CN103708525A - Production method of high-bulk density fine-grain low-chlorine rare earth carbonate and its oxide - Google Patents

Production method of high-bulk density fine-grain low-chlorine rare earth carbonate and its oxide Download PDF

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CN103708525A
CN103708525A CN201310624215.6A CN201310624215A CN103708525A CN 103708525 A CN103708525 A CN 103708525A CN 201310624215 A CN201310624215 A CN 201310624215A CN 103708525 A CN103708525 A CN 103708525A
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rare earth
carbonate
bulk density
alkali
production
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CN103708525B (en
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李永绣
丁龙
周新木
张尚虎
方中心
周雪珍
李静
刘艳珠
李东平
韩满旋
申淞夫
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GANSU RARE EARTH NEW MATERIAL CO Ltd
Nanchang University
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GANSU RARE EARTH NEW MATERIAL CO Ltd
Nanchang University
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Abstract

The invention discloses a preparation method a high-bulk density fine-grain low-chlorine rare earth carbonate and its oxide. According to the preparation method, lanthanite-type or tengerite-type rare earth carbonate is put into an alkaline hydrothermal solution having a pH more than 7 and a temperature more than 80 DEG C and the mixed solution undergoes a reaction for more than 30min under the conditions of a liquid-solid ratio of 1: 1 to 50: 1 and a mole ratio of an alkali to the rare earth of 0.5: 1 to 1.1: 1, wherein improvement of the pH value and the temperature is conducive to phase transformation reaction and reaction time shortening; after alkali conversion requirements are satisfied, through filtration, the high-bulk density fine-grain low-chlorine rare earth subcarbonate or deposition products comprising the high-bulk density fine-grain low-chlorine rare earth subcarbonate as a principal crystalline phase is obtained; and the deposition products are calcined to form the corresponding rare earth oxide. The preparation method easily realizes process control, produces the required product, is suitable for production of various single-rare earth elements and mixed rare earth and does not discharge pollutants. Through combination with the original carbonate production method, the production method provided by the invention can improve the production technology of the rare earth carbonate and its oxide and obviously improve product quality.

Description

The production method of high bulk density fine particle low chlorine root rare earth carbonate and oxide compound
 
Technical field
The present invention relates to a kind of method of producing high bulk density fine particle low chlorine root rare earth carbonate and oxide compound thereof.Belong to rare-earth wet method metallurgy and rare earth material field.
Background technology
Carbonated rare earth, as a kind of intermediate raw material and rare earth material presoma of rare earth metallurgy process, is well applied in rare-earth industry.According to the difference of carbonated rare earth kind and requirement, developed many covers carbonated rare earth precipitated crystal method, industrial, be widely used, comprise the production of Rare-earth Mine mixed rare earth carbonate and the production of the single carbonated rare earth of separation plant.Wherein most widely used be University Of Nanchang patented technology " method for crystallizing and sedimenting rare-earth carbonate " (CN1141882A).The method can realize the rapid crystallization of carbonated rare earth, and has guaranteed the purity of product, and its mode of production can be step, can be also continous way, or marginal semi continuous.According to this patented technology, by selecting different crystal region (feed molar ratio is different with temperature range), can produce the rare-earth products with different characteristics.For example: lanthanite type carbonated rare earth, water water chestnut yttrium type carbonated rare earth, low chlorine root carbonated rare earth, high bulk density basic carbonate rare earth.These products are because the crystal region of selecting is different, and the crystal habit of product, phase structure, granular size, bulk density, total amount of rare earth and chloride content have bigger difference.But be also difficult to obtain meeting the carbonated rare earth product of the requirements such as bulk density is high, good dispersity, total amount of rare earth is high, chloride content is low, particle is thin at present simultaneously.
Rare earth carbonate is as the presoma of preparing fluorescent RE powder, polishing powder from rare earth, rare earth permanent-magnetic material, hydrogen storage material and structured material etc., its every quality index is the principal element that affects its performance, wherein main index, except general chemical constitution index, also has bulk density, chloride content and the particle characteristic of product.In order to reach the requirement of these indexs, conventionally need to adopt oxalate precipitation method to produce.The method is good to the separation selectivity of foreign ion, and product purity is high, and bulk density is large, is guaranteeing to have obvious advantage aspect quality product.But the price of oxalic acid is high, poisonous.The environmental benefit of its application and economic benefit are all undesirable.For this reason, people have carried out a large amount of crystallizations about carbonated rare earth and precipitation technology research, have also obtained good effect, and in industrial production, have obtained application.The process that but the precipitation of carbonated rare earth and crystallization are complexity and being difficult to accurately to be controlled, no matter be, change the feed molar ratio of rare earth and precipitation agent or change feed way, because the solubility product of carbonated rare earth is little, easily form amorphous sediment, and the hole of precipitation is many, bulk density is little, and chloride content is high, is difficult to meet production and the growth requirement of growing rare earth new material.For this reason, need to develop the new rare earth carbonate that can simultaneously meet the low chloride content of high bulk density fine particle and the production technology of oxide compound thereof.
The precipitation of carbonated rare earth and crystallization are the processes that a complexity and being difficult to is accurately controlled because precipitation and crystallization are not only subject to the impact of Thermodynamics, and more main be the impact that is subject to kinetic factor.Meanwhile, the solubility product of carbonated rare earth is little, easily forms amorphous precipitated.A series of result of study shows: the crystal property of carbonated rare earth and crystallized product are all subject to the impact of crystallisation process.Under different feed molar ratio and temperature condition, can obtain different products, and crystallization velocity, granule-morphology and size there is very big difference.For example the low proportioning region under normal temperature condition (precipitation agent is not enough, and rare earth ion is excessive) easily obtains the positive carbonate containing eight crystal water of lanthanite type structure, and crystallization velocity is very fast.Product pattern is sheet and the adhesion of bar plate crystal at the macroaggregate of, and granule interior hole is many, and bulk density is little, and total amount of rare earth is between 40-50%, and chloride content is at hundreds of mg/kg; And at high mixture ratio region (precipitation agent is excessive), crystallization velocity is slow, easily obtain plate crystal, bulk density is low, and chloride content can be controlled at below 50 mg/kg.The low proportioning region of (40-80 ℃) under mesophilic condition, can obtain the positive carbonate containing 2-3 crystal water of water water chestnut yttrium type structure, crystallization velocity is fast, product pattern is the aggregate of wire crystallization adhesion, bulk density is little, total amount of rare earth is between 60-68%, and chloride content can be controlled at below 100 mg/kg easily.Under hot conditions, (more than 80 ℃), can obtain subcarbonate, and crystallization velocity is fast, the aggregate that product is spheroidal particle, and bulk density is high, and chloride content is sometimes higher than 1%, generally between 1000-6000mg/kg.Therefore, adopt aforesaid method to be all difficult to obtain meeting the rare-earth products of high bulk density, low chlorine root, fine particle requirement simultaneously.
Summary of the invention
The object of the invention is to provide for the deficiencies in the prior art the production method of a kind of high bulk density fine particle low chlorine root rare earth carbonate and oxide compound.
Technological line of the present invention is: the phase transformation characteristic based between carbonated rare earth is studied and determined new carbonated rare earth preparation method.Its main policies is to obtain in advance the positive carbonate of big particle agglomerate intermediate rare earth, through solid-liquid separation and after fully removing foreign ion, by phase, change to obtain fine particle high purity product, in phase transition process, there is the hydrolysis reaction of carbonate and the dissolving-recrystallization of crystallization, make the positive carbonate of the low bulk density of the high chlorine root of macrobead in this process, by above-mentioned effect, obtain the subcarbonate of the high bulk density of low chlorine root fine granularity, then calcine and obtain oxide compound.The distinguishing feature of this approach is to have overcome thin (micron, submicron be nano level yardstick even) particulate product in the past to produce the shortcoming of upper liquid-solid separation difficulty.
The production method processing step of a kind of high bulk density fine particle low chlorine root rare earth carbonate of the present invention and oxide compound is as follows:
[1] lanthanite type or water water chestnut yttrium type carbonated rare earth are placed in to pH value more than 7 and 80 ℃ of above hot alkali water solution of temperature react more than 30 minutes, optimal ph scope is between 10~13, optimum temperature range is between 90~100 ℃, its solid-to-liquid ratio is 1-50:1, and alkali is 0.5-1:1 with the ratio of the amount of substance of rare earth; Carbonated rare earth used can be Rare Earth Elements Determination or their mixed carbonate; The alkali of described regulator solution alkalescence can be the oxyhydroxide of sodium, potassium, ammonium; Phase transformation reaction is with intermittent type or continous way or marginal semi continuous mode, to carry out in reactor, reactor or reactive tank, or in continous way mode, carries out in tubular reactor; The carbonated rare earth that phase conversion reaction is required and alkali adopt one or many or continuous mode to add according to above-mentioned different reactive mode;
[2] reactant step [1] being obtained obtains the basic carbonate rare earth that high bulk density, fine particle and low chlorine root require or take its precipitated product that is principal crystalline phase without cold filtration;
[3] by the calcining of gained precipitated product, obtain corresponding rare earth oxide;
[4] it is capable of circulation as the alkali aqueous solution in step [1] in filtrate, adding after alkali, or is directly used in preparation precipitation agent and is recycled in carbonated rare earth is produced.
Beneficial effect of the present invention:
In the present invention, carbonated rare earth used can be Rare Earth Elements Determination or their mixed carbonate, and they can directly be bought from the market, also can adopt existing method for crystallizing and sedimenting rare-earth carbonate oneself to produce; Alkali used can be the oxyhydroxide of sodium, potassium, ammonium; Phase transformation reaction can be in various types of reactors, reactor, reactive tank be carried out with intermittent type or continous way or marginal semi continuous mode, also can in tubular reactor, in continous way mode, carry out; The carbonated rare earth that phase conversion reaction is required and alkali can according to above-mentioned different reactive mode adopt disposable or repeatedly even continuous mode add.Filtrate can all recycle, and therefore, its filter operation need not be cooling, is preferably under hot condition and completes, and hot solution can be circulated immediately, saves energy.
The present invention also can require to determine according to quality product and carry out crystalline phase transforming degree, and products obtained therefrom is soda ash formula carbonated rare earth preferably, can be also to take the mixed crystallization product that includes the positive carbonated rare earth of part or rare earth hydrate that basic carbonate rare earth is principal crystalline phase.This is conducive to each manufacturer and according to market demands, regulates and controls bulk density and the chloride content of product, regulates product granularity and size-grade distribution, determines corresponding alkali dosage and reaction times.The reinforced precipitated crystal long reaction time of high temperature of existing industrial employing, operating environment is poor, and chlorine root is carried secretly with adsorptive capacity large, and washing process is very long, and bath water amount is large.And employing the art of this patent can overcome above-mentioned deficiency, Reaction time shorten, reduces washing water consumption, and energy efficient also reduces discharge of wastewater.Method is simple, has application prospect very widely.
Accompanying drawing explanation
The low chlorine root of the high bulk density fine particle rare earth carbonate production process schematic diagram that Fig. 1, phase transformation reaction combine with crystallizing and sedimenting rare-earth carbonate and form;
Fig. 2, the lanthanite type praseodymium carbonate neodymium changing trend diagram of pH during ageing in the hydrothermal solution of different Initial pHs;
The SEM comparison of lanthanite type praseodymium carbonate neodymium (A) and basic carbonate praseodymium neodymium (B) before and after Fig. 3, inversion of phases;
Fig. 4, inversion of phases pH and time are to sample D 50(A), the impact of dispersed (B), bulk density (C) and chlorine root (D);
The XRD comparison of Fig. 5, lanthanite type praseodymium carbonate neodymium ageing different time gained sample under different pH values;
XRD comparison before and after Fig. 6, water water chestnut yttrium type praseodymium carbonate neodymium inversion of phases;
The SEM comparison of water water chestnut yttrium type praseodymium carbonate neodymium (A) and basic carbonate praseodymium neodymium (B) before and after Fig. 7, inversion of phases;
The comparison of the size-grade distribution of water water chestnut yttrium type praseodymium carbonate neodymium (A) and basic carbonate praseodymium neodymium (B) before and after Fig. 8, inversion of phases;
Fig. 9, lanthanite type Phosbloc carry out the pH value changing trend diagram in phase conversion reaction process under different pH;
The SEM comparison of lanthanite type Phosbloc (A) and basic carbonate lanthanum (B) before and after Figure 10, inversion of phases;
Figure 11, lanthanite type sample inversion of phases pH and time are to sample D 50(A), the impact of dispersed (B), bulk density (C) and chlorine root (D);
The XRD comparison of Figure 12, lanthanite type Phosbloc ageing different time gained sample under different pH values;
Figure 13, lanthanite type cerous carbonate carry out the pH value changing trend diagram in phase conversion reaction process under different pH;
The SEM comparison of lanthanite type cerous carbonate (A) and basic carbonate cerium (B) before and after Figure 14, inversion of phases;
Figure 15, inversion of phases pH and time are to sample D 50(A), the impact of dispersed (B), bulk density (C) and chlorine root (D);
The XRD comparison of Figure 16, lanthanite type cerous carbonate ageing different time gained sample under different pH values;
Figure 17, Phosbloc and cerous carbonate are at pH=13 and constantly add the variation diagram of pH in the phase conversion reaction process of alkali.
Embodiment
Embodiment 1
30g lanthanite type praseodymium carbonate neodymium is added in beaker, add the distilled water of 300ml.Under room temperature, the pH of water or sodium hydroxide solution difference regulator solution is 7,9,11,12,13,14.Be placed in the thermostat water bath constant temperature ageing of 95 ℃, (total reaction times is no more than 5h) sampling at set intervals, with the pH value of at room temperature measuring aaerosol solution after water quench, the variation of recording pH value in reaction process; Phenomenon in observing response process, sees in reaction process and has a large amount of bubbles to overflow, and treats that bubble, overflowing and supernatant liquor clarification, reacts and finishes, and filtering and washing after having reacted is dried gained crystallization and obtain subcarbonate sample at 50 ℃.Resulting praseodymium carbonate neodymium sample is carried out to the analytical tests such as XRD, SEM, granularity, bulk density, chloride content.
The variation of pH value in reaction process is drawn as Fig. 2.Result shows, during pH=14, whole reaction process pH value is substantially constant, when initial pH is within the scope of 7-12, lanthanite type praseodymium carbonate neodymium changes the pH value of solution after basic carbonate praseodymium neodymium completely into and all can be reduced to below 9, within the qualified claimed range in industrial discharge water.Initial pH is 13 o'clock, and after transforming completely, pH value of solution is 9.48, and this class waste water can not directly discharge, but can continue to add alkali for alkali conversion reaction, recycle or for preparing precipitation agent.SEM is as Fig. 3, and wherein A figure is the lanthanite type praseodymium carbonate neodymium of preparing under normal temperature, and its pattern is the stacked agglomerating particles of tabular crystal, has many holes.The solid bulk density of this pattern is little, and the chlorion of its forming process parcel is also many.B figure is basic carbonate praseodymium neodymium, owing to having there is phase conversion, causes the original macrobead of assembling to dissociate, the product good dispersity obtaining, and the pattern of particle is more carefully and more uniform.Fig. 4 is granularity, size-grade distribution, the bulk density of ageing different time gained sample under different Initial pHs, the measurement result of chloride content.Result shows: crystallization conversion can cause significantly reducing of grain graininess, and particle distribution range narrows down, and dispersed little, bulk density increases, and chloride ion content also significantly reduces.There is depolymerization and the recrystallization of crystal in these presentation of results, grain graininess is reduced in inversion of phases process, distribution narrow, and then be convenient to the accumulation between particle, cause bulk density to increase; Also can make the chlorion that was originally wrapped in granule interior discharge, thereby the chloride content in product is reduced.The XRD results of comparison of difference Initial pH different ageing institute sample thief is as Fig. 5.As can be drawn from Figure 5, lanthanite type praseodymium carbonate neodymium all can be realized phase and transform within the scope of the pH of experiment, but change the needed time of subsalt completely into, is different.At pH=13 and 14, can in 1h, complete inversion of phases.In pH=7 and 9, the XRD of ageing 3h gained sample shows the diffraction peak that still has lanthanite type praseodymium carbonate neodymium, but the data of chlorine root, bulk density and the granularity of contrast Fig. 4, phase conversion reaction has still reached the effect that reduces chlorine root and granularity raising bulk density, and just the reaction times is long.To sum up best reaction pH is between 11 ~ 13, and the reaction times can be controlled in 2h, have a good application prospect.
Embodiment 2
Adopt the similar method of embodiment 1, using water water chestnut yttrium type praseodymium carbonate neodymium instead is raw material, by inversion of phases, prepares basic carbonate praseodymium neodymium.20g water water chestnut yttrium type praseodymium carbonate neodymium sample is placed in 1200ml water, and under pH=12,95 ℃ of poach 15h of constant temperature obtain pure basic carbonate praseodymium neodymium, calcine and obtain oxide compound.By resulting praseodymium carbonate neodymium sample carry out XRD, SEM, granularity, bulk density, chloride content and etc. analytical test.XRD result is as Fig. 6.As we know from the figure, after inversion of phases after, water water chestnut yttrium type praseodymium carbonate neodymium thing disappears mutually, the thing of product is basic carbonate praseodymium neodymium mutually.SEM is as Fig. 7, from figure, can obtain, 95 ℃ of waters bath with thermostatic control process after the pattern of sample there is obvious variation, from the elongated crystallization of water water chestnut yttrium type of long strip shape, become short and small bar-shaped subsalt, proved that from another point of view before and after processing, the thing of sample is different mutually, occurred to change mutually.Size-grade distribution is as Fig. 8, from Fig. 8 A, and the D of water water chestnut yttrium type praseodymium carbonate neodymium 50=28.15 μ m, the known D that wants to transform rear subsalt from Fig. 8 B 50=3.037 μ m, pass through D 50variation, can know that the particle of crystal obviously diminishes and attenuates after inversion of phases.Record, the 1487ppm of chloride content before transforming becomes the 166ppm after conversion simultaneously, and chloride content sharply reduces, and bulk density is brought up to the 1.10g/ml after inversion of phases by the 0.6g/ml before transforming.To sum up, by inversion of phases, by the water water chestnut yttrium type praseodymium carbonate neodymium of the low bulk density of high chlorine root macrobead, obtained the basic carbonate praseodymium neodymium of the high bulk density of the low chlorine root of fine particle.
Embodiment 3
30g lanthanite type Phosbloc is added in beaker, the distilled water that adds 300ml, under room temperature, the pH of water or sodium hydroxide solution difference regulator solution is 10,11,12,13, constant temperature ageing in the thermostat water bath of 95 ℃, (total reaction times is no more than 5h) sampling at set intervals, with the pH value of at room temperature measuring aaerosol solution after water quench, the variation of recording pH value in reaction process; Phenomenon in observing response process, sees in reaction process and has a large amount of bubbles to overflow, and treats that bubble, overflowing and supernatant liquor clarification, reacts and finishes.Filtering and washing after having reacted is dried gained crystallization and obtain subcarbonate sample at 50 ℃, obtains oxide compound sample after 1000 ℃ of calcinings.To resulting Phosbloc sample carry out XRD, SEM, granularity, bulk density, chloride content and etc. analytical test.
In reaction process, the variation of pH is as Fig. 9, and as we know from the figure, in the initial 50min of reaction, pH sharply declines, and after question response 4h, pH value is all less than 9; SEM is as Figure 10, and Figure 10 A is the SEM figure before transforming, and Figure 10 B is the SEM figure after transforming.Can find out, before and after transforming there is obvious variation in the pattern of sample, from bulk sheet accumulation type particle, becomes the spherical subsalt of the uniform class of compact grain, and this bulk density that proves from the side sample is improving greatly through bulk density after inversion of phases; Figure 11 is granularity, size-grade distribution, the bulk density of ageing different time gained sample under different Initial pHs, the measurement result of chloride content.Result shows, crystallization conversion can cause significantly reducing of grain graininess, and particle distribution range narrows down, and dispersed little, bulk density increases, and chloride ion content also significantly reduces; Under different pH, the XRD of different time sampling is relatively as Figure 12.From figure, result can be found out, locates to still have the diffraction peak of lanthanite type Phosbloc after inversion of phases in 2 θ=10 °, not yet transforms completely.But the data of chloride content, bulk density and size-grade distribution that contrast records, can know that it has obtained the fine grain basic carbonate lanthanum of the low chlorine root of high bulk density after inversion of phases.Therefore, in actual production, can not pursue completely and to transform, as long as product reaches, reduce chlorine root, improve bulk density and reduce the requirement of granularity.In fact, between pH=12 ~ 13, digestion time 2 ~ 4h can make most of lanthanite type Phosbloc be converted into basic carbonate lanthanum, the product that to obtain take basic carbonate lanthanum be principal crystalline phase.After calcining, obtain rare earth oxide.
Embodiment 4
30g lanthanite type cerous carbonate is added in beaker, the distilled water that adds 300ml, under room temperature, the pH of water or sodium hydroxide solution difference regulator solution is 10,11,12,13,14, constant temperature ageing in the thermostat water bath of 95 ℃, (total reaction times is no more than 5h) sampling at set intervals, with the pH value of at room temperature measuring aaerosol solution after water quench, the variation of recording pH value in reaction process; Phenomenon in observing response process, seeing in reaction process has a large amount of bubbles to overflow, treat that bubble is in effusion and supernatant liquor clarification, reaction finishes, filtering and washing after having reacted, gained crystallization is dried and obtained at 50 ℃ subcarbonate sample, after 1000 ℃ of calcinings, obtain oxide compound sample.To resulting cerous carbonate sample carry out XRD, SEM, granularity, bulk density, chloride content and etc. analytical test.
In reaction process, the variation of pH is as Figure 13.As we know from the figure, in the initial 50min of reaction, pH sharply declines, until pH value is all less than 9 after reaction 4h; SEM is as Figure 14, and Figure 14 A is the SEM figure before transforming, and Figure 14 B is the SEM figure after transforming, and prove that obvious variation has occurred the pattern that transforms front and back sample, from bulk sheet accumulation type particle, becomes the subsalt of the uniform spherical particle of compact grain; Figure 15 is granularity, size-grade distribution, the bulk density of ageing different time gained sample under different Initial pHs, the measurement result of chloride content.Result shows, crystallization conversion can cause significantly reducing of grain graininess, and particle distribution range narrows down, and dispersed little, bulk density increases, and chloride ion content also significantly reduces; Under different pH, the XRD of different time sampling is relatively as Figure 16, as can be seen from the figure, pH=10 and 11 o'clock, after inversion of phases, still have the diffraction peak of obvious lanthanite type cerous carbonate, not yet transform completely, pH=12 and 13 o'clock, inversion of phases was than more completely, the data of chloride content, bulk density and size-grade distribution that contrast records, can know and after inversion of phases, can obtain the fine grain basic carbonate cerium of the low chlorine root of high bulk density.To sum up, reaching reduction chlorine root raising bulk density and reducing under the requirement of granularity, between pH=12 ~ 13, digestion time 2 ~ 4h can prepare basic carbonate cerium by lanthanite type cerous carbonate inversion of phases.
Embodiment 5
Lanthanite type cerous carbonate and Phosbloc that 20g is dry are placed in respectively 2 clean beakers, add respectively 300ml distilled water, at room temperature with the NaOH of 10mol/L, regulate pH=13, this two beaker is placed in to 95 ℃ of water waters bath with thermostatic control, pH value under 5min assaying reaction solution room temperature, the phenomenon in observing response process.Along with the carrying out of reaction, pH value declines, and has a large amount of bubbles to overflow.When pH value is less than 12, the NaOH that drips 10mol/L remains in 12 ~ 13 scope pH value, until the pH of reaction no longer declines and is not less than 12, bubble is no longer overflowed and supernatant liquor clarification, stop dripping NaOH, the ratio between the amount of the alkali that calculating drips and the amount of the rare earth carbonate adding.The add-on of known lanthanum and cerium is respectively 0.0665mol and 0.0662mol, and the add-on of the NaOH of 10mol/L is 5.75ml, i.e. 0.0575mol, and the ratio that calculates their amount of substance is: La:OH -=1:0.8651, Ce:OH -=1:0.8687.Prove that actual consumption amount hydroxy is smaller than theoretic 1:1, this is because the hydrolysis reaction of the carbonate out that dissociates can produce a part of hydroxide radical.When not needing to transform completely, can add less alkali; When guaranteeing rare earth carbonate generation inversion of phases as much as possible, can improve the consumption of alkali.Integrate consideration, in conversion process, the dosage of alkali is counted between 0.5 ~ 1.1 with the ratio of the amount of substance of hydroxide radical and rare earth.
Figure 17 is the variation diagram of pH value in conversion process, and the part that the pH in figure sharply declines is free OH in Phosbloc and cerous carbonate and solution -reaction.The speed declining from pH, reacted required time about 30 minutes.After adding alkali to regulate pH, pH rises, since bubble after reaction times 75min, do not overflowing, and supernatant liquor clear.Now to the 4h to last during this period of time in the pH of solution be in a stable state, and bubble no longer overflows, supernatant liquor clear after precipitation sedimentation, can infer that inversion of phases completes, pH value is almost constant.
In actual production process, in order to accelerate inversion of phases process, we can make conversion reaction within the scope of a higher pH, carry out all the time, between 12-13.After inversion of phases completes, the pH value of supernatant liquor remains between 12 ~ 13, can be directly used in conversion reaction next time after filtering out solid product.For this reason, alkali conversion process can be designed to periodical operation process, also can be designed to the operate continuously process of continuous charging and continuous discharge, or marginal semi continuous operation process.The regulation and control of carbonated rare earth and alkali dosage can be directly observing and controlling by pH value realize.The equipment of realizing alkali conversion operation can be reactor, reactive tank, the retort of all size.In conversion operation, can also adopt pipe reaction crystallizer continuously, carbonated rare earth is exactly to realize the required time that transforms from entering to the time out, and after filtering, solution reenters reaction tubes, and solution is realized continuous circulation and used.Only have the concentration of sodium carbonate and sodium-chlor in the clear liquid to reach certain numerical value, in the time of can having influence on the chloride content in product, not continuing on for alkali transforms, but use instead in precipitating rare earth, prepare positive carbonate, not only make water obtain recycle, the sodium carbonate that conversion process produces has also obtained utilization, the main sodium chloride-containing of filtrate or ammonium chloride after precipitating rare earth, can electrolytic preparation sodium hydroxide and hydrochloric acid, or be converted into hydrochloric acid and vitriol with additive method, make whole process form a systemic circulation, improved the utilization ratio of water, guaranteed the maximum utilization of resource, avoided waste.

Claims (3)

1. a production method for high bulk density fine particle low chlorine root rare earth carbonate and oxide compound, is characterized in that:
[1] lanthanite type or water water chestnut yttrium type carbonated rare earth are placed in to pH value more than 7 and 80 ℃ of above hot alkali water solution of temperature react more than 30 minutes, its solid-to-liquid ratio is 1-50:1, and alkali is 0.5-1:1 with the ratio of the amount of substance of rare earth; Phase transformation reaction is with intermittent type or continous way or marginal semi continuous mode, to carry out in reactor, reactor or reactive tank, or in continous way mode, carries out in tubular reactor; The carbonated rare earth that phase conversion reaction is required and alkali adopt one or many or continuous mode to add according to above-mentioned different reactive mode;
[2] reactant step [1] being obtained obtains the basic carbonate rare earth that high bulk density, fine particle and low chlorine root require or take its precipitated product that is principal crystalline phase without cold filtration;
[3] by the calcining of gained precipitated product, obtain corresponding rare earth oxide;
[4] it is capable of circulation as the alkali aqueous solution in step [1] in filtrate, adding after alkali, or is directly used in preparation precipitation agent and is recycled in carbonated rare earth is produced.
2. the production method of a kind of high bulk density fine particle low chlorine root rare earth carbonate according to claim 1 and oxide compound, is characterized in that: described carbonated rare earth is Rare Earth Elements Determination or their mixed carbonate.
3. the production method of a kind of high bulk density fine particle low chlorine root rare earth carbonate according to claim 1 and oxide compound, is characterized in that: the alkali of described regulator solution alkalescence is the oxyhydroxide of sodium, potassium, ammonium.
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CN106915761A (en) * 2015-12-28 2017-07-04 安集微电子科技(上海)有限公司 A kind of cerium oxide preparation method and its application in STI chemically mechanical polishings
CN106915760A (en) * 2015-12-28 2017-07-04 安集微电子科技(上海)有限公司 A kind of preparation method of cerium oxide and its application in STI polishing fields
CN107043122A (en) * 2017-05-18 2017-08-15 赣州晨光稀土新材料股份有限公司 A kind of continuous method for producing rare earth compound precipitation
CN107188215A (en) * 2017-05-24 2017-09-22 中国北方稀土(集团)高科技股份有限公司 The method that reaction end is automatically adjusted in carbonated rare earth continuous precipitation production process

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CN105800664A (en) * 2014-12-29 2016-07-27 安集微电子(上海)有限公司 Method for preparing ceria abrasive and application thereof in CMP (Chemical Mechanical Polishing)
CN106915761A (en) * 2015-12-28 2017-07-04 安集微电子科技(上海)有限公司 A kind of cerium oxide preparation method and its application in STI chemically mechanical polishings
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CN107043122A (en) * 2017-05-18 2017-08-15 赣州晨光稀土新材料股份有限公司 A kind of continuous method for producing rare earth compound precipitation
CN107188215A (en) * 2017-05-24 2017-09-22 中国北方稀土(集团)高科技股份有限公司 The method that reaction end is automatically adjusted in carbonated rare earth continuous precipitation production process

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