CN109200987A - Lithium adsorbent and preparation method thereof - Google Patents
Lithium adsorbent and preparation method thereof Download PDFInfo
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- CN109200987A CN109200987A CN201710523111.4A CN201710523111A CN109200987A CN 109200987 A CN109200987 A CN 109200987A CN 201710523111 A CN201710523111 A CN 201710523111A CN 109200987 A CN109200987 A CN 109200987A
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Abstract
The invention discloses a kind of lithium adsorbents and preparation method thereof.The chemical formula of the lithium adsorbent is LiClAlxMy(OH)3x+ny·mH2O, wherein x+y=2,3 < 3x+ny < 10,0 < y≤1,1 < m < 3, element M are transition metal, and n is the chemical valence of element M, 2≤n≤4.Lithium adsorbent of the present invention in aluminium hydroxide lattice structure by introducing transition metal M element, form a kind of relative complex crystal phase, compared to common lithium aluminium compound, the structure of this lithium adsorbent with special crystal phase is relatively stable, has the adsorbance significantly improved, desorption rate, adsorption efficiency, desorption efficiency, absorption stability and desorption stability.
Description
Technical field
The present invention relates to the preparation fields of lithium adsorbent, and in particular to a kind of lithium adsorbent and preparation method thereof.
Background technique
As lithium metal and its compound are in the extensive use of the numerous areas such as material, new energy, demand is increasingly
Greatly, traditional lithium ore proposes the demand that lithium has been unable to meet market.China is salt lake bittern lithium resource state very rich
Family, therefore how to develop salt lake bittern lithium resource and just become more and more important.(aluminium salt) lithium adsorbent is high to lithium ion selectivity,
Adsorption capacity is big and environmentally friendly, and absorption method is considered as that the salt lake bittern of current most prospects for commercial application proposes lithium method.
The chemical formula of existing (aluminium salt) lithium adsorbent is LiCl2Al (OH)3·mH2O (1 < m < 3), with the following two kinds preparation side
Method.
The first preparation method of above-mentioned (aluminium salt) lithium adsorbent includes: to mix aluminium hydroxide and lithium hydroxide solution,
Heating water bath for a period of time after, instill certain density hydrochloric acid, pH value is transferred to 2-8, dries solid at a certain temperature after centrifugation
It is dry, lithium aluminium compound is obtained after grinding gas is broken.In this approach, lithium chloride is embedded into the lattice of aluminium hydroxide, forms one
The new object phase of kind, wherein the insertion and abjection of lithium chloride are reversible, in order to maintain the knot of this new object phase of lithium aluminium compound
Structure is stablized, and the abjection amount maximum of lithium chloride can only achieve the 50% of theoretical value, and adsorbance is limited, so adsorbance is poor；And
It is attached in multiple adsorption-desorption, it maintains another 50% lithium chloride of stable structure that can also deviate from desorption, causes lithium aluminium multiple
Object structure collapses are closed, aluminium hydroxide object phase is formed, adsorbance is lost, so sorption cycle performance is poor.
Second of preparation method of above-mentioned (aluminium salt) lithium adsorbent includes: by aluminium hydroxide and chlorination lithium powder by certain
Metering is put into ball milling instrument than mixing, a certain amount of zirconium pearl is added, dry grind to mixed material, after a period of time, extract
Material, grinds to obtain lithium aluminium compound.Energy, lithium chloride are provided using the shock of mechanical milling process zirconium pearl in by this method
As the transient energy of offer is embedded into lithium hydroxide lattice, new object phase lithium aluminium compound is formed, what this shock provided
Energy is often non-uniform, within the regular hour, it cannot be guaranteed that each point has the energy of this shock, it is final at
Containing a small amount of unconverted object phase without adsorbance, i.e. aluminium hydroxide in product, the adsorption/desorption amount of material is affected；This
Outside, the lithium aluminium compound that this method is prepared maintains the granular size and pattern of raw aluminum hydroxide, and specific surface is smaller, inhales
Attached speed is slower, low efficiency.
Summary of the invention
It is of the existing technology the purpose of the invention is to overcome the problems, such as, a kind of lithium adsorbent and its preparation side are provided
Method, to improve the adsorbance and adsorption efficiency of existing lithium adsorbent.
To achieve the goals above, one aspect of the present invention provides a kind of lithium adsorbent, and the chemical formula of the lithium adsorbent is
LiCl·AlxMy(OH)3x+ny·mH2O, wherein x+y=2,3 < 3x+ny < 10,0 < y≤1,1 < m < 3, element M are transition metal, n
For the chemical valence of element M, 2≤n≤4.
Second aspect of the present invention provides a kind of preparation method of lithium adsorbent, the preparation method the following steps are included: S1,
Al(OH)3With M (OH)nIt is added into lithium hydroxide aqueous solution, obtains the mixing that viscosity is greater than 3000cp through wet grinding, stirring
Slurry A, wherein Al (OH)3With M (OH)nMolar ratio be (2-y): y, and 0 < y≤1；Element M is transition metal, and n is element M
Chemical valence, 2≤n≤4；The hydrochloric acid that concentration is 0.5-5mol/L is added into the mixed slurry A by S2, under agitation, until
The pH value of mixed slurry be 2-8, continue stirring until pH value it is constant until, obtain mixed slurry B；S3, by the mixed slurry B into
Row drying obtains the lithium adsorbent.
Third aspect present invention provides a kind of lithium adsorbent of preparation of the above method according to the present invention.
Lithium adsorbent of the present invention and preparation method thereof, by introducing transition metal M element in aluminium hydroxide lattice structure,
Form a kind of relative complex crystal phase, compared to common lithium aluminium compound, this structure with special crystal phase lithium adsorbent
It is relatively stable, have the adsorbance significantly improved, desorption rate, adsorption efficiency, desorption efficiency, absorption stability and desorption steady
It is qualitative.
Detailed description of the invention
Fig. 1 is that scanning electron microscope (SEM) photograph of the lithium adsorbent prepared by embodiment according to the present invention 1 under 1 μm is general；
Fig. 2 is that scanning electron microscope (SEM) photograph of the lithium adsorbent prepared by embodiment according to the present invention 1 under 5 μm is general.
Fig. 3 is that scanning electron microscope (SEM) photograph of the lithium adsorbent at 500nm prepared by comparative example 1 is general according to prior art；
Fig. 4 is that scanning electron microscope (SEM) photograph of the lithium adsorbent under 5 μm prepared by comparative example 1 is general according to prior art.
Specific embodiment
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
In order to improve the adsorbance and adsorption efficiency of (aluminium salt) lithium adsorbent, a kind of lithium absorption is provided in the present invention
Agent, the chemical formula of the lithium adsorbent are LiClAlxMy(OH)3x+ny·mH2O, wherein x+y=2,3 < 3x+ny < 10,0 < y≤1,1
< m < 3, element M are transition metal, and n is the chemical valence of element M, 2≤n≤4.
Lithium adsorbent according to the present invention, under preferable case, 4 < 3x+ny < 8.
Lithium adsorbent according to the present invention, under preferable case, 0 < y≤0.5, preferably x:y=1:(0.1-0.3).
Lithium adsorbent according to the present invention, under preferable case, the element M be selected from Sc, Ti, V, Cr, Mn, Fe, Co,
One or more of Ni, Cu and Zn；The more preferable element M is selected from one or more of Mn, Fe, Cu and Zn.
Lithium adsorbent according to the present invention, under preferable case, the specific surface area of the lithium adsorbent is 25-35m2/g。
Meanwhile provide a kind of preparation method of lithium adsorbent in the present invention, the preparation method the following steps are included:
S1、Al(OH)3With M (OH)nIt is added into lithium hydroxide aqueous solution, obtains viscosity through wet grinding (such as sand milling), stirring and be greater than
The mixed slurry A of 3000cp, wherein Al (OH)3With M (OH)nMolar ratio be (2-y): y, and 0 < y≤1；Element M is transition gold
Belong to, n is the chemical valence of element M, 2≤n≤4；S2, under agitation, (dropwise addition) concentration, which is added, into the mixed slurry A is
The hydrochloric acid of 0.5-5mol/L (preferably 1-2mol/L) persistently stirs until the pH value of mixed slurry is 2-8 (preferable ph 4-6)
It mixes until pH value is constant, obtains mixed slurry B；S3, the mixed slurry B is dried, obtains the lithium adsorbent.
Above-mentioned preparation method according to the present invention, under preferable case, the Al (OH)3With M (OH)nMolar ratio be (2-
Y): y, wherein 0 < y≤1, preferably 0 < y≤0.5, more preferable Al (OH)3With M (OH)nMolar ratio be 1:(0.1-0.3).
Above-mentioned preparation method according to the present invention, under preferable case, the element M be selected from Sc, Ti, V, Cr, Mn, Fe,
One or more of Co, Ni, Cu, Zn and Ga；It is preferred that the element M is selected from one or more of Mn, Fe, Cu and Zn.
Above-mentioned preparation method according to the present invention, under preferable case, the concentration of the lithium hydroxide aqueous solution is 1-
10mol/L, preferably 2-5mol/L.
Above-mentioned preparation method according to the present invention under preferable case, makes the partial size D50 of particulate matter in the sand grinding process
≤2.0μm.Wherein partial size D50 is volume weighting average grain diameter, is using particle by Malvern laser particle analyzer to light
Diffraction phenomena measurement obtains.
Above-mentioned preparation method according to the present invention, under preferable case, stirring obtains the mixed slurry A that viscosity is greater than 3000cp
The step of selected from any one of such as under type:
Mode one: simple stirring 16-40h is to obtain the mixed slurry A that viscosity is greater than 3000cp, although this mode time
It is relatively long, but be conducive to improve the stability of prepared lithium adsorbent；
Mode two: it first stirs 15-18h and obtains premixed slurries, then under condition of water bath heating, preferably 50-80 DEG C (excellent
Select 60-70 DEG C) the premixed slurries 2-5h is stood or stirred in water-bath to obtain the mixed slurry A that viscosity is greater than 3000cp；
This method can while improving the production efficiency, the opposite stability for keeping prepared lithium adsorbent；
Mode three: under condition of water bath heating, preferably 50-80 DEG C (preferably 60-70 DEG C) stirred in water bath 5-10h is to obtain
Viscosity is greater than the mixed slurry A of 3000cp；Although this method may lithium adsorbent prepared by relative reduction stability,
But production efficiency can be greatly improved.
Above-mentioned preparation method according to the present invention, under preferable case, the viscosity of the mixed slurry A is 3000-6000cp.
Above-mentioned preparation method according to the present invention, wherein method of the dry step using spray drying, preferably spraying
Dry step using the spray drying of conventional granulates object process, under preferable case, the spray drying step
In, outlet temperature is 100-110 DEG C.
Meanwhile a kind of lithium adsorbent prepared according to the above method is additionally provided in the present invention.The lithium adsorbent, the lithium
The chemical formula of adsorbent is LiClAlxMy(OH)3x+ny·mH2O, wherein x+y=2,3 < 3x+ny < 10,0 < y≤1,1 < m < 3 are first
Plain M is transition metal, and n is the chemical valence of element M, 2≤n≤4.Method lithium adsorbent obtained produced according to the present invention and sheet
The lithium adsorbent of invention foregoing description feature having the same, illustrates referring to foregoing description.
The beneficial effect of lithium adsorbent of the present invention and preparation method thereof is further illustrated below with reference to specific embodiment.
Raw material employed in following examples and comparative examples is as follows:
LiOH·H2O: Sichuan Xing Shengli industry company, purity 99.5% are commercially available from.
Aluminium hydroxide: the continent Zhong Lvzhong Co., Ltd, purity 99.5% are commercially available from.
Iron hydroxide: Guangzhou brilliance chemistry Materials Co., Ltd, purity 99.5% are commercially available from.
Kocide SD: Guangzhou brilliance chemistry Materials Co., Ltd, purity 99.5% are commercially available from.
Zinc hydroxide: Guangzhou brilliance chemistry Materials Co., Ltd, purity 99.5% are commercially available from.
Manganous hydroxide: Guangzhou brilliance chemistry Materials Co., Ltd, purity 99.5% are commercially available from.
Nickel hydroxide: Guangzhou brilliance chemistry Materials Co., Ltd, purity 99.5% are commercially available from.
The test item involved in following examples and comparative examples and method:
Scanning electron microscope (SEM) test: S4800 instrument, voltage 5KV, respectively under 0.5W, 2W, 5W, 10W multiple are used
It takes pictures.Powder sample is sticked on conductive tape, and carries out metal spraying processing, and sample is done in a vacuum drying oven before being tested
Dry preservation.
X-ray diffraction (XRD) test: Shimadzu XRD-7000, X-ray (Cu): voltage 40Kv, scanning speed 2deg/ are used
Min, sample inclination 0.05deg；Continuous scanning；Adjustment time 1.5s.
Constituent content test: with ICP test Al, Li, the content of element M (Mn, Zn, Cu, Fe), Cl is tested with ion chromatography
Content.
The measurement of specific surface area: low temperature nitrogen absorption method test powders are passed through using Bei Shide BET surface analysis instrument
Specific surface area.
Embodiment 1
For illustrating lithium adsorbent of the present invention and preparation method thereof.
Weigh 59.2g LiOHH2O is dissolved in 0.5L deionized water, is formed LiOH aqueous solution, is weighed 180.3g Al
(OH)3With 49.4gFe (OH)3It sequentially adds in the LiOH aqueous solution prepared, is sufficiently stirred, after being stirred with the sand mill of 0.5L
Slurry be continuously sanded 2 hours (particulate matter D50 be 1.86 μm) after, pour into 1L agitator and continuously stir 16h, tested viscosity is
5230cp。
The hydrochloric acid of the 3mol/L prepared is squeezed into above-mentioned slurry by the speed of 0.5ml/s with metering pump, on-line monitoring slurry
The pH value of material changes, and until the pH value of slurry is maintained at 4~5, hydrochloric acid is squeezed into stopping, continuing to stir 10min, final pH value is
4.75, slurry is dried with spray drying, 260 DEG C of inlet temperature, 105 DEG C of outlet temperature, the material after drying is lithium
Adsorbent (is denoted as S1).
By constituent content test it is found that the lithium adsorbent is with its total weight, the content of Al is 19.8 weight %, Li's
Content is that the content that the content of 3.12 weight %, Fe is 8.45 weight %, Cl is 15.68 weight %；By XRD test it is found that
The lithium adsorbent is relative to LiClAl1.66Fe0.34(OH)6·1.099H2There are diffraction maximums at O, it can be seen that, lithium absorption
The chemical formula of agent is LiClAl1.66Fe0.34(OH)6·1.099H2O。
Using the aforementioned lithium adsorbent of scanning electron microscopic observation, as depicted in figs. 1 and 2, Fig. 1 and Fig. 2 is that the lithium adsorbent is different
Scanning electron microscope (SEM) photograph under size, the primary particle size phase of lithium adsorbent prepared according to the present invention it can be seen from Fig. 1 and Fig. 2
To smaller, the average value for being measured its primary particle size is 95nm, and aggregate particle size average value is 8.3 μm；In view of prepared by the present invention
Lithium adsorbent primary particle partial size it is smaller, the specific surface area of relative increase is made it have, through measuring aforementioned lithium adsorbent
Specific surface area be 28.3m2/g。
Embodiment 2
For illustrating lithium adsorbent of the present invention and preparation method thereof.
Using the preparation method of lithium adsorbent in embodiment 1, difference is, Fe (OH)3Dosage be 29.03g；It is prepared
Lithium adsorbent be denoted as S2.The chemical formula for being measured the lithium adsorbent is LiClAl1.8Fe0.2(OH)6·1.099H2O, once
The average value of partial size is 87nm, and aggregate particle size is 8.8 μm；Specific surface area is 27.7m2/g。
Embodiment 3
For illustrating lithium adsorbent of the present invention and preparation method thereof.
Using the preparation method of lithium adsorbent in embodiment 1, difference is, Fe (OH)3Dosage be 72.65g；It is prepared
Lithium adsorbent be denoted as S3.The chemical formula for being measured the lithium adsorbent is LiClAl1.5Fe0.5(OH)6·1.099H2O, once
The average value of partial size is 106nm, and aggregate particle size is 9.4 μm；Specific surface area is 26.4m2/g。
Embodiment 4
For illustrating lithium adsorbent of the present invention and preparation method thereof.
Using the preparation method of lithium adsorbent in embodiment 1, difference is, Fe (OH)3Dosage be 116.52g；It is made
Standby lithium adsorbent is denoted as S4.The chemical formula for being measured the lithium adsorbent is LiClAl1.2Fe0.8(OH)6·1.099H2O, one
The average value of secondary partial size is 138nm, and aggregate particle size is 11.5 μm；Specific surface area is 20.6m2/g。
Embodiment 5
For illustrating lithium adsorbent of the present invention and preparation method thereof.
Weigh 63.74g LiOHH2O is dissolved in 0.5L deionized water, is formed LiOH aqueous solution, is weighed 196.5g Al
(OH)3With 25.6g Cu (OH)2It sequentially adds in the LiOH aqueous solution prepared, is sufficiently stirred, after being stirred with the sand mill of 0.5L
Slurry be continuously sanded 2.5 hours (particulate matter D50 be 1.58 μm) after, pour into 1L agitator and continuously stir 18h, tested viscosity is
2856cp, by slurry in 70 DEG C of water-bath water-bath 1.5h, testing size viscosity 5584cp.
The hydrochloric acid of the 2mol/L prepared is squeezed into on-line monitoring after water-bath in slurry by the speed of 0.5ml/s with metering pump
The pH value of slurry changes, and until the pH value of slurry is maintained at 4~5, hydrochloric acid is squeezed into stopping, continuing to stir 10min, final pH value is
4.25, slurry is dried with spray drying, 280 DEG C of inlet temperature, 100 DEG C of outlet temperature, the material after drying is lithium
Adsorbent (is denoted as S5).
Pass through constituent content test (content of Al, Li, element M being tested with ICP, with the content of particle chromatography test Cl)
It is found that the lithium adsorbent is with its total weight, the content that the content of Al is 19.9 weight %, Li is containing for 3.08 weight %, Cu
The content that amount is 8.83 weight %, Cl is 15.57 weight %；By XRD test it is found that the lithium adsorbent is relative to LiCl
Al1.68Cu0.31(OH)5.66·mH2There are diffraction maximums at O (1 < m < 3), it can be seen that, the chemical formula of the lithium adsorbent is LiCl
Al1.68Cu0.31(OH)5.66·mH2O(1<m<3).The primary particle size average value for being measured the lithium adsorbent is 75nm, aggregate particle size
Average value is 9.6 μm, specific surface area 33.5m2/g。
Embodiment 6
Weigh 80.0g LiOHH2O is dissolved in 1L deionized water, is formed LiOH aqueous solution, is weighed 205.0g Al (OH)3、
36.2gMn(OH)3With 49.4gZn (OH)2It sequentially adds in the LiOH aqueous solution prepared, is sufficiently stirred, will be stirred with the sand mill of 1L
After slurry after mixing continuously is sanded 3 hours (particulate matter D50 is 1.35 μm), pours into 1L agitator and continuously stir 18h, tested viscosity
For 4996cp.
The hydrochloric acid of the 3mol/L prepared is squeezed into above-mentioned slurry by the speed of certain 1ml/s with metering pump, is monitored online
The pH value of slurry changes, and until the pH value of slurry is maintained at 4~5, hydrochloric acid is squeezed into stopping, continuing to stir 10min, final pH value is
4.06, slurry is dried with spray drying, 300 DEG C of inlet temperature, 110 DEG C of outlet temperature, the material after drying is lithium
Adsorbent (is denoted as S6).
By constituent content test it is found that the lithium adsorbent is with its total weight, the content of Al is 15.6 weight %, Li's
Content is that the content that the content that the content of 2.94 weight %, Mn is 5.56 weight %, Zn is 10.39 weight %, Cl is 15.57 weights
Measure %；By XRD test it is found that the lithium adsorbent is with respect to LiClAl1.38Mn0.24Zn0.38(OH)5.62·mH2At O (1 < m < 3)
There are diffraction maximums, it can be seen that, the chemical formula of the lithium adsorbent is LiClAl1.38Mn0.24Zn0.38(OH)5.62·mH2O(1<m<
3).The primary particle size average value for being measured the lithium adsorbent is 78nm, and aggregate particle size average value is 8.8 μm, and specific surface area is
31.2m2/g。
Embodiment 7
For illustrating lithium adsorbent of the present invention and preparation method thereof.
Weigh 63.74g LiOHH2O is dissolved in 0.5L deionized water, is formed LiOH aqueous solution, is weighed 196.5g Al
(OH)3It sequentially adds in the LiOH aqueous solution prepared, is sufficiently stirred with 35.99g NiOH, after being stirred with the sand mill of 0.5L
Slurry be continuously sanded 2.5 hours (particulate matter D50 be 1.65 μm) after, pour into 1L agitator and continuously stir 18h, tested viscosity is
2865cp, by slurry in 70 DEG C of water-bath water-bath 1.5h, testing size viscosity 4433cp.
The hydrochloric acid of the 2mol/L prepared is squeezed into on-line monitoring after water-bath in slurry by the speed of 0.5ml/s with metering pump
The pH value of slurry changes, and until the pH value of slurry is maintained at 4~5, hydrochloric acid is squeezed into stopping, continuing to stir 10min, final pH value is
4.25, slurry is dried with spray drying, 280 DEG C of inlet temperature, 100 DEG C of outlet temperature, the material after drying is lithium
Adsorbent (is denoted as S5).
By constituent content test it is found that the lithium adsorbent is with its total weight, the 22.98 weight % of content of Al, Li's
Content is that the content that the content of 2.90 weight %, Ni is 9.42 weight %, Cl is 17.98 weight %；By XRD test it is found that
The lithium adsorbent is relative to LiClAl1.68Ni0.32(OH)5.36·mH2There are diffraction maximums at O (1 < m < 3), it can be seen that, the lithium
The chemical formula of adsorbent is LiClAl1.68Ni0.32(OH)5.36·mH2O(1<m<3).Measured the primary grain of the lithium adsorbent
Diameter average value is 75nm, and aggregate particle size average value is 9.6 μm, specific surface area 30.3m2/g。
Comparative example 1
Weigh 74.0g LiOHH2O is dissolved in 0.5L deionized water, is formed LiOH aqueous solution, is weighed 250.6g Al
(OH)3It is added in the LiOH aqueous solution for preparing, is sufficiently stirred, it is small that the slurry after stirring is continuously sanded 3 with the sand mill of 0.5L
When (particulate matter D50 be 1.75 μm) after, pour into 1L agitator and continuously stir 18h, tested viscosity 5262cp.
The hydrochloric acid of the 3mol/L prepared is squeezed into above-mentioned slurry by the speed of 0.5ml/s with metering pump, on-line monitoring slurry
The pH value of material changes, and until the pH value of slurry is maintained at 4~5, hydrochloric acid is squeezed into stopping, continuing to stir 10min, final pH value is
4.75, slurry is dried with spray drying, 260 DEG C of inlet temperature, 105 DEG C of outlet temperature, the material after drying is lithium
Adsorbent (is denoted as D1).
By constituent content test it is found that the lithium adsorbent is with its total weight, the content of Al is containing for 25 weight %, Li
The content that amount is 3.25 weight %, Cl is 16.43 weight %, H2The content of O is 9.15 weight %；It is tested by XRD it is found that should
Lithium adsorbent is relative to LiCl2Al (OH)3·1.099H2There are diffraction maximums at O, it can be seen that, the chemical formula of the lithium adsorbent
For LiCl2Al (OH)3·1.099H2O。
Using the aforementioned lithium adsorbent of scanning electron microscopic observation, as shown in Figure 3 and Figure 4, Fig. 3 and Fig. 4 is that the lithium adsorbent is different
Scanning electron microscope (SEM) photograph under size, the primary particle size phase of lithium adsorbent prepared according to the present invention it can be seen from Fig. 3 and Fig. 4
To larger, the average value for being measured its primary particle size is 150nm, and aggregate particle size is 4.8 μm；It is inhaled in view of lithium prepared by the present invention
The partial size of attached dose of primary particle is larger, makes it have the specific surface area of opposite reduction, through the ratio table for measuring aforementioned lithium adsorbent
Area is 23.6m2/g。
Comparative example 2
75.0g chlorination lithium powder and 250.6g aluminium-hydroxide powder are weighed, it is dry that the two is mixed to (zirconium pearl) in ball milling instrument
4.0h is ground, it is 3.5 μm that partial size is crushed to after taking-up, obtains lithium adsorbent (being denoted as D2).
Test
Lithium aluminium compound prepared by embodiment 1 to 7 and comparative example 1 to 2 is subjected to adsorbance test.
Adsorb weight testing method:
Desorption rate: it is eluted three times with liquid-solid ratio for 50 pairs of adsorbents with deionized water, middling speed (20Hz) is stirred at room temperature every time
It mixes lasting 1 hour, is centrifugated；Elution solution every time is collected, Li constituent content, 80 DEG C of the adsorbent isolated drying are tested；
Efficiency is desorbed: primary for 50 pairs of adsorbents elutions with liquid-solid ratio with deionized water, middling speed (20Hz) stirs at room temperature
Continue 1 hour, is centrifugated；Elution solution is collected, Li constituent content, 80 DEG C of the adsorbent isolated drying are tested；
Absorption is energy: the brine (lithium content 272.86ppm) extracted with salt lake, carries out absorption in fact for 40 with liquid-solid ratio
It tests, low speed (10Hz) stirring at room temperature continues 1 hour, filters；Filtrate is collected, Li content is tested；
Adsorption efficiency: the brine (lithium content 272.86ppm) extracted with salt lake carries out absorption in fact for 40 with liquid-solid ratio
It tests, low speed (10Hz) stirring at room temperature continues 0.5 hour, filters；Filtrate is collected, Li content is tested；
Stability test: being desorbed repeatedly and adsorb, the Li content data that test is the 10th time and the 100th time.
Test result: as shown in Table 1 and Table 2.
Table 1.
| S1 | S2 | S3 | S4 | D1 | |
| Lithium content, % are desorbed for the first time | 2.77 | 2.68 | 2.63 | 2.07 | 1.87 |
| After absorption in brine lithium content, ppm | 26.78 | 28.69 | 29.86 | 86.72 | 165.57 |
| Adsorbance for the first time, mg/g | 10.64 | 10.23 | 9.86 | 7.68 | 4.45 |
| Desorption rate in unit time, %/h | 2.32 | 2.26 | 2.21 | 1.94 | 1.25 |
| Adsorbance in unit time (0.5h), mg/g/h | 9.33 | 9.30 | 9.25 | 7.25 | 2.36 |
| 10th desorption lithium content, % | 1.98 | 1.98 | 1.96 | 1.81 | 1.68 |
| 10th adsorbance, mg/g | 10.96 | 10.86 | 10.85 | 6.88 | 4.32 |
| 100th desorption lithium content, % | 2.05 | 1.98 | 2.01 | 1.76 | 1.34 |
| 100th adsorbance, mg/g | 10.88 | 10.89 | 10.79 | 6.64 | 3.89 |
Table 2.
| S1 | S5 | S6 | S7 | D2 | |
| Lithium content, % are desorbed for the first time | 2.77 | 2.77 | 3.35 | 2.35 | 1.42 |
| After absorption in brine lithium content, ppm | 26.78 | 22.51 | 12.56 | 58.29 | 186.35 |
| Adsorbance for the first time, mg/g | 10.64 | 11.83 | 14.33 | 8.77 | 3.98 |
| Desorption rate in unit time, %/h | 2.32 | 2.36 | 3.15 | 2.08 | 0.91 |
| Adsorbance in unit time (0.5h), mg/g/h | 9.33 | 9.68 | 10.25 | 8.26 | 2.85 |
| 10th desorption lithium content, % | 1.98 | 2.15 | 3.05 | 1.89 | 1.13 |
| 10th adsorbance, mg/g | 10.96 | 11.74 | 14.68 | 8.87 | 3.68 |
| 100th desorption lithium content, % | 2.05 | 2.07 | 2.98 | 1.88 | 0.96 |
| 100th adsorbance, mg/g | 10.88 | 11.98 | 14.72 | 8.81 | 3.36 |
Be desorbed for the first time in Tables 1 and 2 lithium content, the 10th desorption lithium content, the 100th desorption lithium content be relative to
The total amount of lithium adsorbent calculates before being desorbed.
It can be seen from data in Tables 1 and 2 compared with comparative example 1 and prepared lithium adsorbent D1 and D2, according to this
The adsorption effect of lithium adsorbent S1-S7, desorption effect prepared by inventive method, adsorption efficiency, desorption efficiency all have obviously
Progress；And after 10 times and 100 times recyclings, the adsorbance and desorption rate of lithium adsorbent S1-S7 be not obvious
It reduces, it is seen that it also has preferable absorption stability and desorption stability.
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In skill of the invention
In art conception range, can with various simple variants of the technical solution of the present invention are made, including each technical characteristic with it is any its
Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, is belonged to
Protection scope of the present invention.
Claims (14)
1. a kind of lithium adsorbent, which is characterized in that the chemical formula of the lithium adsorbent is LiClAlxMy(OH)3x+ny·mH2O,
Wherein x+y=2,3 < 3x+ny < 10,0 < y≤1,1 < m < 3, element M are transition metal, and n is the chemical valence of element M, 2≤n≤4.
2. lithium adsorbent according to claim 1, wherein 4 < 3x+ny < 8.
3. lithium adsorbent according to claim 1, wherein 0 < y≤0.5, preferably x:y=1:(0.1-0.3).
4. lithium adsorbent according to claim 1, wherein the element M be selected from Sc, Ti, V, Cr, Mn, Fe, Co, Ni,
One or more of Cu and Zn；It is preferred that the element M is selected from one or more of Mn, Fe, Cu and Zn.
5. lithium adsorbent as claimed in any of claims 1 to 4, wherein the specific surface area of the lithium adsorbent is
25-35m2/g。
6. a kind of preparation method of lithium adsorbent, which is characterized in that the preparation method comprises the following steps:
S1、Al(OH)3With M (OH)nIt is added into lithium hydroxide aqueous solution, obtains viscosity through wet grinding, stirring and be greater than 3000cp
Mixed slurry A；Wherein Al (OH)3With M (OH)nMolar ratio be (2-y): y, and 0 < y≤1；Element M is transition metal, and n is
The chemical valence of element M, 2≤n≤4；
S2, under agitation the hydrochloric acid that concentration is 0.5-5mol/L is added into mixed slurry A, until the pH value of mixed slurry
For 2-8, continue stirring until pH value it is constant until, obtain mixed slurry B；
S3, the mixed slurry B is dried, obtains the lithium adsorbent.
7. preparation method according to claim 6, wherein 0 < y≤0.5, preferably Al (OH)3With M (OH)nMolar ratio be
1:(0.1-0.3).
8. preparation method according to claim 6, wherein the element M be selected from Sc, Ti, V, Cr, Mn, Fe, Co, Ni,
One or more of Cu and Zn；It is preferred that the element M is selected from one or more of Mn, Fe, Cu and Zn.
9. preparation method according to claim 6, wherein the concentration of the lithium hydroxide aqueous solution is 1-10mol/L, excellent
It is selected as 2-5mol/L.
10. preparation method according to claim 6, wherein the sand grinding process make the partial size D50 of particulate matter≤
2.0μm。
11. preparation method according to claim 6, wherein stirring obtains the step of mixed slurry A of the viscosity greater than 3000cp
Rapid is selected from any one of such as under type:
Mode one: simple stirring 16-40h is to obtain the mixed slurry A that viscosity is greater than 3000cp；Or
Mode two: it first stirs 15-18h and obtains premixed slurries, then under condition of water bath heating, in preferably 50-80 DEG C of water-bath
The premixed slurries 2-5h is stood or stirred to obtain the mixed slurry A that viscosity is greater than 3000cp；
Mode three: under condition of water bath heating, preferably 50-80 DEG C of stirred in water bath 5-10h is to obtain viscosity greater than 3000cp
Mixed slurry A.
12. preparation method according to claim 6, wherein the viscosity of the mixed slurry A is 3000-6000cp.
13. preparation method according to claim 6, wherein excellent using the method for spray drying in the step of the drying
In the step of being selected in spray drying, outlet temperature is 100-110 DEG C.
14. the lithium adsorbent of the preparation of method described in a kind of any one of claim 6 to 13.
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