CN106636689A - Method for extracting rare earth from precipitation sludge of rare earth wastewater pool - Google Patents
Method for extracting rare earth from precipitation sludge of rare earth wastewater pool Download PDFInfo
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- CN106636689A CN106636689A CN201710003563.XA CN201710003563A CN106636689A CN 106636689 A CN106636689 A CN 106636689A CN 201710003563 A CN201710003563 A CN 201710003563A CN 106636689 A CN106636689 A CN 106636689A
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- rare earth
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- roasting
- acid
- leachate
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- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 82
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 77
- 238000001556 precipitation Methods 0.000 title claims abstract description 43
- 239000002351 wastewater Substances 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 title claims abstract description 20
- 239000010802 sludge Substances 0.000 title abstract 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 54
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 18
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims abstract description 14
- 235000011130 ammonium sulphate Nutrition 0.000 claims abstract description 14
- 239000002253 acid Substances 0.000 claims abstract description 12
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 9
- 239000011707 mineral Substances 0.000 claims abstract description 9
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims abstract description 8
- 239000002893 slag Substances 0.000 claims description 32
- 238000001035 drying Methods 0.000 claims description 17
- 239000007787 solid Substances 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- -1 rare-earth salts Chemical class 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 159000000013 aluminium salts Chemical class 0.000 claims description 3
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims description 3
- 159000000007 calcium salts Chemical class 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 230000001376 precipitating effect Effects 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 230000003750 conditioning effect Effects 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 22
- 239000011575 calcium Substances 0.000 abstract description 20
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 abstract description 17
- 229910052791 calcium Inorganic materials 0.000 abstract description 17
- 238000011084 recovery Methods 0.000 abstract description 14
- 229910052742 iron Inorganic materials 0.000 abstract description 11
- 229910052782 aluminium Inorganic materials 0.000 abstract description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 10
- 238000002386 leaching Methods 0.000 abstract description 8
- 239000012535 impurity Substances 0.000 abstract description 5
- 238000000926 separation method Methods 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000007790 solid phase Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 19
- 239000000047 product Substances 0.000 description 17
- 239000004411 aluminium Substances 0.000 description 9
- 238000000605 extraction Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000003723 Smelting Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 2
- 229910001424 calcium ion Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 150000003891 oxalate salts Chemical class 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- QXDMQSPYEZFLGF-UHFFFAOYSA-L calcium oxalate Chemical compound [Ca+2].[O-]C(=O)C([O-])=O QXDMQSPYEZFLGF-UHFFFAOYSA-L 0.000 description 1
- 125000005587 carbonate group Chemical group 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- VEPSWGHMGZQCIN-UHFFFAOYSA-H ferric oxalate Chemical compound [Fe+3].[Fe+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O VEPSWGHMGZQCIN-UHFFFAOYSA-H 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 239000003978 infusion fluid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000003900 soil pollution Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Classifications
-
- 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
-
- 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
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
-
- 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 recovering rare earth from precipitation sludge of a rare earth wastewater pool, comprising the main steps: firstly, preroasting the precipitation sludge of the rare earth wastewater pool, then leaching the roasted product with mineral acid to obtain a leach solution containing rare earth, and sequentially adding ammonium sulfate and oxalic acid to the leach solution so the rare earth is separated from soluble impurities in a manner of solid phase precipitation. The method has a simple process, convenient operation and low cost, solves the problem of difficult complete separation in a condition of coexistence of rare earth and calcium in a solution, can efficiently recover the rare earth in the precipitation sludge of the rare earth wastewater pool, and realizes separation of rare earth from calcium, aluminum and iron; the recovery rate of rare earth reaches above 99%; and the recovered rare earth oxide can be returned to a production main flow of a rare earth smeltery.
Description
Technical field
The present invention relates to industrial waste residue disposal technical field, in particular to one kind from the precipitation slag of RE waste water pond
The method of recovering rare earth.
Background technology
Rare earth is a kind of non-renewable grand strategy resource, and its consumption increases increasingly, in rare-earth smelting production process
Middle to produce a large amount of waste water, smelting enterprise need to generally be equipped with special wastewater disposal basin and collect.Zwitterion species in waste water is more, and
Easily combine and produce precipitation, substantial amounts of solids of sedimentation slag will be piled up in the wastewater disposal basin that accumulates over a long period.Slag Rare-Earth Content is left up to 30%
The right side, also with metals such as calcium, iron, aluminium.As effective process not in time not only results in the waste of valuable rare earth resources, and if
The careless heap of these precipitation slags is abandoned, environment can be had a huge impact, cause soil and water pollution.
The process of RE waste water pond precipitation slag at present is mainly using first acidleach, the scheme of rear purification enrichment.From leachate
The method of purification enrichment rare earth mainly has the neutralizing hydrolysis precipitation method, oxalate precipitation method, extraction etc..The precipitation method are relatively simple, lead to
Normal open overregulates pH, makes rare earth and is separated from water with rare earth hydrate Precipitation, but at that time impurity was not golden in pH controls
Category ion such as Ca2+、Al3+、Fe3+It is co-precipitated Deng can also generate hydroxide；And the precipitation particle of formation is relatively fine, or even in glue
State, causes precipitation enrichment difficult.During using oxalic acid precipitation rare earth, because oxalic acid aluminium, the solubility of ferric oxalate are far longer than oxalic acid
Rare earth, is capable of achieving rare earth and separates with iron, aluminium, but the calcium ion in solution also easily reacts to form precipitation with oxalic acid, is unfavorable for dilute
The separation of soil and calcium.Extraction enrichment times are big, efficiency high, can realize plural serial stage and automatic continuous operation, but calcium,
Organic phase emulsification, extraction system split-phase difficulty, after any special measures back extraction, back extraction are easily caused when iron, iron tramp content overproof
Liquid impurity ion content is still difficult up to standard.Research shows, precipitation slag middle rare earth in RE waste water pond is mainly with oxalates and carbonate
Form is present；And precipitating that solid impurity particle is small and dense packing, this causes Ore Leaching extremely difficult.Therefore, calcium in leachate, iron,
Aluminium and high efficiency rare-earth separation are the crucial problems that RE waste water precipitates Slag treatment.
The content of the invention
The present invention is directed to above-mentioned technical problem, there is provided a kind of method of recovering rare earth in precipitation slag from RE waste water pond.
Specifically include following steps.
（1）By RE waste water pond precipitation slag at 800 ~ 900 DEG C 1 ~ 3h of preroast, obtain product of roasting, the rare earth gives up
Water sedimentation slag contains 15 ~ 35wt.% rare-earth salts, 10 ~ 25 wt.% calcium salts, 0.5 ~ 1.5wt.% molysite and aluminium salt, and above content is equal
In terms of oxide.
（2）The product of roasting is ground to into that -150 μm ~+74 μm laggard water-fillings are molten, is filtered and is dried.
（3）Product of roasting after drying is according to 2：1~10：The liquid-solid ratio of 1mL/g adds mineral acid to be leached, after filtration
The leachate containing rare earth is obtained, the mineral acid is at least one in sulfuric acid, hydrochloric acid, nitric acid, and mineral acid concentration is 1 ~ 6mol/
L。
（4）Add ammonium sulfate solids toward the leachate containing rare earth, control ammonium sulfate in leachate concentration be 30 ~
100g/L, stirs to ammonium sulfate all dissolving, stops stirring, adds oxalic acid solution, and oxalic acid addition is precipitating rare earth institute
1 ~ 2 times of theoretical amount is needed, it is 1.5 ~ 2 to adjust solution ph, to stand and be filtrated to get filter residue after 4 ~ 8h.
（5）By filter residue calcination at 900 ~ 1500 DEG C, rare earth oxide is obtained.
Further, step（3）Described in containing rare earth leachate middle rare earth concentration be 1.13 g/L ~ 30.10 g/L.
Further, step（4）Middle reaction temperature is 30 ~ 90 DEG C.
Further, step（4）Described in oxalic acid solution concentration be 1.2 ~ 2.5g/L.
Further, step（4）Middle employing ammoniacal liquor and hydrochloric acid conditioning solution pH value.
Step of the present invention（1）In, precipitation slag middle rare earth in RE waste water pond is mainly in the form of oxalates and carbonate
Exist, Jing after preroast, rare-earth salts, calcium salt, aluminium salt and molysite are changed into into corresponding oxide.
Step of the present invention（2）In, using the water miscible impurity in water dissolves product of roasting part that can be removed, product of roasting
Reaction can be made more abundant after being ground to -150 μm ~+74 μm.
Step of the present invention（3）In, the product of roasting after drying using mineral acid can by rare earth, calcium, aluminium, iron leach into
In entering solution, preferably described mineral acid is hydrochloric acid, and the leachate middle rare earth concentration for obtaining is 1.13 g/L ~ 30.10 g/L.
Step of the present invention（4）In, add ammonium sulfate, the calcium in leachate to generate soluble (NH4)2[Ca
(SO4)2] complex compound；Oxalic acid solution is added, it is 1.5 ~ 2 to control solution ph, and the rare earth in leachate will generate rare earth oxalate
Precipitation, aluminium and iron will generate soluble double salt, so as to realize that rare earth and calcium, aluminium, iron tramp are efficiently separated；Need special
Illustrate, plus stirring must be stopped during oxalic acid solution, only under conditions of standing, and keep the concentration of ammonium sulfate to be
30 ~ 100g/L, (NH4)2[Ca(SO4)2] complex compound just can stable existence, will otherwise generate calcium oxalate precipitation.It is preferred that reacting
Temperature is 30 ~ 90 DEG C, is conducive to being further ensured that (NH4)2[Ca(SO4)2] complex compound stablizes.
Present invention process is simple, is easy to operation, with low cost, solves and has been difficult under solution middle rare earth and calcium Coexistence Situation
Fully separating problem, the rare earth in the precipitation slag of energy high efficiente callback RE waste water pond, realizes that rare earth is separated with calcium, aluminium, iron, rare earth
The rate of recovery is up to more than 99%.Calcium content as little as 0.12% in the earth oxide product of acquisition, iron, aluminium content are as little as
Less than 0.1%, the rare earth oxide of recovery can return to rare-earth smelting factory production main flow.
Description of the drawings
The process chart of the rare earth reclaimed from the precipitation slag of RE waste water pond that Fig. 1 is provided for the present invention.
Specific embodiment
In order to more clearly state the present invention, the present invention is further described with reference to embodiment.
Embodiment 1
RE waste water pond precipitation slag 10g is taken, the wherein content of REO is 30.66 wt.%, and CaO content is 29.72 wt.%,
Taking-up after roasting 1.5h at 850 DEG C, further levigate, the water-soluble, filtration of product of roasting and drying, the product of roasting after drying is in salt
Acid concentration 3mol/L, liquid-solid ratio 6:1mL/g, reaction temperature are obtained containing rare earth to leach 1.0h under conditions of 80 DEG C after filtration
The infusion solution 130ml of 23.03g/L, the leaching rate of its middle rare earth is 97.65%.Under the conditions of 30 DEG C, add toward re dip solution
Enter 10.4g ammonium sulfate, after being sufficiently stirred for dissolving, stop stirring, add the oxalic acid of 1.2 times of theoretical amounts, adjusting pH value of solution is
6h is stood at 1.5 ~ 2,80 DEG C, filtration, washing, drying obtain 7.07g precipitation slags, and precipitation slag Rare-Earth Content is 41.97
Wt.%, the wt.% of calcium content 0.2, be computed the solution middle rare earth rate of recovery be 99.10%, deliming rate 99.52%.Jing calcinations, oxidation
Rare earth weight is 2.97g, and the total rare earth (TRE) rate of recovery is 96.90%.
Embodiment 2
RE waste water pond precipitation slag 50g is taken, the wherein content of REO is 27.55 wt.%, and CaO content is 26.54 wt.%,
Taking-up after roasting 2h at 900 DEG C, further levigate, the water-soluble, filtration of product of roasting and drying, the product of roasting after drying is in nitric acid
Concentration 4mol/L, liquid-solid ratio 7:1mL/g, reaction temperature are obtained containing rare earth 23.70g/L to leach 1.0h under conditions of 70 DEG C
Leachate 580ml, the leaching rate of its middle rare earth is 99.79%.Under the conditions of 50 DEG C, 17.4g ammonium sulfate is added toward leachate, filled
After dividing stirring and dissolving, stop stirring, add the oxalic acid of 1.5 times of theoretical amounts, it is standing at 1.5 ~ 2,90 DEG C to adjust pH value of solution
4h, filters, washing, drying obtain 37.81g precipitation slags, and precipitation slag Rare-Earth Content is 28.77wt.%, calcium content 5.23
Wt.%, be computed the solution middle rare earth rate of recovery be 79.14%, deliming rate 85.01%.Jing calcinations, rare earth oxide weight is
10.78g, the total rare earth (TRE) rate of recovery is 78.25%.
Embodiment 3
RE waste water pond precipitation slag 25g is taken, the wherein content of REO is 31.68 wt.%, and CaO content is 28.53 wt.%, 800
Taking-up after roasting 2h at DEG C, further levigate, the water-soluble, filtration of product of roasting and drying, the product of roasting after drying is dense in sulfuric acid
Degree 3mol/L, liquid-solid ratio 8:1mL/g, reaction temperature obtain the leaching containing rare earth 23.10g/L to leach 1.5h under conditions of 60 DEG C
Go out liquid 310ml, the leaching rate of its middle rare earth is 90.33%.26.35g ammonium sulfate is added toward leachate, after being sufficiently stirred for dissolving,
Stop stirring, add the oxalic acid of 1.3 times of theoretical amounts, it is 1.5 ~ 2,50 DEG C of standing 8h to adjust pH value of solution, filters, washs, dries
Dry to obtain 17.58g precipitation slags, precipitation slag Rare-Earth Content is 41.10 wt.%, the wt.% of calcium content 0.18, is computed obtaining solution
The middle rare earth rate of recovery is 99.36%, deliming rate 99.56%.Jing calcinations, rare earth oxide weight is 7.11g, and the total rare earth (TRE) rate of recovery is
89.82%。
Embodiment 4
RE waste water pond precipitation slag 30g is taken, the wherein content of REO is 31.21 wt.%, and CaO content is 29.18 wt.%,
Taking-up after roasting 1.5h at 850 DEG C, further levigate, the water-soluble, filtration of product of roasting and drying, the product of roasting after drying is in salt
Acid concentration 5mol/L, liquid-solid ratio 7:1mL/g, reaction temperature are obtained containing rare earth 24.45g/L to leach 2h under conditions of 70 DEG C
Leachate 381ml, the leaching rate of its middle rare earth is 99.51%.31g ammonium sulfate is added toward leachate, after being sufficiently stirred for dissolving,
Stopping stirring, adds the oxalic acid of 1.25 times of theoretical amounts, adjusts pH value of solution to stand 5h at 1.5 ~ 2,70 DEG C, filter, wash,
Drying obtains 21.45g precipitation slags, and precipitation slag Rare-Earth Content is 43.24 wt.%, the wt.% of calcium content 0.22, is computed molten
The liquid middle rare earth rate of recovery is 99.52%, deliming rate 99.46%.Jing calcinations, rare earth oxide weight is 9.27g, and the total rare earth (TRE) rate of recovery is
99.06%。
Embodiment 5
RE waste water pond precipitation slag 30g is taken, the wherein content of REO is 31.21 wt.%, and CaO content is 29.18 wt.%,
Taking-up after roasting 1.5h at 850 DEG C, further levigate, the water-soluble, filtration of product of roasting and drying, the product of roasting after drying is in salt
Acid concentration 5mol/L, liquid-solid ratio 7:1mL/g, reaction temperature are obtained containing rare earth 22.18g/L to leach 2h under conditions of 70 DEG C
Leachate 420ml, the leaching rate of its middle rare earth is 99.49%.21g ammonium sulfate is added toward leachate, after being sufficiently stirred for dissolving,
Stopping stirring, adds the oxalic acid of 1.2 times of theoretical amounts, adjusts pH value of solution to stand 6h at 1.5 ~ 2,70 DEG C, filter, wash,
Drying obtains 26.11g precipitation slags, and precipitation slag Rare-Earth Content is 34.81 wt.%, the wt.% of calcium content 2.63, is computed molten
The liquid middle rare earth rate of recovery is 97.52%, deliming rate 93.56%.Jing calcinations, rare earth oxide weight is 9.12g, and the total rare earth (TRE) rate of recovery is
97.4%。
Knowable to every test data of above-described embodiment, the present invention, in efficiently and thoroughly having reclaimed wastewater disposal basin precipitation slag
Rare earth, highest recovery more than 99%, process is simple, be easy to operation.
These are only the preferred embodiment of the present invention, it is noted that for those skilled in the art come
Say, on the premise of without departing from the technology of the present invention principle, some improvement and replacement can also be made, these improve and replace also should
It is considered as protection scope of the present invention.
Claims (5)
1. in a kind of precipitation slag from RE waste water pond recovering rare earth method, it is characterised in that comprise the following steps：
（1）By RE waste water pond precipitation slag at 800 ~ 900 DEG C 1 ~ 3h of preroast, obtain product of roasting, the RE waste water sinks
Mud contains 15 ~ 35wt.% rare-earth salts, 10 ~ 25 wt.% calcium salts, 0.5 ~ 1.5wt.% molysite and aluminium salt, and above content is with oxidation
Thing meter；
（2）The product of roasting is ground to into that -150 μm ~+74 μm laggard water-fillings are molten, is filtered and is dried；
（3）Product of roasting after drying is according to 2：1~10：The liquid-solid ratio of 1mL/g adds mineral acid to be leached, and obtains after filtration
Leachate containing rare earth, the mineral acid is at least one in sulfuric acid, hydrochloric acid, nitric acid, and mineral acid concentration is 1 ~ 6mol/L；
（4）Add ammonium sulfate solids toward the leachate containing rare earth, control ammonium sulfate in leachate concentration be 30 ~
100g/L, stirs to ammonium sulfate all dissolving, stops stirring, adds oxalic acid solution, and oxalic acid addition is precipitating rare earth institute
1 ~ 2 times of theoretical amount is needed, it is 1.5 ~ 2 to adjust solution ph, to stand and be filtrated to get filter residue after 4 ~ 8h；
（5）By filter residue calcination at 900 ~ 1500 DEG C, rare earth oxide is obtained.
2. method according to claim 1, it is characterised in that step（3）Described in containing rare earth leachate middle rare earth it is dense
Degree can be 1.13 g/L ~ 30.10 g/L.
3. method according to claim 1, it is characterised in that step（4）Middle reaction temperature is 30 ~ 90 DEG C.
4. method according to claim 1, it is characterised in that step（4）Described in oxalic acid solution concentration be 1.2 ~
2.5g/L。
5. method according to claim 1, it is characterised in that step（4）Middle employing ammoniacal liquor or hydrochloric acid conditioning solution pH value.
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Cited By (10)
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| CN108004410A (en) * | 2017-12-15 | 2018-05-08 | 清远先导材料有限公司 | A kind of extracting method of rare earth silicate crystals element |
| WO2018195642A1 (en) * | 2017-04-26 | 2018-11-01 | Her Majesty The Queen In Right Of Canada As Represented By The Minister Of Natural Resources Canada | Direct oxalate precipitation for rare earth elements recovery |
| CN110156217A (en) * | 2018-02-14 | 2019-08-23 | 中铝稀土（宜兴）有限公司 | A kind of processing method of rare earth processing waste water |
| CN111439773A (en) * | 2020-05-18 | 2020-07-24 | 龙南县和利稀土冶炼有限公司 | Method for recovering rare earth oxide from rare earth oxide waste residues |
| CN111500859A (en) * | 2020-05-18 | 2020-08-07 | 龙南县和利稀土冶炼有限公司 | Extraction method of rare earth oxide |
| CN111593213A (en) * | 2020-05-20 | 2020-08-28 | 赣州稀土龙南冶炼分离有限公司 | Method for extracting rare earth from rare earth organic slag |
| CN112662900A (en) * | 2020-12-04 | 2021-04-16 | 江西理工大学 | Method for co-recovering rare earth in leaching mother liquor by coprecipitation acid dissolution and selective precipitation |
| CN114921667A (en) * | 2022-06-28 | 2022-08-19 | 中山大学 | Method for recovering rare earth and biomass high value-added products from hyper-enriched plants |
| CN115072761A (en) * | 2022-08-01 | 2022-09-20 | 中国煤炭地质总局勘查研究总院 | Method for extracting mixed rare earth oxide from fly ash roasting product |
| CN115323199A (en) * | 2021-11-12 | 2022-11-11 | 虔东稀土集团股份有限公司 | Method for recovering rare earth elements |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101363079A (en) * | 2007-08-10 | 2009-02-11 | 有研稀土新材料股份有限公司 | Smelting method of iron rich mengite rare-earth mine |
| CN101705380A (en) * | 2009-11-30 | 2010-05-12 | 北京有色金属研究总院 | Method for recovering rare earth from rare earth-containing aluminum-silicon materials |
| CN102660688A (en) * | 2012-05-10 | 2012-09-12 | 北京科技大学 | Method for recovering rare earth from waste rare earth luminescent material |
| CN103361498A (en) * | 2013-06-20 | 2013-10-23 | 工信华鑫科技有限公司 | Method for separating impurities from rare earth in rare-earth-ore leaching solution to purify rare earth |
| WO2014071510A1 (en) * | 2012-11-08 | 2014-05-15 | Electrochem Technologies & Materials Inc. | Process for recovering rare earth oxides from phosphors, fluorescent lamps and light bulbs, cathode ray tubes and other industrial wastes |
| WO2016058007A2 (en) * | 2014-10-10 | 2016-04-14 | Rare Element Resources, Ltd. | Processing for the extraction of rare earth elements |
-
2017
- 2017-01-04 CN CN201710003563.XA patent/CN106636689B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101363079A (en) * | 2007-08-10 | 2009-02-11 | 有研稀土新材料股份有限公司 | Smelting method of iron rich mengite rare-earth mine |
| CN101705380A (en) * | 2009-11-30 | 2010-05-12 | 北京有色金属研究总院 | Method for recovering rare earth from rare earth-containing aluminum-silicon materials |
| CN102660688A (en) * | 2012-05-10 | 2012-09-12 | 北京科技大学 | Method for recovering rare earth from waste rare earth luminescent material |
| WO2014071510A1 (en) * | 2012-11-08 | 2014-05-15 | Electrochem Technologies & Materials Inc. | Process for recovering rare earth oxides from phosphors, fluorescent lamps and light bulbs, cathode ray tubes and other industrial wastes |
| CN103361498A (en) * | 2013-06-20 | 2013-10-23 | 工信华鑫科技有限公司 | Method for separating impurities from rare earth in rare-earth-ore leaching solution to purify rare earth |
| WO2016058007A2 (en) * | 2014-10-10 | 2016-04-14 | Rare Element Resources, Ltd. | Processing for the extraction of rare earth elements |
Non-Patent Citations (1)
| Title |
|---|
| CHENNA RAO BORRA ET AL.: "Selective recovery of rare earths from bauxite residue by combination of sulfation, roasting and leaching", 《MINERALS ENGINEERING》 * |
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| WO2018195642A1 (en) * | 2017-04-26 | 2018-11-01 | Her Majesty The Queen In Right Of Canada As Represented By The Minister Of Natural Resources Canada | Direct oxalate precipitation for rare earth elements recovery |
| CN108004410B (en) * | 2017-12-15 | 2019-09-03 | 清远先导材料有限公司 | A kind of extracting method of rare earth silicate crystals element |
| CN108004410A (en) * | 2017-12-15 | 2018-05-08 | 清远先导材料有限公司 | A kind of extracting method of rare earth silicate crystals element |
| CN110156217B (en) * | 2018-02-14 | 2022-09-27 | 中稀(宜兴)稀土新材料有限公司 | Method for treating rare earth processing wastewater |
| CN110156217A (en) * | 2018-02-14 | 2019-08-23 | 中铝稀土（宜兴）有限公司 | A kind of processing method of rare earth processing waste water |
| CN111439773A (en) * | 2020-05-18 | 2020-07-24 | 龙南县和利稀土冶炼有限公司 | Method for recovering rare earth oxide from rare earth oxide waste residues |
| CN111500859A (en) * | 2020-05-18 | 2020-08-07 | 龙南县和利稀土冶炼有限公司 | Extraction method of rare earth oxide |
| CN111593213A (en) * | 2020-05-20 | 2020-08-28 | 赣州稀土龙南冶炼分离有限公司 | Method for extracting rare earth from rare earth organic slag |
| CN112662900A (en) * | 2020-12-04 | 2021-04-16 | 江西理工大学 | Method for co-recovering rare earth in leaching mother liquor by coprecipitation acid dissolution and selective precipitation |
| CN115323199A (en) * | 2021-11-12 | 2022-11-11 | 虔东稀土集团股份有限公司 | Method for recovering rare earth elements |
| CN115323199B (en) * | 2021-11-12 | 2023-09-29 | 虔东稀土集团股份有限公司 | Rare earth element recovery method |
| CN114921667A (en) * | 2022-06-28 | 2022-08-19 | 中山大学 | Method for recovering rare earth and biomass high value-added products from hyper-enriched plants |
| CN114921667B (en) * | 2022-06-28 | 2023-10-13 | 中山大学 | Method for recovering rare earth and biomass high value-added products from super-enriched plants |
| CN115072761A (en) * | 2022-08-01 | 2022-09-20 | 中国煤炭地质总局勘查研究总院 | Method for extracting mixed rare earth oxide from fly ash roasting product |
| CN115072761B (en) * | 2022-08-01 | 2023-09-19 | 中国煤炭地质总局勘查研究总院 | Method for extracting mixed rare earth oxide from fly ash roasting product |
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