CN114703365B - Composite leaching agent for weathered crust leaching rare earth ore - Google Patents
Composite leaching agent for weathered crust leaching rare earth ore Download PDFInfo
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- 238000002386 leaching Methods 0.000 title claims abstract description 236
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 117
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 110
- 239000002131 composite material Substances 0.000 title claims abstract description 63
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 84
- 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 26
- 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 5
- 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 5
- 239000002509 fulvic acid Substances 0.000 claims description 5
- 229940095100 fulvic acid Drugs 0.000 claims description 5
- 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 2
- 239000001166 ammonium sulphate Substances 0.000 claims 1
- 238000003900 soil pollution Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 30
- 238000000034 method Methods 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 13
- -1 rare earth ions Chemical class 0.000 description 12
- 238000002156 mixing Methods 0.000 description 10
- 230000008569 process Effects 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 8
- 230000001105 regulatory effect Effects 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 125000002843 carboxylic acid group Chemical group 0.000 description 6
- 125000000524 functional group Chemical group 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 6
- 239000002689 soil Substances 0.000 description 6
- 230000008901 benefit Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000002734 clay mineral Substances 0.000 description 4
- 238000011065 in-situ storage Methods 0.000 description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 description 4
- 238000005342 ion exchange Methods 0.000 description 4
- 239000011707 mineral Substances 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 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
- 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
- 239000000203 mixture Substances 0.000 description 3
- 150000007524 organic acids Chemical class 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 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
- 239000012466 permeate Substances 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
- 239000000126 substance Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 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
- 230000009471 action 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
- 238000010668 complexation reaction Methods 0.000 description 1
- 238000003926 complexometric titration Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000006253 efflorescence Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 239000010438 granite Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 230000033116 oxidation-reduction process Effects 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
- 230000008092 positive effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000005303 weighing Methods 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
Abstract
The invention discloses a composite leaching agent for weathered crust leaching 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 weathered crust leaching rare earth ore.
Description
Technical Field
The invention belongs to the technical field of hydrometallurgy, and particularly relates to a composite leaching agent for weathered crust leaching rare earth ore.
Background
The weathered crust leaching rare earth ore (also called ion adsorption type rare earth ore) can effectively fill the defects of more light rare earth and less medium and heavy rare earth of mineral type rare earth ore 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 weathered crust leaching rare earth ore is formed by the long-term physical, biological and chemical weathering of raw rock containing rare earth minerals (such as granite or volcanic rock). Rare earth elements in the ore are mainly adsorbed on clay minerals through hydration or hydroxyl hydration ions, the exploitation of weathered crust leaching rare earth ores generally adopts an in-situ leaching process, the rare earth ions are exchanged in leaching solution through ion exchange by electrolyte solution, and then the rare earth is recovered through precipitation; and ammonium sulfate is generally used as leaching agent in industry to leach rare earth ore.
The rare earth in situ leaching process involves a typical liquid-solid interface reaction: firstly, injecting leaching agent solution into ore body, making leaching agent solution permeate flow in the ore body under the action of gravity, then making cation in the leaching agent solution and rare earth adsorbed on clay mineral produce ion exchange reaction, making rare earth ion exchange into the solution, finally making the solution permeate flow into mountain area and collecting rare earth leaching liquor. The weathering degree and the ore body structure of the weathering crust leaching type rare earth ore can influence the seepage condition of the leaching agent in the ore body, and in certain areas, due to compact ore body structure, pore double electric layers and the surface bound water of mineral particles are easy to form, so that the pore flow area is reduced, the seepage speed of leaching liquid is seriously influenced, and the phenomena of trailing of rare earth concentration, low rare earth leaching rate and the like are generated. And because of different thicknesses of weathered layers, a large number of leaching dead areas and dead areas exist in the leaching process of the weathered crust leaching rare earth ore, so that the recovery rate of rare earth is low. These all result in waste of rare earth resources.
When the traditional ammonium sulfate leaching agent is used for leaching weathered crust leaching rare earth ores, a large amount of ammonium ions in the leaching agent solution can be adsorbed by clay minerals, so that the ammonium ions are led to be inserted into mineral lattices during ion exchange reaction, 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 ore bodies is reduced, the seepage speed is influenced, and the leaching rate of rare earth is lower. Meanwhile, when the use concentration of ammonium salt is too high during leaching, a large amount of ammonia nitrogen wastewater is generated to cause environmental pollution. Therefore, in order to improve the seepage and mass transfer processes of rare earth leaching, the effective seepage speed and the leaching and mass transfer efficiency of rare earth are improved, the resource consumption is reduced, and the environmental pollution is reduced. It is necessary to further explore and optimize the novel leaching agent to accelerate the rare earth leaching rate, improve the mass transfer efficiency of the rare earth and the solution seepage speed so as to realize the efficient and environment-friendly leaching of the weathering crust leaching rare earth ore.
Disclosure of Invention
Aiming at the problems and the defects existing in the prior art, the invention provides a composite leaching agent for weathered crust leaching 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 pollution of soil can be effectively reduced, and the environment-friendly and efficient leaching of the weathering crust leaching type rare earth ore is realized.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a composite leaching agent for weathered crust leaching 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 complex structural composition, the element composition comprises C, H, O, N and the like, and the content of the fulvic acid is more than 90wt% (FA ≡90%); wherein fulvic acid is one of humic acid substances with relatively smaller molecular weight, the molecular weight is generally more than 3000 (usually about 3000-5000), and compared with humic acid, the humic acid has the advantages of loose benzene ring connection form, lower hydrocarbon content, higher oxygen content, relatively sufficient organic carbon chain content and higher carboxyl content; besides rich carboxylic acid groups, the leaching agent also contains other active functional groups such as phenolic hydroxyl groups, alcoholic hydroxyl groups, phenol and the like, and the existence of the active functional groups such as phenolic hydroxyl groups, alcoholic hydroxyl groups and the like can promote the coordination reaction between the leaching agent solution and rare earth ions, increase the diffusion concentration difference of the rare earth ions, and is beneficial to strengthening the rapid and efficient leaching of the rare earth.
In the scheme, the concentration of the 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 the 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; the pH regulator is adopted for regulating.
Preferably, the pH value of the composite leaching agent is 5.5-6.0.
In the above 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 is sulfuric acid with the concentration of 2mol/L.
In the scheme, when the composite leaching agent is used for leaching the weathered shell leaching rare earth ore, the adopted liquid-solid ratio is 1-3:1; the leaching time is 670min or less; the leaching rate of rare earth is more than 89%.
Preferably, the liquid-solid ratio can be 2:1.
Preferably, under the condition 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, the leaching time of the weathering crust leaching rare earth ore can reach below 600 min.
More preferably, the concentration of the humic acid is 0.022 to 0.025 weight percent, and the leaching time of the weathered crust leaching rare earth ore can reach below 500 minutes under the condition that the concentration of the ammonium sulfate is 0.07 to 0.08 mol/L; can have both good leaching efficiency (significantly shortened leaching time and ensured higher leaching rate) and cost effectiveness.
The humic acid introduced by the invention has complex molecular structure and composition, contains a plurality of active functional groups such as carboxylic acid groups and a large number of organic carbon chains, can react with rare earth to generate a complex, increases the diffusion concentration difference of rare earth ions, and further improves the leaching rate and mass transfer efficiency of 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 utilizes the unique molecular structure and a large number of active functional groups such as carboxylic acid groups, can better cooperate with rare earth ions, strengthens the leaching of rare earth, and improves the leaching rate of rare earth; meanwhile, humic acid has large molecular weight and contains a large number of organic carbon chains, and the organic carbon chains have good hydrophobic property, so that the diffusion speed of rare earth ions can be accelerated, the seepage speed of leaching solution is promoted, and the seepage process of leaching is enhanced; humic acid has good solubility and fluidity, can carry out complexation with metal cations, has stronger amphoteric molecular characteristics compared with other small molecular organic acids because hydrophilic groups mainly comprising phenolic hydroxyl groups and hydrophobic groups mainly comprising carboxylic acid groups exist in the humic acid, and can form porous aggregates in acidic media to enable the humic acid molecules to have certain specific surface area.
Compared with the prior art, the invention has at least the following beneficial effects:
1) Compared with the traditional ammonium sulfate leaching agent, the humic acid-ammonium sulfate compound leaching agent can effectively promote the leaching of rare earth under the precondition that the leaching rate of the rare earth is not affected, obviously shortens the time for the rare earth to reach leaching balance, and can realize the efficient leaching of the weathering crust leaching type 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 stronger coordination, adsorption and oxidation-reduction capabilities, has a large number of active functional groups such as carboxylic acid groups and organic carbon chains, can fully play the role of reinforcing rare earth seepage process by hydrophobicity of the organic carbon chains, improving the coordination of the carboxylic acid groups and rare earth, improving the rare earth leaching rate and performing synergistic leaching with ammonium sulfate; the method has no harm to mine soil, and can effectively reduce the consumption of ammonium sulfate in the rare earth leaching process due to the unique structural property and different active functional groups, reduce the residue of ammonium after mine leaching, and play a certain role in promoting the treatment of mine tailings and the restoration of environmental pollution.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
In the following examples, column leaching tests were used to simulate the rare earth ore leaching process in situ, and the basic steps were: weighing 150g of mixed rare earth ore sample dried in a drying oven at 50 ℃ on an electronic platform scale by a quartering method, uniformly loading into a glass leaching column, horizontally placing 1-2 layers of filter paper on the ore sample, adding humic acid-ammonium sulfate compound leaching solution at a constant flow rate by a constant flow peristaltic pump to leach rare earth, collecting rare earth leaching solution of the glass column by a precise measuring cylinder, measuring the volume of the rare earth leaching solution, and then measuring the content of rare earth in the leaching solution by an EDTA complexometric titration method.
In the following examples, humic acid was provided by Allatin, wherein the content of fulvic acid was 90% or more, i.e. FA. Gtoreq.90%; the molecular weight of fulvic acid is more than 3000.
Example 1
A composite leaching agent for weathered crust leaching rare earth ore, the preparation method comprises the following steps:
6.607g of ammonium sulfate and 0.05g of humic acid are uniformly 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 regulated to 5.5 by sulfuric acid with the concentration of 2.0 mol/L; and uniformly mixing to obtain the composite leaching agent.
The composite leaching agent obtained in the embodiment is applied to leaching of weathered crust leaching rare earth ores, and comprises the following specific steps: aiming at a certain mixed weathered crust leaching 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; and 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 the rare earth leaching solution.
Tests prove that the leaching time of the composite leaching agent obtained by the embodiment is 625 minutes, the leaching time of the rare earth reaches balance, and is shortened by 160 minutes compared with the leaching time of the traditional ammonium sulfate leaching agent in comparative example 1, and the leaching rate of the rare earth is 90.1%.
Example 2
A composite leaching agent for weathered crust leaching rare earth ore, the preparation method comprises the following steps:
6.607g of ammonium sulfate and 0.1g of humic acid are uniformly 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 the pH value of the solution is regulated to 5.5 by using dilute sulfuric acid with the concentration of 2.0 mol/L; and uniformly mixing to obtain the composite leaching agent.
The composite leaching agent obtained in this example was applied to leaching of weathered crust leaching rare earth ores by the method described in reference to example 1. Tests prove that the time for reaching balance of the rare earth leaching by adopting the composite leaching agent obtained in the embodiment is 475min, the leaching time is shortened by 310min compared with the leaching time of the traditional ammonium sulfate leaching agent in comparative example 1, and the leaching rate of the rare earth is 90.8%.
Example 3
A composite leaching agent for weathered crust leaching rare earth ore, the preparation method comprises the following steps:
6.607g of ammonium sulfate and 0.25g of humic acid are uniformly 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 the pH value of the solution is regulated to 5.5 by using dilute sulfuric acid with the concentration of 2.0 mol/L; and uniformly mixing to obtain the composite leaching agent.
The composite leaching agent obtained in this example was applied to leaching of weathered crust leaching rare earth ores by the method described in reference to example 1. Tests prove that the leaching time of the composite leaching agent obtained in the embodiment is 662min, the leaching time of the rare earth reaches equilibrium, and is shortened by 123min compared with the leaching time of the traditional ammonium sulfate leaching agent in comparative example 1, and the leaching rate of the rare earth is 89.8%; compared with the embodiment 2, it can be seen that further increasing the content of humic acid is unfavorable for the rare earth to ensure the rapid and efficient leaching of the rare earth.
Example 4
A composite leaching agent for weathered crust leaching rare earth ore, the preparation method comprises the following steps:
6.607g of ammonium sulfate and 0.1g of humic acid are uniformly 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 the pH value of the solution is regulated to 6 by using dilute sulfuric acid with the concentration of 2.0 mol/L; and uniformly mixing to obtain the composite leaching agent.
The composite leaching agent obtained in this example was applied to leaching of weathered crust leaching rare earth ores by the method described in reference to example 1. Tests prove that the leaching time of the composite leaching agent obtained by the embodiment is 511min, the leaching time of the rare earth reaches equilibrium, and is 274min shorter than that of the traditional ammonium sulfate leaching agent in comparative example 1, and the leaching rate of the rare earth is 89.6%.
Example 5
A composite leaching agent for weathered crust leaching rare earth ore, the preparation method comprises the following steps:
6.607g of ammonium sulfate and 0.1g of humic acid are uniformly 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 the pH value of the solution is regulated to 6.5 by dilute sulfuric acid with the concentration of 2.0 mol/L; and uniformly mixing to obtain the composite leaching agent.
The composite leaching agent obtained in this example was applied to leaching of weathered crust leaching rare earth ores by the method described in reference to example 1. Tests prove that the leaching time of the composite leaching agent obtained by the embodiment is 523min, the leaching time of the rare earth reaches equilibrium, and compared with the leaching time of the traditional ammonium sulfate leaching agent in comparative example 1, the leaching time of the composite leaching agent is shortened by 262min, and the leaching rate of the rare earth is 89.5%.
Example 6
A composite leaching agent for weathered crust leaching rare earth ore, the preparation method comprises the following steps:
uniformly mixing 4.955g of ammonium sulfate and 0.1g of humic acid 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 adjusting the pH value of the solution to 5.5 by using dilute sulfuric acid with the concentration of 2.0 mol/L; and uniformly mixing to obtain the composite leaching agent.
The composite leaching agent obtained in this example was applied to leaching of weathered crust leaching rare earth ores by the method described in reference to example 1. Tests prove that the time for reaching equilibrium of rare earth leaching by adopting the composite leaching agent obtained in the embodiment is 532min, the leaching time is 253min shorter than that of the traditional ammonium sulfate leaching agent in comparative example 1, and the leaching rate of rare earth is 89.9%.
Example 7
A composite leaching agent for weathered crust leaching rare earth ore, the preparation method comprises the following steps:
3.3035g of ammonium sulfate and 0.1g of humic acid are uniformly 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 the pH value of the solution is regulated to 5.5 by dilute sulfuric acid with the concentration of 2.0 mol/L; and uniformly mixing to obtain the composite leaching agent.
The composite leaching agent obtained in this example was applied to leaching of weathered crust leaching rare earth ores by the method described in reference to example 1. Tests prove that the time for reaching equilibrium of rare earth leaching by adopting the composite leaching agent obtained in the embodiment is 582min, the leaching time is 203min shorter than that of the traditional ammonium sulfate leaching agent in comparative example 1, and the leaching rate of rare earth is 89.4%.
Example 8
A composite leaching agent for weathered crust leaching rare earth ore, the preparation method comprises the following steps:
uniformly mixing 4.955g of ammonium sulfate and 0.125g of humic acid 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%), and adjusting the pH value of the solution to 5.5 by using dilute sulfuric acid with the concentration of 2.0 mol/L; and uniformly mixing to obtain the composite leaching agent.
The composite leaching agent obtained in this example was applied to leaching of weathered crust leaching rare earth ores by the method described in reference to example 1. Tests prove that the time for reaching equilibrium of rare earth leaching by adopting the composite leaching agent obtained in the embodiment is 462min, the leaching time is 323min shorter than that of the traditional ammonium sulfate leaching agent in comparative example 1, and the leaching rate of rare earth is 90.5%.
Comparative example 1
A traditional ammonium sulfate leaching agent adopts an ammonium sulfate aqueous solution with the concentration of 0.1mol/L, the pH value of the solution is regulated to be 5.5 by dilute sulfuric acid with the concentration of 2.0mol/L, and the composite leaching agent obtained in the embodiment is applied to leaching weathered crust leaching rare earth ore by the method described in reference to the embodiment 1.
Tests prove that the time for reaching equilibrium by adopting the traditional ammonium sulfate leaching agent is 785min, and the leaching rate of rare earth is 89.3%.
Comparative example 2
The compound leaching agent formed by small molecular organic acid and ammonium sulfate is prepared by uniformly dissolving 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%); the pH of the solution was then adjusted to 5.5 with dilute sulfuric acid at a concentration of 2.0 mol/L.
The composite leaching agent obtained in this comparative example was applied to leaching of weathered crust leaching rare earth ores by the method described in reference example 1. Tests prove that the leaching time of the composite leaching agent obtained in the comparative example is 734min, the leaching time of the rare earth reaches balance, and is only shortened by 51min compared with the leaching time of the traditional ammonium sulfate leaching agent in the comparative example 1, and the leaching rate of the rare earth is 89.4%.
The result shows that compared with the traditional ammonium sulfate leaching agent and the rare earth leaching means of the micromolecular organic acid (formic acid) and ammonium sulfate compound leaching agent, the novel humic acid-ammonium sulfate compound leaching agent has the advantages that the leaching balance time is obviously shortened, the consumption of ammonium sulfate can be further reduced, the reduction of the residual ammonium content in soil is facilitated, and a certain positive effect is played on vegetation protection and environmental management of mines.
The above examples are presented for clarity of illustration only and are not limiting of the embodiments. Other variations and modifications of the above description will be apparent to those of ordinary skill in the art, and it is not necessary or exhaustive of all embodiments, and thus all obvious variations or modifications that come within the scope of the invention are desired to be protected.
Claims (6)
1. The application of the composite leaching agent in the weathered shell leaching 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 raw materials;
the humic acid contains more than 90wt% of fulvic acid and has a molecular weight of more than 3000;
when the composite leaching agent is used for leaching the weathered shell leaching rare earth ore, the adopted liquid-solid ratio is (1-3) 1; the leaching time is 670min or less; the leaching rate of rare earth is more than 89%.
2. The use according to claim 1, characterized in that the concentration of humic acid in the complex leaching agent is 0.01-0.05 wt%.
3. The use according to claim 1, wherein the concentration of ammonium sulphate in the composite leaching agent is 0.01-0.1 mol/L.
4. The use of claim 1, wherein the composite leaching agent is further adjusted to a pH value of 5.0-7.0 using a pH adjuster.
5. The use according to claim 4, wherein the pH adjuster is one or more of sulfuric acid, hydrochloric acid, nitric acid; the concentration is 1-3 mol/L.
6. The use according to claim 1, wherein the solvent used in the complex leach solution is water.
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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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| 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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| 试论有机质在华南花岗岩风化壳REE溶出、迁移和富集中的作用;陈志澄，陈达慧，俞受，庄文明，洪华华，符群策;地球化学;第23卷(第02期);168-178 * |
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