CN110607440B - In-situ leaching method for ionic rare earth ore - Google Patents
In-situ leaching method for ionic rare earth ore Download PDFInfo
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- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 106
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 97
- 238000002386 leaching Methods 0.000 title claims abstract description 73
- 238000000034 method Methods 0.000 title claims abstract description 26
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 23
- 239000000243 solution Substances 0.000 claims abstract description 51
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 36
- 238000003756 stirring Methods 0.000 claims abstract description 32
- 239000000706 filtrate Substances 0.000 claims abstract description 28
- 239000007787 solid Substances 0.000 claims abstract description 27
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims abstract description 26
- 239000003463 adsorbent Substances 0.000 claims abstract description 26
- 229910000514 dolomite Inorganic materials 0.000 claims abstract description 24
- 239000010459 dolomite Substances 0.000 claims abstract description 24
- 238000002156 mixing Methods 0.000 claims abstract description 22
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims abstract description 13
- 235000017557 sodium bicarbonate Nutrition 0.000 claims abstract description 13
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 12
- 238000001914 filtration Methods 0.000 claims abstract description 12
- 239000002002 slurry Substances 0.000 claims abstract description 12
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 11
- 239000002244 precipitate Substances 0.000 claims abstract description 11
- 239000012535 impurity Substances 0.000 claims abstract description 8
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims abstract description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000000605 extraction Methods 0.000 claims abstract description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 7
- 238000002791 soaking Methods 0.000 claims abstract description 7
- 238000009777 vacuum freeze-drying Methods 0.000 claims abstract description 7
- 238000001354 calcination Methods 0.000 claims abstract description 6
- 238000002347 injection Methods 0.000 claims abstract description 6
- 239000007924 injection Substances 0.000 claims abstract description 6
- -1 rare earth nitrate Chemical class 0.000 claims abstract description 6
- 238000000926 separation method Methods 0.000 claims abstract description 6
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 20
- RAZLJUXJEOEYAM-UHFFFAOYSA-N 2-[bis[2-(2,6-dioxomorpholin-4-yl)ethyl]azaniumyl]acetate Chemical compound C1C(=O)OC(=O)CN1CCN(CC(=O)O)CCN1CC(=O)OC(=O)C1 RAZLJUXJEOEYAM-UHFFFAOYSA-N 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 10
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 10
- 239000000725 suspension Substances 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- FSVCELGFZIQNCK-UHFFFAOYSA-N N,N-bis(2-hydroxyethyl)glycine Chemical compound OCCN(CCO)CC(O)=O FSVCELGFZIQNCK-UHFFFAOYSA-N 0.000 claims description 6
- 239000004094 surface-active agent Substances 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 239000013335 mesoporous material Substances 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- 238000007873 sieving Methods 0.000 claims description 5
- 239000006228 supernatant Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 4
- 238000005065 mining Methods 0.000 abstract description 6
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 abstract description 5
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052921 ammonium sulfate Inorganic materials 0.000 abstract description 4
- 235000011130 ammonium sulphate Nutrition 0.000 abstract description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 description 15
- 239000011707 mineral Substances 0.000 description 15
- 235000010755 mineral Nutrition 0.000 description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 150000003863 ammonium salts Chemical class 0.000 description 3
- 239000004927 clay Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002734 clay mineral Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 239000007785 strong electrolyte Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
- C22B3/08—Sulfuric acid, other sulfurated acids or salts thereof
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/22—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition
-
- 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
-
- 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
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- Engineering & Computer Science (AREA)
- Geology (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Environmental & Geological Engineering (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Geochemistry & Mineralogy (AREA)
- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses an in-situ leaching method of ionic rare earth ore, which comprises the following steps: (1) preparing an ore leaching agent: crushing dolomite, mixing the crushed dolomite with sulfuric acid to prepare slurry A, and mixing the slurry A with an auxiliary agent to obtain an ore leaching agent; (2) in-situ leaching: injecting an ore leaching agent into the injection point, and collecting leachate; (3) removing impurities from the rare earth leachate: adding sodium bicarbonate solution into the leaching solution, and filtering to remove precipitate to obtain filtrate; (4) rare earth extraction: adding a rare earth adsorbent into the filtrate, stirring, standing and filtering to obtain a solid; then soaking and desorbing the solid nitric acid solution, performing centrifugal separation to obtain a rare earth nitrate solution, and then performing vacuum freeze drying and calcination on the rare earth nitrate solution to obtain the nano rare earth oxide. The invention can not only improve the mining efficiency of the rare earth ore, but also solve the problem of ammonia nitrogen pollution without using ammonium sulfate as an ore leaching agent.
Description
Technical Field
The invention belongs to the technical field of mineral processing engineering, and particularly relates to an in-situ leaching method of ionic rare earth ore.
Background
Rare Earth (Rare Earth) is a general name of seventeen metal elements including lanthanide elements, scandium and yttrium in a chemical periodic table, and 250 Rare Earth ores exist in nature. The rare earth element is widely used in agriculture, aerospace, electronic manufacturing industry, transportation industry, medical industry and the like, has important significance for high and new technology and economy, and is called industrial gold. China is the first rare earth resource country in the world and is called rare earth kingdom. The proven rare earth resource reserves in China are 4300 ten thousand tons, which account for 43 percent of the total reserves in the world, and the annual output of the rare earth elements in China already accounts for more than 95 percent of the total output in the world.
The Ion type rare earth ore, namely Ion adsorbed rare earth ore (Ion adsorbed deposite), is a novel rare earth ore specific to China. The "ion adsorption" is a method in which rare earth elements are adsorbed in clay minerals in an ionic state, without being present as compounds. The rare earth is easy to be transferred into solution by strong electrolyte exchange, and does not need technological processes of crushing, ore dressing and the like, but can be directly leached to obtain mixed rare earth oxide, so that the ore has the characteristics of high content of heavy rare earth elements, large economic content, low grade, large coverage, suitability for manual and semi-mechanical mining in hilly lands, simple mining and leaching processes and the like. At present, ammonium sulfate is mostly used as an ore leaching agent for mining and leaching of ionic rare earth ores, but the use of ammonium salts such as ammonium sulfate causes ammonia nitrogen pollution, so that mountains, water bodies and surrounding environments in rare earth ore areas are seriously damaged. With the enhancement of the national environmental protection management, the process for leaching rare earth by using ammonium salt can not meet the requirement of environmental protection, and a new rare earth leaching process without environmental pollution needs to be developed, so that the green and environmental-friendly exploitation of ionic rare earth is realized, and good economic benefit and social benefit are obtained.
Disclosure of Invention
Aiming at the defects, the invention provides an in-situ leaching method of the ionic rare earth ore, which can improve the mining efficiency of the rare earth ore, does not use ammonium sulfate as a leaching agent and solves the problem of ammonia nitrogen pollution.
The invention is realized by adopting the following technical scheme:
an in-situ leaching method of ionic rare earth ore comprises the following steps:
(1) preparing an ore leaching agent: crushing dolomite, sieving the crushed dolomite with a 150-200-mesh sieve, mixing the dolomite and sulfuric acid according to the mass ratio of 1 (1-3) to prepare slurry A, and stirring and mixing the slurry A and an auxiliary agent according to the volume ratio of 10 (1-2) for 2-3 hours to obtain an ore leaching agent, wherein the pH value of the ore leaching agent is 4-4.5; the auxiliary agent comprises the following components in parts by volume: 2-5 parts of Gemini surfactant and 1-3 parts of dihydroxyethyl glycine;
(2) in-situ leaching: injecting the mineral leaching agent with the pH value of 4-4.5 obtained in the step (1) into the injection point, wherein the solid-to-solid ratio of the mineral leaching agent is 0.8-0.9L/kg, then collecting the leachate, and when the pH value of the leachate is more than 6.0 and the concentration of rare earth in the leachate is more than 0.1g/L, adjusting the solid-to-solid ratio of the mineral leaching agent to be 0.6-0.7L/kg;
(3) removing impurities from the rare earth leachate: adding a sodium bicarbonate solution into the leachate collected in the step (2) to adjust the pH value to 5-6, stirring for 2-3 h, standing, and filtering to remove precipitates to obtain a filtrate;
(4) rare earth extraction: adding a rare earth adsorbent into the filtrate obtained in the step (3), stirring for 2-3 h at 10-20 ℃, standing for 1-2 h, and filtering to obtain a solid; and then soaking and desorbing the solid by using a nitric acid solution with the mass concentration of 20-30% at 35-45 ℃, performing centrifugal separation to obtain a rare earth nitrate solution, performing vacuum freeze drying on the rare earth nitrate solution to obtain powder, and grinding the powder and calcining at high temperature to obtain the nano rare earth oxide.
Furthermore, in the step (1), the content of Al in the dolomite is less than 0.15 percent, the content of Fe is less than 0.07 percent, and the dolomite with low content of aluminum and iron is selected, so that the influence of the aluminum and the iron on the rare earth leaching and leachate impurity removal process is favorably reduced.
Further, the mass concentration of the sodium bicarbonate solution in the step (3) is 20-25%.
Further, in the step (4), the rare earth adsorbent is added into the filtrate according to the proportion that 10-20 g of the rare earth adsorbent is added into every 1L of the filtrate.
Further, after the rare earth adsorbent is added into the filtrate in the step (4), the pH value of the filtrate is adjusted to 6.5-7.5 by using a sodium bicarbonate solution with the mass concentration of 20-25%, and then the filtrate is stirred at the speed of 100-200 r/min, and the pH value of the filtrate is controlled to be beneficial to adsorption of rare earth.
Further, the rare earth adsorbent in the step (4) is obtained by functionalizing the SBA-15 mesoporous material with diethylenetriaminepentaacetic dianhydride, and the specific preparation method comprises the steps of mixing SBA-15 with absolute ethyl alcohol according to the mass-to-volume ratio of 1g to 100ml, magnetically stirring for 30min at room temperature, adding 3-aminopropyltriethoxysilane with one tenth of the volume of the absolute ethyl alcohol, uniformly mixing, refluxing and stirring for 24h at 80 ℃, cooling, centrifuging, washing the solid with the absolute ethyl alcohol for 3 times, and performing vacuum drying to obtain amino-modified SBA-15; dissolving diethylenetriaminepentaacetic dianhydride, 4-dimethylaminopyridine, amino-modified SBA-15 and 1-propyl phosphoric anhydride in an N-N dimethylformamide solution, and stirring overnight at room temperature to obtain a suspension, wherein the mass ratio of the diethylenetriaminepentaacetic dianhydride, the 4-dimethylaminopyridine, the amino-modified SBA-15 and the 1-propyl phosphoric anhydride is 1.1:0.5:1:1.2, and the mass-volume ratio of the amino-modified SBA-15 to the N-dimethylformamide solution is 1g:25 ml; centrifuging the suspension at 25 deg.C and 3000r/min for 15min, removing supernatant, washing the precipitate with N-N dimethylformamide solution for 4 times, and vacuum drying to obtain the rare earth adsorbent.
Compared with the prior art, the technical scheme has the following beneficial effects:
1. according to the invention, the dolomite and the sulfuric acid are mixed to prepare the mineral leaching agent, rare earth in rare earth tailings can be effectively recovered, ammonium salt is not used, the ammonia nitrogen content of wastewater cannot be increased, the problem of ammonia nitrogen pollution in rare earth mining is solved, meanwhile, a proper amount of Gemini surfactant and dihydroxyethyl glycine are selected and added into the mineral leaching agent as auxiliaries, the auxiliaries and the rare earth form a complex, the leaching of the rare earth is strengthened, the leaching rate of the rare earth is improved, meanwhile, the added auxiliaries neutralize the electronegativity of the clay surface under the action of adsorption and the like, clay particles can be bridged to effectively inhibit the migration of the particles, and the clay expansion is favorably prevented.
2. The method uses the specially prepared rare earth adsorbent to extract rare earth from the rare earth leaching solution after impurity removal, improves the extraction efficiency of the rare earth, and can obtain the nano-scale rare earth oxide through nitric acid soaking desorption, vacuum freeze drying and high-temperature calcination.
Detailed Description
The invention is further illustrated by the following examples, which are not to be construed as limiting the invention thereto. The specific experimental conditions and methods not indicated in the following examples are generally conventional means well known to those skilled in the art.
Example 1:
an in-situ leaching method of ionic rare earth ore comprises the following steps:
(1) preparing an ore leaching agent: crushing dolomite, sieving the crushed dolomite with a 150-mesh sieve, mixing the dolomite and sulfuric acid according to the mass ratio of 1:2 to prepare slurry A, and stirring and mixing the slurry A and an auxiliary agent according to the volume ratio of 10:1.5 for 2.5 hours to obtain an ore leaching agent, wherein the pH value of the ore leaching agent is 4.2; the auxiliary agent comprises the following components in parts by volume: 5 parts of Gemini surfactant and 3 parts of dihydroxyethyl glycine; calculated by mass percent, the content of Al in the dolomite is less than 0.15 percent, and the content of Fe is less than 0.07 percent;
(2) in-situ leaching: injecting the mineral leaching agent obtained in the step (1) into the injection point, wherein the solid-to-solid ratio of the mineral leaching agent is 0.85L/kg, collecting the leachate, and adjusting the solid-to-solid ratio of the mineral leaching agent to 0.65L/kg when the pH value of the leachate is more than 6.0 and the concentration of rare earth in the leachate is more than 0.1 g/L;
(3) removing impurities from the rare earth leachate: adding a sodium bicarbonate solution with the mass concentration of 20% into the leachate collected in the step (2) to adjust the pH value to 5, stirring for 2.5h, standing, and filtering to remove precipitates to obtain a filtrate;
(4) rare earth extraction: adding 15g of rare earth adsorbent into the filtrate obtained in the step (3) according to the proportion that 15g of rare earth adsorbent is added into every 1L of the filtrate, adjusting the pH value of the filtrate to be 7.5 by using a sodium bicarbonate solution with the mass concentration of 20%, stirring for 2.5h at the temperature of 20 ℃ and the speed of 100r/min, standing for 1h, and filtering to obtain a solid; then soaking and desorbing the solid by using a nitric acid solution with the mass concentration of 30% at 40 ℃, performing centrifugal separation to obtain a nitrate solution of the rare earth, then performing vacuum freeze drying on the nitrate solution of the rare earth to obtain powder, and grinding the powder and calcining at high temperature to obtain the nano rare earth oxide;
the rare earth adsorbent is obtained by functionalizing an SBA-15 mesoporous material with diethylenetriaminepentaacetic dianhydride, and is prepared by mixing SBA-15 and absolute ethyl alcohol according to the mass-volume ratio of 1g to 100ml, magnetically stirring at room temperature for 30min, then adding 3-aminopropyltriethoxysilane with one tenth of the volume of the absolute ethyl alcohol, uniformly mixing at 80 ℃, refluxing and stirring for 24h, cooling, centrifuging, washing the solid with the absolute ethyl alcohol for 3 times, and drying in vacuum to obtain amino modified SBA-15; dissolving diethylenetriaminepentaacetic dianhydride, 4-dimethylaminopyridine, amino-modified SBA-15 and 1-propyl phosphoric anhydride in an N-N dimethylformamide solution, and stirring overnight at room temperature to obtain a suspension, wherein the mass ratio of the diethylenetriaminepentaacetic dianhydride, the 4-dimethylaminopyridine, the amino-modified SBA-15 and the 1-propyl phosphoric anhydride is 1.1:0.5:1:1.2, and the mass-volume ratio of the amino-modified SBA-15 to the N-dimethylformamide solution is 1g:25 ml; centrifuging the suspension at 25 deg.C and 3000r/min for 15min, removing supernatant, washing the precipitate with N-N dimethylformamide solution for 4 times, and vacuum drying to obtain the rare earth adsorbent.
The ion type rare earth ore in-situ leaching is carried out according to the method, and the leaching rate of the rare earth is 96.12 percent.
Example 2:
an in-situ leaching method of ionic rare earth ore comprises the following steps:
(1) preparing an ore leaching agent: crushing dolomite, sieving the crushed dolomite with a 200-mesh sieve, mixing the dolomite and sulfuric acid according to the mass ratio of 1:3 to prepare slurry A, and stirring and mixing the slurry A and an auxiliary agent according to the volume ratio of 10:2 for 3 hours to obtain an ore leaching agent, wherein the pH value of the ore leaching agent is 4.5; the auxiliary agent comprises the following components in parts by volume: 3 parts of Gemini surfactant and 1 part of dihydroxyethyl glycine; calculated by mass percent, the content of Al in the dolomite is less than 0.15 percent, and the content of Fe is less than 0.07 percent;
(2) in-situ leaching: injecting the mineral leaching agent obtained in the step (1) into the injection point, wherein the solid-to-solid ratio of the mineral leaching agent is 0.9L/kg, collecting the leachate, and adjusting the solid-to-solid ratio of the mineral leaching agent to 0.6L/kg when the pH value of the leachate is more than 6.0 and the concentration of rare earth in the leachate is more than 0.1 g/L;
(3) removing impurities from the rare earth leachate: adding a sodium bicarbonate solution with the mass concentration of 25% into the leachate collected in the step (2) to adjust the pH value to 5.5, stirring for 3 hours, standing, and filtering to remove precipitates to obtain a filtrate;
(4) rare earth extraction: adding 20g of rare earth adsorbent into the filtrate obtained in the step (3) according to the proportion that 20g of rare earth adsorbent is added into every 1L of the filtrate, adjusting the pH value of the filtrate to be 7.0 by using a sodium bicarbonate solution with the mass concentration of 25%, stirring for 3h at 10 ℃ and the speed of 1050r/min, standing for 1.5h, and filtering to obtain a solid; then soaking and desorbing the solid by using a nitric acid solution with the mass concentration of 20% at 35 ℃, performing centrifugal separation to obtain a nitrate solution of rare earth, performing vacuum freeze drying on the nitrate solution of rare earth to obtain powder, and grinding the powder and calcining at high temperature to obtain the nano rare earth oxide;
the rare earth adsorbent is obtained by functionalizing an SBA-15 mesoporous material with diethylenetriaminepentaacetic dianhydride, and is prepared by mixing SBA-15 and absolute ethyl alcohol according to the mass-volume ratio of 1g to 100ml, magnetically stirring at room temperature for 30min, then adding 3-aminopropyltriethoxysilane with one tenth of the volume of the absolute ethyl alcohol, uniformly mixing at 80 ℃, refluxing and stirring for 24h, cooling, centrifuging, washing the solid with the absolute ethyl alcohol for 3 times, and drying in vacuum to obtain amino modified SBA-15; dissolving diethylenetriaminepentaacetic dianhydride, 4-dimethylaminopyridine, amino-modified SBA-15 and 1-propyl phosphoric anhydride in an N-N dimethylformamide solution, and stirring overnight at room temperature to obtain a suspension, wherein the mass ratio of the diethylenetriaminepentaacetic dianhydride, the 4-dimethylaminopyridine, the amino-modified SBA-15 and the 1-propyl phosphoric anhydride is 1.1:0.5:1:1.2, and the mass-volume ratio of the amino-modified SBA-15 to the N-dimethylformamide solution is 1g:25 ml; centrifuging the suspension at 25 deg.C and 3000r/min for 15min, removing supernatant, washing the precipitate with N-N dimethylformamide solution for 4 times, and vacuum drying to obtain the rare earth adsorbent.
The in-situ leaching of the ionic rare earth ore is carried out according to the method, and the leaching rate of the rare earth is 94.83 percent.
Example 3:
an in-situ leaching method of ionic rare earth ore comprises the following steps:
(1) preparing an ore leaching agent: crushing dolomite, sieving the crushed dolomite with a 180-mesh sieve, mixing the dolomite and sulfuric acid according to the mass ratio of 1:1 to prepare slurry A, and stirring and mixing the slurry A and an auxiliary agent according to the volume ratio of 10:1 for 2 hours to obtain an ore leaching agent, wherein the pH value of the ore leaching agent is 4.0; the auxiliary agent comprises the following components in parts by volume: 2 parts of Gemini surfactant and 2 parts of dihydroxyethyl glycine; calculated by mass percent, the content of Al in the dolomite is less than 0.15 percent, and the content of Fe is less than 0.07 percent;
(2) in-situ leaching: injecting the mineral leaching agent obtained in the step (1) into the injection point, wherein the solid-to-solid ratio of the mineral leaching agent is 0.8L/kg, collecting the leachate, and adjusting the solid-to-solid ratio of the mineral leaching agent to 0.7L/kg when the pH value of the leachate is more than 6.0 and the concentration of rare earth in the leachate is more than 0.1 g/L;
(3) removing impurities from the rare earth leachate: adding a sodium bicarbonate solution with the mass concentration of 22% into the leachate collected in the step (2) to adjust the pH value to 6, stirring for 2 hours, standing, and filtering to remove precipitates to obtain a filtrate;
(4) rare earth extraction: adding the rare earth adsorbent into the filtrate obtained in the step (3) according to the proportion that 10g of the rare earth adsorbent is added into every 1L of the filtrate, adjusting the pH value of the filtrate to be 6.5 by using a sodium bicarbonate solution with the mass concentration of 22%, stirring for 2 hours at the temperature of 15 ℃ and the speed of 200r/min, standing for 2 hours, and filtering to obtain a solid; then soaking and desorbing the solid by using a nitric acid solution with the mass concentration of 25% at 45 ℃, performing centrifugal separation to obtain a nitrate solution of rare earth, performing vacuum freeze drying on the nitrate solution of rare earth to obtain powder, and grinding the powder and calcining at high temperature to obtain the nano rare earth oxide;
the rare earth adsorbent is obtained by functionalizing an SBA-15 mesoporous material with diethylenetriaminepentaacetic dianhydride, and is prepared by mixing SBA-15 and absolute ethyl alcohol according to the mass-volume ratio of 1g to 100ml, magnetically stirring at room temperature for 30min, then adding 3-aminopropyltriethoxysilane with one tenth of the volume of the absolute ethyl alcohol, uniformly mixing at 80 ℃, refluxing and stirring for 24h, cooling, centrifuging, washing the solid with the absolute ethyl alcohol for 3 times, and drying in vacuum to obtain amino modified SBA-15; dissolving diethylenetriaminepentaacetic dianhydride, 4-dimethylaminopyridine, amino-modified SBA-15 and 1-propyl phosphoric anhydride in an N-N dimethylformamide solution, and stirring overnight at room temperature to obtain a suspension, wherein the mass ratio of the diethylenetriaminepentaacetic dianhydride, the 4-dimethylaminopyridine, the amino-modified SBA-15 and the 1-propyl phosphoric anhydride is 1.1:0.5:1:1.2, and the mass-volume ratio of the amino-modified SBA-15 to the N-dimethylformamide solution is 1g:25 ml; centrifuging the suspension at 25 deg.C and 3000r/min for 15min, removing supernatant, washing the precipitate with N-N dimethylformamide solution for 4 times, and vacuum drying to obtain the rare earth adsorbent.
The ion type rare earth ore in-situ leaching is carried out according to the method, and the leaching rate of the rare earth is 94.90 percent.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.
Claims (5)
1. An in-situ leaching method of ionic rare earth ore is characterized in that: the method comprises the following steps:
(1) preparing an ore leaching agent: crushing dolomite, sieving the crushed dolomite with a 150-200-mesh sieve, mixing the dolomite and sulfuric acid according to the mass ratio of 1 (1-3) to prepare slurry A, and stirring and mixing the slurry A and an auxiliary agent according to the volume ratio of 10 (1-2) for 2-3 hours to obtain an ore leaching agent, wherein the pH value of the ore leaching agent is 4-4.5; the auxiliary agent comprises the following components in parts by volume: 2-5 parts of Gemini surfactant and 1-3 parts of dihydroxyethyl glycine;
(2) in-situ leaching: injecting the leaching agent obtained in the step (1) into the injection point, wherein the leaching solution solid-to-solid ratio is 0.8-0.9L/kg, then collecting the leachate, and when the pH value of the leachate is more than 6.0 and the concentration of rare earth in the leachate is more than 0.1g/L, adjusting the leaching solution solid-to-solid ratio to be 0.6-0.7L/kg;
(3) removing impurities from the rare earth leachate: adding a sodium bicarbonate solution into the leachate collected in the step (2) to adjust the pH value to 5-6, stirring for 2-3 h, standing, and filtering to remove precipitates to obtain a filtrate;
(4) rare earth extraction: adding a rare earth adsorbent into the filtrate obtained in the step (3), stirring for 2-3 h at 10-20 ℃, standing for 1-2 h, and filtering to obtain a solid; then soaking and desorbing the solid by using a nitric acid solution with the mass concentration of 20-30% at 35-45 ℃, performing centrifugal separation to obtain a rare earth nitrate solution, then performing vacuum freeze drying on the rare earth nitrate solution to obtain powder, and grinding the powder and calcining at high temperature to obtain the nano rare earth oxide;
the rare earth adsorbent is obtained by functionalizing an SBA-15 mesoporous material with diethylenetriaminepentaacetic dianhydride, and is prepared by mixing SBA-15 and absolute ethyl alcohol according to the mass-volume ratio of 1g to 100ml, magnetically stirring at room temperature for 30min, then adding 3-aminopropyltriethoxysilane with one tenth of the volume of the absolute ethyl alcohol, uniformly mixing at 80 ℃, refluxing and stirring for 24h, cooling, centrifuging, washing the solid with the absolute ethyl alcohol for 3 times, and drying in vacuum to obtain amino modified SBA-15; dissolving diethylenetriaminepentaacetic dianhydride, 4-dimethylaminopyridine, amino-modified SBA-15 and 1-propyl phosphoric anhydride in an N-N dimethylformamide solution, and stirring overnight at room temperature to obtain a suspension, wherein the mass ratio of the diethylenetriaminepentaacetic dianhydride, the 4-dimethylaminopyridine, the amino-modified SBA-15 and the 1-propyl phosphoric anhydride is 1.1:0.5:1:1.2, and the mass-volume ratio of the amino-modified SBA-15 to the N-dimethylformamide solution is 1g:25 ml; centrifuging the suspension at 25 deg.C and 3000r/min for 15min, removing supernatant, washing the precipitate with N-N dimethylformamide solution for 4 times, and vacuum drying to obtain the rare earth adsorbent.
2. The in-situ leaching process of ionic rare earth ores according to claim 1, wherein: in the step (1), the content of Al in the dolomite is less than 0.15 percent and the content of Fe is less than 0.07 percent by weight percentage.
3. The in-situ leaching process of ionic rare earth ores according to claim 1, wherein: in the step (3), the mass concentration of the sodium bicarbonate solution is 20-25%.
4. The in-situ leaching process of ionic rare earth ores according to claim 1, wherein: and (4) adding the rare earth adsorbent into the filtrate according to the proportion that 10-20 g of the rare earth adsorbent is added into every 1L of the filtrate.
5. The in-situ leaching process of ionic rare earth ores according to claim 4, wherein: and (4) adding a rare earth adsorbent into the filtrate in the step (4), adjusting the pH value of the filtrate to be 6.5-7.5 by using a sodium bicarbonate solution with the mass concentration of 20-25%, and then stirring at the speed of 100-200 r/min.
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| CN105087924A (en) * | 2015-10-11 | 2015-11-25 | 江西理工大学 | Auxiliary leaching agent used for reinforced leaching of ion-type rare earth ores and leaching method thereof |
| CN105331835A (en) * | 2015-10-11 | 2016-02-17 | 江西理工大学 | Auxiliary leaching agent applied to ion-absorbed rare earth ore leaching process and ore leaching method of auxiliary leaching agent |
| CN106435172A (en) * | 2016-10-14 | 2017-02-22 | 赣州弘茂稀土工程有限公司 | Process for performing classifying split-flow treatment on rare earth sin-situ leaching mother solution |
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| CN104232948A (en) * | 2014-10-10 | 2014-12-24 | 江西理工大学 | Process method for recovering rare earth from ionic type rare earth low-concentration leachate |
| CN105087924A (en) * | 2015-10-11 | 2015-11-25 | 江西理工大学 | Auxiliary leaching agent used for reinforced leaching of ion-type rare earth ores and leaching method thereof |
| CN105331835A (en) * | 2015-10-11 | 2016-02-17 | 江西理工大学 | Auxiliary leaching agent applied to ion-absorbed rare earth ore leaching process and ore leaching method of auxiliary leaching agent |
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Effective date of registration: 20230511 Address after: No. 21 Honghua Street, Honghua Town, Zhongshan County, Hezhou City, Guangxi Zhuang Autonomous Region, 542600 Patentee after: Hezhou Rare Earth Mining Co.,Ltd. Address before: Floor 16, building 3, Xingning Pioneer Park, 31 Songbai Road, Xingning District, Nanning City, Guangxi Zhuang Autonomous Region, 530012 Patentee before: CHINALCO GUANGXI NONFERROUS RARE EARTH DEVELOPMENT CO.,LTD. |