CN103436697A - Rare-earth carbonate crystallizing and precipitating method for processing aluminum-containing rare-earth feed liquid - Google Patents
Rare-earth carbonate crystallizing and precipitating method for processing aluminum-containing rare-earth feed liquid Download PDFInfo
- Publication number
- CN103436697A CN103436697A CN2013103552589A CN201310355258A CN103436697A CN 103436697 A CN103436697 A CN 103436697A CN 2013103552589 A CN2013103552589 A CN 2013103552589A CN 201310355258 A CN201310355258 A CN 201310355258A CN 103436697 A CN103436697 A CN 103436697A
- Authority
- CN
- China
- Prior art keywords
- rare earth
- carbonate
- rare
- amount
- substance
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention discloses a rare-earth carbonate crystallizing and precipitating method for processing aluminum-containing rare-earth feed liquid. According to the method, influence of impurities to crystallization of rare-earth carbonate is reduced by controlling reaction and aging temperature, so as to obtain rare-earth carbonate with high rare-earth gross, quick crystallization speed, and convenience to filter and wash. The reaction and aging crystallization temperature is maintained above 75 DEG C. The amount ratio of carbonate (bicarbonate) to rare earth during the reaction is 0.2:1 (0.4:1) to 10:1 (20:1), but when the reaction is nearly ended, the amount ratio is controlled to be 1.4:1 (2.2:1) to 1.8: 1(3.2:1); and the pH value of the solution is controlled between 4.5 to 7.5. Along with improvement of the amount ratio of carbonate (bicarbonate) to rare earth, the crystallization speed is slowed down; the aging time is prolonged; and the chlorine root content is reduced. The feeding method can be any one of positive sequence, inverted sequence and synchronous feeding methods. The method has the advantages of high crystallization speed, high rare-earth gross in the product, large bulk density, and low consumption of a precipitant.
Description
Technical field
The present invention relates to the method for crystallizing and sedimenting rare-earth carbonate of the rare earth feed liquid that a kind of processing contains the impurity such as aluminium, belong to rare-earth wet method metallurgy and domain of inorganic chemistry.
Background technology
The carbonated rare earth crystallization is a production process main in the Rare Earth Production process, is the key link during Rare Earth Separation and rare earth material are produced.From mishmetal, former expect final single high pure rare earth product process at least will be through a crystallizing and sedimenting rare-earth carbonate process, and what have will be through crystallizing and sedimenting rare-earth carbonate process repeatedly.Because need to pass through a plurality of separation phases from the mishmetal to the single rare earth, carbonated rare earth can be the intermediate mutually be connected between each separation phase, also can go out qualified carbonated rare earth by the carbonate crystallization precipitation, through calcining, produce qualified single rare earth oxide.Therefore, on rare-earth industry is produced, seem extremely important, calculate by the rare earth oxide treatment capacities of annual 150000 tons, with the circulate product in market of the rare earth oxide product form of carbonated rare earth and the production of calcining carbonated rare earth, even surpassed 150,000 tons.
The widespread use of crystallizing and sedimenting rare-earth carbonate technology is that the production cost of the method is lower, and environmental pollution is little, and the product application scope is wide.Since nineteen ninety-five, University Of Nanchang " method for crystallizing and sedimenting rare-earth carbonate " patented technology implements in factory in succession, solved the reactive crystallization difficult problem of many rare earth feed liquids, its application surface relates to most of rare earth feed liquid of mine and separation plant, comprise the praseodymium neodymium of northern rare earth extraction defiber output and the carbonate crystallization of neodymium feed liquid, obtained good effect.But use in addition the oxalate precipitation method in some highly purified single rare earth productions, what it was mainly considered is purity requirement and physical property requirement.What also have some need to adopt oxalate precipitation is that those adopt carbonate crystallization can't reach the rare earth feed liquid of operational requirement and quality product requirement, and one of them typical example is praseodymium neodymium and the neodymium feed liquid of ion type rareearth extracting and separating line output.Because such feed liquid contains aluminium and other impurity, adopt current widespread use method for crystallizing and sedimenting rare-earth carbonate to be difficult to obtain desirable crystalline product, even adopt the naphthenic acid extraction process to remove aluminium to below 200ppm, also still can not well realizing rapid crystallization.This may be not merely also wherein the content height problem of aluminium, and what also have impurity exists form problem, for example organic phase of the aluminium of colloidal state and microemulsion-like etc.Therefore, propose and develop a kind of praseodymium neodymium and neodymium feed liquid carbonate crystallization precipitation technology that can meet ion type rareearth extracting and separating line output and be very important.Press the treatment capacity of annual 50000 tons of ion type rareearth and calculate, wherein the praseodymium neodymium accounts for 30% left and right, has every year the Praseodymium trioxide neodymium of 1.5 ten thousand tons still to need to adopt the oxalate precipitation method, and its production cost is higher approximately 10,000 yuan than carbonate crystallization method.Therefore, if can address this problem, will save production cost every year 1.5 hundred million yuan.
Summary of the invention
The objective of the invention is provides the method for crystallizing and sedimenting rare-earth carbonate of a kind of processing containing the aluminium rare earth feed liquid for the deficiencies in the prior art, to solve the crystallization production difficult problem containing the rare earth feed liquid of aluminium and other impurity.
Principle of the present invention is: fundamental research in early stage result shows, adopts the crystallization velocity difference of carbonate deposition carbonated rare earth out under differing temps, and crystallization type and quality product are also different.Under normal temperature and lower temperature, what obtain is eight aqueous carbonate rare earths, and water content is high, and the raising Tc can obtain water water chestnut yttrium type carbonated rare earth between arriving 35-75 ℃, and water content reduces, and total amount of rare earth is higher.But these two kinds of crystallized forms are subject to the impact of foreign ion larger, and especially, when containing aluminium, crystallization velocity is very slow, even has been difficult to crystallization.By a large amount of experiments, find, the crystallization velocity of basic carbonate rare earth is subject to the impact of foreign ion little, and the formation of basic carbonate rare earth need to improve reaction and Tc.
Processing of the present invention containing the method for crystallizing and sedimenting rare-earth carbonate of aluminium rare earth feed liquid can take that positive sequence is reinforced, upside-down load(ing), synchronous any in reinforced three kinds of feed way, the concrete technology step is as follows:
(1) positive sequence feed way
Rare earth feed liquid is put into to reactor, be heated to more than 75 ℃, under agitation add sodium carbonate, sodium bicarbonate, volatile salt, a kind of in bicarbonate of ammonia, keep the temperature of reaction process all more than 75 ℃, the reaction process Rare Earth Ion is excessive, until carbonate reaches 1.5:1 with the ratio of the amount of substance of rare earth, or the ratio of supercarbonate and the amount of substance of rare earth while reaching 2.4:1 rare earth precipitated fully, continue to stir 10-40 minute, continuing to add precipitation agent to carbonate is 1.5:1～1.8:1 with the ratio of the amount of substance of rare earth, or supercarbonate is 2.4:1～3.2:1 with the ratio of the amount of substance of rare earth, stir to stop in a moment stirring and carry out aging crystallization, or squeeze into another retort aging crystallization 1-24 hour, Aging Temperature is more than 75 ℃, ageing is carried out liquid-solid separation and washing after finishing, until in filtrate without chlorion, solid crystal is the rare earth carbonate product, filtrate cycle is used or is entered water treating pond and discharges after treatment,
(2) upside-down load(ing) mode
Sodium carbonate or sodium bicarbonate are put into to reactor, be heated to more than 75 ℃, under agitation add rare earth feed liquid, keep the temperature of reaction process all more than 75 ℃, in reaction process, sodium carbonate or sodium bicarbonate are excessive, until carbonate reaches 1.5:1 with the ratio of the amount of substance of rare earth, or the ratio of supercarbonate and the amount of substance of rare earth while reaching 2.4:1 sodium carbonate or sodium bicarbonate be consumed fully, continue to stir 10-40 minute, suitably adding precipitation agent to carbonate is that 1.5:1～1.8:1 or supercarbonate are 2.5:1～3.2:1 with the ratio of the amount of substance of rare earth with the ratio of the amount of substance of rare earth, stir to stop in a moment stirring and carry out aging crystallization, or squeeze into another retort aging crystallization 1-24 hour, Aging Temperature is more than 75 ℃, ageing is carried out liquid-solid separation and washing after finishing, until in filtrate without chlorion, solid crystal is the rare earth carbonate product, filtrate cycle is used or is entered water treating pond and discharges after treatment.
(3) synchronous feed way
Add in advance a certain amount of water and carbonated rare earth crystal seed in reactor, or the slurry containing crystal seed of reserving after the last consignment of crystalline deposit, to stirring, can normally carry out, be heated to more than 75 ℃, under agitation making carbonate and the ratio of the amount of substance of rare earth is that 1.3:1～1.8:1 or supercarbonate are 1.6:1～2.6:1 with the ratio of the amount of substance of rare earth, add rare earth feed liquid and carbonate or supercarbonate simultaneously, keep the temperature of reaction process all more than 75 ℃, pH is controlled between 4.5 ~ 7.5, after having fed in raw material, continue to stir 10-40 minute, suitably adding precipitation agent or rare earth feed liquid to carbonate is that 1.5:1～1.8:1 or supercarbonate are 2.4:1～3.2:1 with the ratio of the amount of substance of rare earth with the ratio of the amount of substance of rare earth, stir to stop in a moment stirring and carry out aging crystallization, or squeeze into another retort aging crystallization 1-24 hour, Aging Temperature is more than 75 ℃, ageing is carried out liquid-solid separation and washing after finishing, until in filtrate without chlorion, solid crystal is produced rare earth carbonate product, filtrate cycle is used or is entered water treating pond and discharges after treatment.
Beneficial effect of the present invention: principal feature of the present invention is to have utilized carbonate sedimentation and the fast feature of crystallization velocity under high temperature, still can rapid crystallization and sedimentation after making praseodymium neodymium feed liquid that aluminum content is high and precipitation agent reacting, obtain crystal formation better, the praseodymium carbonate neodymium precipitation that bulk density is high.Although it is higher to improve the energy consumption of precipitated crystal temperature within the unit time, crystallization velocity is fast, and the required time is short, and the energy consumption of unit weight product can't raise.And the consumption of precipitation agent, than the little near sixth left and right of precipitated crystal under mesophilic range, can obviously be cut down the consumption of raw materials.In fact, manufacturer can require (bulk density, chloride content, content of rare earth etc.) to determine concrete operational condition (feed molar ratio, temperature, time etc.) according to quality product separately, obtain the rare-earth products of plurality of specifications.Therefore, of the present invention widely applicable, have broad application prospects.
The accompanying drawing explanation
Fig. 1, the XRD figure with sodium bicarbonate as precipitation agent gained praseodymium carbonate neodymium;
Fig. 2, the SEM figure with sodium bicarbonate as precipitation agent gained praseodymium carbonate neodymium;
Fig. 3, the XRD figure with bicarbonate of ammonia as precipitation agent gained praseodymium carbonate neodymium;
Fig. 4, the SEM figure with bicarbonate of ammonia as precipitation agent gained praseodymium carbonate neodymium;
After Fig. 5, interpolation aluminum chloride, concentration is 500ppm, the pH changing trend diagram in reaction and ageing process;
The XRD figure that after Fig. 6, interpolation aluminum chloride, concentration is 500ppm gained praseodymium carbonate neodymium;
The SEM figure that after Fig. 7, interpolation aluminum chloride, concentration is 500ppm gained praseodymium carbonate neodymium;
After Fig. 8, interpolation aluminum chloride, concentration is 1000ppm, the pH changing trend diagram in reaction and ageing process;
The XRD figure that after Fig. 9, interpolation aluminum chloride, concentration is 1000ppm gained praseodymium carbonate neodymium;
The SEM figure that after Figure 10, interpolation aluminum chloride, concentration is 1000ppm gained praseodymium carbonate neodymium;
Figure 11, sodium carbonate are that precipitation agent reacts the XRD figure of gained praseodymium carbonate neodymium under 75 ℃;
Figure 12, sodium carbonate are the SEM figure that precipitation agent reacts gained praseodymium carbonate neodymium under 75 ℃;
Figure 13, sodium carbonate are that precipitation agent reacts the XRD figure of gained praseodymium carbonate neodymium under 80 ℃;
Figure 14, sodium carbonate are the SEM figure that precipitation agent reacts gained praseodymium carbonate neodymium under 80 ℃;
Figure 15, sodium carbonate are that precipitation agent reacts the XRD figure of gained praseodymium carbonate neodymium under 85 ℃;
Figure 16, sodium carbonate are the SEM figure that precipitation agent reacts gained praseodymium carbonate neodymium under 85 ℃;
Figure 17, sodium carbonate are that precipitation agent reacts the XRD figure of gained praseodymium carbonate neodymium under 90 ℃;
Figure 18, sodium carbonate are the SEM figure that precipitation agent reacts gained praseodymium carbonate neodymium under 90 ℃;
Figure 19, sodium carbonate are that precipitation agent reacts the XRD figure of gained praseodymium carbonate neodymium under 95 ℃;
Figure 20, sodium carbonate are the SEM figure that precipitation agent reacts gained praseodymium carbonate neodymium under 95 ℃;
The XRD figure that Figure 21, sodium carbonate are precipitation agent synchronous reinforced gained praseodymium carbonate neodymium under 95 degree;
The SEM figure that Figure 22, sodium carbonate are precipitation agent synchronous reinforced gained praseodymium carbonate neodymium under 95 ℃;
Figure 23, sodium carbonate are the XRD figure of precipitation agent at 95 ℃ of lower upside-down load(ing) gained praseodymium carbonate neodymiums;
Figure 24, sodium carbonate are that precipitation agent is at the SEM of 95 ℃ of lower upside-down load(ing) gained praseodymium carbonate neodymiums figure.
Embodiment
Adopt sodium bicarbonate to do precipitation agent, by positive sequence charging reaction mode, process southern praseodymium neodymium feed liquid.The South Ore Deposit praseodymium neodymium feed liquid 50ml that to get concentration be 1mol/L is in a clean beaker and be placed in 95 ℃ of water-baths and heat, and presses amount of substance (Pr+Nd): NaHCO
3=1:1.9 takes sodium bicarbonate solid 15.96g.Start slowly to add sodium bicarbonate solid in the beaker of feed liquid to be equipped with after the temperature-stable of feed liquid, the limit edged stirs.Control speed, the constant paste of precipitation of take in beaker is principle.Continue again to stir 10 ~ 15min after adding sodium bicarbonate.Suspension is placed in to 95 ℃ of thermostat water bath ageing 5h, and beds of precipitation volume is 50ml by the 300ml sedimentation.After completing, ageing carries out solid-liquid separation, and its filtration washing is not muddy to silver nitrate solution.Under filter cake normal temperature, dry, the gained solid sample is taken away and is carried out XRD, SEM sign.Adopting the chloride content of surveying in its carbonate by pharaoh's serpents-nitric acid iron processes is 666ppm.Adopting the carbonate middle-weight rare earths total amount of EDTA volumetric determination is 72.31%, and close with the theoretical value of subcarbonate chemical formula gained, shaking real bulk density is 1.00g/ml.The XRD result is as Fig. 1, shows that the phase of praseodymium carbonate neodymium is subcarbonate, and the SEM result is as Fig. 2, the dumbbell shape coacervate that the wire crystallization that the praseodymium carbonate neodymium that can see gained is a bundle a bundle forms.This coacervate can be regarded wire crystallization from the adhesion of middle position as to the scattered length of double-headed furuncle, and middle in conjunction with closely and two is comparatively sparse, the wire crystallization at two at high temperature is hydrolyzed and becomes more round and smooth.
Adopt bicarbonate of ammonia to do precipitation agent, by positive sequence charging reaction mode, process southern praseodymium neodymium feed liquid.According to the similar method of embodiment 1, change precipitation agent into bicarbonate of ammonia.The South Ore Deposit praseodymium neodymium feed liquid 50ml that to get concentration be 1mol/L is in a clean beaker and be placed in 95 ℃ of water-baths and heat, and presses amount of substance (Pr+Nd): NH
4hCO
3=1:1.9 takes sodium bicarbonate solid 15.1g.Start slowly to add sodium bicarbonate solid in the beaker of feed liquid to be equipped with after the temperature-stable of feed liquid, the limit edged stirs.Control speed, the constant paste of precipitation of take in beaker is principle.Suitably keep the skin wet in reinforced process, add sodium bicarbonate and continue afterwards to stir the suspension that 10 ~ 15min obtains the 300ml left and right again, be placed in 95 ℃ of thermostat water bath ageing 5h, beds of precipitation volume is 50ml by the 300ml sedimentation.After completing, ageing carries out solid-liquid separation, and its filtration washing is not muddy to silver nitrate solution.Under filter cake normal temperature, dry, the gained solid sample is taken away and is carried out XRD, SEM sign.The XRD result, as Fig. 3, shows that the phase of praseodymium carbonate neodymium is subcarbonate.The SEM result is as Fig. 4, from Electronic Speculum figure, can see very similar the crystallization shape of gained praseodymium carbonate neodymium and embodiment 1.The chloride ion content analytical results of gained carbonate is 321ppm, and carbonate middle-weight rare earths total amount is 75.55%, close with the theoretical value of subcarbonate chemical formula gained, and shaking real bulk density is 1.05g/ml.
Embodiment 3
Praseodymium neodymium feed liquid+aluminum chloride (Al
3+=500ppm), adopt sodium carbonate to make precipitation agent, use the positive sequence feed way.Adopt sodium carbonate to do precipitation agent, by positive sequence charging reaction mode, process the southern praseodymium neodymium feed liquid containing aluminium 500ppm.According to the similar method of embodiment 1, change precipitation agent into sodium carbonate.The South Ore Deposit praseodymium neodymium feed liquid 50ml that to get concentration be 1mol/L, in a clean beaker, adds six water crystallization aluminum chloride 1.2753g, beaker is put into to the thermostat water bath of 95 ℃, and after al dissolution to be chlorinated, now the pH=1.65 of feed liquid, be equivalent to additional Al
3+concentration be 500ug/ml.By (Pr+Nd): Na
2cO
3=1:1.4, measure 1mol/L Na with graduated cylinder
2cO
3solution 70ml joins in constant pressure funnel, starts to drip sodium carbonate solution after feed temperature reaches controlling valu, control speed, and stir on dropping limit, limit, uses the variation of pH value in the pH meter monitoring reaction course simultaneously.If occurring in beaker becoming to stick with paste to add appropriate water, continue again to stir 10 ~ 15min after sodium carbonate to be dripped midway.Adding afterwards water, to make the volume of suspension be 300ml, surveys its pH=4.70.Suspension is placed in to 95 ℃ of thermostat water baths and carries out ageing 5h.Fig. 5 is the variation of pH value in reaction and ageing process, its pH<5.0, whole experimentation front and back, be conducive to the rapid subsidence crystallization and the praseodymium carbonate neodymium crystal bulk density that makes to obtain higher.After ageing completes, by sedimentation and filtration, wash to silver nitrate solution not muddy.Under normal temperature, drying obtains required sample.By the gained solid sample signs such as carrying out XRD, SEM of taking away.The XRD result, as Fig. 6, shows that the phase of praseodymium carbonate neodymium is subcarbonate.The SEM result, as Fig. 7, can see from Electronic Speculum figure, and similar in the pattern of gained praseodymium carbonate neodymium and embodiment 1 is the dumbbell shape coacervate, just also has some tiny wire or strip xln.The existence of proof aluminium can produce some tiny crystallizations.The chloride content recorded is 978ppm, and carbonate middle-weight rare earths total amount is 72.33%, close with the theoretical value of subcarbonate chemical formula gained, and shaking real bulk density is 1.40g/ml.Explanation can realize praseodymium carbonate neodymium rapid subsidence and obtain bulk density high under this kind of experiment condition, the praseodymium carbonate neodymium crystal that total amount of rare earth is high.
Embodiment 4
Praseodymium neodymium feed liquid+aluminum chloride (Al
3+=1000ppm), adopt sodium carbonate to make precipitation agent, use the positive sequence feed way.The South Ore Deposit praseodymium neodymium feed liquid 50ml that the dilution of learning from else's experience is 1mol/L, in a clean beaker, measures 1mol/LNa with graduated cylinder
2cO
3solution 80ml joins in constant pressure funnel, Pr+Nd:Na
2cO
3=1:1.6 adds six water crystallization aluminum chloride 2.6166g in the beaker that feed liquid is housed, and puts it in the thermostat water bath of 95 ℃, after al dissolution to be chlorinated, and the pH=1.85 of feed liquid now.Treat to start to drip sodium carbonate solution after temperature-stable, control speed, stir on dropping limit, limit, uses the variation of pH value in the pH meter monitoring reaction course simultaneously.If occurring in beaker becoming to stick with paste to add appropriate water, continue again to stir 10 ~ 15min after sodium carbonate to be dripped midway.Adding afterwards the volume that water makes suspension is 300ml, now Al
3+concentration be 1000ug/ml, survey its pH=4.57.Suspension is placed in to 95 ℃ of thermostat water baths and carries out ageing 5h, wash to silver nitrate solution not muddy by sedimentation and filtration after ageing completes.Dry and survey the chloride content in its carbonate by pharaoh's serpents-nitric acid iron processes under normal temperature.The gained solid sample signs such as carrying out XRD, SEM of taking away.The variation of pH value from its reaction and ageing process, its pH<5.0 before and after whole experimentation, the praseodymium carbonate neodymium crystal bulk density that is beneficial to its rapid subsidence crystallization and makes to obtain is higher accordingly, but disadvantageously because the too fast chloride content that makes of settling velocity is higher.In carbonate, chloride content is 935ppm, and total amount of rare earth is 74.92%, close with the theoretical value of subcarbonate chemical formula gained.The XRD of Fig. 9 also proves that the phase of gained praseodymium carbonate neodymium is subcarbonate, and shaking real bulk density is 1.10g/ml.SEM, as Figure 10, shows that gained praseodymium carbonate neodymium is to consist of large dumb-bell shape coacervate and little strip crystallization.
Praseodymium neodymium feed liquid is made precipitation agent in the lower precipitation of differing temps (75,80,85,90,95 ℃) with sodium carbonate.Each 50ml of South Ore Deposit praseodymium neodymium feed liquid that the dilution of minute learning from else's experience is 1mol/L, in five clean beakers, separately measures 5 parts with the 100ml graduated cylinder, every part of 1mol/LNa
2cO
360ml joins in five constant pressure funnels, Pr+Nd:Na
2cO
3=1:1.2, and put it in the thermostat water bath of five differing tempss of 70,80,85,90,95 ℃, treat to start to drip sodium carbonate solution after temperature-stable, control speed, stir on dropping limit, limit, if occurring in beaker becoming to stick with paste to add appropriate water, continue again to stir 10 ~ 15min after sodium carbonate to be dripped midway.Adding afterwards the volume that water makes suspension is 300ml, and the thermostat water bath that suspension is placed in to each differing temps carries out ageing, and at different temperature, its precipitation volume is the required asynchronism(-nization) of 50ml by the 300ml sedimentation, so its digestion time is also different.After ageing completes, by sedimentation and filtration, wash to silver nitrate solution not muddy.Under normal temperature, dry, pharaoh's serpents for sample-nitric acid iron processes is surveyed its chloride content, the volumetric determination total amount of rare earth.The results are shown in Table 1.Temperature raises and can reduce digestion time as seen from the table, and higher its digestion time of temperature is shorter, and its chloride content is higher, and bulk density is also higher accordingly.75, under 80,85,90,95 ℃ reaction gained solid XRD result as Figure 11,13,15,17,19, from the XRD result, the positive carbonate that under 75 ℃, the praseodymium carbonate neodymium of preparation is water water chestnut yttrium type, the praseodymium carbonate neodymium of the preparation mixture that is positive carbonate and two kinds of different crystal forms carbonate of subcarbonate under 80 and 85 ℃, the praseodymium carbonate neodymium of preparation is all subcarbonate basically under 90 ℃.The SEM result is as Figure 12,14,16,18,20, known from each figure, and the crystallization shape of the praseodymium carbonate neodymium prepared under differing temps is different.The sample of 75 ℃ of lower crystallizations is typical two-way broom-shaped coacervates that are comprised of the wire crystallization of a bundle a bundle.This coacervate can be regarded linear crystallization from the adhesion of middle position as to the scattered length of double-headed furuncle, middle in conjunction with closely and two is comparatively sparse.Improve Tc, the lines overstriking of crystallization broadens, and is also the rare loose middle compact coacervate in two, to the 85 ℃ of crystallizations that can observe constantly two, becomes round and smooth.
Chloride content, total amount of rare earth and the bulk density data of products therefrom at the different precipitated crystal temperature of table 1
Embodiment 6
Praseodymium neodymium feed liquid is made precipitation agent with sodium carbonate and is precipitated with synchronous feed way.Measuring through dilution is South Ore Deposit praseodymium neodymium feed liquid 50ml and the 1mol/LNa of 1mol/L
2cO
3solution 80ml joins respectively in two constant pressure funnels, Pr+Nd:Na
2cO
3=1:1.6, be placed in 95 ℃ of water-baths by the beaker that a small amount of water is housed, and treats after temperature-stable that the cock of simultaneously opening two funnels drips feed liquid and sodium carbonate, control speed, and the limit edged stirs.If occurring in beaker becoming to stick with paste to add appropriate water, continue again to stir 10 ~ 15min after waiting to add midway.Suspension is placed in to 95 ℃ of thermostat water baths and carries out ageing 5h, beds of precipitation volume is 50ml by the 300ml sedimentation.After ageing completes, that its filtration washing is not muddy to silver nitrate solution.Pharaoh's serpents for sample after drying under normal temperature-nitric acid iron processes is surveyed the chloride content in its carbonate, and result is 655ppm; The total amount of rare earth recorded is 74.37%, close with the theoretical value of subcarbonate chemical formula gained, and shaking real bulk density is 1.15g/ml praseodymium carbonate neodymium solid.The gained solid sample is taken away and is carried out XRD and SEM figure and see respectively Figure 21 and Figure 22.The proof product is subcarbonate, and particle is the dumb-bell shape coacervate.
Embodiment 7
Praseodymium neodymium feed liquid takes the upside-down load(ing) mode to precipitate with sodium carbonate as precipitation agent.Measure through dilution and join in constant pressure funnel for the South Ore Deposit praseodymium neodymium feed liquid 50ml of 1mol/L, get 1mol/LNa
2cO
3solution 75ml joins in clean beaker, Pr+Nd:Na
2cO
3=1:1.5, be placed in 95 ℃ of water-baths by the beaker that sodium carbonate is housed, treats to start to drip feed liquid after temperature-stable, and control speed, the limit edged stirs.If occurring in beaker becoming to stick with paste to add appropriate water, continue again to stir 10 ~ 15min after waiting to add midway.Suspension is placed in to 95 ℃ of thermostat water baths and carries out ageing 5h, beds of precipitation volume is 50ml by the 300ml sedimentation.After ageing completes, that its filtration washing is not muddy to silver nitrate solution.In carbonate samples, chloride content is 881ppm, and total amount of rare earth is 76.33%, close with the theoretical value of subcarbonate chemical formula gained, and shaking real bulk density is 1.15g/ml praseodymium carbonate neodymium solid.The gained solid sample is taken away and is carried out XRD and SEM and characterize and see respectively Figure 23 and Figure 24, proves that product is subcarbonate, and particle is the dumb-bell shape coacervate after weathering.
Claims (1)
1. a processing, containing the method for crystallizing and sedimenting rare-earth carbonate of aluminium rare earth feed liquid, is characterized in that: described method can take that positive sequence is reinforced, upside-down load(ing), synchronously any in reinforced three kinds of feed way, and the concrete technology step is as follows:
(1) positive sequence feed way
Rare earth feed liquid is put into to reactor, be heated to more than 75 ℃, under agitation add sodium carbonate, sodium bicarbonate, volatile salt, a kind of in bicarbonate of ammonia, keep the temperature of reaction process all more than 75 ℃, the reaction process Rare Earth Ion is excessive, until carbonate reaches 1.5:1 with the ratio of the amount of substance of rare earth, or the ratio of supercarbonate and the amount of substance of rare earth while reaching 2.4:1 rare earth precipitated fully, continue to stir 10-40 minute, continuing to add precipitation agent to carbonate is 1.5:1～1.8:1 with the ratio of the amount of substance of rare earth, or supercarbonate is 2.4:1～3.2:1 with the ratio of the amount of substance of rare earth, stir to stop in a moment stirring and carry out aging crystallization, or squeeze into another retort aging crystallization 1-24 hour, Aging Temperature is more than 75 ℃, ageing is carried out liquid-solid separation and washing after finishing, until in filtrate without chlorion, solid crystal is the rare earth carbonate product, filtrate cycle is used or is entered water treating pond and discharges after treatment,
(2) upside-down load(ing) mode
Sodium carbonate or sodium bicarbonate are put into to reactor, be heated to more than 75 ℃, under agitation add rare earth feed liquid, keep the temperature of reaction process all more than 75 ℃, in reaction process, sodium carbonate or sodium bicarbonate are excessive, until carbonate reaches 1.5:1 with the ratio of the amount of substance of rare earth, or the ratio of supercarbonate and the amount of substance of rare earth while reaching 2.4:1 sodium carbonate or sodium bicarbonate be consumed fully, continue to stir 10-40 minute, suitably adding precipitation agent to carbonate is that 1.5:1～1.8:1 or supercarbonate are 2.5:1～3.2:1 with the ratio of the amount of substance of rare earth with the ratio of the amount of substance of rare earth, stir to stop in a moment stirring and carry out aging crystallization, or squeeze into another retort aging crystallization 1-24 hour, Aging Temperature is more than 75 ℃, ageing is carried out liquid-solid separation and washing after finishing, until in filtrate without chlorion, solid crystal is the rare earth carbonate product, filtrate cycle is used or is entered water treating pond and discharges after treatment,
(3) synchronous feed way
Add in advance a certain amount of water and carbonated rare earth crystal seed in reactor, or the slurry containing crystal seed of reserving after the last consignment of crystalline deposit, to stirring, can normally carry out, be heated to more than 75 ℃, under agitation making carbonate and the ratio of the amount of substance of rare earth is that 1.3:1～1.8:1 or supercarbonate are 1.6:1～2.6:1 with the ratio of the amount of substance of rare earth, add rare earth feed liquid and carbonate or supercarbonate simultaneously, keep the temperature of reaction process all more than 75 ℃, pH is controlled between 4.5 ~ 7.5, after having fed in raw material, continue to stir 10-40 minute, suitably adding precipitation agent or rare earth feed liquid to carbonate is that 1.5:1～1.8:1 or supercarbonate are 2.4:1～3.2:1 with the ratio of the amount of substance of rare earth with the ratio of the amount of substance of rare earth, stir to stop in a moment stirring and carry out aging crystallization, or squeeze into another retort aging crystallization 1-24 hour, Aging Temperature is more than 75 ℃, ageing is carried out liquid-solid separation and washing after finishing, until in filtrate without chlorion, solid crystal is produced rare earth carbonate product, filtrate cycle is used or is entered water treating pond and discharges after treatment.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013103552589A CN103436697A (en) | 2013-08-15 | 2013-08-15 | Rare-earth carbonate crystallizing and precipitating method for processing aluminum-containing rare-earth feed liquid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013103552589A CN103436697A (en) | 2013-08-15 | 2013-08-15 | Rare-earth carbonate crystallizing and precipitating method for processing aluminum-containing rare-earth feed liquid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103436697A true CN103436697A (en) | 2013-12-11 |
Family
ID=49690410
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2013103552589A Pending CN103436697A (en) | 2013-08-15 | 2013-08-15 | Rare-earth carbonate crystallizing and precipitating method for processing aluminum-containing rare-earth feed liquid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103436697A (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103952555A (en) * | 2014-05-19 | 2014-07-30 | 淄博包钢灵芝稀土高科技股份有限公司 | Method for precipitating cerium-containing rare-earth carbonate |
| CN103952554A (en) * | 2014-05-19 | 2014-07-30 | 淄博包钢灵芝稀土高科技股份有限公司 | Method for precipitating excellent-acid-solubility cerium-containing rare-earth carbonate |
| CN105219962A (en) * | 2015-09-30 | 2016-01-06 | 中铝广西国盛稀土开发有限公司 | A kind of method of recovering rare earth element from carbonic acid precipitating rare earth mother liquor |
| CN108130433A (en) * | 2017-11-29 | 2018-06-08 | 中铝广西国盛稀土开发有限公司 | A kind of method that rare-earth precipitation process effectively removes chlorine, sodium ion |
| CN110282651A (en) * | 2019-08-09 | 2019-09-27 | 赣州有色冶金研究所 | A method of high-purity rare earth oxide is prepared using compound precipitants |
| CN110408778A (en) * | 2019-07-02 | 2019-11-05 | 江西万弘高新技术材料有限公司 | A kind of heavy rare earth of sodium carbonate and sodium bicarbonate mixed precipitation |
| CN110964913A (en) * | 2019-12-25 | 2020-04-07 | 中稀(常州)稀土新材料有限公司 | Method for preparing praseodymium-neodymium enrichment by adopting light soda ash precipitation |
| CN111118312A (en) * | 2019-12-21 | 2020-05-08 | 钢研集团稀土科技有限公司 | Method for removing chlorine radicals and aluminum ions in alkali-precipitated high-aluminum rare earth solution |
| CN115367782A (en) * | 2022-08-22 | 2022-11-22 | 吉水金诚新材料加工有限公司 | Method for preparing low-chlorine rare earth carbonate |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007231378A (en) * | 2006-03-01 | 2007-09-13 | Nippon Magnetic Dressing Co Ltd | Method for collecting rare earth |
| CN102978398A (en) * | 2012-12-12 | 2013-03-20 | 南昌大学 | Method for obviously lowering chlorine content in process of carbonic acid rare earth crystallization |
| WO2013085052A1 (en) * | 2011-12-09 | 2013-06-13 | 日本軽金属株式会社 | Rare earth element recovery method |
| CN103224248A (en) * | 2013-04-03 | 2013-07-31 | 南昌大学 | Method of preparing rare earth carbonate and recycling materials thereof |
-
2013
- 2013-08-15 CN CN2013103552589A patent/CN103436697A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007231378A (en) * | 2006-03-01 | 2007-09-13 | Nippon Magnetic Dressing Co Ltd | Method for collecting rare earth |
| WO2013085052A1 (en) * | 2011-12-09 | 2013-06-13 | 日本軽金属株式会社 | Rare earth element recovery method |
| CN102978398A (en) * | 2012-12-12 | 2013-03-20 | 南昌大学 | Method for obviously lowering chlorine content in process of carbonic acid rare earth crystallization |
| CN103224248A (en) * | 2013-04-03 | 2013-07-31 | 南昌大学 | Method of preparing rare earth carbonate and recycling materials thereof |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103952555A (en) * | 2014-05-19 | 2014-07-30 | 淄博包钢灵芝稀土高科技股份有限公司 | Method for precipitating cerium-containing rare-earth carbonate |
| CN103952554A (en) * | 2014-05-19 | 2014-07-30 | 淄博包钢灵芝稀土高科技股份有限公司 | Method for precipitating excellent-acid-solubility cerium-containing rare-earth carbonate |
| CN103952554B (en) * | 2014-05-19 | 2016-06-22 | 淄博包钢灵芝稀土高科技股份有限公司 | Precipitate the carbothiolic acid dissolubility method containing cerium carbonated rare earth |
| CN105219962A (en) * | 2015-09-30 | 2016-01-06 | 中铝广西国盛稀土开发有限公司 | A kind of method of recovering rare earth element from carbonic acid precipitating rare earth mother liquor |
| CN108130433A (en) * | 2017-11-29 | 2018-06-08 | 中铝广西国盛稀土开发有限公司 | A kind of method that rare-earth precipitation process effectively removes chlorine, sodium ion |
| CN110408778A (en) * | 2019-07-02 | 2019-11-05 | 江西万弘高新技术材料有限公司 | A kind of heavy rare earth of sodium carbonate and sodium bicarbonate mixed precipitation |
| CN110282651A (en) * | 2019-08-09 | 2019-09-27 | 赣州有色冶金研究所 | A method of high-purity rare earth oxide is prepared using compound precipitants |
| CN110282651B (en) * | 2019-08-09 | 2021-09-14 | 赣州有色冶金研究所有限公司 | Method for preparing high-purity rare earth oxide by using composite precipitator |
| CN111118312A (en) * | 2019-12-21 | 2020-05-08 | 钢研集团稀土科技有限公司 | Method for removing chlorine radicals and aluminum ions in alkali-precipitated high-aluminum rare earth solution |
| CN110964913A (en) * | 2019-12-25 | 2020-04-07 | 中稀(常州)稀土新材料有限公司 | Method for preparing praseodymium-neodymium enrichment by adopting light soda ash precipitation |
| CN115367782A (en) * | 2022-08-22 | 2022-11-22 | 吉水金诚新材料加工有限公司 | Method for preparing low-chlorine rare earth carbonate |
| CN115367782B (en) * | 2022-08-22 | 2023-08-18 | 吉水金诚新材料加工有限公司 | Method for preparing low-chloride rare earth carbonate |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103436697A (en) | Rare-earth carbonate crystallizing and precipitating method for processing aluminum-containing rare-earth feed liquid | |
| CN102267713B (en) | Method for producing high-quality light calcium carbonate by ammonium salt circulation process | |
| CN103789551B (en) | Prepare manganese sulfate electrolyte with electrolytic manganese anode mud and reclaim plumbous method | |
| CN103539283B (en) | Comprehensive treatment method for removing Sb and Bi impurities in Cu electrolyte | |
| CN103101935A (en) | Method for preparing lithium carbonate from coal ash | |
| CN105695751A (en) | Purification process of manganese anode slime | |
| US20150252446A1 (en) | Method for Producing a High-purity Nanometer Zinc Oxide from Steel Plant Smoke and Dust by Ammonia Decarburization | |
| CN102732731A (en) | Method for extracting valuable metals and refining zinc sulphate monohydrate from zinc-containing waste material | |
| CN111115665A (en) | Method for recycling lithium-potassium-rich aluminum electrolyte | |
| CN102951668A (en) | Method for co-producing calcium sulphate and magnesium hydrate by ammonia alkali waste liquid and concentrated seawater | |
| CN1304607C (en) | Shielding iron removing method in high purity aluminium oxide preparation process | |
| CN104561614A (en) | Process for recycling rare earth from south ion adsorption type rare earth ore leaching mother liquor | |
| CN104962739A (en) | Quick impurity removing method for rare earth leach liquor of weathering crust elution-deposited rare earth ores | |
| CN104073634A (en) | Method for removing iron of nickel ore leaching liquid or electrolytic anode liquid | |
| CN103708525B (en) | Production method of high-bulk density fine-grain low-chlorine rare earth carbonate and its oxide | |
| CN102703982A (en) | Method for preparing magnesium carbonate trihydrate crystal whisker by utilizing serpentine | |
| CN104774561A (en) | Method for preparing rare earth polishing powder and recovering ammonium salt by using fluorine-containing niobium-tantalum wastewater | |
| Ge et al. | Minerals recovery from a rare earth extraction wastewater by a combined chemical precipitation and membrane distillation process | |
| CN109022835A (en) | The method without rare earth in ammonium rare earth mother solution is recycled in precisely removal of impurities fractional precipitation | |
| CN102491406B (en) | Method for preparing gallium sulfate | |
| CN103508481B (en) | The method of preparation spectrally-pure superfine silver chloride | |
| CN103265056B (en) | Method for extracting industrial slat from salt mixture | |
| CN107502762A (en) | The method that ion type rareearth leaches mother liquor one-step method removing impurity by means of precipitation Extraction of rare earth | |
| CN104195332B (en) | A kind of preparation method of crystal carbonated rare earth | |
| CN102978399B (en) | Method for producing low chloride fine particle high purity rare earth compound through ultrasonic-assisted oxalate deposition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20131211 |