CN105543475A - Method for enriching and recovering rare earth from rare earth-containing phosphorite - Google Patents

Method for enriching and recovering rare earth from rare earth-containing phosphorite Download PDF

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CN105543475A
CN105543475A CN201610076773.7A CN201610076773A CN105543475A CN 105543475 A CN105543475 A CN 105543475A CN 201610076773 A CN201610076773 A CN 201610076773A CN 105543475 A CN105543475 A CN 105543475A
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phosphoric acid
acid
rare earth
sulfuric acid
mixed slurry
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CN105543475B (en
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蒋训雄
冯林永
范艳青
汪胜东
张登高
刘巍
靳冉公
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Beijing General Research Institute of Mining and Metallurgy
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Beijing General Research Institute of Mining and Metallurgy
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
    • C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
    • C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
    • C22B3/08—Sulfuric acid, other sulfurated acids or salts thereof
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B59/00—Obtaining rare earth metals
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Abstract

The invention discloses a method for enriching and recovering rare earth from rare earth-containing phosphorite. Adding the phosphorite containing the rare earth and the mixed acid of phosphoric acid and sulfuric acid into a mixing reaction tank to react to obtain mixed slurry, and carrying out solid-liquid separation to obtain rare earth enriched slag and leachate. Adding the leachate and a proper amount of sulfuric acid into a phosphoric acid regeneration stirring tank for mixing reaction to obtain mixed slurry containing phosphoric acid and gypsum; and returning a part of the mixed slurry as return slurry to the regeneration stirring tank, and performing solid-liquid separation on the rest of the mixed slurry to obtain a phosphoric acid solution and gypsum residues. And opening a part of the phosphoric acid solution, adjusting components, returning the components as mixed acid for recycling, and producing phosphoric acid from the rest part. The invention adopts the mixed acid which mainly takes phosphoric acid and contains a proper amount of sulfuric acid to leach the phosphorite containing rare earth, thereby not only effectively removing impurities such as calcium, magnesium, aluminum, phosphorus and the like, but also reducing the dissolution loss of the rare earth by utilizing the adsorption effect of newly generated a small amount of gypsum, further realizing selective leaching impurity removal, improving the rare earth enrichment ratio in slag and reducing the dissolution loss of the rare earth.

Description

From the method containing enrichment rare earth phosphate rock and recovering rare earth
Technical field
The invention belongs to enrichment and the synthetical recovery field of association rare earth, particularly relating to a kind of by adopting the mixing acid of phosphoric acid and sulfuric acid to leach removal of impurities, from the method containing enrichment rare earth phosphate rock and recovering rare earth.
Background technology
General association rare earth in phosphorus ore, not etc., reach as high as more than 5%, low does not only have about 0.1% to content of rare earth.Because rare earth is present in the phosphate mineral of phosphatic rock with isomorphism form, the concentration effect of physical concentration to rare earth is poor, therefore can only be separated and recovering rare earth by chemical process.Due to the low and detrimental impurity phosphorus of rare earth grade and calcium contents high, the difficulty directly leaching recovering rare earth is large, cost is high, and relying on production process of phosphoric acid to realize rare earth synthetical recovery is reasonable approach.Current Wet-process Phosphoric Acid Production process both domestic and external all adopts two water thing methods in sulfuric acid process, but in two water thing method Wet-process Phosphoric Acid Production processes, phosphatic rock forms a large amount of phosphogypsum when decomposing, and phosphogypsum has very strong adsorptive power to rare earth, causes acid hemolysis process rare earth to be difficult to leach.US4636369 discloses and introduce aluminum ion, iron ion, silicon ion or its hybrid ionic in phosphoric acid by wet process ore pulp, increases rare earth solubleness in the solution, and rare earth leaching yield is 56%.Chinese patent 200710178377.6 discloses and add organic or inorganic surfactant in sulfuric acid decomposition phosphorite process, and phosphogypsum crystal formation is changed and reduces the absorption to rare earth, the leaching yield of rare earth can reach 80%.Chinese patent 201010217142.5 discloses a kind of method that phosphoric acid leaches rare earth, and under the condition of temperature higher than 65 DEG C, leach the phosphorus ore containing rare earth 0.14% with phosphoric acid, rare earth leaching yield can reach about 90%.Although above-mentioned various method can leach rare earth preferably, due to obtained high containing re dip solution phosphoric acid concentration, even containing impurity such as a large amount of calcium, from solution, further recovering rare earth is difficult.
Preferentially removed the impurity such as the phosphorus in phosphorus ore, calcium, iron, aluminium by preimpregnation, improving rare-earth enrichment ratio, is a kind of promising method to the synthetical recovery of association rare earth in phosphorus ore.Chinese patent 201110143415.0 discloses a kind of method of rare-earth separating from phosphorus ore, it adopts phosphoric acid to be leaching agent, phosphorus concentrate containing rare earth is mixed with phosphoric acid solution, leach at 15 ~ 50 DEG C, the impurity such as phosphorus, calcium, iron, aluminium are leached and enters solution, and most of rare earth is stayed in leached mud, obtain rare-earth enrichment slag.But phosphoric acid also has certain solvability to rare earth, as the method for a kind of phosphoric acid leaching rare earth that Chinese patent 201010217142.5 is announced, be namely, by phosphoric acid, rare earth is leached to the phosphorus ore containing rare earth 0.14%.Therefore, phosphoric acid is adopted to leach the impurity such as phosphorus, calcium, iron, aluminium removed in advance in phosphorus ore, strict to leaching condition control overflow, and still have the rare earth of considerable part to be dissolved into solution, cause dispersion and the loss of rare earth, affect the rate of recovery of rare earth and the concentration ratio in rare earth slag.
Summary of the invention
The object of the invention is the deficiency existed for prior art, particularly leach for phosphoric acid the part rare earth existed in enrichment rare earth to be dissolved and the problem such as slip solid-liquid separation difficulty, provide a kind of mixing acid of phosphoric acid and sulfuric acid that adopts from the method containing enrichment rare earth phosphate rock and recovering rare earth.
Object of the present invention is achieved through the following technical solutions.
From the method containing enrichment rare earth phosphate rock and recovering rare earth, it is characterized in that comprising the following steps:
(1) levigate is added hybrid reaction groove containing rare earth phosphate rock and react for some time together with appropriate mixing acid, obtain mixed slurry-1, then solid-liquid separation, obtain rare-earth enrichment slag and leach liquor-1, described mixing acid is based on phosphoric acid, containing the phosphoric acid of moderate amount of sulfuric acid and sulfuric acid mixing acid, the phosphoric acid quality concentration in mixing acid is (with P 2o 5meter) be 10% ~ 55%, sulfuric acid concentration is (with SO 4 2-meter) be 3 ~ 25g/L;
(2) leach liquor-1 that step (1) obtains is joined phosphoric acid regenerating stirring tank and hybrid reaction for some time together with moderate amount of sulfuric acid, obtain the mixed slurry-2 of phosphoric acid and gypsum;
(3) step (2) is obtained mixed slurry-2 solid-liquid separation, obtain phosphoric acid solution and gypsum tailings;
(4) opened a way by the phosphoric acid solution that step (3) obtains and return step (1) after a part of adjusting component and recycle as mixing acid, the phosphoric acid solution of rest part is for the production of phosphoric acid.
In the present invention, mixed slurry-1 and mixed slurry-2 refer to the different mixed slurries successively obtained according to technical process respectively, and leach liquor-1 and leach liquor-2 refer to the different leach liquors successively obtained according to technical process respectively.
Of the present invention from the method containing enrichment rare earth phosphate rock and recovering rare earth, adding hybrid reaction groove containing rare earth phosphate rock and react for some time together with appropriate mixing acid described in step (1), the add-on of mixing acid adds by mixing acid and the liquid-solid volume and mass ratio 5 ~ 10:1L/kg containing rare earth phosphate rock, temperature of reaction is 20 DEG C ~ 110 DEG C, preferably 30 ~ 60 DEG C, reaction times 0.5 ~ 8h.
Of the present invention from the method containing enrichment rare earth phosphate rock and recovering rare earth, leach liquor-1 described in step (2) joins phosphoric acid regenerating stirring tank and hybrid reaction for some time together with sulfuric acid, be leach liquor-1 and mass concentration are not less than 90% industrial sulphuric acid together with add phosphoric acid regenerating stirring tank and mix, the add-on of sulfuric acid is 0.7 ~ 1.2 times of calcium mole number in leach liquor-1 by mole ratio, hybrid reaction temperature 60 C ~ 110 DEG C, reaction times 0.5 ~ 4h.
Of the present invention from the method containing enrichment rare earth phosphate rock and recovering rare earth, the mixed slurry-1 that step (1) obtains can be divided into two portions, wherein a part is as returning in hybrid reaction groove that slurry turns back to described in step (1), to improve rare-earth enrichment ratio and to improve slip settling property, rest part carries out solid-liquid separation, obtains rare-earth enrichment slag and leach liquor-2.
Of the present invention from the method containing enrichment rare earth phosphate rock and recovering rare earth, mixed slurry-2 solid-liquid separation of the phosphoric acid described in step (3) and gypsum, that this mixed slurry-2 is divided into two portions, wherein a part of mixed slurry-2 is as returning in regenerating stirring tank that slurry turns back to described in step (2), the mixed slurry-2 of rest part carries out solid-liquid separation, obtains phosphoric acid solution and gypsum tailings.
Of the present invention from the method containing enrichment rare earth phosphate rock and recovering rare earth, wherein a part of mixed slurry-2 described above is as returning in regenerating stirring tank that slurry turns back to described in step (2), and it returns 0.5 ~ 20 times that slurry amount is the volume of step (2) described leach liquor-1.
Of the present invention from the method containing enrichment rare earth phosphate rock and recovering rare earth, the rare-earth enrichment slag acid that step (1) obtains is leached, obtain the leach liquor-2 containing rare earth, then by one or more method recovering rare earths in extraction process, ion exchange adsorption, the precipitator method, crystallization process, described acid is one or more the mixture in sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid, preferred nitric acid.
Of the present invention from the method containing enrichment rare earth phosphate rock and recovering rare earth, adjusting component described in step (4), be that the phosphoric acid solution of open circuit is mixed with one or more the mixture in water, rare-earth enrichment wash heat water, gypsum tailings wash water, sulfuric acid, phosphorus ore, obtain phosphoric acid quality concentration (with P 2o 5meter) 15% ~ 35%, sulfuric acid concentration is (with SO 4 2-meter) phosphoric acid of 5 ~ 15g/L and the mixing acid of sulfuric acid returns step (1) and recycles.When the phosphoric acid solution of open circuit is mixed with sulfuric acid or phosphorus ore, need to carry out solid-liquid separation with disgorging, then as mixing acid after pulp reaction certain hour.
Of the present invention from the method containing enrichment rare earth phosphate rock and recovering rare earth, the leach liquor-1 that step (1) obtains first can send into ageing tank ageing 1 ~ 5h at 80 DEG C ~ 110 DEG C, to improve rare-earth enrichment ratio further and to reduce rare earth solution loss, then filter, filtrate enters step (2) and add the mixing of phosphoric acid regenerating stirring tank together with sulfuric acid.
Of the present invention from the method containing enrichment rare earth phosphate rock and recovering rare earth, described containing rare earth phosphate rock be ore reduction, after fine grinding containing rare earth phosphate rock or the Phosphoric concentration bearing rare-earths that obtains after ore dressing.
Of the present invention from the method containing enrichment rare earth phosphate rock and recovering rare earth, the mixing acid described in step (1) is obtained by step (4), or is prepared by industrial phosphoric acid and industrial sulphuric acid and water and obtain.
Of the present invention from the method containing enrichment rare earth phosphate rock and recovering rare earth, the mixing acid based on phosphoric acid, containing moderate amount of sulfuric acid is adopted to leach containing rare earth phosphate rock, and in conjunction with ageing, return the methods such as slurry, can effectively remove containing impurity such as the calcium in rare earth phosphate rock, magnesium, aluminium, phosphorus, reduce the solution loss of rare earth simultaneously, possess good impurity removing effect, rare-earth enrichment ratio and the rate of recovery high, and flow process is simple, processing condition are easy to features such as manipulating, solid-liquid separation is easy.
Accompanying drawing explanation
Accompanying drawing is the principle process flow sheet of the inventive method.
Embodiment
Below in conjunction with accompanying drawing the present invention made and further illustrating.
From the method containing enrichment rare earth phosphate rock and recovering rare earth, by the Phosphoric concentration bearing rare-earths containing rare earth phosphate rock or obtain through ore dressing, add hybrid reaction groove with mixing acid and react, described mixing acid is that phosphoric acid mass concentration is (with P 2o 5meter) 10% ~ 55%, sulfuric acid concentration is (with SO 4 2-meter) phosphoric acid of 3 ~ 25g/L and the mixing acid of sulfuric acid, the add-on of mixing acid adds by mixing acid and the liquid-solid volume and mass ratio 5:1 ~ 10:1 containing rare earth phosphate rock or Phosphoric concentration bearing rare-earths, temperature of reaction is 20 DEG C ~ 110 DEG C, and reaction times 0.5 ~ 8h, obtains mixed slurry-1; Mixed slurry-1 is through solid-liquid separation, obtain rare-earth enrichment slag and leach liquor-1, this leach liquor and moderate amount of sulfuric acid are added hybrid reaction in phosphoric acid regenerating stirring tank, phosphoric acid is regenerated, the add-on of sulfuric acid is 0.7 ~ 1.2 times of calcium mole number in leach liquor-1 by mole ratio, temperature of reaction 60 DEG C ~ 110 DEG C, reaction times 0.5 ~ 4h, obtains mixed slurry-2; The mixed slurry-2 obtained is divided into two portions, and wherein a part turns back in regenerating stirring tank as returning slurry, and rest part carries out solid-liquid separation, obtains phosphoric acid solution and gypsum tailings, returns slurry amount for joining 0.5 ~ 20 times of leach liquor-1 volume in regenerating stirring tank; By obtained a phosphoric acid solution open circuit part, add one or more mixture in suitable quantity of water, rare-earth enrichment wash heat water, gypsum tailings wash water, sulfuric acid, phosphorus ore with adjusting component, obtain phosphoric acid quality concentration (with P 2o 5meter) 10% ~ 55%, sulfuric acid concentration is (with SO 4 2-meter) phosphoric acid of 3 ~ 25g/L and the mixing acid of sulfuric acid returns and recycles, and the phosphoric acid solution of rest part is for the production of phosphoric acid.
The rare-earth enrichment slag that aforesaid method obtains can leach with the mixture of one or more in sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid, obtain the leach liquor-2 containing rare earth, then by one or more method recovering rare earths in extraction process, ion exchange adsorption, the precipitator method, crystallization process.Preferred scheme is, the rare-earth enrichment slag nitric acid obtained leaches, and obtains the leach liquor-2 containing rare earth, then by one or more method recovering rare earths in extraction process, ion exchange adsorption, the precipitator method, crystallization process.
In some implementation methods, the mixed slurry-1 obtained can be divided into two portions, wherein a part is as returning in hybrid reaction groove that slurry turns back to described in step (1), to improve rare-earth enrichment ratio and to improve slip settling property, rest part carries out solid-liquid separation, obtains rare-earth enrichment slag and leach liquor-1.
Be further described method of the present invention with nonlimiting examples below, to contribute to understanding content of the present invention and advantage thereof, and not as limiting the scope of the present invention, protection scope of the present invention is determined by claims.
Embodiment 1
Phosphoric acid mass concentration is mixed with (with P with industrial phosphoric acid, industrial sulphuric acid and water 2o 5meter) 35%, sulfuric acid concentration is (with SO 4 2-meter) phosphoric acid of 10g/L and the mixing acid of sulfuric acid, then get this mixing acid appropriate with containing rare earth 0.14% containing rare earth phosphate rock powder by liquid-solid volume and mass ratio 5:1L/kg hybrid reaction, temperature of reaction is 30 DEG C, and reaction times 2h, obtains mixed slurry-1; Mixed slurry-1, through solid-liquid separation, obtains rare-earth enrichment slag and leach liquor-1, and the rare-earth enrichment slag Rare-Earth Content 1% obtained, rare earth 95% is enriched in slag.Filter after this rare-earth enrichment slag is leached with nitric acid, obtain the leach liquor-2 containing rare earth, then adopt P204 extraction process recovering rare earth from leach liquor-2.
Embodiment 2
The leach liquor-1 obtained in above-described embodiment 1 is added phosphoric acid regenerating stirring tank hybrid reaction with moderate amount of sulfuric acid, phosphoric acid is regenerated, and the add-on of sulfuric acid is 1 times of calcium mole number in leach liquor-1 by mole ratio, temperature of reaction 80 DEG C, reaction times 1h, obtains mixed slurry-2; The mixed slurry-2 obtained is divided into two portions, and wherein a part turns back in regenerating stirring tank as returning slurry, and rest part carries out solid-liquid separation, obtains phosphoric acid solution and gypsum tailings.Obtained phosphoric acid solution is added suitable quantity of water and industrial sulphuric acid adjusting component, obtain phosphoric acid mass concentration (with P 2o 5meter) 35%, sulfuric acid concentration is (with SO 4 2-meter) phosphoric acid of 15g/L and the mixing acid of sulfuric acid, then get this mixing acid appropriate with containing rare earth 0.14% containing rare earth phosphate rock powder by liquid-solid volume and mass ratio 5:1L/kg hybrid reaction, temperature of reaction is 30 DEG C, and reaction times 2h, obtains mixed slurry-1; Mixed slurry-1, through solid-liquid separation, obtains rare-earth enrichment slag and leach liquor-1.
Embodiment 3
The leach liquor-1 obtained in above-described embodiment 1 is added phosphoric acid regenerating stirring tank with moderate amount of sulfuric acid, and add the mixed slurry-1 obtained in appropriate embodiment 2, hybrid reaction for some time, phosphoric acid is regenerated, the add-on of sulfuric acid is 1 times of calcium mole number in leach liquor-1 by mole ratio, temperature of reaction 80 DEG C, reaction times 1h, obtains mixed slurry-2; The mixed slurry-2 obtained is divided into two portions, and wherein a part turns back in regenerating stirring tank as returning slurry, and rest part carries out solid-liquid separation, obtains phosphoric acid solution and gypsum tailings.Obtained phosphoric acid solution is added suitable quantity of water and industrial sulphuric acid adjusting component, obtain phosphoric acid mass concentration (with P 2o 5meter) 35%, sulfuric acid concentration is (with SO 4 2-meter) phosphoric acid of 15g/L and the mixing acid of sulfuric acid, then get this mixing acid appropriate with containing rare earth 0.14% containing rare earth phosphate rock powder by liquid-solid volume and mass ratio 5:1L/kg hybrid reaction, temperature of reaction is 30 DEG C, and reaction times 2h, obtains mixed slurry-1; Mixed slurry-1, through solid-liquid separation, obtains rare-earth enrichment slag and leach liquor-1.To obtain leach liquor-1 ageing 1h at 90 DEG C, then filter, filter cake is incorporated in rare-earth enrichment slag.Rare-earth enrichment slag Rare-Earth Content 1.1%, rare earth 97% is enriched in slag.
Embodiment 4
Phosphoric acid mass concentration embodiment 3 obtained is (with P 2o 5meter) 35%, sulfuric acid concentration is (with SO 4 2-meter) phosphoric acid of 10g/L and the mixing acid of sulfuric acid, with containing rare earth 2.5% containing rare earth phosphate rock powder by liquid-solid volume and mass ratio 5:1L/kg hybrid reaction, temperature of reaction is 50 DEG C, and reaction times 1h, obtains mixed slurry-1; Mixed slurry-1 is through solid-liquid separation, obtain rare-earth enrichment slag and leach liquor-1, this leach liquor and moderate amount of sulfuric acid are added hybrid reaction in phosphoric acid regenerating stirring tank, phosphoric acid is regenerated, the add-on of sulfuric acid is 1 times of calcium mole number in leach liquor-1 by mole ratio, temperature of reaction 60 DEG C, reaction times 1h, obtains mixed slurry-2; The mixed slurry-2 obtained is divided into two portions, and wherein a part turns back in regenerating stirring tank as returning slurry, and rest part carries out solid-liquid separation, obtains phosphoric acid solution and gypsum tailings, returns slurry amount for joining 10 times of leach liquor-1 volume in regenerating stirring tank; By obtained a phosphoric acid solution open circuit part, add suitable quantity of water and sulfuric acid with adjusting component, obtain phosphoric acid quality concentration (with P 2o 5meter) 35%, sulfuric acid concentration is (with SO 4 2-meter) phosphoric acid of 10g/L and the mixing acid of sulfuric acid returns and recycles, and the phosphoric acid solution of rest part is for the production of phosphoric acid.
Embodiment 5
Phosphoric acid mass concentration embodiment 4 obtained is (with P 2o 5meter) 35%, sulfuric acid concentration is (with SO 4 2-meter) phosphoric acid of 10g/L and the mixing acid of sulfuric acid, with the Phosphoric concentration bearing rare-earths powder containing rare earth 7% by liquid-solid volume and mass ratio 5:1L/kg hybrid reaction, temperature of reaction is 50 DEG C, and reaction times 1h, obtains mixed slurry-1; Mixed slurry-1 is through solid-liquid separation, obtain rare-earth enrichment slag and leach liquor-1, this leach liquor and moderate amount of sulfuric acid are added hybrid reaction in phosphoric acid regenerating stirring tank, phosphoric acid is regenerated, the add-on of sulfuric acid is 1 times of calcium mole number in leach liquor-1 by mole ratio, temperature of reaction 80 DEG C, reaction times 1h, obtains mixed slurry-2; The mixed slurry-2 obtained is divided into two portions, wherein a part turns back in regenerating stirring tank as returning slurry, rest part carries out solid-liquid separation, obtains phosphoric acid solution and gypsum tailings, returns slurry amount for joining 10 times of leach liquor-1 volume in phosphoric acid regenerating stirring tank; By obtained a phosphoric acid solution open circuit part, add suitable quantity of water and sulfuric acid with adjusting component, obtain phosphoric acid quality concentration (with P 2o 5meter) 30%, sulfuric acid concentration is (with SO 4 2-meter) phosphoric acid of 15g/L and the mixing acid of sulfuric acid returns and recycles, and the phosphoric acid solution of rest part is for the production of phosphoric acid.
Embodiment 6
Phosphoric acid mass concentration embodiment 5 obtained is (with P 2o 5meter) 30%, sulfuric acid concentration is (with SO 4 2-meter) phosphoric acid of 15g/L and the mixing acid of sulfuric acid, with the Phosphoric concentration bearing rare-earths powder containing rare earth 7% by liquid-solid volume and mass ratio 5:1L/kg hybrid reaction, temperature of reaction is 50 DEG C, and reaction times 1h, obtains mixed slurry-1; Mixed slurry-1 is through solid-liquid separation, obtain rare-earth enrichment slag and leach liquor-1, this leach liquor and moderate amount of sulfuric acid are added hybrid reaction in phosphoric acid regenerating stirring tank, phosphoric acid is regenerated, the add-on of sulfuric acid is 1.2 times of calcium mole number in leach liquor-1 by mole ratio, temperature of reaction 80 DEG C, reaction times 1h, obtains mixed slurry-2; The mixed slurry-2 obtained is divided into two portions, wherein a part turns back in regenerating stirring tank as returning slurry, rest part carries out solid-liquid separation, obtains phosphoric acid solution and gypsum tailings, returns slurry amount for joining 10 times of leach liquor-1 volume in phosphoric acid regenerating stirring tank; By obtained a phosphoric acid solution open circuit part, filter with adjusting component after adding suitable quantity of water and phosphorus ore stirring 30min, obtain phosphoric acid quality concentration (with P 2o 5meter) 30%, sulfuric acid concentration is (with SO 4 2-meter) phosphoric acid of 5g/L and the mixing acid of sulfuric acid returns and recycles, and the phosphoric acid solution of rest part is for the production of phosphoric acid.

Claims (10)

1., from the method containing enrichment rare earth phosphate rock and recovering rare earth, it is characterized in that, comprise the following steps:
(1) levigate is added hybrid reaction groove containing rare earth phosphate rock and react for some time together with appropriate mixing acid, obtain mixed slurry-1, then solid-liquid separation, obtain rare-earth enrichment slag and leach liquor-1, described mixing acid is based on phosphoric acid, containing the phosphoric acid of moderate amount of sulfuric acid and sulfuric acid mixing acid, the phosphoric acid quality concentration in mixing acid is (with P 2o 5meter) be 10% ~ 55%, sulfuric acid concentration is (with SO 4 2-meter) be 3 ~ 25g/L;
(2) leach liquor-1 that step (1) obtains is joined phosphoric acid regenerating stirring tank and hybrid reaction for some time together with moderate amount of sulfuric acid, obtain the mixed slurry-2 of phosphoric acid and gypsum;
(3) step (2) is obtained mixed slurry-2 solid-liquid separation, obtain phosphoric acid solution and gypsum tailings;
(4) opened a way by the phosphoric acid solution that step (3) obtains and return step (1) after a part of adjusting component and recycle as mixing acid, the phosphoric acid solution of rest part is for the production of phosphoric acid.
2. method according to claim 1, it is characterized in that, the mixing acid added in step (1) be 5 ~ 10:1L/kg containing the liquid-solid volume of rare earth phosphate rock and mass ratio, temperature of reaction is 20 DEG C ~ 110 DEG C, preferably 30 DEG C ~ 60 DEG C, reaction times 0.5 ~ 8h.
3. method according to claim 1, it is characterized in that, sulfuric acid described in step (2) is the industrial sulphuric acid that mass concentration is not less than 90%, in the sulfuric acid added and leach liquor-1, the mol ratio of calcium ion is 0.7 ~ 1.2:1, hybrid reaction temperature 60 C ~ 110 DEG C, reaction times 0.5 ~ 4h.
4. method according to claim 1, it is characterized in that, the mixed slurry-1 that step (1) obtains is divided into two portions, and a part is as returning in hybrid reaction groove that slurry turns back to described in step (1), and rest part solid-liquid separation obtains rare-earth enrichment slag and leach liquor-1.
5. method according to claim 1, it is characterized in that, the mixed slurry-2 that step (2) obtains is divided into two portions, a part is as returning in regenerating stirring tank that slurry turns back to described in step (2), and rest part carries out solid-liquid separation by step (3) and obtains phosphoric acid solution and gypsum tailings.
6. method according to claim 5, is characterized in that, the part mixed slurry-2 returning slurry is 0.5 ~ 20 times of step (2) described leach liquor-1 volume.
7. method according to claim 1, it is characterized in that, the rare-earth enrichment slag Ore Leaching that step (1) obtains, obtain the leach liquor-2 containing rare earth, then by one or more method recovering rare earths in extraction process, ion exchange adsorption, the precipitator method, crystallization process, described acid is one or more the mixture in sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid, preferred nitric acid.
8. method according to claim 1, it is characterized in that, adjusting component described in step (4), be that the phosphoric acid solution of open circuit is mixed with one or more the mixture in water, rare-earth enrichment wash heat water, gypsum tailings wash water, sulfuric acid, phosphorus ore, control phosphoric acid quality concentration (with P 2o 5meter) be 15% ~ 35%, sulfuric acid concentration is (with SO 4 2-meter) be 5 ~ 15g/L; When being mixed with sulfuric acid or phosphorus ore by the phosphoric acid solution of open circuit, after pulp reaction certain hour, solid-liquid separation is with disgorging, then as mixing acid.
9. method according to claim 1, it is characterized in that, ageing tank ageing 1 ~ 5h at 80 DEG C ~ 110 DEG C sent into by the leach liquor-1 that step (1) obtains, and then filters, and filtrate enters step (2) and add the mixing of phosphoric acid regenerating stirring tank together with sulfuric acid.
10. method according to claim 1, is characterized in that, the mixing acid described in step (1) can be obtained by step (4), also can be prepared by industrial phosphoric acid, industrial sulphuric acid and water and obtain.
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* Cited by examiner, † Cited by third party
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CN107746977A (en) * 2017-12-13 2018-03-02 济南大学 The method of recovering rare earth from containing rare earth phosphate rock

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CN102312089A (en) * 2010-07-01 2012-01-11 北京矿冶研究总院 Method for recovering rare earth from rare earth-containing phosphorite

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CN102312089A (en) * 2010-07-01 2012-01-11 北京矿冶研究总院 Method for recovering rare earth from rare earth-containing phosphorite
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Publication number Priority date Publication date Assignee Title
CN107522183A (en) * 2016-06-21 2017-12-29 有研稀土新材料股份有限公司 The decomposition method of phosphorus ore
CN107746977A (en) * 2017-12-13 2018-03-02 济南大学 The method of recovering rare earth from containing rare earth phosphate rock

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