CN102872791B - 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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- CN102872791B CN102872791B CN201210394616.2A CN201210394616A CN102872791B CN 102872791 B CN102872791 B CN 102872791B CN 201210394616 A CN201210394616 A CN 201210394616A CN 102872791 B CN102872791 B CN 102872791B
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- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 56
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 239000003463 adsorbent Substances 0.000 title claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 22
- 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 26
- 229910052744 lithium Inorganic materials 0.000 claims description 20
- 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
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 15
- 238000003860 storage Methods 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 13
- 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
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 abstract 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
- 238000001035 drying Methods 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
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 28
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-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
- 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
- 239000011572 manganese Substances 0.000 description 7
- 229910052742 iron Inorganic materials 0.000 description 5
- 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
- 238000010298 pulverizing process 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
- 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
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 230000008859 change Effects 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
- 238000002441 X-ray diffraction Methods 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
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- 238000009792 diffusion process Methods 0.000 description 1
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- 230000007613 environmental effect Effects 0.000 description 1
- 238000011049 filling Methods 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
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- 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
- 238000001228 spectrum Methods 0.000 description 1
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- 150000003608 titanium Chemical class 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 Fe3O4 superparamagnetic material as the core and taking a nanometer lithium-manganese oxide lithium ion sieve thin film as the shell to form a Fe3O4/LixMnyO4 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 one can be from the aqueous solution rapid extraction lithium ion, and the magnetic nano lithium ion sieve adsorbent that can separate from the aqueous solution fast under magnetic field force effect and preparation method thereof.
Background technology
Lithium is the grand strategy goods and materials of national economy and national defense construction, has the good reputation of " energy metal that promotes world's progress ".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, liquid metal lithium is desirable nuclear reactor catalyst carrier, and lithium compound is best rocket solid fuel, and lithium base lubricating agent is widely used in the lubricated of auto parts and components.Conventional Inorganic-ion-exchange agent mainly contains oxide, hydroxide, heteropolyacid salt and composite salt.Wherein ion sieve oxide has ion sieve effect and lithium ion " memory " function, lithium in solution is had to special efficacy selective, and the alkali and alkaline earth metal ions ions such as the potassium coexisting, sodium, calcium, magnesium are had to good separating effect, become the most effective lithium adsorbent in seawater, bittern.Lithium manganese oxide ion sieve is considered to one of absorption property and the best lithium adsorbent of application prospect, is generally mixed by a certain percentage by lithium compound and manganese compound, after sintering, pickling, makes, and conventional manganese compound 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 expensive reagent, and cost is high, production procedure is long.In Extracting Lithium from Seawater research, adopt 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 in metal oxide, first to import object ion, generate composite metal oxide, do not changing under the prerequisite of crystal structure, object ion is therefrom extracted out, obtained porous type structure.This material has the object ion of accepting former importing and the trend that forms best crystal structure, therefore in the situation that having different kinds of ions to exist, the object ion of former importing is had to screening and memory function, be also referred to as ion memory material, mainly comprise: monoclinic system metaantimmonic acid, spinel-type titanium oxide and Mn oxide etc.Wherein lithium manganese oxide type ion sieve most study, its distribution coefficient Ka (adsorbance (mgg of Ka=lithium to lithium in seawater
-1concentration (the mgml of lithium in)/solution
-1) can reach 10
4～10
5; Li
+/ 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 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, with the precursor solution filling colloidal crystal template of lithium salts and titanium salt, through suction filtration, dry, two sections of constant temperature calcinings, acidleach and dry again after obtain 3DOM titanium oxygen ' lithium ionic sieve ', this invention has obviously improved the activated adoption phase ratio in ion-sieve material by the 3DOM structure control of material, strengthen the diffusion inside ability in ion transport, it is a kind of double hole channel functional material simultaneously with macropore and micropore, but also there is obvious deficiency further improving aspect the rate of adsorption of lithium ion sieve and switching performance.
Summary of the invention
The object of this invention is to provide the magnetic nano lithium ion sieve adsorbent that a kind of chemical stability is good, lithium ion adsorption capacity is large, superparamagnetism is strong and have accordingly that technique is simple, output is large, the preparation method of the low feature of cost.
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/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 comprising the following steps:
1) by containing of preparing
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 by setting flow simultaneously.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 flow process with the containing of both sides
with
solution generation multiple impacts form nucleocapsid structure
slurries;
2) product, from reactor outlet flows out, is put into water heating kettle aging, and aging rear suction filtration, washing, dry, put into water heating kettle after weighing and add
carry out hydro-thermal reaction and obtain product
;
3) finally will
carry out suction filtration, washing, dry, roasting is consisted of
magnetic Nano lithium ion sieve particle, this particle can be directly used in and from the aqueous solution, extract lithium ion after the de-lithium of acidleach.
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, in step 1, the material of Road narrows formula impact flow reactor is polytetrafluoroethylene (PTFE), 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, when two stock material liquid clash into, flow velocity equates, projected angle of impact is between 100 ° to 140 °, and after clashing into, the flow velocity of feed liquid in sprue is between 1m/s to 4m/s.The two stock material liquid that flow into import 3 and import 4 are introduced into the side runner on both sides, enter again 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.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 step 1 and the ratio of 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
solution bump against after generate Fe
3o
4fe in slurries
3o
4concentration between 0.05mol/L ~ 0.15mol/L, in reactor outlet as product retain
slurry pH value is between 7 to 12.
As preferably, in step 2, hydrothermal aging temperature is 100 ℃ to 140 ℃, 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 12h to 100h.
As preferably, the dry temperature in 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, in step 3, the process of the de-lithium of acidleach is specially: will
particle is scattered in and in deionized water, breaks into slurries, in strong stirring to the hydrochloric acid solution that slowly drips 1mol/L in slurries, make hydrogen ion and intragranular lithium ion generation exchange adsorption in solution, when the pH of slurries value is down to 2 and while no longer rebounding, de-lithium process finishes.
Compared with prior art, the invention has the advantages that:
1. magnetic Nano lithium ion sieve chemical stability is good, 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.
Accompanying drawing explanation
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
tEM transmission electron microscope photo;
Fig. 4 is of the present invention
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, the preparation method of magnetic Nano lithium ion sieve, concrete steps are:
By containing of configuring
with
solution, contain
solution, contain
with
solution be respectively charged in 4 storage tanks.Open nitrogen cylinder, under nitrogen pressure effect, 4 feed liquids in storage tank are extruded rapidly along pipeline separately and 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 formulas impact flow reactor prepares magnetic Nano lithium ion sieve as shown in Figure 1, in Road narrows formula impact flow reactor, the width of Road narrows is 1mm, 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 °, in knockout process moment generate black
slurries, Fe
3o
4slurries forward in rapid flow process with the containing of both sides
with
solution generation multiple impacts converge, collision angle is 30 °, in collision process reaction generate
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 exit.Gained slurries with
under hydrothermal condition, reaction generates
, obtain through suction filtration, washing, dry, roasting
particle is scattered in and in deionized water, breaks into slurries, in strong stirring slurries to the hydrochloric acid solution that drips 1mol/L in slurries, control the pH value of slurries terminal near 2.0, make hydrogen ion and intragranular lithium ion generation exchange adsorption in slurries, obtain magnetic Nano lithium ion sieve product.
Below the product making is characterized and performance test:
One, particle characterizes:
Two, properties of product test:
Above-mentioned sample 5g second step in specific implementation method is carried out to the de-lithium of acidleach, the Initial pH of slurries is 10.51, in the hydrochloric acid process that drips 1mol/L, slurry pH value reduces gradually, when being reduced to, slurry pH value finishes dropping process while no longer rebounding in 2 and 10 minutes, in 14 hours, drip altogether the hydrochloric acid solution of 96 milliliters, adopt Fe in the particle before atomic absorption spectrometry acidleach and the filtrate after acidleach, Mn, the content of Li, 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 0.43%, the very low explanation of molten loss rate of Fe ion is coated dense.By after the lithium ion sieve of acidleach is washed after filtration, being dipped in brute force in 1000ml deionized water stirs evenly, the Initial pH of measuring slurries is 3.75, then the lithium hydroxide solution of 0.1mol/L is dropwise joined in suspension, control rate of addition slurry pH value is maintained between 8.0 ± 0.1 all the time, measure the volume that drips lithium hydroxide solution every 1min, after 1h, finish dropping process, slurries are filtered, and gained filtrate is water white transparency substantially.Measure the ion concentration in filtrate, result shows that the molten loss rate of Fe and Mn is respectively 0.0024% and 0.038%.In accompanying drawing 6, abscissa is titration time, and ordinate is the volume of dripped 0.1mol/L lithium hydroxide solution per minute, and the curve in accompanying drawing 6 is each loose curve forming after matching.In addition, in slurries, the content of Li is 1.611mg/L at initial 10min end after measured, and after 1h, is increased to 2.859mg/L.
Do detailed statement with example below: 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 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 nitrogen pressure effect, 4 stock material liquid enter in Road narrows formula impinging stream reaction device, the flow of controlling 4 stock material liquid is 300ml/min, before in 12 branch flow passages of every side, 5 block, and feed liquid flows out in 7 branch flow passages from behind.In the time that being 12, the pH of product feed liquid value starts to connect material.Product is put into water heating kettle, hydrothermal temperature is controlled at after 120 ℃ of ageing times arrive 12h and pours out, and through suction filtration, washing, be dried, pulverize, weigh after 3 grams, more again pours in water heating kettle, add the lithium hydroxide solution of 6mol/L, 50ml to carry out hydro-thermal reaction, hydrothermal temperature is controlled at 120 ℃, and the hydro-thermal reaction time is controlled at 24h, carries out suction filtration, washing, dry, pulverizing after hydro-thermal reaction finishes, 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 machine, form homodisperse slurries through high-speed stirred, slurries are poured into when stirring in beaker, to the hydrochloric acid solution that drips 1mol/L in slurries, control the pH value of slurries terminal near 2.0, the lithium ion of hydrogen ion and particle surface is replaced, obtain 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 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 nitrogen pressure effect, 4 stock material liquid enter in Road narrows formula impinging stream reaction device, the flow of controlling 4 stock material liquid is 150ml/min, before in 12 branch flow passages of every side, 9 block, and feed liquid flows out in 3 branch flow passages from behind.In the time that being 10, the pH of product feed liquid value starts to connect material.Product is put into water heating kettle, hydrothermal temperature is controlled at after 100 ℃ of ageing times arrive 100h and pours out, and through suction filtration, washing, be dried, pulverize, weigh after 2 grams, more again pours in water heating kettle, add the lithium hydroxide solution of 4mol/L, 50ml to carry out hydro-thermal reaction, hydrothermal temperature is controlled at 180 ℃, and the hydro-thermal reaction time is controlled at 12h, carries out suction filtration, washing, dry, pulverizing after hydro-thermal reaction finishes, 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 machine, form homodisperse slurries through high-speed stirred, slurries are poured into when stirring in beaker, to the hydrochloric acid solution that drips 1mol/L in slurries, control the pH value of slurries terminal near 2.0, the lithium ion of hydrogen ion and particle surface is replaced, obtain 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 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 nitrogen pressure effect, 4 stock material liquid enter in Road narrows formula impinging stream reaction device, the flow of controlling 4 stock material liquid is 600ml/min, before in 12 branch flow passages of every side, 7 block, and feed liquid flows out in 5 branch flow passages from behind.In the time that being 9, the pH of product feed liquid value starts to connect material.Product is put into water heating kettle, hydrothermal temperature is controlled at after 140 ℃ of ageing times arrive 12h and pours out, and through suction filtration, washing, be dried, pulverize, weigh after 4 grams, more again pours in water heating kettle, add the lithium hydroxide solution of 8mol/L, 50ml to carry out hydro-thermal reaction, hydrothermal temperature is controlled at 100 ℃, and the hydro-thermal reaction time is controlled at 100h, carries out suction filtration, washing, dry, pulverizing after hydro-thermal reaction finishes, 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 machine, form homodisperse slurries through high-speed stirred, slurries are poured into when stirring in beaker, to the hydrochloric acid solution that drips 1mol/L in slurries, control the pH value of slurries terminal near 2.0, the lithium ion of hydrogen ion and particle surface is replaced, obtain 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 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 nitrogen pressure effect, 4 stock material liquid enter in Road narrows formula impinging stream reaction device, the flow of controlling 4 stock material liquid is 450ml/min, before in 12 branch flow passages of every side, 3 block, and feed liquid flows out in 9 branch flow passages from behind.In the time that being 7, the pH of product feed liquid value starts to connect material.Product is put into water heating kettle, hydrothermal temperature is controlled at after 130 ℃ of ageing times arrive 50h and pours out, and through suction filtration, washing, be dried, pulverize, weigh after 1 gram, more again pours in water heating kettle, add the lithium hydroxide solution of 2mol/L, 50ml to carry out hydro-thermal reaction, hydrothermal temperature is controlled at 160 ℃, and the hydro-thermal reaction time is controlled at 16h, carries out suction filtration, washing, dry, pulverizing after hydro-thermal reaction finishes, 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 machine, form homodisperse slurries through high-speed stirred, slurries are poured into when stirring in beaker, to the hydrochloric acid solution that drips 1mol/L in slurries, control the pH value of slurries terminal near 2.0, the lithium ion of hydrogen ion and particle surface is replaced, obtain magnetic Nano lithium ion sieve.
Although described the present invention in conjunction with preferred embodiment; so it is not in order to limit the present invention; any those skilled in the art; without departing 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, the scope that therefore protection scope of the present invention ought limit depending on proposed claim is as the criterion.
Claims (7)
1. the preparation method of magnetic nano lithium ion sieve adsorbent, is characterized in that comprising the following steps:
1) by containing of preparing
with
solution, contain
solution, contain
with
solution be respectively charged into four storage tanks; Feed liquid in four storage tanks is entered as required in four imports of Road narrows formula impact flow reactor simultaneously, 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) product, from reactor outlet flows out, is put into water heating kettle aging, and aging rear suction filtration, washing, dry, put into water heating kettle after weighing and add
carry out hydro-thermal reaction and obtain product
;
3) finally will
carry out suction filtration, washing, dry, roasting is consisted of
magnetic Nano lithium ion sieve particle, then this particle is taken off to lithium through acidleach; Wherein the ratio of x/y is 1.
2. the preparation method of magnetic nano lithium ion sieve adsorbent according to claim 1, it is characterized in that: in described step 1, the Road narrows of Road narrows formula impact flow reactor are " shark's fin type " layout, 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, when two stock material liquid clash into, flow velocity equates, projected angle of impact is between 100 ° to 140 °, and after clashing into, the flow velocity of feed liquid in sprue is between 1m/s to 4m/s; The two stock material liquid that flow into import 3 and import 4 are introduced into the side runner on both sides, enter again 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, 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 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, between 20 ℃ to 90 ℃, wherein contains
with
solution in
mol ratio between 1.6 to 2.4, this solution with contain
solution bump against after generate Fe
3o
4fe in slurries
3o
4concentration between 0.05mol/L ~ 0.15mol/L, in reactor outlet as product retain
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: in described step 2, hydrothermal aging temperature is 100 ℃ to 140 ℃, 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 12h to 100h.
6. the preparation method of magnetic nano lithium ion sieve adsorbent according to claim 1, is characterized in that: the dry temperature in 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 described step 3 is specially: will
particle is scattered in and in deionized water, breaks into slurries, in strong stirring to the hydrochloric acid solution that slowly drips 1mol/L in slurries, make hydrogen ion and intragranular lithium ion generation exchange adsorption in solution, when the pH of slurries value is down to 2 and while no longer rebounding, de-lithium process finishes.
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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 |
| CN108258247B (en) * | 2018-01-26 | 2020-08-11 | 天津市职业大学 | Conductive lithium antimonate ion adsorbent and preparation method thereof |
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