CN103708525B - 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 PDFInfo
- Publication number
- CN103708525B CN103708525B CN201310624215.6A CN201310624215A CN103708525B CN 103708525 B CN103708525 B CN 103708525B CN 201310624215 A CN201310624215 A CN 201310624215A CN 103708525 B CN103708525 B CN 103708525B
- Authority
- CN
- China
- Prior art keywords
- rare earth
- bulk density
- carbonate
- alkali
- reaction
- 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.)
- Expired - Fee Related
Links
Landscapes
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
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
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 of rare earth metallurgy process and rare earth material presoma, is well applied in rare-earth industry.According to the difference of carbonated rare earth kind and requirement, develop many covers carbonated rare earth precipitated crystal method, be industrially widely used, comprised 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 is patented technology " method for crystallizing and sedimenting rare-earth carbonate " (CN1141882A) of University Of Nanchang.The method can realize the rapid crystallization of carbonated rare earth, and ensure that the purity of product, and its mode of production can be step, also can be continous way, or marginal semi continuous.According to this patented technology, by selecting different crystal regions (feed molar ratio is different with temperature range), the rare-earth products with different characteristics can be produced.Such as: 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 due to the crystal region selected different, the crystal habit of product, Phase stracture, granular size, bulk density, total amount of rare earth and chloride content have bigger difference.But be also difficult to the carbonated rare earth product simultaneously being met the requirements such as bulk density is high, good dispersity, total amount of rare earth are high, chloride content is low, particle is thin at present.
Rare earth carbonate is as the presoma 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 affecting its performance, wherein main index, except general chemical constitution index, also has the bulk density of product, chloride content and particle characteristic.In order to reach the requirement of these indexs, usually 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, in guarantee quality product, have obvious advantage.But the price of oxalic acid is high, poisonous.Environmental benefit and the economic benefit of its application are all undesirable.For this reason, people have carried out a large amount of crystallizations about carbonated rare earth and precipitation technology is studied, and also achieve good effect, and obtain application in industrial production.But the precipitation of carbonated rare earth and crystallization are a complexity and are difficult to the process of accurately control, be no matter change rare earth and precipitation agent feed molar ratio or change feed way, because the solubility product of carbonated rare earth is little, easy formation amorphous sediment, and the hole of precipitation is many, bulk density is little, and chloride content is high, is difficult to the production and the growth requirement that meet growing rare earth new material.For this reason, need to develop and new can meet the rare earth carbonate of the low chloride content of high bulk density fine particle and the production technology of oxide compound thereof simultaneously.
The precipitation of carbonated rare earth and crystallization are a complexity and are difficult to the process of accurately control, because precipitation and crystallization are not only by the impact of Thermodynamics, and more importantly by the impact of kinetic factor.Meanwhile, the solubility product of carbonated rare earth is little, is easily formed amorphous precipitated.A series of result of study shows: the crystal property of carbonated rare earth and crystallized product are all by the impact of crystallisation process.Can obtain different products under different feed molar ratio and temperature condition, and crystallization velocity, granule-morphology and size there is very big difference.Low proportioning region (precipitation agent is not enough, and rare earth ion is excessive) such as under normal temperature condition easily obtains the positive carbonate containing eight crystal water of lanthanite type structure, and crystallization velocity is very fast.Product morphology is sheet and the adhesion of bar plate crystal at the macroaggregate of a piece, 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 control at below 50mg/kg.The low proportioning region of (40-80 DEG C) under mesophilic condition, the positive carbonate containing 2-3 crystal water of water water chestnut yttrium type structure can be obtained, crystallization velocity is fast, product morphology is the aggregate of wire crystallization adhesion, bulk density is little, total amount of rare earth is between 60-68%, and chloride content can control at below 100mg/kg easily.Under the high temperature conditions (more than 80 DEG C), can obtain subcarbonate, crystallization velocity is fast, and product is the aggregate of spheroidal particle, and bulk density is high, chloride content sometimes higher than 1%, generally between 1000-6000mg/kg.Therefore, aforesaid method is adopted all to be difficult to the rare-earth products simultaneously being met high bulk density, low chlorine root, fine particle requirement.
Summary of the invention
The object of the invention is the production method that a kind of high bulk density fine particle low chlorine root rare earth carbonate and oxide compound are provided for the deficiencies in the prior art.
Technological line of the present invention is: determine new carbonated rare earth preparation method based on the phase in version properties study between carbonated rare earth.Its main policies obtains the positive carbonate of big particle agglomerate intermediate rare earth in advance, changed by phase after solid-liquid separation also fully removes foreign ion and obtain fine particle high purity product, the hydrolysis reaction of carbonate and the dissolving-recrystallization of crystallization is there is in phase in version process, make the positive carbonate of the low bulk density of macrobead height chlorine root be obtained the subcarbonate of low chlorine root fine granularity height bulk density in this process by above-mentioned effect, then calcine and obtain oxide compound.The distinguishing feature of this approach overcomes thin (micron, submicron even nano-scale dimension) particulate product in the past to produce the shortcoming of upper solid-liquor separation difficulty.
The production method processing step of a kind of high bulk density fine particle of the present invention low chlorine root rare earth carbonate and oxide compound is as follows:
[1] lanthanite type or water water chestnut yttrium type carbonated rare earth are placed in the hot alkali water solution reaction more than 30 minutes of pH value more than 7 and temperature more than 80 DEG C, optimal ph scope is between 10 ~ 13, optimum temperature range is between 90 ~ 100 DEG C, 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 in version reaction carries out with intermittent type or continous way or marginal semi continuous mode in reactor, reactor or reactive tank, or carry out in continous way mode in tubular reactor; Carbonated rare earth needed for phase conversion reaction and alkali adopt one or many or continuous print mode to add according to above-mentioned different reactive mode;
[2] reactant step [1] obtained obtains without the need to cold filtration basic carbonate rare earth that high bulk density, fine particle and low chlorine root require or the precipitated product that is principal crystalline phase with it;
[3] gained precipitated product is calcined, obtain corresponding rare earth oxide;
[4] to add after alkali the i.e. alkali aqueous solution be used as in step [1] capable of circulation in filtrate, or be directly used in preparation precipitation agent and recycled in carbonated rare earth is produced.
Beneficial effect of the present invention:
Carbonated rare earth used in the present invention can be Rare Earth Elements Determination or their mixed carbonate, and they can directly commercially, 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 in version reaction can be carried out with intermittent type or continous way or marginal semi continuous mode in various types of reactor, reactor, reactive tank, also can carry out in continous way mode in tubular reactor; Carbonated rare earth needed for phase conversion reaction and alkali can according to above-mentioned different reactive mode adopt disposable or repeatedly even continuous print mode add.Filtrate can all recycle, and therefore, its filter operation need not cool, and preferably completes under thermal conditions, and the solution of heat is circulated immediately, saves energy.
The present invention also can require determine to carry out crystalline phase transforming degree according to quality product, and products obtained therefrom is soda ash formula carbonated rare earth preferably, also can be with the mixed crystallization product of basic carbonate rare earth to be principal crystalline phase the include positive carbonated rare earth of part or rare earth hydrate.This is conducive to each manufacturer regulates and controls product bulk density and chloride content according to market demands, regulates product granularity and size-grade distribution, determines corresponding alkali dosage and reaction times.The high temperature that applicable industry adopts feeds in raw material precipitated crystal long reaction time, and 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 adopt the art of this patent, can overcome above-mentioned deficiency, Reaction time shorten, reduce washing water consumption, energy efficient also reduces discharge of wastewater.Method is simple, has application prospect widely.
Accompanying drawing explanation
The reaction of Fig. 1, phase in version to combine with crystallizing and sedimenting rare-earth carbonate the high bulk density low chlorine root fine particle rare earth carbonate production process schematic diagram formed;
Fig. 2, the lanthanite type praseodymium carbonate neodymium changing trend diagram of solution ph during ageing in the hydrothermal solution of different initial ph value;
Before and after Fig. 3, inversion of phases, the SEM of lanthanite type praseodymium carbonate neodymium (A) and basic carbonate praseodymium neodymium (B) compares;
Fig. 4, inversion of phases pH and time are to sample D
50(A), the impact of dispersiveness (B), bulk density (C) and chlorine root (D);
The XRD of Fig. 5, lanthanite type praseodymium carbonate neodymium ageing different time gained sample at various ph values compares;
Before and after Fig. 6, water water chestnut yttrium type praseodymium carbonate neodymium inversion of phases, XRD compares;
Before and after Fig. 7, inversion of phases, the SEM of water water chestnut yttrium type praseodymium carbonate neodymium (A) and basic carbonate praseodymium neodymium (B) compares;
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;
Before and after Figure 10, inversion of phases, the SEM of lanthanite type Phosbloc (A) and basic carbonate lanthanum (B) compares;
Figure 11, lanthanite type sample inversion of phases pH and time are to sample D
50(A), the impact of dispersiveness (B), bulk density (C) and chlorine root (D);
The XRD of Figure 12, lanthanite type Phosbloc ageing different time gained sample at various ph values compares;
Figure 13, lanthanite type cerous carbonate carry out the pH value changing trend diagram in phase conversion reaction process under different pH;
Before and after Figure 14, inversion of phases, the SEM of lanthanite type cerous carbonate (A) and basic carbonate cerium (B) compares;
Figure 15, inversion of phases pH and time are to sample D
50(A), the impact of dispersiveness (B), bulk density (C) and chlorine root (D);
The XRD of Figure 16, lanthanite type cerous carbonate ageing different time gained sample at various ph values compares;
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, adds the distilled water of 300ml.The pH of regulator solution is distinguished 7,9,11,12,13,14 with water or sodium hydroxide solution under room temperature.Be placed in the thermostat water bath constant temperature ageing of 95 DEG C, at set intervals (total reaction times is no more than 5h) sampling, by the pH value at room temperature measuring aaerosol solution after water quench, the change of pH value in record reaction process; Phenomenon in observing response process, sees in reaction process and has a large amount of bubble to overflow, and treats bubble not overflowing and supernatant liquor clarification, then reacts end, filtering and washing after having reacted, gained crystallization dried at 50 DEG C and obtain subcarbonate sample.The analytical tests such as XRD, SEM, granularity, bulk density, chloride content are carried out to obtained praseodymium carbonate neodymium sample.
The change 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, after lanthanite type praseodymium carbonate neodymium changes basic carbonate praseodymium neodymium completely into, the pH value of solution all can be reduced to less than 9, within the Eligibility requirements scope being in industrial discharge water.When initial ph value is 13, after transforming completely, pH value of solution is 9.48, and this kind of 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 prepared 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, transforms owing to there occurs phase, causes the original macrobead assembled to dissociate, the product good dispersity obtained, and the pattern of particle more carefully and more uniform.Fig. 4 is the measurement result of the granularity of ageing different time gained sample under different initial ph value, size-grade distribution, bulk density, chloride content.Result shows: crystallization conversion can cause the remarkable reduction of grain graininess, and particle distribution range narrows, and dispersed little, bulk density increases, and chloride ion content also significantly reduces.These results illustrate in inversion of phases process, there occurs crystal depolymerization and recrystallization, grain graininess are reduced, distribution narrow, and then are convenient to the accumulation between particle, cause bulk density to increase; Also the chlorion being originally wrapped in granule interior can be made to discharge, thus the chloride content in product is reduced.The XRD results of comparison of different initial ph value different ageing institutes sample thief is as Fig. 5.As can be drawn from Figure 5, lanthanite type praseodymium carbonate neodymium all can realize phase and transform within the scope of the pH of experiment, but the time of changing into completely required for subsalt is different.Inversion of phases can be completed in 1h at pH=13 and 14.When pH=7 and 9, the XRD display of ageing 3h gained sample still has the diffraction peak of lanthanite type praseodymium carbonate neodymium, but the data of the chlorine root of contrast Fig. 4, bulk density and granularity, phase conversion reaction still reaches the effect reducing 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 control within 2h, has a good application prospect.
Embodiment 2
Adopt the method that embodiment 1 is similar, using water water chestnut yttrium type praseodymium carbonate neodymium instead is raw material, prepares basic carbonate praseodymium neodymium by inversion of phases.20g water water chestnut yttrium type praseodymium carbonate neodymium sample is placed in 1200ml water, and under pH=12, constant temperature 95 DEG C of poach 15h obtain pure basic carbonate praseodymium neodymium, calcine and obtain oxide compound.Obtained praseodymium carbonate neodymium sample is carried 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 after inversion of phases, water water chestnut yttrium type praseodymium carbonate neodymium thing disappears mutually, and the thing of product is basic carbonate praseodymium neodymium mutually.SEM is as Fig. 7, can obtain from figure, after 95 DEG C of water bath with thermostatic control process, the pattern of sample there occurs obvious change, becomes short and small rod-like basic type salt from the elongated crystallization of water water chestnut yttrium type of long strip shape, the thing demonstrating sample before and after process is from another point of view different mutually, there occurs phase in version.Size-grade distribution as Fig. 8, from Fig. 8 A, the D of water water chestnut yttrium type praseodymium carbonate neodymium
50=28.15 μm, knownly from Fig. 8 B want the D transforming rear subsalt
50=3.037 μm, pass through D
50change, after can knowing inversion of phases, the particle of crystal obviously diminishes and attenuates.Record, chloride content becomes the 166ppm after conversion from the 1487ppm before transforming, and chloride content sharply reduces simultaneously, and bulk density brings up to the 1.10g/ml after inversion of phases by the 0.6g/ml before transforming.To sum up, by inversion of phases, obtained the basic carbonate praseodymium neodymium of fine particle low chlorine root height bulk density by the water water chestnut yttrium type praseodymium carbonate neodymium of the low bulk density of high chlorine root macrobead.
Embodiment 3
30g lanthanite type Phosbloc is added in beaker, add the distilled water of 300ml, the pH of regulator solution is distinguished 10,11,12,13 with water or sodium hydroxide solution under room temperature, constant temperature ageing in the thermostat water bath of 95 DEG C, (total reaction times is no more than 5h) sampling at set intervals, by the pH value at room temperature measuring aaerosol solution after water quench, the change of pH value in record reaction process; Phenomenon in observing response process, sees in reaction process and has a large amount of bubble to overflow, and treats bubble not overflowing and supernatant liquor clarification, then reacts end.Filtering and washing after having reacted, dries gained crystallization and obtains subcarbonate sample at 50 DEG C, after 1000 DEG C of calcinings, obtain oxide samples.To obtained Phosbloc sample carry out XRD, SEM, granularity, bulk density, chloride content and etc. analytical test.
In reaction process, the change of pH is as Fig. 9, and as we know from the figure, in the 50min that reaction is initial, pH sharply declines, and after question response 4h, pH value is all less than 9; SEM as Figure 10, Figure 10 A be transform before SEM figure, Figure 10 B be transform after SEM figure.Can find out, before and after transforming, the pattern of sample there occurs obvious change, and become the spherical subsalt of the uniform class of compact grain from bulk sheet accumulation type particle, this proves that the bulk density of sample improves greatly at bulk density after inversion of phases from the side; Figure 11 is the measurement result of the granularity of ageing different time gained sample under different initial ph value, size-grade distribution, bulk density, chloride content.Result shows, crystallization conversion can cause the remarkable reduction of grain graininess, and particle distribution range narrows, and dispersed little, bulk density increases, and chloride ion content also significantly reduces; Under different pH, the XRD of different time sampling compares as Figure 12.Result as can be seen from figure, still has the diffraction peak of lanthanite type Phosbloc at ° place, 2 θ=10 after inversion of phases, not yet transform completely.But contrast the data of chloride content, bulk density and the size-grade distribution recorded, can know that it obtains the fine grain basic carbonate lanthanum of high bulk density low chlorine root after inversion of phases.Therefore, can not pursue in actual production and transform completely, as long as product reaches the requirement reducing chlorine root, improve bulk density and reduction 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 with basic carbonate lanthanum be principal crystalline phase.Rare earth oxide is obtained after calcining.
Embodiment 4
30g lanthanite type cerous carbonate is added in beaker, add the distilled water of 300ml, the pH of regulator solution is distinguished 10,11,12,13,14 with water or sodium hydroxide solution under room temperature, constant temperature ageing in the thermostat water bath of 95 DEG C, (total reaction times is no more than 5h) sampling at set intervals, by the pH value at room temperature measuring aaerosol solution after water quench, the change of pH value in record reaction process; Phenomenon in observing response process, see in reaction process and have a large amount of bubble to overflow, treat that bubble is not being overflowed and supernatant liquor clarification, then react end, filtering and washing after having reacted, gained crystallization dried at 50 DEG C and obtains subcarbonate sample, after 1000 DEG C of calcinings, obtaining oxide samples.To obtained cerous carbonate sample carry out XRD, SEM, granularity, bulk density, chloride content and etc. analytical test.
In reaction process, the change of pH is as Figure 13.As we know from the figure, in the 50min that reaction is initial, pH sharply declines, until pH value is all less than 9 after reaction 4h; SEM as Figure 14, Figure 14 A be transform before SEM figure, Figure 14 B be transform after SEM figure, proves transform front and back sample pattern there occurs obvious change, become the subsalt of the uniform spherical particle of compact grain from bulk sheet accumulation type particle; Figure 15 is the measurement result of the granularity of ageing different time gained sample under different initial ph value, size-grade distribution, bulk density, chloride content.Result shows, crystallization conversion can cause the remarkable reduction of grain graininess, and particle distribution range narrows, and dispersed little, bulk density increases, and chloride ion content also significantly reduces; Under different pH, the XRD of different time sampling compares as Figure 16, as can be seen from the figure, when pH=10 and 11, the diffraction peak of obvious lanthanite type cerous carbonate is still had after inversion of phases, not yet transform completely, when pH=12 and 13, inversion of phases is than more completely, contrast the data of chloride content, bulk density and size-grade distribution recorded, can know and can obtain the fine grain basic carbonate cerium of high bulk density low chlorine root after inversion of phases.To sum up, reaching under the requirement reducing chlorine root raising bulk density and reduce granularity, between pH=12 ~ 13, digestion time 2 ~ 4h can prepare basic carbonate cerium by lanthanite type cerous carbonate inversion of phases.
Embodiment 5
The lanthanite type cerous carbonate of 20g drying and Phosbloc are placed in 2 clean beakers respectively, add 300ml distilled water respectively, at room temperature regulate pH=13 with the NaOH of 10mol/L, this two beaker is placed in 95 DEG C 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 bubble to overflow.When pH value is less than 12, the NaOH dripping 10mol/L makes pH value remain in the scope of 12 ~ 13, until the pH of reaction no longer declines and is not less than 12, bubble is no longer overflowed and supernatant liquor clarification, then stop dripping NaOH, the ratio between the amount calculating the alkali dripped and the amount of rare earth carbonate added.The add-on of known lanthanum and cerium is that the add-on of the NaOH of 0.0665mol and 0.0662mol, 10mol/L is 5.75ml, i.e. 0.0575mol respectively, and the ratio calculating their amount of substance is: La:OH
-=1:0.8651, Ce:OH
-=1:0.8687.The hydrolysis reaction of free carbonate out proves that actual consumption amount hydroxy is smaller than theoretic 1:1, this is because can produce a part of hydroxide radical.When not needing to transform completely, alkali can be added less; When rare earth carbonate generation inversion of phases as much as possible will be ensured, then 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 OH free in Phosbloc and cerous carbonate and solution
-reaction.From the speed that pH declines, the time needed for reaction was at about 30 minutes.After adding alkali adjustment pH, pH rises, and after from reaction times 75min, bubble is not in effusion, supernatant liquor clear.Now to last 4h during this period of time in the pH of solution be in a stable state, and bubble is no longer overflowed, supernatant liquor clear after settle, and 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 carry out, such as between 12-13 within the scope of a higher pH all the time.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 batch process procedures, 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 directly be realized by the observing and controlling of pH value.The equipment realizing alkali conversion operation can be reactor, reactive tank, the retort of all size.Can also adopt pipe reaction crystallizer in continuous conversion operation, carbonated rare earth is exactly realize the time needed for conversion from entering to the time out, and after filtering, solution reenters reaction tubes, and solution realizes continuous circulation and uses.The concentration when sodium carbonate in clear liquid and sodium-chlor is only had to reach certain numerical value, when can have influence on the chloride content in product, then do not continue on for alkali to transform, but use instead and prepare positive carbonate in precipitating rare earth, water is not only made to obtain recycle, the sodium carbonate that conversion process produces have also been obtained utilization, the main sodium chloride-containing of filtrate after precipitating rare earth or ammonium chloride, can electrolytic preparation sodium hydroxide and hydrochloric acid, or be converted into hydrochloric acid and vitriol with additive method, whole process is made to define a systemic circulation, improve the utilization ratio of water, ensure that the maximum utilization of resource, avoid 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 the hot alkali water solution reaction more than 30 minutes of pH value more than 7 and temperature more than 80 DEG C, 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 in version reaction carries out with intermittent type or continous way or marginal semi continuous mode in reactor, reactor or reactive tank, or carry out in continous way mode in tubular reactor; Carbonated rare earth needed for phase conversion reaction and alkali adopt one or many or continuous print mode to add according to above-mentioned different reactive mode;
[2] reactant step [1] obtained obtains without the need to cold filtration basic carbonate rare earth that high bulk density, fine particle and low chlorine root require or the precipitated product that is principal crystalline phase with it;
[3] gained precipitated product is calcined, obtain corresponding rare earth oxide;
[4] to add after alkali the i.e. alkali aqueous solution be used as in step [1] capable of circulation in filtrate, or be directly used in preparation precipitation agent and 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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310624215.6A CN103708525B (en) | 2013-11-29 | 2013-11-29 | Production method of high-bulk density fine-grain low-chlorine rare earth carbonate and its oxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310624215.6A CN103708525B (en) | 2013-11-29 | 2013-11-29 | Production method of high-bulk density fine-grain low-chlorine rare earth carbonate and its oxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103708525A CN103708525A (en) | 2014-04-09 |
| CN103708525B true CN103708525B (en) | 2015-07-15 |
Family
ID=50401928
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310624215.6A Expired - Fee Related CN103708525B (en) | 2013-11-29 | 2013-11-29 | Production method of high-bulk density fine-grain low-chlorine rare earth carbonate and its oxide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103708525B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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) |
| CN106915761B (en) * | 2015-12-28 | 2021-04-30 | 安集微电子科技（上海）股份有限公司 | Cerium oxide preparation method and application thereof in STI (shallow trench isolation) chemical mechanical polishing |
| CN106915760B (en) * | 2015-12-28 | 2021-04-30 | 安集微电子科技（上海）股份有限公司 | Preparation method of cerium oxide and application of cerium oxide in STI polishing field |
| 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 |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60166223A (en) * | 1984-02-09 | 1985-08-29 | Asahi Chem Ind Co Ltd | Preparation of basic chloride of rare earth element |
| FR2608583B1 (en) * | 1986-12-19 | 1990-12-07 | Rhone Poulenc Chimie | CERIC OXIDE WITH NEW MORPHOLOGICAL CHARACTERISTICS AND PROCESS FOR OBTAINING SAME |
| CN1054356C (en) * | 1995-07-05 | 2000-07-12 | 南昌大学 | Method for crystallizing and sedimenting rare-earth carbonate |
| CN102978398B (en) * | 2012-12-12 | 2014-06-18 | 南昌大学 | Method for obviously lowering chlorine content in process of carbonic acid rare earth crystallization |
| CN103172101B (en) * | 2012-12-13 | 2014-12-17 | 浙江海洋学院 | Preparation method of alkali-type cerous carbonate |
| CN103351017B (en) * | 2013-07-01 | 2014-10-29 | 南昌大学 | Preparation method of fine-grained, high-bulk-density, ball-shaped, rare earth carbonate and oxide thereof |
-
2013
- 2013-11-29 CN CN201310624215.6A patent/CN103708525B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN103708525A (en) | 2014-04-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103708525B (en) | Production method of high-bulk density fine-grain low-chlorine rare earth carbonate and its oxide | |
| RU2437700C2 (en) | Device and method of producing compounds by precipitation | |
| CN111362298B (en) | Preparation method of indium oxide spherical powder with controllable particle shape | |
| CN100484882C (en) | Method of preparing electronic grade nickel carbonate by sodium carbonate deposition | |
| CN108910932B (en) | Method for preparing narrow-distribution superfine yttrium oxide by sodium carbonate precipitation | |
| CN101570348B (en) | Preparation method for compact crystallographic form cobalt hydrate | |
| Kim et al. | Agglomeration of nickel/cobalt/manganese hydroxide crystals in Couette–Taylor crystallizer | |
| CN102659164B (en) | Preparation method for copper and aluminium hydrotalcite | |
| CN110112386B (en) | Preparation method of high-nickel ternary positive electrode precursor | |
| US9045349B2 (en) | Method for preparing porous alumina | |
| CN102030348B (en) | Device and method for continuously preparing magnesium hydroxide flame retardant | |
| CN102190320A (en) | Method for preparing trihydrated magnesium carbonate by using continuous crystallization process | |
| CN109354077B (en) | Multi-crystal form ternary precursor and preparation method thereof | |
| CN103482658A (en) | Membrane refining process of medicinal sodium chloride | |
| US10858262B2 (en) | Gel with high dispersibility and method for preparing same | |
| CN105293567B (en) | Flaky porous nanometer zinc oxide and preparation method thereof | |
| CN109437261A (en) | A kind of sheeted nanometer magnesium hydroxide raw powder's production technology | |
| CN102703982B (en) | Method for preparing magnesium carbonate trihydrate crystal whisker by utilizing serpentine | |
| Li et al. | Precipitating sandy aluminium hydroxide from sodium aluminate solution by the neutralization of sodium bicarbonate | |
| CN111943240B (en) | Method for preparing coarse-grained aluminum hydroxide by decomposing sodium aluminate solution with ultralow seed crystal amount | |
| CN113582256A (en) | High-nickel single crystal positive electrode material, precursor thereof and preparation method of precursor | |
| CN116199270B (en) | Treatment process for reducing wastewater in cobalt oxide production process | |
| CN101229924B (en) | Method for preparing high-purity magnesium hydroxide by using atomized ammonia as precipitator | |
| CN113830817A (en) | Cerium-based oxide material and preparation method of precursor thereof | |
| CN108793224B (en) | Method for preparing narrow-distribution crystal form yttrium carbonate by sodium carbonate precipitation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150715 Termination date: 20211129 |