CN106957961B - A method of recovering rare earth and aluminium from weathered superficial leaching rare-earth ore - Google Patents
A method of recovering rare earth and aluminium from weathered superficial leaching rare-earth ore Download PDFInfo
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Abstract
The invention discloses a kind of methods of recovering rare earth and aluminium in weathered superficial leaching rare-earth ore, weathered superficial leaching rare-earth ore, which is leached, by leaching agent obtains re dip solution, then auxiliary agent is added into re dip solution, then calcium oxide is added into leachate again to be precipitated, control assistant concentration, temperature and pH, it is coordinated calcium ion and auxiliary molecules, achievees the purpose that calcium sulfate is prevented to generate with this, reduces the generation of precipitation process calcium sulfate.The addition of auxiliary agent can be returned for soaking mine simultaneously, played the role of enhanced leaching in acid condition, improved the leaching rate of rare earth.There is no dedoping step in the method, is avoided that the loss of dedoping step rare earth.This method has got rid of ammonia and nitrogen pollution, avoid the loss of traditional handicraft dedoping step bring rare earth, improve rare earth yield, synthetical recovery bauxite resource, the final product for obtaining purity qualification.
Description
Technical field
The present invention relates to field of rare earth hydrometallurgy, return from weathered superficial leaching rare-earth ore in particular to one kind
The method for receiving rare earth and aluminium.
Background technique
Weathered superficial leaching rare-earth ore is a kind of novel external rare-earth mineral, in 1969 for the first time in Jiangxi Province of China Ganzhou
City is found.Such mineral are distributed widely in the provinces such as the Jiangxi, Guangdong, Guangxi of south China, and rare earth partition is complete, radiation
Property it is low, and be rich in middle heavy rare earth element, be the Strategic mineral resources of China's preciousness.The development and utilization of ion type rareearth ore can solve
Certainly monazite, bastnaesite, mixed type Rare Earth Mine etc. almost only produce light rare earth and in lacking the problem of heavy rare earth.Ordinary circumstance
Under, in weathered superficial leaching rare-earth ore full phase rare earth grade be 0.05%-0.3%, wherein the rare earth element of 60%-95% be with
Ion mutually exists, and ion phase rare earth is adsorbed in clay by electrostatic interaction in the form of rare earth hydrated ion or hydroxyl hydrated ion
On mineral, when the rare earth ion (ion phase rare earth) that these are attracted on clay mineral encounters the active cation of chemical property
(such as Na+、Mg2+、Ca2+、NH4 +Deng) when, it can be desorbed by its exchange.Currently, weathered superficial leaching rare-earth ore generallys use ammonium sulfate
It leaching, obtained re dip solution is using ammonium hydrogen carbonate removal of impurities, ammonium hydrogen carbonate or oxalic acid precipitation recovering rare earth, using roasting,
Obtain the mixed rare-earth oxide concentrate that content of rare earth is calculated as 92% or more with REO.According to statistics, it is dilute to produce ionic every year for China
60,000 tons or so of native concentrate, a large amount of ammonium sulfate and ammonium hydrogen carbonate are used in ion type rareearth ore recovery process, are produced a large amount of
Ammonia nitrogen waste water, cause mining area water system ammonia nitrogen to severely exceed, water eutrophication causes great threat to ecological safety.
It is novel with regard to being developed in terms of leaching agent in order to solve the problems, such as the ammonia nitrogen in weathered superficial leaching rare-earth ore extraction process
Leaching agent without ammonia such as magnesium sulfate, potassium sulfate, compound no ammonia leaching agent etc., at the same also studied many leaching agents such as fulvic acid,
EDTA etc. reduces the dosage of ammonium sulfate leaching agent, and wherein some applications have been obtained in magnesium sulfate leaching agent.And with regard to precipitating reagent
Aspect, the exploitation without ammonia precipitation agent such as magnesia, calcium oxide, sodium hydroxide also have a large amount of reports.If CN101037219 is to aoxidize
Magnesium slurry is as the rare earth in precipitating reagent precipitating rare earth solution；Wherein magnesium oxide precipitation agent is very slightly soluble substance, precipitation reaction
Time is long, and the rate of deposition to guarantee rare earth in solution, precipitating reagent need excess, and excessive unreacted completely precipitates at this time
Agent will go into rare-earth precipitation enriched substance, greatly reduce rare earth ore concentrate product purity.For this problem, brainstrust is also mentioned
Relevant solution (CN103436720, CN102190325, CN104152693) is gone out, but has been problematic in that and fails
Really implement.CN101475202 is using the intermixture that calcium oxide or calcium oxide and crystal seed form as precipitating reagent precipitating rare earth solution
In rare earth belong to micro-soluble material and for calcium oxide precipitating reagent, precipitation reaction is very fast, and sedimentation effect is good, but weathering crust drenches
There is sulfate in the leaching agent of product type Rare Earth Mine, causes individually to use calcium oxide conduct containing a large amount of sulfate radical in leachate
Precipitating reagent can generate a large amount of calcium sulfate precipitation during precipitating ion mine leachate, equally substantially reduce rare earth essence
The purity of mineral products cannot obtain qualified product.
Furthermore the processing of current leachate is by the way of the reprecipitation that first cleans, in dedoping step, 6% or so rare earth
Removal of impurities slag will be entered and cause the loss of rare earth, while bauxite resource also has different degrees of loss.
In conclusion how the method for a kind of recovering rare earth from ion adsorption type rare earth ore and aluminium is provided, it is dilute to improve
The native rate of recovery gets rid of ammonia and nitrogen pollution, reduces production cost, obtains the rare-earth products of purity qualification, have become and urgently solve at present
Certainly the technical issues of.
Summary of the invention
The method of the main purpose of the present invention is to provide a kind of from weathered superficial leaching rare-earth ore recovering rare earth and aluminium,
To get rid of ammonia and nitrogen pollution, reduce production cost, obtains the rare-earth products of purity qualification.
To achieve the goals above, the present invention provides a kind of from weathered superficial leaching rare-earth ore recovering rare earth and aluminium
Method includes the following steps.
(1) leachate that weathered superficial leaching rare-earth ore obtains is leached using leaching agent, the content of aluminium in the leachate
For 0.05-0.50g/L, content of rare earth is 0.3 ~ 3.5g/L, in terms of REO.
(2) poly-aspartate, poly-epoxy succinic acid, polyacrylic acid, aminotrimethylenephosphonic acid, second are added into leachate
Diamines tetramethylene pitches Alendronate, 2- phosphate -1,2, and one or more of 4- butane tricarboxylate is used as auxiliary agent, controls auxiliary agent
Total mol concentration be 0.05 ~ 0.30mol/L.
(3) calcium oxide is added into leachate again to be precipitated, precipitation temperature is 15 ~ 50 DEG C, and control precipitating terminal pH is
9.0~11.0；Then acquisition mother liquor of precipitation of ammonium and precipitation slag after being separated by solid-liquid separation, washing.
(4) it is 1.5-3.0 that mother liquor of precipitation of ammonium, which adjusts pH, is returned after supplementing leaching agent for soaking mine.
(5) precipitation slag stir washing using sodium hydroxide solution, and control liquid-solid ratio is 1:0.5 ~ 1:3.0；Then solid-liquid point
From, washing, obtain cleaning solution and washed-residue.
(6) washed-residue can roasting direct obtain the rare earth ore concentrate that calcium and aluminium content are both less than 2wt.%.Maturing temperature is 600
DEG C~1000 DEG C, calcining time is 0.5h~5.0h.
Further, leaching agent in the step (1) is containing magnesium, sodium, the sulfate liquor of potassium or containing magnesium, sodium, potassium
The mixed solution of sulfate and chloride.
Further, the auxiliary agent in the step (2) is that poly-aspartate and ethylenediamine tetramethylene pitch the mixed of Alendronate
Close object, molar ratio 0.5:1-3.0:1.
Further, the precipitation temperature in the step (3) is preferably 40~50 DEG C.
Further, in the step (5) cleaning solution can acid adding adjust back pH to 6.0 ~ 8.0, obtain aluminium hydroxide by-product.
Further, the concentration of sodium hydroxide solution is 0.3-1.0mol/L in the step (5).
Further, washed-residue can also directly adopt the molten acquisition rare-earth liquid of hydrochloric acid in the step (6), for extracting work
Sequence.
The present invention leaches weathered superficial leaching rare-earth ore by leaching agent and obtains re dip solution, then toward re dip solution
Calcium oxide is then added into leachate again and is precipitated for middle addition auxiliary agent, and control assistant concentration, precipitation temperature and pH make calcium
Ion and auxiliary molecules coordination, are achieved the purpose that calcium sulfate is prevented to generate with this, reduce the generation of precipitation process calcium sulfate.Simultaneously
The addition of auxiliary agent can be returned for soaking mine, played the role of enhanced leaching in acid condition, improved the leaching rate of rare earth.Furthermore
There is no dedoping step in the method, is avoided that the loss of dedoping step rare earth.In addition, aluminium ion also shape in calcium oxide precipitation process
At aluminium hydroxide, the both sexes of aluminium hydroxide are then utilized, is washed using sodium hydroxide solution and removes and recycle aluminium element, finally obtained
Obtain the product of purity qualification.This method has got rid of ammonia and nitrogen pollution, improve rare earth yield, synthetical recovery bauxite resource.Simultaneously
Reduce the formation of calcium oxide precipitation process calcium sulfate, the product of purity qualification is obtained while reducing production cost.
Detailed description of the invention
Fig. 1: the process flow chart of technical solution of the present invention.
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.
Leachate is precipitated using ammonium hydrogen carbonate at present, there are problems that ammonia and nitrogen pollution, in order to solve this problem,
Rare earth worker proposes the new technology of oxidation calcium precipitate enrichment rare earth, but the technology is caused due to the generation there are calcium sulfate
The problems such as rare-earth products purity is not high.Meanwhile weathered superficial leaching rare-earth ore leachate first cleans the technique meeting precipitated afterwards at present
Cause the loss of rare earth.
The present invention provides the methods of the recovering rare earth from weathered superficial leaching rare-earth ore and aluminium, include the following steps.
(1) leachate that weathered superficial leaching rare-earth ore obtains is leached using leaching agent, the content of aluminium in the leachate
For 0.05-0.50g/L, in terms of REO, content of rare earth is 0.3 ~ 3.5g/L.
(2) poly-aspartate, poly-epoxy succinic acid, polyacrylic acid, aminotrimethylenephosphonic acid, second are added into leachate
Diamines tetramethylene pitches Alendronate, 2- phosphate -1,2, and one or more of 4- butane tricarboxylate is used as auxiliary agent, controls auxiliary agent
Total mol concentration be 0.05 ~ 0.30mol/L.
(3) calcium oxide is added into leachate again to be precipitated, precipitation temperature is 15 ~ 50 DEG C, and control precipitating terminal pH is
9.0~11.0；Then acquisition mother liquor of precipitation of ammonium and precipitation slag after being separated by solid-liquid separation, washing.
(4) it is 1.5-3.0 that mother liquor of precipitation of ammonium, which adjusts pH, is returned after supplementing leaching agent for soaking mine.
(5) precipitation slag stir washing using sodium hydroxide solution, and control liquid-solid ratio is 1:0.5 ~ 1:3.0；Then solid-liquid point
From, washing, obtain cleaning solution and washed-residue.
(6) washed-residue can roasting direct obtain the rare earth ore concentrate that calcium and aluminium content are both less than 2wt.%.Maturing temperature is 600
DEG C~1000 DEG C, calcining time is 0.5h~5.0h.
The leaching agent that the present invention uses is containing magnesium, sodium, the sulfate liquor of potassium or containing magnesium, sodium, the sulfate of potassium and chlorination
The mixed solution of object.Sulfate leaching agent has the function of reducing the impurity such as calcium, lead in leachate, while the harm to environment
It is small.Final to obtain leachate, the content of aluminium is 0.05-0.50g/L in leachate, and content of rare earth is 0.3 ~ 3.5g/L, with REO
Meter.
Poly-aspartate, poly-epoxy succinic acid, polyacrylic acid, aminotrimethylenephosphonic acid, second two are added into leachate
Amine tetramethylene pitches Alendronate, 2- phosphate -1,2, and one or more of 4- butane tricarboxylate is used as auxiliary agent, controls auxiliary agent
Total mol concentration is 0.05 ~ 0.30mol/L.Then calcium oxide is added into leachate again to be precipitated, it will be dilute in leachate
Soil and aluminium coprecipitation get off, and precipitation temperature is 15 ~ 50 DEG C, and control precipitating terminal pH is 9.0 ~ 11.0；It is carried out after precipitating
It is separated by solid-liquid separation, mother liquor of precipitation of ammonium and precipitation slag is obtained after washing；Poly-aspartate, poly-epoxy succinic acid, polyacrylic acid, amino trimethylene
Methylphosphonic acid, ethylenediamine tetramethylene pitch Alendronate, 2- phosphate -1,2, and 4- butane tricarboxylate auxiliary agent can be with calcium, magnesium plasma
It is coordinated, without influencing rare-earth precipitation.Although edetate disodium, 1-hydroxy ethylidene-1,1-diphosphonic acid, nitrilotriacetic acid, ammonia
The organic substances such as base sulfonic acid can also be used as auxiliary agent and calcium ion and be coordinated, but since it with rare earth has very big binding ability,
Will lead to precipitation process cannot generate rare earth hydrate precipitating.The total mol concentration for controlling auxiliary agent is 0.05 ~ 0.30mol/L, is
In order to enable the calcium ion that the calcium ion of leachate itself and precipitating are added can be combined largely by auxiliary agent.And auxiliary agent and rare earth
Binding ability and system temperature and pH have much relations, and precipitation temperature is 15 ~ 50 DEG C in control system, and precipitating terminal pH is
When 9.0 ~ 11.0, the combination of auxiliary agent and calcium ion is strong compared with the ability of other ions, can more preferably play the mesh for preventing calcium sulfate from generating
's.Wherein the control of pH is particularly important, and at different pH, the complexing power of auxiliary agent and effects of ion differs greatly, in pH
When being 9.0 ~ 11.0, the complexing energy of the rare earth ion and aluminium ion of trivalent with binding ability hydroxy compared with itself and auxiliary agent in system
Power is stronger, and corresponding hydroxide precipitating can be generated；And iron, copper, zinc, magnesium, calcium plasma and the auxiliary agent of divalent can form stabilization
Complex compound, play prevent it from forming hydroxide precipitating or calcium sulfate precipitation and the problem of lower product purity.It is preferred that heavy
Precipitation temperature is 40~50 DEG C during shallow lake, and at this temperature, binding ability is stronger, better effect.In addition, the auxiliary agent
Pitch the complex of Alendronate for poly-aspartate and ethylenediamine tetramethylene, molar ratio 0.5:1-3.0:1, with this condition,
Poly-aspartate and ethylenediamine tetramethylene fork Alendronate can play the role of collaborative combination calcium ion, increase the choosing to calcium ion
Selecting property binding ability preferably prevents the generation of calcium sulfate.
It is 1.5-3.0 that mother liquor of precipitation of ammonium, which adjusts pH, is returned after supplementing leaching agent for soaking mine；Under normal circumstances, for soaking mine
The pH of leaching agent solution be 2.0-5.0, the molar concentration of leaching agent is 0.1-0.3mol/L, therefore mother liquor of precipitation of ammonium needs to adjust
It could be recycled after pH and leaching agent concentration.Select herein adjust mother liquor of precipitation of ammonium pH be 1.5-3.0, at this ph, auxiliary agent and
The binding ability of trivalent ion is stronger compared with bivalent ions binding ability, and reinforced rare earth leaching can be played during leaching
Effect rare earth leaching rate can be improved to play the effect for helping leaching.
And precipitation slag is washed using 0.3-1.0mol/L sodium hydroxide solution, control liquid-solid ratio is 1:0.5 ~ 1:3.0；
It is separated by solid-liquid separation, washes after washing, obtain cleaning solution and washed-residue；With this condition, aluminium hydroxide, which can dissolve, becomes inclined aluminium
Acid sodium solution, and rare earth does not lose, depositing technology can be reduced the loss of rare earth after the more traditional leachate of this method first cleans,
Increase the rate of recovery of rare earth.
Cleaning solution can acid adding adjust back pH to 6.0 ~ 8.0, at this time meta-aluminic acid root generates aluminium hydroxide again, acquisition aluminium hydroxide
By-product.And washed-residue can roasting direct obtain the rare earth ore concentrate that calcium and aluminium content are both less than 2wt.%.Maturing temperature be 600 DEG C ~
1000 DEG C, calcining time is 0.5h ~ 5.0h.Furthermore since impurity content is few in washed-residue, the molten acquisition of hydrochloric acid can also be directlyed adopt
Rare-earth liquid is used for extraction process.
Further illustrate that one kind provided by the invention is recycled from weathered superficial leaching rare-earth ore below in conjunction with embodiment
The method of rare earth and aluminium.
Comparative example 1: leaching weathered superficial leaching rare-earth ore using Adlerika, and the content for obtaining aluminium is 0.5g/
L, content of rare earth be 3g/L(in terms of REO) leachate.Calcium oxide is added into leachate to be precipitated, precipitation temperature 50
DEG C, precipitating terminal pH is 11；Then acquisition mother liquor of precipitation of ammonium and precipitation slag after being separated by solid-liquid separation, washing.It is 3 that mother liquor of precipitation of ammonium, which adjusts pH,
It returns after supplementing magnesium sulfate for soaking mine.Precipitation slag uses concentration stir washing for the sodium hydroxide solution of 1mol/L, controls liquid
Gu than being 1:3；Then it is separated by solid-liquid separation, washes, obtain cleaning solution and washed-residue.It is 8.0 that cleaning solution acid adding, which adjusts back pH, obtains hydrogen-oxygen
Change aluminium by-product.Washed-residue roasts 5 hours at 1000 DEG C, and acquisition calcium content is 3.77wt.%, aluminium content is 1.18wt.%'s
Rare earth ore concentrate.
Embodiment 1: leaching weathered superficial leaching rare-earth ore using Adlerika, and the content for obtaining aluminium is 0.05g/L, dilute
Native content be 0.3g/L(in terms of REO) leachate.Poly-aspartate auxiliary agent is added into leachate, controls the total moles of auxiliary agent
Concentration is 0.05mol/L.Calcium oxide is added into leachate again to be precipitated, precipitation temperature is 20 DEG C, and precipitating terminal pH is
9.0；Then acquisition mother liquor of precipitation of ammonium and precipitation slag after being separated by solid-liquid separation, washing.It is 1.5 that mother liquor of precipitation of ammonium, which adjusts pH, after supplementing magnesium sulfate
It returns for soaking mine.Precipitation slag uses concentration stir washing for the sodium hydroxide solution of 0.3mol/L, and control liquid-solid ratio is 1:
0.5；Then it is separated by solid-liquid separation, washes, obtain cleaning solution and washed-residue.It is 6.0 that cleaning solution acid adding, which adjusts back pH, obtains aluminium hydroxide pair
Product.Washed-residue roasts 0.5 hour at 600 DEG C, obtains the rare earth essence that calcium content is 1.31wt.%, aluminium content is 1.52wt.%
Mine.
Embodiment 2: weathered superficial leaching rare-earth ore is leached using the sulfate liquor containing magnesium and sodium, the content for obtaining aluminium is
0.1g/L, content of rare earth be 0.5g/L(in terms of REO) leachate.Polyacrylic acid auxiliary agent is added into leachate, controls auxiliary agent
Total mol concentration be 0.05mol/L.Calcium oxide is added into leachate again to be precipitated, precipitation temperature is 20 DEG C, and precipitating is eventually
Point pH is 9.0；Then acquisition mother liquor of precipitation of ammonium and precipitation slag after being separated by solid-liquid separation, washing.It is 2.0 that mother liquor of precipitation of ammonium, which adjusts pH, supplements sulphur
It returns after sour magnesium and sodium sulphate for soaking mine.Precipitation slag uses concentration stir washing for the sodium hydroxide solution of 0.3mol/L, control
Liquid-solid ratio processed is 1:0.5；Then it is separated by solid-liquid separation, washes, obtain cleaning solution and washed-residue.It is 6.0 that cleaning solution acid adding, which adjusts back pH, is obtained
Obtain aluminium hydroxide by-product.Washed-residue roasts 0.5 hour at 600 DEG C, and acquisition calcium content is 1.28wt.%, aluminium content is
The rare earth ore concentrate of 1.47wt.%.
Embodiment 3: weathered superficial leaching rare-earth ore is leached using containing magnesium, the sulfate of potassium and chloride solution, obtains aluminium
Content be 0.3g/L, content of rare earth is 2g/L(in terms of REO) leachate.Poly-aspartate, second two are added into leachate
Amine tetramethylene pitches the mixed aid (molar ratio 0.5:1) of Alendronate, and the total mol concentration for controlling auxiliary agent is 0.2mol/L.It is past again
Calcium oxide is added in leachate to be precipitated, precipitation temperature is 40 DEG C, and precipitating terminal pH is 10.0；Then it is separated by solid-liquid separation, washes
Mother liquor of precipitation of ammonium and precipitation slag are obtained afterwards.Mother liquor of precipitation of ammonium adjust pH be 2.0, supplement containing magnesium, potassium sulfate and chloride solution after
It returns for soaking mine.Precipitation slag uses concentration stir washing for the sodium hydroxide solution of 0.5mol/L, and control liquid-solid ratio is 1:1；
Then it is separated by solid-liquid separation, washes, obtain cleaning solution and washed-residue.It is 7.0 that cleaning solution acid adding, which adjusts back pH, obtains aluminium hydroxide by-product
Object.Washed-residue roasts 2 hours at 800 DEG C, obtain calcium content be 0.95wt.%, the rare earth ore concentrate that aluminium content is 1.01wt.%.
Embodiment 4: weathered superficial leaching rare-earth ore is leached using containing magnesium, the sulfate of potassium and chloride solution, obtains aluminium
Content be 0.3g/L, content of rare earth is 2.5g/L(in terms of REO) leachate.Poly-aspartate is added into leachate, gathers
The mixed aid (molar ratio 0.5:1) of Epoxysuccinic acid, the total mol concentration for controlling auxiliary agent is 0.2mol/L.Again into leachate
Calcium oxide is added to be precipitated, precipitation temperature is 30 DEG C, and precipitating terminal pH is 10.0；Then it is separated by solid-liquid separation, sunk after washing
Shallow lake mother liquor and precipitation slag.It is 2.0 that mother liquor of precipitation of ammonium, which adjusts pH, supplement containing magnesium, potassium sulfate and chloride solution after return and be used for
Soak mine.Precipitation slag uses concentration stir washing for the sodium hydroxide solution of 0.5mol/L, and control liquid-solid ratio is 1:1；Then solid-liquid
Separation, washing, obtain cleaning solution and washed-residue.It is 7.0 that cleaning solution acid adding, which adjusts back pH, obtains aluminium hydroxide by-product.Washed-residue
Roasted 2 hours at 800 DEG C, obtain calcium content be 1.17wt.%, the rare earth ore concentrate that aluminium content is 1.21wt.%.
Embodiment 5: leaching weathered superficial leaching rare-earth ore using Adlerika, and the content for obtaining aluminium is 0.5g/L, dilute
Native content be 3g/L(in terms of REO) leachate.Ethylenediamine tetramethylene is added into leachate and pitches Alendronate, controls auxiliary agent
Total mol concentration is 0.3mol/L.Calcium oxide is added into leachate again to be precipitated, precipitation temperature is 50 DEG C, precipitates terminal pH
It is 11.0；Then acquisition mother liquor of precipitation of ammonium and precipitation slag after being separated by solid-liquid separation, washing.It is 3.0 that mother liquor of precipitation of ammonium, which adjusts pH, supplements magnesium sulfate
After return for soaking mine.Precipitation slag uses concentration stir washing for the sodium hydroxide solution of 1mol/L, and control liquid-solid ratio is 1:3；
Then it is separated by solid-liquid separation, washes, obtain cleaning solution and washed-residue.It is 8.0 that cleaning solution acid adding, which adjusts back pH, obtains aluminium hydroxide by-product
Object.Washed-residue roasts 5 hours at 1000 DEG C, obtain calcium content be 1.26wt.%, the rare earth ore concentrate that aluminium content is 1.23wt.%.
Embodiment 6: leaching weathered superficial leaching rare-earth ore using Adlerika, and the content for obtaining aluminium is 0.5g/L, dilute
Native content be 3.5g/L(in terms of REO) leachate.Poly-aspartate is added into leachate, ethylenediamine tetramethylene pitches phosphonic acids
The mixed aid (molar ratio 3:1) of sodium, the total mol concentration for controlling auxiliary agent is 0.3mol/L.Calcium oxide is added into leachate again
It is precipitated, precipitation temperature is 15 DEG C, and precipitating terminal pH is 11.0；Then it is separated by solid-liquid separation, mother liquor of precipitation of ammonium is obtained after washing and is sunk
Mud.It is 3.0 that mother liquor of precipitation of ammonium, which adjusts pH, is returned after supplementing magnesium sulfate for soaking mine.Precipitation slag uses concentration for the hydrogen of 1mol/L
Sodium hydroxide solution stir washing, and control liquid-solid ratio is 1:3；Then it is separated by solid-liquid separation, washes, obtain cleaning solution and washed-residue.Washing
It is 8.0 that liquid acid adding, which adjusts back pH, obtains aluminium hydroxide by-product.Washed-residue roasts 5 hours at 1000 DEG C, obtains calcium content and is
1.21wt.%, the rare earth ore concentrate that aluminium content is 1.14wt.%.
Claims (6)
1. a kind of method of the recovering rare earth from weathered superficial leaching rare-earth ore and aluminium, which is characterized in that the method it is specific
Step includes:
(1) leachate that weathered superficial leaching rare-earth ore obtains is leached using leaching agent, the content of aluminium is in the leachate
0.05-0.50g/L, content of rare earth is 0.3 ~ 3.5g/L, in terms of REO；The leaching agent be containing magnesium, sodium, potassium sulfate liquor
Or containing magnesium, sodium, the sulfate of potassium and chloride mixed solution；
(2) poly-aspartate, poly-epoxy succinic acid, polyacrylic acid, aminotrimethylenephosphonic acid, ethylenediamine are added into leachate
Tetramethylene pitches Alendronate, 2- phosphate -1,2, and one or more of 4- butane tricarboxylate is used as auxiliary agent, controls the total of auxiliary agent
Molar concentration is 0.05 ~ 0.30mol/L；
(3) again into leachate be added calcium oxide precipitated, precipitation temperature be 15 ~ 50 DEG C, control precipitating terminal pH be 9.0 ~
11.0；Then acquisition mother liquor of precipitation of ammonium and precipitation slag after being separated by solid-liquid separation, washing；
(4) it is 1.5-3.0 that mother liquor of precipitation of ammonium, which adjusts pH, is returned after supplementing leaching agent for soaking mine；
(5) precipitation slag stir washing using sodium hydroxide solution, and control liquid-solid ratio is 1:0.5 ~ 1:3.0；Then it is separated by solid-liquid separation, water
It washes, obtains cleaning solution and washed-residue；
(6) washed-residue roasting direct obtains the rare earth ore concentrate that calcium and aluminium content are both less than 2wt.%, and maturing temperature is 600 DEG C~
1000 DEG C, calcining time is 0.5h~5.0h.
2. the method according to claim 1, wherein the auxiliary agent in the step (2) is poly-aspartate and second
Diamines tetramethylene pitches the mixture of Alendronate, molar ratio 0.5:1-3.0:1.
3. the method according to claim 1, wherein the precipitation temperature in the step (3) is preferably 40~50
℃。
4. the method according to claim 1, wherein in the step (5) cleaning solution acid adding readjustment pH to 6.0 ~
8.0, obtain aluminium hydroxide by-product.
5. the method according to claim 1, wherein the concentration of sodium hydroxide solution is in the step (5)
0.3-1.0mol/L。
6. the method according to claim 1, wherein washed-residue directlys adopt that hydrochloric acid is molten to be obtained in the step (6)
Rare-earth liquid is obtained, extraction process is used for.
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| CN111498879A (en) * | 2020-04-30 | 2020-08-07 | 中国地质科学院矿产综合利用研究所 | Method for directly preparing sodium metaaluminate from impurity-removed waste residues of weathering crust leaching type rare earth ore leachate |
| 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 |
| CN112662900B (en) * | 2020-12-04 | 2022-12-23 | 江西理工大学 | Method for co-recovering rare earth in leaching mother liquor by dissolving and selectively precipitating coprecipitation acid |
| CN112680605B (en) * | 2020-12-11 | 2022-08-09 | 江西理工大学 | Method for synchronously recovering rare earth in leaching mother liquor by utilizing cascade precipitation process |
| CN114737069B (en) * | 2022-03-09 | 2023-07-21 | 中南大学 | Method for removing aluminum from ion type rare earth mine leaching solution |
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