CN114410991A - Method for preparing rare earth carbonate from ionic rare earth ore - Google Patents
Method for preparing rare earth carbonate from ionic rare earth ore Download PDFInfo
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- CN114410991A CN114410991A CN202210091350.8A CN202210091350A CN114410991A CN 114410991 A CN114410991 A CN 114410991A CN 202210091350 A CN202210091350 A CN 202210091350A CN 114410991 A CN114410991 A CN 114410991A
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- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 105
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 72
- 238000000034 method Methods 0.000 title claims abstract description 36
- -1 rare earth carbonate Chemical class 0.000 title claims abstract description 30
- 239000011347 resin Substances 0.000 claims abstract description 81
- 229920005989 resin Polymers 0.000 claims abstract description 81
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 55
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 52
- 239000007788 liquid Substances 0.000 claims abstract description 46
- 238000000605 extraction Methods 0.000 claims abstract description 33
- 239000002253 acid Substances 0.000 claims abstract description 20
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 14
- 238000002386 leaching Methods 0.000 claims description 60
- 239000003795 chemical substances by application Substances 0.000 claims description 44
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 33
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 23
- 239000011707 mineral Substances 0.000 claims description 23
- CSNNHWWHGAXBCP-UHFFFAOYSA-L magnesium sulphate Substances [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 17
- 238000001179 sorption measurement Methods 0.000 claims description 16
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 9
- 238000003795 desorption Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 239000011541 reaction mixture Substances 0.000 claims 1
- 238000001556 precipitation Methods 0.000 abstract description 12
- 239000012535 impurity Substances 0.000 abstract description 8
- 229910052791 calcium Inorganic materials 0.000 abstract description 4
- 229910052710 silicon Inorganic materials 0.000 abstract description 4
- 229910052749 magnesium Inorganic materials 0.000 abstract description 3
- 238000003723 Smelting Methods 0.000 abstract description 2
- 238000005272 metallurgy Methods 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- 238000002336 sorption--desorption measurement Methods 0.000 abstract description 2
- 239000003153 chemical reaction reagent Substances 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 39
- 235000010755 mineral Nutrition 0.000 description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 239000000047 product Substances 0.000 description 13
- 239000000706 filtrate Substances 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 10
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 10
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 10
- 239000000292 calcium oxide Substances 0.000 description 9
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 9
- 235000019341 magnesium sulphate Nutrition 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 238000001914 filtration Methods 0.000 description 7
- 238000005086 pumping Methods 0.000 description 7
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 7
- 235000010234 sodium benzoate Nutrition 0.000 description 7
- 239000004299 sodium benzoate Substances 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 6
- 230000003472 neutralizing effect Effects 0.000 description 6
- 239000005711 Benzoic acid Substances 0.000 description 5
- 235000010233 benzoic acid Nutrition 0.000 description 5
- 239000000395 magnesium oxide Substances 0.000 description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 5
- 235000017557 sodium bicarbonate Nutrition 0.000 description 5
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 229910052593 corundum Inorganic materials 0.000 description 4
- QWDJLDTYWNBUKE-UHFFFAOYSA-L magnesium bicarbonate Chemical compound [Mg+2].OC([O-])=O.OC([O-])=O QWDJLDTYWNBUKE-UHFFFAOYSA-L 0.000 description 4
- 229910000022 magnesium bicarbonate Inorganic materials 0.000 description 4
- 239000002370 magnesium bicarbonate Substances 0.000 description 4
- 235000014824 magnesium bicarbonate Nutrition 0.000 description 4
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 description 4
- 239000011575 calcium Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 235000010235 potassium benzoate Nutrition 0.000 description 1
- 239000004300 potassium benzoate Substances 0.000 description 1
- 229940103091 potassium benzoate Drugs 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Images
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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
- 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
- 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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Environmental & Geological Engineering (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Organic Chemistry (AREA)
- Geochemistry & Mineralogy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention provides a method for preparing rare earth carbonate from ionic rare earth ore, belonging to the technical field of rare earth metallurgy. The invention uses the extraction resin for adsorption-desorption, can realize the removal of impurities Mg and Fe and most of Si and Ca, the extraction resin can be recycled, the high-efficiency removal of Al can be realized through the procedures of residual acid neutralization of the desorbed liquid and Al removal by an aluminum remover, the rare earth loss is less, and the aluminum remover can be recycled. Finally, the rare earth carbonate product with the total rare earth content of more than 93wt percent after the rare earth is calcined can be obtained through precipitation. The method has the advantages of good production environment, high impurity removal rate, low consumption of chemical reagents, high purity of rare earth precipitation products, low impurity content and low later-stage rare earth smelting separation cost.
Description
Technical Field
The invention relates to the technical field of rare earth metallurgy, in particular to a method for preparing rare earth carbonate from ionic rare earth ore.
Background
The ion type rare earth ore leaching process is developed to date, ammonium sulfate is generally adopted as a leaching agent, ammonium bicarbonate is adopted as a precipitating agent, and the ion type rare earth ore leaching process has the fatal defects of ammonia nitrogen pollution, influence on groundwater quality and the like. In order to solve the problem of ammonia nitrogen pollution, technologies such as ammonia-free ore leaching and ammonia-free precipitation are developed successively. The currently reported ammonia-free mineral leaching agents include magnesium sulfate, magnesium chloride, calcium chloride, ferric sulfate, aluminum chloride, aluminum sulfate and the like, wherein the mineral leaching agent which has the widest application prospect and is industrially applied is magnesium sulfate. The method for preparing rare earth carbonate from ionic rare earth ore mainly comprises the following steps:
(1) calcium oxide precipitation method: CaO is used as a precipitator to carry out precipitation and enrichment on the low-concentration sulfuric acid rare earth leaching solution, and the purity of rare earth in a precipitation product is 83.81%. However, the rare earth product has low rare earth purity, CaO in the rare earth product is easy to exceed the standard, and a deep impurity removal process is also needed.
(2) Magnesium oxide/hydroxide precipitation: chinese patent publication No. CN101037219A discloses that magnesium oxide is used as a precipitant, magnesium oxide slurry and rare earth feed liquid are subjected to precipitation reaction, filtered and washed to finally produce rare earth hydroxide. Rare earth grade (TREO) is 41-46%, SO4 2-1.55-2.25% of MgO, 0.4-0.5% of CaO, 0.3-0.4% of Al2O3The content is 0.01-0.02%, and the rare earth product has low rare earth purity.
(3) And (3) magnesium bicarbonate precipitation: magnesium bicarbonate as precipitant, when n (HCO)3-)：n(RE3+) When the ratio is more than 3.15:1, the rare earth can be completely recovered, and the recovery and utilization of the magnesium sulfate serving as the mineral leaching agent can also be realized. However, magnesium bicarbonate belongs to a metastable substance, and has complex preparation process and higher condition requirement.
The rare earth content of the precipitate obtained by the method is not high.
Disclosure of Invention
In view of the above, the present invention aims to provide a method for preparing rare earth carbonate from ionic rare earth ore. The preparation method of the invention has the advantages of higher purity of the rare earth precipitation product and less impurity content.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a method for preparing rare earth carbonate from ionic rare earth ore, which comprises the following steps:
mixing an ore leaching agent and ionic rare earth ore for leaching to obtain a leaching solution, wherein the ore leaching agent is MgSO4A solution;
pretreating the levextrel resin with acid to obtain pretreated resin;
adsorbing the leachate by using the pretreatment resin, and sequentially washing and desorbing the adsorbed resin to obtain desorbed liquid;
sequentially carrying out acid neutralization and aluminum removal on the desorbed liquid to obtain a removed aluminum liquid;
and adjusting the pH value of the molten aluminum removal liquid to 1.0-1.5 and 7-8 in sequence to obtain the rare earth carbonate.
Preferably, the pH value of the mineral leaching agent is 2.5-5.5, and the mass fraction of the mineral leaching agent is 1-5%.
Preferably, the dosage ratio of the ionic rare earth ore to the mineral leaching agent in the mineral leaching process is 1kg: 0.22-0.88L.
Preferably, the pretreatment uses hydrochloric acid, the concentration of the hydrochloric acid is 0.8-1.2 mol/L, and the volume ratio of the hydrochloric acid to the extraction resin is (1-3): 1.
preferably, the extraction resin comprises P507 extraction resin and/or P204 extraction resin.
Preferably, the adsorption is to make the leachate flow through the pretreatment resin, and the linear velocity of the flow is 0.1-100 cm/min.
Preferably, the desorbent used for said desorption comprises H2SO4And/or HCl, H in the desorbent+The concentration of (b) is 1 to 8 mol/L.
Preferably, the linear velocity of the desorbent is 0.1-100 cm/min.
Preferably, the acid is neutralized to a pH value of 3.6 to 3.8.
Preferably, the molar ratio of the aluminum removing agent used for aluminum removal to aluminum element in a neutralization solution obtained by acid neutralization is (3-9): 1.
the invention provides a method for preparing rare earth carbonate from ionic rare earth ore, which comprises the following steps: mixing an ore leaching agent and ionic rare earth ore for leaching to obtain a leaching solution, wherein the ore leaching agent is a magnesium sulfate solution; pretreating the levextrel resin with acid to obtain pretreated resin; adsorbing the leachate by using the pretreatment resin, and sequentially washing and desorbing the adsorbed resin to obtain desorbed liquid; sequentially carrying out acid neutralization and aluminum removal on the desorbed liquid to obtain a removed aluminum liquid; and adjusting the pH value of the molten aluminum removal liquid to 1.0-1.5 and 7-8 in sequence to obtain the rare earth carbonate.
The invention has the beneficial effects that: compared with the traditional process, the method has the following advantages:
1. the rare earth solution is enriched and purified by the extraction resin, the extraction resin can realize the removal of impurities Mg and Fe and most of Si and Ca through resin adsorption-desorption, and the extraction resin can be recycled; the processes of neutralizing the residual liquid acid after desorption and removing Al by the aluminum remover can realize high-efficiency removal of Al, have less rare earth loss and can recycle the aluminum remover;
2. compared with the precipitation method of calcium oxide, magnesium oxide and magnesium bicarbonate, the method of the invention has the advantages that the purity of the rare earth precipitation product is higher, the impurity content is less, and the later-stage rare earth smelting separation cost is lower; the data of the examples show that the rare earth carbonate product of the present invention has a total rare earth content of more than 93 wt% after firing.
Drawings
FIG. 1 is a flow chart of the method for preparing rare earth carbonate from ionic rare earth ore according to the invention.
Detailed Description
The invention provides a method for preparing rare earth carbonate from ionic rare earth ore, which comprises the following steps:
mixing an ore leaching agent and ionic rare earth ore for leaching to obtain a leaching solution, wherein the ore leaching agent is a magnesium sulfate solution;
pretreating the levextrel resin with acid to obtain pretreated resin;
adsorbing the leachate by using the pretreatment resin, and sequentially washing and desorbing the adsorbed resin to obtain desorbed liquid;
sequentially carrying out acid neutralization and aluminum removal on the desorbed liquid to obtain a removed aluminum liquid;
and adjusting the pH value of the molten aluminum removal liquid to 1.0-1.5 and 7-8 in sequence to obtain the rare earth carbonate.
The invention mixes an ore leaching agent and ionic rare earth ore for leaching ore to obtain a leaching solution, wherein the ore leaching agent is a magnesium sulfate solution.
The source of the ionic rare earth ore is not particularly limited in the present invention, and a source known to those skilled in the art may be used.
In the invention, the pH value of the mineral leaching agent is preferably 2.5-5.5, more preferably 4.5-5, and the mass fraction of the mineral leaching agent is preferably 1-5%, more preferably 2-3%. The solvent for adjusting the pH value of the mineral leaching agent is not specially limited, and the pH value of the mineral leaching agent can be ensured to be 2.5-5.5.
In the invention, the dosage ratio of the ionic rare earth ore to the mineral leaching agent during mineral leaching is preferably 1kg: 0.22-0.88L.
In the present invention, the leachate preferably comprises the following components in the following concentrations: REO 0.1-5 g/L, Al2O3 0.001～5g/L，Fe2O30.001-5 g/L CaO, 0.001-3 g/L CaO. The time and temperature of the leaching are not particularly limited in the present invention, and preferably, the concentration of each component in the leaching solution meets the above requirements.
The invention uses acid to pretreat the extraction resin to obtain the pretreated resin.
In the invention, the pretreatment preferably uses hydrochloric acid, the concentration of the hydrochloric acid is preferably 0.8-1.2 mol/L, and the volume ratio of the hydrochloric acid to the extraction resin is preferably (1-3): 1. in the present invention, the pretreatment serves to remove entrained impurities.
In the invention, the pretreatment time is preferably 12 to 36 hours.
In the present invention, the extraction resin preferably comprises P507 extraction resin and/or P204 extraction resin.
In the invention, the grain size of the extraction resin is preferably 75-150 μm.
In the invention, the pretreatment is preferably followed by water washing, and the pretreatment is preferably carried out by water washing until the pH value is 5-6.
After leachate and pretreatment resin are obtained, the leachate is adsorbed by the pretreatment resin, and the adsorbed resin is sequentially washed and desorbed to obtain desorbed liquid.
In the invention, the adsorption is preferably carried out by allowing the leachate to flow through the pretreatment resin, and the linear velocity of the flow is preferably 0.1-100 cm/min.
According to the invention, the pre-treated resin is preferably uniformly loaded into a resin column, the flow rate is accurately controlled by a constant flow pump, the leachate is pumped, the leachate flows through the resin column to form adsorbed liquid, and the adsorbed liquid is preferably sampled and detected every 1 hour until the resin is completely saturated in adsorption.
In the present invention, pure water is preferably used for the water washing.
In the invention, the volume ratio of the pure water to the extraction resin is preferably (1-3): 1.
In the present invention, the washing is preferably performed by pumping pure water into the resin column, and the washing serves to wash the residual rare earth leachate.
In the present invention, the desorbent used for the desorption preferably comprises H2SO4And/or HCl, H in the desorbent+The concentration of (b) is preferably 1 to 8mol/L, more preferably 4.5 to 6 mol/L.
In the invention, the linear velocity of the desorbent is preferably 0.1-100 cm/min, and more preferably 0.3-1 cm/min.
According to the invention, the desorbent is preferably pumped into the resin column by using a constant flow pump, the obtained desorbed liquid is preferably sampled and detected every 1 hour, and the dosage of the desorbent is preferably until the desorbed liquid does not contain rare earth ions.
After the desorbed liquid is obtained, the desorbed liquid is sequentially subjected to acid neutralization and aluminum removal to obtain a removed aluminum liquid.
In the invention, the acid is neutralized to a pH value of preferably 3.6-3.8.
In the present invention, the neutralizing agent used for the acid neutralization preferably includes one or more of sodium hydroxide, sodium carbonate and sodium bicarbonate.
In the present invention, the neutralizer is preferably used in the form of a neutralizer solution, and the concentration of the neutralizer solution is preferably 0.1 to 10mol/L, and more preferably 6 to 8 mol/L. The dosage of the neutralizing agent is not specially limited, and the pH value of the obtained neutralizing liquid can be guaranteed to be 3.6-3.8.
In the invention, the molar ratio of the aluminum removing agent used for aluminum removal to the aluminum element in the neutralization solution obtained by acid neutralization is preferably (3-9): 1. in the present invention, the aluminum remover preferably comprises one or more of benzoic acid, sodium benzoate and potassium benzoate.
In the invention, the aluminum remover is preferably used in the form of an aluminum remover aqueous solution, and the aluminum remover aqueous solution is preferably prepared by mixing the aluminum remover and water according to the volume ratio of 1 (1-3).
According to the invention, the aluminum remover water solution is preferably added into the neutralized solution, and the adding speed is preferably 1-20 mL/min.
In the invention, the pH value is preferably controlled to be 3.6-4.0 in the adding process.
In the invention, the aluminum removal is preferably carried out under the condition of stirring, and the stirring time is preferably 0.5-4 hours.
In the invention, the pH value of the aluminum removal end point is preferably 4.0-4.1.
After the aluminum removal is finished, the system after the aluminum removal is preferably filtered to obtain the aluminum-removed liquid and filter residues. The present invention is not limited to the specific filtration method, and the filtration method may be a method known to those skilled in the art.
After the molten aluminum is removed, the pH value of the molten aluminum is sequentially adjusted to 1.0-1.5 and 7-8, and the rare earth carbonate is obtained.
In the invention, the effect of adjusting the pH value of the aluminum removing liquid to 1.0-1.5 is to recover the aluminum removing agent, and the aluminum removing agent is preferably recycled.
In the invention, the pH value is preferably adjusted to 1.0-1.5 by using 8-10 mol/L sulfuric acid.
In the invention, the pH value is adjusted to 1.0-1.5, preferably under the condition of stirring, and the stirring time is preferably 0.5-3 hours.
After the stirring is finished, the invention preferably carries out filtration to obtain filtrate and filter residue, wherein the filter residue is the recovered aluminum removing agent.
In the invention, sodium carbonate and/or sodium bicarbonate are preferably used for adjusting the pH value of the filtrate to 7-8, and the rare earth carbonate is obtained.
The dosage of the sodium carbonate and the sodium bicarbonate is not specially limited, and the pH value of the filtrate can be ensured to be 7-8.
FIG. 1 is a flow chart of the method for preparing rare earth carbonate from ionic rare earth ore according to the invention.
In order to further illustrate the present invention, the method for preparing rare earth carbonate from ionic rare earth ore provided by the present invention is described in detail with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
Table 1 shows the composition of the ionic rare earth ore.
Table 1 rare earth element distribution table unit of ionic rare earth ore: wt.%
The ionic RE content of the ionic rare earth ore is 0.0396 wt%.
Mineral leaching
Preparing a magnesium sulfate mineral leaching agent with the mass fraction of 2% according to the solid-to-liquid ratio of 1kg to 0.66L, adjusting the pH value to be 5.0, adding ionic rare earth ore to leach, collecting leachate, adding top water to wash after the mineral leaching agent is drained, washing until the washing liquor does not contain rare earth, and combining the leachate to obtain the ionic rare earth leaching agent. The leachate composition is shown in table 2:
TABLE 2 leachate Components
Pretreatment of levextrel resin
The extraction resin is P507, and the following steps are carried out: hydrochloric acid 1: 1 (volume ratio) is soaked by hydrochloric acid, the concentration of the hydrochloric acid is 1.0mol/L, the soaking time is 24 hours, and after the pretreatment is finished, the water is washed until the pH value is 5-6.
Adsorption of levextrel resin
And (2) uniformly filling the pretreated extraction resin into a resin column, accurately controlling the flow rate by using a constant flow pump, pumping the rare earth leaching solution obtained in the step (1) at the flow rate of 0.85cm/min, enabling the leaching solution to flow through the resin column to be an adsorbed solution, sampling and detecting the adsorbed solution every 1 hour until the rare earth concentrations of the adsorbed solution and the rare earth leaching solution are equal, namely, the adsorption saturation of the extraction resin is realized, and the adsorption process of the extraction resin is stopped. 98.72 wt% of the aluminum was adsorbed into the extraction resin. Fe. Mg, SO4 2-The adsorption rate of Si and Ca was 1.92% and 1.79%, respectively, without adsorbing into the resin. The post-adsorption liquid composition is shown in table 3:
TABLE 3 post-adsorption liquid composition
Extraction of resin
Pumping pure water into the resin column, washing until no entrainment exists, cleaning residual rare earth leaching liquid in the extraction resin, and draining water.
Stripping of levextrel resin
Preparation 2.25mol/L H2SO4Pumping into resin column with constant flow pump at a rate of 0.3cm/min as desorbent, desorbing the solution every 1 hrSampling and detecting, desorbing until the desorbed liquid does not contain rare earth, and washing the resin after desorption for recycling.
Post-desorption liquid neutralization
Preparing 8mol/L solution by using sodium hydroxide as a neutralizer, adding the solution into the desorbed solution, stirring, and neutralizing the pH value to 3.60.
Removing aluminium
According to the weight percentage of sodium benzoate: al 4.5: 1 (molar ratio), preparing an aluminum removing agent into an aqueous solution, slowly adding the aqueous solution into the neutralized solution, controlling the pH to be 4.0 in the process, stirring for 2 hours, adjusting the pH to be 4.0 at the end point, and filtering to obtain filtrate and filter residue. The Al concentration of the aluminum-removed liquid is 4.52mg/L, the Al removal rate is 99.89%, and the rare earth loss rate is only 0.3%.
Recovering aluminum removing agent
Adjusting the obtained filtrate to pH 1.0, stirring for 1 hour, filtering to obtain filtrate and filter residue, wherein the filter residue is benzoic acid, and the benzoic acid is treated by sodium hydroxide to obtain sodium benzoate as an aluminum remover, and the sodium benzoate can be returned for aluminum removal and recycling.
Precipitated rare earths
And adjusting the pH of the filtrate to 7.0 by using sodium carbonate and sodium bicarbonate to obtain the rare earth carbonate product.
Burning rare earth carbonate product at 950 deg.c for 3 hr to obtain RE oxide containing REO in 94.32 wt% and Fe2O3 0.048wt％，SiO2 0.16wt％，Al2O30.37 wt% and CaO < 0.01 wt%. The ignition loss of the rare earth carbonate product is 0.46 percent.
Example 2
Table 4 shows the rare earth element distribution table for the ionic rare earth ore.
Table 4 ionic rare earth element distribution table unit for rare earth ore: wt.%
The content of the ionic RE in the ionic rare earth ore is 0.110 wt%.
Mineral leaching
Preparing a magnesium sulfate mineral leaching agent with the mass fraction of 3% according to the solid-to-liquid ratio of 1kg to 0.55L, adjusting the pH value to be 4.5, adding ionic rare earth ore to leach, collecting leachate, adding top water to wash after the mineral leaching agent is drained, washing until the washing liquor does not contain rare earth, and combining the leachate to obtain the ionic rare earth leaching agent. The leachate composition is shown in table 5:
TABLE 5 leachate composition
Pretreatment of levextrel resin
The extraction resin is P507, and the following steps are carried out: hydrochloric acid 1: 1 (volume ratio) is soaked by hydrochloric acid, the concentration of the hydrochloric acid is 1.0mol/L, the soaking time is 36 hours, and after the pretreatment is finished, the water is washed until the pH value is 5-6.
Adsorption of levextrel resin
And (2) uniformly filling the pretreated extraction resin into a resin column, accurately controlling the flow rate by using a constant flow pump, pumping the rare earth leaching solution obtained in the step (1) at the flow rate of 1.5cm/min, enabling the leaching solution to flow through the resin column to be an adsorbed solution, sampling and detecting the adsorbed solution every 1 hour until the rare earth concentrations of the adsorbed solution and the rare earth leaching solution are equal, namely, the adsorption saturation of the extraction resin is realized, and the adsorption process of the extraction resin is stopped. 91.67% of the aluminum was adsorbed into the resin. Fe. SO (SO)4 2-The adsorption rate of Si, Ca and Mg was 2.03%, 3.66% and 0.52%, respectively, without entering the resin. The post-adsorption liquid composition is shown in table 6:
TABLE 6 post-adsorption liquid composition
Extraction of resin
Pumping pure water into the resin column, washing until no entrainment exists, cleaning residual rare earth leaching liquid in the extraction resin, and draining water.
Stripping of levextrel resin
Preparation 3mol/L H2SO4Pumping into resin column with constant flow pump at 0.6cm/min as desorbent, sampling and detecting the desorbed liquid every 1 hr until the desorbed liquid contains no rare earth, and washing with water for recycling.
Post-desorption liquid neutralization
Preparing 6mol/L solution by using sodium hydroxide as a neutralizer, adding the solution into the desorbed solution, stirring, and neutralizing the pH value to 3.80.
Removing aluminium
According to the weight percentage of sodium benzoate: al 6: 1 (molar ratio), preparing an aluminum removing agent into an aqueous solution, slowly adding the aqueous solution into the neutralized solution, controlling the pH to be 4.0 in the process, stirring for 2 hours, adjusting the pH to be 4.0 at the end point, and filtering to obtain filtrate and filter residue. The Al concentration of the aluminum-removed liquid is 5.13mg/L, the Al removal rate is 98.3 percent, and the rare earth loss rate is only 2.26 percent.
Recovering aluminum removing agent
Adjusting the obtained filtrate to pH 1.5, stirring for 2 hours, filtering to obtain filtrate and filter residue, wherein the filter residue is benzoic acid, and the benzoic acid is treated by sodium hydroxide to obtain sodium benzoate as an aluminum remover, and the sodium benzoate can be returned for aluminum removal and recycling.
Precipitated rare earths
And adjusting the pH of the filtrate to 7.5 by using sodium carbonate and sodium bicarbonate to obtain the rare earth carbonate product.
Burning rare earth carbonate product at 950 deg.c for 3 hr to obtain rare earth oxide with the oxide components including REO in 93.00 wt% and Fe2O3 0.13wt％，SiO2 0.33wt％，Al2O30.65 wt% and CaO < 0.01 wt%. The ignition loss of the rare earth carbonate product is 3.21 percent.
The foregoing is merely a preferred embodiment of the invention and is not intended to limit the invention in any manner. It should be noted that, for those skilled in the art, without departing from the principle of the present invention, several improvements and modifications can be made, and these improvements and modifications should also be construed as the protection scope of the present invention.
Claims (10)
1. A method for preparing rare earth carbonate from ionic rare earth ore is characterized by comprising the following steps:
mixing an ore leaching agent and ionic rare earth ore for leaching to obtain a leaching solution, wherein the ore leaching agent is MgSO4A solution;
pretreating the levextrel resin with acid to obtain pretreated resin;
adsorbing the leachate by using the pretreatment resin, and sequentially washing and desorbing the adsorbed resin to obtain desorbed liquid;
sequentially carrying out acid neutralization and aluminum removal on the desorbed liquid to obtain a removed aluminum liquid;
and adjusting the pH value of the molten aluminum removal liquid to 1.0-1.5 and 7-8 in sequence to obtain the rare earth carbonate.
2. The preparation method according to claim 1, wherein the pH value of the mineral leaching agent is 2.5-5.5, and the mass fraction of the mineral leaching agent is 1-5%.
3. The preparation method according to claim 1 or 2, wherein the dosage ratio of the ionic rare earth ore to the mineral leaching agent during mineral leaching is 1kg: 0.22-0.88L.
4. The preparation method according to claim 1, wherein the acid is hydrochloric acid, the concentration of the hydrochloric acid is 0.8-1.2 mol/L, and the volume ratio of the hydrochloric acid to the extraction resin is (1-3): 1.
5. the method of claim 1 or 4, wherein the extraction resin comprises a P507 extraction resin and/or a P204 extraction resin.
6. The method according to claim 1, wherein the adsorption is carried out by flowing the leachate through the pretreatment resin, and the linear velocity of the leachate is 0.1-100 cm/min.
7. The method according to claim 1, wherein the reaction mixture is heated to a temperature in the reaction mixtureThe desorbent used for desorption comprises H2SO4And/or HCl, H in the desorbent+The concentration of (b) is 1 to 8 mol/L.
8. The preparation method according to claim 7, wherein the linear velocity of the desorbent is 0.1-100 cm/min.
9. The method according to claim 1, wherein the acid is neutralized to a pH of 3.6 to 3.8.
10. The preparation method according to claim 1, wherein the molar ratio of the aluminum removing agent used for aluminum removal to the aluminum element in the neutralized liquid obtained by acid neutralization is (3-9): 1.
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| CN102190325A (en) * | 2010-03-17 | 2011-09-21 | 北京有色金属研究总院 | Method for recovering rare earth from ionic type rare earth crude ore |
| CN102965506A (en) * | 2012-12-14 | 2013-03-13 | 葛新芳 | Method for removing aluminum from rare earth solution by benzoate precipitation method |
| CN104152693A (en) * | 2014-07-16 | 2014-11-19 | 江西理工大学 | Method for precipitating rare earth from ionic rare earth ore magnesium sulfate leaching solution |
| CN112359232A (en) * | 2020-10-14 | 2021-02-12 | 南昌华亮光电有限责任公司 | Ion adsorption type rare earth extraction method using calcium chloride as leaching agent |
| KR102277491B1 (en) * | 2020-10-12 | 2021-07-15 | 주식회사두합크린텍 | Method for phosphorus removal and retrieving from wastewater |
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| CN102190325A (en) * | 2010-03-17 | 2011-09-21 | 北京有色金属研究总院 | Method for recovering rare earth from ionic type rare earth crude ore |
| CN102965506A (en) * | 2012-12-14 | 2013-03-13 | 葛新芳 | Method for removing aluminum from rare earth solution by benzoate precipitation method |
| CN104152693A (en) * | 2014-07-16 | 2014-11-19 | 江西理工大学 | Method for precipitating rare earth from ionic rare earth ore magnesium sulfate leaching solution |
| KR102277491B1 (en) * | 2020-10-12 | 2021-07-15 | 주식회사두합크린텍 | Method for phosphorus removal and retrieving from wastewater |
| CN112359232A (en) * | 2020-10-14 | 2021-02-12 | 南昌华亮光电有限责任公司 | Ion adsorption type rare earth extraction method using calcium chloride as leaching agent |
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