CN111204812A - Preparation method of metal cation-doped modified lithium ion sieve - Google Patents
Preparation method of metal cation-doped modified lithium ion sieve Download PDFInfo
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 23
- 239000002184 metal Substances 0.000 title claims abstract description 23
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical class [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims description 10
- 238000002360 preparation method Methods 0.000 title abstract description 14
- 239000000243 solution Substances 0.000 claims abstract description 70
- 150000002500 ions Chemical class 0.000 claims abstract description 63
- 239000011572 manganese Substances 0.000 claims abstract description 62
- 239000002243 precursor Substances 0.000 claims abstract description 60
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 44
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 36
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 33
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims abstract description 30
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000000843 powder Substances 0.000 claims abstract description 24
- 239000002253 acid Substances 0.000 claims abstract description 22
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 18
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000003463 adsorbent Substances 0.000 claims abstract description 17
- -1 cation modified lithium ion Chemical class 0.000 claims abstract description 8
- 239000012266 salt solution Substances 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 239000000463 material Substances 0.000 claims abstract description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 42
- 238000005406 washing Methods 0.000 claims description 20
- 229910001437 manganese ion Inorganic materials 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 15
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- 229910001416 lithium ion Inorganic materials 0.000 claims description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 150000001768 cations Chemical class 0.000 claims description 8
- CHPZKNULDCNCBW-UHFFFAOYSA-N gallium nitrate Chemical compound [Ga+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CHPZKNULDCNCBW-UHFFFAOYSA-N 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- 229940044658 gallium nitrate Drugs 0.000 claims description 4
- UPWPDUACHOATKO-UHFFFAOYSA-K gallium trichloride Chemical group Cl[Ga](Cl)Cl UPWPDUACHOATKO-UHFFFAOYSA-K 0.000 claims description 4
- 229940071125 manganese acetate Drugs 0.000 claims description 4
- 235000006748 manganese carbonate Nutrition 0.000 claims description 4
- 239000011656 manganese carbonate Substances 0.000 claims description 4
- 229940093474 manganese carbonate Drugs 0.000 claims description 4
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 4
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims description 4
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- ZVYYAYJIGYODSD-LNTINUHCSA-K (z)-4-bis[[(z)-4-oxopent-2-en-2-yl]oxy]gallanyloxypent-3-en-2-one Chemical compound [Ga+3].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O ZVYYAYJIGYODSD-LNTINUHCSA-K 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical group Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 150000002258 gallium Chemical class 0.000 claims description 2
- 229910000373 gallium sulfate Inorganic materials 0.000 claims description 2
- SBDRYJMIQMDXRH-UHFFFAOYSA-N gallium;sulfuric acid Chemical compound [Ga].OS(O)(=O)=O SBDRYJMIQMDXRH-UHFFFAOYSA-N 0.000 claims description 2
- 150000002696 manganese Chemical class 0.000 claims description 2
- 235000002867 manganese chloride Nutrition 0.000 claims description 2
- 239000011565 manganese chloride Substances 0.000 claims description 2
- 229940099607 manganese chloride Drugs 0.000 claims description 2
- 229940099596 manganese sulfate Drugs 0.000 claims description 2
- 235000007079 manganese sulphate Nutrition 0.000 claims description 2
- 239000011702 manganese sulphate Substances 0.000 claims description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims 1
- 239000011259 mixed solution Substances 0.000 abstract description 22
- 238000004090 dissolution Methods 0.000 abstract description 21
- 239000013078 crystal Substances 0.000 abstract description 8
- 238000004064 recycling Methods 0.000 abstract description 2
- 238000004140 cleaning Methods 0.000 abstract 1
- 238000001179 sorption measurement Methods 0.000 description 47
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 26
- 239000000203 mixture Substances 0.000 description 24
- 238000003756 stirring Methods 0.000 description 23
- 239000008367 deionised water Substances 0.000 description 22
- 229910021641 deionized water Inorganic materials 0.000 description 22
- 239000000047 product Substances 0.000 description 22
- 239000002245 particle Substances 0.000 description 17
- 229910052596 spinel Inorganic materials 0.000 description 15
- 239000011029 spinel Substances 0.000 description 15
- 238000012512 characterization method Methods 0.000 description 12
- 238000005259 measurement Methods 0.000 description 12
- 238000001914 filtration Methods 0.000 description 11
- 239000004809 Teflon Substances 0.000 description 10
- 229920006362 Teflon® Polymers 0.000 description 10
- 238000005054 agglomeration Methods 0.000 description 10
- 230000002776 aggregation Effects 0.000 description 10
- 238000000227 grinding Methods 0.000 description 10
- 239000002244 precipitate Substances 0.000 description 10
- 238000007605 air drying Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 6
- 229910004251 HMn2O4 Inorganic materials 0.000 description 5
- VFLRPJJARDQRAC-UHFFFAOYSA-N gallium manganese Chemical compound [Mn].[Ga] VFLRPJJARDQRAC-UHFFFAOYSA-N 0.000 description 5
- 125000004122 cyclic group Chemical group 0.000 description 4
- CNFDGXZLMLFIJV-UHFFFAOYSA-L manganese(II) chloride tetrahydrate Chemical compound O.O.O.O.[Cl-].[Cl-].[Mn+2] CNFDGXZLMLFIJV-UHFFFAOYSA-L 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- RJYMRRJVDRJMJW-UHFFFAOYSA-L dibromomanganese Chemical compound Br[Mn]Br RJYMRRJVDRJMJW-UHFFFAOYSA-L 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 230000005536 Jahn Teller effect Effects 0.000 description 1
- 229910018663 Mn O Inorganic materials 0.000 description 1
- 229910003176 Mn-O Inorganic materials 0.000 description 1
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- GCICAPWZNUIIDV-UHFFFAOYSA-N lithium magnesium Chemical compound [Li].[Mg] GCICAPWZNUIIDV-UHFFFAOYSA-N 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910000348 titanium sulfate Inorganic materials 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/12—Manganates manganites or permanganates
- C01G45/1221—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof
- C01G45/1242—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type [Mn2O4]-, e.g. LiMn2O4, Li[MxMn2-x]O4
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
-
- 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 provides a preparation method of a doped metal cation modified lithium ion sieve, wherein the molecular formula of the doped modified ion sieve is as follows: HGaxMn2‑xO4And x is 0.05-1. The preparation method comprises the following specific steps: at normal temperature, gallium source and manganese source are mixed according to molar ratio n (Ga)3+:Mn2+) X: 2-x preparing a mixed salt solution; mixing a lithium source and a hydrogen peroxide solution according to a certain proportion to prepare a lithium solution. And slowly dropwise adding a lithium solution into the mixed solution, and carrying out hydrothermal reaction at a certain temperature to obtain the precursor of the ionic sieve doped with metal gallium ions. Finally, the precursor powder material is subjected to acid cleaning treatment to obtain the ion sieve adsorbent HGa doped with metal gallium ionsxMn2‑xO4. The adsorbent prepared by the invention has stable crystal structure and can effectively reduceThe problem of dissolution loss of the traditional ionic sieve is reduced, and the repeated recycling performance is improved.
Description
Technical Field
The invention relates to a preparation method of a metal cation doped modified lithium ion sieve, which is used for solving the problem of dissolution loss of the traditional lithium ion sieve in the adsorption and desorption processes and further improving the cyclic usability of the traditional lithium ion sieve.
Background
Lithium and its compound resources are always important energy sources for economic development in China and even all over the world, and have wide application in the fields of batteries, aerospace, chemical engineering and the like. The mature lithium extraction technology at present comprises a precipitation method, an evaporative crystallization method, an adsorption method and the like. The ion sieve adsorption lithium extraction method is one of the adsorption methods with development prospect, and has the advantages of high adsorption efficiency, green economy, simple preparation process and the like. Because the ion sieve has a unique spinel structure and has the capability of screening and memorizing lithium ions, the ion sieve can still keep the adsorptivity and selectivity for lithium ions when absorbing and extracting lithium in a salt lake brine system with high lithium-magnesium ratio. However, LiMn2O4As the most studied precursor in manganese ion sieves, Mn exists in the precursor3+Disproportionation reaction and Jahn-Teller effect are easy to occur in the adsorption and desorption process; furthermore, cations in the microscopically ionic sieve may be positionally deviated as the number of times of adsorption increases. These all cause Mn dissolution loss, and then destroy the spinel structure of the ion sieve, so that the adsorption capacity of the ion sieve is reduced in the recycling process.
Aiming at the problem of Mn dissolution loss, the modification is mainly carried out by taking the measures of doping and surface modification at present. The doping is generally classified into cation doping, anion doping, and anion-cation composite doping. Doping of metal cations is intended to replace Mn3+Thereby reducing the content of Mn, increasing the average valence of Mn, reducing the solution loss, and simultaneously still maintaining the spinel structure. The nickel ion doping of the ion sieve with the quantity ratio of the lithium manganese substance of 0.7 is carried out by von Linyong et al, and the characterization shows that doping elements enter the crystal lattice of the ion sieve, the dissolution loss is reduced, but the reduction degree of the saturation adsorption capacity is too large (non-polar Metals, 2008, (06): 31-33). The method of coprecipitation and thermal crystallization is used for preparing the titanium-doped ion sieve, the saturated adsorption capacity of the titanium-doped ion sieve to lithium ions reaches 5.96mmol/g, and Ti4+And Mn4+The dissolution losses are all low (applied chemistry, 2006, (04): 357-361). However, the preparation process is complicated in steps and long in period.
In order to solve the problem of dissolution loss of the traditional powder ion sieve, appropriate metal cations still need to be explored in the doping aspect, the original spinel structure is not damaged on the basis of simple preparation process, the adsorption quantity of lithium is ensured, the dissolution loss is reduced, and the effect of improving the cyclic utilization is achieved.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a preparation method of a doped metal cation modified lithium ion sieve, which adds metal Ga in the preparation process of an ion sieve precursor3+Substituting for small amounts of Mn in the crystal3 +Further, the dissolution loss is reduced, the stability and the cyclicity in practical utilization are improved, and a preparation method of the composite material is correspondingly provided.
The technical scheme provided by the invention is as follows: a method for preparing a modified lithium ion sieve doped with metal cations is characterized in that a gallium source and a manganese source are mixed according to the molecular formula of the doped modified ion sieve of HGaxMn2-xO4Mixing the salt solution with the molar ratio of x to 0.05-1; mixing a lithium source and a hydrogen peroxide solution in proportion to prepare a lithium solution; then slowly dripping a lithium solution into the mixed salt solution, and carrying out hydrothermal reaction at a certain temperature to obtain an ionic sieve precursor doped with metal gallium ions; finally, the precursor powder material is subjected to acid washing treatment, and finally the ion sieve adsorbent HGa doped with metal gallium ions is obtainedxMn2-xO4。
Preferably, the manganese source is a soluble inorganic or organic manganese salt, more preferably manganese chloride, manganese nitrate, manganese carbonate, manganese acetate or manganese sulfate; the gallium source is soluble inorganic or organic gallium salt, and more preferably gallium chloride, gallium nitrate, gallium sulfate or gallium acetylacetonate; preferably the lithium source is lithium hydroxide; the solvent in the solution is water.
Preferably, the total ion concentration of gallium and manganese in the mixed salt solution is 0.1-3 mol/L; the concentration of hydrogen peroxide in the lithium solution is 0.20-1.57 mol/L; slowly dripping the lithium solution into the mixed salt solution to control Li+/(Mn2++Ga3+) The molar ratio of (1-6) to (1).
The temperature of the hydrothermal reaction is preferably 110-160 ℃, and the time of the hydrothermal reaction is 8-14 h. The dropping rate of the lithium solution is preferably 1mL-10 mL/min.
Preferably, the acid solution in the acid washing treatment is hydrochloric acid, sulfuric acid, phosphoric acid, oxalic acid, nitric acid, formic acid or acetic acid solution; the concentration of the acid solution is 0.02mol/L-0.16 mol/L; the soaking time is 0.5-24 h.
The invention prepares a lithium source, a manganese source, a gallium source and an oxidant into a mixed solution according to a certain proportion, and synthesizes an ion sieve precursor by one-step hydrothermal synthesis. And obtaining the ion sieve adsorbent after acid leaching and lithium removal.
Has the advantages that:
1. the invention adopts trivalent gallium ions as doping modified metal cations for the first time. This ion not only has a valence state and Mn3+Uniform and ionic radius and Mn3+In close proximity, the doping does not cause significant expansion or contraction of the lattice structure. As described above, Ga is contained in an appropriate amount3+The doping is extremely easy to replace and occupy Mn3+The position of (2) improves the average valence of Mn, and increases the stability of the spinel structure of the ion sieve, thereby achieving the modification purpose of reducing the dissolution loss. Meanwhile, the Ga-O bond energy is slightly larger than the Mn-O bond energy, the adsorption performance of the doped ion sieve is not obviously reduced, and the cyclic adsorption performance is superior to that of the traditional ion sieve.
2. Compared with the traditional ionic sieve, the doped modified ionic sieve has more excellent appearance and smaller average particle size of particles, so that the ionic sieve is beneficial to fully contacting with a solution during adsorption, the problem of poor fluidity of the ionic sieve is relieved to a certain extent, and the cyclic adsorption stability of the material is kept.
3. The preparation method has the advantages of simple preparation process, mild preparation conditions, no need of calcination, greenness and economy. Is easy to realize industrial production.
Drawings
FIG. 1 shows LiGa obtained in example 1 of the present invention0.2Mn1.8O4XRD pattern of the precursor.
FIG. 2 shows HGa obtained after acid leaching for lithium removal in example 1 of the present invention0.2Mn1.8O4XRD pattern of ion sieve.
FIG. 3 is a diagram showing LiGa obtained in example 1 of the present invention0.2Mn1.8O4SEM image of the precursor.
FIG. 4 shows LiGa obtained in example 1 of the present invention0.2Mn1.8O4And (5) performing appearance photo of the precursor.
Detailed Description
Example 1: (the addition amount x of gallium is 0.2, the ion concentration of the gallium-manganese mixed solution is 0.5mol/L, and the molar ratio Li+/(Mn2++Ga3+)＝4：1)
Weighing 0.0225mol of manganese chloride tetrahydrate and 0.0025mol of gallium nitrate hydrate, adding 50mL of deionized water, and stirring until the mixture is completely dissolved to obtain a mixed solution of gallium and manganese. 0.1mol of hydrated lithium hydroxide is weighed and added into 50mL of deionized water, after the mixture is stirred for a period of time, 4mL of 30% hydrogen peroxide solution is added and stirred continuously until the mixture is fully dissolved, and then the lithium solution is dripped into the mixed solution at the speed of 5 mL/min. After stirring for a while, the black precipitate was transferred to a 200mL Teflon lined reactor and subjected to hydrothermal reaction at 120 ℃ for 8h in an electrothermal constant temperature forced air drying oven. Filtering and grinding the product to obtain a doped precursor LiGa0.2Mn1.8O4. The precursor is subjected to acid washing treatment in 0.1mol/L dilute hydrochloric acid solution for 0.5h, and the product is washed and dried to obtain the ion sieve adsorbent HGa doped with metal gallium ions0.2Mn1.8O4. The appearance characteristics are shown in fig. 4. XRD characterization is carried out on the precursor and the ion sieve, and the results are respectively shown in figures 1 and 2, the precursor and the ion sieve are both shown to be good spinel structures, the characteristic peaks are well coincided, the strength is high, and the crystal stability is good. And then performing SEM characterization on the powder, wherein the result is shown in FIG. 3, and the powder particles have small particle size and no obvious agglomeration phenomenon. The ICP measurement showed an adsorption capacity of 26.34 mg/g. After 5 times of circulating adsorption, the adsorption capacity is reduced to 21.86mg/g, and the dissolution loss of manganese is 2.9%.
Example 2: (the addition amount x of gallium is 0.3, the ion concentration of the gallium-manganese mixed solution is 1mol/L, and the molar ratio Li+/(Mn2++Ga3+) Is 5: 1),
weighing 0.0425mol of manganese carbonate and 0mol of manganese carbonate0075mol of anhydrous gallium chloride, adding 50mL of deionized water, and stirring until the solution is completely dissolved to obtain a mixed solution of gallium and manganese. 0.25mol of hydrated lithium hydroxide is weighed and added into 50mL of deionized water, 5mL of 30% hydrogen peroxide solution is added after stirring for a period of time, and after the mixture is continuously stirred until the lithium solution is fully dissolved, the lithium solution is dropwise added into the mixed solution at the speed of 4 mL/min. After stirring for a further period of time, the black precipitate was transferred to a 200mL Teflon lined reactor and subjected to hydrothermal reaction at 160 ℃ for 14h in an electrically heated constant temperature forced air drying oven. Filtering and grinding the product to obtain a doped precursor LiGa0.3Mn1.7O4. Acid washing the precursor in 0.08mol/L dilute nitric acid solution for 24h, washing and drying the product to obtain the ion sieve adsorbent HGa doped with metal gallium ions0.3Mn1.7O4. XRD characterization is carried out on the precursor and the ion sieve, and the results show that the precursor and the ion sieve are in a good spinel structure, the characteristic peaks are well matched, the strength is high, and the crystal stability is good. And then SEM representation is carried out on the powder, and the powder particles have smaller particle size and no obvious agglomeration phenomenon. The result of ICP measurement showed an adsorption capacity of 23.78 mg/g. After 5 times of circulating adsorption, the adsorption capacity is reduced to 19.26mg/g, and the dissolution loss of manganese is 3.4%.
Example 3: (the addition amount x of gallium is 0.05, the ion concentration of the gallium-manganese mixed solution is 3mol/L, and the molar ratio Li+/(Mn2++Ga3+) Is 1: 1)
0.14625mol of manganese bromide and 0.00375mol of anhydrous gallium chloride are weighed, 50mL of deionized water is added, and the mixture is stirred until the mixture is completely dissolved to obtain a mixed solution of gallium and manganese. 0.15mol of hydrated lithium hydroxide is weighed and added into 50mL of deionized water, 8mL of 30% hydrogen peroxide solution is added after stirring for a period of time, and after the solution is continuously stirred until the solution is fully dissolved, the lithium solution is dropwise added into the mixed solution at the speed of 1 mL/min. After stirring for a further period of time, the black precipitate was transferred to a 200mL Teflon lined reactor and subjected to a hydrothermal reaction at 140 ℃ for 10h in an electrothermal constant temperature forced air drying oven. Filtering and grinding the product to obtain a doped precursor LiGa0.05Mn1.95O4. The precursor is subjected to acid washing treatment for 2 hours in 0.02mol/L dilute acetic acid solution,washing and drying the product to obtain the ion sieve adsorbent HGa doped with metal gallium ions0.05Mn1.95O4. XRD characterization is carried out on the precursor and the ion sieve, and the results show that the precursor and the ion sieve are in a good spinel structure, the characteristic peaks are well matched, the strength is high, and the crystal stability is good. And then SEM representation is carried out on the powder, and the powder particles have smaller particle size and no obvious agglomeration phenomenon. The ICP measurement showed an adsorption capacity of 24.39 mg/g. After 5 times of circulating adsorption, the adsorption capacity is reduced to 19.02mg/g, and the dissolution loss of manganese is 4.6%.
Example 4: (the addition amount x of gallium is 1, the ion concentration of the gallium-manganese mixed solution is 0.1mol/L, and the molar ratio Li+/(Mn2++Ga3+) Is as follows (6): 1)
weighing 0.0025mol of manganese acetate and 0.0025mol of hydrated gallium nitrate, adding 50mL of deionized water, and stirring until the mixture is completely dissolved to obtain a mixed solution of gallium and manganese. 0.03mol of hydrated lithium hydroxide is weighed and added into 50mL of deionized water, 1mL of 30% hydrogen peroxide solution is added after stirring for a period of time, and after the solution is continuously stirred until the solution is fully dissolved, the lithium solution is dropwise added into the mixed solution at the speed of 10 mL/min. After stirring for a further period of time, the black precipitate was transferred to a 200mL Teflon lined reactor and subjected to hydrothermal reaction at 110 ℃ for 11h in an electrothermal constant temperature forced air drying oven. Filtering and grinding the product to obtain a doped precursor LiGa1Mn1O4. Acid washing the precursor in 0.16mol/L diluted phosphoric acid solution for 3h, washing and drying the product to obtain the ion sieve adsorbent HGa doped with metal gallium ions1Mn1O4. XRD characterization is carried out on the precursor and the ion sieve, and the results show that the precursor and the ion sieve are in a good spinel structure, the characteristic peaks are well matched, the strength is high, and the crystal stability is good. And then SEM representation is carried out on the powder, and the powder particles have smaller particle size and no obvious agglomeration phenomenon. The result of ICP measurement showed an adsorption capacity of 22.78 mg/g. After 5 times of circulating adsorption, the adsorption capacity is reduced to 18.44mg/g, and the dissolution loss of manganese is 3.2%.
Example 5: (the addition amount x of gallium is 0.1, the ion concentration of the gallium-manganese mixed solution is 0.4mol/L, and the molar ratio Li+/(Mn2++Ga3+) Is 3：1)
0.019mol of manganese chloride tetrahydrate and 0.001mol of gallium acetylacetonate are weighed, 50mL of deionized water is added, and the mixture is stirred until the mixture is completely dissolved to obtain a mixed solution of gallium and manganese. 0.06mol of hydrated lithium hydroxide is weighed and added into 50mL of deionized water, after the mixture is stirred for a period of time, 3mL of 30% hydrogen peroxide solution is added, the mixture is continuously stirred until the mixture is fully dissolved, and then the lithium solution is dropwise added into the mixed solution at the speed of 6 mL/min. After stirring for a further period of time, the black precipitate was transferred to a 200mL Teflon lined reactor and subjected to hydrothermal reaction at 150 ℃ for 10h in an electrothermal constant temperature forced air drying oven. Filtering and grinding the product to obtain a doped precursor LiGa0.1Mn1.9O4. The precursor is subjected to acid washing treatment in 0.06mol/L dilute sulfuric acid solution for 4 hours, and the product is washed and dried to obtain the ion sieve adsorbent HGa doped with metal gallium ions0.1Mn1.9O4. XRD characterization is carried out on the precursor and the ion sieve, and the results show that the precursor and the ion sieve are in a good spinel structure, the characteristic peaks are well matched, the strength is high, and the crystal stability is good. And then SEM representation is carried out on the powder, and the powder particles have smaller particle size and no obvious agglomeration phenomenon. The result of ICP measurement showed an adsorption capacity of 23.27 mg/g. After 4 times of circulating adsorption, the adsorption capacity is reduced to 18.41mg/g, and the dissolution loss of manganese is 4.0%.
Comparative example 1: (the adding amount x of gallium is 0, the concentration of the manganese ion solution is 0.5mol/L, and the molar ratio of lithium to manganese is 4: 1), 0.025mol of manganese chloride tetrahydrate is weighed, 50mL of deionized water is added, and the mixture is stirred until the manganese ion solution is completely dissolved, so that the manganese ion solution is obtained. 0.1mol of hydrated lithium hydroxide is weighed and added into 50mL of deionized water, after the mixture is stirred for a period of time, 4mL of 30% hydrogen peroxide solution is added and stirred continuously until the mixture is fully dissolved, and then the lithium solution is dripped into the mixed solution at the speed of 5 mL/min. After stirring for a while, the black precipitate was transferred to a 200mL Teflon lined reactor and subjected to hydrothermal reaction at 120 ℃ for 8h in an electrothermal constant temperature forced air drying oven. Filtering and grinding the product to obtain a precursor LiMn2O4. The precursor is subjected to acid washing treatment in 0.1mol/L dilute hydrochloric acid solution for 0.5h, and the product is washed and dried to obtain ion sieve adsorbent HMn2O4. XRD characterization is carried out on the precursor and the ion sieve, the precursor and the ion sieve are both shown to be good spinel structures, and all characteristic peaks are well coincided and have high strength. And then SEM representation is carried out on the powder, and the powder particles are uniformly dispersed and have no obvious agglomeration phenomenon. The ICP measurement showed an adsorption capacity of 26.99 mg/g. After 5 times of circulating adsorption, the adsorption capacity is reduced to 18.62mg/g, and the dissolution loss of manganese is 7.8%.
Comparative example 2: (the adding amount x of gallium is 0, the concentration of the manganese ion solution is 1mol/L, and the molar ratio of lithium to manganese is 5: 1), weighing 0.05mol of manganese carbonate, adding 50mL of deionized water, and stirring until the manganese ion solution is completely dissolved to obtain the manganese ion solution. 0.25mol of hydrated lithium hydroxide is weighed and added into 50mL of deionized water, 5mL of 30% hydrogen peroxide solution is added after stirring for a period of time, and after the mixture is continuously stirred until the lithium solution is fully dissolved, the lithium solution is dropwise added into the mixed solution at the speed of 4 mL/min. After stirring for a further period of time, the black precipitate was transferred to a 200mL Teflon lined reactor and subjected to hydrothermal reaction at 160 ℃ for 14h in an electrically heated constant temperature forced air drying oven. Filtering and grinding the product to obtain a precursor LiMn2O4. The precursor is subjected to acid washing treatment in 0.08mol/L dilute nitric acid solution for 24 hours, and the product is washed and dried to obtain ion sieve adsorbent HMn2O4. XRD characterization is carried out on the precursor and the ion sieve, and the results show that the precursor and the ion sieve are both in a good spinel structure, and each characteristic peak is well coincided and has higher strength. And then SEM representation is carried out on the powder, and the powder particles are uniformly dispersed and have no obvious agglomeration phenomenon. The ICP measurement showed an adsorption capacity of 25.17 mg/g. After 5 times of circulating adsorption, the adsorption capacity is reduced to 17.10mg/g, and the dissolution loss of manganese is 8.4%.
Comparative example 3: (the adding amount x of gallium is 0, the concentration of the manganese ion solution is 3mol/L, and the molar ratio of lithium to manganese is 1: 1) 0.15mol of manganese bromide is weighed, 50mL of deionized water is added, and the mixture is stirred until the manganese ion solution is completely dissolved to obtain the manganese ion solution. 0.15mol of hydrated lithium hydroxide is weighed and added into 50mL of deionized water, 8mL of 30% hydrogen peroxide solution is added after stirring for a period of time, and after the solution is continuously stirred until the solution is fully dissolved, the lithium solution is dropwise added into the mixed solution at the speed of 1 mL/min. After stirring for a further period of time, the black precipitate was transferred to a 200mL Teflon liner for reactionIn the kettle, the hydrothermal reaction is carried out for 10 hours in an electric heating constant temperature air-blast drying oven at the temperature of 140 ℃. Filtering and grinding the product to obtain a precursor LiMn2O4. The precursor is subjected to acid washing treatment in 0.02mol/L dilute acetic acid solution for 2 hours, and the product is washed and dried to obtain ion sieve adsorbent HMn2O4. XRD characterization is carried out on the precursor and the ion sieve, and the results show that the precursor and the ion sieve are both in a good spinel structure, and each characteristic peak is well coincided and has higher strength. And then SEM representation is carried out on the powder, and the powder particles are uniformly dispersed and have no obvious agglomeration phenomenon. The ICP measurement showed an adsorption capacity of 24.52 mg/g. After 5 times of circulating adsorption, the adsorption capacity is reduced to 16.43mg/g, and the dissolution loss of manganese is 8.9%.
Comparative example 4: (the adding amount x of gallium is 0, the concentration of the manganese ion solution is 0.1mol/L, and the molar ratio of lithium to manganese is 6: 1) 0.005mol of manganese acetate is weighed, 50mL of deionized water is added, and the mixture is stirred until the manganese ion solution is completely dissolved to obtain the manganese ion solution. 0.03mol of hydrated lithium hydroxide is weighed and added into 50mL of deionized water, 1mL of 30% hydrogen peroxide solution is added after stirring for a period of time, and after the solution is continuously stirred until the solution is fully dissolved, the lithium solution is dropwise added into the mixed solution at the speed of 10 mL/min. After stirring for a further period of time, the black precipitate was transferred to a 200mL Teflon lined reactor and subjected to hydrothermal reaction at 110 ℃ for 11h in an electrothermal constant temperature forced air drying oven. Filtering and grinding the product to obtain a precursor LiMn2O4. The precursor is subjected to acid washing treatment in 0.16mol/L diluted phosphoric acid solution for 3 hours, and the product is washed and dried to obtain ion sieve adsorbent HMn2O4. XRD characterization is carried out on the precursor and the ion sieve, and the results show that the precursor and the ion sieve are both in a good spinel structure, and each characteristic peak is well coincided and has higher strength. And then SEM representation is carried out on the powder, and the powder particles are uniformly distributed and have no obvious agglomeration phenomenon. The ICP measurement showed an adsorption capacity of 23.89 mg/g. After 5 times of circulating adsorption, the adsorption capacity is reduced to 16.25mg/g, and the dissolution loss of manganese is 8.5 percent.
Comparative example 5: (the adding amount x of gallium is 0, the concentration of the manganese ion solution is 0.4mol/L, and the molar ratio of lithium to manganese is 3: 1) 0.02mol of manganese chloride tetrahydrate is weighed, 50mL of deionized water is added, and the mixture is stirred until the manganese ion solution is completely dissolved to obtain the manganese ion solution. 0.06mol of hydrated lithium hydroxide is weighed and added into 50mL of deionized water, after the mixture is stirred for a period of time, 3mL of 30% hydrogen peroxide solution is added, the mixture is continuously stirred until the mixture is fully dissolved, and then the lithium solution is dropwise added into the mixed solution at the speed of 6 mL/min. After stirring for a further period of time, the black precipitate was transferred to a 200mL Teflon lined reactor and subjected to hydrothermal reaction at 150 ℃ for 10h in an electrothermal constant temperature forced air drying oven. Filtering and grinding the product to obtain a precursor LiMn2O4. The precursor is subjected to acid washing treatment in 0.06mol/L dilute sulfuric acid solution for 4 hours, and the product is washed and dried to obtain ion sieve adsorbent HMn2O4. XRD characterization is carried out on the precursor and the ion sieve, and the results show that the precursor and the ion sieve are both in a good spinel structure, and each characteristic peak is well coincided and has higher strength. And then SEM representation is carried out on the powder, and the powder particles are uniformly distributed and have no obvious agglomeration phenomenon. The ICP measurement showed an adsorption capacity of 23.89 mg/g. After 5 times of circulating adsorption, the adsorption capacity is reduced to 16.25mg/g, and the dissolution loss of manganese is 8.5 percent.
Comparative example 6
Hydrated lithium hydroxide is used as a lithium source, electrolytic manganese dioxide is used as a manganese source, and NiCO is used as a catalyst3·2Ni(OH)2·4H2O is a nickel source, the molar ratio of lithium to manganese is 0.7, and the synthesized precursor of the doped ion sieve is Li1.235NixMn1.765-xO4. The doping amount x is selected to be 0.15. Fully stirring and dispersing hydrated lithium hydroxide in absolute ethyl alcohol, and then electrolyzing manganese dioxide and NiCO3·2Ni(OH)2·4H2Adding O, stirring, and evaporating to dryness at low temperature. And mixing the product by a high-speed pulverizer, pretreating at 480 ℃ for 4h, and roasting at 650 ℃ for 6h to obtain the nickel-doped precursor. And (3) carrying out acid washing treatment on the precursor in 0.5mol/L dilute hydrochloric acid solution for 10 hours, and washing and drying the product to obtain the ion sieve adsorbent. ICP measurement showed 18.3mg/g of adsorption capacity and 7.3% of manganese dissolution loss.
Comparative example 7
Dissolving 11.4mmol of lithium nitrate in 15ml of deionized water, adding 14.2mmol of manganese dioxide and 0.042mmol of titanium sulfate, and stirring in a water bath at 80 ℃ until water is completely removed; mixing the obtained mixtureTransferring the mixture into a muffle furnace, and calcining the mixture for 24 hours at 350 ℃ to obtain a precursor Li4Mn4.75Ti0.25O12. Taking 0.8g of precursor, putting the precursor into 200mL of 0.5mol/L ammonium persulfate solution, putting the solution into a constant-temperature water bath oscillator, oscillating at the frequency of 130rpm, controlling the temperature to be constant at 30 ℃, and reacting for 12 hours to leach out Li in the precursor+(ii) a Further filtering, completely washing with deionized water, and drying in static air at 60 deg.C for 3h to obtain Mn as adsorbent of the ion sieve0.95Ti0.05O2·0.31H2And O. ICP measurement showed 3.2mmol/g of adsorption capacity and 0.7% of manganese dissolved loss.
Claims (7)
1. A method for preparing a modified lithium ion sieve doped with metal cations is characterized in that a gallium source and a manganese source are mixed according to the molecular formula of the doped modified ion sieve of HGaxMn2-xO4Mixing the salt solution with the molar ratio of x to 0.05-1; mixing a lithium source and a hydrogen peroxide solution in proportion to prepare a lithium solution; then, dropwise adding a lithium solution into the mixed salt solution, and carrying out hydrothermal reaction at a certain temperature to obtain an ionic sieve precursor doped with metal gallium ions; finally, the precursor powder material is subjected to acid washing treatment, and finally the ion sieve adsorbent HGa doped with metal gallium ions is obtainedxMn2-xO4。
2. The method according to claim 1, wherein the manganese source is a soluble inorganic or organic manganese salt; the gallium source is soluble inorganic or organic gallium salt; the lithium source adopts lithium hydroxide.
3. The method according to claim 1, wherein the manganese source is manganese chloride, manganese nitrate, manganese carbonate, manganese acetate or manganese sulfate; the gallium source is gallium chloride, gallium nitrate, gallium sulfate or gallium acetylacetonate.
4. The method according to claim 1, wherein the total amount of gallium and manganese ions in the mixed salt solutionThe concentration is 0.1mol/L-3 mol/L; the concentration of hydrogen peroxide in the lithium solution is 0.20-1.57 mol/L; dropwise adding lithium solution into mixed salt solution to control Li+/(Mn2++Ga3+) The molar ratio of (1-6) to (1).
5. The method of claim 1, wherein: the temperature of the hydrothermal reaction is 110-160 ℃, and the time of the hydrothermal reaction is 8-14 h.
6. The method of claim 1, wherein: the dropping speed of the lithium solution is 1mL-10 mL/min.
7. The method of claim 1, wherein: the acid solution in the acid washing treatment is hydrochloric acid, sulfuric acid, phosphoric acid, oxalic acid, nitric acid, formic acid or acetic acid solution; the concentration of the acid solution is 0.02mol/L-0.16 mol/L; the soaking time is 0.5-24 h.
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