CN110282651A - A method of high-purity rare earth oxide is prepared using compound precipitants - Google Patents
A method of high-purity rare earth oxide is prepared using compound precipitants Download PDFInfo
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- C01F17/00—Compounds of rare earth metals
- C01F17/20—Compounds containing only rare earth metals as the metal element
- C01F17/206—Compounds containing only rare earth metals as the metal element oxide or hydroxide being the only anion
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- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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Abstract
The present invention relates to technical field of rare-earth hydrometallurgy, provide a kind of method for preparing high-purity rare earth oxide using compound precipitants.First crystal seed is added in reactor by the present invention, and rare earth chloride liquid and composite precipitation agent solution is then added and carries out precipitation reaction, is then successively aged, solid-liquor separation and washing, gained carbonated rare earth calcination is obtained high-purity rare earth oxide；The compound precipitants that the present invention uses include sodium bicarbonate and sodium carbonate, and the mass ratio of sodium bicarbonate and sodium carbonate is 0.2~10:1.The present invention precipitates rare earth chloride using compound precipitants, the comprehensive advantage for playing sodium bicarbonate and sodium carbonate of energy, the generation of carbon dioxide when reducing sodium bicarbonate precipitating, it reduces bubble and risks slot risk, it is too strong and generate starchiness product rare earth hydrate to also prevent sodium carbonate alkalinity, the few carbonated rare earth of good crystallinity, stable crystal form, narrow particle size distribution, impurity content is prepared, the high-purity rare earth oxide indices of gained are better than the requirement of national standard after calcination.
Description
Technical field
The present invention relates to technical field of rare-earth hydrometallurgy, in particular to a kind of to prepare high pure zirconia using compound precipitants
The method of rare earth.
Background technique
Rare earth element is all widely used in fields such as petroleum, chemical industry, metallurgy, weaving, ceramics, glass, permanent-magnet materials,
And with the development of science and technology the value of rare earth oxide will be increasing.The preparation method of rare earth oxide is generally molten to rare earth
Precipitating reagent is added in liquid, then the rare earth compound calcination being precipitated out is obtained into rare earth oxide.To produce the higher oxidation of purity
Rare earth need to be settled out the few rare earth chemical combination of good crystallinity, stable crystal form, narrow particle size distribution, impurity content in rare-earth precipitation process
Object.Currently, rare-earth precipitation generallys use oxalate precipitation method, this method has apparent advantage in terms of guaranteeing product quality, produces
Object purity is high, can be effectively controlled the content of wherein non-rare earth impurity, but production cost is higher, oxalic acid toxicity is stronger, application
Environmental benefit and economic benefit are undesirable.
In addition, traditional rare-earth precipitation mostly uses ammonium hydrogen carbonate to make precipitating reagent, its advantage is that obtained carbonated rare earth particle
It is coarse, more easy to wash, and cost is relatively low, but ammonium bicarbonate precipitation can generate a large amount of ammonia nitrogen waste waters, ammonia nitrogen is main in water body
Oxygen consumption pollutant, the ammonia nitrogen of high-content will cause earth's surface water eutrophication, and excessive consumption oxygen in water seriously affects water quality.
In order to preserve the ecological environment, mitigates water pollution, clearly advised in " rare-earth industry pollutant emission standard " (GB26451-2011)
Fixed, from January 1st, 2014, the ammonia nitrogen direct emission limit value of rare-earth trade was reduced to 15mg/L, ammonia nitrogen waste water pair by 25mg/L
The influence of environment has caused the attention of environment protection field and global range.Ammonia nitrogen waste water seriously affects environment, so that bicarbonate
Ammonia-sinking shallow lake technique faces the problem of qualified discharge after severe water process.
Currently, use sodium bicarbonate, sodium carbonate replace ammonium hydrogen carbonate as rare-earth precipitation agent be the hot spot paid close attention to jointly in the industry.
Precipitating reagent needed for the production of carbonated rare earth is cheap, from a wealth of sources, to environment and human body close friend, most potential substitution oxalic acid
Rare earth and be used for rare-earth industry production, therefore, replace oxalic acid, ammonium hydrogen carbonate to precipitate as precipitating reagent with sodium carbonate or sodium bicarbonate
Rare earth is a kind of more satisfactory way.But it is easy to form amorphous precipitated to do precipitating reagent with sodium carbonate or sodium bicarbonate, contains
There are a large amount of water and impurity, it is difficult to filtering and washing, and product purity is lower；It is difficult to control, holds when especially sodium carbonate precipitates
Easy partial over-alkali generates rare earth hydrate, forms starchiness product, crystallinity is bad, and the crystallization conversion time is long, needs digestion time
It is longer, Na when washing+、Cl-It is not easy to wash, it be easy to cause contaminant overstandard in oxide；Sodium bicarbonate, which makees precipitating reagent, to be generated
A large amount of CO2Gas, precipitating reagent consumption is big, and utilization rate is lower, is easy to emit slot, and then influence production efficiency.
Summary of the invention
It is an object of that present invention to provide a kind of methods for preparing high-purity rare earth oxide using compound precipitants.The present invention utilizes
Compound precipitants precipitate rare earth ion, and gained precipitated product good crystallinity, stable crystal form, narrow particle size distribution, impurity contain
Amount is few, gained rare earth oxide purity is high.
In order to achieve the above-mentioned object of the invention, the present invention the following technical schemes are provided:
A method of high-purity rare earth oxide is prepared using compound precipitants, comprising the following steps:
Crystal seed is added in reactor, rare earth chloride liquid is then added into reactor and composite precipitation agent solution carries out
Then precipitation reaction is successively aged, solid-liquor separation and washing, obtains carbonated rare earth；
By the carbonated rare earth calcination, high-purity rare earth oxide is obtained；
Wherein, the precipitating reagent in the composite precipitation agent solution includes sodium bicarbonate and sodium carbonate；The sodium bicarbonate and
The mass ratio of sodium carbonate is 0.2~10:1；
Mass content >=99% of REO in high-purity rare earth oxide.
Preferably, the total concentration of sodium bicarbonate and sodium carbonate is 50~200g/L in the composite precipitation agent solution.
Preferably, the REO concentration in the rare earth chloride liquid is 0.2~1.5mol/L；The rare earth chloride liquid
PH value is 0.5~2.5.
Preferably, the crystal seed includes carbonated rare earth and/or rare earth oxalate.
Preferably, the additional amount of the crystal seed is the 2~20% of total rare earth (TRE) quality；The total rare earth (TRE) quality is with rare earth chloride
The content meter of REO in feed liquid.
Preferably, in the rare earth chloride liquid and composite precipitation agent solution adition process, mixed liquor in reactor
PH value control is 4~5.5.
Preferably, the endpoint pH of the precipitation reaction is 6.5~7.5.
Preferably, the time of the ageing be 2~for 24 hours.
Preferably, the temperature of the calcination is 850~1000 DEG C, and the time is 1.5~3h.
The present invention provides a kind of method for preparing high-purity rare earth oxide using compound precipitants, the present invention first adds crystal seed
Enter in reactor, rare earth chloride liquid and composite precipitation agent solution be then added into reactor and carries out precipitation reaction, then according to
It is secondary be aged, solid-liquor separation and washing, high-purity rare earth oxide is can be obtained into obtained carbonated rare earth calcination；The present invention uses
Precipitating reagent include sodium bicarbonate and sodium carbonate, and the mass ratio of sodium bicarbonate and sodium carbonate is 0.2~10:1.The present invention uses
Compound precipitants precipitate rare earth chloride liquid, compared with the precipitating reagent of the single composition such as sodium bicarbonate, sodium carbonate, ammonium hydrogen carbonate,
Compound precipitants of the invention can integrate the advantage for playing sodium bicarbonate and sodium carbonate, titanium dioxide when reducing sodium bicarbonate precipitating
The generation of carbon reduces bubble and risks slot risk, increase the effective rate of utilization of unit mass precipitating reagent, also prevents carbonic acid soda
Property it is too strong and generate starchiness product rare earth hydrate, improve production efficiency, alleviate washing pressure, improve washing effect
The few carbonated rare earth of good crystallinity, stable crystal form, narrow particle size distribution, impurity content is prepared in fruit；Meanwhile side of the invention
Method realizes low cost, cleaning, environmentally friendly production, provides effective guarantee for the exploitation and development of rare earth material；In addition, this
Invention applicability is wide, can realize on the basis of not changing prior art equipment in commercial scale, strong operability,
At low cost, economic benefit is obvious.Embodiment the result shows that, rare earth oxide chlorinity≤0.03%, REO prepared by the present invention >=
99.00%, precipitation process REO yield >=98.00%.
Detailed description of the invention
Fig. 1 is the process flow chart of the embodiment of the present invention；
Fig. 2 is that the SEM of 4 gained carbonated rare earth of embodiment schemes；
Fig. 3 is the particle size distribution figure of 4 gained carbonated rare earth of embodiment；
Fig. 4 is the XRD diagram of carbonated rare earth obtained by Examples 1 to 3.
Specific embodiment
The present invention provides a kind of methods for preparing high-purity rare earth oxide using compound precipitants, comprising the following steps:
Crystal seed is added in reactor, rare earth chloride liquid is then added into reactor and composite precipitation agent solution carries out
Then precipitation reaction is successively aged, solid-liquor separation and washing, obtains carbonated rare earth；
By the carbonated rare earth calcination, high-purity rare earth oxide is obtained；REO (rare earth oxide) in high-purity rare earth oxide
Mass content >=99%.
In the present invention, the precipitating reagent in the composite precipitation agent solution includes sodium bicarbonate and sodium carbonate；The carbonic acid
The mass ratio of hydrogen sodium and sodium carbonate is 0.2~10:1, preferably 0.5~8:1, further preferably 1~5:1；It is described compound heavy
The total concentration of sodium bicarbonate and sodium carbonate is preferably 50~200g/L, more preferably 100~150g/L in the agent solution of shallow lake；It is described multiple
The solvent for closing precipitant solution is preferably water.The present invention is compound precipitants to rare earth chloride liquid using sodium bicarbonate and sodium carbonate
It is precipitated, by controlling the proportion of sodium bicarbonate and sodium carbonate, can integrate to the greatest extent and play sodium bicarbonate and carbonic acid
The advantage of sodium avoids the defect of the two, increases the effective rate of utilization of precipitating reagent.
In the present invention, the REO concentration in the rare earth chloride liquid is preferably 0.2~1.5mol/L, and more preferably 0.5
~1mol/L；The pH value of the rare earth chloride liquid is preferably 0.5~2.5, and more preferably 1~2.The present invention is dilute to the chlorination
The source of soil does not have particular/special requirement, in a specific embodiment of the present invention, preferably directly miscellaneous using obtaining after extraction and separation
Matter content rare earth chloride liquid up to standard；In a specific embodiment of the present invention, it is come out after the completion of extraction and separation from extraction tank
The pH value of rare earth chloride liquid is generally in 0.5~2.5 range, direct use, without further adjusting, if extraction tank goes out
The REO excessive concentration in rare earth chloride liquid come, then use of water is preferred or low concentration feed liquid dilution, and REO concentration is too low, fits
Amount be added high concentration feed liquid, with obtain REO concentration meet the present invention claims rare earth chloride liquid.Rare earth chloride liquid concentration mistake
Height, will appear when precipitating that reunion is serious, impurity wraps up serious phenomenon, and precipitated product is difficult to wash；Rare earth chloride liquid concentration
It is too low, it can generate amorphous precipitated, be unfavorable for crystallizing, and required digestion time is long；The present invention is by the REO in rare earth chloride liquid
Concentration controls within the above range, can reduce the impurity content in precipitated product, guarantee the granularity and granulated of carbonated rare earth
Looks are conducive to the carbonated rare earth for obtaining good crystallinity.
The present invention does not have particular/special requirement to the rare earth chloride type in the rare earth chloride liquid, can be single chlorination
Rare earth or mixed chlorinated rare earth can be specifically lanthanum chloride, praseodymium chloride neodymium etc..
In the present invention, the crystal seed is preferably carbonated rare earth and/or rare earth oxalate；The additional amount of the crystal seed is preferably
The 2~20% of total rare earth (TRE) quality, more preferably 5~15%；The total rare earth (TRE) quality is with the content of REO in rare earth chloride liquid
Meter；The present invention can effectively shorten the crystallization conversion time in precipitation process by pre-add crystal seed, increase crystal carbonated rare earth
Granularity improves crystal form and size distribution, reduces fine particle, keeps size distribution more uniform, further increase the physical property of product and refer to
Mark, to impurity (such as Cl reduced in product-、Na+) content has obvious effect.
The present invention does not have particular/special requirement to the reactor, is specifically as follows beaker, settling box etc..
The present invention preferably feeds under agitation and precipitation reaction；The present invention preferably before crystal seed is added,
Part water is first added into reactor, in order to stir, the present invention does not have particular/special requirement to the amount for adding water, can not have stirring
Paddle, convenient for stirring；Be added crystal seed after, the present invention be added into reactor rare earth chloride liquid and composite precipitation agent solution into
Row precipitation reaction；In the present invention, in the rare earth chloride liquid and composite precipitation agent solution adition process, mixing in reactor
The pH value of feed liquid is preferably controlled to 4~5.5.In the present invention, the rare earth chloride liquid and composite precipitation agent solution preferably with
Certain flow is added in reactor, passes through the pH value model of feed liquid in reactor during the flow control charging of both control
It encloses, specific flow velocity is controlled according to reactor size, and the pH value of precipitation process can be made to meet the requirements.It was feeding
Cheng Zhong should minimize the pH value fluctuation of feed liquid in reactor, and pH value fluctuation is smaller, and obtained carbonated rare earth size distribution is got over
Narrow, crystal form is more stable, and impurity content is fewer.
In a specific embodiment of the present invention, the pH of feed liquid in a part of rare earth chloride liquid to reactor is preferably first added
Then value remaining rare earth chloride liquid and composite precipitation agent solution is added in reactor jointly again, less than 4 to ensure to precipitate
Journey is gone on smoothly, and is avoided first being added partial over-alkali after precipitating reagent and is generated rare earth hydrate.
In the present invention, rare earth chloride liquid is finished somewhat ahead of the addition of composite precipitation agent solution, continuously adds composite precipitation
Agent solution, precipitation reaction continues to occur in reactor, after feed liquid reaches endpoint pH in reactor, stops that composite precipitation is added
Agent solution；In the present invention, the endpoint pH of precipitation reaction is preferably 6.5~7.5, and more preferably 7；After reaching endpoint pH,
The present invention preferably stops stirring, and starts to be aged；In the present invention, the time of the ageing be preferably 2~for 24 hours, more preferably
For 2h.
After the completion of ageing, the present invention will be aged feed liquid and carry out solid-liquor separation, obtain carbonated rare earth；The side of the solid-liquor separation
Method preferably filters；After the completion of suction filtration, present invention preferably uses deionized waters to wash obtained solid product, solid to remove
The water-solubility impurity ion of body surface；The carbonated rare earth well-crystallized that the present invention is precipitated using compound precipitants sinks
The impurity contained in shallow lake is few, is easy to carry out solid-liquor separation, and the Na in precipitating+And Cl-It is easy to remove by washing.In this hair
In bright, it is again sharp with liquid step that the washing lotion of filtrate obtained by solid-liquor separation and washing generation is preferably returned to composite precipitation agent solution
With, or be discharged into waste water station and handled.
After obtaining carbonated rare earth, the carbonated rare earth is carried out calcination by the present invention, obtains high-purity rare earth oxide.In the present invention
In, the temperature of the calcination is preferably 850~1000 DEG C, and the time is preferably 1.5~3h.The present invention is to calcination process device therefor
And heating rate etc. carries out calcination according to method well known to those skilled in the art without particular/special requirement.
Scheme provided by the invention is described in detail below with reference to embodiment, but they cannot be interpreted as pair
The restriction of the scope of the present invention.
The process flow chart of the embodiment of the present invention is as shown in Figure 1.
Embodiment 1
200mL deionized water is first added in advance into 15L keg, 100g lanthanum carbonate crystal seed is added, prepares 3728mL chlorination
Lanthanum feed liquid, REO concentration are 100g/L, 5950mL composite precipitation agent solution (195g sodium bicarbonate+485g sodium carbonate, mNaHCO3:
mNa2CO3=0.4:1), concentration 114.3g/L, temperature is 20 DEG C, and under appropriate stirring condition, lanthanum chloride feed liquid first is added extremely
In container then the pH value of feed liquid controls lanthanum chloride feed velocity and precipitating reagent velocity ratio is about 1:2 less than 4, and suitably adjusts
Flow between the two, controlling precipitation process pH value range is 4~5.5, is finished until solution is added, endpoint pH 6.5~
7.5, then stop stirring, be aged 2h, filters, make that precipitating is washed with deionized, obtain carbonated rare earth, finally at 850 DEG C
Calcination 2h obtains rare earth oxide.
Embodiment 2
200mL deionized water is first added in advance into 15L keg, 100g lanthanum carbonate crystal seed is added, prepares 3728mL chlorination
Lanthanum feed liquid, REO concentration are 100g/L, 5950mL composite precipitation agent solution (108g sodium bicarbonate+540g sodium carbonate, mNaHCO3:
mNa2CO3=0.2:1), concentration 108.9g/L, temperature is 20 DEG C, and under appropriate stirring condition, lanthanum chloride feed liquid first is added extremely
The pH value of feed liquid then controls lanthanum chloride feed velocity and precipitating reagent velocity ratio is about 1:2 less than 4 in container, suitably adjusts two
Flow between person, control precipitation process pH value range are 4~5.5, are finished until solution is added, endpoint pH 6.5~7.5,
Stop stirring, be aged 2h, filter, deionized water washing precipitating obtains carbonated rare earth, finally calcination 2h obtains oxygen at 850 DEG C
Change rare earth.
Embodiment 3
Take 8.4kg sodium bicarbonate and 41.9kg sodium carbonate (mNaHCO3:mNa2CO3=0.2:1) it is dissolved in 1000L liquid dispensing tank
In, add 370L water to prepare compound precipitants, concentration 135g/L squeezes into spare in high-order storage tank, preparation lanthanum chloride feed liquid 350L,
Measuring its REO concentration is 131.9g/L, initial pH value 1.8.Deionized water is added in advance in settling box and did not had agitating paddle, is added
10kg lanthanum carbonate crystal seed opens stirring, and the pH value of feed liquid in lanthanum chloride feed liquid to settling box is first added less than 4, chlorine is then added
To change lanthanum feed liquid and composite precipitation agent solution, suitably adjusts flow between the two, control precipitation process pH value range is 4~5.5,
Until feed liquid addition finishes, endpoint pH 6.5~7.5 stops stirring, is aged 2h, filters, and deionized water washing precipitating obtains
Carbonated rare earth, last calcination obtain rare earth oxide.
Embodiment 4
Take 12kg sodium bicarbonate and 39.7kg sodium carbonate (mNaHCO3:mNa2CO3=0.3:1) it is dissolved in 1000L liquid dispensing tank
In, add 370L water to prepare compound precipitants, concentration 139.7g/L squeezes into spare in high-order storage tank, preparation lanthanum chloride feed liquid
350L, measuring its concentration is 131.9g/L, initial pH value 1.8.Deionized water is added in advance in settling box and did not had agitating paddle, adds
Enter 10kg lanthanum carbonate crystal seed, open stirring, the pH value of feed liquid in lanthanum chloride feed liquid to settling box is first added less than 4, is then added
Lanthanum chloride feed liquid and composite precipitation agent solution are controlled pH value range 4~5.5 by both control flow in precipitation process,
Until feed liquid addition finishes, endpoint pH 6.5~7.5 stops stirring, and rare earth concentration in supernatant is measured after ageing 2h and is less than
10mg/L is filtered, and deionized water washing precipitating obtains carbonated rare earth, finally calcination 2h obtains rare earth oxide at 850 DEG C.
Embodiment 5
Take 15.2kg sodium bicarbonate and 37.6kg sodium carbonate (mNaHCO3:mNa2CO3=0.4:1) 1000L is dissolved in liquid
In bucket, 370L water is added to prepare compound precipitants, concentration 142.7g/L squeezes into spare in high-order storage tank, preparation lanthanum chloride feed liquid
350L, measuring its concentration is 131.9g/L, initial pH value 1.8.Deionized water is added in advance in settling box and did not had agitating paddle, adds
Enter 10kg lanthanum carbonate crystal seed, open stirring, the pH value of feed liquid in lanthanum chloride feed liquid to settling box is first added less than 4, is then added
Lanthanum chloride feed liquid and composite precipitation agent solution are controlled pH value range 4~5.5 by both control flow in precipitation process,
It is finished until solution is added, endpoint pH 6.5~7.5；Stop stirring, rare earth concentration in supernatant is measured after ageing 2h and is less than
10mg/L is filtered, and deionized water washing precipitating obtains carbonated rare earth, finally calcination 2h obtains rare earth oxide at 850 DEG C.
Embodiment 6
500L deionized water is added into 1000L liquid dispensing tank, weighs 20.5kg sodium bicarbonate and 50.8kg sodium carbonate
(mNaHCO3:mNa2CO3=0.4:1) compound precipitants are prepared, concentration 142.7g/L is squeezed into spare in high-order storage tank；It takes
(mass percentage i.e. in feed liquid in terms of praseodymium oxide and neodymia is respectively 20% to certain Rare Earth Separation factory 20-80 praseodymium chloride neodymium
With 80%) feed liquid 350L, measuring its REO concentration is 150g/L, initial pH value 1.8.Deionized water is added in advance in settling box
Agitating paddle is not crossed, 10kg praseodymium carbonate neodymium crystal seed is added, opens stirring, the pH value of feed liquid in lanthanum chloride feed liquid to settling box is first added
Less than 4, praseodymium chloride neodymium feed liquid and composite precipitation agent solution is then added, passes through both control flow in precipitation process for pH value model
System is contained 4~5.5, until the addition of praseodymium chloride neodymium feed liquid finishes, control endpoint pH 6.5~7.5 stops stirring, is aged 2h
Rare earth concentration in supernatant is measured afterwards and is less than 10mg/L, is filtered, deionized water washs to obtain qualified carbonated rare earth, finally 850
Calcination 2h obtains rare earth oxide at DEG C.
Quality analysis:
(1) granularity and chemical composition analysis
Testing graininess is carried out to carbonated rare earth obtained in Examples 1 to 6, and to gained rare earth oxide after calcination
Credit analysis, acquired results are shown in Table 1；
Chlorine, REO total amount, Na in 1 carbonated rare earth granularity of table, Span and rare earth oxide+Content and REO yield dependency number
According to table
Percentage composition in table 1 is mass percentage.
It is in table 1 the result shows that, the embodiment of the present invention 1~6 makees compound precipitants using sodium bicarbonate and sodium carbonate, prepares
Obtained carbonated rare earth granule size is stable, is evenly distributed, and chlorine, sodium ion impurity content are low in the rare earth oxide after calcination, dilute
Native total amount is high, and index of correlation is better than requirements of the national standard.
Fig. 2 is the SEM figure of the carbonated rare earth prepared in embodiment 4, according to fig. 2 as can be seen that carbonic acid prepared by embodiment 4
Rare earth epigranular；SEM detection, acquired results and Fig. 2 phase are carried out to Examples 1 to 3 and 5~6 gained carbonated rare earth of embodiment
Seemingly.
Fig. 3 is the particle size distribution figure of 4 gained carbonated rare earth of embodiment；Table 2 is the granularity point of 4 gained carbonated rare earth of embodiment
Cloth data；
The particle size distribution data of 2 embodiment of table, 4 gained carbonated rare earth
| D10/μm | D25/μm | D50/μm | D75/μm | D90/μm |
| 8.693 | 12.622 | 17.16 | 22.122 | 27.638 |
| D97/μm | D(3,2)/μm | D(4,3)/μm | Span | Weight specific surface area/m2/kg |
| 34.774 | 14.867 | 17.927 | 1.104 | 149.473 |
According to Fig. 3 and table 2 as can be seen that the narrower particle size distribution of 4 gained carbonated rare earth of embodiment.
(2) XRD is detected
It is characterized using crystalline characteristics of the X-ray diffraction to the carbonated rare earth sediment of Examples 1 to 3, acquired results
As shown in figure 4, can be seen that the diffraction peak intensity of carbonated rare earth obtained by Examples 1 to 3 according to Fig. 4, sharp and symmetrical, each feature
The PDF card feature peak energy matched well at peak and corresponding standard substance, peak type is good, illustrates that the carbonated rare earth is well-crystallized's
Crystalline precipitation is the corresponding substance of PDF card, and without obvious other impurities.
XRD detection is carried out to 4~6 gained carbonated rare earth of embodiment, acquired results are similar with Fig. 4.
As seen from the above embodiment, the compound precipitants that method provided by the invention is formed using sodium bicarbonate and sodium carbonate
High-purity rare earth oxide is prepared, the advantage of sodium bicarbonate and sodium carbonate can be integrated, avoids the defect of the two, gained carbonated rare earth knot
Crystalline substance is good, stable crystal form, narrow particle size distribution, impurity content are few, and gained rare earth oxide purity is high, indices are better than after calcination
The requirement of national standard.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (9)
1. a kind of method for preparing high-purity rare earth oxide using compound precipitants, which comprises the following steps:
Crystal seed is added in reactor, rare earth chloride liquid then is added into reactor and composite precipitation agent solution is precipitated
Then reaction is successively aged, solid-liquor separation and washing, obtains carbonated rare earth；
By the carbonated rare earth calcination, high-purity rare earth oxide is obtained；
Wherein, the precipitating reagent in the composite precipitation agent solution includes sodium bicarbonate and sodium carbonate；The sodium bicarbonate and carbonic acid
The mass ratio of sodium is 0.2~10:1；
Mass content >=99% of REO in high-purity rare earth oxide.
2. the method according to claim 1, wherein sodium bicarbonate and sodium carbonate in the composite precipitation agent solution
Total concentration be 50~200g/L.
3. the method according to claim 1, wherein REO concentration in the rare earth chloride liquid be 0.2~
1.5mol/L；The pH value of the rare earth chloride liquid is 0.5~2.5.
4. the method according to claim 1, wherein the crystal seed includes carbonated rare earth and/or rare earth oxalate.
5. method according to claim 1 or 4, which is characterized in that the additional amount of the crystal seed be total rare earth (TRE) quality 2~
20%；The total rare earth (TRE) quality is with the content meter of REO in rare earth chloride liquid.
6. the method according to claim 1, wherein the rare earth chloride liquid and composite precipitation agent solution are added
In the process, the pH value control of mixed liquor is 4~5.5 in reactor.
7. the method according to claim 1, wherein the endpoint pH of the precipitation reaction is 6.5~7.5.
8. the method according to claim 1, wherein the time of the ageing be 2~for 24 hours.
9. the time is the method according to claim 1, wherein the temperature of the calcination is 850~1000 DEG C
1.5~3h.
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Cited By (3)
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| CN111939924A (en) * | 2020-08-21 | 2020-11-17 | 赣州有色冶金研究所 | Composite catalyst for ozone oxidation and preparation method thereof |
| CN114249346A (en) * | 2022-02-14 | 2022-03-29 | 江西离子型稀土工程技术研究有限公司 | Anhydrous rare earth fluoride and preparation method and application thereof |
| CN115627372A (en) * | 2022-09-30 | 2023-01-20 | 中稀(广西)金源稀土新材料有限公司 | Rare earth precipitation method |
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