CN115074550A - Lithium extractant for lithium-containing red mud and method for extracting lithium from lithium-containing red mud - Google Patents
Lithium extractant for lithium-containing red mud and method for extracting lithium from lithium-containing red mud Download PDFInfo
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- lithium
- red mud
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 244
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 244
- 238000000034 method Methods 0.000 title claims abstract description 45
- -1 ammonium ions Chemical class 0.000 claims abstract description 28
- 150000001875 compounds Chemical class 0.000 claims abstract description 12
- 239000000463 material Substances 0.000 claims description 35
- 239000007787 solid Substances 0.000 claims description 28
- 238000001035 drying Methods 0.000 claims description 19
- 238000000227 grinding Methods 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 16
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 14
- 238000000926 separation method Methods 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 12
- 150000003863 ammonium salts Chemical class 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 9
- 235000019270 ammonium chloride Nutrition 0.000 claims description 7
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 7
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 7
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 7
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 6
- 239000001099 ammonium carbonate Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 3
- XZXYQEHISUMZAT-UHFFFAOYSA-N 2-[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol Chemical compound CC1=CC=C(O)C(CC=2C(=CC=C(C)C=2)O)=C1 XZXYQEHISUMZAT-UHFFFAOYSA-N 0.000 claims description 3
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 3
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 3
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 3
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 claims description 3
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 claims description 3
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 3
- 229940107816 ammonium iodide Drugs 0.000 claims description 3
- 238000000605 extraction Methods 0.000 abstract description 52
- 238000006243 chemical reaction Methods 0.000 abstract description 47
- 150000002500 ions Chemical class 0.000 abstract description 40
- 239000003795 chemical substances by application Substances 0.000 abstract description 23
- 229910052782 aluminium Inorganic materials 0.000 abstract description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052710 silicon Inorganic materials 0.000 abstract description 8
- 239000010703 silicon Substances 0.000 abstract description 8
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 6
- 239000012535 impurity Substances 0.000 abstract description 5
- 229910003002 lithium salt Inorganic materials 0.000 abstract description 4
- 159000000002 lithium salts Chemical class 0.000 abstract description 4
- 238000002360 preparation method Methods 0.000 abstract description 4
- 229910010199 LiAl Inorganic materials 0.000 abstract description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 abstract description 3
- 238000006467 substitution reaction Methods 0.000 abstract description 3
- 238000005342 ion exchange Methods 0.000 description 9
- 238000002386 leaching Methods 0.000 description 9
- 239000000706 filtrate Substances 0.000 description 8
- 230000035484 reaction time Effects 0.000 description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 229910052733 gallium Inorganic materials 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910052706 scandium Inorganic materials 0.000 description 2
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 229910001388 sodium aluminate Inorganic materials 0.000 description 2
- 239000002910 solid waste Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910052925 anhydrite Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 1
- 229910052663 cancrinite Inorganic materials 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002223 garnet Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 150000008040 ionic compounds Chemical class 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
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
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
- C22B26/12—Obtaining lithium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention provides a lithium extracting agent for lithium-containing red mud and a method for extracting lithium from the lithium-containing red mud, belonging to the technical field of lithium extraction, wherein the lithium extracting agent comprises the following components: a compound containing ammonium ions. The lithium extracting agent comprises a compound containing ammonium ions, and lithium in the red mud is replaced by LiAl according to the principle of ion replacement 2 (OH) 7 ·2H 2 O form exists, is a layered structure, and Li is added for maintaining charge balance + In octahedral cavities of aluminum hydroxide, NH during extraction 4 + With Li + Ion substitution reaction occurs, so that Li + And the lithium ion is subjected to ion replacement reaction in the solution, so that the high-efficiency and selective extraction of lithium from the lithium-containing red mud is realized, the content of impurities such as silicon, aluminum and the like in the extracted solution is low, and the subsequent preparation of high-quality lithium salt is facilitated.
Description
Technical Field
The application relates to the technical field of lithium extraction, in particular to a lithium extracting agent for lithium-containing red mud and a method for extracting lithium from the lithium-containing red mud.
Background
The red mud is solid waste generated in the alumina industry, 1-1.5 tons of red mud are generated in each 1 ton of alumina, and the total amount of red mud piled globally approaches 40 hundred million tons. The chemical components of the red mud are determined by ore components and a production process, and the red mud mainly contains elements such as sodium, aluminum, silicon, iron, calcium, titanium and the like, and also contains rare metals such as gallium, scandium, vanadium, lithium and the like, so that the red mud is a potential secondary solid resource.
At present, no report related to lithium extraction by taking lithium-containing red mud as a raw material exists in the prior art.
Disclosure of Invention
The application provides a lithium extracting agent for lithium-containing red mud and a method for extracting lithium from the lithium-containing red mud, which aim to solve the problem that the prior art is blank for extracting lithium from the lithium-containing red mud.
In a first aspect, the present application provides a lithium extractant for lithium-containing red mud, the lithium extractant comprising the following components: a compound containing ammonium ions.
Further, the compound containing an ammonium ion includes an ammonium salt.
Further, the ammonium salt includes at least one of ammonium sulfate, ammonium chloride, ammonium nitrate, ammonium carbonate, ammonium bicarbonate, ammonium bisulfate, ammonium fluoride, ammonium iodide, and ammonium bromide.
Further, the lithium extractant further includes: a solvent.
Further, the solvent includes: and (3) water.
In a second aspect, the present application provides a method for extracting lithium from lithium-containing red mud, the method comprising:
obtaining lithium-containing red mud;
mixing the lithium-containing red mud with the lithium extraction agent of the first aspect to obtain a first mixed material;
heating and stirring the first mixed material to obtain a second mixed material;
and carrying out solid-liquid separation on the second mixed material to obtain a lithium-rich solution.
Further, the content of ammonium ions in the first mixed material is 5 to 30 wt% in terms of weight fraction.
Further, the liquid-solid ratio in the first mixed material is 1-15.
Further, the first mixed material is heated and stirred to obtain a second mixed material, and the specific process comprises the following steps:
and heating and stirring the first mixed material at the temperature of 200-280 ℃ for 1-4 h to obtain a second mixed material.
Further, the lithium-containing red mud is obtained by the following specific processes:
drying the lithium-containing red mud, and grinding to obtain the lithium-containing red mud.
Compared with the prior art, the technical scheme provided by the embodiment of the application has the following advantages:
the embodiment of the application provides a lithium extraction agent for lithium-containing red mud, the lithium extraction agent comprises a compound containing ammonium ions, and lithium in the red mud is LiAl by adopting an ion replacement principle 2 (OH) 7 ·2H 2 O form exists, and is a layered structure, and Li is used for keeping charge balance + In octahedral cavities of aluminum hydroxide, NH during extraction 4 + With Li + Ion substitution reaction occurs, so that Li + And the lithium ion is subjected to ion replacement reaction in the solution, so that the high-efficiency and selective extraction of lithium from the lithium-containing red mud is realized, the content of impurities such as silicon, aluminum and the like in the extracted solution is low, and the subsequent preparation of high-quality lithium salt is facilitated.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the invention and together with the description, serve to explain the principles of the invention.
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without inventive exercise.
Fig. 1 is a schematic flow chart of a method for extracting lithium from lithium-containing red mud provided by the present application;
fig. 2 is a schematic operation flow diagram of a method for extracting lithium from lithium-containing red mud provided in embodiment 1 of the present application.
Detailed Description
The present invention will be described in detail below with reference to specific embodiments and examples, and the advantages and various effects of the present invention will be more clearly apparent therefrom. It will be understood by those skilled in the art that these specific embodiments and examples are illustrative of the invention and are not to be construed as limiting the invention.
Throughout the specification, unless otherwise specifically noted, terms used herein should be understood as having meanings as commonly used in the art. Accordingly, unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. If there is a conflict, the present specification will control.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
The red mud is solid waste generated in the alumina industry, 1-1.5 tons of red mud are generated per 1 ton of alumina, and the total amount of red mud globally stockpiled is close to 40 hundred million tons. The chemical components of the red mud are determined by ore components and a production process, and the red mud mainly contains elements such as sodium, aluminum, silicon, iron, calcium, titanium and the like, and also contains rare metals such as gallium, scandium, vanadium, lithium and the like, so that the red mud is a potential secondary solid resource. During the high temperature digestion process, about 80% of lithium in the anhydrite ore enters the sodium aluminate solution, and 20% enters the red mud. In the red mud separation and washing process, the equilibrium concentration of lithium in the sodium aluminate solution is reduced along with the reduction of the concentration of caustic alkali, and part of lithium in the solution is separated out in the red mud separation process and enters the red mud again, so that the lithium content in the discharged red mud is high. According to investigation of Li in red mud discharged by alumina enterprises in Henan province 2 The O content is usually 0.1-0.2%, and for an enterprise producing 100 ten thousand tons of aluminum oxide annually, the lithium resource amount taken away by discharged red mud per year exceeds 3000tLEC (lithium carbonate equivalent), so that the method causes extremely high yieldAnd large resource waste.
At present, no relevant report of extracting lithium by taking lithium-containing red mud as a raw material exists in the prior art.
In order to solve the technical problems, the embodiment of the invention provides the following general ideas:
in a first aspect, the present application provides a lithium extractant for lithium-containing red mud, comprising the following components: a compound containing ammonium ions.
The embodiment of the application provides a lithium extraction agent for lithium-containing red mud, the lithium extraction agent comprises a compound containing ammonium ions, and lithium in the red mud is LiAl by adopting an ion replacement principle 2 (OH) 7 ·2H 2 O form exists, and is a layered structure, and Li is used for keeping charge balance + In octahedral cavities of aluminum hydroxide, NH during extraction 4 + With Li + Ion substitution reaction occurs, so that Li + And the lithium ion is subjected to ion replacement reaction in the solution, so that the high-efficiency and selective extraction of lithium from the lithium-containing red mud is realized, the content of impurities such as silicon, aluminum and the like in the extracted solution is low, and the subsequent preparation of high-quality lithium salt is facilitated.
In the application, the aluminum and silicon in cancrinite and hydrated garnet in the red mud hardly undergo leaching reaction in the ammonium ion solution, so that the content of impurities such as silicon, aluminum and magnesium in the leaching solution is low, and sodium and potassium ions in the leaching solution have no influence on subsequent lithium extraction, so that the selective lithium extraction can be realized.
As an implementation of an embodiment of the present invention, the compound containing ammonium ions includes an ammonium salt.
In the present application, the ammonium salt refers to an ionic compound composed of an ammonium ion and an acid ion, and is generally obtained by reacting ammonia with an acid.
As an implementation of the embodiment of the present invention, the ammonium salt includes at least one of ammonium sulfate, ammonium chloride, ammonium nitrate, ammonium carbonate, ammonium bicarbonate, ammonium bisulfate, ammonium fluoride, ammonium iodide, and ammonium bromide.
As an implementation of the embodiments of the present invention, the lithium extractant further includes: a solvent.
The lithium extraction agent for lithium-containing red mud provided by the embodiment of the application can exist in the form of a solid reagent and also can exist in the form of a liquid reagent. The lithium extractant may be suitably added with a solvent for practical purposes, such as convenience in storage and transportation. Specifically, when an ammonium salt is used as the compound containing ammonium ions, the solid ammonium salt is poor in thermal stability and is easily decomposed by heat, and a solvent may be added to the lithium extractant to facilitate long-term storage and prevent the deterioration of the lithium extractant.
In addition, in the application, the ratio of the solvent to the compound containing ammonium ions in the lithium extraction agent is not particularly limited, and when the lithium extraction agent is specifically applied to the process of extracting lithium from lithium-containing red mud, the dosage of the solvent can be adaptively increased or decreased on the application site, so that the ammonium ions in the on-site application system are kept at a certain effective concentration, and the efficient and selective extraction of lithium from the lithium-containing red mud can be realized.
As an embodiment of the embodiments of the present invention, the solvent includes: and (3) water.
In a second aspect, the present application provides a method for extracting lithium from lithium-containing red mud, as shown in fig. 1, the method comprising:
obtaining lithium-containing red mud;
mixing the lithium-containing red mud with the lithium extraction agent of the first aspect to obtain a first mixed material;
heating and stirring the first mixed material to obtain a second mixed material;
and carrying out solid-liquid separation on the second mixed material to obtain a lithium-rich solution.
According to the method for extracting lithium from lithium-containing red mud provided by the embodiment of the application, the lithium extracting agent in the first aspect is mixed with the lithium-containing red mud, and then the mixture is heated and stirred to perform an ion displacement reaction, so that lithium in the lithium-containing red mud enters a solution, the high-efficiency and selective extraction of lithium from the lithium-containing red mud is realized, the content of impurities such as silicon, aluminum and the like in the leached solution is low, a lithium-rich solution is obtained, and the subsequent preparation of high-quality lithium salt is facilitated.
According to the method for extracting lithium from lithium-containing red mud, provided by the embodiment of the application, the ammonium salt and the like are used as lithium extracting agents, so that the high-efficiency extraction of lithium can be realized, the roasting process with high energy consumption is avoided, and the method is energy-saving and environment-friendly; the extraction process does not need strong sulfuric acid, and is environment-friendly; beneficial ammonium ions can be introduced while extracting lithium, which is beneficial to the soil improvement of the red mud.
As an implementation manner of the embodiment of the invention, the content of the ammonium ions in the first mixed material is 5 wt% to 30 wt% in terms of weight fraction.
In the application, the control of the ion exchange reaction rate is mainly realized by controlling the content of ammonium ions in the first mixed material, and the adverse effect of the excessively low content of the ammonium ions in the first mixed material is that the leaching rate of lithium is low; the adverse effect of too high a content of ammonium ions in the first mixture is to increase the solution viscosity and reduce the leaching rate of lithium. Therefore, the content of the ammonium ions in the first mixed material is controlled to be 5-30 wt%.
As an implementation manner of the embodiment of the invention, the liquid-solid ratio in the first mixed material is 1-15.
In the application, the reaction rate is influenced by the excessively low ratio of the liquid-solid ratio in the first mixed material, and the lithium extraction efficiency is reduced; the liquid-solid ratio is too large, and the lithium concentration in the leaching solution is low. Therefore, the liquid-solid ratio in the first mixed material is controlled to be 1-15.
In the present application, the liquid-solid ratio refers to the ratio of the mass of a solvent such as water to the mass of a solid material in the first mixed material system. In some embodiments, the liquid-to-solid ratio in the first mixed feed can be 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, and the like.
As an implementation manner of the embodiment of the present invention, the first mixed material is heated and stirred to obtain a second mixed material, and the specific process includes:
and heating and stirring the first mixed material at the temperature of 200-280 ℃ for 1-4 h to obtain a second mixed material.
In the application, the temperature for heating and stirring the first mixed material is too low, and the reaction rate is low; ammonium salt is easily decomposed when the temperature is too high, the reaction rate is influenced, and the lithium extraction effect is reduced. Therefore, the temperature is controlled to be 200 ℃ to 280 ℃.
Herein, in some embodiments, the heating and stirring temperature may be 210 ℃, 220 ℃, 230 ℃, 240 ℃, 250 ℃, 260 ℃, 270 ℃, 280 ℃ and the like; the stirring time can be 1h, 2h, 3h, 4h and the like.
As an implementation manner of the embodiment of the invention, the lithium-containing red mud is obtained by the following specific processes:
drying the lithium-containing red mud, and grinding to obtain the lithium-containing red mud.
In the present application, in order to improve the lithium extraction efficiency, the lithium-containing red mud may be dried and ground in advance. In some embodiments, optionally, the lithium-containing red mud may be dried at 150-200 ℃ for 2-4h, and then ground to a particle size of less than 200 mesh to obtain the lithium-containing red mud.
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The experimental methods of the following examples, which are not specified under specific conditions, are generally determined according to national standards. If there is no corresponding national standard, it is carried out according to the usual international standards, to the conventional conditions or to the conditions recommended by the manufacturer.
Throughout the specification, unless otherwise specifically noted, terms used herein should be understood as having meanings as commonly used in the art. Accordingly, unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. If there is a conflict, the present specification will control. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention. For example, the room temperature may be a temperature within a range of 10 to 35 ℃.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
Example 1
The embodiment provides a method for extracting lithium from lithium-containing red mud, as shown in fig. 2, which includes the following steps:
s1, obtaining lithium-containing red mud;
s2, drying the lithium-containing red mud; wherein: drying temperature: at 150 ℃, the time is 2 hours;
s3, grinding the dried lithium-containing red mud; wherein: grinding the lithium-containing red mud to the granularity of less than 200 meshes;
s4, adding the ground lithium-containing red mud into a lithium extractant solution, mixing and heating the mixture, and performing ion replacement lithium extraction reaction; wherein: the lithium extractant comprises ammonium sulfate; the mass fraction of ammonium ions in the ion replacement lithium extraction reaction system is 5%; the temperature of the ion replacement reaction is 200 ℃; the solid-to-solid ratio of the ion exchange reaction solution is 1; the ion replacement reaction time is 1 h;
s5, after the reaction is finished, carrying out solid-liquid separation, wherein the solid is modified red mud; the filtrate is the lithium-rich solution.
In this example, the leaching rate of lithium was 60%.
Example 2
The embodiment provides a method for extracting lithium from lithium-containing red mud, which comprises the following steps:
s1, obtaining lithium-containing red mud;
s2, drying the lithium-containing red mud; wherein: drying temperature: at 150 ℃, the time is 3 hours;
s3, grinding the dried lithium-containing red mud; wherein: grinding the lithium-containing red mud to the granularity of less than 200 meshes;
s4, adding the ground lithium-containing red mud into a lithium extractant solution, mixing and heating the mixture, and performing ion replacement lithium extraction reaction; wherein: the lithium extractant comprises ammonium sulfate; the mass fraction of ammonium ions in the ion replacement lithium extraction reaction system is 10 percent; the temperature of the ion replacement reaction is 250 ℃; the solid-to-solid ratio of the ion exchange reaction liquid is 5; the ion replacement reaction time is 2 hours;
s5, after the reaction is finished, carrying out solid-liquid separation, wherein the solid is modified red mud; the filtrate is the lithium-rich solution.
In this example, the lithium extraction rate was 65%.
Example 3
The embodiment provides a method for extracting lithium from lithium-containing red mud, which comprises the following steps:
s1, obtaining lithium-containing red mud;
s2, drying the lithium-containing red mud; wherein: drying temperature: at 150 ℃, the time is 4 hours;
s3, grinding the dried lithium-containing red mud; wherein: grinding the lithium-containing red mud to the granularity of less than 200 meshes;
s4, adding the ground lithium-containing red mud into a lithium extractant solution, mixing and heating the mixture, and performing ion replacement lithium extraction reaction; wherein: the lithium extracting agent is ammonium sulfate; the mass fraction of ammonium ions in the ion replacement lithium extraction reaction system is 15%; the temperature of the ion replacement reaction is 270 ℃; the solid-to-solid ratio of the ion exchange reaction solution is 10; the ion replacement reaction time is 3 hours;
s5, after the reaction is finished, carrying out solid-liquid separation, wherein the solid is modified red mud; the filtrate is the lithium-rich solution.
In this example, the lithium extraction rate was 68%.
Example 4
The embodiment provides a method for extracting lithium from lithium-containing red mud, which comprises the following steps:
s1, obtaining lithium-containing red mud;
s2, drying the lithium-containing red mud; wherein: drying temperature: at 200 ℃ for 2 h;
s3, grinding the dried lithium-containing red mud; wherein: grinding the lithium-containing red mud to the granularity of less than 200 meshes;
s4, adding the ground lithium-containing red mud into a lithium extractant solution, mixing and heating the mixture, and performing ion replacement lithium extraction reaction; wherein: the lithium extracting agent is ammonium sulfate; the mass fraction of ammonium ions in the ion replacement lithium extraction reaction system is 20%; the temperature of the ion replacement reaction is 280 ℃; the solid-to-solid ratio of the ion exchange reaction solution is 15; the ion replacement reaction time is 4 h;
s5, after the reaction is finished, carrying out solid-liquid separation, wherein the solid is modified red mud; the filtrate is the lithium-rich solution.
In this example, the leaching rate of lithium was 80%.
Example 5
The embodiment provides a method for extracting lithium from lithium-containing red mud, which comprises the following steps:
s1, obtaining lithium-containing red mud;
s2, drying the lithium-containing red mud; wherein: drying temperature: the temperature is 200 ℃ and the time is 3 h;
s3, grinding the dried lithium-containing red mud; wherein: grinding the lithium-containing red mud to the granularity of less than 200 meshes;
s4, adding the ground lithium-containing red mud into a lithium extractant solution, mixing and heating the mixture, and performing ion replacement lithium extraction reaction; wherein: the lithium extraction agent is ammonium chloride; the mass fraction of ammonium ions in the ion replacement lithium extraction reaction system is 25%; the temperature of the ion replacement reaction is 260 ℃; the solid-to-solid ratio of the ion exchange reaction solution is 1; the ion replacement reaction time is 2 hours;
s5, after the reaction is finished, carrying out solid-liquid separation, wherein the solid is modified red mud; the filtrate is the lithium-rich solution.
In this example, the lithium extraction rate was 75%.
Example 6
The embodiment provides a method for extracting lithium from lithium-containing red mud, which comprises the following steps:
s1, obtaining lithium-containing red mud;
s2, drying the lithium-containing red mud; wherein: drying temperature: at 200 ℃ for 4 h;
s3, grinding the dried lithium-containing red mud; wherein: grinding the lithium-containing red mud to the granularity of less than 200 meshes;
s4, adding the ground lithium-containing red mud into a lithium extractant solution, mixing and heating the mixture, and performing ion replacement lithium extraction reaction; wherein: the lithium extraction agent is ammonium chloride; the mass fraction of ammonium ions in the ion replacement lithium extraction reaction system is 25%; the temperature of the ion replacement reaction is 280 ℃; the solid-to-solid ratio of the ion exchange reaction solution is 10; the ion replacement reaction time is 4 h;
s5, after the reaction is finished, carrying out solid-liquid separation, wherein the solid is modified red mud; the filtrate is the lithium-rich solution.
In this example, the leaching rate of lithium was 85%.
Example 7
The embodiment provides a method for extracting lithium from lithium-containing red mud, which comprises the following steps:
s1, obtaining lithium-containing red mud;
s2, drying the lithium-containing red mud; wherein: drying temperature: at 200 ℃ for 4 h;
s3, grinding the dried lithium-containing red mud; wherein: grinding the lithium-containing red mud to the granularity of less than 200 meshes;
s4, adding the ground lithium-containing red mud into a lithium extractant solution, mixing and heating the mixture, and performing ion replacement lithium extraction reaction; wherein: the lithium extraction agent is ammonium chloride; the mass fraction of ammonium ions in the ion replacement lithium extraction reaction system is 30 percent; the temperature of the ion replacement reaction is 280 ℃; the solid-to-solid ratio of the ion exchange reaction solution is 15; the ion replacement reaction time is 4 h;
s5, after the reaction is finished, carrying out solid-liquid separation, wherein the solid is modified red mud; the filtrate is the lithium-rich solution.
In this example, the lithium extraction rate was 90%.
Example 8
The embodiment provides a method for extracting lithium from lithium-containing red mud, which comprises the following steps:
s1, obtaining lithium-containing red mud;
s2, drying the lithium-containing red mud; wherein: drying temperature: at 200 ℃ for 4 h;
s3, grinding the dried lithium-containing red mud; wherein: grinding the lithium-containing red mud to the granularity of less than 200 meshes;
s4, adding the ground lithium-containing red mud into a lithium extractant solution, mixing and heating the mixture, and performing ion replacement lithium extraction reaction; wherein: the lithium extraction agent is ammonium chloride; the mass fraction of ammonium ions in the ion replacement lithium extraction reaction system is 26%; the temperature of the ion replacement reaction is 250 ℃; the solid-to-solid ratio of the ion exchange reaction solution is 15; the ion replacement reaction time is 4 h;
s5, after the reaction is finished, carrying out solid-liquid separation, wherein the solid is modified red mud; the filtrate is the lithium-rich solution.
In this example, the lithium extraction rate was 78%.
It is noted that, in this document, relational terms such as "first" and "second," and the like, may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising … …" does not exclude the presence of other identical elements in a process, method, article, or apparatus that comprises the element.
The foregoing are merely exemplary embodiments of the present invention, which enable those skilled in the art to understand or practice the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A lithium extractant for lithium-containing red mud is characterized by comprising the following components: a compound containing ammonium ions.
2. The lithium extractant for lithium-containing red mud according to claim 1, characterized in that the compound containing ammonium ions comprises an ammonium salt.
3. The lithium extractant for lithium-containing red mud of claim 2, characterized in that the ammonium salt comprises at least one of ammonium sulfate, ammonium chloride, ammonium nitrate, ammonium carbonate, ammonium bicarbonate, ammonium bisulfate, ammonium fluoride, ammonium iodide, and ammonium bromide.
4. The lithium extractant for lithium-containing red mud according to any one of claims 1 to 3, further comprising: a solvent.
5. The lithium extractant for lithium-containing red mud according to claim 4, characterized in that the solvent comprises: and (3) water.
6. A method for extracting lithium from lithium-containing red mud is characterized by comprising the following steps:
obtaining lithium-containing red mud;
mixing the lithium-containing red mud with the lithium extractant of any one of claims 1 to 5 to obtain a first mixed material;
heating and stirring the first mixed material to obtain a second mixed material;
and carrying out solid-liquid separation on the second mixed material to obtain a lithium-rich solution.
7. The method according to claim 6, wherein the content of ammonium ions in the first mixed material is 5-30 wt.% in terms of weight fraction.
8. The method for extracting lithium from lithium-containing red mud according to claim 6, wherein the liquid-solid ratio in the first mixed material is 1-15.
9. The method according to claim 6, wherein the first mixture is heated and stirred to obtain a second mixture, and the specific process comprises:
and heating and stirring the first mixed material at the temperature of 200-280 ℃ for 1-4 h to obtain a second mixed material.
10. The method for extracting lithium from lithium-containing red mud according to claim 6, wherein the lithium-containing red mud is obtained by the following specific processes:
drying the lithium-containing red mud, and grinding to obtain the lithium-containing red mud.
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