CN101024505A - Method for preparing super-fine high-purity Neodymia oxide by using Pr-Nd riched material - Google Patents
Method for preparing super-fine high-purity Neodymia oxide by using Pr-Nd riched material Download PDFInfo
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- CN101024505A CN101024505A CNA2007100199477A CN200710019947A CN101024505A CN 101024505 A CN101024505 A CN 101024505A CN A2007100199477 A CNA2007100199477 A CN A2007100199477A CN 200710019947 A CN200710019947 A CN 200710019947A CN 101024505 A CN101024505 A CN 101024505A
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Abstract
The invention relates to a method to make neodymium oxide that includes the following steps: mixing raw material, taking ultrasonic fractional extraction to gain enriched liquid containing Nd(NO3)3, taking ultrasonic to gain refined liquid of Nd(NO3)3, taking adsorption and trash extraction, taking solid-liquid separation, taking ultrasonic crystal deposition to gain Nd2(CO3)3 crystal deposit, taking solid-liquid separation, drying and burning to gain the superfine high purity neodymium 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 Neodymium trioxide, particularly a kind of is the method for the ultra-fine high-purity neodymium oxide of feedstock production with praseodymium-neodymium Pr-Nd enriched substance, belongs to the hydrometallurgy field.
Background technology
Ultra-fine high-purity neodymium oxide (Nd
2O
3) product is meant Neodymium trioxide content 〉=99.99%, the Neodymium trioxide product of grain diameter≤10.0 μ m.Ultra-fine high-purity neodymium oxide has been obtained in materials such as rare earth permanent magnet, laser, glass, pottery and superconductor preferably and has been used, and can satisfy the demand of high grade product, is important light rare earths oxide product.At present, China prepares ultra-fine high-purity N d
2O
3Main raw material have following 4 kinds: (1) sulfuric acid rare earth [RE
2(SO
4)
3], it is by Baotou rare earth ore concentrate (REO 〉=50%, Nd
2O
317%) RE that makes after the processing
2(SO
4)
3Solution; (2) rare earth chloride (RECl
3), it is by Sichuan Mianning rare earth ore concentrate [REO 〉=50%, Nd
2O
313%] handles and make RECl
3(3) RECl in rare earth ion ore deposit
3, it is to contain ion type rareearth concentrate (REO 〉=92%, the Nd of rare earth (as La, Pr, Nd and Sm)
2O
329%) through the molten RECl that obtains with filtering of acid
3(4) praseodymium-neodymium enriched substance (Nd
2O
327%), it is that extracting and separating makes (Nd-Pr) Cl
3Solution.Nd
2O
3The preparation method mainly contain extraction separation method and ion exchange method.What generally adopt at present is that extraction separation method prepares ultra-fine high-purity N d
2O
3, raw materials used employing RE
2(SO
4)
3Perhaps RECl
3, extraction agent commonly used has di-(2-ethylhexyl)phosphoric acid (being called for short P204) or di-2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester (being called for short P507).Utilize organic solvent from its not miscible aqueous solution method that the extract extraction separation is come out be referred to as organic solvent fluid-liquid-liquid extraction method, be called for short solvent extration, it is a kind of mass transfer process of material being transferred to another liquid phase from a liquid phase.The separating device of solvent extration has mixer-settler, centrifugal extractor etc., the used extraction agent of purification rare earth has: be cation extractant such as P204, the P507 of representative with the acid phosphoric acid ester, be the anionresin liquid N1923 of representative with amine and be three kinds of the solvent extraction agents of representative with neutral phosphates such as TBP, P350.The viscosity of these extraction agents and proportion are all very high, and is not easily separated with water, with the kerosene equal solvent its dilution used again usually.The subject matter of these method for separating and preparing 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 equipment etc., existing technology generally will just can be finished whole extraction process by the 70-100 level, that have even reach and just can finish whole extraction process by hundreds of grades, rare earth extraction speed and separation efficiency are low, the extraction time is long, this has caused the increase of production cost, and throughput is difficult to improve; (2), neodymium oxalate crystalline deposit poor effect: to add oxalic acid in the purified neodymium nitrate solution is that to generate that the neodymium oxalate 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.Rear earth element nd be difficult to form crystal form carbonate, and the neodymium carbonate 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 neodymium 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 Neodymium trioxide product prepared generally is difficult to obtain Nd
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, even particle size distribution, a kind of praseodymium-neodymium Pr-Nd enriched substance that purity is high prepare the method for ultra-fine high-purity neodymium oxide.
The technical scheme that realizes above-mentioned purpose is: a kind of praseodymium-neodymium Pr-Nd enriched substance prepares the method for ultra-fine high-purity neodymium oxide, is to be raw material with praseodymium-neodymium Pr-Nd enriched substance, and described method steps is as follows:
(1) mix: praseodymium-neodymium Pr-Nd enriched substance, nitric acid, water are carried out mix, separate through solid-liquid, remove insoluble impurities, obtain praseodymium-neodymium Pr-Nd 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 praseodymium-neodymium Pr-Nd enriched substance feed liquid, extraction liquid, washing lotion, 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, and extraction phase is for containing neodymium-samarium Nd-Sm pregnant solution, and extracting phase is for containing lanthanum-praseodymium La-Pr pregnant solution, and extraction phase and extracting phase all can further be recycled, and central exit liquid is for containing neodymium nitrate Nd (NO
3)
3Pregnant solution, enter next step;
(3) ultrasonic extraction: in ultrasonic extraction equipment, add and contain neodymium nitrate Nd (NO
3)
3Pregnant solution, extraction liquid, the volume ratio of adding is 1: 0.5-5.0, operational condition is ultrasonic frequency 19-80kHz, ultrasonication intensity 0.2-20.0W/cm
2, service temperature is 5-60 ℃, carries out ultrasonic extraction, containing extraction liquid in the extraction phase and valency rare earth composition, recyclable utilization, raffinate are arranged is neodymium nitrate Nd (NO
3)
3Refined liquid enters next step;
(4) adsorption-edulcoration: the neodymium nitrate Nd (NO that obtains in the previous step fractionation extraction
3)
3In the refined liquid, add the adsorption-edulcoration agent, carry out further degree of depth adsorption-edulcoration;
(5) solid-liquid separates: separate through solid-liquid, remove impurity, liquid phase is the pure neodymium nitrate Nd (NO that makes
3)
3Refined liquid enters next step; Solid phase can reclaim useful material through washing, and washings reclaims use after treatment;
(6) ultrasonic crystalline deposit: in ultrasonic crystallizer, add pure neodymium nitrate Nd (NO
3)
3Refined liquid, crystalline deposit agent bicarbonate of ammonia or volatile salt, neodymium nitrate Nd (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 neodymium carbonate Nd
2(CO
3)
3The crystalline deposit thing enters next step;
(7) solid-liquid separates: separate through solid-liquid, obtaining solid phase is neodymium carbonate Nd
2(CO
3)
3The crystalline deposit thing enters next step; Liquid phase is through evaporation concentration, recyclable ammonium nitrate;
(8) dry, calcination:, obtain neodymium carbonate Nd 25-800 ℃ of drying
2(CO
3)
3800-900 ℃ of following calcination, obtain Neodymium trioxide Nd
2O
3Content 〉=99.99%, grain diameter are the ultra-fine high-purity neodymium oxide product of 0.01-10.0 μ m.
Prioritization scheme of the present invention is that the operational condition in ultrasonic fractionation extraction, ultrasonic extraction, the ultrasonic crystalline deposit is ultrasonic frequency 25kHz, ultrasonication intensity 2.0W/cm
2, ultrasonic fractionation extraction, ultrasonic extraction service temperature are 40 ℃, ultrasonic crystalline deposit service temperature is 10 ℃.The best results of ultrasonic with this understanding fractionation extraction, ultrasonic extraction and ultrasonic crystalline deposit.Described ultrasonic extraction equipment includes extraction plant and ultrasonic generating unit, extraction plant is any in still formula, slot type, the tubular type, ultrasonic generating unit is any in sonde-type, vibrator type, the vibration plate formula, ultrasonic extraction equipment can be a kind of the combining in a kind of extraction plant and sonde-type, vibrator type, the ultrasonic generating unit of vibration plate formula in still formula, slot type, the tubular type, also can be any two or three combine in a kind of extraction plant and sonde-type, vibrator type, the ultrasonic generating unit of vibration plate formula in still formula, slot type, the tubular type.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.
The present invention mainly adopts ultrasonic fractionation extraction-ultrasonic extraction-ultrasonic crystalline deposit-chemically treated 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 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.(2) the ultrasonic crystalline deposit of neodymium carbonate: 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 Neodymium 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.Bicarbonate of ammonia or volatile salt are nontoxic, replace 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: rear earth element nd is difficult to form crystal form carbonate, and the neodymium 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 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, disengaging time shortens greatly, 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 progression of extraction reduces greatly, is generally the 15-20 level and just can finishes; (2) bicarbonate of ammonia of neodymium nitrate or volatile salt crystalline deposit: adopt the crystalline deposit agent of bicarbonate of ammonia or volatile salt as neodymium nitrate formulations prepared from solutions neodymium carbonate, 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 reduces the consumption of chemical reagent, moreover, because in neodymium carbonate crystalline deposit precipitation process, the employing ultrasonic technique is strengthened, and has further improved the speed and the efficient of crystallization precipitation process, has improved neodymium carbonate crystalline granularity and size-grade distribution, the Neodymium trioxide product particle particle diameter of preparing is little, even particle size distribution, the purity height is prepared Neodymium trioxide Nd
2O
3Content 〉=99.99%, grain diameter are the ultra-fine high-purity neodymium oxide product of 0.01-10.0 μ m.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; (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: praseodymium-neodymium Pr-Nd enriched substance, HNO
3, TBP extraction agent, kerosene, NH
4HCO
3
As depicted in figs. 1 and 2, a kind of praseodymium-neodymium Pr-Nd enriched substance prepares the method for ultra-fine high-purity neodymium oxide, is to be raw material with praseodymium-neodymium Pr-Nd enriched substance, and described method steps is as follows:
(1) mix: praseodymium-neodymium Pr-Nd, nitric acid, water are carried out mix, separate through solid-liquid, remove insoluble impurities, obtain praseodymium-neodymium Pr-Nd 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 praseodymium-neodymium Pr-Nd enriched substance feed liquid, extraction liquid, washing lotion, 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 extraction phase is for containing neodymium-samarium Nd-Sm pregnant solution, and extracting phase is for containing lanthanum-praseodymium La-Pr pregnant solution, and extraction phase and extracting phase all can further be recycled, and central exit liquid is for containing neodymium nitrate Nd (NO
3)
3Pregnant solution, enter next step;
(3) ultrasonic extraction: in the extraction kettle that has the probe type ultrasonic generating unit, add and contain praseodymium nitrate Pr (NO
3)
3Pregnant solution, extraction liquid, the volume ratio of adding is 1: 0.5, 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 extraction, containing extraction liquid in the extraction phase and valency rare earth composition, recyclable utilization, raffinate are arranged is neodymium nitrate Nd (NO
3)
3Refined liquid enters next step;
(4) adsorption-edulcoration: the neodymium nitrate Nd (NO that obtains in the previous step fractionation extraction
3)
3In the refined liquid, add the adsorption-edulcoration agent, carry out further degree of depth adsorption-edulcoration;
(5) solid-liquid separates: separate through solid-liquid, remove impurity, liquid phase is the pure neodymium nitrate Nd (NO that makes
3)
3Refined liquid enters next step; Solid phase can reclaim useful materials through washing, and washings reclaims use after treatment;
(6) ultrasonic crystalline deposit: in the crystallization kettle that has the probe type ultrasonic generating unit, add pure neodymium nitrate Nd (NO
3)
3Refined liquid, crystalline deposit agent bicarbonate of ammonia NH
4HCO
3, neodymium nitrate Nd (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 neodymium carbonate Nd
2(CO
3)
3The crystalline deposit thing enters next step;
(7) solid-liquid separates: separate through solid-liquid, obtaining solid phase is neodymium carbonate Nd
2(CO
3)
3The crystalline deposit thing enters next step; Liquid phase is through evaporation concentration, recyclable ammonium nitrate;
(8) dry, calcination:, obtain neodymium carbonate Nd 25-800 ℃ of drying
2(CO
3)
3800-900 ℃ of following calcination, obtain Neodymium trioxide Nd
2O
3Content 〉=99.99%, grain diameter are the ultra-fine high-purity neodymium 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: praseodymium-neodymium Pr-Nd enriched substance, HNO
3, TBP extraction agent, sulfonated kerosene, (NH
4)
2CO
3
As shown in figures 1 and 3, a kind of praseodymium-neodymium Pr-Nd enriched substance prepares the method for ultra-fine high-purity neodymium oxide, is to be raw material with praseodymium-neodymium Pr-Nd enriched substance, and described method steps is as follows:
(1) mix: praseodymium-neodymium Pr-Nd, nitric acid, water are carried out mix, separate through solid-liquid, remove insoluble impurities, obtain praseodymium-neodymium Pr-Nd 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 praseodymium-neodymium Pr-Nd enriched substance feed liquid, 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 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, and extraction phase is for containing neodymium-samarium Nd-Sm pregnant solution, and extracting phase is for containing lanthanum-praseodymium La-Pr pregnant solution, and extraction phase and extracting phase all can further be recycled, and central exit liquid is for containing neodymium nitrate Nd (NO
3)
3Pregnant solution, enter next step;
(3) ultrasonic extraction: in the extraction tank that has the ultrasonic generating unit of vibrator type, add and contain praseodymium nitrate Pr (NO
3)
3Pregnant solution, extraction liquid, the volume ratio of adding is 1: 5.0, 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 extraction, containing extraction liquid in the extraction phase and valency rare earth composition, recyclable utilization, raffinate are arranged is neodymium nitrate Nd (NO
3)
3Refined liquid enters next step;
(4) adsorption-edulcoration: the neodymium nitrate Nd (NO that obtains in the previous step fractionation extraction
3)
3In the refined liquid, add the adsorption-edulcoration agent, carry out further degree of depth adsorption-edulcoration;
(5) solid-liquid separates: separate through solid-liquid, remove impurity, liquid phase is the pure neodymium nitrate Nd (NO that makes
3)
3Refined liquid enters next step; Solid phase can reclaim useful materials through washing, and washings reclaims use after treatment;
(6) ultrasonic crystalline deposit: in the crystallizer tank that has the ultrasonic generating unit of vibrator type, add pure neodymium nitrate Nd (NO
3)
3Refined liquid, crystalline deposit agent volatile salt (NH
4)
2CO
3, neodymium nitrate Nd (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 neodymium carbonate Nd
2(CO
3)
3The crystalline deposit thing enters next step;
(7) solid-liquid separates: separate through solid-liquid, obtaining solid phase is neodymium carbonate Nd
2(CO
3)
3The crystalline deposit thing enters next step; Liquid phase is through evaporation concentration, recyclable ammonium nitrate;
(8) dry, calcination:, obtain neodymium carbonate Nd 25-800 ℃ of drying
2(CO
3)
3800-900 ℃ of following calcination, obtain Neodymium trioxide Nd
2O
3Content 〉=99.99%, grain diameter are the ultra-fine high-purity neodymium oxide product of 1.0-2.0 μ m.
Embodiment three
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: praseodymium-neodymium Pr-Nd enriched substance, HNO
3, TBP extraction agent, No. 200 gasoline, NH
4HCO
3
As Fig. 1 and shown in Figure 5, a kind of praseodymium-neodymium Pr-Nd enriched substance prepares the method for ultra-fine high-purity neodymium oxide, is to be raw material with praseodymium-neodymium Pr-Nd enriched substance, and described method steps is as follows:
(1) mix: praseodymium-neodymium Pr-Nd, nitric acid, water are carried out mix, separate through solid-liquid, remove insoluble impurities, obtain praseodymium-neodymium Pr-Nd 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 praseodymium-neodymium Pr-Nd enriched substance feed liquid, extraction liquid, washing lotion, 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, and extraction phase is for containing neodymium-samarium Nd-Sm pregnant solution, and extracting phase is for containing lanthanum-praseodymium La-Pr pregnant solution, and extraction phase and extracting phase all can further be recycled, and central exit liquid is for containing neodymium nitrate Nd (NO
3)
3Pregnant solution, enter next step;
(3) ultrasonic extraction: in the extracting tube that has the ultrasonic generating unit of vibration plate formula, add and contain praseodymium nitrate Pr (NO
3)
3Pregnant solution, extraction liquid, the volume ratio of adding is 1: 2.5, 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 extraction, containing extraction liquid in the extraction phase and valency rare earth composition, recyclable utilization, raffinate are arranged is neodymium nitrate Nd (NO
3)
3Refined liquid enters next step;
(4) adsorption-edulcoration: the neodymium nitrate Nd (NO that obtains in the previous step fractionation extraction
3)
3In the refined liquid, add the adsorption-edulcoration agent, carry out further degree of depth adsorption-edulcoration;
(5) solid-liquid separates: separate through solid-liquid, remove impurity, liquid phase is the pure neodymium nitrate Nd (NO that makes
3)
3Refined liquid enters next step; Solid phase can reclaim useful materials through washing, and washings reclaims use after treatment;
(6) ultrasonic crystalline deposit: in the crystallizer that has the ultrasonic generating unit of vibration plate formula, add pure neodymium nitrate Nd (NO
3)
3Refined liquid, crystalline deposit agent bicarbonate of ammonia NH
4HCO
3, neodymium nitrate Nd (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 neodymium carbonate Nd
2(CO
3)
3The crystalline deposit thing enters next step;
(7) solid-liquid separates: separate through solid-liquid, obtaining solid phase is neodymium carbonate Nd
2(CO
3)
3The crystalline deposit thing enters next step; Liquid phase is through evaporation concentration, recyclable ammonium nitrate;
(8) dry, calcination:, obtain neodymium carbonate Nd 25-800 ℃ of drying
2(CO
3)
3800-900 ℃ of following calcination, obtain Neodymium trioxide Nd
2O
3Content 〉=99.99%, grain diameter are the ultra-fine high-purity neodymium 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 make 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, ultrasonic extraction, 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 and ultrasonic 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 praseodymium-neodymium Pr-Nd enriched substance prepares the method for ultra-fine high-purity neodymium oxide, is to be raw material with praseodymium-neodymium Pr-Nd enriched substance, it is characterized in that described method steps is as follows:
(1) mix: praseodymium-neodymium Pr-Nd enriched substance, nitric acid, water are carried out mix, separate through solid-liquid, remove insoluble impurities, obtain praseodymium-neodymium Pr-Nd 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 praseodymium-neodymium Pr-Nd enriched substance feed liquid, extraction liquid, washing lotion, 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 for containing neodymium nitrate Nd (NO
3)
3Pregnant solution, enter next step;
(3) ultrasonic extraction: in ultrasonic extraction equipment, add and contain neodymium nitrate Nd (NO
3)
3Pregnant solution, extraction liquid, the volume ratio of adding is 1: 0.5-5.0, operational condition is ultrasonic frequency 19-80kHz, ultrasonication intensity 0.2-20.0W/cm
2, service temperature is 5-60 ℃, carries out ultrasonic extraction, raffinate is neodymium nitrate Nd (NO
3)
3Refined liquid enters next step;
(4) adsorption-edulcoration: the neodymium nitrate Nd (NO that obtains in the previous step fractionation extraction
3)
3In the refined liquid, add the adsorption-edulcoration agent, carry out further degree of depth adsorption-edulcoration;
(5) solid-liquid separates: separate through solid-liquid, remove impurity, liquid phase is the pure neodymium nitrate Nd (NO that makes
3)
3Refined liquid enters next step;
(6) ultrasonic crystalline deposit: in ultrasonic crystallizer, add pure neodymium nitrate Nd (NO
3)
3Refined liquid, crystalline deposit agent bicarbonate of ammonia or volatile salt, neodymium nitrate Nd (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 neodymium carbonate Nd
2(CO
3)
3The crystalline deposit thing enters next step;
(7) solid-liquid separates: separate through solid-liquid, obtaining solid phase is neodymium carbonate Nd
2(CO
3)
3The crystalline deposit thing enters next step; Liquid phase is through evaporation concentration, recyclable ammonium nitrate;
(8) dry, calcination:, obtain neodymium carbonate Nd 25-800 ℃ of drying
2(CO
3)
3800-900 ℃ of following calcination, obtain Neodymium trioxide Nd
2O
3Content 〉=99.99%, grain diameter are the ultra-fine high-purity neodymium oxide product of 0.01-10.0 μ m.
2, praseodymium according to claim 1-neodymium Pr-Nd enriched substance prepares the method for ultra-fine high-purity neodymium oxide, it is characterized in that: the operational condition in ultrasonic fractionation extraction, ultrasonic extraction, the ultrasonic crystalline deposit is ultrasonic frequency 25kHz, ultrasonication intensity 2.0W/cm
2, the service temperature of ultrasonic fractionation extraction and ultrasonic extraction is 40 ℃, the service temperature of ultrasonic crystalline deposit is 10 ℃.
3, praseodymium according to claim 1-neodymium Pr-Nd enriched substance prepares the method for ultra-fine high-purity neodymium oxide, it 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, praseodymium according to claim 3-neodymium Pr-Nd enriched substance prepares the method for ultra-fine high-purity neodymium oxide, 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 (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103030167A (en) * | 2012-09-22 | 2013-04-10 | 包头市京瑞新材料有限公司 | Method for preparing spherical neodymium carbonate peroxide |
| CN111304469A (en) * | 2020-03-05 | 2020-06-19 | 赣州嘉源新材料有限公司 | Preparation method of high-dispersity ultrafine neodymium oxide |
-
2007
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103030167A (en) * | 2012-09-22 | 2013-04-10 | 包头市京瑞新材料有限公司 | Method for preparing spherical neodymium carbonate peroxide |
| CN103030167B (en) * | 2012-09-22 | 2014-10-08 | 包头市京瑞新材料有限公司 | Method for preparing spherical neodymium carbonate peroxide |
| CN111304469A (en) * | 2020-03-05 | 2020-06-19 | 赣州嘉源新材料有限公司 | Preparation method of high-dispersity ultrafine neodymium oxide |
| CN111304469B (en) * | 2020-03-05 | 2022-04-26 | 赣州嘉源新材料有限公司 | Preparation method of high-dispersity ultrafine neodymium oxide |
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