CN102872791A - Magnetic nanometer lithium ion sieve adsorbent and preparation method thereof - Google Patents
Magnetic nanometer lithium ion sieve adsorbent and preparation method thereof Download PDFInfo
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- CN102872791A CN102872791A CN2012103946162A CN201210394616A CN102872791A CN 102872791 A CN102872791 A CN 102872791A CN 2012103946162 A CN2012103946162 A CN 2012103946162A CN 201210394616 A CN201210394616 A CN 201210394616A CN 102872791 A CN102872791 A CN 102872791A
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- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 61
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 239000003463 adsorbent Substances 0.000 title claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000001035 drying Methods 0.000 claims abstract description 17
- 230000008569 process Effects 0.000 claims abstract description 15
- 238000000967 suction filtration Methods 0.000 claims abstract description 15
- 238000001179 sorption measurement Methods 0.000 claims abstract description 8
- 239000002002 slurry Substances 0.000 claims description 49
- 239000007788 liquid Substances 0.000 claims description 40
- 230000008676 import Effects 0.000 claims description 33
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 27
- 239000002245 particle Substances 0.000 claims description 25
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 19
- 229910052744 lithium Inorganic materials 0.000 claims description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 16
- 238000003860 storage Methods 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- 230000032683 aging Effects 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 6
- 241000251730 Chondrichthyes Species 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- 239000000126 substance Substances 0.000 abstract description 4
- SAEVTEVJHJGDLY-UHFFFAOYSA-N dilithium;manganese(2+);oxygen(2-) Chemical compound [Li+].[Li+].[O-2].[O-2].[Mn+2] SAEVTEVJHJGDLY-UHFFFAOYSA-N 0.000 abstract 1
- 238000005201 scrubbing Methods 0.000 abstract 1
- 239000010409 thin film Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 42
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 29
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 28
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 16
- 239000000047 product Substances 0.000 description 15
- 229910052757 nitrogen Inorganic materials 0.000 description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 150000002500 ions Chemical class 0.000 description 12
- 239000002243 precursor Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 8
- 239000011572 manganese Substances 0.000 description 8
- 229940099596 manganese sulfate Drugs 0.000 description 8
- 239000011702 manganese sulphate Substances 0.000 description 8
- 235000007079 manganese sulphate Nutrition 0.000 description 8
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 8
- 239000011259 mixed solution Substances 0.000 description 8
- 238000010298 pulverizing process Methods 0.000 description 8
- 229910052742 iron Inorganic materials 0.000 description 6
- 239000013535 sea water Substances 0.000 description 5
- 238000005245 sintering Methods 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 229910021653 sulphate ion Inorganic materials 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- 241001131796 Botaurus stellaris Species 0.000 description 2
- 229910003174 MnOOH Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000002131 composite material Chemical class 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 150000002642 lithium compounds Chemical class 0.000 description 2
- 229910002102 lithium manganese oxide Inorganic materials 0.000 description 2
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 150000002697 manganese compounds Chemical class 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 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
- 229910000733 Li alloy Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 101100513612 Microdochium nivale MnCO gene Proteins 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 1
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 239000011964 heteropoly acid Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical class [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 229910001338 liquidmetal Inorganic materials 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 230000005415 magnetization Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 230000006386 memory function Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000004449 solid propellant Substances 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
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- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention aims to provide a type of magnetic nanometer lithium ion sieve adsorbent which has good chemical stability, big lithium ion adsorption capacity and strong superparamagnetism, and a corresponding preparation method thereof which has the characteristics of simple process, big yield and low cost. The preparation method includes the steps of reaction process in a gut type impinging stream reactor, suction filtration, water scrubbing, drying, roasting and the like. The magnetic nanometer lithium ion sieve adsorbent is prepared by taking nanometer superparamagnetic material as the core and taking a nanometer lithium-manganese oxide lithium ion sieve thin film as the shell to form a nuclear shell structure, wherein the x/y ratio is 1. Compared with the prior art, the invention has the advantages that the magnetic nanometer lithium ion sieve adsorbent has good chemical stability, big lithium ion adsorption capacity and strong superparamagnetism, and the preparation method is simple in process, big in yield and low in cost.
Description
Technical field
The present invention relates to a kind of lithium ion sieve, especially a kind of can be from the aqueous solution rapid extraction lithium ion, and the magnetic nano lithium ion sieve adsorbent that can under the magnetic field force effect, from the aqueous solution, separate fast and preparation method thereof.
Background technology
Lithium is the grand strategy goods and materials of national economy and national defense construction, and the good reputation of " energy metal that promotes world's progress " is arranged.Lithium alloy is for the manufacture of empty day aircraft, lithium battery is the power supply of mobile communication equipment and plug-in type electromagnetic electrical automobile, the liquid metal lithium is desirable nuclear reactor catalyst carrier, and lithium compound is best rocket solid fuel, and the lithium base lubricating agent is widely used in the lubricated of auto parts and components.Inorganic-ion-exchange agent commonly used mainly contains oxide, hydroxide, heteropolyacid salt and composite salt.Wherein the ion sieve oxide has ion sieve effect and lithium ion " memory " function, lithium in the solution had special efficacy selective, and the alkali and alkaline earth metal ions ions such as potassium, sodium, calcium, magnesium of coexistence are had good separating effect, become the most effective lithium adsorbent in seawater, the bittern.The lithium manganese oxide ion sieve is considered to one of best lithium adsorbent of absorption property and application prospect, is generally mixed by a certain percentage by lithium compound and manganese compound, makes after sintering, pickling, and manganese compound commonly used has MnOOH, MnCO
3, electrolytic manganese dioxide etc.From application point, so far, the Inorganic-ion-exchange agent of the better performances of development is all manually synthetic by the reagent of costliness, and cost is high, production procedure is long.In Extracting Lithium from Seawater research, adopt the ion-sieve type metal oxide sorbents from seawater, to extract the method not only economy but also environmental protection of lithium ion, its principle is to import first object ion in metal oxide, generate composite metal oxide, under the prerequisite that does not change crystal structure, object ion is therefrom extracted out, obtained the porous type structure.This material has the object ion of accepting former importing and the trend that consists of best crystal structure, therefore in the situation that there is different kinds of ions to exist, object ion to former importing has screening and memory function, be also referred to as the ion memory material, mainly comprise: monoclinic system metaantimmonic acid, spinel-type titanium oxide and Mn oxide etc.Lithium manganese oxide type ion sieve most study wherein, its (adsorbance (mgg of Ka=lithium of distribution coefficient Ka to lithium in the seawater
-1Concentration (the mgml of lithium in the)/solution
-1) can reach 10
4～10
5Li
+/ Na
+, K
+Distribution coefficient is all 10
4Above, can be effectively from containing Na
+, K
+, Ca
2+, Mg
2+, Sr
2+Deng selective extraction lithium in seawater, salt lake (bittern) and the GEOTHERMAL WATER.
Patent publication No. is the Chinese patent " preparation method of three-dimensional ordered macroporous (3DOM) titanium oxygen ' lithium ionic sieve ' " of CN101342479, the method is by synthetic polymethyl methacrylate colloidal crystal template, precursor solution with lithium salts and titanium salt is filled colloidal crystal template, through suction filtration, dry, two sections constant temperature calcinings, acidleach and obtain 3DOM titanium oxygen ' lithium ionic sieve ' after the drying again, this invention has obviously improved the activated adoption phase ratio in the ion-sieve material by the 3DOM structure control of material, strengthened the diffusion inside ability in the ion transport, be a kind of double hole channel functional material that has simultaneously macropore and micropore, but also have obvious deficiency aspect the rate of adsorption that further improves lithium ion sieve and the switching performance.
Summary of the invention
The purpose of this invention is to provide the magnetic nano lithium ion sieve adsorbent that a kind of chemical stability is good, the lithium ion adsorption capacity is large, superparamagnetism is strong and have accordingly the preparation method that technique is simple, output is large, cost hangs down characteristics.
First technical characterictic of the present invention is super-paramagnetism nano lithium-Mn oxide lithium ion sieve, consists of
, wherein the ratio of x/y is 1.The average grain diameter of magnetic Nano lithium ion sieve between 20 to 60nm, specific area 20 to 60m
2Between/the g, its housing lithium ion sieve film average thickness is more than 2nm.
Second technical characterictic of the present invention is the preparation method of super-paramagnetism nano lithium-Mn oxide lithium ion sieve, it is characterized in that may further comprise the steps:
What 1) will prepare contains
With
Solution, contain
Solution, contain
With
Solution be respectively charged into four storage tanks; Feed liquid in four storage tanks is entered in four imports of Road narrows formula impact flow reactor simultaneously by setting flow.Wherein contain
With
Solution in import 1, contain
With
Solution in import 2, contain
With
Solution in import 3 and import 4.Contain
With
Solution first with contain
Solution bump against, generate
Slurries, Fe
3O
4Slurries forward in the flow process with the containing of both sides
With
Solution generation multiple impacts form nucleocapsid structure
Slurries;
2) after product flows out from reactor outlet, put into water heating kettle aging, aging rear suction filtration, washing, drying are put into water heating kettle after weighing and are added
Carry out hydro-thermal reaction and obtain product
3) at last will
Carrying out suction filtration, washing, drying, roasting is consisted of
Magnetic Nano lithium ion sieve particle, this particle can be directly used in after lithium is taken off in acidleach and extract lithium ion from the aqueous solution.
The magnetic Nano lithium ion sieve is with nanometer
Superparamagnetic material is that kernel, nanometer lithium-Mn oxide lithium ion sieve film are shell, consists of
Nucleocapsid structure, wherein x/y ratio is 1.
As improvement, the material of Road narrows formula impact flow reactor is polytetrafluoroethylene (PTFE) in the step 1, and Road narrows are " shark's fin type " layout, comprises four imports and an outlet, and Road narrows are divided into sprue, side runner and branch flow passage, and the width of Road narrows is between 0.5mm to 1.5mm.Flow into two stock material liquid of import 1 and import 2 along Road narrows are in the collision of sprue port separately, flow velocity equates during two stock material liquid bump, and projected angle of impact is between 100 ° to 140 °, and the flow velocity of feed liquid in sprue is between 1m/s to 4m/s behind the bump.The two stock material liquid that flow into import 3 and import 4 are introduced into the side runner on both sides, enter again the branch flow passage from side runner, material liquid side in the branch flow passage port of export and sprue is hit, side breakhead degree is between 45 ° to 90 °, the opening number of both sides branch flow passage is adjustable between 1 to 12, is preferably between 3 to 9.The both sides branch flow passage can be blocked or open in any combination mode as required.
As preferably, the feed liquid flow that enters import 3 and import 4 in the step 1 and the ratio of the feed liquid flow that enters import 1 and import 2 be the initial temperature of 1, four stock material liquid between 20 ℃ to 90 ℃, wherein contain
With
Solution in
Mol ratio between 1.6 to 2.4, this solution with contain
The Fe that generates after bumping against of solution
3O
4Fe in the slurries
3O
4Concentration between 0.05mol/L ~ 0.15mol/L, keep as product in the reactor outlet
Slurry pH value is between 7 to 12.
As preferably, the hydrothermal aging temperature is 100 ℃ to 140 ℃ in the step 2, and the hydrothermal aging time is 12h to 36h, and hydrothermal temperature is between 100 ℃ to 180 ℃, and lithium hydroxide concentration is at 2mol/L to 8mol/L, and the hydro-thermal reaction time is between the 12h to 100h.
As preferably, the temperature of the drying in the step 3 is more than 60 ℃, and the temperature of roasting is between 300 ℃ to 550 ℃, and roasting time is between 1h to 8h.
As improvement, the process that lithium is taken off in acidleach in the step 3 is specially: will
Particle is scattered in and breaks into slurries in the deionized water, in strong stirring, slowly drip the hydrochloric acid solution of 1mol/L in the slurries, make hydrogen ion and intragranular lithium ion generation exchange adsorption in the solution, be down to 2 and when no longer rebounding when the pH of slurries value, take off the lithium process and finish.
Compared with prior art, the invention has the advantages that:
1. magnetic Nano lithium ion sieve chemical stability is good, the lithium ion adsorption capacity is large, superparamagnetism is strong;
2. preparation method's technique of the present invention is simple, output is large, cost is low.
Description of drawings
Fig. 1 is Road narrows formula impinging stream reaction installation drawing of the present invention and preparation
The technological process of slurries;
Fig. 2 is
With
XRD spectra;
Fig. 3 is of the present invention
The TEM transmission electron microscope photo;
Fig. 4 is of the present invention
The TEM transmission electron microscope photo;
Fig. 5 is that the magnetic induction intensity of magnetic Nano lithium ion sieve of the present invention is with the curve of change of magnetic field strength;
Fig. 6 is the rate curve of magnetic Nano lithium ion sieve absorption lithium ion of the present invention.
The specific embodiment
Below in conjunction with attached embodiment the present invention is described in further detail.
Embodiment 1: referring to figs. 1 through Fig. 6, and the preparation method of magnetic Nano lithium ion sieve, concrete steps are:
With containing of configuring
With
Solution, contain
Solution, contain
With
Solution be respectively charged in 4 storage tanks.Open nitrogen cylinder, under the nitrogen pressure effect, feed liquid in 4 storage tanks is extruded rapidly along pipeline separately enter in 4 entrances of Road narrows formula impact flow reactor through flowmeter, regulate and control well the flow of 4 stock material liquid.Adopt process that Road narrows formula impact flow reactor prepares the magnetic Nano lithium ion sieve as shown in Figure 1, the width of Road narrows is 1mm in Road narrows formula impact flow reactor, and the degree of depth is 5mm.Contain
With
Solution in import 1, contain
Solution in import 2, contain
With
In import 3 and import 4, contain
With
Solution first with contain
Solution bump against, projected angle of impact is 120 °, moment generates black in knockout process
Slurries, Fe
3O
4Slurries forward in the rapid flow process with the containing of both sides
With
Solution generation multiple impacts converge, collision angle is 30 °, reaction generates in collision process
Fast deposition arrives
The surface of colloidal particle forms nucleocapsid structure
Colloidal particle, product flows out from reactor outlet, and slurry pH value is measured with pH meter in the exit.The gained slurries with
Reaction generates under hydrothermal condition
, obtain through suction filtration, washing, drying, roasting
Particle is scattered in breaks into slurries in the deionized water, in the strong stirring slurries, drip the hydrochloric acid solution of 1mol/L in the slurries, the pH value of control slurries terminal point is near 2.0, make hydrogen ion and intragranular lithium ion generation exchange adsorption in the slurries, obtain magnetic Nano lithium ion sieve product.
The below characterizes and performance test the product that makes:
One, particle characterizes:
Two, properties of product test:
Above-mentioned sample 5g second step in specific implementation method is carried out acidleach take off lithium, the Initial pH of slurries is 10.51, slurry pH value reduces gradually in the hydrochloric acid process that drips 1mol/L, when being reduced to, slurry pH value finishes the dropping process when no longer rebounding in 2 and 10 minutes, dripped altogether 96 milliliters hydrochloric acid solution in 14 hours, adopt Fe in the front particle of atomic absorption spectrometry acidleach and the filtrate after the acidleach, Mn, the content of Li, the result shows that the leaching rate of Li reaches 89.2%, the molten loss rate of Fe is 0.084%, the molten loss rate of Mn is that the very low explanation of the molten loss rate of 0.43%, Fe ion coats dense.After will washing after filtration through the lithium ion sieve of acidleach, be dipped in that brute force stirs evenly in the 1000ml deionized water, the Initial pH of measuring slurries is 3.75, then the lithium hydroxide solution with 0.1mol/L dropwise joins in the suspension, the control rate of addition maintains between 8.0 ± 0.1 slurry pH value all the time, measures the volume that drips lithium hydroxide solution every 1min, finishes the dropping process behind the 1h, slurries are filtered, and gained filtrate is water white transparency substantially.Measure the ion concentration in the filtrate, the result shows that the molten loss rate of Fe and Mn is respectively 0.0024% and 0.038%.Abscissa is titration time in the accompanying drawing 6, and ordinate is the volume of the 0.1mol/L lithium hydroxide solution that drips of per minute, and the curve in the accompanying drawing 6 is curve that each loose point forms after match.In addition, the content of Li is 1.611mg/L at initial 10min end in the slurries after measured, and increases to 2.859mg/L behind the 1h.
The below does detailed statement with example: preparation sulphate of iron mixed solution 900ml, wherein Fe
2+Concentration is 0.3mol/L, Fe
3+/ Fe
2+Mol ratio is 1.6; Preparation sodium hydroxide solution 900ml concentration is 3.6mol/L; Preparation manganese sulfate and hydrogen peroxide mixed solution 1800ml, wherein manganese sulfate concentration is 0.39mol/L, hydrogen peroxide concentration is 0.195mol/L; And pour into separately in the storage tank, the volume of 4 kinds of feed liquids is 900ml, and initial temperature is 25 ℃.Open nitrogen cylinder, making pressure is that the nitrogen of 0.5MPa enters in above-mentioned 4 storage tanks simultaneously, under the nitrogen pressure effect, 4 stock material liquid enter in the Road narrows formula impinging stream reaction device, the flow of controlling 4 stock material liquid is 300ml/min, 5 of fronts block in 12 branch flow passages of every side, and feed liquid flows out in 7 branch flow passages from behind.When being 12, the pH of product feed liquid value begins to connect material.Product is put into water heating kettle, hydrothermal temperature is controlled to be poured out after 120 ℃ of ageing times arrive 12h, behind suction filtration, washing, drying, 3 grams of pulverizing, weigh, again pours in the water heating kettle again, the lithium hydroxide solution that adds 6mol/L, 50ml carries out hydro-thermal reaction, hydrothermal temperature is controlled at 120 ℃, and the hydro-thermal reaction time is controlled at 24h, and hydro-thermal reaction is carried out suction filtration, washing, drying, pulverizing after finishing, then carry out high-temperature roasting, sintering temperature is controlled at 400 ℃, and roasting time is 4h, obtains
Magnetic Nano lithium ion sieve precursor particle.Pouring the deionized water of precursor particle and 600ml into height stirs in the machine, form homodisperse slurries through high-speed stirred, slurries are poured into when stirring in the beaker, drip the hydrochloric acid solution of 1mol/L in the slurries, the pH value of control slurries terminal point is near 2.0, the lithium ion of hydrogen ion and particle surface is replaced, obtain the magnetic Nano lithium ion sieve.Shell lithium ion sieve film average thickness is at 2nm to 30nm.
Embodiment 2: preparation sulphate of iron mixed solution 900ml, wherein Fe
2+Concentration is 0.1mol/L, Fe
3+/ Fe
2+Mol ratio is 1.8; Preparation sodium hydroxide solution 900ml, concentration is 1.3mol/L, preparation manganese sulfate and hydrogen peroxide mixed solution 1800ml, wherein manganese sulfate concentration is 0.14mol/L, hydrogen peroxide concentration is 0.07mol/L; And pour into separately in the storage tank, the volume of 4 kinds of feed liquids is 900ml, and initial temperature is 25 ℃.Open nitrogen cylinder, making pressure is that the nitrogen of 0.5MPa enters in above-mentioned 4 storage tanks simultaneously, under the nitrogen pressure effect, 4 stock material liquid enter in the Road narrows formula impinging stream reaction device, the flow of controlling 4 stock material liquid is 150ml/min, 9 of fronts block in 12 branch flow passages of every side, and feed liquid flows out in 3 branch flow passages from behind.When being 10, the pH of product feed liquid value begins to connect material.Product is put into water heating kettle, hydrothermal temperature is controlled to be poured out after 100 ℃ of ageing times arrive 100h, behind suction filtration, washing, drying, 2 grams of pulverizing, weigh, again pours in the water heating kettle again, the lithium hydroxide solution that adds 4mol/L, 50ml carries out hydro-thermal reaction, hydrothermal temperature is controlled at 180 ℃, and the hydro-thermal reaction time is controlled at 12h, and hydro-thermal reaction is carried out suction filtration, washing, drying, pulverizing after finishing, then carry out high-temperature roasting, sintering temperature is controlled at 300 ℃, and roasting time is 8h, obtains
Magnetic Nano lithium ion sieve precursor particle.Pouring the deionized water of precursor particle and 600ml into height stirs in the machine, form homodisperse slurries through high-speed stirred, slurries are poured into when stirring in the beaker, drip the hydrochloric acid solution of 1mol/L in the slurries, the pH value of control slurries terminal point is near 2.0, the lithium ion of hydrogen ion and particle surface is replaced, obtain the magnetic Nano lithium ion sieve.
Embodiment 3: preparation sulphate of iron mixed solution 900ml, wherein Fe
2+Concentration is 0.2mol/L, Fe
3+/ Fe
2+Mol ratio is 2.0; Preparation sodium hydroxide solution 900ml, concentration is 2.8mol/L, preparation manganese sulfate and hydrogen peroxide mixed solution 1800ml, wherein manganese sulfate concentration is 0.3mol/L, hydrogen peroxide concentration is 0.15mol/L; And pour into separately in the storage tank, the volume of 4 kinds of feed liquids is 900ml, and initial temperature is 25 ℃.Open nitrogen cylinder, making pressure is that the nitrogen of 0.5MPa enters in above-mentioned 4 storage tanks simultaneously, under the nitrogen pressure effect, 4 stock material liquid enter in the Road narrows formula impinging stream reaction device, the flow of controlling 4 stock material liquid is 600ml/min, 7 of fronts block in 12 branch flow passages of every side, and feed liquid flows out in 5 branch flow passages from behind.When being 9, the pH of product feed liquid value begins to connect material.Product is put into water heating kettle, hydrothermal temperature is controlled to be poured out after 140 ℃ of ageing times arrive 12h, behind suction filtration, washing, drying, 4 grams of pulverizing, weigh, again pours in the water heating kettle again, the lithium hydroxide solution that adds 8mol/L, 50ml carries out hydro-thermal reaction, hydrothermal temperature is controlled at 100 ℃, and the hydro-thermal reaction time is controlled at 100h, and hydro-thermal reaction is carried out suction filtration, washing, drying, pulverizing after finishing, then carry out high-temperature roasting, sintering temperature is controlled at 550 ℃, and roasting time is 1h, obtains
Magnetic Nano lithium ion sieve precursor particle.Pouring the deionized water of precursor particle and 600ml into height stirs in the machine, form homodisperse slurries through high-speed stirred, slurries are poured into when stirring in the beaker, drip the hydrochloric acid solution of 1mol/L in the slurries, the pH value of control slurries terminal point is near 2.0, the lithium ion of hydrogen ion and particle surface is replaced, obtain the magnetic Nano lithium ion sieve.
Embodiment 4: preparation sulphate of iron mixed solution 900ml, wherein Fe
2+Concentration is 0.15mol/L, Fe
3+/ Fe
2+Mol ratio is 2.4; Preparation sodium hydroxide solution 900ml, concentration is 2.4mol/L, preparation manganese sulfate and hydrogen peroxide mixed solution 1800ml, wherein manganese sulfate concentration is 0.51mol/L, hydrogen peroxide concentration is 0.255mol/L; And pour into separately in the storage tank, the volume of 4 kinds of feed liquids is 900ml, and initial temperature is 25 ℃.Open nitrogen cylinder, making pressure is that the nitrogen of 0.5MPa enters in above-mentioned 4 storage tanks simultaneously, under the nitrogen pressure effect, 4 stock material liquid enter in the Road narrows formula impinging stream reaction device, the flow of controlling 4 stock material liquid is 450ml/min, 3 of fronts block in 12 branch flow passages of every side, and feed liquid flows out in 9 branch flow passages from behind.When being 7, the pH of product feed liquid value begins to connect material.Product is put into water heating kettle, hydrothermal temperature is controlled to be poured out after 130 ℃ of ageing times arrive 50h, behind suction filtration, washing, drying, 1 gram of pulverizing, weigh, again pours in the water heating kettle again, the lithium hydroxide solution that adds 2mol/L, 50ml carries out hydro-thermal reaction, hydrothermal temperature is controlled at 160 ℃, and the hydro-thermal reaction time is controlled at 16h, and hydro-thermal reaction is carried out suction filtration, washing, drying, pulverizing after finishing, then carry out high-temperature roasting, sintering temperature is controlled at 450 ℃, and roasting time is 2h, obtains
Magnetic Nano lithium ion sieve precursor particle.Pouring the deionized water of precursor particle and 600ml into height stirs in the machine, form homodisperse slurries through high-speed stirred, slurries are poured into when stirring in the beaker, drip the hydrochloric acid solution of 1mol/L in the slurries, the pH value of control slurries terminal point is near 2.0, the lithium ion of hydrogen ion and particle surface is replaced, obtain the magnetic Nano lithium ion sieve.
Although described the present invention in conjunction with preferred embodiment; so it is not to limit the present invention; any those skilled in the art; in the situation that do not break away from the spirit and scope of the present invention; can implement to the theme of listing displacement and the modification of various changes, coordinate here, so protection scope of the present invention is as the criterion when looking the claim restricted portion that proposes.
Claims (9)
1. the preparation method of magnetic nano lithium ion sieve adsorbent is characterized in that may further comprise the steps:
What 1) will prepare contains
With
Solution, contain
Solution, contain
With
Solution be respectively charged into four storage tanks; Feed liquid in four storage tanks is entered as required simultaneously in four imports of Road narrows formula impact flow reactor, wherein contain
With
Solution in import 1, contain
Solution in import 2, contain
With
Solution in import 3 and import 4, contain
With
Solution first with contain
Solution bump against, generate
Slurries, Fe
3O
4Slurries again with the containing of both sides
With
Solution generation multiple impacts form nucleocapsid structure
Slurries;
2) after product flows out from reactor outlet, put into water heating kettle aging, aging rear suction filtration, washing, drying are put into water heating kettle after weighing and are added
Carry out hydro-thermal reaction and obtain product
3) at last will
Carrying out suction filtration, washing, drying, roasting is consisted of
Magnetic Nano lithium ion sieve particle.
2. the preparation method of magnetic nano lithium ion sieve adsorbent according to claim 1, it is characterized in that: the Road narrows of Road narrows formula impact flow reactor are " shark's fin type " layout in the described step 1, comprise four imports and an outlet, Road narrows are divided into sprue, side runner and branch flow passage, and the width of Road narrows is between 0.5mm to 1.5mm; Flow into two stock material liquid of import 1 and import 2 along Road narrows are in the collision of sprue port separately, flow velocity equates during two stock material liquid bump, and projected angle of impact is between 100 ° to 140 °, and the flow velocity of feed liquid in sprue is between 1m/s to 4m/s behind the bump; The two stock material liquid that flow into import 3 and import 4 are introduced into the side runner on both sides, enter again the branch flow passage from side runner, material liquid side in the branch flow passage port of export and sprue is hit, and side breakhead degree is between 45 ° to 90 °, and the opening number of both sides branch flow passage is between 1 to 12.
3. the preparation method of magnetic nano lithium ion sieve adsorbent according to claim 1, it is characterized in that: described both sides branch flow passage can be blocked or open in any combination mode as required.
4. the preparation method of magnetic nano lithium ion sieve adsorbent according to claim 1, it is characterized in that: the feed liquid flow that enters import 3 and import 4 in the described step 1 is 1 with the ratio of the feed liquid flow that enters import 1 and import 2, the initial temperature of four stock material liquid wherein contains between 20 ℃ to 90 ℃
With
Solution in
Mol ratio between 1.6 to 2.4, this solution with contain
The Fe that generates after bumping against of solution
3O
4Fe in the slurries
3O
4Concentration between 0.05mol/L ~ 0.15mol/L, keep as product in the reactor outlet
Slurry pH value is between 7 to 12.
5. the preparation method of magnetic nano lithium ion sieve adsorbent according to claim 1, it is characterized in that: the hydrothermal aging temperature is 100 ℃ to 140 ℃ in the described step 2, the hydrothermal aging time is 12h to 36h, hydrothermal temperature is between 100 ℃ to 180 ℃, lithium hydroxide concentration is at 2mol/L to 8mol/L, and the hydro-thermal reaction time is between the 12h to 100h.
6. the preparation method of magnetic nano lithium ion sieve adsorbent according to claim 1, it is characterized in that: the temperature of the drying in the described step 3 is below 60 ℃, and the temperature of roasting is between 300 ℃ to 550 ℃, and roasting time is between 1h to 8h.
7. preparation method according to claim 3 is characterized in that the process of the acidleach in the described step 3 is specially: will
Particle is scattered in and breaks into slurries in the deionized water, in strong stirring, slowly drip the hydrochloric acid solution of 1mol/L in the slurries, make hydrogen ion and intragranular lithium ion generation exchange adsorption in the solution, be down to 2 and when no longer rebounding when the pH of slurries value, take off the lithium process and finish.
8. the magnetic Nano lithium ion sieve for preparing to 7 described methods according to claim 1 is characterized in that this magnetic nano lithium ion sieve adsorbent is with nanometer
Superparamagnetic material is that kernel, nanometer lithium-Mn oxide lithium ion sieve film are shell, consists of
Nucleocapsid structure, wherein x/y ratio is 1.
9. magnetic Nano lithium ion sieve according to claim 8 is characterized in that the average grain diameter of described nucleocapsid structure between 20 to 60nm, specific area 20 to 60m
2Between/the g, its housing lithium ion sieve film average thickness is more than 2nm.
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| CN103127888A (en) * | 2013-03-18 | 2013-06-05 | 浙江海洋学院 | Fish-shaped reactor |
| CN104128137A (en) * | 2014-08-04 | 2014-11-05 | 浙江海洋学院 | Double fish-shaped reactor |
| CN104941569A (en) * | 2015-06-17 | 2015-09-30 | 浙江工业大学 | Method for preparing manganese-based lithium-ion sieve adsorbent |
| CN106435220A (en) * | 2016-09-06 | 2017-02-22 | 南京工业大学 | Method for reducing magnesium-lithium ratio of salt lake brine |
| CN108212074A (en) * | 2016-12-12 | 2018-06-29 | 中国科学院过程工程研究所 | It is a kind of can the metatitanic acid type lithium ion sieve of Magnetic Isolation, preparation method and applications |
| CN108258247A (en) * | 2018-01-26 | 2018-07-06 | 天津市职业大学 | A kind of metaantimmonic acid lithium ion adsorbent of conduction and preparation method thereof |
| CN109078601A (en) * | 2018-09-06 | 2018-12-25 | 青海师范大学 | A kind of preparation method of nanotube-shaped Mn oxide lithium ion sieve adsorbant |
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| CN103127888A (en) * | 2013-03-18 | 2013-06-05 | 浙江海洋学院 | Fish-shaped reactor |
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| CN105396521A (en) * | 2014-08-04 | 2016-03-16 | 浙江海洋学院 | Double-fish-shaped reactor |
| CN104941569A (en) * | 2015-06-17 | 2015-09-30 | 浙江工业大学 | Method for preparing manganese-based lithium-ion sieve adsorbent |
| CN106435220A (en) * | 2016-09-06 | 2017-02-22 | 南京工业大学 | Method for reducing magnesium-lithium ratio of salt lake brine |
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| CN108212074B (en) * | 2016-12-12 | 2020-09-04 | 中国科学院过程工程研究所 | Metatitanic acid type lithium ion sieve capable of being magnetically separated, preparation method and application thereof |
| CN108258247A (en) * | 2018-01-26 | 2018-07-06 | 天津市职业大学 | A kind of metaantimmonic acid lithium ion adsorbent of conduction and preparation method thereof |
| CN108258247B (en) * | 2018-01-26 | 2020-08-11 | 天津市职业大学 | Conductive lithium antimonate ion adsorbent and preparation method thereof |
| CN109078601A (en) * | 2018-09-06 | 2018-12-25 | 青海师范大学 | A kind of preparation method of nanotube-shaped Mn oxide lithium ion sieve adsorbant |
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