CN105132720A - 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, reclaim the method for ion adsorption type rare earth ore leach liquor middle-weight rare earths in particular to a kind of fractional precipitation.
Background technology
Since 20 century 70s, the strategic position of rare earth element grows with each passing day, and has become grand strategy resource indispensable in hi-tech development and Transform of Traditional Industrial Equipment process, is described as " VITAMIN of modern industry " and " novel material treasure-house ".Rare earth is all classified as " the strategic element of 21 century " by beautiful, Deng developed country, in addition strategic reserves and primary study; China also lists rare earth material in preferential theme and the emphasis support direction of basic raw material in manufacture field in " National Program for Medium-to Long-term Scientific and Technological Development (2006-2020) ".
According to the difference of physico-chemical property between rare earth element, be grouped into light, in, heavy rare earths.Wherein in europium, terbium, dysprosium etc., heavy rare earths reserves are few, breach large, it is high to be worth, substitutability is little, being widely used in the high and new technology such as defence and military, aerospace field, is the critical material preparing high performance magnetic material, luminescent material, laser crystals, high-tech pottery etc.At present, middle heavy rare earths 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 higher than light rare earths ore deposit more than ten times even tens times.Ion adsorption type rare earth ore is a kind of novel external rare-earth mineral, is found first, is distributed widely in southern seven provinces such as China Jiangxi, Guangdong, Guangxi, Hunan, Fujian, Yunnan, Zhejiang in 1969 in Ganzhou City of Jiangxi Province of China.This type of mineral ree distribution pattern is complete, and radioactivity is low, and is rich in middle heavy rare earth element, is the Strategic mineral resources of China's preciousness.
Generally, in ion adsorption type rare earth ore, full phase rare earth grade is 0.05%-0.3%, wherein the rare earth element of 60%-95% exists with Ion Phase, Ion Phase rare earth is adsorbed on clay mineral with the form of rare earth hydrated ion or hydroxyl hydrated ion by electrostatic interaction, and the rare earth ion (Ion Phase rare earth) be attracted on clay mineral when these runs into the active positively charged ion of chemical property (as Na
+, Mg
2+, Ca
2+, NH
4 +deng) time, desorb can be exchanged by it.China scientific worker, according to this feature, develops the leaching technology such as the leaching agent such as sodium-chlor, ammonium sulfate and bucket leaching, pond leaching, dump leaching and original place leaching in succession.At present, ion adsorption type rare earth ore adopts ammonium sulfate to leach usually, and the re dip solution obtained adopts bicarbonate of ammonia removal of impurities, bicarbonate of ammonia or oxalic acid precipitation recovering rare earth, then through roasting, obtains content of rare earth counts 90% mixed rare-earth oxide concentrate with REO.Ion ore deposit re dip solution rare earth concentration is low, general at about 2g/L, foreign matter content is high, and it is lower that existing bicarbonate of ammonia/oxalic acid precipitation recovering rare earth technique exists rare earth yield, chemical reagent consumption is large, and production cost is high, there is the problem such as ammonia nitrogen waste water, oxalic acid discharge of wastewater.
In order to reduce production cost, reduce ammonia and nitrogen pollution, CN101037219 is using magnesium oxide slurry as the rare earth in precipitation agent precipitating rare earth solution simultaneously; The mixture that CN101475202 forms using calcium oxide or calcium oxide and crystal seed is as the rare earth in precipitation agent precipitating rare earth solution.Although precipitation agent used in above-mentioned patent can reduce costs, eliminate ammonia and nitrogen pollution simultaneously, but when aforesaid method is used for precipitating ion adsorptive type rare-earth mineral leach liquor, because magnesium oxide is very slightly soluble material, the precipitin reaction time is long, and for ensureing the deposition rate of solution middle-weight rare earths, it is excessive that precipitation agent needs, and now excessive unreacted completely precipitation agent will enter into rare-earth precipitation enriched substance, greatly reduce rare earth ore concentrate product purity.And calcium oxide belongs to micro-soluble material, precipitin reaction is very fast, but owing to containing a large amount of sulfate radicals in the leach liquor of ion ore deposit, adopts separately calcium oxide as precipitation agent, it can produce a large amount of calcium sulfate precipitations in the process of precipitating ion ore deposit leach liquor, the same purity reducing rare earth ore concentrate product.
And in order to solve the problem of above-mentioned rare earth ore concentrate product purity, CN103436720 proposes the method precipitation low concentration of rare earth leach liquor adopting magnesium hydroxide/calcium hydroxide and sodium hydroxide two-step precipitation.But employ expensive sodium hydroxide in this technique, considerably increase production cost, not easily obtain the good rare earth hydrate of crystal property simultaneously, make rare-earth precipitation enriched substance water ratio high, reduce production production capacity, add production energy consumption.CN102190325(method from ion type rareearth raw ore recovering rare earth) disclose using Magnesium hydrogen carbonate or/and the Calcium hydrogen carbonate aqueous solution is as the rare earth precipitation agent precipitation leach liquor, obtain carbonated rare earth, reduce production cost, but the pure Magnesium hydrogen carbonate of preparation, or/and Calcium hydrogen carbonate aqueous solution equipment is more complicated, is invested larger.CN104152693 discloses and adopts containing magnesium precipitation agent precipitation low concentration of rare earth leach liquor, and then pass into carbon dioxide toward containing in magnesium rare-earth precipitation thing, the object passing into carbonic acid gas is the speed adding fast response and the magnesium removed in precipitated product, make the magnesium in throw out change diffluent Magnesium hydrogen carbonate into and enter solution, rare earth changes carbonated rare earth throw out into.But paper " Effectofimpurityionsonthepreparationofnovelsaponifierfor rareearthextraction " (Jounalofrareearth, the 34 volume first phases in 2013) result of study show, deposit in case at rare earth, major part magnesium compound carbonization cannot generate magnesium bicarbonate solution, but generate carbonic acid magnesium precipitate, essence cannot improve the purity of rare earth ore concentrate product.
Therefore, still both can not reduce production cost in the method for current ion adsorption type rare earth ore leach liquor recovering rare earth, reduce ammonia and nitrogen pollution, ensure again the purity of product middle-weight rare earths.
Summary of the invention
Main purpose of the present invention is to provide a kind of fractional precipitation to reclaim the method for ion adsorption type rare earth ore leach liquor middle-weight rare earths, to reduce production cost, to reduce ammonia and nitrogen pollution, and ensures the purity of product middle-weight rare earths, and is easy to industrialization.
To achieve these goals, a kind of fractional precipitation is provided to reclaim the method for ion adsorption type rare earth ore leach liquor middle-weight rare earths, comprise the following steps: first add in the ion adsorption type rare earth ore leach liquor after removal of impurities process and carry out precipitin reaction containing magnesium basic cpd, and then add calcic basic cpd and carry out precipitin reaction, obtain rare-earth precipitation enriched substance and mother liquor of precipitation of ammonium after solid-liquid separation; Wherein, in magnesium oxide, the add-on containing magnesium basic cpd is the Xwt% of the completely required theoretical amount of described leach liquor Rare Earth Ion precipitation; In calcium oxide, the add-on of calcic basic cpd is the Ywt% of the completely required theoretical amount of described leach liquor Rare Earth Ion precipitation, 10%≤X%≤80%, 25%≤Y%≤120%, 105%≤X%+Y%≤130%.
Further, in the ion adsorption type rare earth ore leach liquor after removal of impurities process, the concentration of sulfate ion is 0.2g/L ~ 20g/L.
Further, in REO, the concentration of the ion adsorption type rare earth ore leach liquor middle-weight rare earths after removal of impurities process is 0.2 ~ 30g/L.
Further, containing magnesium basic cpd be magnesium oxide, magnesium hydroxide, magnesium-containing mineral product of roasting at least one.
Further, calcic basic cpd is at least one in the product of roasting of calcium oxide, calcium hydroxide, calcium mineral.
Further, magnesium-containing mineral is at least one in serpentine, magnesite, water magnesium ore deposit.
Further, calcium mineral is at least one in Wingdale, marble, calcite.
Further, in magnesium oxide, the add-on containing magnesium basic cpd is the Xwt% of the completely required theoretical amount of described leach liquor Rare Earth Ion precipitation; In calcium oxide, the add-on of calcic basic cpd is the Ywt% of the completely required theoretical amount of described leach liquor Rare Earth Ion precipitation, 30%≤X%≤70%, 35%≤Y%≤100%, 105%≤X%+Y%≤130%.
Further, add and carry out in the step of precipitin reaction containing magnesium basic cpd, temperature of reaction is 5 DEG C ~ 90 DEG C; Adding calcic basic cpd carries out in the step of precipitin reaction, and temperature of reaction is 5 DEG C ~ 90 DEG C.
Further, in REO, the content of the mother liquor of precipitation of ammonium middle-weight rare earths obtained after precipitation is below 0.1g/L.
The present invention is by first joining in the ion adsorption type rare earth ore leach liquor after removal of impurities process as precipitation agent containing magnesium basic cpd, now higher rare earth concentration is conducive to the dissolving of sl. sol. magnesium basic cpd, it is made fully to react, then calcic basic cpd is joined in leach liquor as precipitation agent and precipitate remaining rare earth, carry out solid-liquid separation, to obtain rare-earth precipitation enriched substance.Cheaper starting materials that the method adopts is easy to get and process is simple and easy to control, reduce production cost, get rid of the problem of ammonia and nitrogen pollution in ion adsorption type rare earth ore leach liquor precipitation process, simultaneously by controlling the add-on containing magnesium/calc-alkaline compound, precipitation agent is dissolved as far as possible completely, improve the purity of rare-earth precipitation enriched substance, and the sulfate ion in leach liquor and calcium ion can form the good calcium sulfate precipitation of a small amount of crystal property, the crystallization of rare earth hydrate can be induced, also can solve the problem that rare earth hydrate not easily forms crystalline precipitation.
Embodiment
It should be noted that, when not conflicting, the embodiment in the application and the feature in embodiment can combine mutually.The application is described in detail below in conjunction with embodiment.
From background technology, both can not reduce production cost in the method for existing ion adsorption type rare earth ore leach liquor recovering rare earth, reduce ammonia and nitrogen pollution, ensure again the purity of product middle-weight rare earths.
The invention provides a kind of method that ion adsorption type rare earth ore leach liquor middle-weight rare earths is reclaimed in fractional precipitation, comprise the following steps: first add in the ion adsorption type rare earth ore leach liquor after removal of impurities process and carry out precipitin reaction containing magnesium basic cpd, and then add calcic basic cpd and carry out precipitin reaction, obtain rare-earth precipitation enriched substance and mother liquor of precipitation of ammonium after solid-liquid separation; Wherein, in magnesium oxide, the add-on containing magnesium basic cpd is the Xwt% of the completely required theoretical amount of described leach liquor Rare Earth Ion precipitation; In calcium oxide, the add-on of calcic basic cpd is the Ywt% of the completely required theoretical amount of described leach liquor Rare Earth Ion precipitation, 10%≤X%≤80%, 25%≤Y%≤120%, 105%≤X%+Y%≤130%.
The present invention be directed to the ion adsorption type rare earth ore leach liquor after removal of impurities process and carry out fractional precipitation recovering rare earth, in described leach liquor, the concentration of sulfate ion is 0.2g/L ~ 20g/L, and the concentration of rare earth is that 0.2 ~ 30g/L(is in REO).This leach liquor is obtain in existing industrial ion adsorption type rare earth ore extraction process, by ion adsorption type rare earth ore by leaching agent solution leachings such as ammonium sulfate/magnesium sulfate, and then the ion adsorption type rare earth ore leach liquor after removal of impurities process described in directly obtaining after the removal of impurities such as bicarbonate of ammonia/sodium hydroxide/sodium bicarbonate/magnesium oxide.In addition, owing to having sulfate radical to exist in ion adsorption type rare earth ore soil itself, therefore adopt the leaching agent (as ammonium nitrate, ammonium chloride, sodium-chlor, calcium chloride etc.) of non-sulfuric acid salt also can obtain the ion adsorption type rare earth ore leach liquor described in the present invention.
First add and carry out precipitin reaction containing magnesium basic cpd, and then add calcic basic cpd and carry out precipitin reaction, and add-on 10%≤X%≤80% controlled containing magnesium/calc-alkaline compound, 25%≤Y%≤120%, 105%≤X%+Y%≤130%, obtains rare-earth precipitation enriched substance and mother liquor of precipitation of ammonium after solid-liquid separation.Because the basic cpd containing magnesium/calcium has advantage simple and easy to get, with low cost for precipitating the rare earth reclaimed in leach liquor, there is not ammonia and nitrogen pollution in precipitation process, and the calcium ions and magnesium ions that precipitation produces can be used for soaking ore deposit process.But low containing magnesium basic cpd solubleness in water, alkalescence is weak, easily affect separately the purity of final rare-earth products by its precipitation.And solubleness is higher in calcic basic cpd water, alkalescence is comparatively strong, is conducive to reducing the precipitin reaction time, controlling final precipitated product purity, but easily forms a large amount of calcium sulfate precipitation by its precipitation also existence separately, reduces the problem of product purity.Therefore first add a certain amount of containing magnesium basic cpd in the present invention in leach liquor, make its accelerate dissolution reaction under the condition of high rare earth concentration, reduce insolubles and remain.And then add remaining rare earth in calcic basic cpd precipitation leach liquor, because its solubleness is comparatively large, not easily there is insolubles and remain.Provide calcium ion adding of calcic basic cpd simultaneously, be conducive to the formation of a small amount of calcium sulfate in system, be conducive to the crystallization of inducing rare earth hydrate.
Add-on preferably containing magnesium/calc-alkaline compound is 30%≤X%≤70%, 35%≤Y%≤100%, 105%≤X%+Y%≤130%.In above-mentioned preferable range, being under higher rare earth concentration, carry out the precipitation process containing magnesium basic cpd to better ensure, being conducive to improving settling rate, being conducive to the amount controlling insolubles in final precipitated product simultaneously, improving the purity of rare-earth products.Take into account the Ksp of calcium sulfate simultaneously, make precipitate remaining rare earth ion completely in the precipitation process of calcic basic cpd, simultaneously generate a small amount of calcium sulfate precipitation with reacting with sulfate ion in raw material, be conducive to the crystalline precipitation of inducing rare earth hydrate, and be unlikely to generate the purity that too much calcium sulfate consequently affects precipitated product.
What adopted is at least one in the product of roasting of magnesium oxide, magnesium hydroxide, magnesium-containing mineral containing magnesium basic cpd.Magnesium-containing mineral is at least one in serpentine, magnesite, water magnesium ore deposit.The calcic basic cpd adopted is at least one in the product of roasting of calcium oxide, calcium hydroxide, calcium mineral.Calcium mineral is at least one in Wingdale, marble, calcite.Compared with traditional precipitation agent sodium hydroxide, sodium carbonate, oxalic acid etc., above-mentioned containing magnesium/calc-alkaline compound is cheap and easy to get and process is simple and easy to control, be conducive to reducing production cost.
Carry out in the step of precipitin reaction containing magnesium basic cpd adding, temperature of reaction is 5 DEG C ~ 90 DEG C.Reaction is carried out at normal temperatures, also can be suitable heat, and is conducive to accelerating precipitin reaction speed.Reaction times can adjust according to practical situation.
Carry out in the step of precipitin reaction adding calcic basic cpd, temperature of reaction is 5 DEG C ~ 90 DEG C.Similarly, reaction is carried out at normal temperatures, also can be suitable heat, and is conducive to accelerating precipitin reaction speed.Reaction times can adjust according to practical situation.
The present invention adopts the rare earth in fractional precipitation recovery ion adsorption type rare earth ore, 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 after calcining; The content of the mother liquor of precipitation of ammonium middle-weight rare earths obtained after precipitation is below 0.1g/L (in REO), to ensure that rare earth has higher recovery.
The method that ion adsorption type rare earth ore leach liquor middle-weight rare earths is reclaimed in fractional precipitation provided by the invention is further illustrated below in conjunction with embodiment.
Comparative example 1
Learn from else's experience the ion adsorption type rare earth ore leach liquor 10L after removal of impurities process, and its rare earth concentration is 1.5g/L(REO meter), sulfate concentration is 4.0g/L.By 110% of the completely required theoretical amount of described leach liquor Rare Earth Ion precipitation, 9.12g calcium oxide is added in leach liquor, react 3 hours at 40 DEG C, carry out solid-liquid separation after reaction terminates and obtain rare-earth precipitation enriched substance and mother liquor of precipitation of ammonium, mother liquor of precipitation of ammonium middle-weight rare earths concentration is 0.03g/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 86.5wt%(REO meter).
Comparative example 2
Learn from else's experience the ion adsorption type rare earth ore leach liquor 10L after removal of impurities process, and its rare earth concentration is 1.5g/L(REO meter), sulfate concentration is 4.0g/L.By 110% of the completely required theoretical amount of described leach liquor Rare Earth Ion precipitation, 6.51g magnesium oxide is added in leach liquor, react 3 hours at 40 DEG C, carry out solid-liquid separation after reaction terminates and obtain rare-earth precipitation enriched substance and mother liquor of precipitation of ammonium, the solid-liquid separation time used is 110min.Mother liquor of precipitation of ammonium middle-weight rare earths concentration is 0.05g/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 79.7wt%(REO meter).
Embodiment 1
Learn from else's experience the ion adsorption type rare earth ore leach liquor 10L after removal of impurities process, and its rare earth concentration is 1.5g/L(REO meter), sulfate concentration is 4.0g/L.First by 60% of the completely required theoretical amount of described leach liquor Rare Earth Ion precipitation, 3.55g magnesium oxide is added in leach liquor, react 2 hours at 40 DEG C, then by 50% of the completely required theoretical amount of described leach liquor Rare Earth Ion precipitation, in leach liquor, add 4.14g calcium oxide, react 1 hour at 40 DEG C.Carry out solid-liquid separation after reaction terminates and obtain rare-earth precipitation enriched substance and mother liquor of precipitation of ammonium, the solid-liquid separation time used is 20min.Mother liquor of precipitation of ammonium middle-weight rare earths 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 92.5wt%(REO meter).
Embodiment 2
Learn from else's experience the ion adsorption type rare earth ore leach liquor 100L after removal of impurities process, and its rare earth concentration is 0.2g/L(REO meter), sulfate concentration is 2.0g/L.First by 30% of the completely required theoretical amount of described leach liquor Rare Earth Ion precipitation, 2.37g magnesium hydroxide (in magnesium oxide) is added in leach liquor, react 2 hours at 60 DEG C, then by 85% of the completely required theoretical amount of described leach liquor Rare Earth Ion precipitation, in leach liquor, add 9.39g calcium hydroxide (in calcium oxide), react 1 hour at 60 DEG C.Carry out solid-liquid separation after reaction terminates and obtain rare-earth precipitation enriched substance and mother liquor of precipitation of ammonium, mother liquor of precipitation of ammonium middle-weight rare earths concentration is 0.005g/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 91.7wt%(REO meter).
Embodiment 3
Learn from else's experience the ion adsorption type rare earth ore leach liquor 100L after removal of impurities process, and its rare earth concentration is 0.2g/L(REO meter), sulfate concentration is 2.0g/L.First by 13% of the completely required theoretical amount of described leach liquor Rare Earth Ion precipitation, 1.03g magnesium hydroxide (in magnesium oxide) is added in leach liquor, react 2 hours at 60 DEG C, then by 102% of the completely required theoretical amount of described leach liquor Rare Earth Ion precipitation, in leach liquor, add 11.27g calcium hydroxide (in calcium oxide), react 1 hour at 60 DEG C.Carry out solid-liquid separation after reaction terminates and obtain rare-earth precipitation enriched substance and mother liquor of precipitation of ammonium, mother liquor of precipitation of ammonium middle-weight rare earths concentration is 0.004g/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 90.3wt%(REO meter).
Embodiment 4
Learn from else's experience the ion adsorption type rare earth ore leach liquor 10L after removal of impurities process, and its rare earth concentration is 10g/L(REO meter), sulfate concentration is 0.2g/L.First by 10% of the completely required theoretical amount of described leach liquor Rare Earth Ion precipitation, 3.95g magnesium oxide is added in leach liquor, react 1 hour at 80 DEG C, then by 120% of the completely required theoretical amount of described leach liquor Rare Earth Ion precipitation, in leach liquor, add 66.32g calcium hydroxide (in calcium oxide), react 2 hours at 5 DEG C.Carry out solid-liquid separation after reaction terminates and obtain rare-earth precipitation enriched substance and mother liquor of precipitation of ammonium, mother liquor of precipitation of ammonium middle-weight rare earths 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 meter).
Embodiment 5
Learn from else's experience the ion adsorption type rare earth ore leach liquor 10L after removal of impurities process, and its rare earth concentration is 30g/L(REO meter), sulfate concentration is 20g/L.First by 80% of the completely required theoretical amount of described leach liquor Rare Earth Ion precipitation, 94.74g magnesium hydroxide (in magnesium oxide) is added in leach liquor, react 2 hours at 90 DEG C, then by 25% of the completely required theoretical amount of described leach liquor Rare Earth Ion precipitation, in leach liquor, add 41.45g calcium hydroxide (in calcium oxide), react 2 hours at 15 DEG C.Carry out solid-liquid separation after reaction terminates and obtain rare-earth precipitation enriched substance and mother liquor of precipitation of ammonium, mother liquor of precipitation of ammonium middle-weight rare earths concentration is 0.1g/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 89.1wt%(REO meter).
Embodiment 6
Learn from else's experience the ion adsorption type rare earth ore leach liquor 10L after removal of impurities process, and its rare earth concentration is 20g/L(REO meter), sulfate concentration is 8g/L.First by 70% of the completely required theoretical amount of described leach liquor Rare Earth Ion precipitation, the roasting magnesite product (in magnesium oxide) that 55.26g is 98.5wt% containing magnesium oxide is added in leach liquor, react 3 hours at 25 DEG C, then by 35% of the completely required theoretical amount of described leach liquor Rare Earth Ion precipitation, in leach liquor, add 38.68g calcium hydroxide (in calcium oxide), react 0.5 hour at 90 DEG C.Carry out solid-liquid separation after reaction terminates and obtain rare-earth precipitation enriched substance and mother liquor of precipitation of ammonium, mother liquor of precipitation of ammonium middle-weight rare earths concentration is 0.1g/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 90.2wt%(REO meter).
Embodiment 7
Learn from else's experience the ion adsorption type rare earth ore leach liquor 10L after removal of impurities process, and its rare earth concentration is 5g/L(REO meter), sulfate concentration is 1g/L.First by 20% of the completely required theoretical amount of described leach liquor Rare Earth Ion precipitation, 3.95g magnesium oxide is added in leach liquor, react 2 hours at 5 DEG C, then by 100% of the completely required theoretical amount of described leach liquor Rare Earth Ion precipitation, in leach liquor, add the calcite product of roasting (in calcium oxide) that 27.63g is 98wt% containing calcium oxide, react 3 hours at 25 DEG C.Carry out solid-liquid separation after reaction terminates and obtain rare-earth precipitation enriched substance and mother liquor of precipitation of ammonium, mother liquor of precipitation of ammonium middle-weight rare earths concentration is 0.05g/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 89.4wt%(REO meter).
Embodiment 8
Learn from else's experience the ion adsorption type rare earth ore leach liquor 10L after removal of impurities process, and its rare earth concentration is 3g/L(REO meter), sulfate concentration is 15g/L.First by 75% of the completely required theoretical amount of described leach liquor Rare Earth Ion precipitation, the mixture (mass ratio of magnesium oxide and magnesium hydroxide is 1:1) (in magnesium oxide) of 8.88g magnesium oxide and magnesium hydroxide is added in leach liquor, react 3 hours at 25 DEG C, then by 35% of the completely required theoretical amount of described leach liquor Rare Earth Ion precipitation, in leach liquor, add the mixture (mass ratio of calcium oxide and calcium hydroxide is 1:1) (in calcium oxide) of 5.80g calcium oxide and calcium hydroxide, react 1 hour at 25 DEG C.Carry out solid-liquid separation after reaction terminates and obtain rare-earth precipitation enriched substance and mother liquor of precipitation of ammonium, mother liquor of precipitation of ammonium middle-weight rare earths concentration is 0.04g/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 89.7wt%(REO meter).
Embodiment 9
Ion type rareearth mine, Longnan, rare-earth mineral layer thickness 6 meters, rare earth average grade 0.13%.These ore body rare earth reserves are 54 tons, adopt in_situ leaching technique, complete ore body surface and beat the operations such as fluid injection well, liquid-collecting hole, cloth pipeline.Prepare 2% ammonium sulfate leaching agent 8000m
3.Leaching agent 350m is injected every day with liquid charge pump
3, start leach liquor middle-weight rare earths concentration and be less than 0.2g/L, whole blowback continues leaching ore deposit, after Steep cencentration is greater than 0.2g/L, carry out receipts liquid, in leaching process, ammonium sulfate concentrations in leaching agent can be lowered depending on practical situation, when the leach liquor Rare-Earth Content collected is close to reserves, change the drip washing of note clear water and receive liquid.The leach liquor collected adopts the ammonium bicarbonate soln of 10g/L to regulate pH about 5 to carry out removal of impurities process.
Learn from else's experience the ion adsorption type rare earth ore leach liquor 10L after magnesium oxide removal of impurities process, and its rare earth concentration is 1.0g/L(REO meter), sulfate concentration is 3.6g/L.First by 65% of the completely required theoretical amount of described leach liquor Rare Earth Ion precipitation, the mixture (in magnesium oxide) of 2.57g magnesium hydroxide is added in leach liquor, react 3 hours at 25 DEG C, then by 35% of the completely required theoretical amount of described leach liquor Rare Earth Ion precipitation, in leach liquor, add 2.49g calcium oxide, react 1.5 hours at 25 DEG C.Carry out solid-liquid separation after reaction terminates and obtain rare-earth precipitation enriched substance and mother liquor of precipitation of ammonium, mother liquor of precipitation of ammonium middle-weight rare earths 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 92.2wt%(REO meter).
Claims (10)
1. the method for a fractional precipitation recovery ion adsorption type rare earth ore leach liquor middle-weight rare earths, it is characterized in that, first add in the ion adsorption type rare earth ore leach liquor after removal of impurities process and carry out precipitin reaction containing magnesium basic cpd, and then add calcic basic cpd and carry out precipitin reaction, obtain rare-earth precipitation enriched substance and mother liquor of precipitation of ammonium after solid-liquid separation;
Wherein, in magnesium oxide, the add-on containing magnesium basic cpd is the Xwt% of the completely required theoretical amount of described leach liquor Rare Earth Ion precipitation; In calcium oxide, the add-on of calcic basic cpd is the Ywt% of the completely required theoretical amount of described leach liquor Rare Earth Ion precipitation, 10%≤X%≤80%, 25%≤Y%≤120%, 105%≤X%+Y%≤130%.
2. method according to claim 1, is characterized in that, in described leach liquor, the concentration of sulfate ion is 0.2g/L ~ 20g/L.
3. method according to claim 1 and 2, is characterized in that, in REO, the concentration of described leach liquor middle-weight rare earths is 0.2 ~ 30g/L.
4. method according to claim 1, is characterized in that, described is at least one in the product of roasting of magnesium oxide, magnesium hydroxide, magnesium-containing mineral containing magnesium basic cpd.
5. method according to claim 1, is characterized in that, described calcic basic cpd is at least one in the product of roasting of calcium oxide, calcium hydroxide, calcium mineral.
6. method according to claim 4, is characterized in that, described magnesium-containing mineral is at least one in serpentine, magnesite, water magnesium ore deposit.
7. method according to claim 5, is characterized in that, described calcium mineral is at least one in Wingdale, marble, calcite.
8. the method according to claim 1 or 4 or 5, is characterized in that, 30%≤X%≤70%, 35%≤Y%≤100%, 105%≤X%+Y%≤130%.
9. method according to claim 1, is characterized in that, described in add and carry out in the step of precipitin reaction containing magnesium basic cpd, temperature of reaction is 5 DEG C ~ 90 DEG C; The described calcic basic cpd that adds carries out in the step of precipitin reaction, and temperature of reaction is 5 DEG C ~ 90 DEG C.
10. method according to claim 1, is characterized in that, in REO, the content of described mother liquor of precipitation of ammonium middle-weight rare earths is below 0.1g/L.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
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| CN105506287A (en) * | 2016-01-13 | 2016-04-20 | 龙南县锦易矿业有限公司 | Process for recycling rare earth from Southern rare earth ore through leached mother liquor precipitation method |
| CN105779792A (en) * | 2016-03-29 | 2016-07-20 | 江西理工大学 | Method for preparing low-impurity-content rare earth hydrate |
| CN105803199A (en) * | 2016-03-29 | 2016-07-27 | 江西理工大学 | Method for preparing low-sulfur rare earth oxide through hydroxide precipitation |
| CN106435172A (en) * | 2016-10-14 | 2017-02-22 | 赣州弘茂稀土工程有限公司 | Process for performing classifying split-flow treatment on rare earth sin-situ leaching mother solution |
| CN106967881A (en) * | 2017-05-26 | 2017-07-21 | 江西理工大学 | A kind of method of the Extraction of rare earth from weathered superficial leaching rare-earth ore |
| CN107190156A (en) * | 2017-05-26 | 2017-09-22 | 江西理工大学 | A kind of method of the Extraction of rare earth from ion adsorption type rare earth ore |
| CN108893606A (en) * | 2018-08-30 | 2018-11-27 | 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 |
| CN112281003A (en) * | 2020-11-02 | 2021-01-29 | 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 |
| 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 |
| 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 |
| 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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| CN105506287A (en) * | 2016-01-13 | 2016-04-20 | 龙南县锦易矿业有限公司 | Process for recycling rare earth from Southern rare earth ore through leached mother liquor precipitation method |
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| CN105803199A (en) * | 2016-03-29 | 2016-07-27 | 江西理工大学 | Method for preparing low-sulfur rare earth oxide through hydroxide precipitation |
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| CN106435172A (en) * | 2016-10-14 | 2017-02-22 | 赣州弘茂稀土工程有限公司 | Process for performing classifying split-flow treatment on rare earth sin-situ leaching mother solution |
| 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 |
| CN106967881A (en) * | 2017-05-26 | 2017-07-21 | 江西理工大学 | A kind of method of the Extraction of rare earth from weathered superficial leaching rare-earth ore |
| CN107190156A (en) * | 2017-05-26 | 2017-09-22 | 江西理工大学 | A kind of method of the Extraction of rare earth from ion adsorption type rare earth ore |
| 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 |
| CN108893606A (en) * | 2018-08-30 | 2018-11-27 | 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 |
| CN112281003A (en) * | 2020-11-02 | 2021-01-29 | 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 |
| 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 |
| 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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