NL2035520B1 - A Method of Recovering Rare Earths from Rare Earth Bioleaching Solution by Solution Structure Transformation - Google Patents
A Method of Recovering Rare Earths from Rare Earth Bioleaching Solution by Solution Structure Transformation Download PDFInfo
- Publication number
- NL2035520B1 NL2035520B1 NL2035520A NL2035520A NL2035520B1 NL 2035520 B1 NL2035520 B1 NL 2035520B1 NL 2035520 A NL2035520 A NL 2035520A NL 2035520 A NL2035520 A NL 2035520A NL 2035520 B1 NL2035520 B1 NL 2035520B1
- Authority
- NL
- Netherlands
- Prior art keywords
- solution
- rare earth
- biological
- bioleaching
- earth metals
- Prior art date
Links
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 129
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 107
- 238000000034 method Methods 0.000 title claims abstract description 40
- 230000009466 transformation Effects 0.000 title abstract description 23
- 239000000047 product Substances 0.000 claims abstract description 26
- 239000002244 precipitate Substances 0.000 claims abstract description 24
- 239000000126 substance Substances 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims description 67
- 239000000706 filtrate Substances 0.000 claims description 53
- 239000003795 chemical substances by application Substances 0.000 claims description 29
- 238000002386 leaching Methods 0.000 claims description 28
- 239000007791 liquid phase Substances 0.000 claims description 22
- 239000007790 solid phase Substances 0.000 claims description 22
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- 239000012141 concentrate Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 10
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 9
- 239000000292 calcium oxide Substances 0.000 claims description 9
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 9
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 239000011575 calcium Substances 0.000 claims description 8
- 229910052791 calcium Inorganic materials 0.000 claims description 8
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 8
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 7
- 239000013078 crystal Substances 0.000 claims description 7
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical group [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 6
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 6
- 230000000996 additive effect Effects 0.000 claims description 6
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 6
- 239000001099 ammonium carbonate Substances 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 5
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 5
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 4
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims description 4
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 4
- 239000000920 calcium hydroxide Substances 0.000 claims description 4
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 229920002472 Starch Polymers 0.000 claims description 3
- 229920002401 polyacrylamide Polymers 0.000 claims description 3
- 239000008107 starch Substances 0.000 claims description 3
- 235000019698 starch Nutrition 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 230000003213 activating effect Effects 0.000 claims description 2
- 239000000203 mixture Substances 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
- 244000275012 Sesbania cannabina Species 0.000 claims 1
- 230000032683 aging Effects 0.000 claims 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 claims 1
- 159000000007 calcium salts Chemical class 0.000 claims 1
- 239000002904 solvent Substances 0.000 claims 1
- 238000001556 precipitation Methods 0.000 abstract description 64
- 230000008901 benefit Effects 0.000 abstract description 6
- 150000002500 ions Chemical class 0.000 abstract description 4
- 239000012535 impurity Substances 0.000 abstract description 3
- 230000004913 activation Effects 0.000 abstract description 2
- 230000002431 foraging effect Effects 0.000 description 17
- 239000007788 liquid Substances 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 9
- 238000004064 recycling Methods 0.000 description 9
- 230000008929 regeneration Effects 0.000 description 9
- 238000011069 regeneration method Methods 0.000 description 9
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 8
- 239000004411 aluminium Substances 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 8
- 238000001914 filtration Methods 0.000 description 8
- 238000011084 recovery Methods 0.000 description 8
- 230000008569 process Effects 0.000 description 7
- -1 bastnaesite Chemical compound 0.000 description 6
- 229910000019 calcium carbonate Inorganic materials 0.000 description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 description 4
- 239000011707 mineral Substances 0.000 description 4
- 235000010755 mineral Nutrition 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 241000219782 Sesbania Species 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 244000005700 microbiome Species 0.000 description 3
- 239000001164 aluminium sulphate Substances 0.000 description 2
- 235000011128 aluminium sulphate Nutrition 0.000 description 2
- 238000010668 complexation reaction Methods 0.000 description 2
- BUACSMWVFUNQET-UHFFFAOYSA-H dialuminum;trisulfate;hydrate Chemical compound O.[Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BUACSMWVFUNQET-UHFFFAOYSA-H 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000002207 metabolite Substances 0.000 description 2
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 2
- 239000002910 solid waste Substances 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 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
- 230000001276 controlling effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000010793 electronic waste Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000012761 high-performance material Substances 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 239000000463 material Substances 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
- 230000000813 microbial effect Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052590 monazite Inorganic materials 0.000 description 1
- 239000002245 particle Substances 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
- 238000010248 power generation Methods 0.000 description 1
- 238000010903 primary nucleation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000005067 remediation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000002364 soil amendment Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 238000009827 uniform distribution Methods 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
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/18—Extraction of metal compounds from ores or concentrates by wet processes with the aid of microorganisms or enzymes, e.g. bacteria or algae
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Organic Chemistry (AREA)
- Geology (AREA)
- Environmental & Geological Engineering (AREA)
- Metallurgy (AREA)
- Materials Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Inorganic Chemistry (AREA)
- Biochemistry (AREA)
- Biotechnology (AREA)
- Microbiology (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
Disclosed is a method of recovering rare earths from rare earth bioleaching solution by solution structure transformation. The invented method comprises the following steps: 1) Obtain a bioleaching solution rich in rare earths; 2) Activate the chemical coordination bonds; 3) Break down and reconstitute the chemical coordination bonds; 4) Precipitate and recover the rare earths. The present invention precipitates and recovers the rare earths from their complexes in high efficiency, by exploiting the principles of chemical coordination bond activation, breaking down and reconstitution, and by solution structure transformation-rare earth precipitation. It not only solves the technical difficulty that the rare earth in the bioleaching solution cannot be directly precipitated, but also can remove partial impurity ions at the transformation stage, and thus improve the rare earth precipitation efficiency and product quality. This invention has several advantages, such as high precipitation efficiency, low cost, environment-friendly, easy operation, high overall utilization rate of resources, etc., and thus is of great potential for industrial application.
Description
A Method of Recovering Rare Earths from Rare Earth Bioleaching Solution by Solution
Structure Transformation
The present invention is established for the field of mineral processing and hydrometallurgy, and specifically involves a method of recovering rare earths from rare earth bioleaching solution by solution structure transformation.
Prior Art
Rare earth elements (REE) are indispensable key raw materials in numerous high-tech areas such as power generation and storage, aerospace, defence military, electronic information, medical health and high-performance materials, etc. Rare earth elements are strategically key metal resources, considered as "mother of all new materials". The sources of rare earths mainly include mineral rare earth, ion type rare earth ore and solid wastes. The mineral rare earth source includes monazite, bastnaesite, xenotime and the like. The ion type rare earth ore is also known as the weathered crust elution-deposited rare earth ore. And the solid wastes include tailings, smelter slags, electronic wastes, spent catalysts and the like. In recent years, one serious challenge faced by the rare earth industry is to overcome the environmental pollution and ecological destruction problems in the development and utilization process of rare earths, and to achieve clean and efficient utilization of rare earths.
As the environmental protection standards rise higher and higher, numerous deficiencies of the conventional rare earth extraction techniques have been gradually exposed. For its advantages of low carbon, environment-friendly and low cost, etc., biohydrometallurgical {bioleaching or bioextraction) has been considered one of the most important directions for future clean and efficient extraction of rare earths, compared to chemical extraction techniques.
Bioleaching leaches out the rare earth elements mainly by the direction actions of microorganisms and the indirectly actions of microbial metabolites. And the rare earth elements are further recovered from the leaching solution, thereby achieving the clean and efficient utilization of rare earths. In contrast to chemical leaching, bioleaching typically operates at conditions of normal temperature and normal pressure. The required conditions of leaching process are mild, with low energy consumption, safe and environment friendly. The process can contributes to environmental pollutant degradation, soil amendment, and ecological remediation. During the processes of microorganism growth, metabolism and leaching, CO: can be efficiently absorbed and pinned down, contributing to "carbon peaking, carbon neutrality". Therefore, it is of great interest to develop biohydrometallurgical techniques for rare earths.
However, during the bioleaching process, the leaching of the rare earths is achieved by microorganisms and their various metabolites through the chemical reactions such as bonding/complexation. By leaching, the rare earth elements are transferred into the bioleaching solution, but they mainly exist in the form of various types of rare earth coordination compounds (complexes), with extremely complicated chemical status. Due to the large bonding energy of the coardination bond, these rare earth complexes are very stable. It is difficult to effectively precipitate and gather rare earths out of the bioleaching solution with conventional precipitants and precipitation methods, which is an important bottleneck and challenge limiting the industrial applications of rare earth biohydrometallurgical techniques.
The present invention provides a method of efficiently recover rare earth elements from rare earth bioleaching solutions through solution structure transformation. This method ensures the precipitation rate of rare earths while also reduces the content of impurity elements, thereby obtaining a rare earth concentrate product of high quality.
The method, provided by this invention, of recovering rare earths from a rare earth bioleaching solution through solution structure transformation comprises the following steps: 1) obtaining a bioleaching solution rich in rare earths; 2) adding H* into the bioleaching solution rich in rare earths of Step 1), so that the pH value of the solution can be adjusted to the specified range, then stirring the bioleaching solution to facilitate the reactions of activating the chemical coordination bonds of the rare earth complexes in the bioleaching solution; 3) adding a solution of transformation agent into the bioleaching solution at the end of Step 2), when the pH value of the bioleaching solution reaches the specified range, stopping the addition of the transformation agent solution, stirring the bioleaching solution to facilitate the reactions, and the transformed bioleaching solution is obtained; 4) allowing the transformed bioleaching solution in Step 3) to stand to separate the solid and liquid phases, so that a clear filtrate solution is obtained; 5) adding a solution of precipitant into the clear filtrate solution obtained at the end of step 4) until the pH value rises to a set range, and then adding seed crystals into the filtrate solution and stirring it to facilitate the reactions, and after the reactions are finished, allowing the filtrate solution stand for aging to separate the solid and liquid phases, dehydrate the precipitates to dry them, and obtaining the rare earth product, the said solution of precipitant being prepared from precipitant and water.
Preferably, in Step 2), the agent adding H* is at least one of sulfuric acid, hydrochloric acid and nitric acid;
Preferably, in said Step 2), the said pH value is set to be 2 - 5. The said stirring of facilitating the reactions is carried out at 30 - 55°C and the reaction time period is 1.5 - 3.5 h.
Preferably, in Step 3), the solution transformation agent is a composition of a calcium- containing compound and an additive, wherein the calcium-containing compound is any one of a calcium-containing oxide, a calcium-containing hydroxide and a calcium-containing inorganic salt.
And the additive is at least one of polyacrylamide, starch, sesbania gum, polyaluminium chloride and polyaluminium sulphate. In the said solution transformation agent, the mass ratio of the calcium-containing compound to the additive is 5: 1 - 10:1.
Preferably, in said Step 3), the solution transformation agent is added in at a constant rate.
The pH value is raised to 3 - 6. The said stirring of facilitating the reactions is carried out at 20 - 50°C and the reaction time period is 2 - 4 h.
Preferably, in said Step 4), the standing time period is 3 - 4 h.
Preferably, in said Step 5),the molar concentration of the precipitant solution is 1 - 3 mol/l;
The pH value is raised to 7.5 - 10.5; The said stirring of facilitating the reactions is carried out at 20 - 50°C. The reaction time period is 2 - 3 h, and the standing time period for aging is 4 - 10 h.
Preferably, in said Step 5), the precipitant is any one of carbonate, bicarbonate, alkali metal oxide or alkali metal hydroxide.
Further preferably, in step 5), the said carbonate is sodium carbonate ; The said bicarbonate is ammonium bicarbonate or sodium bicarbonate ; The said alkali metal oxide is calcium oxide or sodium oxide ; The said alkali metal hydroxide is calcium hydroxide or sodium hydroxide.
Preferably, in said Step 5), the seed crystals are rare earth concentrate with uniform size, and they are added in an amount of 1% - 3% by weight of the rare earth precipitate.
The present invention works as follows:
The present invention first adds H* into the bioleaching solution rich in rare earth complexes.
Through the competing coordination actions between H* and H20 with the rare earth complexes, the coordination bonds of rare earth complexes are activated at a suitable temperature. And then, a transformation agent more reactive with the complex anion and with a higher complexation stability constant is added into the bioleaching solution, leading to the breaking down and reconstitution of the coordination bonds. The rare earth complexes are therefore converted to free rare earths or to be with broken valence bond structure. Through such structural reconstitution of coordination bonds, the bioleaching solution transformation is achieved; The solid and liquid phases of the transformed bioleaching solution are separated. The filtrate is transferred to a precipitation tank. And then a precipitant is added to the filtrate, while a small amount of seed crystals are added into the filtrate to suppress primary nucleation and reduce solution supersaturation. In this way, the crystallization process is regulated to obtain rare earth precipitation product with large particle size and uniform distribution. After the precipitation is finished, the solid and liquid phases are separated, and the solid items are dried by dehydration to obtain high quality rare earth product, and the remained liquid can be used for the regeneration and recycling of leaching agent.
Beneficial Advantages of the Present Invention: 1) The present invention utilizes the principles of activation, breaking down and reconstitution of the coordination bonds to precipitate and recover rare earths out of the bioleaching solution through solution transformation-rare earth precipitation. The present invention is highly efficient, with low cost, and capable of producing a crystalline rare earth precipitate that can be easily obtained by solid-liquid separation; 2) The present invention can remove partial impurity ions at the solution transformation stage, which is advantageous for improving rare earth precipitation efficiency and product quality; 3) In the process of the present invention, after the precipitation and recovery of rare earths is completed, the bioleaching agent can be regenerated and recycled.
This can improve the overall utilization rate of resources and economic benefits. 4) Multiple precipitants are optional in the precipitation stage in the present invention, which breaks through the limitation in the conventional methods that only the precipitants with same cationic as in the leaching agent can be used. By controlling the precipitation conditions and the addition of seed crystals, the high quality rare earth product can be produced; 5) The present invention also has advantages such as green environmental friendliness, high product quality, easy operation, high comprehensive utilization of resources, and good industrial application prospects. The present invention has several advantages, such as environment-friendly, high product quality, easy operation, high overall utilization rate of resources, etc., and thus is of great potential for industrial application.
In order to make the technical solution of the present invention easy to understand, the present invention will now be further described with reference to application cases. It should be noted that the specific application cases described herein are merely illustrative of the present invention and are not intended to limit the present invention.
The leaching solutions obtained in the below application cases and comparative cases are produced mainly by leaching rare earth minerals or secondary resources containing rare earths with the method disclosed in Chinese Patent CN 113293287 A.
Application Case 1
A bioleaching solution rich in rare earths was obtained ; A small amount of sulfuric acid was added to this bioleaching solution, and the pH value of this bioleaching solution was adjusted to 2.0. The this bioleaching solution was stirred to facilitate the reactions at 35°C for 2.5 h, and then a solution of transformation agent was prepared by mixing calcium carbonate and polyacrylamide in ratio of 5:1 by mass, and added into the bioleaching solution until the pH value of the latter solution rose to 3.0. The bioleaching solution was stirred to facilitate the reactions at 35°C for 3.5 h, and the solution was stood for 4 h to separate the solid and liquid phases. The clear filtrate liquid was transferred to a precipitation tank. A bicarbonate solution with a concentration of 1.8 mol/l was prepared and added into the clear filtrate liquid at a constant rate. When the pH value of the filtrate rose to 8.5, the addition of bicarbonate solution was stopped. The filtrate solution was stirred to facilitate the reactions at 40°C. Seeds of 2% rare earth concentrate were added, and the reactions proceeded for 3 h. The filtrate solution was then stood for aging for 6 h. By then,
the solid and liquid phases were separated. By filtering, the rare earth precipitates were obtained.
And by further dehydrating the rare earth precipitates, the rare earth product was obtained. The remainder solution can be used in the regeneration and recycling of the leaching agent. The final precipitation rate (recovery rate) of the rare earth was 98.5%, and a high quality rare earth 5 carbonate concentrate product was obtained.
The concentrations of rare earth elements and aluminium in the bioleaching solution before and after precipitation of this Application Case are shown in Table 1.
Table 1 Concentrations of rare earth element and aluminium in bioleaching solution before and after the precipitation of Application Case 1 ‘Elements Y La Ce Pr Nd Sm Eu Gd
Concentration before precipitation (mg/) 111 196 50.5 496 1748 39.2 3.7 36.7
Concentration after orecipiation (mg/) 18 33 054 083 0.29 34 032 035 “Elements TD Dy Ho _ Er Tm Yb Lu Al
Concentration before orecipitation (mg/) 5.2 243 43 10.6 0.76 6.5 0.74 320.2
Concentration after orecipitation (mg) 0.57 0.76 043 0.03 0.11 1.2 0.16 218.8
Comparative Case 1
A bioleaching solution rich in rare earths was obtained. A conventional precipitation method was performed, in which an ammonium bicarbonate solution of 1.8 mol/l was added into this bioleaching solution at constant rate, until the pH value of the bioleaching solution rose to 8.5.
The reactions proceeded at 40°C for 3 h. The bioleaching solution was stood for aging for 6 h.
The final precipitation rate (recovery rate) of the rare earth was only 1.2%.
Application Case 2
A bioleaching solution rich in rare earths was obtained. A small amount of nitric acid was added to this bioleaching solution, and the pH value of this bioleaching solution was adjusted to 2.5. This bioleaching solution was stirred to facilitate the reactions at 30°C for 3.5 h. And then calcium oxide and sesbania gum were mixed homogeneously in a ratio of 8:1 by mass as the solution of transformation agent, which was added to the bioleaching solution until the pH value of the latter solution rose to 3.0.The solution was then stirred to facilitate the reactions at 45°C for 2.5 h, and then was stood for 3 h to separate the solid and liquid phases. The clear filtrate liquid was transferred to a precipitation tank. A calcium oxide solution (as OH) with a concentration of 1.0 mol/l was prepared and added into the clear filtrate solution at a constant rate. When the pH value of the filtrate solution rose to 9.5, the addition of the calcium oxide solution was stopped.
The filtrate solution was stirred to facilitate the reactions at 35°C. Seeds of 1.5% rare earth concentrate were added, and the reactions proceeded for 2 h. The filtrate solution was then stood for aging for 6 h. By then, the solid and liquid phases were separated. By filtering, the rare earth precipitates were obtained. And by further dehydrating the rare earth precipitates, the rare earth product was obtained. The remainder solution can be used in the regeneration and recycling of the leaching agent. The final precipitation rate (recovery rate) of the rare earth was 99.1%, and a high-quality rare earth oxide product was obtained.
Comparative Case 2
A bioleaching solution rich in rare earths was obtained. A conventional precipitation method was performed, in which a 1.0 mol/l calcium oxide solution (as OH) was added to the bioleaching solution at a constant rate until the pH value of the bioleaching solution rose to 9.5. The reactions proceeded at 35°C for 3 h. The bioleaching solution was then stood for aging for 6 h. The final precipitation rate of the rare earth was only 2.8%.
Application Case 3
A bioleaching solution rich in rare earths was obtained. A small amount of hydrochloric acid was added to this bioleaching solution, and the pH value of this bioleaching solution was adjusted to 3.0. The bioleaching solution was stirred to facilitate the reactions at 50°C for 1.5 h. Then calcium oxide and polyaluminium chloride were mixed homogeneously in a ratio of 10:1 by mass as the solution of transformation agent, which was added to the bioleaching solution until the pH value of the latter solution pH rose to 3.5. The bioleaching solution was then stirred to facilitate the reactions at 45°C for 2.5 h, and then was stood for 3 h to separate the solid and liquid phases.
The clear filtrate liquid was transferred to a precipitation tank. A solution of sodium hydroxide with a concentration of 2.5 mol/l was prepared and added to the clear filtrate liquid at a constant rate.
When the pH value of the filtrate rose to 7.5, the addition of sodium hydroxide solution was stopped. The filtrate solution was then stirred to facilitate the reactions at 30°C. Seeds of 2% of rare earth concentrate were added and the reactions proceeded for 2 h. The filtrate solution was then stood for aging for 4.5 h. By then, the solid and liquid phases were separated. By filtering, the rare earth precipitates were obtained. And by further dehydrating the rare earth precipitates, the rare earth product was obtained. The remainder solution can be used in the regeneration and recycling of the leaching agent. The final precipitation rate (recovery rate) of the rare earth was 97.1%, and a high-quality rare earth oxide product was obtained.
The concentrations of rare earth elements and aluminium in the bioleaching solution before and after precipitation of this Application Case are shown in Table 2.
Table 2 Concentrations of rare earth element and aluminium in bioleaching solution before and after the precipitation of Application Case 3 “Elements NY La Ce Pr Nd Sm Eu Gd
Concentration before precipitation (mg/l) 102 206 459 59.5 175 41 35 407
Concentration after precipitation (mg/l) 0.88 5.3 034 0.23 229 14 0.02 0.15 “Elements Tb Dy Ho Er Tm Yb Lu Al
Concentration before precipitation (mg/l) 8.2 183 23 92 055 55 1.14 3336
Concentration after precipitation (mg/l) 0.07 0.55 0.13 0.03 0 1.2 0.02 292.8
Comparative Case 3
A bioleaching solution rich in rare earths was obtained. A conventional precipitation method was performed, in which a 2.5 mol/l sodium hydroxide solution was added to the bioleaching solution at a constant rate until the pH of the bioleaching solution rose to 7.5. The reactions proceeded at 30°Cfor 3 h. The bioleaching solution was stood for aging for 6 h. The final precipitation rate of the rare earth was only 1.6%.
Application Case 4
A bioleaching solution rich in rare earths was obtained. A small amount of sulfuric acid was added to this bioleaching solution, and the pH value of this bioleaching solution was adjusted 4.0.
The bioleaching solution was stirred to facilitate the reactions at 55°C for 1.5 h. Then, calcium oxide and polymerized aluminium sulphate were mixed homogeneously in a ratio of 6:1 by mass as the solution of transformation agent, which was added to the bioleaching solution until the pH value of the latter solution rose to 5.0. The bioleaching solution was then stirred to facilitate the reactions at 45°C for 2.5 h, and then was stood for 3 h to separate the solid and liquid phases.
The clear filtrate liquid was transferred to a precipitation tank. A sodium bicarbonate solution with a concentration of 2.0 mol/l was prepared and added to the clear filtrate liquid at a constant rate until the pH value of the filtrate rose to 8.5. The filtrate solution was then stirred to facilitate the reactions at 25°C. Seeds of 1% of rare earth concentrate were added and the reactions proceeded for 2 h, and then the filtrate solution was stood for aging for 5.5 h. By then, the solid and liquid phases were separated. By filtering, the rare earth precipitates were obtained. And by further dehydrating the rare earth precipitates, the rare earth product was obtained. The remainder solution can be used in the regeneration and recycling of the leaching agent. The final precipitation rate (recovery rate) of the rare earth was 99.1%, and a high quality rare earth carbonate product was obtained.
Comparative Case 4
A bioleaching solution rich in rare earths was obtained. A conventional precipitation method was performed, in which a 2.0 mol/l sodium bicarbonate solution was added to the bioleaching solution at a constant rate until the pH value of the bioleaching solution rose to 8.5. The reactions proceeded at 25°C for 3 h. The bioleaching solution was stood for aging for 6 h. The final precipitation rate of the rare earth was only 1.8%.
Application Case 5
A bioleaching solution rich in rare earths was obtained. A small amount of hydrochloric acid was added to this bioleaching solution. And the pH value of this bioleaching solution was adjusted to 5.0. This bioleaching solution was stirred to facilitated the reactions at 35°C for 3.0 h. Then, calcium hydroxide and starch were mixed homogeneously in a ratio of 7:1 by mass as the solution of transformation agent, which was added to the bioleaching solution until pH value of the latter solution rose to 8.0. The bioleaching solution was then stirred to facilitate the reactions at 20°C for 2.5 h, and was further stood for 3 h to separate the solid and liquid phases. The clear filtrate liquid was transferred to a precipitate tank. A sodium carbonate solution with a concentration of 1.0 mol/l was prepared and added to the clear filtrate liquid at a constant rate until the pH value of the filtrate rose to 10.0. The filtrate solution was stirred to facilitate the reactions at 45°C. Seeds of 1.5% of rare earth concentrate were added and the reactions proceeded for 2 h, and then the filtrate solution was stood for aging for 5.5 h. By then, the solid and liquid phases were separated.
By filtering, the rare earth precipitates were obtained. And by further dehydrating the rare earth precipitates, the rare earth product was obtained. The remainder solution can be used in the regeneration and recycling of the leaching agent. The final precipitation rate of rare earth was 99.1%, and a high quality rare earth carbonate product was obtained.
The concentrations of rare earth elements and aluminium in the bioleaching solution before and after precipitation of this Application Case are shown in Table 3.
Table 3 Concentrations of rare earth element and aluminium in bioleaching solution before and after the precipitation of Application Case 5 ‘Elements Y La Ce Pr Nd Sm Eu Gd
Concentration before precipitation (mg/l) 122 190 60 445 1825 424 22 41
Concentration after precipitation (mg/l) 1.02 23 04 015 1.89 0.94 0 0.22 “Elements Tb Dy Ho Er Tm Yb Lu Al
Concentration before precipitation (mg/l) 6.5 243 6.2 89 102 82 0.55 306
Concentration after precipitation (mg/l 0 065 0.22 0 0.06 0.82 0 275
Comparative Case 5
A bioleaching solution rich in rare earths was obtained. A conventional precipitation method was performed, in which a 1.0 mol/l sodium carbonate solution was added to the bioleaching solution at a constant rate. When the pH value of the bioleaching solution rose to 10.0, the addition of sodium carbonate solution was stopped. The reactions proceeded at 45°C for 3h and then the bioleaching solution was stood for aging for 6 h. The final precipitation rate of the rare earth was only 1.6%.
Application Case 6
A bioleaching solution rich in rare earths was obtained. A small amount of nitric acid to this bioleaching solution, The pH value of this bioleaching solution was adjusted to 2.5. The bioleaching solution was stirred to facilitate the reactions at 30°C for 3.0 h. And then calcium carbonate and polymerized aluminium sulphate was mixed homogeneously in a ratio of 5:1 by mass as the solution of transformation agent, which was added to the bioleaching solution until the pH value of the latter solution rose to 5.0. Then, the bioleaching solution was further stirred to facilitate the reactions at 45°C for 2.5 h. Next, the bioleaching solution was further stood for 3 h to separate the solid and liquid phases. The clear filtrate liquid was transferred to a precipitation tank. A ammonium bicarbonate solution with a concentration of 1.5 mol/l was prepared and added into the clear filtrate liquid at a constant rate, until the pH value of the filtrate rose to 9.0. The filtrate solution was then stirred to facilitate the reactions at 50°C. Seeds of 1.0% of rare earth concentrate were added and the reactions proceeded for 2 h. The filtrate solution was then stood for aging for 8 h. By then, the solid and liquid phases were separated. By filtering, the rare earth precipitates were obtained. And by further dehydrating the rare earth precipitates, the rare earth product was obtained. The remainder solution can be used in the regeneration and recycling of the leaching agent. The final precipitation rate of rare earth was 98.9%, and a high quality rare earth carbonate product was obtained.
Comparative Case 6
A bioleaching solution rich in rare earths was obtained. A conventional precipitation method was performed, in which a 1.5 mol/l ammonium bicarbonate solution was added to the bioleaching solution at a constant rate. When the pH value of the bioleaching solution rose to 9.0, the addition of ammonium bicarbonate solution was stopped. The reactions proceeded at 50°C for 2 h and then the bioleaching solution was stood for aging for 8 h. The final precipitation of the rare earth was only 5.6%.
Application Case 7
A bioleaching solution rich in rare earths was obtained. A small amount of sulfuric acid to the bioleaching solution and the pH value of the bioleaching solution was adjusted to 2.5. The bioleaching solution was stirred at 35°C for 3.0 h ‚and then calcium carbonate and sesbania gum were mixed homogeneously in a ratio of 6:1 by mass as the solution of transformation agent, which was added to the bioleaching solution until the pH value of the latter solution rose to 3.5.
The bioleaching solution was stirred to facilitate the reactions at 25°C for 2.5 h. The bioleaching solution was then stood for 3 h to separate the solid and liquid phases. The clear filtrate liquid was transferred to a precipitation tank. A sodium carbonate solution with a concentration of 3.0 mol/l was prepared and added to the clear filtrate liquid at a constant rate until the pH value of the filtrate rose to 10.5. The filtrate solution was then stirred to facilitate the reactions at 20°C. Seeds of 1.0% rare earth concentrate, was added to the filtrate solution, and the reactions proceeded for 4 h. The filtrate solution was then stood for aging for 10 h. By then, the solid and liquid phases were separated. By filtering, the rare earth precipitates were obtained. And by further dehydrating the rare earth precipitates, the rare earth product was obtained. The remainder solution can be used in the regeneration and recycling of the leaching agent. The final precipitation rate (recovery rate) of the rare earth was 99.1%, and a high-quality rare earth carbonate product was obtained.
Comparative Case 7
A bioleaching solution rich in rare earths was obtained. A conventional precipitation method was performed, in which a 3.0 mol/l sodium carbonate solution was added to the bioleaching solution at a constant rate. When the pH value of the bioleaching solution rose to 10.5, the addition of sodium carbonate solution was stopped. The reactions proceeded at 20°C for 3 h and then the bioleaching solution was stood for aging for 10 h. The final precipitation rate of the rare earth was only 3.7%.
Application Case 8
A bioleaching solution rich in rare earths was obtained, and a small amount of sulfuric acid was added to this bioleaching solution, so that the pH value of this bioleaching solution was adjusted to 2.5. The bioleaching solution was stirred to facilitate the reactions at 30°C for 3.0 h.
Then, calcium carbonate and polyaluminium chloride were mixed in a mass ratio of 8:1 as the solution of transformation agent, and added to the bioleaching solution until the pH value of the latter solution rose to 4.5. The bioleaching solution was further stirred to facilitate the reactions at 50°C for 2 h, so that the solid and liquid phases were separated. Next, the bioleaching solution was stood for 2 h. The obtained clear filtrate solution was transferred to a precipitation tank. A solution of sadium bicarbonate with a concentration of 1.5 mol/l was prepared and added to the clear filtrate solution at a constant rate until the pH value of the filtrate solution rose to 8.5. The filtrate solution was stirred to facilitate the reactions at 20°C. Seed crystals of 1.0% rare earth concentrate were added to the filtrate solution. The reactions proceeded for 2.5 hours, and then the filtrate solution was stood for 10 hours for the solid and liquid phases to separate. The rare earth precipitates were obtained by filtering, which were further dehydrated and dried to obtain the rare earth product. The remainder solution can be used in the regeneration and recycling of the leaching agent. The final recovery rate of the rare earth was 98.4%, and a high-quality rare earth carbonate product was obtained.
The concentrations of rare earth elements and aluminium in the bioleaching solution before and after precipitation of this Application Case are shown in Table 4.
Table 4 Concentrations of rare earth element and aluminium in bioleaching solution before and after the precipitation of Application Case 8 “Elements ~~ Y La Ce Pr Nd Sm Eu Gd
Concentration before precipitation (mg/l) 99 201 58 44 1901 374 1.9 36.7
Concentration after precipitation (mg/l) 20 35 094 023 208 044 0 0.4 “Elements TD Dy Ho Er Tm Yb Lu Al
Concentration before precipitation (mg/l) 4.9 28 8.8 101 092 59 064 3459
Concentration after precipitation (mg/l) 0.06 0.21 0.34 0.09 0 042 0.04 2952
Comparative Case 8
A bioleaching solution rich in rare earths was obtained. A conventional precipitation method was performed, in which an sodium bicarbonate solution of 1.5 mol/l was added into this bioleaching solution at a constant rate, until the pH value of the bioleaching solution rose to 8.5.
The reactions proceeded at 20°C for 2.5 h. The bioleaching solution was stood for aging for 10 h.
The final precipitation rate of the rare earth was only 1.2%.
Claims (10)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202211362411.6A CN115679131B (en) | 2022-11-02 | 2022-11-02 | Method for recovering rare earth from rare earth bioleaching solution through solution structure transformation |
Publications (2)
Publication Number | Publication Date |
---|---|
NL2035520A NL2035520A (en) | 2024-05-24 |
NL2035520B1 true NL2035520B1 (en) | 2024-06-06 |
Family
ID=85048941
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
NL2035520A NL2035520B1 (en) | 2022-11-02 | 2023-08-01 | A Method of Recovering Rare Earths from Rare Earth Bioleaching Solution by Solution Structure Transformation |
Country Status (2)
Country | Link |
---|---|
CN (1) | CN115679131B (en) |
NL (1) | NL2035520B1 (en) |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN100457928C (en) * | 2007-03-22 | 2009-02-04 | 广东富远稀土新材料股份有限公司 | Carbonate deposition method of crystal type heavy rare earth |
CN101475202A (en) * | 2008-10-28 | 2009-07-08 | 黄日平 | Rare earth solution precipitating agent production process using calcium oxide |
EP2813585A1 (en) * | 2013-06-14 | 2014-12-17 | B.R.A.I.N. Biotechnology Research And Information Network AG | Process of isolating rare earth elements |
RU2537634C1 (en) * | 2013-06-20 | 2015-01-10 | Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Московский государственный технический университет имени Н.Э. Баумана" (МГТУ им. Н.Э. Баумана) | Method of extracting rare earth and noble metals from ash and slag |
CN104098492B (en) * | 2014-07-29 | 2016-06-29 | 景德镇陶瓷大学 | A kind of method utilizing homogeneous rare earth compounding to prepare strong reducing property thiourea dioxide when room temperature weak base |
CN109097565B (en) * | 2018-08-03 | 2019-11-01 | 江西理工大学 | A method of the high-efficiency cleaning Extraction of rare earth from ion adsorption type rare earth ore |
CN113025817B (en) * | 2021-03-09 | 2021-12-31 | 中南大学 | Method for extracting weathering crust elution-deposited rare earth ore |
-
2022
- 2022-11-02 CN CN202211362411.6A patent/CN115679131B/en active Active
-
2023
- 2023-08-01 NL NL2035520A patent/NL2035520B1/en active
Also Published As
Publication number | Publication date |
---|---|
NL2035520A (en) | 2024-05-24 |
CN115679131A (en) | 2023-02-03 |
CN115679131B (en) | 2024-03-01 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN102206755B (en) | Method for separating and recovering valuable elements from neodymium-iron-boron wastes | |
CN111842411B (en) | Red mud full-recycling method | |
CN109777960B (en) | Method for separating and recovering lithium and aluminum from fly ash | |
CN112939046A (en) | Comprehensive recycling method of coal-based solid waste | |
NL2033897B1 (en) | Method for synchronously leaching rare earth, fluorine and lithium acid leaching solution from rare earth electrolytic molten salt slag | |
CN113292057B (en) | Recovery method of waste lithium iron phosphate battery | |
CN112981100B (en) | Comprehensive utilization method of red mud by full wet method | |
CN109336147B (en) | Method for producing alumina by using industrial solid waste rich in alumina | |
CN113120938B (en) | Method for preparing calcium fluoride by using fluorine-containing wastewater | |
CN111690810B (en) | Red mud recycling-soil treatment method | |
CN109721081B (en) | Method for extracting lithium from lithium-rich fly ash alkaline mother liquor | |
CN110479207A (en) | A kind of method that the alkali fusion activation of electrolytic manganese residues microwave prepares high adsorption value fluorite | |
CN109777972B (en) | Method for extracting scandium from coal gangue through concentrated sulfuric acid activated leaching | |
NL2035520B1 (en) | A Method of Recovering Rare Earths from Rare Earth Bioleaching Solution by Solution Structure Transformation | |
CN112813284A (en) | Method for extracting aluminum from aluminum-containing mineral | |
CN114107706B (en) | Method for purifying and removing impurities from ion type rare earth ore leaching solution | |
CN113430377B (en) | Method for comprehensively extracting valuable components from coal gangue | |
CN115505740A (en) | Resource method for treating red mud by adopting nitrate wastewater | |
CN114672644A (en) | Method for recovering gallium from brown corundum dust collecting material | |
CN113735179A (en) | Method for preparing high-purity ferric sulfate by using ferro-manganese | |
CN108821303B (en) | Comprehensive utilization method of boric sludge | |
CN101880771A (en) | Method for recovering magnesium from magnesium-contained waste liquid | |
CN114477292B (en) | Method for directly preparing ammonium metatungstate from tungsten mineral | |
CN113336252B (en) | Method for removing calcium from pickle liquor of coal-based solid waste | |
CN114107659B (en) | Complexing impurity removal method for ion type rare earth ore leaching solution |