CN115595458A - Method for recovering rare earth from bioleaching solution through configuration conversion and self-precipitation of rare earth complex - Google Patents
Method for recovering rare earth from bioleaching solution through configuration conversion and self-precipitation of rare earth complex Download PDFInfo
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- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 256
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 230
- 238000001556 precipitation Methods 0.000 title claims abstract description 67
- 238000000034 method Methods 0.000 title claims abstract description 44
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 38
- 238000002386 leaching Methods 0.000 claims abstract description 26
- 239000002994 raw material Substances 0.000 claims abstract description 22
- 239000003446 ligand Substances 0.000 claims abstract description 20
- 238000001914 filtration Methods 0.000 claims abstract description 10
- 239000008394 flocculating agent Substances 0.000 claims abstract description 3
- 238000011084 recovery Methods 0.000 claims abstract description 3
- 239000007788 liquid Substances 0.000 claims description 35
- 239000012141 concentrate Substances 0.000 claims description 25
- 238000000926 separation method Methods 0.000 claims description 24
- -1 rare earth salts Chemical class 0.000 claims description 23
- 239000003795 chemical substances by application Substances 0.000 claims description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 239000002244 precipitate Substances 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 16
- 230000001131 transforming effect Effects 0.000 claims description 16
- 239000013078 crystal Substances 0.000 claims description 15
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 14
- 239000000706 filtrate Substances 0.000 claims description 14
- 230000032683 aging Effects 0.000 claims description 13
- 239000012716 precipitator Substances 0.000 claims description 13
- 230000009466 transformation Effects 0.000 claims description 12
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 7
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 7
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 7
- 239000001099 ammonium carbonate Substances 0.000 claims description 7
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 7
- 239000000292 calcium oxide Substances 0.000 claims description 7
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 7
- 238000000605 extraction Methods 0.000 claims description 7
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- 229920001732 Lignosulfonate Polymers 0.000 claims description 4
- 229920002401 polyacrylamide Polymers 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 230000002431 foraging effect Effects 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 2
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 2
- 239000000920 calcium hydroxide Substances 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 2
- 229910001948 sodium oxide Inorganic materials 0.000 claims description 2
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 2
- 239000000243 solution Substances 0.000 abstract description 111
- 239000007864 aqueous solution Substances 0.000 abstract description 12
- 230000001376 precipitating effect Effects 0.000 abstract description 8
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 239000012535 impurity Substances 0.000 abstract description 3
- 150000002500 ions Chemical class 0.000 abstract description 3
- 239000003814 drug Substances 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 27
- 238000001035 drying Methods 0.000 description 11
- 239000007787 solid Substances 0.000 description 11
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 10
- 229910052500 inorganic mineral Inorganic materials 0.000 description 8
- 239000011707 mineral Substances 0.000 description 8
- 235000010755 mineral Nutrition 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 244000005700 microbiome Species 0.000 description 6
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 5
- 235000017557 sodium bicarbonate Nutrition 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000002207 metabolite Substances 0.000 description 4
- 238000005065 mining Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000005272 metallurgy Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- 241001052560 Thallis Species 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000001580 bacterial effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 229910000420 cerium oxide Inorganic materials 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000010793 electronic waste Substances 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 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 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 2
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000013386 optimize process Methods 0.000 description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 2
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910017569 La2(CO3)3 Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- IKNAJTLCCWPIQD-UHFFFAOYSA-K cerium(3+);lanthanum(3+);neodymium(3+);oxygen(2-);phosphate Chemical compound [O-2].[La+3].[Ce+3].[Nd+3].[O-]P([O-])([O-])=O IKNAJTLCCWPIQD-UHFFFAOYSA-K 0.000 description 1
- GHLITDDQOMIBFS-UHFFFAOYSA-H cerium(3+);tricarbonate Chemical compound [Ce+3].[Ce+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O GHLITDDQOMIBFS-UHFFFAOYSA-H 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000012258 culturing Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- NZPIUJUFIFZSPW-UHFFFAOYSA-H lanthanum carbonate Chemical compound [La+3].[La+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O NZPIUJUFIFZSPW-UHFFFAOYSA-H 0.000 description 1
- 229960001633 lanthanum carbonate Drugs 0.000 description 1
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052590 monazite Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- UXBZSSBXGPYSIL-UHFFFAOYSA-N phosphoric acid;yttrium(3+) Chemical compound [Y+3].OP(O)(O)=O UXBZSSBXGPYSIL-UHFFFAOYSA-N 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000010903 primary nucleation Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- QVOIJBIQBYRBCF-UHFFFAOYSA-H yttrium(3+);tricarbonate Chemical compound [Y+3].[Y+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O QVOIJBIQBYRBCF-UHFFFAOYSA-H 0.000 description 1
- 229910000164 yttrium(III) phosphate Inorganic materials 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
- 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
-
- 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 bioleaching solution by self-precipitation through configuration conversion of a rare earth complex, which comprises the following steps of 1) obtaining the bioleaching solution rich in the rare earth complex; 2) Adjusting the pH value of the biological leaching solution, adding a flocculating agent, standing, and filtering to obtain a rare earth complex raw material solution; 3) The rare earth complex is subjected to configuration conversion and self-precipitation recovery; 4) And (4) precipitating and recovering the free ionic state rare earth. According to the invention, by utilizing the solubility difference of the rare earth complex under different configurations, the rare earth complex in the bioleaching solution is converted from a soluble 1 type (rare earth: ligand) to a soluble 2 type (rare earth: ligand) into an insoluble 1 type (rare earth: ligand) through configuration conversion, so that the self-precipitation of the rare earth complex is realized, and no new impurity ions are introduced. The method has the advantages of high precipitation efficiency, environmental protection, low cost, high product quality, high added value, easy operation, recyclable aqueous solution and medicament, high comprehensive utilization rate of resources and the like, and has good industrial application prospect.
Description
Technical Field
The invention belongs to the field of mineral processing and hydrometallurgy, and particularly relates to a method for recovering rare earth from bioleaching solution through self-precipitation of rare earth complex configuration conversion.
Background
Rare Earth Elements (REE) are called as industrial vitamins and novel material treasury in the 21 st century, have excellent magnetic, optical and electrical properties, have substitutable effects on improving product performance and improving production efficiency, are widely applied to high-tech fields such as aviation, high-efficiency catalysts, wind turbines, satellites, national defense and light material manufacturing and the like, and belong to strategic resources. At present, china dominates the global rare earth production, and rare earth resources can be divided into mineral rare earth (monazite, bastnaesite, xenotime and the like), ionic rare earth ore (also called weathering crust elution type rare earth ore) and partial rare earth-containing waste (tailings, smelting slag, electronic waste, waste catalyst and the like). Under the condition of high-speed development of new energy industry, the situation of increasing rare earth demand is continuous, but the development of rare earth industry in China is not mature enough. The method solves the problem of environmental pollution in the rare earth mining and selecting process, realizes the clean and efficient utilization of the rare earth, and is a serious challenge in the rare earth industry.
Along with the national requirements for more strict environmental protection standards and protective mining policies for rare earth resources, the traditional rare earth extraction technology has many defects because it involves violent reaction conditions such as strong acid, strong alkali, high-concentration salt ions, high temperature and the like, and simultaneously produces radioactive and heavy metal pollutants and wastewater which is difficult to treat. The biological metallurgy (bioleaching/biological extraction) technology has the advantages of low carbon, carbon reduction, environmental protection, low cost and the like, has obvious advantages in low-grade ore treatment, and has industrial application in the field of various metal resources. The biological metallurgy technology based on the direct action of the microorganisms and the indirect action of metabolites thereof does not cause pollution to the mining area environment and underground water systems, and the propagation and metabolism of the microorganisms can also promote the degradation of environmental pollutants, soil improvement and ecological restoration. Therefore, the extraction of rare earth by the biological metallurgy technology is an important breakthrough for realizing clean and efficient extraction of rare earth resources, and is one of the innovative technologies in the rare earth industry.
Recently, research groups have reported the extraction of rare earth elements from mineral-type rare earth, ionic-type rare earth ore and electronic waste using biotechnology. Chinese patents CN 113293287A and CN113046554B respectively disclose a method for leaching weathering crust elution type rare earth ore by using microorganisms and microorganism metabolites, which comprises the following steps: 1) Activating microorganisms, and then culturing to obtain a bacterial suspension; 2) Then the bacterial suspension, the thalli or the metabolite without the thalli is used as a leaching medium to leach the weathering crust elution-deposited rare earth ore to obtain a leaching solution containing rare earth. Compared with the traditional process, the method has the advantages of good leaching effect, strong selectivity, green and environment-friendly leaching process and no pollution to the soil and underground water system of the mining area. However, how to effectively recover rare earth elements from a bioleaching solution containing rare earth has not been reported. Different from chemical leaching, microorganisms and metabolites thereof mostly form complexes with rare earth elements through complexation and then are transferred into a solution from a solid phase, and the physicochemical properties of various rare earth complexes (complexes) in a biological leaching solution are obviously different from those of free rare earth. Because the rare earth complex has stable chemical properties, the conventional precipitant and precipitation method are difficult to effectively precipitate and enrich the rare earth in the bioleaching solution, and a precipitation method aiming at the rare earth complex is urgently needed. This is a significant bottleneck and challenge limiting the application of the rare earth biometallurgical industry.
Disclosure of Invention
The invention aims to provide a method for carrying out precipitation enrichment on rare earth complexes in bioleaching liquid. According to the method, the rare earth complex in the rare earth bioleaching solution is selectively precipitated in a rare earth complex configuration conversion-self precipitation mode, so that a high-value rare earth functional material precursor and a high-quality rare earth concentrate product can be obtained while the rare earth precipitation rate is ensured.
The invention provides a method for recovering rare earth from bioleaching solution by self-precipitation through configurational transformation of a rare earth complex, which comprises the following steps:
1) Obtaining a bioleaching solution rich in rare earth complexes;
2) Adjusting the pH of the bioleaching solution obtained in the step 1) to a proper range, adding a flocculating agent, standing, and filtering to obtain a rare earth complex raw material solution;
3) The configuration conversion self-precipitation recovery of the rare earth complex: adding a rare earth complex configuration transforming agent into the raw material liquid obtained in the step 2), and when the rare earth in the solution: stopping adding the rare earth complex configuration transforming agent after the molar ratio of the ligand reaches a set value, adjusting the pH value of the solution to a proper range, stirring, standing for aging after complete reaction, and performing solid-liquid separation to obtain high-purity rare earth complex precipitate and filtrate;
4) And (3) recovering free ionic state rare earth precipitation: adding a precipitator into the filtrate obtained in the step 3), stopping adding the precipitator after the pH value of the solution rises to a set range, stirring, inoculating seed crystals, standing and aging after complete reaction, and performing solid-liquid separation to obtain rare earth precipitate.
Preferably, in the step 2), the pH is preferably in the range of 5 to 8.
Preferably, in the step 2), the flocculant is an inorganic flocculant or an organic polymeric flocculant, wherein the inorganic flocculant is any one of polyaluminum sulfate PAS, polyaluminum chloride PAC, polyferric chloride PFC, polyferric sulfate PFS and polysilicic acid flocculant PSAA, and the organic polymeric flocculant is any one of polyacrylamide, styrene sulfonate, lignosulfonate and sodium polyacrylate.
The rare earth complex is converted into self-precipitation in a configuration mode, and the rare earth complex in the bioleaching solution is converted into an insoluble 1 type (rare earth: ligand) from a soluble 1 type (rare earth: ligand) to a soluble 2 type (rare earth: ligand) by the configuration conversion by utilizing the solubility difference of the rare earth complex under different configurations.
Preferably, in the step 3), the rare earth complex configuration transforming agent is a solution containing free rare earth, wherein the solution containing free rare earth is obtained by dissolving any one of rare earth salts, rare earth oxides, rare earth hydroxides, rare earth fluorides and rare earth concentrates, or is one of an extraction liquid and a raffinate in a rare earth separation process; the concentration of the rare earth complex configuration transforming agent is 0.1-0.5 mol/L.
When the rare earth complex configuration transforming agent is prepared, the rare earth distribution needed by the special application of the subsequent rare earth complex precipitation or the economic cost can be adjusted.
Preferably, the rare earth salt is any one of rare earth nitrate, rare earth chloride, rare earth carbonate, rare earth sulfate and rare earth oxalate.
Preferably, in the step 3), when the rare earth: stopping adding the rare earth complex configuration transforming agent when the molar ratio of the ligand is 1.1-1.4; the pH is suitably in the range of 5 to 8; the stirring speed is 80-300 rpm, the reaction temperature is 20-50 ℃, the reaction time is 1-3 h, and the aging time is 2-8 h.
Preferably, in the step 4), the precipitant is any one of carbonate, bicarbonate, alkali metal oxide and alkali metal hydroxide.
Further preferably, in the step 4), the precipitant is any one of sodium carbonate, ammonium bicarbonate, sodium bicarbonate, calcium oxide, calcium hydroxide, sodium oxide and sodium hydroxide.
Preferably, in the step 4), the concentration of the precipitating agent is 1-5 mol/L; stopping adding the precipitator when the pH value is 6-11; the reaction temperature is 20-50 ℃, the reaction time is 3-6 h, and the aging time is 4-6 h.
Preferably, in the step 4), the seed crystal is any one of rare earth concentrate, rare earth oxide or rare earth carbonate with uniform particle size, and the seed crystal access amount is 1-3%. The seed crystal access amount is relative to the rare earth precipitation in the rare earth feed liquid.
The primary nucleation is inhibited by inoculating a proper amount of seed crystals, the supersaturation degree of the solution is reduced, and the crystallization process is regulated to obtain the rare earth precipitation product with large particle size, uniform distribution and easy filtration.
The invention has the beneficial effects that: 1) According to the invention, the rare earth complex in the bioleaching solution is selectively precipitated in a configuration conversion self-precipitation manner to obtain high-quality rare earth complex precipitate, and the method has the advantages of high precipitation efficiency, low cost, easiness in solid-liquid separation and capability of using the precipitate product as a precursor of a high-value rare earth micro-nano functional material; 2) The self-precipitation process of the rare earth complex has selectivity, and the coprecipitation of other impurity ions in the solution can be effectively reduced; 3) The residual rare earth in the final residual liquid can be subjected to two-stage precipitation in various precipitation modes, the limitation that only the cationic precipitator which is the same as the leaching agent can be used in the traditional process is broken through, and a high-quality rare earth product is obtained by precipitation condition control and seed crystal access; 4) The invention utilizes the solubility difference of the rare earth complex under different configurations to ensure that the rare earth complex in the bioleaching solution is mixed from a soluble state 1: ligand) is converted into the insoluble state of type 1: ligand), realizes the self-precipitation of the rare earth complex, and does not introduce new impurity ions; 5) The process has the advantages of high precipitation efficiency, environmental protection, low cost, high product quality, high added value, easy operation, recyclable aqueous solution and medicament, high comprehensive utilization rate of resources and the like, and has good industrial application prospect.
Detailed Description
In order to make the technical means, the creation characteristics, the achievement purposes and the effects of the invention easy to understand, the invention is further described in the following combined with the embodiment. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The invention provides a method for efficiently recovering rare earth from bioleaching solution by a rare earth complex configuration conversion self-precipitation method, which comprises the following steps: bioleaching rare earth minerals or rare earth-containing secondary resources under proper conditions to obtain a bioleaching solution rich in rare earth complexes, adjusting the pH of the bioleaching solution to a set range, adding a small amount of flocculant to separate fine suspended substances in the bioleaching solution, and filtering to obtain a raw material solution rich in rare earth complexes; and preparing a rare earth complex configuration transforming agent with proper concentration, adding the transforming agent into the raw material liquid, realizing self-precipitation of the rare earth complex through configuration transformation under optimized process conditions by utilizing the solubility difference of the rare earth complex under different configurations, and obtaining high-quality rare earth complex precipitate after solid-liquid separation. And after the self-precipitation process of the rare earth complex is finished, completely recovering the residual rare earth in the final residual liquid through two-stage precipitation, adding the prepared precipitator into the residual liquid until the pH value is increased to a set range, inoculating crystal seeds, precipitating under the optimized process condition, carrying out solid-liquid separation after the precipitation is finished, and dehydrating and drying the solid to obtain the high-quality rare earth product.
Example 1
Bioleaching rare earth minerals or rare earth-containing secondary resources under proper conditions to obtain a bioleaching solution rich in rare earth complexes, adjusting the pH of the bioleaching solution to 5.5, preparing 0.02% polyacrylamide aqueous solution, adding the polyacrylamide aqueous solution into the bioleaching solution at a constant speed, standing for 4 hours, and carrying out solid-liquid separation to obtain a raw material solution containing the rare earth complexes; lanthanum nitrate solution with concentration of 0.2mol/L is prepared as a configuration transforming agent and is added into the raw material solution at a constant speed, so that the rare earth in the raw material solution: stopping adding the ligand when the molar ratio of the ligand is 1.1, adjusting the pH value of the solution to be 5.0, stirring and reacting for 2.5 hours at 25 ℃ to realize the configuration conversion self-precipitation of the rare earth complex, standing for 2 hours, then carrying out solid-liquid separation to obtain solid and filtrate, and drying the solid to obtain a high-quality rare earth concentrate product; when the self-precipitation of the rare earth complex is finished completely, preparing an ammonium bicarbonate solution with the concentration of 2.0mol/L, adding the ammonium bicarbonate solution into the filtrate at a constant speed, stopping adding the ammonium bicarbonate solution when the pH of the solution rises to 8.0, carrying out stirring reaction at 40 ℃, inoculating 2% of rare earth concentrate seed crystals, reacting for 3 hours, then standing and aging for 6 hours, carrying out solid-liquid separation, filtering to obtain rare earth precipitate, dehydrating and drying to obtain a rare earth product, wherein the final precipitation rate of the rare earth is 99.0%, and obtaining a high-quality rare earth concentrate product.
The method is not adopted, but the ammonium bicarbonate precipitator is directly used for precipitating the rare earth complex in the biological leaching solution, and the optimized reaction conditions are as follows: under the condition of 35 ℃, adding 2.0mol/L ammonium bicarbonate solution at constant speed until the pH value of the bioleaching solution rises to 8.0, reacting for 3 hours, then standing and aging for 6 hours, wherein the final precipitation rate of the rare earth is only 1.2 percent. Compared with a conventional precipitation mode, the method disclosed by the invention can effectively precipitate the rare earth complex in the bioleaching solution under an optimized condition, and obtain a high-quality rare earth concentrate product.
Example 2
Biologically leaching rare earth minerals or secondary resources containing rare earth under proper conditions to obtain a biological leaching solution rich in rare earth complexes, adjusting the pH of the biological leaching solution to 6.0, preparing a 0.01% polyaluminum sulfate aqueous solution, adding the aqueous solution into the biological leaching solution at a constant speed, standing for 2.5 hours, and carrying out solid-liquid separation to obtain a rare earth complex-containing raw material solution. Preparing a lanthanum chloride solution with the concentration of 0.3mol/L as a configuration transforming agent, and adding the lanthanum chloride solution into the raw material liquid at a constant speed to ensure that the rare earth in the raw material liquid: stopping adding when the molar ratio of the ligand is 1.2, adjusting the pH value of the solution to 5.5, stirring and reacting for 3.0h at 20 ℃ to realize the configuration conversion self-precipitation of the rare earth complex, standing for 2 h, performing solid-liquid separation to obtain solid and filtrate, and drying the solid to obtain a high-quality rare earth concentrate product. Preparing a sodium carbonate solution with the concentration of 2.0mol/L, adding the sodium carbonate solution into the filtrate at a constant speed, stopping adding the sodium carbonate solution when the pH value of the solution rises to 7.5, carrying out stirring reaction at 30 ℃, inoculating 2% of rare earth concentrate seed crystals, reacting for 4.5 hours, standing and aging for 4 hours, carrying out solid-liquid separation, filtering to obtain rare earth precipitates, dehydrating and drying to obtain rare earth products, wherein the final precipitation rate of the rare earth is 97.4%, and obtaining the high-quality rare earth concentrate products.
The method is not adopted, but the sodium carbonate precipitator is directly used for precipitating the rare earth complex in the biological leaching solution, and the optimized reaction conditions are as follows: under the condition of 30 ℃, 2.0mol/L sodium carbonate solution is added at a constant speed until the pH value of the bioleaching solution rises to 7.5, the reaction is carried out for 4.5 hours, then the mixture is kept stand and aged for 4 hours, and the final precipitation rate of the rare earth is only 0.9 percent. Compared with a conventional precipitation mode, the method disclosed by the invention can effectively precipitate the rare earth complex in the biological leaching solution under an optimized condition, and obtain a high-quality rare earth concentrate product.
Example 3
Bioleaching rare earth minerals or rare earth-containing secondary resources under proper conditions to obtain a bioleaching solution rich in rare earth complexes, adjusting the pH of the bioleaching solution to 6.5, preparing a polymeric ferric sulfate aqueous solution with the concentration of 0.03%, adding the polymeric ferric sulfate aqueous solution into the bioleaching solution at a constant speed, standing for 3.5 hours, and carrying out solid-liquid separation to obtain a rare earth-containing complex raw material solution. Dissolving mixed rare earth carbonate (lanthanum carbonate, cerium carbonate and yttrium carbonate) into an acid solution to prepare a mixed rare earth solution with the concentration of 0.1mol/L as a configuration transforming agent, and adding the mixed rare earth solution into a raw material solution at a constant speed to ensure that the content of rare earth in the raw material solution is as follows: stopping adding the ligand when the molar ratio of the ligand is 1.25, adjusting the pH value of the solution to be 6.0, stirring and reacting for 2.0 hours at the temperature of 30 ℃ to realize the configuration conversion self-precipitation of the rare earth complex, standing for 3.0 hours, then carrying out solid-liquid separation to obtain solid and filtrate, and drying the solid to obtain a high-quality rare earth concentrate product. And when the self-precipitation of the rare earth complex is completely finished, preparing a calcium oxide solution with the concentration of 1.5mol/L, adding the calcium oxide solution into the filtrate at a constant speed, stopping adding the calcium oxide solution when the pH value of the solution rises to 9.5, carrying out stirring reaction at 30 ℃, inoculating 2% of rare earth concentrate seed crystals, reacting for 5.5 hours, standing and aging for 5 hours, carrying out solid-liquid separation, filtering to obtain rare earth precipitate, dehydrating and drying to obtain a rare earth product, wherein the final precipitation rate of the rare earth is 96.8%, and thus obtaining the high-quality rare earth concentrate product.
The method is not adopted, but the calcium oxide precipitator is directly used for precipitating the rare earth complex in the biological leaching solution, and the optimized reaction conditions are as follows: under the condition of 30 ℃, 1.5mol/L of calcium oxide solution is added at uniform speed until the pH value of the bioleaching solution rises to 9.5, the reaction lasts for 5.5 hours, then the mixture is kept stand and aged for 5 hours, and the final precipitation rate of the rare earth is only 0.3 percent. Compared with a conventional precipitation mode, the method disclosed by the invention can effectively precipitate the rare earth complex in the bioleaching solution under an optimized condition, and obtain a high-quality rare earth concentrate product.
Example 4
Biologically leaching rare earth minerals or secondary resources containing rare earth under proper conditions to obtain biological leachate rich in rare earth complexes, adjusting the pH of the biological leachate to 5.0, preparing 0.03 percent lignosulfonate aqueous solution, adding the lignosulfonate aqueous solution into the biological leachate at a constant speed, standing for 4.0 hours, and carrying out solid-liquid separation to obtain a rare earth complex-containing raw material solution. Dissolving mixed rare earth oxides (lanthanum oxide, cerium oxide and yttrium oxide) into an acid solution to prepare a solution with the concentration of 0.25mol/L as a configuration transforming agent, and adding the solution into a raw material solution at a constant speed to ensure that the rare earth in the raw material solution: stopping adding when the molar ratio of the ligand is 1.3, adjusting the pH value of the solution to be 6.5, stirring and reacting for 1.5h at 40 ℃ to realize the configuration conversion self-precipitation of the rare earth complex, standing for 2.5h, then carrying out solid-liquid separation to obtain solid and filtrate, and drying the solid to obtain a high-quality rare earth concentrate product. When the self-precipitation of the rare earth complex is finished completely, preparing a sodium hydroxide solution with the concentration of 3.0mol/L, adding the sodium hydroxide solution into the filtrate at a constant speed until the pH value of the solution rises to 9.5, carrying out stirring reaction at 40 ℃, inoculating 2% of rare earth concentrate seed crystals, reacting for 4.0 hours, then standing and aging for 5 hours, carrying out solid-liquid separation, filtering to obtain rare earth precipitate, dehydrating and drying to obtain a rare earth product, wherein the final precipitation rate of the rare earth is 96.8%, and thus the high-quality rare earth concentrate product is obtained.
The method is not adopted, but the sodium hydroxide precipitator is directly used for precipitating the rare earth complex in the biological leaching solution, and the optimized reaction conditions are as follows: adding 3.0mol/L sodium hydroxide solution at a constant speed at 40 ℃ until the pH value of the bioleaching solution rises to 9.5, reacting for 4.0 hours, standing and aging for 5 hours, wherein the final precipitation rate of the rare earth is only 0.7%. Compared with a conventional precipitation mode, the method disclosed by the invention can effectively precipitate the rare earth complex in the bioleaching solution under an optimized condition, and obtain a high-quality rare earth concentrate product.
Example 5
Biologically leaching rare earth minerals or secondary resources containing rare earth under proper conditions to obtain a biological leaching solution rich in rare earth complexes, adjusting the pH of the biological leaching solution to 5.0, preparing a 0.05% polymeric ferric chloride aqueous solution, adding the polymeric ferric chloride aqueous solution into the biological leaching solution at a constant speed, standing for 4.5 hours, and carrying out solid-liquid separation to obtain a raw material solution containing the rare earth complexes. Dissolving mixed rare earth oxides (lanthanum oxide, cerium oxide and yttrium oxide) into an acid solution to prepare a solution with the concentration of 0.35mol/L as a configuration transforming agent, and adding the solution into a raw material liquid at a constant speed to ensure that the rare earth in the raw material liquid: stopping adding the ligand when the molar ratio of the ligand is 1.4, adjusting the pH value of the solution to be 6.5, stirring and reacting for 2.5 hours at 44 ℃ to realize the configuration conversion self-precipitation of the rare earth complex, standing for 4.0 hours, then carrying out solid-liquid separation to obtain solid and filtrate, and drying the solid to obtain a high-quality rare earth concentrate product. Preparing a sodium bicarbonate solution with the concentration of 2.5mol/L, adding the sodium bicarbonate solution into the filtrate at a constant speed, stopping adding the sodium bicarbonate solution when the pH value of the solution rises to 7.5, carrying out stirring reaction at 35 ℃, inoculating 2% of rare earth concentrate seed crystals, reacting for 3.0 hours, standing and aging for 4 hours, carrying out solid-liquid separation, filtering to obtain rare earth precipitates, dehydrating and drying to obtain rare earth products, wherein the final precipitation rate of the rare earth is 98.2%, and obtaining the high-quality rare earth concentrate products.
The method is not adopted, the sodium bicarbonate precipitator is directly used for precipitating the rare earth complex in the biological leaching solution, and the optimized reaction conditions are as follows: adding 2.5mol/L sodium bicarbonate solution at a constant speed at 35 ℃ until the pH of the bioleaching solution rises to 7.5, reacting for 3.0 hours, standing and aging for 4 hours, wherein the final precipitation rate of the rare earth is only 1.4%. Compared with a conventional precipitation mode, the method disclosed by the invention can effectively precipitate the rare earth complex in the biological leaching solution under an optimized condition, and obtain a high-quality rare earth concentrate product.
Claims (10)
1. A method for recovering rare earth from a bioleaching solution by configurational transformation of a rare earth complex from precipitation, comprising the steps of:
1) Obtaining a bioleaching solution rich in rare earth complexes;
2) Adjusting the pH value of the biological leaching solution in the step 1) to a proper range, adding a flocculating agent, standing, and filtering to obtain a rare earth complex raw material solution;
3) The configuration conversion self-precipitation recovery of the rare earth complex: adding a rare earth complex configuration converting agent into the raw material liquid obtained in the step 2), and when the rare earth in the solution: stopping adding the rare earth complex configuration transforming agent after the molar ratio of the ligand reaches a set value, adjusting the pH value of the solution to a proper range, stirring, standing for aging after complete reaction, and performing solid-liquid separation to obtain high-purity rare earth complex precipitate and filtrate;
4) And (3) recovering free ionic state rare earth precipitation: adding a precipitator into the filtrate obtained in the step 3), stopping adding the precipitator after the pH value of the solution rises to a set range, stirring, inoculating seed crystals, standing for aging after complete reaction, and performing solid-liquid separation to obtain rare earth precipitate.
2. The method for recovering rare earth from bioleaching solution by configurational transformation of rare earth complexes from precipitation according to claim 1, wherein in the step 2), the pH is suitably in the range of 5 to 8.
3. The method for recovering rare earth from bioleaching solution by configurational transformation of rare earth complex from precipitation according to claim 1, wherein in the step 2), the flocculant is an inorganic flocculant or an organic polymeric flocculant, wherein the inorganic flocculant is any one of polyaluminum sulfate PAS, polyaluminum chloride PAC, polyferric chloride PFC, polyferric sulfate PFS and polysilicic acid flocculant PSAA, and the organic polymeric flocculant is any one of polyacrylamide, styrene sulfonate, lignosulfonate and sodium polyacrylate.
4. The method for recovering rare earth from bioleaching solution by means of configurational transformation of rare earth complex from precipitation according to claim 1, wherein in the step 3), the configurational transformation agent of rare earth complex is a solution containing free rare earth, wherein the solution containing free rare earth is obtained by dissolving any one of rare earth salts, rare earth oxides, rare earth hydroxides, rare earth fluorides and rare earth concentrates, or is one of an extraction solution and a raffinate solution in a rare earth separation process; the concentration of the rare earth complex configuration transforming agent is 0.1-0.5 mol/L.
5. The method for recovering rare earth from bioleaching solution by configurational transformation of rare earth complexes from precipitation according to claim 4, wherein the rare earth salts are any one of rare earth nitrates, rare earth chlorides, rare earth carbonates, rare earth sulfates and rare earth oxalates.
6. The method for recovering rare earth from bioleaching solution by configurational transformation of rare earth complexes from precipitation according to claim 1, wherein in the step 3), when the ratio of rare earth: stopping adding the rare earth complex configuration transforming agent when the molar ratio of the ligand is 1.1-1.4; the pH is suitably in the range of 5 to 8; the stirring speed is 80-300 rpm, the reaction temperature is 20-50 ℃, the reaction time is 1-3 h, and the aging time is 2-8 h.
7. The method for recovering rare earth from bioleaching solution by configurational conversion of rare earth complexes from precipitation according to claim 1, wherein in the step 4), the precipitant is any one of carbonate, bicarbonate, alkali metal oxide and alkali metal hydroxide.
8. The method for recovering rare earth from bioleaching solution by configurational transformation of rare earth complexes from precipitation according to claim 7, wherein in the step 4), the precipitant is any one of sodium carbonate, ammonium bicarbonate, sodium bicarbonate, calcium oxide, calcium hydroxide, sodium oxide and sodium hydroxide.
9. The method for recovering rare earth from bioleaching solution by configurational transformation of rare earth complexes from precipitation according to claim 1, wherein in the step 4), the concentration of the precipitant is 1 to 5mol/L; stopping adding the precipitator when the pH value is 6-11; the reaction temperature is 20-50 ℃, the reaction time is 3-6 h, and the aging time is 4-6 h.
10. The method for recovering rare earth from bioleaching solution by configurational transformation and self-precipitation of rare earth complexes according to claim 1, wherein in the step 4), the seed crystal is any one of rare earth concentrate, rare earth oxide or rare earth carbonate with uniform particle size, and the seed crystal is added in an amount of 1-3%.
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