CN100370039C - Method for separating rare-earth element and fluorapatite, calcium chloraphosphate and calcium phosphate - Google Patents
Method for separating rare-earth element and fluorapatite, calcium chloraphosphate and calcium phosphate Download PDFInfo
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- CN100370039C CN100370039C CNB200610047937XA CN200610047937A CN100370039C CN 100370039 C CN100370039 C CN 100370039C CN B200610047937X A CNB200610047937X A CN B200610047937XA CN 200610047937 A CN200610047937 A CN 200610047937A CN 100370039 C CN100370039 C CN 100370039C
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Abstract
The process of separating RE elements from calcium fluorophosphate, calcium chlorophosphate and calcium phosphate is to wash mineral with the mixed solution of hydrochloric acid and citric acid to leach out calcium fluorophosphate, calcium chlorophosphate and calcium phosphate while limiting the leaching of RE elements and other matters. The solution containing calcium fluorophosphate, calcium chlorophosphate and calcium phosphate is alkalized to produce precipitate and recover calcium fluorophosphate, calcium chlorophosphate and calcium phosphate product; and the small amount of RE elements are recovered with P204 or P507 extractant. The said process has calcium fluorophosphate, calcium chlorophosphate and calcium phosphate leaching rate not lower than 95 wt%, RE element leaching rate not higher than 10 wt% and total RE element yield not lower than 97 wt%.
Description
Technical field
The invention belongs to metallurgical technology field, relate to a kind of method of from rare-earth mineral, extracting rare earth element, particularly relate to a kind of from the monazite and monazite and the symbiotic mixed type rare-earth mineral of hamartite that decompose through calcium oxide and contain the monazite and the symbiotic mixed type rare-earth mineral of hamartite of phosphatic rock, with rare earth element and the isolating method of calcium monofluorophosphate, calcium chlorophosphate and calcium phosphate.
Background technology
The symbiotic mixed type rare-earth mineral of monazite and monazite and hamartite is important rare earth resources.Because rare earth element is composed with phosphoric acid salt or phosphoric acid salt and the symbiotic form of fluoro carbonate and is stored in the mineral, the feasible difficulty of decomposing increases, and therefore at present industrial is that the applied production method of raw material extraction rare earth element has only high temperature sulfuric acid baking and sodium hydroxide to decompose two kinds with these type of mineral.By contrast, sodium hydroxide decomposition method process complexity and production cost height, it is extensive that the scope of its application can not show a candle to the high temperature sulfuric acid roasting method.
What the high temperature sulfuric acid roasting method decomposed monazite and the generation of the symbiotic mixed type rare-earth mineral of hamartite process contains HF and SO
2Waste gas is very big to the pollution of environment, for preventing emptying, adopts the water spray to absorb SO at present
3And HF.Illustrate in the practice that the water absorption process in use exists three aspect problems to be difficult to solve: (a) water absorbs SO
3, HF efficient fluctuation is big, SO in the tail gas of handling
2, HF content often exceeds national waste gas emission standard.(b) absorption liquid is H
2SO
4With the HF mixed acid solution.The HF of fluoaluminate method in can absorbent solution is prepared into sodium aluminum fluoride, and the residue dilute sulphuric acid can be sought other purposes.But because the recovery technical process is long, wayward, investment is not more adopted by manufacturer.Adopt lime neutralization-precipitation-clear water emission scenary to handle this waste acid water in the existing production.In addition, by containing HF in the solution, in and the time produce floss, make the solution muddiness, this solution exhaust emission environment.(c) tail gas corrodibility is strong, and facility investment is big, and working cost is also big.Though do not contain HF in the tail gas when high temperature sulfuric acid roasting method decomposes monazite, exist yet and deal with tail gas, contaminated wastewater problem of environment improperly.
In order to seek the clean metallurgical technology of economically feasible pollution-free decomposition monazite and monazite and hamartite mixed type rare-earth mineral, people have researched and developed out calcium oxide+auxiliary agent roasting decomposition monazite and monazite and hamartite mixed type rare-earth mineral, calcium oxide+auxiliary agent and have decomposed the monazite method.The characteristics of these two kinds of methods are that the waste gas environmental pollution of decomposition course is very little, needn't handle or simple process just can be discharged, but calcium monofluorophosphate, calcium chlorophosphate and the calcium phosphate and the rare earth element that generate at decomposition course coexist as in the product of roasting, it can not be directly used in extract rare earth element or produce rare-earth silicon alloy.Separate with rare earth element and do not see relevant report so far as yet about calcium monofluorophosphate, calcium chlorophosphate and calcium phosphate in the method that calcium monofluorophosphate, calcium phosphate are effectively reclaimed in sepn process.
Summary of the invention
The objective of the invention is to overcome the above-mentioned deficiency of prior art, at in the rare-earth mineral or calcium monofluorophosphate, calcium chlorophosphate and calcium phosphate difficulty in the rare-earth mineral after decomposing with separate with rare earth element, and be unfavorable for from wherein extracting rare earth element and with its problem of producing rare earth alloy, providing a kind of new rare earth element and the isolating method of calcium monofluorophosphate, calcium chlorophosphate and calcium phosphate.
This method adopts the mixing solutions of hydrochloric acid and citric acid to wash through mengite rare-earth mine, monazite and the fluorine carbon cerium mishmetal mineral of disaggregating treatment in advance and contains the monazite and the symbiotic mixed type rare-earth mineral of hamartite of phosphatic rock, the characteristics of these mineral are to contain rare earth element (RE by mass percentage simultaneously
xO
y: 25%～65%), calcium monofluorophosphate and calcium phosphate (Ca
5F (PO
4)
3+ Ca
3(PO
4)
2: 3%～20%), all the other are impurity, or contain rare earth element (RE simultaneously
xO
y: 20%～45%), calcium chlorophosphate and calcium phosphate (Ca
5Cl (PO
4)
3+ Ca
3(PO
4)
2: 15%～45%), all the other are impurity.Mixing solutions by hydrochloric acid and citric acid washs calcium monofluorophosphate, calcium chlorophosphate and the calcium phosphate stripping that makes in the mineral, limit simultaneously in rare earth element and other material pass into solutions, make calcium monofluorophosphate, calcium chlorophosphate and calcium phosphate and rare earth element and other separating substances.The solution that contains calcium monofluorophosphate, calcium chlorophosphate and calcium phosphate makes its precipitation and reclaims calcium monofluorophosphate, calcium chlorophosphate and calcium phosphate product through alkalization, and a small amount of rare earth element in the solution adopts di-(2-ethylhexyl)phosphoric acid (P
204) the extraction agent recovery.The solubility rate of calcium monofluorophosphate, calcium chlorophosphate and calcium phosphate 〉=95%, the solubility rate of rare earth element≤10%, the yield of whole process rare earth element 〉=97%.The mineral of the rare earth of this kind mineral also can be other phosphoric acid salt rare-earth minerals contain after disaggregating treatment in advance above major ingredient or contain the rare-earth mineral of phosphatic rock.
The technical scheme that the present invention provides is: the isolating method of this rare earth element and calcium monofluorophosphate, calcium chlorophosphate and calcium phosphate is characterized in that its technological process includes following steps:
(1). the stripping of calcium monofluorophosphate, calcium chlorophosphate and calcium phosphate
At first will contain calcium monofluorophosphate and calcium phosphate, calcium chlorophosphate and calcium phosphate rare-earth mineral with hydrochloric acid and citric acid solution by solid-to-liquid ratio W
(s)/ V
(l)Be to insert in the container that has stirring in 1: 5～1: 20, (solution temperature is little to the stripping influence, can as control condition) stirs 1 hour at least under the condition of normal temperature, and the concentration of hydrochloric acid and citric acid solution is hydrochloric acid 0.1～1.0molL
-1Citric acid 0.01～0.5molL
-1, stripping makes solid-liquid two be separated after finishing after filtration, and solid phase is rare-earth mineral or the rare-earth mineral after decomposing behind the dephosphorization, can be further used as the raw material of producing rare-earth silicon alloy or extracting rare earth element and use, and solution is used to reclaim calcium monofluorophosphate or calcium phosphate;
(2). reclaim calcium monofluorophosphate, calcium chlorophosphate and calcium phosphate
The solution that contains calcium monofluorophosphate, calcium chlorophosphate and calcium phosphate changes in the container that has stirring, and normal temperature (solution temperature is little to stripping influence, can as control condition), (NaOH solution also can be with containing NH to add NaOH solution under the stirring condition
4OH, Ca (OH)
2, the material of CaO replaces) and regulate acidity to pH 〉=8, make calcium monofluorophosphate and calcium phosphate precipitation, detect P content in the solution less than 0.2mgL with chemical analysis method
-1The time, can filter, make throw out and solution separating, throw out is calcium monofluorophosphate and calcium phosphate product;
(3) rare earth element is reclaimed in solvent extraction
The solution of filtering calcium monofluorophosphate and calcium phosphate is regulated pH=1～3 with hydrochloric acid, and wherein ree content is (with REO
3/2Meter) less than 20gL
-1, with it as feed liquid, di-(2-ethylhexyl)phosphoric acid (P
204) extraction agent dilutes with kerosene, the volume ratio of extraction agent and kerosene is 1: 1～1: 2, and as organic phase, the volume ratio of feed liquid and organic phase is 1: 1～1: 3 with it, by 4 stage countercurrent mode extracting rare-earth elements, the organic phase of supported rare earth element hydrochloric acid soln (HCl:3～6molL
-1) with the 6 stage countercurrent modes rare earth element of stripping.The aqueous solution that the reextraction gained contains rare earth element can be used for further through oxalic acid or ammonium bicarbonate precipitation, and 850～900 ℃ of calcinations prepare mixed rare-earth oxide; Also can be used for further preparing the crystallization rare earth chloride through evaporation concentration; Also can further adopt di-(2-ethylhexyl)phosphoric acid (P
204) extraction agent system or 2-ethylhexyl phosphonic acid two (2-ethylhexyl) ester (P
507) the extraction system separation, again through oxalic acid or ammonium bicarbonate precipitation, 850～900 ℃ of calcinations prepare single rare earth oxide product such as lanthanum trioxide, cerium oxide, Praseodymium trioxide, Neodymium trioxide, europium sesquioxide.Purpose to better implement the present invention still contains hydrochloric acid and citric acid in the raffinate behind the extracting rare-earth element, adding hydrochloric acid and citric acid, to be mixed with concentration be hydrochloric acid 0.1～1.0molL
-1, citric acid 0.01～0.5molL
-1Behind the mixing solutions, the stripping operation of returning calcium monofluorophosphate, calcium chlorophosphate and calcium phosphate continues to recycle.
In technique scheme, 2-ethylhexyl phosphonic acid two of the present invention (2-ethylhexyl) ester (P
507) belonging to acidic organophosphorus extractant, the principle of extracting rare-earth element is similar, also can substitute di-(2-ethylhexyl)phosphoric acid (P in this technology
204) use, its processing condition are roughly the same.
Compared with prior art, the invention has the beneficial effects as follows:
(1). dephosphorization rate is high and can reclaim calcium monofluorophosphate or calcium phosphate;
(2). the rare earth element yield is greater than 93%.
(3). hydrochloric acid and citric acid mixing solutions reusable edible, reduced production cost and waste water output.
Embodiment
Below in conjunction with specific embodiment technical scheme of the present invention is described in detail:
Embodiment 1
The product of calcium oxide+auxiliary agent roasting monazite, its chemical constitution such as table 1.Technological process includes following steps:
(1). the stripping of calcium chlorophosphate and calcium phosphate
Being raw material with this kind product with the processing condition of hydrochloric acid and citric acid mixing solutions stripping calcium chlorophosphate and calcium phosphate is: solid-to-liquid ratio=1: 10; Under the condition of normal temperature, stirred 1～2 hour; The concentration of hydrochloric acid and citric acid mixing solutions is hydrochloric acid 0.35molL
-1Citric acid 0.04molL
-1After stripping finishes, then with vacuum suction rate or centrifuging, filter press method solid-liquid two is separated again.Solid phase is the rare-earth mineral behind the dephosphorization, and its main chemical constitution is: RE
xO
y〉=78%, Ca
5Cl (PO
4)
3+ Ca
3(PO
4)
2≤ 1%.
(2). reclaim calcium phosphate
Solution is used to reclaim calcium phosphate, and its processing condition are: (concentration of NaOH solution is 0.5molL to add NaOH solution under the stirring condition
-1) regulate acidity to pH=9～10, make calcium phosphate precipitation, continuation was stirred 1 hour, stopped to stir, and static for some time (about 1～4 hour) is grown up to precipitating fully calcium phosphate crystal, and the P content in the sampling detection solution is less than 0.2mgL
-1The time, promptly available vacuum suction filter or centrifugal filtering method filtering separation throw out and solution.Throw out is the calcium phosphate product.
(3) rare earth element is reclaimed in solvent extraction
Contain rare earth element in the solution (with REO
3/2Meter) 6～7gL
-1As feed liquid, use di-(2-ethylhexyl)phosphoric acid (P with it
204) extraction agent extraction recovery rare earth element, concrete processing condition are: solution is at first regulated pH=1～3 with hydrochloric acid, di-(2-ethylhexyl)phosphoric acid (P
204) extraction agent dilutes with kerosene, the volume ratio of extraction agent and kerosene be 1: 2 as organic phase, secondly the volume ratio of feed liquid and organic phase is 1: 2,, by 4 stage countercurrent mode extracting rare-earth elements, the organic phase hydrochloric acid soln (HCl:6molL of extraction supported rare earth element
-1) with the 6 stage countercurrent modes rare earth element of stripping.The aqueous solution that the reextraction gained contains rare earth element can be used for further through oxalic acid or ammonium bicarbonate precipitation, and 850～900 ℃ of calcinations prepare mixed rare-earth oxide.Organic phase is returned counter-current extraction rare earth operation and is recycled.Still contain hydrochloric acid and citric acid in the raffinate behind the extracting rare-earth element, adding hydrochloric acid and citric acid, to be mixed with concentration be hydrochloric acid 0.35molL
-1Citric acid 0.04molL
-1Returning the stripping operation behind the mixing solutions continues to recycle.This technological process rare earth total recovery is 97%, dephosphorization rate 98%, and the citric acid utilization ratio is greater than 80%.
The chemical constitution of the product of table 1. calcium oxide+auxiliary agent roasting monazite
| Composition | RE xO y | Ca 5Cl(PO 4) 3+Ca 3(PO 4) 2 | Other mineral |
| %/quality | 44.2 | 45.1 | 10.7 |
Embodiment 2
The chemical constitution such as the table 2 of calcium oxide+auxiliary agent roasting monazite and hamartite mixed type rare-earth mineral product, technological process includes following steps:
(1). the stripping of calcium monofluorophosphate and calcium phosphate
Being raw material with this kind product with the processing condition of hydrochloric acid and citric acid solution stripping calcium monofluorophosphate and calcium phosphate is: solid-to-liquid ratio=1: 14; Under the condition of normal temperature, stirred 1～2 hour; The concentration of hydrochloric acid and citric acid solution is hydrochloric acid 0.35molL
-1Citric acid 0.02molL
-1Stripping then is separated solid-liquid two with vacuum suction filter or centrifugal filtering method after finishing again.Solid phase is the rare-earth mineral behind the dephosphorization, and its main chemical constitution is: RE
xO
y〉=63%, Ca
5F (PO
4)
3+ Ca
3(PO
4)
2≤ 1%.
(2). reclaim calcium monofluorophosphate and calcium phosphate
Solution is used to reclaim calcium monofluorophosphate and calcium phosphate, and processing condition are with embodiment 1.
(3) rare earth element is reclaimed in solvent extraction
Solution reclaims rare earth element with solvent extraction method after extracting calcium monofluorophosphate and calcium phosphate, and the volume ratio of feed liquid and organic phase is 1: 3, and all the other processing condition are with embodiment 1.The aqueous solution that the reextraction gained contains rare earth element can be used for further preparing the crystallization rare earth chloride through evaporation concentration; Still contain hydrochloric acid and citric acid in the raffinate behind the extracting rare-earth element, adding hydrochloric acid and citric acid, to be mixed with concentration be hydrochloric acid 0.35molL
-1Citric acid 0.02molL
-1Returning the stripping operation behind the mixing solutions continues to recycle.This technological process rare earth total recovery is 97%, dephosphorization rate 98%, and the citric acid utilization ratio is greater than 80%.
The chemical constitution of the product of table 2. calcium oxide+auxiliary agent roasting monazite and hamartite mixed type rare-earth mineral
| Composition | RE xO y | Ca 5F(PO 4) 3+Ca 3(PO 4) 2 | CaF 2 | Auxiliary agent | SiO 2 | Other mineral |
| %/quality | 45.3 | 20.01 | 9.09 | 8.78 | 1.21 | 16.61 |
Embodiment 3
Contain monazite and hamartite mixed type low rare earth grade mineral its chemical constitution such as table 3 of phosphatic rock, technological process includes following steps:
(1). the stripping of calcium monofluorophosphate and calcium phosphate
Being raw material with this kind product with the processing condition of hydrochloric acid and citric acid solution stripping calcium monofluorophosphate is: solid-to-liquid ratio=1: 5; Under the condition of normal temperature, stirred 1～2 hour; The concentration of hydrochloric acid and citric acid solution is hydrochloric acid 1.0mo1L
-1Citric acid 0.5molL
-1Stripping then is separated solid-liquid two with vacuum suction filter or centrifugal filtering method after finishing again.Solid phase is the rare-earth mineral behind the dephosphorization, and its main chemical constitution is: RE
xO
y〉=33%, Ca
5F (PO
4)
3+ Ca
3(PO
4)
2≤ 1%.
(2). reclaim calcium monofluorophosphate and calcium phosphate
Solution is used to reclaim calcium monofluorophosphate or calcium phosphate, and its processing condition are with specific embodiment 1.Contain rare earth element hardly in the solution behind extraction calcium monofluorophosphate or the calcium phosphate, needn't reclaim rare earth element with specific embodiment 1 described solvent extraction method, but still contain hydrochloric acid and citric acid in the solution, need adding hydrochloric acid and citric acid, to be mixed with concentration be hydrochloric acid 1.0molL
-1Citric acid 0.5molL
-1Returning the stripping operation behind the mixing solutions continues to recycle.This technological process rare earth total recovery is 95%, and dephosphorylation calcium rate is 95%, and the citric acid utilization ratio is greater than 80%.
Table 3. contains monazite and its chemical constitution of hamartite mixed type rare-earth mineral of phosphatic rock
| Composition | RE xO y | Ca 5F(PO 4) 3+Ca 3(PO 4) 2 | CaF 2 | SiO 2 | Other mineral |
| %/quality | 31 | 7.95 | 22.38 | 1.32 | 37.35 |
Embodiment 4
The monazite of calcium oxide+high rare earth grade of auxiliary agent roasting and the product chemical constitution such as the table 4 of hamartite mixed type rare-earth mineral, technological process includes following steps:
(1). the stripping of calcium monofluorophosphate and calcium phosphate
At first will contain calcium monofluorophosphate and calcium phosphate rare-earth mineral with hydrochloric acid and citric acid solution by solid-to-liquid ratio=insert in the container that have stirring at 1: 20, under the condition of normal temperature, stirred at least 1 hour, the concentration of hydrochloric acid and citric acid solution is hydrochloric acid 0.1molL
-1Citric acid 0.01molL
-1, stripping makes solid-liquid two be separated after finishing after filtration, and solid phase is rare-earth mineral or the rare-earth mineral after decomposing: the RE behind the dephosphorization
xO
y〉=75.8%, Ca
5F (PO
4)
3+ Ca
3(PO
4)
2≤ 1%., being further used as the raw material of producing rare-earth silicon alloy or extracting rare earth element and using, solution is used to reclaim calcium monofluorophosphate and calcium phosphate;
(2). reclaim calcium monofluorophosphate and calcium phosphate
The solution that contains calcium monofluorophosphate and calcium phosphate changes in the container that has stirring, adds NaOH solution and regulate acidity to pH 〉=8 under normal temperature, stirring condition, makes calcium monofluorophosphate and calcium phosphate precipitation, detects P content in the solution less than 0.2mgL with chemical analysis method
-1The time, can filter, make throw out and solution separating, throw out is calcium monofluorophosphate and calcium phosphate product;
(3) rare earth element is reclaimed in solvent extraction
The solution of filtering calcium monofluorophosphate and calcium phosphate is regulated pH=3 with hydrochloric acid, and wherein ree content is (with REO
3/2Meter) less than 20gL
-1, with it as feed liquid, di-(2-ethylhexyl)phosphoric acid (P
204) extraction agent dilutes with kerosene, the volume ratio of extraction agent and kerosene is 1: 1, and as organic phase, the volume ratio of feed liquid and organic phase is 1: 1 with it, and by 4 stage countercurrent mode extracting rare-earth elements, the organic phase of supported rare earth element is with hydrochloric acid soln (HCl:6molL
-1) with the 6 stage countercurrent modes rare earth element of stripping.The reextraction gained contains the aqueous solution of rare earth element further through oxalic acid or ammonium bicarbonate precipitation, and 850～900 ℃ of calcinations prepare mixed rare-earth oxide.Still contain hydrochloric acid and citric acid in the raffinate behind the extracting rare-earth element, adding hydrochloric acid and citric acid, to be mixed with concentration be hydrochloric acid 0.1molL
-1, citric acid 0.01molL
-1Behind the mixing solutions, return the stripping operation and continue to recycle.
The chemical constitution of the product of table 4. calcium oxide+auxiliary agent roasting monazite and the high rare earth grade of hamartite mixed type mineral
| Composition | RE xO y | Ca 5F(PO 4) 3+Ca 3(PO 4) 2 | CaF 2 | SiO 2 | Other mineral |
| %/quality | 65.2 | 17.7 | 7.7 | 0.7 | 8.7 |
Embodiment 5
The product of the low rare earth grade monazite of calcium oxide+auxiliary agent roasting, its chemical constitution such as table 5, technological process includes following steps:
(1). the stripping of calcium chlorophosphate and calcium phosphate
At first will contain calcium chlorophosphate and calcium phosphate rare-earth mineral with hydrochloric acid and citric acid solution by solid-to-liquid ratio=insert in the container that have stirring at 1: 5, under the condition of normal temperature, stirred at least 1 hour, the concentration of hydrochloric acid and citric acid solution is hydrochloric acid 1.0molL
-1Citric acid 0.5molL
-1, stripping makes solid-liquid two be separated after finishing after filtration, and solid phase is rare-earth mineral or the rare-earth mineral after decomposing, the wherein RE behind the dephosphorization
xO
y〉=25%, Ca
5F (PO
4)
3+ Ca
3(PO
4)
2≤ 1%, be further used as the raw material of producing rare-earth silicon alloy or extracting rare earth element and use, solution is used to reclaim calcium phosphate;
(2). reclaim calcium phosphate
The solution that contains calcium chlorophosphate and calcium phosphate changes in the container that has stirring, adds NaOH solution and regulate acidity to pH 〉=8 under normal temperature, stirring condition, makes calcium phosphate precipitation, detects P content in the solution less than 0.2mgL with chemical analysis method
-1The time, can filter, make throw out and solution separating, throw out is the calcium phosphate product;
(3) rare earth element is reclaimed in solvent extraction
The solution of filtering calcium phosphate is regulated pH=1～3 with hydrochloric acid, and wherein ree content is (with REO
3/2Meter) less than 20gL
-1, with it as feed liquid, 2-ethylhexyl phosphonic acid two (2-ethylhexyl) ester (P
507) extraction agent dilutes with kerosene, the volume ratio of extraction agent and kerosene is 1: 2, and as organic phase, the volume ratio of feed liquid and organic phase is 1: 2 with it, and by 4 stage countercurrent mode extracting rare-earth elements, the organic phase of supported rare earth element is with hydrochloric acid soln (HCl:3molL
-1) with the 6 stage countercurrent modes rare earth element of stripping.The reextraction gained contains the aqueous solution of rare earth element further through oxalic acid or ammonium bicarbonate precipitation, and 850～900 ℃ of calcinations prepare mixed rare-earth oxide; Also can be used for further preparing the crystallization rare earth chloride through evaporation concentration.Still contain hydrochloric acid and citric acid in the raffinate behind the extracting rare-earth element, adding hydrochloric acid and citric acid, to be mixed with concentration be hydrochloric acid 1.0molL
-1, citric acid 0.5molL
-1Behind the mixing solutions, return the stripping operation and continue to recycle.
The chemical constitution of the low rare earth grade monazite product of table 5. calcium oxide+auxiliary agent roasting
| Composition | RE xO y | Ca 5Cl(PO 4) 3+Ca 3(PO 4) 2 | SiO 2 | Other mineral |
| %/quality | 21.4 | 15.1 | 3.72 | 59.78 |
Embodiment 6
Contain the monazite of phosphatic rock and hamartite mixed type low rare earth grade mineral its chemical constitution such as table 6, technological process is with embodiment 3, the rare-earth mineral behind the dephosphorization, and its main chemical constitution is: RE
xO
y〉=26%, Ca
5F (PO
4)
3+ Ca
3(PO
4)
2≤ 1%.Solution is used to reclaim calcium monofluorophosphate and calcium phosphate.Contain rare earth element hardly in the solution behind extraction calcium monofluorophosphate and the calcium phosphate, needn't reclaim rare earth element with specific embodiment 1 described solvent extraction method, but still contain hydrochloric acid and citric acid in the solution, need adding hydrochloric acid and citric acid, to be mixed with concentration be hydrochloric acid 1.0molL
-1Citric acid 0.1molL
-1Returning the stripping operation behind the mixing solutions continues to recycle.This technological process rare earth total recovery is 95%, and dephosphorylation calcium rate is 95%, and the citric acid utilization ratio is greater than 80%.
Table 6. contains monazite and its chemical constitution of hamartite mixed type rare-earth mineral of phosphatic rock
| Composition | RE xO y | Ca 5F(PO 4) 3+Ca 3(PO 4) 2 | CaF 2 | SiO 2 | Other mineral |
| %/quality | 25.3 | 3.4 | 28.7 | 4.7 | 37.9 |
Claims (4)
1. one kind with rare earth element and the isolating method of calcium monofluorophosphate, calcium chlorophosphate and calcium phosphate, it is characterized in that comprising following processing step:
1. the stripping of calcium monofluorophosphate, calcium chlorophosphate and calcium phosphate
At first will contain calcium monofluorophosphate and calcium phosphate, calcium chlorophosphate and calcium phosphate rare-earth mineral with hydrochloric acid and citric acid solution by solid-to-liquid ratio W
(s)/ V
(1)Be to insert in the container that has stirring in 1: 5～1: 20, under the condition of normal temperature, stirred at least 1 hour that the concentration of hydrochloric acid and citric acid solution is hydrochloric acid 0.1～1.0molL
-1Citric acid 0.01～0.5molL
-1, stripping makes solid-liquid two be separated after finishing after filtration, and solid phase is as the raw material use of producing rare-earth silicon alloy or extracting rare earth element, and solution is used to reclaim calcium monofluorophosphate or calcium phosphate;
2. reclaim calcium monofluorophosphate, calcium chlorophosphate and calcium phosphate
The solution that contains calcium monofluorophosphate, calcium chlorophosphate and calcium phosphate changes in the container that has stirring, regulates acidity to pH 〉=8 under normal temperature, stirring condition, makes calcium monofluorophosphate and calcium phosphate precipitation, detects P content in the solution less than 0.2mgL with chemical analysis method
-1The time, filter, make throw out and solution separating, throw out is calcium monofluorophosphate and calcium phosphate product;
3. rare earth element is reclaimed in solvent extraction
The solution of filtering calcium monofluorophosphate and calcium phosphate is regulated pH=1～3 with hydrochloric acid, and wherein ree content is less than 20gL
-1, with it as feed liquid, P
204Extraction agent dilutes with kerosene, and the volume ratio of extraction agent and kerosene is 1: 1～1: 2, and as organic phase, the volume ratio of feed liquid and organic phase is 1: 1～1: 3 with it, the extracting rare-earth element, and the organic phase of supported rare earth element is with 3～6molL
-1Hydrochloric acid soln reextraction rare earth element, reextraction gained contain the aqueous solution of rare earth element further through oxalic acid or ammonium bicarbonate precipitation, and 850～900 ℃ of calcinations prepare mixed rare-earth oxide; Or further prepare the crystallization rare earth chloride through evaporation concentration; Or further adopt P
204Extraction agent system or P
507Extraction system is separated, and again through oxalic acid or ammonium bicarbonate precipitation, 850～900 ℃ of calcinations prepare lanthanum trioxide, cerium oxide, Praseodymium trioxide, Neodymium trioxide or europium sesquioxide single rare earth oxide product.
2. described with rare earth element and the isolating method of calcium monofluorophosphate, calcium chlorophosphate and calcium phosphate according to claim 1, it is characterized in that step is 3., with 4 stage countercurrent mode extracting rare-earth elements, with the 6 stage countercurrent modes rare earth element of stripping.
3. described with rare earth element and the isolating method of calcium monofluorophosphate, calcium chlorophosphate and calcium phosphate according to claim 1, in it is characterized in that step 3., to add hydrochloric acid and citric acid through the raffinate behind the extracting rare-earth element, being mixed with concentration is hydrochloric acid 0.1～1.0molL
-1, citric acid 0.01～0.5molL
-1Behind the mixing solutions, the stripping operation of returning calcium monofluorophosphate or calcium chlorophosphate and calcium phosphate continues to recycle.
4. described with rare earth element and the isolating method of calcium monofluorophosphate, calcium chlorophosphate and calcium phosphate according to claim 1, it is characterized in that containing the composition of calcium monofluorophosphate and calcium phosphate or calcium chlorophosphate and calcium phosphate rare-earth mineral, contain rare earth element 25%～65%, calcium monofluorophosphate and calcium phosphate 3%～20% by mass percentage simultaneously, all the other are impurity, or containing rare earth element 20%～45%, calcium chlorophosphate and calcium phosphate 15%～45% simultaneously, all the other are impurity.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
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| CN102910606A (en) * | 2012-09-20 | 2013-02-06 | 宁波新桥化工有限公司 | Recovery method of tricalcium phosphate |
| CN107746977B (en) * | 2017-12-13 | 2019-11-01 | 济南大学 | The method of recovering rare earth from containing rare earth phosphate rock |
| CN108559842B (en) * | 2018-07-11 | 2019-10-11 | 钢研集团稀土科技有限公司 | A kind of method that low-concentration hcl Ore Leaching calcium strontium selects Weishan Lake rare earth ore concentrate |
| CN115259475B (en) * | 2022-08-23 | 2023-06-16 | 四川大学 | Method for removing fluorine by rare earth-assisted precipitation |
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| CN1348997A (en) * | 2001-08-28 | 2002-05-15 | 东北大学 | Roasting decomposition process of mengite-RE concentrate and mengite-mixed bastnaesite RE concentrate |
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Non-Patent Citations (2)
| Title |
|---|
| CaO和NaCl焙烧混合稀土精矿过程中的分解反应. 吴文远，胡广勇，孙树臣，陈旭东，涂赣峰.中国稀土学报，第22卷第2期. 2004 * |
| 氧化钙分解人造独居石的反应机理. 吴文远，孙树臣，涂赣峰，费海东.东北大学学报(自然科学版)，第23卷第12期. 2002 * |
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