CN114703365A - Composite leaching agent for weathering crust leaching type rare earth ore - Google Patents
Composite leaching agent for weathering crust leaching type rare earth ore Download PDFInfo
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- 238000002386 leaching Methods 0.000 title claims abstract description 201
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 120
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 112
- 239000002131 composite material Substances 0.000 title claims abstract description 73
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 90
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims abstract description 48
- 235000011130 ammonium sulphate Nutrition 0.000 claims abstract description 48
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims abstract description 47
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000004021 humic acid Substances 0.000 claims abstract description 40
- 239000002994 raw material Substances 0.000 claims abstract description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 20
- 238000010828 elution Methods 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- PUKLDDOGISCFCP-JSQCKWNTSA-N 21-Deoxycortisone Chemical compound C1CC2=CC(=O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@@](C(=O)C)(O)[C@@]1(C)CC2=O PUKLDDOGISCFCP-JSQCKWNTSA-N 0.000 claims description 6
- FCYKAQOGGFGCMD-UHFFFAOYSA-N Fulvic acid Natural products O1C2=CC(O)=C(O)C(C(O)=O)=C2C(=O)C2=C1CC(C)(O)OC2 FCYKAQOGGFGCMD-UHFFFAOYSA-N 0.000 claims description 6
- 239000002509 fulvic acid Substances 0.000 claims description 6
- 229940095100 fulvic acid Drugs 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 239000003002 pH adjusting agent Substances 0.000 claims 1
- 238000003900 soil pollution Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 31
- 238000000034 method Methods 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 13
- -1 rare earth ions Chemical class 0.000 description 12
- 238000002156 mixing Methods 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 239000001117 sulphuric acid Substances 0.000 description 8
- 235000011149 sulphuric acid Nutrition 0.000 description 8
- 125000002843 carboxylic acid group Chemical group 0.000 description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 125000000524 functional group Chemical group 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000002734 clay mineral Substances 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 238000011065 in-situ storage Methods 0.000 description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 description 4
- 239000011707 mineral Substances 0.000 description 4
- 239000002689 soil Substances 0.000 description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000003912 environmental pollution Methods 0.000 description 3
- 235000019253 formic acid Nutrition 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 2
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000010668 complexation reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000002572 peristaltic effect Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000011435 rock Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000010438 granite Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 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
-
- 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
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/16—Extraction of metal compounds from ores or concentrates by wet processes by leaching in organic solutions
- C22B3/1608—Leaching with acyclic or carbocyclic agents
- C22B3/1616—Leaching with acyclic or carbocyclic agents of a single type
- C22B3/165—Leaching with acyclic or carbocyclic agents of a single type with organic acids
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Environmental & Geological Engineering (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Geochemistry & Mineralogy (AREA)
- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a composite leaching agent for weathering crust eluviation type rare earth ore, which is characterized in that the composite leaching agent is a composite leaching solution formed by taking humic acid and ammonium sulfate as main raw materials. The composite leaching agent can effectively promote the leaching efficiency of rare earth, obviously shorten the time for reaching leaching balance, effectively reduce soil pollution and realize the environment-friendly and efficient leaching of weathering crust eluviation type rare earth ore.
Description
Technical Field
The invention belongs to the technical field of wet metallurgy, and particularly relates to a composite leaching agent for weathering crust elution-deposited rare earth ore.
Background
The weathering crust eluviation type rare earth ore (also called ion adsorption type rare earth ore) can effectively fill the defect that the mineral type rare earth ore contains more light rare earth and less medium and heavy rare earth due to the characteristics of being rich in medium and heavy rare earth and the like, and has great commercial utilization value and economic strategic value. The weathering crust leaching type rare earth ore is formed by weathering of raw rock containing rare earth minerals (such as granite or volcanic rock) through physical, biological and chemical actions for years. The rare earth elements in the ore are mainly adsorbed on the clay mineral by hydrated or hydroxyl hydrated ions, the mining of weathering crust elution-deposited rare earth ore usually adopts an in-situ leaching process, the rare earth ions are exchanged in a leaching solution by ion exchange with an electrolyte solution, and then the rare earth is recovered by precipitation; and the industrial method generally adopts ammonium sulfate as a leaching agent to leach the rare earth ore.
The rare earth in-situ leaching process involves a typical liquid-solid interface reaction: firstly, a leaching agent solution is injected into an ore body, the leaching agent solution seeps in the ore body under the action of gravity, then cations in the leaching agent solution and rare earth adsorbed on clay minerals perform ion exchange reaction, rare earth ions are exchanged into the solution, finally the solution seeps to a mountain region, and a rare earth leachate is collected. The weathering degree and the ore body structure of the weathering crust leaching type rare earth ore can influence the seepage condition of a leaching agent in an ore body, and in some areas, because the ore body structure is compact, a pore double electric layer and mineral particle surface bound water are easy to form, so that the pore flow area is reduced, the seepage speed of a leaching solution is seriously influenced, and the phenomena of rare earth concentration tailing or low rare earth leaching rate and the like are generated. And because the weathering crust elution-deposited rare earth ore has different weathering layer thicknesses, a large number of leaching blind areas and dead areas exist in the leaching process, so that the rare earth recovery rate is low. These all result in waste of rare earth resources.
When the traditional ammonium sulfate leaching agent leaches weathering crust leaching type rare earth ore, clay minerals can adsorb ammonium ions in a great amount of leaching agent solution, and ammonium ions are led to intervene in mineral lattices during ion exchange reaction, so that the thickness of a water film on the surface of the clay minerals is increased, a seepage channel is directly influenced, the permeability coefficient of an ore body is reduced, the seepage speed is influenced, and the leaching rate of rare earth is lower. Meanwhile, when the ammonium salt is used for leaching, a large amount of ammonia nitrogen wastewater is generated to cause environmental pollution. Therefore, the method aims to improve the seepage and mass transfer processes of rare earth leaching, improve the effective seepage speed and leaching and mass transfer efficiency of rare earth, reduce resource consumption and reduce environmental pollution. Further exploration and optimization of a novel leaching agent are urgently needed to accelerate the rare earth leaching rate and improve the mass transfer efficiency of the rare earth and the solution seepage speed so as to realize efficient and environment-friendly leaching of the weathering crust elution type rare earth ore.
Disclosure of Invention
The invention aims to solve the problems and the defects in the prior art, and provides a composite leaching agent for weathered crust eluviation type rare earth ore, which is a composite leaching solution formed by taking humic acid and ammonium sulfate as main raw materials, can effectively promote the leaching efficiency of rare earth and shorten the time for reaching leaching balance; meanwhile, the soil pollution can be effectively reduced, and the environmental-friendly and efficient leaching of the weathering crust elution type rare earth ore is realized.
In order to achieve the purpose, the invention adopts the technical scheme that:
a composite leaching agent for weathered crust eluviation type rare earth ore is a composite leaching solution formed by using humic acid and ammonium sulfate as main raw materials.
In the above scheme, the solvent used in the composite leaching solution is water.
In the scheme, the humic acid is a natural macromolecular organic substance with a complex structural composition, the element composition comprises C, H, O, N and the like, wherein the content of fulvic acid is more than 90 wt% (FA ≧ 90%); the fulvic acid is one of humic acid substances with relatively low molecular weight, the molecular weight is generally more than 3000 (usually about 3000-5000), and compared with humic acid, the fulvic acid has the advantages of loose benzene ring connection form, relatively low carbon-hydrogen content, high oxygen content, relatively sufficient organic carbon chain content and high carboxyl content; besides abundant carboxylic acid groups, the rare earth leaching agent also contains phenolic hydroxyl, alcoholic hydroxyl, phenol and other active functional groups, and the presence of the phenol, phenolic hydroxyl, alcoholic hydroxyl and other active functional groups can promote the leaching agent solution and the rare earth ions to perform coordination reaction, increase the diffusion concentration difference of the rare earth ions, and be beneficial to strengthening the rapid and efficient leaching of the rare earth.
In the scheme, the concentration of humic acid in the composite leaching agent is 0.01-0.05 wt%.
Preferably, the concentration of humic acid in the composite leaching solution is 0.018-0.025 wt%.
In the scheme, the concentration of ammonium sulfate in the composite leaching agent is 0.01-0.1 mol/L.
Preferably, the concentration of ammonium sulfate in the composite leaching agent is 0.05-0.1 mol/L.
In the scheme, the pH value of the composite leaching agent is 5.0-7.0; is realized by adopting a pH regulator for regulation.
Preferably, the pH value of the composite leaching agent is 5.5-6.0.
In the scheme, the pH regulator can be one or more of sulfuric acid, hydrochloric acid, nitric acid and the like; the concentration is 1-3 mol/L.
Preferably, the pH regulator can be selected from sulfuric acid, and the concentration of the sulfuric acid is 2 mol/L.
In the scheme, when the weathering crust elution type rare earth ore leaching is carried out by using the composite leaching agent, the liquid-solid ratio is 1-3: 1; the leaching time is below 670 min; the leaching rate of the rare earth is more than 89%.
Preferably, the liquid-solid ratio can be 2: 1.
Preferably, the leaching time of the weathering crust elution type rare earth ore can reach below 600min under the conditions that the concentration of humic acid is 0.018-0.025 wt% and the concentration of ammonium sulfate is 0.05-0.1 mol/L.
More preferably, the leaching time of the weathering crust elution type rare earth ore can reach below 500min under the conditions that the concentration of the humic acid is 0.022-0.025 wt% and the concentration of ammonium sulfate is 0.07-0.08 mol/L; can combine good leaching efficiency (obviously shorten leaching time and ensure higher leaching rate) and cost effectiveness.
The humic acid introduced by the invention has a complex molecular structure and composition, contains various active functional groups such as carboxylic acid groups and the like and a large amount of organic carbon chains, can react with rare earth to generate a complex, and increases the diffusion concentration difference of rare earth ions, thereby improving the leaching rate and the mass transfer efficiency of the rare earth; meanwhile, humic acid is a natural macromolecular compound, is an important organic matter in soil and does not cause harm to the environment and the soil; humic acid can better cooperate with rare earth ions by utilizing the unique molecular structure and a large number of active functional groups such as carboxylic acid groups and the like, so that the leaching of rare earth is enhanced, and the leaching rate of rare earth is improved; meanwhile, the humic acid has a large molecular weight and contains a large number of organic carbon chains which have good hydrophobic property, so that the diffusion speed of rare earth ions can be increased, the seepage speed of the leaching solution can be accelerated, and the seepage process of leaching can be enhanced; the humic acid has good solubility and fluidity, can generate complexation with metal cations, has stronger amphiprotic characteristics compared with other small-molecule organic acids due to the existence of hydrophilic groups mainly comprising phenolic hydroxyl groups and hydrophobic groups mainly comprising carboxylic acid groups in the humic acid, and can form porous aggregates in an acidic medium, so that the humic acid has a certain specific surface area.
Compared with the prior art, the invention at least has the following beneficial effects:
1) the composite leaching agent takes humic acid and ammonium sulfate as main leaching components, and compared with the traditional ammonium sulfate leaching agent, the humic acid-ammonium sulfate composite leaching agent can effectively promote the leaching of rare earth under the precondition that the leaching rate of the rare earth is not influenced, obviously shortens the time for the rare earth to reach the leaching balance, and can realize the high-efficiency leaching of weathered crust elution-deposited rare earth ore; has important economic and environmental benefits;
2) the humic acid adopted by the invention is an important natural organic matter in soil, has strong coordination, adsorption and redox capabilities, simultaneously has a large number of active functional groups such as carboxylic acid groups and organic carbon chains, can fully play the hydrophobicity of the organic carbon chains to strengthen the rare earth seepage process, improves the rare earth leaching rate by the coordination of the carboxylic acid groups and the rare earth, and has the synergistic leaching effect with ammonium sulfate; the rare earth active earth ammonium residue reducing agent has a certain promotion effect on treatment of mine tailings and restoration of environmental pollution.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
In the following examples, a column leaching test is used to simulate the rare earth ore in-situ leaching process, and the operation basic steps are as follows: 150g of mixed rare earth sample dried in a 50 ℃ drying oven is weighed on an electronic platform scale by a quartering method, the mixed rare earth sample is uniformly filled into a glass leaching column, 1-2 layers of filter paper are horizontally placed on the sample, humic acid-ammonium sulfate compound leaching solution is added at a constant flow rate by a constant-current peristaltic pump to leach rare earth, a precise graduated cylinder is used for collecting rare earth leaching solution of the glass column and measuring the volume of the rare earth leaching solution, and then the content of the rare earth in the leaching solution is measured by an EDTA complexation titration method.
In the following examples, the humic acid used was provided by alatin, wherein the fulvic acid content was greater than 90%, i.e. FA ≧ 90%; the molecular weight of fulvic acid is above 3000.
Example 1
A composite leaching agent for weathered crust eluviation type rare earth ore is prepared by the following steps:
6.607g of ammonium sulfate and 0.05g of humic acid are evenly mixed in 500ml of water (wherein the concentration of the ammonium sulfate is 0.1mol/L, and the concentration of the humic acid is 0.01 wt%), and then the pH value of the solution is adjusted to 5.5 by using 2.0mol/L sulfuric acid; and mixing uniformly to obtain the composite leaching agent.
The composite leaching agent obtained in the embodiment is applied to leaching weathering crust elution-deposited rare earth ore, and comprises the following specific steps: aiming at a certain mixed weathering crust leaching type rare earth ore, the average grade of the rare earth ore is 0.14%, and a column leaching test is adopted to simulate the in-situ leaching process of the rare earth ore; uniformly injecting the obtained composite leaching agent into a glass leaching column filled with the mixed rare earth ore at a constant flow rate by using a constant-flow peristaltic pump according to the mass ratio of the composite leaching agent to the rare earth ore of 2:1, and leaching to obtain a rare earth leaching solution.
Tests show that the time for leaching the rare earth by using the composite leaching agent obtained in the embodiment to reach the equilibrium is 625min, the leaching time is shortened by 160min compared with that of the traditional ammonium sulfate leaching agent in a comparative example 1, and the leaching rate of the rare earth is 90.1%.
Example 2
A composite leaching agent for weathered crust eluviation type rare earth ore is prepared by the following steps:
6.607g of ammonium sulfate and 0.1g of humic acid are evenly mixed in 500ml of water (wherein the concentration of the ammonium sulfate is 0.1mol/L, and the concentration of the humic acid is 0.02 wt%), and dilute sulphuric acid with the concentration of 2.0mol/L is used for adjusting the pH value of the solution to 5.5; and mixing uniformly to obtain the composite leaching agent.
The composite leaching agent obtained in the embodiment is applied to leaching weathering crust elution type rare earth ore by the method described in reference example 1. Tests show that the time for the rare earth leaching to reach the equilibrium is 475min by adopting the composite leaching agent obtained in the embodiment, the leaching time is shortened by 310min compared with that of the traditional ammonium sulfate leaching agent in a comparative example 1, and the leaching rate of the rare earth is 90.8%.
Example 3
A composite leaching agent for weathering crust eluviation type rare earth ore is prepared by the following steps:
6.607g of ammonium sulfate and 0.25g of humic acid are evenly mixed in 500ml of water (wherein the concentration of the ammonium sulfate is 0.1mol/L, and the concentration of the humic acid is 0.05 wt%), and dilute sulphuric acid with the concentration of 2.0mol/L is used for adjusting the pH value of the solution to be 5.5; and mixing uniformly to obtain the composite leaching agent.
The composite leaching agent obtained in the embodiment is applied to leaching weathering crust elution type rare earth ore by the method described in reference example 1. Tests show that the time for leaching the rare earth by using the composite leaching agent obtained in the embodiment to reach the equilibrium is 662min, the leaching time is shortened by 123min compared with that of the traditional ammonium sulfate leaching agent in a comparative example 1, and the leaching rate of the rare earth is 89.8%; compared with the example 2, it can be seen that further increasing the content of humic acid is not beneficial to the rare earth to ensure the rapid and efficient leaching of rare earth.
Example 4
A composite leaching agent for weathering crust eluviation type rare earth ore is prepared by the following steps:
6.607g of ammonium sulfate and 0.1g of humic acid are evenly mixed in 500ml of water (wherein the concentration of the ammonium sulfate is 0.1mol/L, and the concentration of the humic acid is 0.02 wt%), and dilute sulphuric acid with the concentration of 2.0mol/L is used for adjusting the pH value of the solution to be 6; and mixing uniformly to obtain the composite leaching agent.
The composite leaching agent obtained in the embodiment is applied to leaching weathering crust elution type rare earth ore by the method described in reference example 1. Tests show that the time for the rare earth leaching to reach the equilibrium is 511min by adopting the composite leaching agent obtained in the embodiment, compared with the traditional ammonium sulfate leaching agent described in comparative example 1, the leaching time is shortened by 274min, and the leaching rate of the rare earth is 89.6%.
Example 5
A composite leaching agent for weathering crust eluviation type rare earth ore is prepared by the following steps:
6.607g of ammonium sulfate and 0.1g of humic acid are evenly mixed in 500ml of water (wherein the concentration of the ammonium sulfate is 0.1mol/L, and the concentration of the humic acid is 0.02%), and dilute sulphuric acid with the concentration of 2.0mol/L is used for adjusting the pH value of the solution to 6.5; and mixing uniformly to obtain the composite leaching agent.
The composite leaching agent obtained in the embodiment is applied to leaching weathering crust elution type rare earth ore by the method described in reference example 1. Tests show that the time for leaching the rare earth to reach the equilibrium is 523min by adopting the composite leaching agent obtained in the embodiment, compared with the traditional ammonium sulfate leaching agent in the comparative example 1, the leaching time is shortened by 262min, and the leaching rate of the rare earth is 89.5%.
Example 6
A composite leaching agent for weathering crust eluviation type rare earth ore is prepared by the following steps:
4.955g of ammonium sulfate and 0.1g of humic acid are evenly mixed in 500ml of water (wherein the concentration of the ammonium sulfate is 0.075mol/L, and the concentration of the humic acid is 0.02%), and dilute sulphuric acid with the concentration of 2.0mol/L is used for adjusting the pH value of the solution to 5.5; and mixing uniformly to obtain the composite leaching agent.
The composite leaching agent obtained in the embodiment is applied to leaching weathering crust elution type rare earth ore by the method described in reference example 1. Tests show that the time for the rare earth leaching to reach the equilibrium is 532min by adopting the composite leaching agent obtained in the embodiment, the leaching time is shortened by 253min compared with the leaching time of the traditional ammonium sulfate leaching agent in a comparative example 1, and the leaching rate of the rare earth is 89.9%.
Example 7
A composite leaching agent for weathering crust eluviation type rare earth ore is prepared by the following steps:
3.3035g of ammonium sulfate and 0.1g of humic acid are evenly mixed in 500ml of water (wherein the concentration of the ammonium sulfate is 0.05mol/L, and the concentration of the humic acid is 0.02%), and dilute sulphuric acid with the concentration of 2.0mol/L is used for adjusting the pH value of the solution to 5.5; and mixing uniformly to obtain the composite leaching agent.
The composite leaching agent obtained in the embodiment is applied to leaching weathering crust elution type rare earth ore by the method described in reference example 1. Tests show that the time for the rare earth leaching to reach the equilibrium is 582min, compared with the traditional ammonium sulfate leaching agent in the comparative example 1, the leaching time is shortened by 203min, and the leaching rate of the rare earth is 89.4%.
Example 8
A composite leaching agent for weathering crust eluviation type rare earth ore is prepared by the following steps:
4.955g of ammonium sulfate and 0.125g of humic acid are evenly mixed in 500ml of water (wherein the concentration of the ammonium sulfate is 0.075mol/L, and the concentration of the humic acid is 0.025 percent), and dilute sulphuric acid with the concentration of 2.0mol/L is used for adjusting the pH value of the solution to 5.5; and mixing uniformly to obtain the composite leaching agent.
The composite leaching agent obtained in the embodiment is applied to leaching weathering crust elution type rare earth ore by the method described in reference example 1. Tests show that the time for the rare earth leaching to reach the equilibrium is 462min by adopting the composite leaching agent obtained in the embodiment, compared with the traditional ammonium sulfate leaching agent described in comparative example 1, the leaching time is shortened by 323min, and the leaching rate of the rare earth is 90.5%.
Comparative example 1
A traditional ammonium sulfate leaching agent adopts 0.1mol/L ammonium sulfate aqueous solution, dilute sulfuric acid with the concentration of 2.0mol/L is used for adjusting the pH value of the solution to be 5.5, and the composite leaching agent obtained in the embodiment is applied to leaching weathering crust elution type rare earth ores by the method described in reference example 1.
Tests show that the time for leaching the rare earth to reach the equilibrium is 785min and the leaching rate of the rare earth is 89.3 percent by adopting the traditional ammonium sulfate leaching agent.
Comparative example 2
A compound leaching agent formed by micromolecular organic acid and ammonium sulfate uniformly dissolves the ammonium sulfate and formic acid in water, wherein the concentration of the ammonium sulfate is 0.1mol/L, and the concentration of the formic acid is 0.008mol/L (0.05 wt%); then the pH value of the solution is adjusted to 5.5 by dilute sulphuric acid with the concentration of 2.0 mol/L.
The composite leaching agent obtained in the comparative example is applied to leaching weathering crust elution type rare earth ore by the method described in reference example 1. Tests show that the time for the rare earth leaching to reach the equilibrium is 734min by adopting the composite leaching agent obtained by the comparative example, compared with the traditional ammonium sulfate leaching agent in the comparative example 1, the leaching time is only shortened by 51min, and the leaching rate of the rare earth is 89.4%.
The results show that compared with the traditional method of leaching rare earth by adopting the novel humic acid-ammonium sulfate composite leaching agent and the traditional ammonium sulfate leaching agent and the method of leaching rare earth by adopting the micromolecular organic acid (formic acid) and ammonium sulfate compound leaching agent, the method can obviously shorten the leaching balance time, further reduce the consumption of ammonium sulfate, be beneficial to reducing the residue of ammonium content in soil and play a certain positive role in protecting vegetation and controlling the environment of mines.
The above embodiments are merely examples for clearly illustrating the present invention and do not limit the present invention. Other variants and modifications of the invention, which are obvious to those skilled in the art and can be made on the basis of the above description, are not necessary or exhaustive for all embodiments, and are therefore within the scope of the invention.
Claims (8)
1. The composite leaching agent for weathered crust eluviation type rare earth ore is characterized in that the composite leaching agent is a composite leaching solution formed by taking humic acid and ammonium sulfate as main raw materials.
2. The composite leaching agent according to claim 1, wherein the fulvic acid content of the humic acid is greater than 90% and the molecular weight is greater than 3000.
3. The composite leaching agent according to claim 1, wherein the concentration of humic acid in the composite leaching agent is 0.01-0.05 wt%.
4. The composite leaching agent according to claim 1, wherein the concentration of ammonium sulfate in the composite leaching agent is 0.01-0.1 mol/L.
5. The composite leaching agent according to claim 1, wherein the pH value of the composite leaching agent is further adjusted to 5.0-7.0 by using a pH adjusting agent.
6. The composite leaching agent according to claim 1, wherein the pH regulator is one or more of sulfuric acid, hydrochloric acid and nitric acid; the concentration is 1-3 mol/L.
7. The composite leaching agent according to claim 1, wherein the solvent used in the composite leaching solution is water.
8. The composite leaching agent according to claim 1, wherein when the composite leaching agent is used for leaching weathered crust elution type rare earth ore, the liquid-solid ratio is (1-3): 1.
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| CN107790489A (en) * | 2017-12-12 | 2018-03-13 | 河南永泽环境科技有限公司 | A kind of method for repairing chromium-polluted soil |
| CN108823436A (en) * | 2018-07-05 | 2018-11-16 | 武汉工程大学 | A kind of compound leaching agent of the formates of weathered superficial leaching rare-earth ore |
| CN109518012A (en) * | 2019-01-17 | 2019-03-26 | 江西理工大学 | A method of using clay mineral separation and concentration rare earth ion |
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