CN108977675A - A kind of method that anti-charging precipitating-baking inphases prepare low sulfur content rare earth oxide - Google Patents
A kind of method that anti-charging precipitating-baking inphases prepare low sulfur content rare earth oxide Download PDFInfo
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Abstract
The invention discloses a kind of methods that anti-charging precipitating-baking inphases prepare low sulfur content rare earth oxide, by being slowly added to rare earth sulfate solution into alkaline precipitating agent, control precipitation reaction temperature, it is washed after precipitating, it is separated by solid-liquid separation, rare earth hydrate is obtained, roasting condition is controlled according to sulfur content in rare earth hydrate, finally obtains rare earth oxide.This method is by the way of anti-charging precipitating, system is set to be constantly in the state of base excess, precipitation reaction temperature is controlled simultaneously, eventually by improvement roasting system, the sulfur content in rare earth oxide, the final rare earth oxide for obtaining sulfur content and being lower than 0.2 wt.% are reduced in terms of being introduced into control and roasting removal two.
Description
Technical field
The present invention relates to field of rare earth hydrometallurgy, prepare in particular to a kind of anti-charging precipitating-baking inphases low
The method of sulfur content rare earth oxide.
Background technique
Rare earth element is because of its unique 4f sub-layer electronic structure, big atomic magnetic moment, strong SO coupling, changeable
Ligancy, the compound formed it into has the functional characters such as magnetic, light, electricity, catalysis of very abundant, is known as " modern work
The vitamin of industry " and " new material treasure-house ".Wherein, rare earth oxide is one kind important in rare earth compound, it is also preparation
The primary raw material of other rare earth compounds, be widely used in rareearth magnetic material, luminescent material, hydrogen storage material, crystalline material,
The preparation of the high field of new materials such as catalysis material.
The smelting separation method multiplicity of rare earth element at present, the acid rare earth solution system being related to is also more, wherein sulfuric acid
With stability height, it is not volatile, it is weak to equipment corrosion the features such as, be widely used in smelt separation process, such as baotite sulphur
Sour roasting method (ZL86105043), the rare earth sulphur ammonium leacheate (97114216.5) of southern ion adsorption type rare earth ore, at sulfuric acid
The rare earth mixture of sulfuric phosphoric acid solution (ZL200910078794.2) etc. generated in reason phosphorite process.Therefore, in rare earth sulfate solution or
The technique of rare-earth enrichment recovery is more universal in mixed acid solution system.The precipitation method are simple, at low cost and be easy to due to reaction process
Industrialized production, so industrially generalling use the rare earth that the precipitation method are come in enriching and recovering rare earth sulfate solution.It is i.e. dilute in sulfuric acid
Precipitating reagent is added in native solution, rare earth is made to be converted to precipitating, to achieve the purpose that enriching and recovering, then through separation, drying or
Thermal decomposition, finally prepares rare earth oxide.Being usually used in the method for rare earth sulfate solution precipitated crystal at present includes oxalic acid
The precipitation method, carbonate precipitation method, hydroxide precipitation method.Wherein precipitating reagent used in hydroxide precipitation method includes hydroxide
Sodium, ammonium hydroxide, magnesia (200710102777.9), calcium oxide (200810175913.1), etc..What hydroxide precipitation method obtained
Rare earth hydrate is other than the presoma that can be used as rare earth oxide, itself also has biggish purposes, as lanthanum hydroxide can be straight
It connects for glass, ceramics and electronics industry etc..However the rare earth in alkaline precipitating agent Direct precipitation rare earth sulfate solution is used, it obtains
To rare earth hydrate in can contain larger amount of sulfate radical, and then it is high to roast sulfur content in the earth oxide product obtained.
If southern ion adsorption type rare earth ore leachate is using the sulfate radical contained in acquisition rare earth ore concentrate after alkaline matter precipitating enrichment, meeting
Increase extraction separation process load, generate calcium sulfate three-phase object, therefore need to smelt separation process in be added barium chloride by its
Removal.For this purpose, hydroxide precipitation method prepare low-sulfur rare earth oxide also have received widespread attention (201610187454.3,
201610187552.7,201610187379.0), propose using will by malic acid, acetylacetone,2,4-pentanedione, lactic acid, acetic acid, succinic acid,
Hydroxyacetic acid, malonic acid etc. are introduced into precipitation process or hydroxide stirring water-washing process, realize low-sulfur rare earth hydrate
Preparation.But this procedure introduces the higher organic matter of price, cost is greatly increased.Secondly, the hydrogen-oxygen obtained by the above method
The sulfate radical content changed in rare earth or rare earth oxide is higher, is 0.5wt.% or so, so that rare earth oxide or hydroxide are dilute
The application range of soil narrows.
Therefore, suitable depositing technology how is selected, in the case where not introducing other auxiliary agents, is precipitated using hydroxide
Method prepares the rare earth oxide of more low sulfur content, be a common concern during hydroxide precipitation method precipitating rare earth and
Urgent problem.
Summary of the invention
It is a primary object of the present invention to precipitate hydrogen-oxygen obtained for the current rare earth sulfate solution hydroxide precipitation method
Change the problem that sulfate radical is excessively high in rare-earth precipitation, simple for process, the easy to operate Direct precipitation of one kind is provided and prepares low-sulfur
The method of rare earth oxide obtains the rare-earth products of purity qualification to reduce production cost.
To achieve the goals above, the present invention provides the anti-charging precipitating-baking inphases of one kind and prepares low sulfur content rare earth oxygen
The method of compound, comprising the following steps:
(1) configuration concentration is the alkaline precipitating agent of 0.2-1.0mol/L, and alkaline precipitating agent is ammonium hydroxide, sodium hydroxide, hydrogen-oxygen
Change one or more of calcium, magnesium hydroxide, calcium oxide, magnesia；
(2) rare earth sulfate solution is slowly added into alkaline precipitating agent, control precipitation reaction temperature is 70-95 DEG C, sulfuric acid
The concentration of rare earth is 0.005-1.0mol/L in earth solution, in terms of REO；
(3) it is washed, is separated by solid-liquid separation after precipitating, obtain rare earth hydrate and mother liquor of precipitation of ammonium, measured in rare earth hydrate
Sulfur content is calculated as X, with SO3Meter；
(4) if X≤0.1wt.%, rare earth hydrate obtains rare earth oxide by 400-500 DEG C of heat preservation roasting 2-4h；If
0.1wt.% < X≤0.5wt.%, rare earth hydrate pass through 400-500 DEG C of heat preservation respectively and roast 2-4h, 800-900 DEG C of heat preservation roastings
2-4h, 1300~1500 DEG C of heat preservations roasting 2-4h are burnt, rare earth oxide is finally obtained.
Further, rare earth sulfate solution is that the southern ion type rareearth ore of sulfate leaching is resulting in the step (2)
Leachate, rare earth concentration 0.005-0.020mol/L, aluminum ions concentration are less than 1g/L, and the concentration of iron ion is less than 1g/
L。
Further, the addition speed of rare earth sulfate solution is 0.5-10mL/min in the step (2).
Further, the additional amount of rare earth sulfate solution is the theoretical amount for precipitating the precipitating reagent in the step (2)
85-95wt.%.
Further, continue heat preservation ageing 1-6h after step (2) the rare earth sulfate solution charging.
Further, in the step (3) during water washing operations, stop when washing when sulfate radical is less than 10ppm in filtrate
Sealing is washed.
Further, sulfur content is lower than 0.2wt.% in rare earth oxide obtained in step (4), with SO3Meter.
The present invention is by being slowly added to concentration for rare earth sulfate solution as the side in the alkaline precipitating agent of 0.2-1.0mol/L
Formula remains that precipitation system is constantly in the state of base excess, competes excessive hydroxyl and sulfate radical；Reaction is controlled simultaneously
Temperature is 70-95 DEG C, and the formation of alkali formula sulfuric acid rare earth is prevented from the angle of thermodynamics and kinetics, prevents sulfate radical from source
It introduces.It washed, be separated by solid-liquid separation after precipitating, obtain rare earth hydrate.According to sulfur content in rare earth hydrate using not
Same roasting system, if sulfur content≤0.1wt.% in rare earth hydrate, rare earth hydrate is obtained by 400-500 DEG C of roasting 2-4h
To rare earth oxide；If sulfur content≤0.5wt.%, rare earth hydrate pass through 400- respectively in 0.1wt.% < rare earth hydrate
2-4h, 800-900 DEG C of roasting 2-4h of 500 DEG C of roastings, 1300~1500 DEG C of roasting 2-4h roast sulphur removal from terminal, final to obtain
Sulfur content is lower than the rare earth oxide of 0.2wt.%.The present invention provides a kind of simple for process, easy to operate directly to sink
The method that shallow lake prepares low-sulfur rare earth oxide obtains the rare-earth products of purity qualification to reduce production cost.
Specific embodiment
It should be noted that in the absence of conflict, the features in the embodiments and the embodiments of the present application can phase
Mutually combination.The application is described in detail below in conjunction with embodiment.
It can be seen from background technology that, using the rare earth in alkaline precipitating agent Direct precipitation rare earth sulfate solution, obtained hydrogen-oxygen
Larger amount of sulfate radical can be contained by changing in rare earth, and then it is high to roast sulfur content in the earth oxide product obtained.Sulfate radical is deposited
In the multiple bonds such as σ key and pi bond, when rare earth sulfate solution is reacted with alkali, the existence form of sulfate radical in the reaction product is more multiple
It is miscellaneous, physical absorption and chemical coordination precipitating has occurred on the surface of rare earth hydrate and inside.Wherein physical absorption state
Sulfate radical can be used a large amount of water to carry out washing removal, and the sulfate radical of chemical coordination adsorbed state cannot be gone using the method for washing
It removes, mainly exists in the form of alkali formula sulfuric acid rare earth, the purity of rare earth oxide is still influenced after roasting, to influence product matter
Amount.
For this purpose, the present invention provides a kind of method that anti-charging precipitating-baking inphases prepare low sulfur content rare earth oxide,
The following steps are included:
(1) configuration concentration is the alkaline precipitating agent of 0.2-1.0mol/L, and alkaline precipitating agent is ammonium hydroxide, sodium hydroxide, hydrogen-oxygen
Change one or more of calcium, magnesium hydroxide, calcium oxide, magnesia；
(2) rare earth sulfate solution is slowly added into alkaline precipitating agent, control precipitation reaction temperature is 70-95 DEG C, sulfuric acid
The concentration of rare earth is 0.005-1.0mol/L in earth solution, in terms of REO；
By the way that rare earth sulfate solution is slowly added into the mode in alkaline precipitating agent, remain that precipitation system is located always
In the state of base excess, compete excessive hydroxyl and sulfate radical；Controlling reaction temperature simultaneously is 70-95 DEG C, at this temperature,
The gibbs enthalpy of formation of alkali formula sulfuric acid rare earth is high compared with the enthalpy of formation of rare earth hydrate, thermodynamically generates and is not easy.Hydroxyl simultaneously
Excessive, it is mobile that precipitation reaction balances the direction formed to rare earth hydrate；Furthermore 70-95 DEG C of temperature is controlled, faster life is easier to
At the rare earth hydrate of crystal form, sulfate radical migration and introducing speed are slow compared with hydroxyl；Thus from the angle of thermodynamics and kinetics
The formation for preventing alkali formula sulfuric acid rare earth prevents the introducing of sulfate radical from source.In addition, the addition speed of rare earth sulfate solution is
0.5-10mL/min, the additional amount of rare earth sulfate solution are the 85%-95% for precipitating the theoretical amount of the precipitating reagent.It is heavy to pay attention to
The control of shallow lake process cannot be controlled according to pH terminal, because temperature is affected to pH, while precipitation system is if it is oxygen
Change the substances such as magnesium, calcium oxide, the variation of pH is smaller, is not easy to measure.It therefore can only be with the addition of sulfuric acid rare earth in precipitation process
Amount is incorporated as precipitating the 85%-95% of the theoretical amount of the precipitating reagent to control, cannot be too high, and being unable to hydroxyl cannot
It is sufficiently excessive, and rare-earth precipitation rate is not high, while can not be too low, such alkali comes too much, to waste precipitating reagent.While if it is
Calcium and magnesium alkaline sedimentation system, sulfuric acid rare earth additional amount is very little, and the calcium and magnesium alkali compounds of filtering can also enter in precipitated product,
Product purity is caused to reduce.In addition, rare earth sulfate solution continues heat preservation ageing 1-6h after feeding, sufficiently make system excessive hydrogen
Oxygen root and sulfate radical competition, and make rare earth hydrate aging crystallization.
Particularly, rare earth sulfate solution is that sulfate leaches the resulting leachate of southern ion type rareearth ore, and rare earth is dense
Degree is 0.005-0.020mol/L, and aluminum ions concentration is less than 1g/L, and the concentration of iron ion is less than 1g/L.Re dip solution is not required to
It cleans, directly carries out anti-charging precipitating, iron aluminium impurity also enters in precipitating in leachate, by roasting described in step (4)
After the processing of firing degree, iron aluminium will form di-iron trioxide, alpha-aluminium oxide, be not easy to be dissolved in rare earth ore concentrate acid dissolution, and
From the extraction process for shortening ion adsorption type rare earth ore, realizes iron aluminium impurity and separated with the simple and effective of rare earth.
(3) it is washed, is separated by solid-liquid separation after precipitating, obtain rare earth hydrate and mother liquor of precipitation of ammonium, measured in rare earth hydrate
Sulfur content is calculated as X, with SO3Meter；
During water washing operations, stop washing when washing sulfate radical in filtrate and being less than 10ppm.It can sufficiently remove in this way
The sulfate radical that physical absorption introduces.
(4) if X≤0.1wt.%, rare earth hydrate obtains rare earth oxide by 400-500 DEG C of heat preservation roasting 2-4h；If
0.1wt.% < X≤0.5wt.%, rare earth hydrate pass through 400-500 DEG C of heat preservation respectively and roast 2-4h, 800-900 DEG C of heat preservation roastings
2-4h, 1300~1500 DEG C of heat preservations roasting 2-4h are burnt, rare earth oxide is finally obtained.
By the way of counter feed, while precipitation process temperature and sulfuric acid rare earth additional amount are controlled, available sulfur content
The rare earth hydrate of≤0.5wt.% is controlled by the fine optimization of deposition condition, it might even be possible to obtain sulfur content≤
The rare earth hydrate of 0.1wt.%.As X≤0.1wt.%, sulfur content is lower, meets the requirements, and roasts by 400-500 DEG C of heat preservation
Rare earth oxide of the sulfur content lower than 0.2wt.% will be can be obtained (with SO after rare earth hydrate roasting water removal by burning 2h3Meter).And
As 0.1wt.% < X≤0.5wt.%, rare earth hydrate passes through 400-500 DEG C of heat preservation respectively and roasts 2-4h, 800-900 DEG C of guarantors
Temperature roasting 2-4h, 1300~1500 DEG C of heat preservations roast 2-4h, finally obtain the rare earth oxide that sulfur content is lower than 0.2wt.%.It is logical
The mode of baking inphases is crossed, the removal of sulphur is more thorough, while obtained rare earth hydrate is also more loose porous, it is not easy to tie
Block；
Further illustrate that a kind of anti-charging precipitating-baking inphases provided by the invention prepare low-sulfur below in conjunction with embodiment
The method of content rare earth oxide.
Comparative example 1
The sodium hydroxide solution of addition 0.5mol/L into the lanthanum sulfate solution of 0.5mol/L, charging rate 5mL/min,
The additional amount of sodium hydroxide is 1.11 times of (the precipitating hydroxides of the amount of rare earth just at this time of complete sulfate precipitate lanthanum theoretical amount
The 90% of the theoretical amount of sodium), feed precipitation process in be always maintained at temperature be 80 DEG C, sodium hydroxide solution feed after 80
DEG C heat preservation ageing 3 it is small after be filtered washing, when wash filtrate in sulfate radical be less than 10ppm when stop washing, acquisition hydroxide
Rare-earth precipitation, it is 0.48wt.% that measurement, which obtains the sulfur content in rare earth hydrate,；Above-mentioned rare earth hydrate is by 900 DEG C of roastings
2h, it is final to obtain the rare earth oxide that sulfur content is 0.60wt.%.
Comparative example 2
The calcium hydroxide slurry of addition 0.5mol/L into the lanthanum sulfate solution of 0.5mol/L, charging rate 5mL/min,
The additional amount of calcium hydroxide is 1.11 times of (the precipitating hydroxides of the amount of rare earth just at this time of complete sulfate precipitate lanthanum theoretical amount
The 90% of the theoretical amount of sodium), feed precipitation process in be always maintained at temperature be 80 DEG C, calcium hydroxide slurry feed after 80
DEG C heat preservation ageing 3 it is small after be filtered washing, when wash filtrate in sulfate radical be less than 10ppm when stop washing, acquisition hydroxide
Rare-earth precipitation, it is 2.54wt.% that measurement, which obtains the sulfur content in rare earth hydrate,；Above-mentioned rare earth hydrate is by 900 DEG C of roastings
2h, it is final to obtain the rare earth oxide that sulfur content is 3.05wt.%.
Comparative example 3
The calcium hydroxide slurry of addition 0.5mol/L into the lanthanum sulfate solution of 0.5mol/L, charging rate 5mL/min,
The additional amount of calcium hydroxide is 1.11 times of (the precipitating hydroxides of the amount of rare earth just at this time of complete sulfate precipitate lanthanum theoretical amount
The 90% of the theoretical amount of sodium), feed precipitation process in be always maintained at temperature be 80 DEG C, calcium hydroxide slurry feed after 80
DEG C heat preservation ageing 3 it is small after be filtered washing, when wash filtrate in sulfate radical be less than 10ppm when stop washing, acquisition hydroxide
Rare-earth precipitation, it is 2.54wt.% that measurement, which obtains the sulfur content in rare earth hydrate,；Above-mentioned rare earth hydrate is by 1400 DEG C of roastings
2h, it is final to obtain the rare earth oxide that sulfur content is 1.98wt.%.
Comparative example 4
The calcium hydroxide slurry of addition 0.5mol/L into the lanthanum sulfate solution of 0.5mol/L, charging rate 5mL/min,
The additional amount of calcium hydroxide is 1.11 times of (the precipitating hydroxides of the amount of rare earth just at this time of complete sulfate precipitate lanthanum theoretical amount
The 90% of the theoretical amount of sodium), feed precipitation process in be always maintained at temperature be 80 DEG C, calcium hydroxide slurry feed after 80
DEG C heat preservation ageing 3 it is small after be filtered washing, when wash filtrate in sulfate radical be less than 10ppm when stop washing, acquisition hydroxide
Rare-earth precipitation, it is 2.54wt.% that measurement, which obtains the sulfur content in rare earth hydrate,；Above-mentioned rare earth hydrate is by 500 DEG C of roastings
It is final to obtain the rare earth oxide that sulfur content is 1.65wt.% after 2h, 800 DEG C of roasting 2h, 1400 DEG C of roasting 2h.
Comparative example 5
The lanthanum sulfate solution of addition 0.5mol/L into the calcium hydroxide slurry of 0.5mol/L, charging rate 5mL/min,
The additional amount of lanthanum sulfate solution be precipitate the calcium hydroxide theoretical amount 90%, feed precipitation process in be always maintained at temperature
Degree is 80 DEG C, washing is filtered after 80 DEG C of heat preservation ageings 3 are small after calcium hydroxide slurry feeds, when sulfuric acid in washing filtrate
Root stops washing when being less than 10ppm, obtains rare earth hydrate precipitating, and the sulfur content that measurement obtains in rare earth hydrate is
0.3wt.%；Above-mentioned rare earth hydrate is final to obtain the rare-earth oxidation that sulfur content is 0.22wt.% after 1400 DEG C of roasting 2h
Object.
Comparative example 6
The lanthanum sulfate solution of addition 0.5mol/L into the calcium hydroxide slurry of 0.5mol/L, charging rate 5mL/min,
The additional amount of lanthanum sulfate solution be precipitate the calcium hydroxide theoretical amount 90%, feed precipitation process in be always maintained at temperature
Degree is 60 DEG C, washing is filtered after 60 DEG C of heat preservation ageings 3 are small after calcium hydroxide slurry feeds, when sulfuric acid in washing filtrate
Root stops washing when being less than 10ppm, obtains rare earth hydrate precipitating, and the sulfur content that measurement obtains in rare earth hydrate is
1.07wt.%；Above-mentioned rare earth hydrate finally obtains sulphur after 500 DEG C of roasting 2h, 800 DEG C of roasting 2h, 1400 DEG C of roasting 2h
Content is the rare earth oxide of 0.41wt.%.
Comparative example 7
The lanthanum sulfate solution of addition 0.5mol/L into the calcium hydroxide slurry of 0.5mol/L, charging rate 5mL/min,
The additional amount of lanthanum sulfate solution be precipitate the calcium hydroxide theoretical amount 100%, feed precipitation process in be always maintained at
Temperature is 80 DEG C, washing is filtered after 80 DEG C of heat preservation ageings 3 are small after calcium hydroxide slurry feeds, when sulphur in washing filtrate
Acid group stops washing when being less than 10ppm, obtains rare earth hydrate precipitating, and the sulfur content that measurement obtains in rare earth hydrate is
1.88wt.%；Above-mentioned rare earth hydrate finally obtains sulphur after 500 DEG C of roasting 2h, 800 DEG C of roasting 2h, 1400 DEG C of roasting 2h
Content is the rare earth oxide of 0.58wt.%.
Embodiment 1
The lanthanum sulfate solution of addition 0.5mol/L into the calcium hydroxide slurry of 0.5mol/L, charging rate 5mL/min,
The additional amount of lanthanum sulfate solution be precipitate the calcium hydroxide theoretical amount 90%, feed precipitation process in be always maintained at temperature
Degree is 80 DEG C, washing is filtered after 80 DEG C of heat preservation ageings 3 are small after calcium hydroxide slurry feeds, when sulfuric acid in washing filtrate
Root stops washing when being less than 10ppm, obtains rare earth hydrate precipitating, and the sulfur content that measurement obtains in rare earth hydrate is
0.3wt.%；Above-mentioned rare earth hydrate finally obtains sulphur after 500 DEG C of roasting 2h, 800 DEG C of roasting 2h, 1400 DEG C of roasting 2h
Content is the rare earth oxide of 0.15wt.%.
Embodiment 2
The yttrium sulfate that 0.8mol/L is added into the sodium hydroxide and ammonia water mixture (molar ratio 9:1) of 1.0mol/L is molten
Liquid, charging rate 10mL/min, the additional amount of yttrium sulfate solution are that the theoretical of the precipitating sodium hydroxide-ammonia water mixture is used
The 95% of amount, being always maintained at temperature in the precipitation process that feeds is 95 DEG C, after charging 95 DEG C of heat preservations be aged 5 it is small after be filtered
Washing stops washing when washing sulfate radical in filtrate and being less than 10ppm, obtains rare earth hydrate precipitating, and measurement obtains hydroxide
Sulfur content in rare earth is 0.42wt.%；Above-mentioned rare earth hydrate is by 400 DEG C of roasting 2h, 900 DEG C of roasting 2h, 1500 DEG C of roastings
It is final to obtain the rare earth oxide that sulfur content is 0.12wt.% after burning 2h.
Embodiment 3
Ion adsorption type rare earth ore is leached using magnesium sulfate, acquisition rare earth concentration is 0.005mol/L, aluminium ion concentration is
240mg/L, iron concentration are the re dip solution of 60mg/L.Above-mentioned rare earth leaching is added into the magnesia slurry of 0.2mol/L
Liquid out, charging rate 0.5mL/min, the additional amount of re dip solution be precipitate the magnesia theoretical amount 85%,
It is 75 DEG C that temperature is always maintained in charging precipitation process, is carried out after 75 DEG C of heat preservation ageings 2 are small after magnesia slurry feeds
Drainage is washed, and is stopped washing when washing sulfate radical in filtrate and being less than 10ppm, is obtained rare earth hydrate precipitating, measurement obtains hydrogen-oxygen
Changing the sulfur content in rare earth is 0.46wt.%；Above-mentioned rare earth hydrate passes through 400 DEG C of roasting 3h, 800 DEG C of roasting 3h, 1400 DEG C
It is final to obtain the rare earth oxide that sulfur content is 0.17wt.% after roasting 3h.And the ferro-aluminum element in leachate roasts to form three
Two iron and alpha-aluminium oxide are aoxidized, is able to achieve preferable separation in subsequent smelting acid dissolution.
Embodiment 4
The praseodymium sulfate neodymium solution (praseodymium neodymium molar ratio 1:1) of 0.3mol/L is added into the calcium oxide slurries of 0.7mol/L, adds
Material speed be 7mL/min, the additional amount of praseodymium sulfate neodymium solution be precipitate the calcium oxide theoretical amount 95%, feed precipitate
Being always maintained at temperature in the process is 95 DEG C, is filtered washing after 95 DEG C of heat preservation ageings 6 are small after calcium oxide slurries feed, when
It washes when sulfate radical in filtrate is less than 10ppm and stops washing, obtain rare earth hydrate precipitating, measurement obtains in rare earth hydrate
Sulfur content is 0.40wt.%；Above-mentioned rare earth hydrate is after 400 DEG C of roasting 2h, 800 DEG C of roasting 2h, 1300 DEG C of roasting 2h, most
The rare earth oxide that sulfur content is 0.15wt.% is obtained eventually.
Embodiment 5
The sulfuric acid terbium solution of addition 0.1mol/L into the magnesium hydroxide slurry of 0.1mol/L, charging rate 3mL/min,
The additional amount of sulfuric acid terbium solution be precipitate the magnesium hydroxide theoretical amount 88%, feed precipitation process in be always maintained at temperature
Degree is 70 DEG C, washing is filtered after 70 DEG C of heat preservation ageings 1 are small after magnesium hydroxide slurry feeds, when sulfuric acid in washing filtrate
Root stops washing when being less than 10ppm, obtains rare earth hydrate precipitating, and the sulfur content that measurement obtains in rare earth hydrate is
0.09wt.%；Above-mentioned rare earth hydrate is final to obtain the rare-earth oxidation that sulfur content is 0.11wt.% after 450 DEG C of roasting 4h
Object.
Embodiment 6
The Dineodymium trisulfate solution of addition 1.0mol/L into the calcium hydroxide slurry of 0.9mol/L, charging rate 8mL/min,
The additional amount of Dineodymium trisulfate solution be precipitate the calcium hydroxide theoretical amount 92%, feed precipitation process in be always maintained at temperature
Degree is 85 DEG C, washing is filtered after 85 DEG C of heat preservation ageings 4 are small after calcium hydroxide slurry feeds, when sulfuric acid in washing filtrate
Root stops washing when being less than 10ppm, obtains rare earth hydrate precipitating, and the sulfur content that measurement obtains in rare earth hydrate is
0.25wt.%；Above-mentioned rare earth hydrate finally obtains sulphur after 450 DEG C of roasting 2h, 750 DEG C of roasting 2h, 1400 DEG C of roasting 2h
Content is the rare earth oxide of 0.13wt.%.
Embodiment 7
Ion adsorption type rare earth ore is leached using ammonium sulfate, acquisition rare earth concentration is 0.006mol/L, aluminium ion concentration is
400mg/L, iron concentration are the re dip solution of 270mg/L.Above-mentioned re dip solution is added into the ammonium hydroxide of 0.4mol/L,
Charging rate is 2.0mL/min, the additional amount of re dip solution be precipitate the ammonium hydroxide theoretical amount 90%, charging precipitating
Being always maintained at temperature in the process is 85 DEG C, washing is filtered after 85 DEG C of heat preservation ageings 6 are small after charging, when in washing filtrate
Sulfate radical stops washing when being less than 10ppm, obtains rare earth hydrate precipitating, and the sulfur content that measurement obtains in rare earth hydrate is
0.38wt.%；Above-mentioned rare earth hydrate finally obtains sulphur after 500 DEG C of roasting 2h, 800 DEG C of roasting 2h, 1400 DEG C of roasting 2h
Content is the rare earth oxide of 0.19wt.%.And the ferro-aluminum element in leachate roasts and to form di-iron trioxide and alpha-aluminium oxide,
Preferable separation is able to achieve in subsequent smelting acid dissolution.
Claims (7)
1. a kind of method that anti-charging precipitating-baking inphases prepare low sulfur content rare earth oxide, which is characterized in that including following
Step:
(1) configuration concentration is the alkaline precipitating agent of 0.2-1.0mol/L, and alkaline precipitating agent is ammonium hydroxide, sodium hydroxide, hydroxide
One or more of calcium, magnesium hydroxide, calcium oxide, magnesia；
(2) rare earth sulfate solution is slowly added into alkaline precipitating agent, control precipitation reaction temperature is 70-95 oC, sulfuric acid rare earth
The concentration of rare earth is 0.005-1.0mol/L in solution, in terms of REO；
(3) it is washed, is separated by solid-liquid separation after precipitating, obtain rare earth hydrate and mother liquor of precipitation of ammonium, measured sulphur in rare earth hydrate and contain
Amount is calculated as X, with SO3Meter；
(4) if X≤0.1wt.%, rare earth hydrate passes through 400-500oC heat preservation roasting 2-4h obtains rare earth oxide；If 0.1
Wt.% < X≤0.5wt.%, rare earth hydrate pass through 400-500 respectivelyoC heat preservation roasting 2-4h, 800-900 oCHeat preservation roasting 2-
4h, 1300 ~ 1500 DEG C of heat preservations roast 2-4h, finally obtain rare earth oxide.
2. the method according to claim 1, wherein rare earth sulfate solution is sulfate leaching in the step (2)
The resulting leachate of southern ion type rareearth ore, rare earth concentration 0.005-0.020mol/L are taken, aluminum ions concentration is less than
The concentration of 1g/L, iron ion are less than 1g/L.
3. the method according to claim 1, wherein in the step (2) rare earth sulfate solution addition speed
For 0.5-10mL/min.
4. the method according to claim 1, wherein the additional amount of rare earth sulfate solution is in the step (2)
Precipitate the 85-95wt.% of the theoretical amount of the precipitating reagent.
5. the method according to claim 1, wherein the step (2) rare earth sulfate solution feed after after
Continuation of insurance temperature ageing 1-6h.
6. the method according to claim 1, wherein being filtered in the step (3) during water washing operations when washing
Stop washing when sulfate radical is less than 10ppm in liquid.
7. the method according to claim 1, wherein sulfur content is low in rare earth oxide obtained in step (4)
In 0.2 wt.%, with SO3Meter.
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