CN109200987B - Lithium adsorbent and preparation method thereof - Google Patents

Lithium adsorbent and preparation method thereof Download PDF

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CN109200987B
CN109200987B CN201710523111.4A CN201710523111A CN109200987B CN 109200987 B CN109200987 B CN 109200987B CN 201710523111 A CN201710523111 A CN 201710523111A CN 109200987 B CN109200987 B CN 109200987B
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lithium
lithium adsorbent
adsorbent
stirring
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CN109200987A (en
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李绍双
万文治
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BYD Co Ltd
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    • B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28016—Particle form
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
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Abstract

The invention discloses a lithium adsorbent and a preparation method thereof. The chemical formula of the lithium adsorbent is LiCl. AlxMy(OH)3x+ny·mH2O, wherein x + y is 2, 3<3x+ny<10，0<y≤1，1<m<3, the element M is transition metal, n is the valence of the element M, and n is more than or equal to 2 and less than or equal to 4. The lithium adsorbent of the invention forms a relatively complex crystal phase by introducing the transition metal M element into the lattice structure of the aluminum hydroxide, and compared with the common lithium-aluminum compound, the lithium adsorbent with the special crystal phase has a relatively stable structure and has obviously improved adsorption capacity, desorption capacity, adsorption efficiency, desorption efficiency, adsorption stability and desorption stability.

Description

Lithium adsorbent and preparation method thereof
Technical Field
The invention relates to the field of preparation of lithium adsorbents, and particularly relates to a lithium adsorbent and a preparation method thereof.
Background
With the wide application of metallic lithium and compounds thereof in various fields such as materials, new energy and the like, the demand of the metallic lithium and the compounds thereof is more and more large, and the traditional lithium extraction from lithium ore cannot meet the market demand. China is a country with abundant lithium resources in salt lake brine, so how to develop the lithium resources in salt lake brine becomes more and more important. The (aluminum salt) lithium adsorbent has high lithium ion selectivity, large adsorption capacity and environmental friendliness, and the adsorption method is considered to be the most promising method for extracting lithium from salt lake brine at present. The existing lithium (aluminium) salt adsorbents have the chemical formula LiCl 2Al (OH)3·mH2O(1<m<3) It has the following two preparation methods.
The first production method of the (aluminum salt) lithium adsorbent described above includes: mixing aluminum hydroxide and lithium hydroxide solution, heating in water bath for a period of time, dripping hydrochloric acid with certain concentration, adjusting pH value to 2-8, centrifuging, drying the solid at a certain temperature, grinding, and gas-crushing to obtain the lithium-aluminum composite. In the method, lithium chloride is inserted into crystal lattices of aluminum hydroxide to form a new phase, wherein the insertion and extraction of the lithium chloride are reversible, and in order to maintain the stable structure of the new phase of the lithium-aluminum composite, the extraction amount of the lithium chloride can only reach 50 percent of a theoretical value at most, and the adsorption amount is limited, so the adsorption amount is poor; after multiple adsorption and desorption, the other 50% lithium chloride maintaining the stable structure is desorbed along with desorption, so that the lithium aluminum composite structure collapses, an aluminum hydroxide phase is formed, and the adsorption amount is lost, so that the adsorption cycle performance is poor.
The second production method of the above (aluminum salt) lithium adsorbent comprises: mixing aluminum hydroxide powder and lithium chloride powder according to a certain metering ratio, putting the mixture into a ball mill, adding a certain amount of zirconium beads, carrying out dry grinding on the mixed material, taking out the material after a period of time, and grinding and crushing the material to obtain the lithium-aluminum composite. According to the method, impact of zirconium beads is utilized to provide energy in the ball milling process, lithium chloride is inserted into lithium hydroxide crystal lattices along with provided instant energy to form a new phase lithium-aluminum composite, the energy provided by the impact is often uneven, the impact energy cannot be guaranteed at each point within a certain time, and a final finished product contains a small amount of unconverted phase without adsorption capacity, namely aluminum hydroxide, so that the adsorption and desorption capacity of the material is influenced; in addition, the lithium-aluminum composite prepared by the method maintains the particle size and the morphology of the raw material aluminum hydroxide, and has the advantages of small specific surface, low adsorption speed and low efficiency.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provides a lithium adsorbent and a preparation method thereof, so as to improve the adsorption quantity and the adsorption efficiency of the conventional lithium adsorbent.
In order to achieve the above object, one aspect of the present invention provides a lithium adsorbent having a chemical formula of LiCl · AlxMy(OH)3x+ny·mH2O, wherein x + y is 2, 3<3x+ny<10，0<y≤1，1<m<3, the element M is transition metal, n is the valence of the element M, and n is more than or equal to 2 and less than or equal to 4.
In a second aspect, the present invention provides a method for preparing a lithium adsorbent, comprising the steps of: s1, Al (OH)3And M (OH)nAdding into lithium hydroxide aqueous solution, grinding by wet method, stirringStirring to obtain mixed slurry A with viscosity of more than 3000cp, wherein Al (OH)3And M (OH)nIn a molar ratio of (2-y): y, and 0<y is less than or equal to 1; the element M is transition metal, n is the valence of the element M, and n is more than or equal to 2 and less than or equal to 4; s2, adding hydrochloric acid with the concentration of 0.5-5mol/L into the mixed slurry A under the stirring condition until the pH value of the mixed slurry is 2-8, and continuously stirring until the pH value is constant to obtain mixed slurry B; s3, drying the mixed slurry B to obtain the lithium adsorbent.
In a third aspect, the present invention provides a lithium adsorbent prepared according to the above-described method of the present invention.
According to the lithium adsorbent and the preparation method thereof, the transition metal M element is introduced into the lattice structure of the aluminum hydroxide to form a relatively complex crystal phase, compared with a common lithium-aluminum compound, the special crystal phase lithium adsorbent has a relatively stable structure, and has the advantages of obviously improved adsorption capacity, desorption capacity, adsorption efficiency, desorption efficiency, adsorption stability and desorption stability.
Drawings
Fig. 1 is a scanning electron micrograph at 1 μm of a lithium adsorbent prepared according to example 1 of the present invention;
fig. 2 is a scanning electron micrograph at 5 μm of the lithium adsorbent prepared according to example 1 of the present invention.
Fig. 3 is a scanning electron micrograph of a lithium adsorbent prepared according to comparative example 1 of the prior art at 500 nm;
fig. 4 is a scanning mirror diagram of a lithium adsorbent prepared according to comparative example 1 of the prior art at 5 μm.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, one or more new ranges of values may be obtained from combinations of values between the endpoints of each range, the endpoints of each range and the individual values, and the individual values of the points, and these ranges of values should be considered as specifically disclosed herein.
In order to improve the adsorption amount and the adsorption efficiency of the (aluminum salt) lithium adsorbent, the invention provides the lithium adsorbent, and the chemical formula of the lithium adsorbent is LiCl & AlxMy(OH)3x+ny·mH2O, wherein x + y is 2, 3<3x+ny<10，0<y≤1，1<m<3, the element M is transition metal, n is the valence of the element M, and n is more than or equal to 2 and less than or equal to 4.
The lithium adsorbent according to the present invention, preferably, 4<3x + ny < 8.
The lithium adsorbent according to the present invention is preferably 0< y.ltoreq.0.5, preferably x: y is 1: (0.1-0.3).
According to the lithium adsorbent of the present invention, preferably, the element M is one or more selected from Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu and Zn; more preferably, the element M is one or more selected from Mn, Fe, Cu and Zn.
The lithium adsorbent according to the present invention preferably has a specific surface area of 25 to 35m2/g。
Meanwhile, the present invention provides a method for preparing a lithium adsorbent, comprising the steps of: s1, Al (OH)3And M (OH)nAdding into lithium hydroxide aqueous solution, wet grinding (such as sand grinding), and stirring to obtain mixed slurry A with viscosity of more than 3000cp, wherein Al (OH)3And M (OH)nIn a molar ratio of (2-y): y, and 0<y is less than or equal to 1; the element M is transition metal, n is the valence of the element M, and n is more than or equal to 2 and less than or equal to 4; s2, adding (dropwise) hydrochloric acid with the concentration of 0.5-5mol/L (preferably 1-2mol/L) into the mixed slurry A under the stirring condition until the pH value of the mixed slurry is 2-8 (preferably 4-6), and continuously stirring until the pH value is constant to obtain mixed slurry B; s3, drying the mixed slurry B to obtain the lithium adsorbent.
According to the above production method of the present invention, preferably, the Al (OH)3And M (OH)nIn a molar ratio of (2-y): y, wherein 0<y.ltoreq.1, preferably 0<y is 0.5, more preferably Al (OH)3And M (OH)nIn a molar ratio of 1: (0.1-0.3).
According to the above preparation method of the present invention, preferably, the element M is one or more selected from Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn and Ga; preferably, the element M is one or more selected from Mn, Fe, Cu and Zn.
According to the above production method of the present invention, the concentration of the lithium hydroxide aqueous solution is preferably 1 to 10mol/L, preferably 2 to 5 mol/L.
According to the above production method of the present invention, it is preferable that the particle diameter D50 of the particulate matter is 2.0 μm or less during the sand grinding. Wherein the particle diameter D50 is a volume weighted average particle diameter measured by a Malvern laser particle sizer using diffraction phenomenon of particles to light.
According to the above production method of the present invention, preferably, the step of stirring to obtain the mixed slurry a having a viscosity of more than 3000cp is selected from any one of the following modes:
the first method is as follows: the mixed slurry A with the viscosity of more than 3000cp is obtained by simply stirring for 16-40h, and the method is relatively long in time, but is beneficial to improving the stability of the prepared lithium adsorbent;
the second method comprises the following steps: firstly stirring for 15-18h to obtain premixed slurry, and then standing or stirring the premixed slurry in a water bath with the water bath heating condition of preferably 50-80 ℃ (preferably 60-70 ℃) for 2-5h to obtain mixed slurry A with the viscosity of more than 3000 cp; the method can improve the production efficiency and relatively maintain the stability of the prepared lithium adsorbent;
the third method comprises the following steps: stirring in a water bath with heating conditions of the water bath, preferably 50-80 ℃ (preferably 60-70 ℃) for 5-10h to obtain mixed slurry A with the viscosity of more than 3000 cp; this method may relatively decrease the stability of the prepared lithium adsorbent, but may greatly improve the production efficiency.
According to the above preparation method of the present invention, it is preferable that the viscosity of the mixed slurry A is 3000-6000 cp.
The above preparation method according to the present invention, wherein the step of drying is performed by spray drying, preferably by conventional spray drying process of particulate matter, and preferably, the outlet temperature in the step of spray drying is 100-110 ℃.
Meanwhile, the invention also provides a lithium adsorbent prepared according to the method. The lithium adsorbent has a chemical formula of LiCl. AlxMy(OH)3x+ny·mH2O, wherein x + y is 2, 3<3x+ny<10，0<y≤1，1<m<3, the element M is transition metal, n is the valence of the element M, and n is more than or equal to 2 and less than or equal to 4. The lithium adsorbent obtained by the preparation method of the present invention has the same characteristics as the lithium adsorbent described in the foregoing description of the present invention, and the detailed description is referred to the foregoing description.
The beneficial effects of the lithium adsorbent and the preparation method thereof according to the present invention will be further described with reference to the following specific examples.
The raw materials used in the following examples and comparative examples are as follows:
LiOH·H2o: commercially available from Sichuan Xing Cheng Li industries, with a purity of 99.5%.
Aluminum hydroxide: commercially available from Zhongzhou aluminum, Inc. at 99.5% purity.
Iron hydroxide: commercially available from Guangzhou Guanghua Chemicals, Inc. at 99.5% purity.
Copper hydroxide: commercially available from Guangzhou Guanghua Chemicals, Inc. at 99.5% purity.
Zinc hydroxide: commercially available from Guangzhou Guanghua Chemicals, Inc. at 99.5% purity.
Manganese hydroxide: commercially available from Guangzhou Guanghua Chemicals, Inc. at 99.5% purity.
Nickel hydroxide: commercially available from Guangzhou Guanghua Chemicals, Inc. at 99.5% purity.
Test items and methods referred to in the following examples and comparative examples:
scanning Electron Microscopy (SEM) testing: a S4800 instrument is adopted, the voltage is 5KV, and pictures are taken at 0.5W, 2W, 5W and 10W times respectively. And adhering the powder sample on a conductive adhesive tape, spraying gold, and drying and storing the sample in a vacuum drying oven before testing.
X-ray diffraction (XRD) test: adopting Shimadzu XRD-7000, X-ray (Cu) with voltage of 40Kv, scanning speed of 2deg/min, sample inclination of 0.05 deg; continuous scanning; the adjustment time was 1.5 s.
And (3) element content testing: the contents of Al, Li and M (Mn, Zn, Cu and Fe) were measured by ICP and the Cl content was measured by ion chromatography.
Measurement of specific surface area: the specific surface area of the powder was measured by a low-temperature nitrogen adsorption method using a bestssted BET specific surface analyzer.
Example 1
For illustrating the lithium adsorbent of the present invention and the preparation method thereof.
59.2g of LiOH. H were weighed2O was dissolved in 0.5L of deionized water to form an aqueous LiOH solution, and 180.3g of Al (OH) was weighed3And 49.4g Fe (OH)3The resulting mixture was added to the prepared aqueous solution of LiOH in this order, stirred thoroughly, and the stirred slurry was continuously sanded with a 0.5L sandmill for 2 hours (particle D50: 1.86 μm), and then poured into a 1L stirring tank and continuously stirred for 16 hours to measure the viscosity as 5230 cp.
And (3) injecting the prepared 3mol/L hydrochloric acid into the slurry at the speed of 0.5ml/S by using a metering pump, monitoring the pH value change of the slurry on line until the pH value of the slurry is kept at 4-5, stopping injecting the hydrochloric acid, continuously stirring for 10min until the pH value is 4.75, drying the slurry by using spray drying, wherein the inlet temperature is 260 ℃, the outlet temperature is 105 ℃, and the dried material is the lithium adsorbent (recorded as S1).
As can be seen from the element content test, the content of Al, Li, Fe, and Cl in the lithium adsorbent was 19.8 wt%, 3.12 wt%, 8.45 wt%, and 15.68 wt%, respectively, based on the total weight of the lithium adsorbent; the XRD test shows that the lithium adsorbent is relative to LiCl. Al1.66Fe0.34(OH)6·1.099H2The diffraction peak was observed at O, and the chemical formula of the lithium adsorbent was LiCl. Al1.66Fe0.34(OH)6·1.099H2O。
The lithium adsorbent is observed by scanning electron microscope, as shown in fig. 1 and 2, and fig. 1 and 2 show the lithium adsorptionAs can be seen from fig. 1 and 2, the lithium adsorbent prepared according to the present invention has a relatively small primary particle size, which is measured to have an average value of 95nm and an average value of 8.3 μm; in view of the fact that the primary particles of the lithium adsorbent prepared according to the present invention have a small particle size and a relatively increased specific surface area, the specific surface area of the foregoing lithium adsorbent was measured to be 28.3m2/g。
Example 2
For illustrating the lithium adsorbent of the present invention and the preparation method thereof.
The preparation method of the lithium adsorbent in example 1 was used except that Fe (OH)3The dosage of the medicine is 29.03 g; the prepared lithium adsorbent is marked as S2. The lithium adsorbent was measured to have a chemical formula of LiCl. Al1.8Fe0.2(OH)6·1.099H2O, the average value of the primary particle size is 87nm, and the secondary particle size is 8.8 mu m; the specific surface area is 27.7m2/g。
Example 3
For illustrating the lithium adsorbent of the present invention and the preparation method thereof.
The preparation method of the lithium adsorbent in example 1 was used except that Fe (OH)3The dosage of the medicine is 72.65 g; the prepared lithium adsorbent is marked as S3. The lithium adsorbent was measured to have a chemical formula of LiCl. Al1.5Fe0.5(OH)6·1.099H2O, the average value of the primary particle size is 106nm, and the secondary particle size is 9.4 mu m; the specific surface area is 26.4m2/g。
Example 4
For illustrating the lithium adsorbent of the present invention and the preparation method thereof.
The preparation method of the lithium adsorbent in example 1 was used except that Fe (OH)3In an amount of 116.52 g; the prepared lithium adsorbent is marked as S4. The lithium adsorbent was measured to have a chemical formula of LiCl. Al1.2Fe0.8(OH)6·1.099H2O, the average value of the primary particle size is 138nm, and the secondary particle size is 11.5 mu m; the specific surface area is 20.6m2/g。
Example 5
For illustrating the lithium adsorbent of the present invention and the preparation method thereof.
63.74g of LiOH. H were weighed2O was dissolved in 0.5L of deionized water to form an aqueous LiOH solution, and 196.5g of Al (OH) was weighed3And 25.6g Cu (OH)2Sequentially adding the mixture into the prepared LiOH aqueous solution, fully stirring, continuously sanding the stirred slurry for 2.5 hours by using a 0.5L sand mill (the particle D50 is 1.58 mu m), pouring the mixture into a 1L stirring barrel, continuously stirring for 18 hours to test the viscosity to be 2856cp, and carrying out water bath on the slurry at 70 ℃ for 1.5 hours to test the viscosity to be 5584 cp.
And (3) pumping the prepared 2mol/L hydrochloric acid into the slurry after the water bath at the speed of 0.5ml/S by using a metering pump, monitoring the pH value change of the slurry on line until the pH value of the slurry is kept at 4-5, stopping pumping the hydrochloric acid, continuously stirring for 10min until the pH value is 4.25, drying the slurry by using spray drying, wherein the inlet temperature is 280 ℃, the outlet temperature is 100 ℃, and the dried material is the lithium adsorbent (recorded as S5).
As can be seen from the element content test (ICP test for Al, Li, element M content, particle chromatography test for Cl content), the content of Al was 19.9 wt%, the content of Li was 3.08 wt%, the content of Cu was 8.83 wt%, and the content of Cl was 15.57 wt%, based on the total weight of the lithium adsorbent; the XRD test shows that the lithium adsorbent is relative to LiCl. Al1.68Cu0.31(OH)5.66·mH2O (1<m<3) The diffraction peak was observed, and it was found that the chemical formula of the lithium adsorbent was LiCl. Al1.68Cu0.31(OH)5.66·mH2O(1<m<3). The lithium adsorbent was measured to have an average primary particle diameter of 75nm, an average secondary particle diameter of 9.6 μm, and a specific surface area of 33.5m2/g。
Example 6
80.0g of LiOH. H was weighed2O was dissolved in 1L of deionized water to form an aqueous LiOH solution, and 205.0g of Al (OH) was weighed3、36.2gMn(OH)3And 49.4g Zn (OH)2Sequentially adding into prepared LiOH aqueous solution, stirring thoroughly, continuously sanding the stirred slurry with 1L sand mill for 3 hr (particle D50 is 1.35 μm), pouring into 1L stirring tankStirring was continued for 18h and the viscosity was tested to be 4996 cp.
And (3) injecting the prepared 3mol/L hydrochloric acid into the slurry at a certain speed of 1ml/S by using a metering pump, monitoring the pH value change of the slurry on line until the pH value of the slurry is kept at 4-5, stopping injecting the hydrochloric acid, continuously stirring for 10min until the pH value is 4.06, drying the slurry by using spray drying, wherein the inlet temperature is 300 ℃, the outlet temperature is 110 ℃, and the dried material is the lithium adsorbent (recorded as S6).
As can be seen from the element content test, the content of Al, Li, Mn, Zn and Cl in the lithium adsorbent was 15.6 wt%, 2.94 wt%, 5.56 wt%, 10.39 wt% and 15.57 wt%, respectively, based on the total weight of the lithium adsorbent; the XRD test shows that the lithium adsorbent is relatively LiCl. Al1.38Mn0.24Zn0.38(OH)5.62·mH2O(1<m<3) The diffraction peak was observed, and the chemical formula of the lithium adsorbent was LiCl. Al1.38Mn0.24Zn0.38(OH)5.62·mH2O(1<m<3). The average value of the primary particle diameter of the lithium adsorbent was measured to be 78nm, the average value of the secondary particle diameter was measured to be 8.8 μm, and the specific surface area was measured to be 31.2m2/g。
Example 7
For illustrating the lithium adsorbent of the present invention and the preparation method thereof.
63.74g of LiOH. H were weighed2O was dissolved in 0.5L of deionized water to form an aqueous LiOH solution, and 196.5g of Al (OH) was weighed3And 35.99g of NiOH are sequentially added into the prepared LiOH aqueous solution, the mixture is fully stirred, the stirred slurry is continuously sanded for 2.5 hours (the particle D50 is 1.65 mu m) by a 0.5L sand mill, then the mixture is poured into a 1L stirring barrel to be continuously stirred for 18 hours, the test viscosity is 2865cp, and the slurry is bathed in a 70 ℃ water bath for 1.5 hours, and the test slurry viscosity is 4433 cp.
And (3) pumping the prepared 2mol/L hydrochloric acid into the slurry after the water bath at the speed of 0.5ml/S by using a metering pump, monitoring the pH value change of the slurry on line until the pH value of the slurry is kept at 4-5, stopping pumping the hydrochloric acid, continuously stirring for 10min until the pH value is 4.25, drying the slurry by using spray drying, wherein the inlet temperature is 280 ℃, the outlet temperature is 100 ℃, and the dried material is the lithium adsorbent (recorded as S7).
It can be seen from the element content test that, based on the total weight of the lithium adsorbent, the content of Al is 22.98 wt%, the content of Li is 2.90 wt%, the content of Ni is 9.42 wt%, and the content of Cl is 17.98 wt%; the XRD test shows that the lithium adsorbent is relative to LiCl. Al1.68Ni0.32(OH)5.36·mH2O(1<m<3) The diffraction peak was observed, and it was found that the chemical formula of the lithium adsorbent was LiCl. Al1.68Ni0.32(OH)5.36·mH2O(1<m<3). The average primary particle diameter of the lithium adsorbent was measured to be 75nm, the average secondary particle diameter was measured to be 9.6 μm, and the specific surface area was measured to be 30.3m2/g。
Comparative example 1
74.0g of LiOH. H was weighed2O was dissolved in 0.5L of deionized water to form an aqueous LiOH solution, and 250.6g of Al (OH) was weighed3Added to the prepared aqueous solution of LiOH, sufficiently stirred, and the stirred slurry was continuously sanded for 3 hours (particle D50 is 1.75 μm) with a 0.5L sander, and then poured into a 1L stirring tank to be continuously stirred for 18 hours, and the viscosity was measured to be 5262 cp.
And (3) injecting the prepared 3mol/L hydrochloric acid into the slurry at the speed of 0.5ml/s by using a metering pump, monitoring the pH value change of the slurry on line until the pH value of the slurry is kept at 4-5, stopping injecting the hydrochloric acid, continuously stirring for 10min until the pH value is 4.75, drying the slurry by using spray drying, wherein the inlet temperature is 260 ℃, the outlet temperature is 105 ℃, and the dried material is the lithium adsorbent (recorded as D1).
As can be seen from the element content test, the content of Al in the lithium adsorbent was 25 wt%, the content of Li was 3.25 wt%, the content of Cl was 16.43 wt%, and H was calculated based on the total weight of the lithium adsorbent2The content of O was 9.15% by weight; the XRD test shows that the lithium adsorbent is relative to LiCl.2Al (OH)3·1.099H2The diffraction peak was observed at O, and the chemical formula of the lithium adsorbent was LiCl.2Al (OH)3·1.099H2O。
The foregoing lithium adsorbents were observed by scanning electron microscopy, as shown in FIGS. 3 and 4, FIGS. 3 and 3Fig. 4 is a scanning electron microscope image of the lithium adsorbent in different sizes, and it can be seen from fig. 3 and 4 that the primary particle size of the lithium adsorbent prepared according to the present invention is relatively large, and the average value of the primary particle size is measured to be 150nm, and the secondary particle size is measured to be 4.8 μm; in view of the fact that the primary particles of the lithium adsorbent prepared according to the present invention have a large particle size and a relatively reduced specific surface area, the specific surface area of the lithium adsorbent was measured to be 23.6m2/g。
Comparative example 2
75.0g of lithium chloride powder and 250.6g of aluminum hydroxide powder are weighed, mixed in a ball mill (zirconium beads), and subjected to dry milling for 4.0h, and the mixture is taken out and crushed to have the particle size of 3.5 microns, so that the lithium adsorbent (recorded as D2) is obtained.
Testing
The lithium aluminum composites prepared in examples 1 to 7 and comparative examples 1 to 2 were subjected to adsorption amount test.
The adsorption quantity test method comprises the following steps:
desorption amount: eluting the adsorbent with deionized water at a liquid-solid ratio of 50 for three times, stirring at a medium speed (20Hz) for 1 hour at room temperature every time, and performing centrifugal separation; collecting the elution solution each time, testing the content of Li element, and drying the separated adsorbent at 80 ℃;
desorption efficiency: eluting the adsorbent once by deionized water with a liquid-solid ratio of 50, stirring at a medium speed (20Hz) at room temperature for 1 hour, and performing centrifugal separation; collecting the elution solution, testing the content of Li element, and drying the separated adsorbent at 80 ℃;
adsorption system energy: performing adsorption experiment with brine (lithium content of 272.86ppm) extracted from salt lake at liquid-solid ratio of 40, stirring at low speed (10Hz) at room temperature for 1 hr, and filtering; collecting filtrate, and testing the content of Li;
adsorption efficiency: performing adsorption experiment with brine (lithium content of 272.86ppm) extracted from salt lake at liquid-solid ratio of 40, stirring at low speed (10Hz) at room temperature for 0.5 hr, and filtering; collecting filtrate and testing the content of Li;
and (3) stability testing: desorption and adsorption were repeated and the Li content data was tested for the 10 th and 100 th runs.
And (3) testing results: as shown in tables 1 and 2.
Table 1.
S1 S2 S3 S4 D1
First desorption of the lithium content% 2.77 2.68 2.63 2.07 1.87
Content of lithium in adsorbed brine, ppm 26.78 28.69 29.86 86.72 165.57
First adsorption amount, mg/g 10.64 10.23 9.86 7.68 4.45
Desorption amount per unit time,%/h 2.32 2.26 2.21 1.94 1.25
Amount of adsorption in unit time (0.5h), mg/g/h 9.33 9.30 9.25 7.25 2.36
Desorption of lithium content at 10 th time% 1.98 1.98 1.96 1.81 1.68
10 th adsorption amount, mg/g 10.96 10.86 10.85 6.88 4.32
Desorption of lithium content at 100 th time% 2.05 1.98 2.01 1.76 1.34
Adsorption quantity at 100 th time, mg/g 10.88 10.89 10.79 6.64 3.89
Table 2.
S1 S5 S6 S7 D2
First desorption of the lithium content% 2.77 2.77 3.35 2.35 1.42
Content of lithium in adsorbed brine, ppm 26.78 22.51 12.56 58.29 186.35
First adsorption amount, mg/g 10.64 11.83 14.33 8.77 3.98
Desorption amount per unit time,%/h 2.32 2.36 3.15 2.08 0.91
Amount of adsorption in unit time (0.5h), mg/g/h 9.33 9.68 10.25 8.26 2.85
Desorption of lithium content at 10 th time% 1.98 2.15 3.05 1.89 1.13
10 th adsorption amount, mg/g 10.96 11.74 14.68 8.87 3.68
Desorption of lithium content at 100 th time% 2.05 2.07 2.98 1.88 0.96
Adsorption quantity at 100 th time, mg/g 10.88 11.98 14.72 8.81 3.36
The first desorption lithium content, the 10 th desorption lithium content, and the 100 th desorption lithium content in tables 1 and 2 were calculated with respect to the total amount of the lithium adsorbent before desorption.
As can be seen from the data in tables 1 and 2, the adsorption effect, desorption effect, adsorption efficiency, and desorption efficiency of the lithium adsorbents S1 to S7 prepared according to the method of the present invention are significantly improved as compared to those of comparative example 1 and the prepared lithium adsorbents D1 and D2; after 10 times and 100 times of circulation use, the adsorption amount and the desorption amount of the lithium adsorbent S1-S7 are not obviously reduced, and the lithium adsorbent also has better adsorption stability and desorption stability.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.

Claims (17)

1. A lithium adsorbent is characterized in that 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, the element M is transition metal, n is the valence of the element M, and n is more than or equal to 2 and less than or equal to 4;
wherein, the element M is one or more selected from Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu and Zn.
2. The lithium sorbent of claim 1, wherein 4<3x + ny < 8.
3. The lithium sorbent of claim 1, wherein 0< y ≦ 0.5.
4. The lithium sorbent of claim 3, wherein x: y = 1: (0.1-0.3).
5. The lithium adsorbent according to claim 1, wherein the element M is one or more selected from Mn, Fe, Cu, and Zn.
6. The lithium adsorbent according to any one of claims 1 to 5, wherein the specific surface area of the lithium adsorbent is 25 to 35m2/g。
7. A preparation method of a lithium adsorbent is characterized by comprising the following steps:
S1、Al(OH)3and M (OH)nAdding the mixture into a lithium hydroxide aqueous solution, and grinding and stirring the mixture by a wet method to obtain mixed slurry A with the viscosity of more than 3000 cp; wherein Al (OH)3And M (OH)nIn a molar ratio of (2-y): y, and 0<y≤1; the element M is transition metal, n is the valence of the element M, and n is more than or equal to 2 and less than or equal to 4;
s2, adding hydrochloric acid with the concentration of 0.5-5mol/L into the mixed slurry A under the stirring condition until the pH value of the mixed slurry is 2-8, and continuously stirring until the pH value is constant to obtain mixed slurry B;
s3, drying the mixed slurry B to obtain the lithium adsorbent;
wherein, the element M is one or more selected from Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu and Zn.
8. The method of claim 7, wherein 0< y ≦ 0.5.
9. The method according to claim 7, wherein Al (OH)3And M (OH)nIn a molar ratio of 1: (0.1-0.3).
10. The production method according to claim 7, wherein the element M is one or more selected from Mn, Fe, Cu and Zn.
11. The production method according to claim 7, wherein the concentration of the aqueous lithium hydroxide solution is 1 to 10 mol/L.
12. The production method according to claim 11, wherein the concentration of the aqueous lithium hydroxide solution is 2 to 5 mol/L.
13. The production method according to claim 7, wherein the particle size D50 ≤ 2.0 μm is obtained during the wet grinding.
14. The production method according to claim 7, wherein the step of obtaining the mixed slurry A having a viscosity of more than 3000cp by stirring is any one selected from the following manners:
the first method is as follows: simply stirring for 16-40h to obtain mixed slurry A with the viscosity of more than 3000 cp; or
The second method comprises the following steps: firstly stirring for 15-18h to obtain premixed slurry, and then standing or stirring the premixed slurry in a water bath at 50-80 ℃ for 2-5h to obtain mixed slurry A with the viscosity of more than 3000 cp;
the third method comprises the following steps: stirring in a water bath at 50-80 ℃ for 5-10h to obtain mixed slurry A with the viscosity of more than 3000 cp.
15. The method according to claim 7, wherein the drying step is a spray drying method.
16. The preparation method as claimed in claim 15, wherein in the step of spray drying, the outlet temperature is 100-110 ℃.
17. A lithium sorbent prepared by the method of any one of claims 7-16.
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