CN105132720B - Method for recovering rare earth in ion adsorption type rare earth ore leaching solution through fractional precipitation - Google Patents
Method for recovering rare earth in ion adsorption type rare earth ore leaching solution through fractional precipitation Download PDFInfo
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Abstract
The invention discloses a method for recovering rare earth in an ion adsorption type rare earth ore leaching solution through fractional precipitation. According to the method, firstly, a magnesium-containing alkaline compound is added to a purified ion adsorption type rare earth ore leaching solution for a precipitation reaction; and then a calcium-containing alkaline compound is further added for a precipitation reaction, and rare earth precipitation concentrates and precipitation mother liquor are obtained after solid-liquid separation. According to the method, raw materials adopted are cheap and easy to obtain, and the process is simple and easy to control, so that the production cost is lowered; the problem of ammonia and nitrogen pollution in the precipitation process of the ion adsorption type rare earth ore leaching solution is solved; meanwhile, the adding amount of the magnesium-containing/calcium-containing alkaline compound is controlled, so that a precipitant is dissolved fully as much as possible, and the purity of the rare earth precipitation concentrates is improved; in addition, sulfate ions and calcium ions in the leaching solution can form a small amount of calcium sulfate precipitate with the good crystallization property; crystals of rare earth hydrate can be induced, and the problem that the rare earth hydrate is not liable to form a crystal form precipitate can be also solved.
Description
Technical field
The present invention relates to field of rare earth hydrometallurgy, reclaims ion type in particular to a kind of fractional precipitation dilute
The method of native ore deposit leachate middle rare earth.
Background technology
Since 20 century 70s, the strategic position of rare earth element grows with each passing day, it has also become hi-tech development and tradition
Grand strategy resource indispensable during industry alteration, is described as " vitamin of modern industry " and " new material treasure-house ".
Rare earth is classified as " the strategic element of 21 century " by beautiful, Deng developed countries, in addition strategic reserves and primary study；China also exists
《National Program for Medium-to Long-term Scientific and Technological Development（2006-2020）》It is middle that rare earth material is listed in basis in manufacture field
The preferential theme and emphasis support direction of raw material.
According to the difference of physicochemical property between rare earth element, be grouped for it is light, in, heavy rare earth.Wherein in europium, terbium, dysprosium etc.
Heavy rare earth reserves are few, breach big, value is high, substitutability is little, are widely used in the high and new technologies such as defence and military, Aero-Space
Field, is the critical material for preparing high performance magnetic material, luminescent material, laser crystal, high-tech ceramics etc..At present, it is middle heavy
Rare earth is mainly derived from China's ion adsorption type rare earth ore, and in its terbium, dysprosium, europium, yttrium etc., heavy rare earth element partition is than light rare earth ore deposit
High more than ten times even tens times.Ion adsorption type rare earth ore is a kind of new external rare-earth mineral, in 1969 first in China
Ganzhou City of Jiangxi Province is found, and is distributed widely in southern seven province such as China Jiangxi, Guangdong, Guangxi, Hunan, Fujian, Yunnan, Zhejiang
Part.Such mineral rare earth partition is complete, and radioactivity is low, and is rich in middle heavy rare earth element, is the valuable Strategic mineral resources of China.
Generally, in ion adsorption type rare earth ore, full phase rare earth grade is 0.05%-0.3%, wherein 60%-95%
Rare earth element be mutually exist with ion, ion phase rare earth with the form of rare earth hydrated ion or hydroxyl hydrated ion pass through electrostatic
Effect is adsorbed on clay mineral, when these are attracted to the rare earth ion on clay mineral（Ion phase rare earth）Run into chemically
The active cation of matter（Such as Na+、Mg2+、Ca2+、NH4 +Deng）When, can be by its exchange desorption.China scientific worker is according to this
Feature, develops the leaching technology such as the leaching agents such as sodium chloride, ammonium sulfate and bucket leaching, pond leaching, dump leaching and original place leaching in succession.Mesh
Before, ion adsorption type rare earth ore is generally leached using ammonium sulfate, and the re dip solution for obtaining adopts ammonium hydrogen carbonate removal of impurities, bicarbonate
Ammonium or oxalic acid precipitation recovering rare earth, then through roasting, obtain the mixed rare-earth oxide concentrate that content of rare earth is calculated as 90% with REO.
Ion ore deposit re dip solution rare earth concentration is low, and typically in 2g/L or so, impurity content is high, and existing ammonium hydrogen carbonate/oxalic acid precipitation is returned
Receiving rare-earth process, to there is rare earth yield relatively low, and chemical reagent consumes big, and production cost is high, there is ammonia nitrogen waste water, oxalic acid waste water
The problems such as discharge.
In order to reduce production cost, while reducing ammonia and nitrogen pollution, CN101037219 is heavy as precipitating reagent using magnesia slurry
Rare earth in the earth solution of shallow lake；CN101475202 is heavy as precipitating reagent with the intermixture of crystal seed composition using calcium oxide or calcium oxide
Rare earth in the earth solution of shallow lake.Although in above-mentioned patent precipitating reagent used can reduces cost, while eliminate ammonia and nitrogen pollution,
It is that, when said method is used for precipitating ion absorbent-type Rare Earth Mine leachate, as magnesia is very slightly soluble material, precipitation is instead
It is long between seasonable, and for ensureing the rate of deposition of solution middle rare earth, precipitating reagent needs excess, and now excessive unreacted completely sinks
Shallow lake agent is will go in rare-earth precipitation enriched substance, greatly reduces rare earth ore concentrate product purity.And calcium oxide belongs to micro-soluble material, sink
Reaction of forming sediment is very fast, but due to containing substantial amounts of sulfate radical in ion ore deposit leachate, individually using calcium oxide as precipitating reagent, its
Substantial amounts of calcium sulfate precipitation can be produced during precipitating ion ore deposit leachate, the same purity for reducing rare earth ore concentrate product.
And in order to solve the problems, such as above-mentioned rare earth ore concentrate product purity, CN103436720 is proposed using magnesium hydroxide/hydrogen-oxygen
Change the method precipitation low concentration of rare earth leachate of calcium and NaOH two-step precipitation.But expensive hydrogen-oxygen used in the technique
Change sodium, considerably increase production cost, while being difficult to obtain the good rare earth hydrate of crystal property so that rare-earth precipitation is enriched with
Water content of matter is high, reduces production production capacity, increased energy consumption.CN102190325（It is a kind of to reclaim from ion type rareearth raw ore
The method of rare earth) rare earth precipitated as precipitating reagent in leachate is disclosed using magnesium bicarbonate or/and the calcium bicarbonate aqueous solution, obtain
Carbonated rare earth is obtained, production cost is reduced, but pure magnesium bicarbonate or/and the calcium bicarbonate aqueous solution equipment of preparation is more multiple
It is miscellaneous, invest larger.CN104152693 is disclosed and is precipitated low concentration of rare earth leachate using containing magnesium precipitation agent, then again toward containing magnesium
Carbon dioxide is passed through in rare-earth precipitation thing, the purpose for being passed through carbon dioxide is to speed up the speed reacted and removes precipitated product
In magnesium, make the magnesium in sediment be changed into diffluent magnesium bicarbonate and enter solution, rare earth is changed into carbonated rare earth sediment.
But paper " Effect of impurity ions on the preparation of novel saponifier for
rare earth extraction”（Jounal of rare earth, the first phases of volume 34 in 2013）Result of study show,
In the presence of rare earth, most of magnesium compound cannot be carbonized generation magnesium bicarbonate solution, but generate carbonic acid magnesium precipitate,
The purity of rare earth ore concentrate product cannot substantially be improved.
Therefore, still can not both reduce in the method for current ion adsorption type rare earth ore leachate recovering rare earth and produce into
Originally ammonia and nitrogen pollution is reduced, ensures the purity of product middle rare earth again.
The content of the invention
Present invention is primarily targeted at providing a kind of fractional precipitation reclaims ion adsorption type rare earth ore leachate middle rare earth
Method, to reduce production cost, reduce ammonia and nitrogen pollution, and ensure the purity of product middle rare earth, and be easy to industrialization.
To achieve these goals, there is provided the side of ion adsorption type rare earth ore leachate middle rare earth is reclaimed in a kind of fractional precipitation
Method, comprises the following steps：Add in ion adsorption type rare earth ore leachate first after processing Jing removal of impurities containing magnesium alkalescence chemical combination
Thing carries out precipitation reaction, and then adding calcic alkali compounds carries out precipitation reaction, obtains rare-earth precipitation rich after separation of solid and liquid
Collection thing and mother liquor of precipitation of ammonium；Wherein, in terms of magnesia, the addition containing magnesium alkali compounds is heavy for the leachate Rare Earth Ion
The X wt% of theoretical amount needed for forming sediment completely；In terms of calcium oxide, the addition of calcic alkali compounds is the leachate middle rare earth
The Y wt% of the completely required theoretical amount of ion precipitation, 10 %≤X %≤80%, 25%≤Y%≤120%, 105%≤X%+ Y%≤
130%。
Further, in the ion adsorption type rare earth ore leachate Jing after removal of impurities process, the concentration of sulfate ion is
0.2g/L~20g/L。
Further, in terms of REO, the concentration of the ion adsorption type rare earth ore leachate middle rare earth Jing after removal of impurities is processed is
0.2~30g/L。
Further, alkali compounds containing magnesium be magnesia, magnesium hydroxide, in the product of roasting of magnesium-containing mineral at least one
Kind.
Further, calcic alkali compounds be calcium oxide, calcium hydroxide, in the product of roasting of calcium mineral at least one
Kind.
Further, magnesium-containing mineral be serpentine, magnesite, at least one in water magnesium ore deposit.
Further, calcium mineral be lime stone, marble, at least one in calcite.
Further, in terms of magnesia, the addition containing magnesium alkali compounds is precipitated for the leachate Rare Earth Ion
The X wt% of theoretical amount needed for completely；In terms of calcium oxide, the addition of calcic alkali compounds be the leachate middle rare earth from
The Y wt% of the completely required theoretical amount of son precipitation, 30 %≤X %≤70%, 35%≤Y%≤100%, 105%≤X%+ Y%≤
130%。
Further, in the step of adding alkali compounds containing magnesium to carry out precipitation reaction, reaction temperature is 5 DEG C～90 DEG C；
In the step of adding calcic alkali compounds to carry out precipitation reaction, reaction temperature is 5 DEG C～90 DEG C.
Further, in terms of REO, the content of the mother liquor of precipitation of ammonium middle rare earth obtained after precipitation is below 0.1g/L.
Ion type by being first added to alkali compounds containing magnesium as precipitating reagent Jing after removal of impurities is processed of the invention
In Rare Earth Mine leachate, now higher rare earth concentration is conducive to the dissolving of sl. sol. magnesium alkali compounds so as to fully react,
Then calcic alkali compounds is added in leachate as precipitating reagent and precipitates remaining rare earth, carry out separation of solid and liquid, to obtain
Obtain rare-earth precipitation enriched substance.The adopted raw material of the method is cheap and easy to get and process is simple and easy to control, reduces production cost, gets rid of
The problem of ammonia and nitrogen pollution in ion adsorption type rare earth ore leachate precipitation process, while by control containing magnesium/calc-alkaline compound
Addition, precipitating reagent is completely dissolved as far as possible, improve the purity of rare-earth precipitation enriched substance, and the sulfate radical in leachate
Ion can form the good calcium sulfate precipitation of a small amount of crystal property with calcium ion, can induce the crystallization of rare earth hydrate, can also solve
Certainly rare earth hydrate is difficult to form the problem of crystalline precipitation.
Specific embodiment
It should be noted that in the case where not conflicting, the feature in embodiment and embodiment in the application can phase
Mutually combine.The application is described in detail below in conjunction with embodiment.
From background technology, in the method for existing ion adsorption type rare earth ore leachate recovering rare earth, can not both reduce life
Produce cost, reduce ammonia and nitrogen pollution, ensure the purity of product middle rare earth again.
The invention provides a kind of method that ion adsorption type rare earth ore leachate middle rare earth is reclaimed in fractional precipitation, including with
Lower step：Alkali compounds containing magnesium is added to be precipitated in ion adsorption type rare earth ore leachate first after processing Jing removal of impurities
Reaction, then adding calcic alkali compounds carries out precipitation reaction, obtains rare-earth precipitation enriched substance and precipitation after separation of solid and liquid
Mother liquor；Wherein, in terms of magnesia, the addition containing magnesium alkali compounds is for needed for leachate Rare Earth Ion precipitation is complete
The X wt% of theoretical amount；In terms of calcium oxide, the addition of calcic alkali compounds has been precipitated for the leachate Rare Earth Ion
The Y wt% of theoretical amount, 10 %≤X %≤80%, 25%≤Y%≤120%, 105%≤X%+ Y%≤130% needed for complete.
The present invention be directed to the ion adsorption type rare earth ore leachate Jing after removal of impurities is processed carries out fractional precipitation recovering rare earth,
In the leachate, the concentration of sulfate ion is 0.2g/L ~ 20g/L, and the concentration of rare earth is 0.2 ~ 30g/L（In terms of REO）.Should
Leachate is to obtain in existing industrial ion adsorption type rare earth ore extraction process, and ion adsorption type rare earth ore is passed through sulphur
The leaching agent solution leaching such as sour ammonium/magnesium sulfate, then again Jing after the removal of impurities such as ammonium hydrogen carbonate/NaOH/sodium acid carbonate/magnesia
Directly obtain the described ion adsorption type rare earth ore leachate Jing after removal of impurities is processed.Further, since ion adsorption type rare earth ore
With the presence of sulfate radical in soil itself, therefore using the leaching agent of non-sulfuric acid salt（Such as ammonium nitrate, ammonium chloride, sodium chloride, chlorination
Calcium etc.）Heretofore described ion adsorption type rare earth ore leachate can also be obtained.
Being firstly added alkali compounds containing magnesium carries out precipitation reaction, and then adding calcic alkali compounds carries out precipitating anti-
Should, and control 10 % of addition≤X %≤80% containing magnesium/calc-alkaline compound, 25%≤Y%≤120%, 105%≤X%+ Y%
≤ 130%, rare-earth precipitation enriched substance and mother liquor of precipitation of ammonium is obtained after separation of solid and liquid.As the alkali compounds containing magnesium/calcium has simply
The advantage being easy to get, with low cost for precipitating the rare earth reclaimed in leachate, there is no ammonia and nitrogen pollution in precipitation process, and precipitation is produced
Calcium ions and magnesium ions can be used for soaking ore deposit process.But the solubility in water of alkali compounds containing magnesium is low, alkalescence is weak, is individually precipitated with which
The purity of final rare-earth products is affected easily.And solubility is higher in calcic alkali compounds water, alkalescence is relatively strong, and it is heavy to advantageously reduce
The final precipitated product purity of shallow lake reaction time, control, but independent there is also with its precipitation easily formed a large amount of calcium sulfate precipitations, drops
The problem of low product purity.Therefore a certain amount of alkali compounds containing magnesium is added toward leachate first in the present invention so as to it is dilute in height
Accelerate dissolving reaction under conditions of native concentration, reduce insoluble matter residual.Then add calcic alkali compounds precipitation leachate
In remaining rare earth, as its solubility is larger, be difficult to exist insoluble matter residual.The addition of calcic alkali compounds is provided simultaneously
Calcium ion, is conducive to the formation of a small amount of calcium sulfate in system, is conducive to inducing the crystallization of rare earth hydrate.
It is preferred that the addition containing magnesium/calc-alkaline compound is 30 %≤X %≤70%, and 35%≤Y%≤100%, 105%≤X%+
Y%≤130%.In above-mentioned preferred scope, it is to preferably ensure to carry out alkali compounds containing magnesium under higher rare earth concentration
Precipitation process, is conducive to improving settling rate, while being conducive to controlling the amount of insoluble matter in final precipitated product, improves rare earth and produces
The purity of product.The Ksp of calcium sulfate is taken into account simultaneously, can precipitate remaining rare earth completely in making the precipitation process of calcic alkali compounds
Ion, while generating a small amount of calcium sulfate precipitation with sulfate ion reaction in raw material, is conducive to inducing rare earth hydrate
Crystalline precipitation, and be unlikely to generate excessive calcium sulfate so that affecting the purity of precipitated product.
The alkali compounds containing magnesium for being adopted is at least in magnesia, magnesium hydroxide, the product of roasting of magnesium-containing mineral
Kind.Magnesium-containing mineral is serpentine, magnesite, at least one in water magnesium ore deposit.The calcic alkali compounds for being adopted for calcium oxide,
At least one in calcium hydroxide, the product of roasting of calcium mineral.Calcium mineral is lime stone, marble, in calcite extremely
Few one kind.It is compared with traditional precipitating reagent NaOH, sodium carbonate, oxalic acid etc., above-mentioned cheap and easy to get containing magnesium/calc-alkaline compound
And process is simple and easy to control, production cost is advantageously reduced.
In the step of adding alkali compounds containing magnesium to carry out precipitation reaction, reaction temperature is 5 DEG C～90 DEG C.Reaction is normal
Carry out under temperature, heating that also can be appropriate, be conducive to accelerating precipitation reaction speed.Reaction time can be adjusted according to actual conditions
It is whole.
In the step of adding calcic alkali compounds to carry out precipitation reaction, reaction temperature is 5 DEG C～90 DEG C.Similarly,
Reaction is carried out at normal temperatures, heating that also can be appropriate, is conducive to quickening precipitation reaction speed.Reaction time can be according to reality
Situation is adjusted.
The present invention reclaims the rare earth in ion adsorption type rare earth ore using fractional precipitation, finally obtains rare-earth precipitation enriched substance
And mother liquor of precipitation of ammonium.Rare-earth precipitation enriched substance can obtain rare earth ore concentrate product Jing after calcining；It is dilute in the mother liquor of precipitation of ammonium obtained after precipitation
The content of soil is below 0.1g/L（In terms of REO）, to ensure that rare earth has higher recovery.
Ion adsorption type rare earth ore leaching is reclaimed in the fractional precipitation that present invention offer is further illustrated below in conjunction with embodiment
The method for going out liquid middle rare earth.
Comparative example 1
Ion adsorption type rare earth ore leachate 10L after removal of impurities of learning from else's experience process, its rare earth concentration are 1.5g/L（REO is counted）、
Sulfate concentration is 4.0g/L.By the 110% of the completely required theoretical amount of leachate Rare Earth Ion precipitation, to leachate
Middle addition 9.12g calcium oxide, reacts 3 hours at 40 DEG C, and reaction carries out separation of solid and liquid and obtains rare-earth precipitation enriched substance after terminating
And mother liquor of precipitation of ammonium, mother liquor of precipitation of ammonium middle rare earth concentration is 0.03g/L（REO is counted）, rare-earth precipitation enriched substance obtained through 800 DEG C of calcinings
Rare earth ore concentrate product, its Purity of Rare Earth are 86.5wt%（REO is counted）.
Comparative example 2
Ion adsorption type rare earth ore leachate 10L after removal of impurities of learning from else's experience process, its rare earth concentration are 1.5g/L（REO is counted）、
Sulfate concentration is 4.0g/L.By the 110% of the completely required theoretical amount of leachate Rare Earth Ion precipitation, to leachate
Middle addition 6.51g magnesia, reacts 3 hours at 40 DEG C, and reaction carries out separation of solid and liquid and obtains rare-earth precipitation enriched substance after terminating
And mother liquor of precipitation of ammonium, the time used by separation of solid and liquid is 110min.Mother liquor of precipitation of ammonium middle rare earth concentration is 0.05g/L（REO is counted）, rare earth sink
Shallow lake enriched substance obtains rare earth ore concentrate product through 800 DEG C of calcinings, and its Purity of Rare Earth is 79.7wt%（REO is counted）.
Embodiment 1
Ion adsorption type rare earth ore leachate 10L after removal of impurities of learning from else's experience process, its rare earth concentration are 1.5g/L（REO is counted）、
Sulfate concentration is 4.0g/L.First by the 60% of the completely required theoretical amount of leachate Rare Earth Ion precipitation, to leaching
3.55g magnesia is added in liquid, is reacted 2 hours at 40 DEG C, it is then completely required by leachate Rare Earth Ion precipitation
The 50% of theoretical amount, adds 4.14g calcium oxide in leachate, reacts 1 hour at 40 DEG C.Reaction carries out solid-liquid after terminating
Separate and obtain rare-earth precipitation enriched substance and mother liquor of precipitation of ammonium, the time used by separation of solid and liquid is 20min.Mother liquor of precipitation of ammonium middle rare earth concentration is
0.02g/L（REO is counted）, rare-earth precipitation enriched substance obtains rare earth ore concentrate product through 800 DEG C of calcinings, and its Purity of Rare Earth is
92.5wt%（REO is counted）.
Embodiment 2
Ion adsorption type rare earth ore leachate 100L after removal of impurities of learning from else's experience process, its rare earth concentration are 0.2g/L（REO is counted）、
Sulfate concentration is 2.0g/L.First by the 30% of the completely required theoretical amount of leachate Rare Earth Ion precipitation, to leaching
2.37g magnesium hydroxides are added in liquid（In terms of magnesia）, at 60 DEG C react 2 hours, then by the leachate middle rare earth from
The 85% of the completely required theoretical amount of son precipitation, adds 9.39g calcium hydroxides in leachate（In terms of calcium oxide）, at 60 DEG C
Reaction 1 hour.Reaction carries out separation of solid and liquid and obtains rare-earth precipitation enriched substance and mother liquor of precipitation of ammonium after terminating, mother liquor of precipitation of ammonium middle rare earth is dense
Spend for 0.005g/L（REO is counted）, rare-earth precipitation enriched substance obtains rare earth ore concentrate product through 800 DEG C of calcinings, and its Purity of Rare Earth is
91.7wt%（REO is counted）.
Embodiment 3
Ion adsorption type rare earth ore leachate 100L after removal of impurities of learning from else's experience process, its rare earth concentration are 0.2g/L（REO is counted）、
Sulfate concentration is 2.0g/L.First by the 13% of the completely required theoretical amount of leachate Rare Earth Ion precipitation, to leaching
1.03g magnesium hydroxides are added in liquid（In terms of magnesia）, at 60 DEG C react 2 hours, then by the leachate middle rare earth from
The 102% of the completely required theoretical amount of son precipitation, adds 11.27g calcium hydroxides in leachate（In terms of calcium oxide）, at 60 DEG C
Lower reaction 1 hour.Reaction carries out separation of solid and liquid and obtains rare-earth precipitation enriched substance and mother liquor of precipitation of ammonium, mother liquor of precipitation of ammonium middle rare earth after terminating
Concentration is 0.004g/L（REO is counted）, rare-earth precipitation enriched substance obtains rare earth ore concentrate product through 800 DEG C of calcinings, its Purity of Rare Earth
For 90.3wt%（REO is counted）.
Embodiment 4
Ion adsorption type rare earth ore leachate 10L after removal of impurities of learning from else's experience process, its rare earth concentration are 10g/L（REO is counted）, sulphur
Acid group concentration is 0.2g/L.First by the 10% of the completely required theoretical amount of leachate Rare Earth Ion precipitation, to leachate
Middle addition 3.95g magnesia, reacts at 80 DEG C 1 hour, then by the completely required reason of leachate Rare Earth Ion precipitation
By the 120% of consumption, 66.32g calcium hydroxides are added in leachate（In terms of calcium oxide）, react 2 hours at 5 DEG C.Reaction knot
Separation of solid and liquid being carried out after beam and obtaining rare-earth precipitation enriched substance and mother liquor of precipitation of ammonium, mother liquor of precipitation of ammonium middle rare earth concentration is 0.02g/L（REO
Meter）, rare-earth precipitation enriched substance obtains rare earth ore concentrate product through 800 DEG C of calcinings, and its Purity of Rare Earth is 90.7wt%（REO is counted）.
Embodiment 5
Ion adsorption type rare earth ore leachate 10L after removal of impurities of learning from else's experience process, its rare earth concentration are 30g/L（REO is counted）, sulphur
Acid group concentration is 20g/L.First by the 80% of the completely required theoretical amount of leachate Rare Earth Ion precipitation, to leachate
Middle addition 94.74g magnesium hydroxides（In terms of magnesia）, react 2 hours at 90 DEG C, then by the leachate Rare Earth Ion
The 25% of the completely required theoretical amount of precipitation, adds 41.45g calcium hydroxides in leachate（In terms of calcium oxide）, it is anti-at 15 DEG C
Answer 2 hours.Reaction carries out separation of solid and liquid and obtains rare-earth precipitation enriched substance and mother liquor of precipitation of ammonium, mother liquor of precipitation of ammonium middle rare earth concentration after terminating
For 0.1g/L（REO is counted）, rare-earth precipitation enriched substance obtains rare earth ore concentrate product through 800 DEG C of calcinings, and its Purity of Rare Earth is
89.1wt%（REO is counted）.
Embodiment 6
Ion adsorption type rare earth ore leachate 10L after removal of impurities of learning from else's experience process, its rare earth concentration are 20g/L（REO is counted）, sulphur
Acid group concentration is 8g/L.First by the 70% of the completely required theoretical amount of leachate Rare Earth Ion precipitation, in leachate
55.26g is added containing the roasting magnesite product that magnesia is 98.5wt%（In terms of magnesia）, reaction 3 hours at 25 DEG C, so
Afterwards by the 35% of the completely required theoretical amount of leachate Rare Earth Ion precipitation, 38.68g hydroxides are added in leachate
Calcium（In terms of calcium oxide）, react 0.5 hour at 90 DEG C.Reaction terminate after carry out separation of solid and liquid obtain rare-earth precipitation enriched substance and
Mother liquor of precipitation of ammonium, mother liquor of precipitation of ammonium middle rare earth concentration are 0.1g/L（REO is counted）, rare-earth precipitation enriched substance obtains dilute through 800 DEG C of calcinings
Native concentrate product, its Purity of Rare Earth are 90.2wt%（REO is counted）.
Embodiment 7
Ion adsorption type rare earth ore leachate 10L after removal of impurities of learning from else's experience process, its rare earth concentration are 5g/L（REO is counted）, sulphur
Acid group concentration is 1g/L.First by the 20% of the completely required theoretical amount of leachate Rare Earth Ion precipitation, in leachate
3.95g magnesia is added, is reacted at 5 DEG C 2 hours, it is theoretical needed for then precipitating completely by the leachate Rare Earth Ion to use
The 100% of amount, adds 27.63g in leachate containing the calcite product of roasting that calcium oxide is 98wt%（In terms of calcium oxide）, 25
React 3 hours at DEG C.Reaction carries out separation of solid and liquid and obtains rare-earth precipitation enriched substance and mother liquor of precipitation of ammonium after terminating, dilute in mother liquor of precipitation of ammonium
Native concentration is 0.05g/L（REO is counted）, rare-earth precipitation enriched substance obtains rare earth ore concentrate product through 800 DEG C of calcinings, its Purity of Rare Earth
For 89.4wt%（REO is counted）.
Embodiment 8
Ion adsorption type rare earth ore leachate 10L after removal of impurities of learning from else's experience process, its rare earth concentration are 3g/L（REO is counted）, sulphur
Acid group concentration is 15g/L.First by the 75% of the completely required theoretical amount of leachate Rare Earth Ion precipitation, to leachate
The mixture of middle addition 8.88g magnesia and magnesium hydroxide（The mass ratio of magnesia and magnesium hydroxide is 1:1）（With magnesia
Meter）, react at 25 DEG C 3 hours, then by the 35% of the completely required theoretical amount of leachate Rare Earth Ion precipitation, to
The mixture of 5.80g calcium oxide and calcium hydroxide is added in leachate（The mass ratio of calcium oxide and calcium hydroxide is 1:1）（With oxygen
Change calcium meter）, react 1 hour at 25 DEG C.Reaction carries out separation of solid and liquid and obtains rare-earth precipitation enriched substance and mother liquor of precipitation of ammonium after terminating,
Mother liquor of precipitation of ammonium middle rare earth concentration is 0.04g/L（REO is counted）, rare-earth precipitation enriched substance through 800 DEG C calcining obtain rare earth ore concentrate product
Product, its Purity of Rare Earth are 89.7wt%（REO is counted）.
Embodiment 9
Longnan ion type rareearth mine, 6 meters of rare earth seam thickness, rare earth average grade 0.13%.The ore body rare earth is stored up
Measure for 54 tons, using in_situ leaching technique, complete ore body surface and beat the operations such as fluid injection well, liquid-collecting hole, cloth pipeline.Prepare 2% sulfuric acid
Ammonium leaching agent 8000m3.Leaching agent 350m is injected daily with topping-up pump3, start leachate middle rare earth concentration and be less than 0.2g/L, all
Blowback continues leaching ore deposit, and Steep cencentration carries out receipts liquid, can lower leaching agent depending on actual conditions in leaching process more than after 0.2g/L
Middle ammonium sulfate concentrations, when the leachate Rare-Earth Content collected is close to reserves, changes the drip washing of note clear water and receive liquid.The leachate collected
The ammonium bicarbonate soln regulation pH of 10g/L is adopted to carry out removal of impurities process for 5 or so.
Ion adsorption type rare earth ore leachate 10L after magnesia removal of impurities of learning from else's experience process, its rare earth concentration are 1.0g/L
（REO is counted）, sulfate concentration be 3.6g/L.First by the completely required theoretical amount of leachate Rare Earth Ion precipitation
65%, the mixture of 2.57g magnesium hydroxides is added in leachate（In terms of magnesia）, react 3 hours at 25 DEG C, then press
Needed for the leachate Rare Earth Ion precipitation is complete, the 35% of theoretical amount, adds 2.49g calcium oxide, in leachate 25
React 1.5 hours at DEG C.Reaction carries out separation of solid and liquid and obtains rare-earth precipitation enriched substance and mother liquor of precipitation of ammonium after terminating, in mother liquor of precipitation of ammonium
Rare earth concentration is 0.02g/L（REO is counted）, rare-earth precipitation enriched substance obtains rare earth ore concentrate product through 800 DEG C of calcinings, and its rare earth is pure
Spend for 92.2wt%（REO is counted）.
Claims (8)
1. a kind of method that ion adsorption type rare earth ore leachate middle rare earth is reclaimed in fractional precipitation, it is characterised in that first in Jing
Add alkali compounds containing magnesium to carry out precipitation reaction in ion adsorption type rare earth ore leachate after removal of impurities process, then add
Calcic alkali compounds carries out precipitation reaction, obtains rare-earth precipitation enriched substance and mother liquor of precipitation of ammonium after separation of solid and liquid；
Wherein, in leachate, the concentration of sulfate ion is 0.2g/L ~ 20g/L；In terms of magnesia, adding containing magnesium alkali compounds
Enter the X wt% of amount theoretical amount for needed for leachate Rare Earth Ion precipitation is complete；In terms of calcium oxide, calcic alkalescence chemical combination
Y wt%, 30 %≤X %≤70% of the addition of thing theoretical amount for needed for leachate Rare Earth Ion precipitation is complete,
35%≤Y%≤100%, 105%≤X%+ Y%≤130%.
2. method according to claim 1, it is characterised in that in terms of REO, the concentration of the leachate middle rare earth is 0.2 ~
30g/L。
3. method according to claim 1, it is characterised in that the alkali compounds containing magnesium be magnesia, magnesium hydroxide,
At least one in the product of roasting of magnesium-containing mineral.
4. method according to claim 1, it is characterised in that the calcic alkali compounds be calcium oxide, calcium hydroxide,
At least one in the product of roasting of calcium mineral.
5. method according to claim 3, it is characterised in that the magnesium-containing mineral is serpentine, magnesite, in water magnesium ore deposit
At least one.
6. method according to claim 4, it is characterised in that the calcium mineral is lime stone, marble, in calcite
At least one.
7. method according to claim 1, it is characterised in that the addition alkali compounds containing magnesium carries out precipitation reaction
In step, reaction temperature is 5 DEG C～90 DEG C；In the step of addition calcic alkali compounds carries out precipitation reaction, reaction temperature
Spend for 5 DEG C～90 DEG C.
8. method according to claim 1, it is characterised in that in terms of REO, the content of the mother liquor of precipitation of ammonium middle rare earth is
Below 0.1g/L.
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| CN105506287B (en) * | 2016-01-13 | 2017-09-19 | 赣州稀土开采技术服务有限公司 | The technique that southern RE ore leaches mother liquor precipitation method recovering rare earth |
| CN105803199B (en) * | 2016-03-29 | 2017-08-25 | 江西理工大学 | A kind of method that hydroxide precipitation method prepares low-sulfur rare earth oxide |
| CN105779792B (en) * | 2016-03-29 | 2018-01-30 | 江西理工大学 | A kind of method for preparing low impurity content rare earth hydrate |
| CN106435172B (en) * | 2016-10-14 | 2018-09-25 | 赣州弘茂稀土工程有限公司 | The technique that classification shunting processing is carried out to rare earth Situ Leaching mother liquor |
| CN106967881B (en) * | 2017-05-26 | 2018-12-04 | 江西理工大学 | A method of the Extraction of rare earth from weathered superficial leaching rare-earth ore |
| CN107190156B (en) * | 2017-05-26 | 2019-06-11 | 江西理工大学 | A method of the Extraction of rare earth from ion adsorption type rare earth ore |
| CN108893606B (en) * | 2018-08-30 | 2019-11-08 | 江西理工大学 | Precipitating, removal of impurities, middling recurrence extract the method without rare earth in ammonium rare earth mother solution |
| CN109097566A (en) * | 2018-09-17 | 2018-12-28 | 江西理工大学 | A method of the recovering rare earth from weathered superficial leaching rare-earth ore |
| CN112359232A (en) * | 2020-10-14 | 2021-02-12 | 南昌华亮光电有限责任公司 | Ion adsorption type rare earth extraction method using calcium chloride as leaching agent |
| CN112281003B (en) * | 2020-11-02 | 2022-09-30 | 广西国盛稀土新材料有限公司 | Impurity removal method for low-grade sulfuric acid rare earth leaching solution |
| CN114774719A (en) * | 2022-04-29 | 2022-07-22 | 王静若 | Treatment method for recovering oxalate from heavy metal in rare earth post-solution after oxalic acid precipitation |
| CN115627372B (en) * | 2022-09-30 | 2023-12-19 | 中稀(广西)金源稀土新材料有限公司 | Rare earth precipitation method |
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| CN101475202A (en) * | 2008-10-28 | 2009-07-08 | 黄日平 | Rare earth solution precipitating agent production process using calcium oxide |
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