CN101012507A - Method for preparing ultra-thin highly-pure terbium oxide by beneficiated gadolinium-terbium - Google Patents
Method for preparing ultra-thin highly-pure terbium oxide by beneficiated gadolinium-terbium Download PDFInfo
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Abstract
The invention discloses a making method of terbium oxide, which comprises the following steps: (1) blending raw material; (2) distilling and extracting through ultrasound; obtaining enriched liquid of TbCl3; (3) fractionating and extracting through ultrasound; obtaining fined liquid of TbCl3; (4) adsorbing impurity; (5) separating solid from liquid; (6) crystallizing; sedimenting Tb2 (CO3) 3; (7) proceeding solid-liquid separation; (8) drying; sintering; obtaining Tb4O7 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 terbium sesquioxide, particularly a kind of is the method for the ultra-fine high purity terbium oxide of feedstock production with gadolinium-terbium Gd-Tb enriched substance, belongs to the hydrometallurgy field.
Background technology
Ultra-fine high purity terbium oxide (Tb
4O
7) product is meant terbium oxide content 〉=99.99%, the terbium sesquioxide product of grain diameter≤10.0 μ m.Terbium belongs to heavy rare earths, and the abundance in the earth's crust is very low, only is 1.1ppm.In China's Bayan Obo rare-earth mineral, terbium sesquioxide is occupancy volume less than 0.01% in total rare earth (TRE), exactly in containing the highest high ruthenium ion type heavy rare earths ore deposit of terbium, the content of terbium also only accounts for the 1.1-1.2% of total rare earth (TRE), terbium has the chemical activity as other rare earth metals, can with many nonmetal generation chemical reactions.Can be positive trivalent and positive tetravalence in the chemical reaction, its divided oxide minor is write as Tb usually
4O
7, be equivalent to two TbO
2With a Tb
2O
3Because terbium is rare and valuable, makes him not obtain practical application for a long time.Over nearly 30 years, along with the fast development of electronics and information industry, a collection of novel terbium base rare earth functional materials arises at the historic moment, and many excellent specific properties of terbium make it become the indispensable a member of many functional materialss, are in irreplaceable status in some Application Areass.Because terbium costs an arm and a leg, and preparation higher-grade terbium is very difficult again, and therefore, people press for to find and a kind ofly can prepare ultra-fine high purity terbium oxide, the method that preparation cost is lower again.General rare earth element is purified very difficult, and solvent extration since throughput than ion exchange method height, thereby the present separation purification that is used for rare earth element as main method, solvent extraction is a water (feed liquid) with after an inconsistent wholly or in part organic phase contacts closely, the material of aqueous phase changes organic phase over to, and the process of redistributing in two-phase.The used extraction agent of purification rare earth has: be the cation extractant of representative such as di-(2-ethylhexyl)phosphoric acid (being called for short P204), di-2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester (being called for short P507) 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.At present, the separating and purifying method of terbium is a raw material with many components ion ore deposit, south (comprising heavy rare earths type ore deposit, Longnan, Jiangxi, light rare earths type ore deposit, Xunwu, the rich europium type of middle yttrium ore deposit, middle transition type ore deposit) and packet header hamartite etc. usually, adopt P507-HCl system extraction grouping to separate and obtain single rare earth straight product or higher-grade enriched substance and part high-purity single rare earth product, use chromatography (extration resin chromatograph and ion-exchange chromatography) to purify then and obtain the high-purity single rare earth product.In the Chinese patent literature of publication number CN85102248A (applying date is on April 1st, 1985, and name is called solvent extraction and divides group rare-earth and enrichment terbium), introduced a kind of method that the fractionation extraction grouping separates gadolinium-terbium and enrichment terbium of from terbium-erbium-yttrium mixed rare earth, carrying out.Be that stock liquid carries out gadolinium-terbium extraction grouping separation at first to contain rare earth oxides such as terbium, cerium, praseodymium, neodymium, samarium, europium, gadolinium, yttrium; Then, the organic phase of the load gadolinium-erbium-yttrium that obtains from the grouping of gadolinium-terbium is that raw material carries out terbium-dysprosium grouping and separates to come the enrichment terbium.The enriched substance that contains terbium sesquioxide 70-90% provides good raw material for terbium sesquioxide separates, dysprosium-erbium, the yttrium enriched substance that contains terbium sesquioxide＜0.2% is to separate the good raw material of purification dysprosium, terbium-yttrium enriched substance that another product contains terbium sesquioxide＜0.01% also is the good raw material of separation purifying gadolinium, the shortcoming of this method be can not the pure terbium of separation and Extraction product, and the enriched substance of intermediates just.Notification number is that (applying date is on June 2nd, 1989 for the Chinese patent literature of CN1017887B, name is called obtaining lanthanides by extraction and separation of solvent) in, be primarily aimed at the deficiency of the technological process of Chinese patent literature CN85102248A introduction, introduce a kind of fractionation extraction and produced the method for pure zirconia terbium (terbium peroxide), with P507 is extraction agent, hydrochloride solution with middle heavy rare earths is stock liquid, and the acidity of stock liquid is pH5-0.5.At first carry out terbium-dysprosium extraction grouping and separate, and then carry out gadolinium-terbium extraction grouping and separate, produce the feed liquid of pure zirconia terbium as fractionation extraction with the organic phase of gadolinium-isolating load terbium enriched substance of terbium extraction grouping at last.This technology can be produced purity greater than 99% terbium sesquioxide, is used to do the green powder of three primary colors fluorescent powder, can obtain 90% left and right sides gadolinium sesquioxide simultaneously and contains 50% above yttrium oxide and contain three kinds of enriched substance of 85% left and right sides dysprosium oxide.This invention common multistage fractionation extraction case that used equipment is all known for the one of ordinary skill in the art in carrying out gadolinium-terbium extraction grouping separation and fractionation extraction process, this extraction tank is the extraction equipment that China's rare-earth trade generally adopts, and its main drawback is to exist mixing and clarification, cell body stability and two pairs of principal contradictions of cell body burden.Mixing is the primary condition of extracting and separating material reallocation, and clarification then is the necessary process that extraction distributes.Mix fully, extraction equilibrium degree height, the distribution capability of extraction agent is not fully exerted, and at this moment, dispersion particle is little, is difficult to assemble phase-splitting, finally influences separating effect.In order to improve the stage efficiency of cell body, certainly will to make thing at the residence time of mixing section lengthening, increase settling time simultaneously, cause the cell body cumulative volume to increase, separating progression increases.And the stability of cell body usually to be rare earth burden by cell body reach, this also certainly will cause the increase of cell body investment.In addition, present documents and materials are produced the further separation and purification of feed liquid of pure zirconia terbium and production purity and are not seen introduction greater than the subsequent technique method of 99.99% terbium sesquioxide to fractionation extraction.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., 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; Existing extraction progression is many, generally will just can finish whole extraction process by the 70-100 level; (2), oxalic acid terbium crystalline deposit poor effect: is that precipitation agent uses with oxalic acid, production cost height, and oxalic acid toxicity is big, contaminate environment.The rare earth element terbium be difficult to form crystal form carbonate, and the terbium 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 oxalic acid terbium 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 terbium sesquioxide product prepared generally is difficult to obtain terbium sesquioxide (Tb
4O
7) content is up to 99.99% purity, particle diameter is big, is difficult to reach≤high-grade terbium oxide of 10.0 μ m, 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 gadolinium-terbium Gd-Tb enriched substance that purity is high prepare the method for ultra-fine high purity terbium oxide.
The technical scheme that realizes above-mentioned purpose is: a kind of gadolinium-terbium Gd-Tb enriched substance prepares the method for ultra-fine high purity terbium oxide, is to be raw material with gadolinium-terbium Gd-Tb enriched substance, and described method steps is as follows:
(1) mix: gadolinium-terbium Gd-Tb enriched substance, hydrochloric acid, water are being carried out mix, separating through solid-liquid, removing insoluble impurities, obtaining gadolinium-terbium Gd-Tb enriched substance feed liquid, the concentration of feed liquid middle-weight rare earths is 0.1-1.2mol/L;
(2) gadolinium-ultrasonic fractionation extraction of terbium Gd-Tb: in ultrasonic extraction equipment, add gadolinium-terbium Gd-Tb 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
2Service temperature is 5-60 ℃, carry out ultrasonic fractionation extraction, the outlet strip aqueous is the dysprosium-yttrium Dy-Y pregnant solution that contains Dy, Ho, Yb, Er, Y, raffinate is the samarium gadolinium Sm Gd pregnant solution that contains Sm, Gd, the outlet organic phase can be used as extraction liquid and recycles, and central exit liquid is for containing terbium chloride TbCl
3Pregnant solution, enter next step;
(3) terbium-ultrasonic fractionation extraction of dysprosium Tb-Dy: in ultrasonic extraction equipment, add and contain terbium chloride TbCl
3Pregnant solution, extraction liquid, washing lotion, the volume ratio of adding 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 the outlet strip aqueous is the holmium-yttrium Ho-Y pregnant solution that contains Ho, Yb, Er, Y, and the outlet organic phase can be used as extraction liquid and recycles, and raffinate is terbium chloride TbCl
3Refined liquid enters next step;
(4) adsorption-edulcoration: the terbium chloride TbCl that obtains in the previous step fractionation extraction
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, and the recyclable utilization of solid phase, liquid phase is the pure terbium chloride TbCl that makes
3Refined liquid enters next step separation;
(6) ultrasonic crystalline deposit: in ultrasonic crystallizer, add pure terbium chloride TbCl
3Refined liquid, crystalline deposit agent bicarbonate of ammonia or volatile salt, terbium chloride TbCl
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 terbium carbonate Tb
2(CO
3)
3The crystalline deposit thing enters next step;
(7) solid-liquid separates: separate through solid-liquid, obtaining solid phase is terbium carbonate Tb
2(CO
3)
3The crystalline deposit thing enters next step; The recyclable ammonium chloride of liquid phase;
(8) dry, calcination:, obtain terbium carbonate Tb 25-800 ℃ of drying
2(CO
3)
3800-900 ℃ of following calcination, obtain Tb
4O
7Content 〉=99.99%, grain diameter are the ultra-fine high purity terbium 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.
The present invention mainly adopts ultrasonic fractionation extraction-ultrasonic fractionation 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 terbium 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 terbium 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 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: the rare earth element praseodymium is difficult to form crystal form carbonate, and the terbium 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, ultrasound intensity during by control stirring and precipitation is accelerated to mix and sedimentary speed, thereby improve extracting and separating speed and separation efficiency greatly, improve 20 to 60 times than traditional extraction method segregation rate, 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) adopt the crystalline deposit agent of bicarbonate of ammonia or volatile salt as terbium chloride formulations prepared from solutions terbium carbonate, because bicarbonate of ammonia or volatile salt price are more cheap, nontoxic than oxalic acid, can reduce production costs, and can improve settling rate and yield, improve quality product and production environment, reduce contaminate environment, also recyclable simultaneously by-product ammonium chloride, rate of recovery height, greatly reduce the consumption of chemical reagent, can reduce production costs significantly.Moreover, because in terbium carbonate crystalline deposit precipitation process, the employing ultrasonic technique is strengthened, the speed and the efficient of crystallization precipitation process have further been improved, improved terbium carbonate crystalline granularity and size-grade distribution, the terbium sesquioxide product purity height of preparing, grain diameter is little, even particle size distribution, its terbium sesquioxide product Tb
4O
7Content 〉=99.99%, grain diameter are 0.01-10.0 μ m, are high-grade ultra-fine high purity terbium oxide products, and 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) adopt the hcl as extraction agent system, hydrochloric acid is than the low price of nitric acid, and littler to the corrodibility of equipment than nitric acid, the ring mirror polluted little, and three-waste pollution is few; (4) 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: gadolinium-terbium Gd-Tb enriched substance, HCl, P507 extraction agent, kerosene, NH
4HCO
3
As depicted in figs. 1 and 2, a kind of gadolinium-terbium Gd-Tb enriched substance prepares the method for ultra-fine high purity terbium oxide, is to be raw material with gadolinium-terbium Gd-Tb enriched substance, and described method steps is as follows:
(1) mix: at the mix stirring tank, gadolinium-terbium Gd-Tb enriched substance, hydrochloric acid, water are carried out mix, separate through solid-liquid, remove insoluble impurities, obtain gadolinium-terbium Gd-Tb enriched substance feed liquid, the concentration of feed liquid middle-weight rare earths is 0.1-1.2mol/L;
(2) gadolinium-ultrasonic fractionation extraction of terbium Gd-Tb: in the extraction kettle that has the probe type ultrasonic generating unit, add gadolinium-terbium Gd-Tb 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 the P507-kerosene of (0.12-0.68mol) P507 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, the outlet strip aqueous is the dysprosium-yttrium Dy-Y pregnant solution that contains Dy, Ho, Yb, Er, Y, raffinate is the samarium gadolinium Sm Gd pregnant solution that contains Sm, Gd, and the outlet organic phase can be used as extraction liquid and recycles, and central exit liquid is for containing terbium chloride TbCl
3Pregnant solution, enter next step;
(3) terbium-ultrasonic fractionation extraction of dysprosium Tb-Dy: in the extraction kettle that has the probe type ultrasonic generating unit, add and contain terbium chloride TbCl
3Pregnant solution, extraction liquid, washing lotion, the volume ratio that adds is 1: 0.5: 0.1, extracted organic phase consist of extracted organic phase consist of the P507-kerosene of (0.12-0.68mol) P507 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 the outlet strip aqueous is the holmium-yttrium Ho-Y pregnant solution that contains Ho, Yb, Er, Y, and the outlet organic phase can be used as extraction liquid and recycles, and raffinate is terbium chloride TbCl
3Refined liquid enters next step;
(4) adsorption-edulcoration: the terbium chloride TbCl that obtains in the previous step fractionation extraction
3In the refined liquid, add activated carbon, carry out further degree of depth adsorption-edulcoration as the adsorption-edulcoration agent;
(5) solid-liquid separates: separate through solid-liquid, remove impurity, solid phase is recycled, and liquid phase is the pure terbium chloride TbCl that makes
3Refined liquid enters next step separation;
(6) ultrasonic crystalline deposit: in the crystallization kettle that has the probe type ultrasonic generating unit, add pure terbium chloride TbCl
3Refined liquid, crystalline deposit agent bicarbonate of ammonia NH
4HCO
3, terbium chloride TbCl
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 terbium carbonate Tb
2(CO
3)
3The crystalline deposit thing enters next step;
(7) solid-liquid separates: separate through solid-liquid, obtaining solid phase is terbium carbonate Tb
2(CO
3)
3The crystalline deposit thing enters next step; Liquid phase reclaims ammonium chloride;
(8) dry, calcination:, obtain terbium carbonate Tb 25-800 ℃ of drying
2(CO
3)
3800-900 ℃ of following calcination, obtain Tb
4O
7Content 〉=99.99%, grain diameter are the ultra-fine high purity terbium 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: gadolinium-terbium Gd-Tb enriched substance, HCl, P507 extraction agent, sulfonated kerosene, (NH
4)
2CO
3
As shown in figures 1 and 3, a kind of gadolinium-terbium Gd-Tb enriched substance prepares the method for ultra-fine high purity terbium oxide, is to be raw material with gadolinium-terbium Gd-Tb enriched substance, and described method steps is as follows:
(1) mix: at the mix stirring tank, gadolinium-terbium Gd-Tb enriched substance, hydrochloric acid, water are carried out mix, separate through solid-liquid, remove insoluble impurities, obtain gadolinium-terbium Gd-Tb enriched substance feed liquid, the concentration of feed liquid middle-weight rare earths is 0.1-1.2mol/L;
(2) gadolinium-ultrasonic fractionation extraction of terbium Gd-Tb: in the extraction tank that has the ultrasonic generating unit of vibrator type, add gadolinium-terbium Gd-Tb 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 P507-sulfonated kerosene of (0.12-0.68mol) P507 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, the outlet strip aqueous is the dysprosium-yttrium Dy-Y pregnant solution that contains Dy, Ho, Yb, Er, Y, raffinate is the samarium gadolinium Sm Gd pregnant solution that contains Sm, Gd, and the outlet organic phase can be used as extraction liquid and recycles, and central exit liquid is for containing terbium chloride TbCl
3Pregnant solution, enter next step;
(3) terbium-ultrasonic fractionation extraction of dysprosium Tb-Dy: in the extraction tank that has the ultrasonic generating unit of vibrator type, add and contain terbium chloride TbCl
3Pregnant solution, extraction liquid, washing lotion, the volume ratio that adds is 1: 5.0: 2.0, extracted organic phase consist of the P507-sulfonated kerosene of (0.12-0.68mol) P507 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 the outlet strip aqueous is the holmium-yttrium Ho-Y pregnant solution that contains Ho, Yb, Er, Y, and the outlet organic phase can be used as extraction liquid and recycles, and raffinate is terbium chloride TbCl
3Refined liquid enters next step;
(4) adsorption-edulcoration: the terbium chloride TbCl that obtains in the previous step fractionation extraction
3In the refined liquid, add ion exchange resin, carry out further degree of depth adsorption-edulcoration as the adsorption-edulcoration agent;
(5) solid-liquid separates: separate through solid-liquid, remove impurity, solid phase is recycled, and liquid phase is the pure terbium chloride TbCl that makes
3Refined liquid enters next step separation;
(6) ultrasonic crystalline deposit: in the crystallizer tank that has the ultrasonic generating unit of vibrator type, add pure terbium chloride TbCl
3Refined liquid, crystalline deposit agent volatile salt (NH
4)
2CO
3, terbium chloride TbCl
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 terbium carbonate Tb
2(CO
3)
3The crystalline deposit thing enters next step;
(7) solid-liquid separates: separate through solid-liquid, obtaining solid phase is terbium carbonate Tb
2(CO
3)
3The crystalline deposit thing enters next step; Liquid phase reclaims ammonium chloride;
(8) dry, calcination:, obtain terbium carbonate Tb 25-800 ℃ of drying
2(CO
3)
3800-900 ℃ of following calcination, obtain Tb
4O
7Content 〉=99.99%, grain diameter are the ultra-fine high purity terbium 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: gadolinium-terbium Gd-Tb enriched substance, HCl, P507 extraction agent, No. 200 gasoline, NH
4HCO
3
As Fig. 1 and shown in Figure 5, a kind of gadolinium-terbium Gd-Tb enriched substance prepares the method for ultra-fine high purity terbium oxide, is to be raw material with gadolinium-terbium Gd-Tb enriched substance, and described method steps is as follows:
(1) mix: at the mix stirring tank, gadolinium-terbium Gd-Tb enriched substance, hydrochloric acid, water are carried out mix, separate through solid-liquid, remove insoluble impurities, obtain gadolinium-terbium Gd-Tb enriched substance feed liquid, the concentration of feed liquid middle-weight rare earths is 0.1-1.2mol/L;
(2) gadolinium-ultrasonic fractionation extraction of terbium Gd-Tb: in the extracting tube that has the ultrasonic generating unit of vibration plate formula, add gadolinium-terbium Gd-Tb 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 the P507-200 gasoline of (0.12-0.68mol) P507 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, the outlet strip aqueous is the dysprosium-yttrium Dy-Y pregnant solution that contains Dy, Ho, Yb, Er, Y, raffinate is the samarium gadolinium Sm Gd pregnant solution that contains Sm, Gd, and the outlet organic phase can be used as extraction liquid and recycles, and central exit liquid is for containing terbium chloride TbCl
3Pregnant solution, enter next step;
(3) terbium-ultrasonic fractionation extraction of dysprosium Tb-Dy: in the extracting tube that has the ultrasonic generating unit of vibration plate formula, add and contain terbium chloride TbCl
3Pregnant solution, extraction liquid, washing lotion, the volume ratio that adds is 1: 2.5: 1.0, extracted organic phase consist of the P507-200 gasoline of (0.12-0.68mol) P507 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 the outlet strip aqueous is the holmium-yttrium Ho-Y pregnant solution that contains Ho, Yb, Er, Y, and the outlet organic phase can be used as extraction liquid and recycles, and raffinate is terbium chloride TbCl
3Refined liquid enters next step;
(4) adsorption-edulcoration: the terbium chloride TbCl that obtains in the previous step fractionation extraction
3In the refined liquid, add activated carbon, carry out further degree of depth adsorption-edulcoration as the adsorption-edulcoration agent;
(5) solid-liquid separates: separate through solid-liquid, remove impurity, solid phase is recycled, and liquid phase is the pure terbium chloride TbCl that makes
3Refined liquid enters next step separation;
(6) ultrasonic crystalline deposit: in the crystallizer that has the ultrasonic generating unit of vibration plate formula, add pure terbium chloride TbCl
3Refined liquid, crystalline deposit agent bicarbonate of ammonia NH
4HCO
3, terbium chloride TbCl
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 terbium carbonate Tb
2(CO
3)
3Crystalline deposit enters next step;
(7) solid-liquid separates: separate through solid-liquid, obtaining solid phase is terbium carbonate Tb
2(CO
3)
3The crystalline deposit thing enters next step; Liquid phase reclaims ammonium chloride;
(8) dry, calcination:, obtain terbium carbonate Tb 25-800 ℃ of drying
2(CO
3)
3800-900 ℃ of following calcination, obtain Tb
4O
7Content 〉=99.99%, grain diameter are the ultra-fine high purity terbium 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 P507 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 P507 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 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 gadolinium-terbium Gd-Tb enriched substance prepares the method for ultra-fine high purity terbium oxide, is to be raw material with gadolinium-terbium Gd-Tb enriched substance, it is characterized in that described method steps is as follows:
(1) mix: gadolinium-terbium Gd-Tb enriched substance, hydrochloric acid, water are carried out mix, separate through solid-liquid, remove insoluble impurities, obtain gadolinium-terbium Gd-Tb enriched substance feed liquid, the concentration of feed liquid middle-weight rare earths is 0.1-1.2mol/L;
(2) gadolinium-ultrasonic fractionation extraction of terbium Gd-Tb: in ultrasonic extraction equipment, add gadolinium-terbium Gd-Tb 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 terbium chloride TbCl
3Pregnant solution, enter next step;
(3) terbium-ultrasonic fractionation extraction of dysprosium Tb-Dy: in ultrasonic extraction equipment, add and contain terbium chloride TbCl
3Pregnant solution, extraction liquid, washing lotion, the volume ratio of adding 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 terbium chloride TbCl
3Refined liquid enters next step;
(4) adsorption-edulcoration: the terbium chloride TbCl that obtains in the previous step fractionation extraction
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, and the recyclable utilization of solid phase, liquid phase is the pure terbium chloride TbCl that makes
3Refined liquid enters next step;
(6) ultrasonic crystalline deposit: in ultrasonic crystallizer, add pure terbium chloride TbCl
3Refined liquid, crystalline deposit agent bicarbonate of ammonia or volatile salt, terbium chloride TbCl
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 terbium carbonate Tb
2(CO
3)
3The crystalline deposit thing enters next step;
(7) solid-liquid separates: separate through solid-liquid, obtaining solid phase is terbium carbonate Tb
2(CO
3)
3The crystalline deposit thing enters next step;
(8) dry, calcination:, obtain Tb 25-800 ℃ of drying
2(CO
3)
3800-900 ℃ of following calcination, obtain Tb
4O
7Content 〉=99.99%, grain diameter are the ultra-fine high purity terbium oxide product of 0.01-10.0 μ m.
2, gadolinium according to claim 1-terbium Gd-Tb enriched substance prepares the method for ultra-fine high purity terbium oxide, it 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, gadolinium according to claim 1-terbium Gd-Tb enriched substance prepares the method for ultra-fine high purity terbium 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, gadolinium according to claim 3-terbium Gd-Tb enriched substance prepares the method for ultra-fine high purity terbium oxide, it 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.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103482669A (en) * | 2013-09-10 | 2014-01-01 | 中铝稀土（常熟）有限公司 | Method for preparing high-purity terbium oxide |
| CN105018755A (en) * | 2015-07-27 | 2015-11-04 | 中国原子能科学研究院 | Method for separating trace europium and terbium from uranium and uranium fission products |
| CN105861858A (en) * | 2016-05-17 | 2016-08-17 | 南昌航空大学 | Technical process for preparing 5N dysprosium through extraction and separation method |
| CN114231763A (en) * | 2021-11-11 | 2022-03-25 | 成都中核高通同位素股份有限公司 | Separation method for extracting terbium from gadolinium terbium mixed solution |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US3582263A (en) * | 1969-10-31 | 1971-06-01 | Sylvania Electric Prod | Solvent extraction process for separating gadolinium from terbium and dysprosium |
| CN1017983B (en) * | 1989-05-20 | 1992-08-26 | 甘肃稀土公司 | Grouping method for fractional extraction of gadolinium, terbium, dysprosium and yttrium |
-
2007
- 2007-02-05 CN CNB2007100199509A patent/CN100424199C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103482669A (en) * | 2013-09-10 | 2014-01-01 | 中铝稀土（常熟）有限公司 | Method for preparing high-purity terbium oxide |
| CN105018755A (en) * | 2015-07-27 | 2015-11-04 | 中国原子能科学研究院 | Method for separating trace europium and terbium from uranium and uranium fission products |
| CN105861858A (en) * | 2016-05-17 | 2016-08-17 | 南昌航空大学 | Technical process for preparing 5N dysprosium through extraction and separation method |
| CN105861858B (en) * | 2016-05-17 | 2017-11-10 | 南昌航空大学 | A kind of extraction separation method prepares the technological process of 5N dysprosiums |
| CN114231763A (en) * | 2021-11-11 | 2022-03-25 | 成都中核高通同位素股份有限公司 | Separation method for extracting terbium from gadolinium terbium mixed solution |
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