CN103121724A - Method for preparing lithium ion sieve MnO2.0.5H2O and precursor thereof Li1.6Mn1.6O4 - Google Patents
Method for preparing lithium ion sieve MnO2.0.5H2O and precursor thereof Li1.6Mn1.6O4 Download PDFInfo
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- CN103121724A CN103121724A CN2012105673808A CN201210567380A CN103121724A CN 103121724 A CN103121724 A CN 103121724A CN 2012105673808 A CN2012105673808 A CN 2012105673808A CN 201210567380 A CN201210567380 A CN 201210567380A CN 103121724 A CN103121724 A CN 103121724A
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Abstract
The invention discloses a method for preparing a lithium ion sieve adsorbent MnO2.0.5H2O and a precursor thereof Li1.6Mn1.6O4. The method comprises the following steps: carrying out one-step hydrothermal synthesis on raw materials inorganic manganese salt and lithium salt to obtain an intermediate, and roasting at low temperature to obtain the required precursor Li1.6Mn1.6O4; and carrying out acid treatment on the precursor to extract Li so as to obtain an H-type ion sieve, washing with water, filtering, and drying to obtain the ion sieve adsorbent MnO2.0.5H2O which has a screening effect on lithium ions. The invention has the advantages of simple process route and mild preparation conditions; and the obtained ion sieve has the advantages of low solution loss, high adsorption rate and high adsorption capacity.
Description
Technical field
The present invention relates to the preparation method of lithium adsorbent, being specifically related to a kind of manganese for preparing is ion(ic)sieve sorbent material MnO
20.5H
2O and presoma Li thereof
1.6Mn
1.6O
4Method.
Background technology
Lithium is the lightest in the world metal, relies on its special physico-chemical property to be widely applied to many fields.Most of lithium resource in the world all is stored in salt lake (seawater), how effectively to extract lithium and become a problem demanding prompt solution from salt lake or seawater.
China is a resource big country, and the lithium resource reserves are very abundant, and especially the liquid lithium lithium resource is abundant especially.The method of extracting separating Li from salt lake brine mainly contains the precipitator method, solvent extration and absorption method.Absorption method considers than additive method, larger advantage is arranged from the environment and economy angle, and is especially more obvious in the advantage of carrying lithium from low grade brine or seawater.Its key is to develop the sorbent material of excellent property, and it requires sorbent material to lithium, high selectivity to be arranged, in order to eliminate the interference of the alkali and alkaline earth metal ions ion that coexists in a large number in bittern.Manganese bioxide ionic sieve has spinel structure, owing to having unique three-dimensional internal tunnel, is beneficial to Li
+Embedding with deviate from, therefore be widely used as electrode materials and the sorbent material of lithium cell.
The manganese bioxide ionic sieve of the adsorptive capacity maximum of report is MnO at present
20.5H
2O, its synthetic method is more single, is all first by synthesizing LiMnO
2, then with LiMnO
2Roasting obtains presoma in air atmosphere.Existing synthetic method generally uses MnOOH as the manganese synthetic LiMnO in source
2, and synthesizing of MnOOH is own with regard to more complicated, high to the operational condition requirement, and MnOOH is unstable in air, is unfavorable for suitability for industrialized production.Also exist simultaneously raw material lithium manganese than high (generally greater than 10), the problem that the hydro-thermal reaction time is long.
Summary of the invention
The object of the invention is to overcome the deficiency that above-mentioned prior art exists, it is ion(ic)sieve sorbent material MnO that a kind of manganese for preparing is provided
20.5H
2O and presoma Li thereof
1.6Mn
1.6O
4Method.The present invention uses permanganate cheap and easy to get and manganous salt to be manganese one step of source Hydrothermal Synthesis LiMnO
2, building-up process is simple, and is easy to control; By low-temperature bake LiMnO
2Obtain the presoma Li of sorbent material
1.6Mn
1.6O
4Then presoma is carried out the solvent leaching, lixiviate goes out Li wherein, has reduced simultaneously the molten damage of manganese, then obtains lithium ion is had the sorbent material of screening effect through washing, filtration, drying; That is to say, the present invention uses better simply operational path to synthesize that adsorptive capacity is high, the ion(ic)sieve sorbent material of good stability.Sorbent material of the present invention can extract lithium from contain the low concentration impurity ion high (as: lithium-containing solutions such as salt lake brine, well water, seawater) of lithium concentration.
The objective of the invention is to be achieved through the following technical solutions:
The present invention relates to a kind of manganese for preparing is ion(ic)sieve sorbent material MnO
20.5H
2O and presoma Li thereof
1.6Mn
1.6O
4Method, comprise the following steps:
(1) permanganate solution and the lithium hydroxide solution flow velocity with 3～10mL/min is joined in manganous salt solution, wherein, the mol ratio of manganous salt and permanganate is (3.8～4.5): 1, and lithium hydroxide and permanganate mol ratio are (12～25): 1;
(2) brown solution that step (1) is obtained tetrafluoroethylene water heating kettle reaction 6～24 hours, obtains intermediate product LiMnO under 150～200 ℃ of conditions
2
(3) with LiMnO
2Washing, after suction filtration under 60～100 ℃ of conditions dry 3～6 hours obtain lithium adsorbent presoma Li after roasting 4～48h under 300～500 ℃ of conditions in air atmosphere
1.6Mn
1.6O
4Atmosphere with oxidisability refers to: reaction is to carry out under the environment that passes into the gas with oxidisability; This gas with oxidisability is air or oxygen;
(4) after the presoma washing that step (3) is obtained, drying is 3～8 hours under still air, obtains described ion(ic)sieve sorbent material MnO after agent is soaked through soaking to take off
20.5H
2O。
Preferably, in step (1), described manganous salt is manganous carbonate, manganous sulfate, manganous fluoride, Manganous chloride tetrahydrate or manganese iodide.
Preferably, in step (1), described permanganate is sodium permanganate, potassium permanganate or calcium permanganate.
Preferably, in step (1), the mol ratio of described manganous salt and permanganate is (4～4.2): 1, and in described lithium hydroxide and permanganate, the mol ratio of elemental lithium and manganese element is (3～5): 1.
Preferably, in step (2), the temperature of described hydro-thermal reaction is 160～180 ℃, and the time is 6～12 hours.
Preferably, in step (3), described atmosphere with oxidisability is warm air atmosphere, and wherein, the flow rate of described warm air is 5～50mL/min, and temperature is 150～200 ℃.
Preferably, in step (3), described temperature with roasting is 350～450 ℃, and the time is 12～24h.During roasting, described atmosphere with oxidisability is warm air atmosphere, and wherein hot air temperature is 180～200 ℃, and the warm air flow rate is 10～50mL/min.
Preferably, in step (4), described drying temperature is 60～120 ℃.
Preferably, in step (4), described washing is specially: the ratio electricity that is washed to presoma is led less than 10
-5Ω
-1m
-1
Preferably, in step (4), described soaking taken off hydrochloric acid, sulfuric acid, nitric acid, hypochlorous acid, chloric acid, perchloric acid or the ammonium sulphite that agent is 0.1～1mol/L.
Compared with prior art, the present invention has following beneficial effect:
1, the hydro-thermal raw material is cheap and easy to get, and the elemental lithium of use and the mol ratio of manganese element are lower, contain the lithium wastage of material few;
2, the hydrothermal method synthetic intermediate LiMnO that uses
2Hydrothermal temperature is lower, can be to 130 ℃, and the hydro-thermal shortest time can be to 6h, and the product component Monosized powder that obtains is even;
3, synthetic method of the present invention, experiment condition, product proportioning are easily controlled, and the condition and range that can obtain desired product is wide;
4, the ion(ic)sieve persursor material Li that synthesizes of the present invention
1.6Mn
1.6O
4, it has spinel structure, stable in properties; The synthetic ion(ic)sieve MnO that obtains
20.5H
2O, it can be used for the lithium-containing solutions such as salt lake brine, seawater and carries lithium, and it is large to have adsorptive capacity, the advantage of good reproducibility.
Description of drawings
By reading the detailed description of non-limiting example being done with reference to the following drawings, it is more obvious that other features, objects and advantages of the present invention will become:
Fig. 1 is the LiMnO that synthesizes under the hydrothermal condition of embodiment 1
2, Li
1.6Mn
1.6O
4, MnO
20.5H
2The XRD figure of O, wherein, X-ray diffractometer is with the whole diffraction region of the angle scanning of 2 θ;
Fig. 2 is the synthetic LiMnO of embodiment 1 condition
2, Li
1.6Mn
1.6O
4, MnO
20.5H
2The SEM figure of O;
Fig. 3 is the synthetic MnO of embodiment 5 conditions
20.5H
2The curve of adsorption kinetics figure of O.
Embodiment
The present invention is described in detail below in conjunction with the drawings and specific embodiments.Following examples will help those skilled in the art further to understand the present invention, but not limit in any form the present invention.Should be pointed out that to those skilled in the art, without departing from the inventive concept of the premise, can also make some distortion and improvement.These all belong to protection scope of the present invention.
Manganese of the present invention is ion(ic)sieve sorbent material MnO
20.5H
2The preparation method of O and presoma thereof comprises the steps:
(1) flow velocity with 3～10mL/min under stirring state adds in the manganese chloride solution of 2～4mol/L with 0.1～0.3mol/L potassium permanganate solution and 3.0～5.0mol/L lithium hydroxide solution, wherein, the mol ratio of Manganous chloride tetrahydrate and potassium permanganate is (3.8～4.5): 1, and lithium hydroxide and potassium permanganate mol ratio are (12～25): 1;
(2) brown solution that step (1) is obtained is transferred to the tetrafluoroethylene water heating kettle of 1L, in 120～200 ℃ of Water Under thermal responses 6～24 hours, obtains intermediate product LiMnO
2
(3) with LiMnO
2After the washing suction filtration under 60～100 ℃ of conditions dry 3～6 hours, (can be air atmosphere or oxygen atmosphere) obtains the presoma Li of lithium adsorbent after roasting 4～48h under 300～500 ℃ of conditions in having the atmosphere of oxidisability
1.6Mn
1.6O
4
(4) presoma that step (3) obtained takes off after agent soaks through soaking, and drying obtains ion(ic)sieve MnO
20.5H
2O。
It is pointed out that the permanganate that the present invention uses is not limited to above-mentioned potassium permanganate, can also be sodium permanganate or calcium permanganate; The manganous salt that uses is not limited to above-mentioned Manganous chloride tetrahydrate, can also be manganous carbonate, manganous sulfate, manganous fluoride or manganese iodide; Hydrochloric acid, sulfuric acid, nitric acid, hypochlorous acid, chloric acid, perchloric acid or the ammonium sulphite that agent is 0.1～1mol/L taken off in above-mentioned soaking.
The preferred technical solution of the present invention is: the mol ratio of preferred manganous salt and permanganate is (4～4.2): 1, and in preferred lithium hydroxide and permanganate, the mol ratio of elemental lithium and manganese element is (3～5): 1; In preferred steps (2), the temperature of hydro-thermal reaction is 160～180 ℃, and the time is 6～12 hours; In preferred steps (3), air atmosphere is warm air atmosphere, and wherein the flow rate of warm air is 5～50mL/min, and temperature is 150～200 ℃, and the temperature of roasting is 350～450 ℃, and the time is 12～24h; In preferred steps (4), drying temperature is 60～120 ℃.Specifically see following examples.
Embodiment 1
The flow velocity with 3mL/min under vigorous stirring adds in the manganese chloride solution of 2mol/L with 0.1mol/L potassium permanganate solution and 5.0mol/L lithium hydroxide solution, wherein, the Manganous chloride tetrahydrate that adds and the mol ratio of potassium permanganate are 4:1, and lithium hydroxide and potassium permanganate mol ratio are 25:1; With the brown solution that the obtains tetrafluoroethylene water heating kettle at 1L, in 180 ℃ of Water Under thermal responses 6 hours, obtain intermediate product LiMnO
2, the XRD figure of this product is seen Fig. 1 (a), SEM figure sees Fig. 2 (a); By Fig. 1 (a), 2 (a) as can be known, can obtain the LiMnO of pure phase under the hydrothermal condition that adopts
2, and the product granularity is more even, and particle diameter is in the 100nm left and right.With LiMnO
2With suction filtration after the deionization washing of 30 times of volumes, drying is 6 hours under 80 ℃ of conditions, obtains lithium adsorbent presoma Li in air atmosphere after roasting 12h under 450 ℃ of conditions
1.6Mn
1.6O
4, this presoma XRD sees Fig. 1 (b), SEM figure sees Fig. 2 (b); By Fig. 1 (b), 2 (b) as can be known, the calcining after product is spinel structure, and XRD does not have the assorted peak of other materials to occur.The product granularity is more even, and the front agglomeration of calcining still less.
Get presoma 0.8g Li
1.6Mn
1.6O
4Add 200mL 0.1mol/L HCl solution, put into the water bath with thermostatic control vibrator with the hunting of frequency of 130rpm, control homo(io)thermism at 30 ℃, reaction 12h soaks the Li in presoma
+Further filter, wash fully with deionized water, lead less than 10 with the ratio electricity of washings
-5Ω
-1m
-1Be standard, suction filtration, in 120 ℃ of still airs dry 8h, namely obtain ion(ic)sieve of the present invention.This ion(ic)sieve XRD figure is seen Fig. 1 (c), and this ion(ic)sieve SEM figure sees Fig. 2 (c); Can find from Fig. 1, before and after pickling, structure there is no obvious change, is still spinel structure.As shown in Figure 2, after pickling, the ion(ic)sieve particle diameter slightly diminishes.Ion(ic)sieve is that in 10mmol/L solution, equilibrium adsorption capacity is 5.6mmol/L at the pH=10.01 lithium concentration.
The flow velocity with 3mL/min under vigorous stirring adds in the manganese chloride solution of 2mol/L with 0.1mol/L potassium permanganate solution and 5.0mol/L lithium hydroxide solution, wherein the mol ratio of Manganous chloride tetrahydrate and potassium permanganate is 4.5:1, and lithium hydroxide and potassium permanganate mol ratio are 16.5:1; The brown solution that obtains is transferred to the tetrafluoroethylene water heating kettle of 1L, in 160 ℃ of Water Under thermal responses 12 hours, obtained intermediate product LiMnO
2With LiMnO
2With suction filtration after the deionization washing of 30 times of volumes, drying is 6 hours under 80 ℃ of conditions, obtains lithium adsorbent presoma Li in air atmosphere after roasting 24h under 350 ℃ of conditions
1.6Mn
1.6O
4Get presoma 0.8g Li
1.6Mn
1.6O
4Add 200mL 0.1mol/L HCl solution, put into the water bath with thermostatic control vibrator with the hunting of frequency of 130rpm, control homo(io)thermism at 30 ℃, reaction 12h soaks the Li in presoma
+Further filter, wash fully with deionized water, lead less than 10 with the ratio electricity of washings
-5Ω
-1m
-1Be standard, suction filtration, in 120 ℃ of still airs dry 8h, namely obtain ion(ic)sieve of the present invention.Ion(ic)sieve is that in 10mmol/L solution, equilibrium adsorption capacity is 5.7mmol/L at the pH=10.01 lithium concentration.
Embodiment 3
Get the presoma 0.8g Li of embodiment 1
1.6Mn
1.6O
4Add 200mL 0.1mol/L (NH
4)
2S
2O
8Solution is put into the water bath with thermostatic control vibrator with the hunting of frequency of 130rpm, controls homo(io)thermism at 30 ℃, and reaction 12h soaks the Li in presoma
+Further filter, wash fully with deionized water, lead less than 10 with the ratio electricity of washings
-5Ω
-1m
-1Be standard, suction filtration, in 60 ℃ of still airs dry 3h, namely obtain ion(ic)sieve sorbent material MnO of the present invention
20.5H
2O。The molten damage of this acid cleaning process manganese is 0%.
Embodiment 4
Take the prepared sample ions sieve adsorbant of 100mg embodiment 3 and put into tool sieve Erlenmeyer flask, add 50mL 10mmol/L mixed ion solutions (Li
+, Na
+, K
+, Ca
2+, and Mg
2+, pH=10.1), be placed in the large-scale shaking table of intelligent multifunctional with the hunting of frequency of 130rpm, control homo(io)thermism at 30 ℃, reaction 120h gets the upper strata stillness of night and monitors the wherein concentration of each ion with IC, the results are shown in Table 1.
The adsorption selectivity of table 1 ion(ic)sieve
As shown in Table 1, this ion(ic)sieve pair is compared with common coexisting ion higher selectivity, to carrying lithium and Extracting Lithium from Seawater has important practical value in the salt lake.
The flow velocity with 3mL/min under vigorous stirring adds in the manganese chloride solution of 3mol/L with 0.2mol/L potassium permanganate solution and 4.0mol/L lithium hydroxide solution, wherein the mol ratio of Manganous chloride tetrahydrate and potassium permanganate is 4.2:1, and in lithium hydroxide and potassium permanganate mol ratio, the mol ratio of elemental lithium and manganese element is 3:1; The brown solution that obtains is transferred to the tetrafluoroethylene water heating kettle of 1L, in 150 ℃ of Water Under thermal responses 6 hours, obtained intermediate product LiMnO
2With LiMnO
2With suction filtration after the deionization washing of 30 times of volumes, drying is 5 hours under 60 ℃ of conditions, obtains lithium adsorbent presoma Li in air atmosphere after roasting 12h under 450 ℃ of conditions
1.6Mn
1.6O
4Get presoma 0.8g Li
1.6Mn
1.6O
4Add 200mL 0.1mol/L HCl solution, put into the water bath with thermostatic control vibrator with the hunting of frequency of 130rpm, control homo(io)thermism at 30 ℃, reaction 12h soaks the Li in presoma
+Further filter, wash fully with deionized water, lead less than 10 with the ratio electricity of washings
-5Ω
-1m
-1Be standard, suction filtration, in 120 ℃ of still airs dry 8h, namely obtain ion(ic)sieve of the present invention.The sample ions sieve that takes the 100mg preparation is put into tool sieve Erlenmeyer flask, add in 100mL 30mmol/L LiCl solution, with ammoniacal liquor-chloride buffer solution regulator solution pH=10.1, be placed in the large-scale shaking table of intelligent multifunctional with the hunting of frequency of 130rpm, control homo(io)thermism at 30 ℃, reaction 10～4320min, get supernatant liquid and monitor the wherein concentration of lithium ion with IC, determine the equilibrium adsorption time, can find out that from kinetics of adsorption line (Fig. 3) ion(ic)sieve absorption reaches balance in 1500min, equilibrium adsorption capacity is 5.85mmol/g.
By the various embodiments described above as can be known, synthetic method of the present invention, easily-controlled experimental conditions, the condition and range that can obtain desired product is wide; The synthetic ion(ic)sieve sorbent material MnO that obtains of the present invention
20.5H
2O, it can be used for the lithium-containing solutions such as salt lake brine, seawater and carries lithium, and it is large to have adsorptive capacity, the advantage of good reproducibility.
Above specific embodiments of the invention are described.It will be appreciated that, the present invention is not limited to above-mentioned specific implementations, and those skilled in the art can make various distortion or modification within the scope of the claims, and this does not affect flesh and blood of the present invention.
Claims (10)
- One kind to prepare manganese be ion(ic)sieve sorbent material MnO 20.5H 2O and presoma Li thereof 1.6Mn 1.6O 4Method, it is characterized in that, comprise the following steps:(1) permanganate solution and the lithium hydroxide solution flow velocity with 3～10mL/min is joined in manganous salt solution, the mol ratio of described lithium hydroxide, manganous salt and permanganate is (12～25): (3.8～4.5): 1;(2) brown solution that step (1) is obtained tetrafluoroethylene water heating kettle reaction 6～24 hours, obtains intermediate product LiMnO under 120～200 ℃ of conditions 2(3) with LiMnO 2Washing, after suction filtration under 60～100 ℃ of conditions dry 3～6 hours, in having the atmosphere of oxidisability in obtaining lithium adsorbent presoma Li after roasting 4～48h under 300 ℃～500 ℃ conditions 1.6Mn 1.6O 4(4) the presoma washing, the drying that step (3) are obtained get described ion(ic)sieve sorbent material MnO through soaking to take off after agent is soaked 20.5H 2O。
- 2. preparing according to claim 1 manganese is ion(ic)sieve sorbent material MnO 20.5H 2O and presoma Li thereof 1.6Mn 1.6O 4Method, it is characterized in that, in step (1), described manganous salt is manganous carbonate, manganous sulfate, manganous fluoride, Manganous chloride tetrahydrate or manganese iodide.
- 3. preparing according to claim 1 manganese is ion(ic)sieve sorbent material MnO 20.5H 2O and presoma Li thereof 1.6Mn 1.6O 4Method, it is characterized in that, in step (1), described permanganate is sodium permanganate, potassium permanganate or calcium permanganate.
- 4. preparing according to claim 1 manganese is ion(ic)sieve sorbent material MnO 20.5H 2O and presoma Li thereof 1.6Mn 1.6O 4Method, it is characterized in that, in step (1), the mol ratio of described manganous salt and permanganate is (4～4.2): 1, in described lithium hydroxide and permanganate, the mol ratio of elemental lithium and manganese element is (3～5): 1.
- 5. preparation manganese according to right 1 is ion(ic)sieve sorbent material MnO 20.5H 2O and presoma Li thereof 1.6Mn 1.6O 4Method, it is characterized in that, in step (2), the temperature of described hydro-thermal reaction is 160～180 ℃, the time is 6～12 hours.
- 6. preparation manganese according to right 1 is ion(ic)sieve sorbent material MnO 20.5H 2O and presoma Li thereof 1.6Mn 1.6O 4Method, it is characterized in that, in step (3), described atmosphere with oxidisability is warm air atmosphere, wherein, the flow rate of described warm air is 5～50mL/min, temperature is 150～200 ℃.
- 7. preparation manganese according to right 1 is ion(ic)sieve sorbent material MnO 20.5H 2O and presoma Li thereof 1.6Mn 1.6O 4Method, it is characterized in that, in step (3), the temperature of described roasting is 350～450 ℃, the time is 12～24h.
- 8. preparation manganese according to right 1 is ion(ic)sieve sorbent material MnO 20.5H 2O and presoma Li thereof 1.6Mn 1.6O 4Method, it is characterized in that, in step (4), described drying temperature is 60～120 ℃.
- 9. preparation manganese according to right 1 is ion(ic)sieve sorbent material MnO 20.5H 2O and presoma Li thereof 1.6Mn 1.6O 4Method, it is characterized in that, in step (4), described washing is specially: the ratio electricity that is washed to presoma is led less than 10 -5Ω -1m -1
- 10. preparation manganese according to right 1 is ion(ic)sieve sorbent material MnO 20.5H 2O and presoma Li thereof 1.6Mn 1.6O 4Method, it is characterized in that, in step (4), described soaking taken off hydrochloric acid, sulfuric acid, nitric acid, hypochlorous acid, chloric acid, perchloric acid or the ammonium sulphite that agent is 0.1～1mol/L.
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