/L;
(2) ultrasonic fractionation extraction: in ultrasonic extraction equipment, add lanthanum enriched substance feed liquid, extraction liquid, strip liquor, the volume ratio of three kinds of proportioning materials is 1: 0.5-5.0: 0.1-2.0, 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, raffinate is lanthanum nitrate La (NO
3)
3Solution enters next step;
(3) adsorption-edulcoration: the lanthanum nitrate La (NO that obtains in the previous step fractionation extraction
3)
3In the solution, add the adsorption-edulcoration agent, carry out adsorption-edulcoration;
(4) solid-liquid separates: separate through solid-liquid, remove impurity, liquid phase is the pure lanthanum nitrate La (NO that makes
3)
3Refined liquid enters next step;
(5) ultrasonic crystalline deposit: in ultrasonic crystallizer, add pure lanthanum nitrate La (NO
3)
3Refined liquid, crystalline deposit agent bicarbonate of ammonia or volatile salt, lanthanum nitrate La (NO
3)
3The mol ratio of 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 Phosbloc La
2(CO
3)
3The crystalline deposit thing enters next step;
(6) solid-liquid separates: separate through solid-liquid, obtaining solid phase is Phosbloc La
2(CO
3)
3The crystalline deposit thing enters next step;
(7) dry, calcination:, obtain Phosbloc La 25-800 ℃ of drying
2(CO
3)
3800-900 ℃ of following calcination, obtain lanthanum trioxide La
2O
3Content 〉=99.99%, grain diameter are the ultra-fine high purity lanthanum oxide product of 0.01-10.0 μ m.
2, the method for preparing ultra-thin highly-pure lanthanum oxide by beneficiated lanthanum according to claim 1 is characterized in that: the operational condition in ultrasonic fractionation extraction, 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 ultra-thin highly-pure lanthanum oxide by beneficiated lanthanum 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 ultra-thin highly-pure lanthanum oxide by beneficiated lanthanum according to claim 3, it is characterized in that: described extraction plant is a still formula extraction plant, it perhaps is the slot type extraction plant, perhaps be the tubular type extraction plant, described crystallization apparatus is the kettle type crystallization device, perhaps is the tank crystallization device, it 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.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104379739A (en) * | 2012-06-05 | 2015-02-25 | 3M创新有限公司 | Lanthanum-based concentration agents for microorganisms |
| CN106044838A (en) * | 2016-07-28 | 2016-10-26 | 乐山沃耐稀电子材料有限公司 | Production technology of low-sulfur lanthanum hydroxide |
| CN106191476A (en) * | 2016-07-11 | 2016-12-07 | 苏州大学 | Method for separating lanthanide |
| CN106315655A (en) * | 2016-07-28 | 2017-01-11 | 乐山沃耐稀电子材料有限公司 | Method for producing high-purity lanthanum carbonate |
| 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 |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3615171A (en) * | 1970-06-15 | 1971-10-26 | George W Mason | Process of separating yttrium from lanthanide rare earths |
| CN1015801B (en) * | 1989-06-15 | 1992-03-11 | 北京大学 | Preparation method of high purity yttrium oxide and lanthanum oxide |
| RU2120408C1 (en) * | 1997-04-02 | 1998-10-20 | Институт химии и технологии редких элементов и минерального сырья Кольского научного центра РАН | Method of extraction of rare-earth element phosphates from apatite concentrate |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104379739A (en) * | 2012-06-05 | 2015-02-25 | 3M创新有限公司 | Lanthanum-based concentration agents for microorganisms |
| US9575059B2 (en) | 2012-06-05 | 2017-02-21 | 3M Innovative Properties Company | Lanthanum-based concentration agents for microorganisms |
| CN106191476A (en) * | 2016-07-11 | 2016-12-07 | 苏州大学 | Method for separating lanthanide |
| CN106191476B (en) * | 2016-07-11 | 2018-10-09 | 苏州大学 | Method for separating lanthanide |
| CN106044838A (en) * | 2016-07-28 | 2016-10-26 | 乐山沃耐稀电子材料有限公司 | Production technology of low-sulfur lanthanum hydroxide |
| CN106315655A (en) * | 2016-07-28 | 2017-01-11 | 乐山沃耐稀电子材料有限公司 | Method for producing high-purity lanthanum carbonate |
| 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 |
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