CN113371737A - Method for removing impurities and co-producing hydrotalcite by lithium-containing refined feed liquid - Google Patents
Method for removing impurities and co-producing hydrotalcite by lithium-containing refined feed liquid Download PDFInfo
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- 239000007788 liquid Substances 0.000 title claims abstract description 119
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 75
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 74
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 title claims abstract description 46
- 229960001545 hydrotalcite Drugs 0.000 title claims abstract description 46
- 229910001701 hydrotalcite Inorganic materials 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 45
- 239000012535 impurity Substances 0.000 title claims abstract description 29
- 150000002736 metal compounds Chemical class 0.000 claims abstract description 52
- 238000001556 precipitation Methods 0.000 claims abstract description 38
- 239000000463 material Substances 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 150000001875 compounds Chemical class 0.000 claims abstract description 20
- 239000002135 nanosheet Substances 0.000 claims abstract description 17
- 238000005406 washing Methods 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 14
- 238000000926 separation method Methods 0.000 claims abstract description 8
- 239000007787 solid Substances 0.000 claims abstract description 5
- 229910052751 metal Inorganic materials 0.000 claims description 38
- 239000002184 metal Substances 0.000 claims description 38
- 239000003513 alkali Substances 0.000 claims description 25
- 239000011777 magnesium Substances 0.000 claims description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 229910021645 metal ion Inorganic materials 0.000 claims description 20
- 229910052749 magnesium Inorganic materials 0.000 claims description 18
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 17
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 17
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 17
- 150000003839 salts Chemical class 0.000 claims description 15
- 229910001416 lithium ion Inorganic materials 0.000 claims description 12
- 239000012528 membrane Substances 0.000 claims description 12
- 239000010936 titanium Substances 0.000 claims description 12
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 11
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Substances [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 11
- 229910052782 aluminium Inorganic materials 0.000 claims description 10
- 239000003463 adsorbent Substances 0.000 claims description 8
- -1 aluminum ions Chemical class 0.000 claims description 8
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 8
- 229910052719 titanium Inorganic materials 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- 238000001179 sorption measurement Methods 0.000 claims description 6
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 5
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 claims description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 5
- 239000004202 carbamide Substances 0.000 claims description 5
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 5
- 239000011572 manganese Substances 0.000 claims description 5
- 229910001437 manganese ion Inorganic materials 0.000 claims description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 4
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 238000000909 electrodialysis Methods 0.000 claims description 3
- 238000001728 nano-filtration Methods 0.000 claims description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 238000000409 membrane extraction Methods 0.000 claims description 2
- 229910001510 metal chloride Inorganic materials 0.000 claims description 2
- 229910001960 metal nitrate Inorganic materials 0.000 claims description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims 1
- 238000007670 refining Methods 0.000 abstract description 6
- 238000002360 preparation method Methods 0.000 abstract description 3
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 26
- 239000002244 precipitate Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 150000001768 cations Chemical class 0.000 description 8
- 238000001228 spectrum Methods 0.000 description 8
- 238000002156 mixing Methods 0.000 description 7
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 6
- 238000003795 desorption Methods 0.000 description 5
- 150000001450 anions Chemical class 0.000 description 4
- 239000011229 interlayer Substances 0.000 description 4
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 4
- 239000000347 magnesium hydroxide Substances 0.000 description 4
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 4
- 229910000000 metal hydroxide Inorganic materials 0.000 description 4
- 150000004692 metal hydroxides Chemical class 0.000 description 4
- 239000010410 layer Substances 0.000 description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 description 3
- GCICAPWZNUIIDV-UHFFFAOYSA-N lithium magnesium Chemical compound [Li].[Mg] GCICAPWZNUIIDV-UHFFFAOYSA-N 0.000 description 3
- 229910003002 lithium salt Inorganic materials 0.000 description 3
- 159000000002 lithium salts Chemical class 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 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 1
- 229910020068 MgAl Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000000502 dialysis Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 239000012527 feed solution Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000005373 pervaporation Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/006—Compounds containing, besides manganese, two or more other elements, with the exception of oxygen or hydrogen
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/009—Compounds containing, besides iron, two or more other elements, with the exception of oxygen or hydrogen
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G9/00—Compounds of zinc
- C01G9/006—Compounds containing, besides zinc, two ore more other elements, with the exception of oxygen or hydrogen
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
Abstract
The invention discloses a method for removing impurities and co-producing hydrotalcite by lithium-containing refined feed liquid, which comprises the following steps: uniformly dispersing a metal compound in a refined lithium-containing feed liquid to obtain a pre-precipitation feed liquid, wherein the metal compound is a first compound or a second compound, the first compound is a divalent metal compound and a high-valence metal compound, the second compound is a high-valence metal compound, and the high-valence metal compound is a trivalent metal compound and/or a tetravalent metal compound; when the pH value of the pre-precipitation material liquid is lower than 7.2, adjusting the pH value of the pre-precipitation material liquid to 7.2-13.5, reacting at a reaction temperature, then carrying out solid-liquid separation, washing and drying a solid part to obtain a hydrotalcite nanosheet, and obtaining a lithium-containing material liquid without impurities from a liquid part; and when the pH value of the pre-precipitation feed liquid is 7.2-13.5, the step of regulating the pH value again is omitted. The method realizes the refining and impurity removal in the lithium-containing feed liquid and the preparation of the high-valued hydrotalcite nanosheet in one step.
Description
Technical Field
The invention belongs to the technical field of inorganic chemistry, and particularly relates to a method for removing impurities and co-producing hydrotalcite by lithium-containing refined feed liquid.
Background
The Qinghai is rich in salt lake resources, wherein the salt lake resources are rich in magnesium, lithium, potassium, sodium and other resources. Wherein, the physical and chemical properties of the magnesium and the lithium are similar, and the separation difficulty is large. The current method for extracting lithium from salt lake mainly comprises the following steps: (1) precipitation, (2) adsorption, (3) calcination, (4) membrane separation, and (5) extraction. The method such as adsorption method, calcination method, membrane separation method and the like has the advantage of well reducing the magnesium-lithium ratio, and is particularly suitable for extracting lithium from salt lakes such as Qinghai, Tibet, Vivian and the like. However, in the purification solution in which the magnesium-lithium ratio is reduced by these methods, a part of magnesium still exists, and the existence of this part of magnesium affects the quality of lithium salts such as lithium carbonate, lithium hydroxide, and lithium chloride, and therefore, it is necessary to purify magnesium in the lithium-containing purification solution. The traditional method for refining and removing magnesium from lithium-containing feed liquid mainly adopts a precipitation method, and the method generally comprises the steps of adding an alkali solution into the lithium-containing feed liquid at a low temperature, converting magnesium ions into magnesium hydroxide, filtering and removing the magnesium hydroxide, so that the method has a good refining and magnesium removing effect, but the by-product magnesium hydroxide has high impurity content, irregular shape and low quality, and is abandoned by most enterprises. However, the part of the by-product magnesium hydroxide not only carries a large amount of lithium, but also wastes lithium and magnesium when being directly discarded; but recycling can increase enterprise costs.
In addition, in the extraction of lithium by the adsorption method, a small amount of magnesium ions may be contained in the lithium-containing feed liquid after elution, and a part of components of a lithium salt adsorbent, such as aluminum, manganese, titanium and the like, are also introduced, and the existence of the part of impurity ions also affects the quality of subsequent lithium products.
The composite metal hydroxide (hydrotalcite, LDHs for short) is a layered material, and the LDHs is assembled by a metal hydroxide layer plate with positive charges and interlayer anions with negative charges, wherein the metal hydroxide layer plate is provided with metal cations with different charges. In the existing LDHs, the metal cations are mainly divalent metal cations and trivalent metal cations, and thus the general structural formula of the LDHs can be represented as follows: [ M ] A+M2+ 1-y-0.5x-2zM3+ yM4+ z(OH)2](An-)y/n·mH2O, wherein M+、M2+、M3+And M4+Respectively represent monovalent metal cations, divalent metal cations, trivalent metal cations and tetravalent metal cations on a metal hydroxide layer plate, An-Represents interlayer anion, x is more than or equal to 0 and less than or equal to 0.4, y is more than or equal to 0 and less than or equal to 0.7, z is more than or equal to 0 and less than or equal to 0.5, and y is more than or equal to 0 and less than or equal to 0.5x and 2z is less than or equal to 1, wherein y and z cannot be 0 at the same time, and m is the molar quantity of interlayer water molecules. Because the structural particularity and the performance of the LDHs are greatly enhanced, the LDHs attract wide interest and high attention in the research fields of catalysis, energy sources, biosensors, adsorption, medicines and the like.
The invention provides a method for removing impurities and co-producing hydrotalcite by lithium-containing refined feed liquid, which realizes the refining impurity removal in the lithium-containing feed liquid and the preparation of high-valued hydrotalcite nanosheets in one step.
Disclosure of Invention
The invention provides a method for removing impurities and co-producing hydrotalcite by lithium-containing refined feed liquid, which realizes the refining impurity removal in the lithium-containing feed liquid and the preparation of high-valued hydrotalcite nanosheets in one step.
A method for removing impurities and co-producing hydrotalcite by lithium-containing refined feed liquid comprises the following steps:
uniformly dispersing a metal compound in a lithium-containing refined feed liquid to obtain a pre-precipitation feed liquid, wherein the metal compound is a first compound or a second compound, the first compound is a divalent metal compound and a high-valence metal compound, the second compound is a high-valence metal compound, the molar ratio of the sum of divalent metal ions to the sum of high-valence metal ions in the pre-precipitation feed liquid is (2-100) to 1, and the high-valence metal compound is a trivalent metal compound and/or a tetravalent metal compound; when the pH value of the pre-precipitation material liquid is lower than 7.2, adjusting the pH value of the pre-precipitation material liquid to 7.2-13.5, reacting for 0.5-24 h at the reaction temperature of 5-160 ℃, then carrying out solid-liquid separation, washing and drying a solid part to obtain a hydrotalcite nanosheet, and obtaining a lithium-containing material liquid without impurities from a liquid part; when the pH value of the pre-precipitation material liquid is 7.2-13.5, the step of adjusting the pH value of the pre-precipitation material liquid to 7.2-13.5 is omitted;
the content of magnesium ions in the lithium-containing refined feed liquid is 0.01-100 g/L, the content of aluminum ions is 0-100 g/L, the content of manganese ions is 0-110 g/L, the content of titanium ions is 0-100 g/L, the content of lithium ions is 0.01-50 g/L, the divalent metal compound is divalent metal salt or divalent metal alkali, the trivalent metal compound is trivalent metal salt or trivalent metal alkali, and the tetravalent metal compound is tetravalent metal salt or tetravalent metal alkali;
the divalent metal ion is Mg2+、Zn2+、Ca2+、Cu2+、Ni2+、Co2+、Fe2+、Mn2+、Cd2+Or Be2+At least one of; the trivalent metal ion being Al3+、Ni3+、Co3+、Fe3+、Mn3+、Cr3+、V3+、Ti3+、In3+Or Ga3+At least one of; the tetravalent metal ion being Sn4+、Ti4+Or Zr4+At least one of (1).
In the technical scheme, the process of adjusting the pH value of the pre-precipitation material liquid to 7.2-13.5 is realized by adding an alkali solution into the pre-precipitation material liquid, wherein the alkali solution is one or more of a NaOH solution, a KOH solution, a LiOH solution, an ammonia water solution, a hydrazine hydrate solution, a hexamethylenetetramine solution or a urea solution.
In the technical scheme, the content of magnesium in the lithium-containing refined feed liquid is 0.1-30 g/L, and the content of lithium is 0.1-20 g/L.
In the technical scheme, the concentration of the alkali solution is 0.1-10 mol/L.
In the technical scheme, the reaction temperature is 80-150 ℃.
In the above technical scheme, the metal salt is metal sulfate, metal nitrate, metal oxalate or metal chloride.
In the above technical scheme, the lithium-containing refined feed liquid is obtained after treatment by an electrodialysis method, a membrane adsorption method and a liquid membrane extraction method, or is obtained after treatment by a nanofiltration membrane, or is subjected to delithiation by an aluminum-based, manganese-based or titanium-based adsorbent.
A method for removing impurities and co-producing hydrotalcite by lithium-containing refined feed liquid comprises the following steps:
uniformly dispersing a metal compound in a lithium-containing refined feed liquid to obtain a pre-precipitation feed liquid, wherein the metal compound is a first compound or a second compound, the first compound is a divalent metal compound and a high-valence metal compound, the second compound is a high-valence metal compound, the molar ratio of the sum of divalent metal ions to the sum of high-valence metal ions in the pre-precipitation feed liquid is (2-100) to 1, and the high-valence metal compound is a trivalent metal compound and/or a tetravalent metal compound; when the pH value of the pre-precipitation material liquid is lower than 7.2, adjusting the pH value of the pre-precipitation material liquid to 7.2-13.5, reacting at the reaction temperature of 90-130 ℃ for 0.5-24 h, then carrying out solid-liquid separation, washing and drying a solid part to obtain a hydrotalcite nanosheet, and obtaining a lithium-containing material liquid without impurities from a liquid part; when the pH value of the pre-precipitation material liquid is 7.2-13.5, the step of adjusting the pH value of the pre-precipitation material liquid to 7.2-13.5 is omitted;
the content of magnesium ions in the lithium-containing refined feed liquid is 0.5-10 g/L, the content of aluminum ions is 0-100 g/L, the content of manganese ions is 0-110 g/L, the content of titanium ions is 0-100 g/L, the content of lithium ions is 0.3-10 g/L, the divalent metal compound is divalent metal salt or divalent metal alkali, the trivalent metal compound is trivalent metal salt or trivalent metal alkali, and the tetravalent metal compound is tetravalent metal salt or tetravalent metal alkali;
the divalent metal ion is Mg2+、Zn2+、Ca2+、Cu2+、Ni2+、Co2+、Fe2+、Mn2+、Cd2+Or Be2+At least one of; the trivalent metal ion being Al3+、Ni3+、Co3+、Fe3+、Mn3+、Cr3+、V3+、Ti3+、In3+Or Ga3+At least one of; the tetravalent metal ion being Sn4+、Ti4+Or Zr4+At least one of;
the process of adjusting the pH value of the pre-precipitation material liquid to 7.2-13.5 is realized by adding an alkali solution into the pre-precipitation material liquid, wherein the alkali solution is one or more of a NaOH solution, a KOH solution, a LiOH solution, an ammonia water solution, a hydrazine hydrate solution, a hexamethylenetetramine solution or a urea solution, and the concentration of the alkali solution is 0.5-5 mol/L.
The invention has the advantages and beneficial effects that:
the method is characterized in that lithium-containing refined feed liquid obtained after electrodialysis and desorption of a nanofiltration membrane or a lithium salt adsorbent is used as a raw material, and after the treatment by the method, impurity removal (magnesium, aluminum, manganese, titanium and the like can be removed) of the lithium-containing feed liquid is realized, and meanwhile, the hydrotalcite magnesium-based functional material with high added value is obtained.
The difference from the prior art is that in the prior art, crystallization is performed at a high temperature after nucleation is performed at a low temperature, and carbonate exists in the system, the solubility of lithium carbonate in water gradually decreases with the increase of the temperature, namely lithium carbonate precipitates at a high temperature, so that the prior art can entrain a large amount of lithium while reducing the magnesium-lithium ratio, and simultaneously carbonate is introduced into the reaction system. The process of the present invention avoids the use of sodium carbonate so that the above-mentioned entrainment problem does not occur.
Secondly, according to the experience of hydrotalcite research, carbonate intercalated hydrotalcite is generally obtained when carbonate exists in the system, so that carbonate intercalated hydrotalcite is obtained in the prior art. The invention avoids using carbonate, so the obtained hydrotalcite interlayer anion is related to the anion in the system.
Drawings
FIG. 1 is an XRD spectrum of hydrotalcite obtained in the first example of the present invention.
FIG. 2 is an SEM image of hydrotalcite prepared in the first example of the present invention.
FIG. 3 is an XRD spectrum of hydrotalcite obtained from example two shown in FIG. 1.
FIG. 4 is an XRD spectrum of hydrotalcite obtained in example III of the present invention.
FIG. 5 is an XRD spectrum of hydrotalcite obtained in example four of the present invention.
For a person skilled in the art, other relevant figures can be obtained from the above figures without inventive effort.
Detailed Description
In order to make the technical solution of the present invention better understood, the technical solution of the present invention is further described below with reference to specific examples.
Example one
A method for removing impurities and co-producing hydrotalcite by lithium-containing refined feed liquid comprises the following steps:
the lithium-containing refined feed liquid filtered by the dialysis membrane is 10L, wherein Mg2+Content of 2.4g/L, Li+The content of the sodium hydroxide is 0.15g/L,171g of Al was added2(SO4)3Uniformly mixing, dropwise adding sodium hydroxide with the concentration of 1mol/l into the lithium-containing refined feed liquid until the pH value is 8, and reacting at 60 ℃ for 2 h. After the reaction is finished, separating, washing and drying the precipitate to obtain hydrotalcite nano-sheets; the separated liquid is further used for preparing a lithium product.
Fig. 1 is an XRD spectrum of the hydrotalcite obtained in example one, and it can be seen that the hydrotalcite obtained is MgAl hydrotalcite intercalated with chloride ions, and the molar ratio of Mg/Al is found to be 2:1 by ICP test, which is close to the charge ratio set by us. As can also be seen from FIG. 2, Mg was produced2The Al-LDHs are all in the shape of a planar hexagonal sheet, and the size of the wafer is in the nanometer scale. The concentration of Mg and Li in the magnesium removal feed liquid is measured by ICP, and the Mg in the neutralization washing liquid of the magnesium removal feed liquid is reduced to be below 100 Mg/L.
Example two
A method for removing impurities and co-producing hydrotalcite by lithium-containing refined feed liquid comprises the following steps:
1000mL of refined lithium-containing feed liquid after membrane treatment is taken, wherein Mg2+The content of (Mg) was 40g/L2+About 1.67mol/l), Li+With a content of 10g/L, 202.1g Fe (NO) was added3)3Uniformly mixing, dropwise adding sodium hydroxide with the concentration of 2mol/L into the lithium-containing refined feed liquid until the pH value is 8.5, and then reacting for 0.5h at 20 ℃. After the reaction is finished, separating, washing and drying the precipitate to obtain hydrotalcite nano-sheets; the separated liquid is further used for preparing a lithium product.
FIG. 3 is the XRD spectrum of MgFe-LDHs obtained in example two. The obtained sample has good purity and high crystallinity. The magnesium content in the feed liquid after impurity removal is lower than 5 ppm.
EXAMPLE III
A method for removing impurities and co-producing hydrotalcite by lithium-containing refined feed liquid comprises the following steps:
taking 100L refined lithium-containing feed liquid after aluminum adsorbent desorption, wherein Mg2+0.024g/L of Al3+The content of Li is 0.054g/L+With a content of 15g/L, 89.2g Zn (NO) was added3)2Mixing evenly, and dripping 0.5mol/l potassium hydroxide into the mixtureThe reaction was carried out at 10 ℃ for 4 hours after refining the feed solution until the pH was 11. After the reaction is finished, separating, washing and drying the precipitate to obtain hydrotalcite nano-sheets; the separated liquid is further used for preparing a lithium product. FIG. 4 is an XRD spectrum of the obtained ZnMgAl-LDHs, which is consistent with the literature report, and the content of magnesium is reduced to below 20ppm and the content of chloride ions is reduced to below 30ppm after impurity removal.
Example four:
a method for removing impurities and co-producing hydrotalcite by lithium-containing refined feed liquid comprises the following steps:
taking 5L lithium-containing refined feed liquid after desorption of manganese adsorbent, wherein Mg2+The content of Mn is 2.4g/L2+Content 5.5g/L, Li+The content of the solution is 15g/L, 66g AlCl is added3Uniformly mixing, dropwise adding 0.5mol/l ammonia water into the refined feed liquid until the pH value is 8.5, and reacting at 50 ℃ for 2 h. After the reaction is finished, separating, washing and drying the precipitate to obtain hydrotalcite nano-sheets; the separated liquid is further used for preparing a lithium product.
FIG. 5 is an XRD spectrum of the obtained MnMgAl-LDHs, which shows that pure LDHs material is obtained, the magnesium content is reduced to 25ppm after impurity removal, and the manganese ion is reduced to below 50 ppm.
Example five:
a method for removing impurities and co-producing hydrotalcite by lithium-containing refined feed liquid comprises the following steps:
taking 1000mL of lithium-containing refined feed liquid after desorption of manganese adsorbent, wherein Mg is contained in the lithium-containing refined feed liquid2+Content of 0.24g/L, Mn4+Content 0.14g/L, Li+The content was 15g/L, and aqueous ammonia having a concentration of 0.5mol/L was added dropwise to the purified feed liquid until pH 10, followed by reaction at 50 ℃ for 2 hours. After the reaction is finished, separating, washing and drying the precipitate to obtain hydrotalcite nano-sheets; the separated liquid is further used for preparing a lithium product.
Example six:
collecting refined lithium-containing feed liquid 100L filtered by a permeation chromatography membrane, wherein Mg2+Content of 2.4g/L, Li+With a content of 10g/L, 937g Al (NO) was added3·9H2Mixing O uniformly, adding urea with the concentration of 5mol/L into the refined feed liquid until the pH value is 10, and reacting at 150 DEG CAnd the time is 12 hours. After the reaction is finished, separating, washing and drying the precipitate to obtain hydrotalcite nano-sheets; the separated liquid is further used for preparing a lithium product.
Example seven:
collecting refined lithium-containing feed liquid 100L filtered by a permeation chromatography membrane, wherein Mg2+Content 2.4g/l, Li+With a content of 10g/L, 937g Al (NO) was added3·9H2O is mixed uniformly, hydrazine hydrate with the concentration of 0.5mol/l is added into the refined feed liquid until the pH value is 9, and the reaction is carried out for 1h at the temperature of 15 ℃. After the reaction is finished, separating, washing and drying the precipitate to obtain hydrotalcite nano-sheets; the separated liquid is further used for preparing a lithium product.
Example eight:
taking 2L refined lithium-containing feed liquid after filtration of a pervaporation membrane, wherein Mg2+Content of 2.4g/L, Li+The content was 10g/L, and 74g of Ca (OH) was added2Then, 68.4g of Al was added2(SO4)3Mixing evenly, and reacting for 12h at 150 ℃. After the reaction is finished, separating, washing and drying the precipitate to obtain hydrotalcite nano-sheets; the separated liquid is further used for preparing a lithium product.
Example nine:
taking 1000ml lithium-containing refined feed liquid after the desorption of the aluminum adsorbent, wherein Al3+Content 0.4g/l, Li+With a content of 10g/l, 3g of Zn (OH) were added2Mixing evenly, and reacting for 12h at 150 ℃. After the reaction is finished, separating, washing and drying the precipitate to obtain hydrotalcite nano-sheets; the separated liquid is further used for preparing a lithium product.
The invention has been described in an illustrative manner, and it is to be understood that any simple variations, modifications or other equivalent changes which can be made by one skilled in the art without departing from the spirit of the invention fall within the scope of the invention.
Claims (8)
1. A method for removing impurities and co-producing hydrotalcite by lithium-containing refined feed liquid is characterized by comprising the following steps:
uniformly dispersing a metal compound in a lithium-containing refined feed liquid to obtain a pre-precipitation feed liquid, wherein the metal compound is a first compound or a second compound, the first compound is a divalent metal compound and a high-valence metal compound, the second compound is a high-valence metal compound, the molar ratio of the sum of divalent metal ions to the sum of high-valence metal ions in the pre-precipitation feed liquid is (2-100) to 1, and the high-valence metal compound is a trivalent metal compound and/or a tetravalent metal compound; when the pH value of the pre-precipitation material liquid is lower than 7.2, adjusting the pH value of the pre-precipitation material liquid to 7.2-13.5, reacting for 0.5-24 h at the reaction temperature of 5-160 ℃, then carrying out solid-liquid separation, washing and drying a solid part to obtain a hydrotalcite nanosheet, and obtaining a lithium-containing material liquid without impurities from a liquid part; when the pH value of the pre-precipitation material liquid is 7.2-13.5, the step of adjusting the pH value of the pre-precipitation material liquid to 7.2-13.5 is omitted;
the content of magnesium ions in the lithium-containing refined feed liquid is 0.01-100 g/L, the content of aluminum ions is 0-100 g/L, the content of manganese ions is 0-110 g/L, the content of titanium ions is 0-100 g/L, the content of lithium ions is 0.01-50 g/L, the divalent metal compound is divalent metal salt or divalent metal alkali, the trivalent metal compound is trivalent metal salt or trivalent metal alkali, and the tetravalent metal compound is tetravalent metal salt or tetravalent metal alkali;
the divalent metal ion is Mg2+、Zn2+、Ca2+、Cu2+、Ni2+、Co2+、Fe2+、Mn2+、Cd2+Or Be2+At least one of; the trivalent metal ion being Al3+、Ni3+、Co3+、Fe3+、Mn3+、Cr3+、V3+、Ti3+、In3+Or Ga3+At least one of; the tetravalent metal ion being Sn4+、Ti4+Or Zr4+At least one of (1).
2. The method according to claim 1, wherein the process of adjusting the pH of the pre-precipitation solution to 7.2-13.5 is performed by adding an alkali solution to the pre-precipitation solution, wherein the alkali solution is one or more of a NaOH solution, a KOH solution, a LiOH solution, an ammonia solution, a hydrazine hydrate solution, a hexamethylenetetramine solution or a urea solution.
3. The method according to claim 1, wherein the lithium-containing refined feed liquid has a magnesium content of 0.1 to 30g/L and a lithium content of 0.1 to 20 g/L.
4. The method according to claim 1, wherein the concentration of the alkali solution is 0.1 to 10 mol/L.
5. The method according to claim 1, wherein the reaction temperature is 80 to 150 ℃.
6. The method of claim 1, wherein the metal salt is a metal sulfate, a metal nitrate, a metal oxalate or a metal chloride.
7. The method according to claim 1, wherein the lithium-containing refined feed liquid is a feed liquid obtained after treatment by an electrodialysis method, a membrane adsorption method or a liquid membrane extraction method, or a feed liquid obtained after treatment by a nanofiltration membrane, or a feed liquid obtained after delithiation by an aluminum-based, manganese-based or titanium-based adsorbent.
8. A method for removing impurities and co-producing hydrotalcite by lithium-containing refined feed liquid is characterized by comprising the following steps:
uniformly dispersing a metal compound in a lithium-containing refined feed liquid to obtain a pre-precipitation feed liquid, wherein the metal compound is a first compound or a second compound, the first compound is a divalent metal compound and a high-valence metal compound, the second compound is a high-valence metal compound, the molar ratio of the sum of divalent metal ions to the sum of high-valence metal ions in the pre-precipitation feed liquid is (2-100) to 1, and the high-valence metal compound is a trivalent metal compound and/or a tetravalent metal compound; when the pH value of the pre-precipitation material liquid is lower than 7.2, adjusting the pH value of the pre-precipitation material liquid to 7.2-13.5, reacting at the reaction temperature of 90-130 ℃ for 0.5-24 h, then carrying out solid-liquid separation, washing and drying a solid part to obtain a hydrotalcite nanosheet, and obtaining a lithium-containing material liquid without impurities from a liquid part; when the pH value of the pre-precipitation material liquid is 7.2-13.5, the step of adjusting the pH value of the pre-precipitation material liquid to 7.2-13.5 is omitted;
the content of magnesium ions in the lithium-containing refined feed liquid is 0.5-10 g/L, the content of aluminum ions is 0-100 g/L, the content of manganese ions is 0-110 g/L, the content of titanium ions is 0-100 g/L, the content of lithium ions is 0.3-10 g/L, the divalent metal compound is divalent metal salt or divalent metal alkali, the trivalent metal compound is trivalent metal salt or trivalent metal alkali, and the tetravalent metal compound is tetravalent metal salt or tetravalent metal alkali;
the divalent metal ion is Mg2+、Zn2+、Ca2+、Cu2+、Ni2+、Co2+、Fe2+、Mn2+、Cd2+Or Be2+At least one of; the trivalent metal ion being Al3+、Ni3+、Co3+、Fe3+、Mn3+、Cr3+、V3+、Ti3+、In3+Or Ga3+At least one of; the tetravalent metal ion being Sn4+、Ti4+Or Zr4+At least one of;
the process of adjusting the pH value of the pre-precipitation material liquid to 7.2-13.5 is realized by adding an alkali solution into the pre-precipitation material liquid, wherein the alkali solution is one or more of a NaOH solution, a KOH solution, a LiOH solution, an ammonia water solution, a hydrazine hydrate solution, a hexamethylenetetramine solution or a urea solution, and the concentration of the alkali solution is 0.5-5 mol/L.
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