CN109317087A - A kind of doped titanic acid lithium adsorbent and preparation method thereof - Google Patents

A kind of doped titanic acid lithium adsorbent and preparation method thereof Download PDF

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CN109317087A
CN109317087A CN201811072111.8A CN201811072111A CN109317087A CN 109317087 A CN109317087 A CN 109317087A CN 201811072111 A CN201811072111 A CN 201811072111A CN 109317087 A CN109317087 A CN 109317087A
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lithium
adsorbent
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salt
titanic acid
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CN109317087B (en
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钟辉
赖先熔
南近山
王诗诗
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Sichuan Panyu Lithium Energy New Material Technology Co., Ltd.
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Chengdu Univeristy of Technology
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • 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
    • B01J20/0251—Compounds of Si, Ge, Sn, Pb
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
    • B01J20/041—Oxides or hydroxides
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    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/002—Compounds containing, besides titanium, two or more other elements, with the exception of oxygen or hydrogen
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
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Abstract

The present invention relates to the adsorbent materials of the separation and Extraction lithium from brine, and in particular to a kind of doped titanic acid lithium adsorbent and preparation method thereof.Doped titanic acid lithium adsorbent HxLi4-xMyTi5-yO12 is to be incorporated into the lattice of Li4Ti5O12 to form presoma Li4MyTi5-yO3 by M, take off what lithium obtained through pickling again, wherein M is one or more of mixing of Ce, Sn, Nb, Zr, Mo, Ta, W, Mn, Hf, x value range 0.0 ~ 4.0, y value range 0.0 ~ 2.0.It is dry by the way that titanium source, lithium source and M salt to be uniformly mixed, it calcines, cooling, pickling obtains doped titanic acid lithium adsorbent.Brine of the doped titanic acid lithium adsorbent prepared in the process of the present invention to Mg/Li ratio greater than 100 carries out absorption and mentions lithium, and lithium adsorption rate is greater than 75%, and magnesium removal efficiency is greater than 99%；It is high to desorb liquid acidity, about 1 ~ 7 times of lithium enrichment times, the molten loss rate of titanium is low, has prospects for commercial application.

Description

A kind of doped titanic acid lithium adsorbent and preparation method thereof
Technical field
The present invention relates to the adsorbent materials of the separation and Extraction lithium from brine, and in particular to a kind of doped titanic acid lithium adsorbent and Preparation method.
Background technique
As lithium battery is widely applied in fields such as automobile, wind-powered electricity generation, IT, critical materials --- lithium and its compound are needed The amount of asking increases severely.International market leads to lithium to the demand of lithium product with every year on average 10% or more speed sustainable growth at present Product market price rises suddenly and sharply at double.Contain in salt lake have the whole world 60% or more lithium resource, from extracting lithium from salt lake brine at For the main path for producing lithium salts both at home and abroad.China's salt lake bittern is resourceful, occupies in the explored lithium resource reserves in the world Second, wherein liquid mine lithium resource accounts for 80% or so of China's lithium resource.But there is height in most of salt lake bittern in China The characteristics of magnesium low lithium, Mg/Li ratio are greater than 30 (mass ratioes), and a small amount of lithium ion coexists with a large amount of magnesium ions, and magnesium ion and lithium ion Property it is similar, this makes to propose the technical problem that lithium becomes generally acknowledged from salt lake brine with high magnesium-lithium ratio, seriously constrains China's lithium money The development and utilization in source.
Salt lake, which proposes lithium technique mainly, the precipitation method, solvent extraction, calcining leaching method, embrane method and absorption method etc..The precipitation method Technology maturation, but be not suitable for brine and low lithium brine of the processing containing a large amount of magnesium ions；Solvent extraction is selectively good, but extractant Volatility is big, is prone to emulsification, frothing, and engineering construction effect is poor；Calcining leaching method can preferably separating magnesium lithium, but energy Consumption is high, and the lithium rate of recovery low (< 40%), economic benefit are bad；Embrane method from salt lake bittern separating magnesium and concentration lithium effect compared with It is good, but film belongs to easily-consumed products, and there are also to be improved at high cost, current technology.For absorption method because of simple process, selectivity is good, lithium recycling Rate is high, pollutes the advantages such as small, is widely studied, is one of the method for most industrial prospect generally acknowledged at present.
Currently, the inorganic adsorbing material of absorption method research mainly has manganese oxidate for lithium (LiMn2O4、Li1.33Mn1.67O4、 Li1.6Mn1.6O4、Li4Mn5O12) and titanium oxidate for lithium (Li2TiO3、Li4Ti5O12) etc..Manganese oxidate for lithium has adsorption capacity big, The advantages that adsorption efficiency is high, but such adsorbent material acid-proof alkaline is poor, is not suitable for alkaline brine or lithium carbonate sinker Mother liquor mentions lithium.The acidproof alkali ability of titanium oxidate for lithium adsorbent is good, but lithium ion is slow in the migration velocity of absorbent interior, absorption effect Rate is low.Patent CN102049238A is in Li4Ti5O12Middle other metals of doping, such as V, Fe, Co, Mn, Al improve adsorbent pair The adsorption capacity of lithium ion；During absorption mentions lithium, by oxidant applying or by external circuit voltage come regulation system potential Make Li+Insertion or abjection adsorbent, avoid the molten damage of adsorbent caused by acid-base condition.The method is the problem is that oxidant applying Higher cost, and by external circuit regulating system potential complex process.Patent CN108212074A mixes magnetism in metatitanic acid lithium Element (iron, cobalt, nickel) replaces the position of partial-titanium, then into pickling take off lithium obtain it is a kind of can Magnetic Isolation titanium system adsorbent, should Adsorbent can be come out after adsorbing lithium by the effect quick separating of externally-applied magnetic field, but big, performance declines in the presence of loss rate molten when desorbing Subtract the problems such as fast, adsorption time is long.
Summary of the invention
In view of the deficienciess of the prior art, the present invention provides a kind of doped titanic acid lithium adsorbent, the doped lithium titanate Adsorbent HxLi4-xMyTi5-yO12It is that Li is incorporated by M4Ti5O12Lattice in formed presoma Li4MyTi5-yO3, then it is de- through pickling What lithium obtained, wherein M is one or more of mixing of Ce, Sn, Nb, Zr, Mo, Ta, W, Mn, Hf, x value range 0.0~ 4.0, y value ranges 0.0~2.0.
Heretofore described M element replaces Li4Ti5O12The position of middle titanium elements be it is random, do not have specific position It limits.
The present invention also provides a kind of preparation methods of doped titanic acid lithium adsorbent, including following key step: will Titanium source, lithium source and M salt are uniformly mixed, dry, and cake of press is calcined, cooling, pickling.
The titanium source is titanium dioxide (rutile-type or anatase titanium dioxide) or metatitanic acid；Lithium source be lithium acetate, lithium hydroxide or Lithium carbonate, M salt are the soluble-salt or insolubility salt of several metals of one of Ce, Sn, Nb, Zr, Mo, Ta, W, Mn, Hf, Preferably soluble-salt mixes these types of raw material such as carbonate, acetate or nitrate.
The additional amount of the mixed process, lithium source and titanium source is added by the molar ratio of Li:Ti=4.0~4.2:5.0, M salt It measures by chemical reaction than addition, the value range of y is 0.0~2.0, and when M is Determination of multiple metal elements, y is every kind of metal member The sum of plain atomicity；The doped lithium titanate sorbent precursor body forms Hydrogen lithium titanate sorbent molecule formula after pickling takes off lithium For HxLi4-xMyTi5-yO12, wherein the value range of y is 0.0~4.0；By solid titanium source, lithium source and M salt and water or acetum Mixing, solid-to-liquid ratio are 1:0.5~7 (mass ratio), 0.5~10h are stirred at 10~95 DEG C, then the material is dried.
The drying process is carried out by least one of spray drying, vacuum drying and forced air drying, dry temperature 80~300 DEG C of degree, drying time 1~for 24 hours, which is calcined.
The calcination process is that dry feedstock is calcined to 10~70h at 450~850 DEG C, preferably 12~50h to get Doped lithium titanate sorbent precursor body is carrying out pickling.
The acid cleaning process be by the HCl of doped lithium titanate sorbent precursor body 0.1mol/L~3.0mol/L or H2SO4, impregnate, 0.5~12h of stirring, remodel to obtain Hydrogen doped titanic acid lithium adsorbent HxLi4-xMyTi5-yO12。
The Hydrogen doped titanic acid lithium adsorbent may be directly applied to salt lake original brine or the brine after being concentrated by evaporation, The principle is as follows:
Load absorption Li+Process: H-SO (Hydrogen)+Li+→ Li-SO (lithium type)+H+
Elution displacement Li+Process: Li-SO (lithium type)+H+→ H-SO (Hydrogen)+Li+
The application method of the Hydrogen doped titanic acid lithium adsorbent is as follows: at the beginning of adjusting salt lake bittern or lithium-containing solution with caustic soda Beginning pH value > 6.5, by the Hydrogen adsorbent be added brine in, stir a period of time after be separated by filtration, obtain absorption mother liquor and Load the adsorbent of lithium；The adsorbent of the load lithium is placed in acid solution and desorbs lithium, is separated by filtration after stirring a period of time, filtrate As rich lithium solution, filter cake is the Hydrogen adsorbent that conversion is restored, reusable.
The present invention has the advantages that
(1) H proposed by the present inventionxLi4-xMyTi5-yO12, the doped metal ion M in lithium titanate improves adsorbent Microcellular structure improves lithium adsorption capacity and selectivity, and when the brine to Mg/Li ratio greater than 100 mentions lithium, lithium adsorption rate is greater than 75%, magnesium removal efficiency is greater than 99%；
(2) doped titanic acid lithium adsorbent proposed by the present invention is good to the adaptability of acid or alkali environment, is not only suitable for sulfate type Salt lake bittern is also applied for the high carbonate type salt lake brine or lithium carbonate sinker mother liquor of alkalinity and mentions lithium, and manganese systems lithium adsorbent Do not have this feature；
(3) doped titanic acid lithium adsorbent proposed by the present invention desorption liquid acidity obtained in desorption lithium process is high, and lithium is rich About 1~7 times of multiple of collection, the molten loss rate of titanium is low, great prospects for commercial application.
Specific implementation method
In order to which the present invention is explained in greater detail, enumerates following instance and be illustrated, but the present invention is not limited to these examples.
Embodiment 1
LiOH·H2O、SnC2O4And H2TiO34.05:0.09:4.91 is mixed in molar ratio, by 55.0g LiOHH2O (point Analyse pure), 6.1g SnC2O4(chemistry is pure) and 156.3g H2TiO3(chemistry is pure) is added in 435g deionized water by solid-to-liquid ratio 1:2 In 60 DEG C of stirring in water bath 3h；Obtained slurry forced air drying 5h at 110 DEG C, it is finely ground, 15h is calcined at 750 DEG C, it is cooling, it grinds Carefully, Li is obtained4Sn0.02Ti4.91O12Sorbent precursor body.Take the 100g Li4Sn0.09Ti4.91O12Being placed in concentration is 1.0mol/L's 4h is impregnated in HCl 3.0L stirring, and Hydrogen lithium ion adsorbent is obtained after filtering.Then the brine formed as shown in table 1 is taken 1000mL, adjusting pH with the NaOH solution of 0.1mol/L is 8.0, the Hydrogen lithium ion adsorbent 42g (dry weight) is added, under stirring 60min is impregnated, filtering obtains absorption mother liquor L1, measure its Li+、Mg2+Content obtains filter cake S1As load has Li+Absorption Agent；In S1The middle hydrochloric acid 100mL that 1.0mol/L concentration is added, stirs lower immersion 50min, and filtering obtains stripping liquid L2, measure it Li+、Mg2+Content, obtain filter cake S2As Hydrogen adsorbent, the Hydrogen adsorbent can be recycled.Measurement result is shown in Table 4, Table 5.
The former brine composition that 1 embodiment 1 of table uses
Component Na+ K+ Mg2+ Ca2+ Li+ B2O3 SO4 2- Cl- Mg/Li ratio
Content (g/L) 67.14 9.32 19.21 5.47 0.18 0.71 7.08 191.38 106.7
Embodiment 2
C2H3O2Li、Zr(NO3)4·5H2O and rutile TiO2It is mixed in molar ratio for 4.04:1.2:3.8, by 78.5g C2H3O2Li (analysis is pure), 151.7g Zr (NO3)4·5H2O (analysis is pure) and 89.4g rutile TiO2(analysis is pure) presses solid-liquid It is added in 480g deionized water than 1:1.5, stirs 8h at 25 DEG C；Obtained slurry forced air drying 4h at 120 DEG C, it is finely ground, 16h is calcined at 800 DEG C, it is cooling, it is finely ground, obtain Li4Zr1.2Ti3.8O12Sorbent precursor body.Take 100g should Li4Zr1.2Ti3.8O12It is placed in the HCl 1.8L that concentration is 1.5mol/L and impregnates 5h, Hydrogen lithium ion adsorbent is obtained after filtering, so The brine 1000mL (pH=9.5) formed as shown in table 2 is taken afterwards, the Hydrogen lithium ion adsorbent 70g (dry weight) is added, under stirring 80min is impregnated, filtering obtains absorption mother liquor L3, measure its Li+、Mg2+Content obtains filter cake S3As load has Li+Absorption Agent.In S3The middle hydrochloric acid 200mL that 1.0mol/L concentration is added, stirs lower immersion 60min, and filtering obtains stripping liquid L4, measure it Li+、Mg2+Content, obtain filter cake S4As Hydrogen adsorbent, the Hydrogen adsorbent can be recycled.Measurement result is shown in Table 4, Table 5.
The carbonate type bittern composition that 2 embodiment 2 of table uses
Component Na+ K+ Li+ B4O7 2- SO4 2- Cl- OH- CO3 2-
Content (g/L) 54.16 7.29 0.36 2.93 7.18 67.74 0.80 10.69
Embodiment 3
Li2CO3、Ce(NO3)3·6H2O and anatase titanium dioxide TiO2It is mixed in molar ratio for 2.03:0.05:4.95, by 48.7g Li2CO3(analysis is pure), 7.0g Ce (NO3)3·6H2O (analysis is pure) and 128.3g TiO2(analysis is pure) is added by solid-to-liquid ratio 1:2.5 Enter in 460g deionized water in 50 DEG C of stirring in water bath 4h；Obtained slurry forced air drying 8h at 105 DEG C, it is finely ground, at 700 DEG C 18h is calcined, it is cooling, it is finely ground, obtain Li4Ce0.05Ti4.95O12Sorbent precursor body.Take the 100g Li4Ce0.05Ti4.95O12It is placed in The HCl 1.0L that concentration is 3.0mol/L impregnates 6h, and Hydrogen lithium ion adsorbent is obtained after filtering, then takes composition as shown in table 3 Brine 200mL (pH > 14), be added the Hydrogen lithium ion adsorbent 45g (dry weight), stir it is lower impregnate 70min, filtering obtains Adsorb mother liquor L5, measure its Li+、Mg2+Content obtains filter cake S5As load has Li+Adsorbent.In S5Middle addition 1.0mol/ The hydrochloric acid 160mL of L concentration, stirs lower immersion 80min, and filtering obtains stripping liquid L6, measure its Li+、Mg2+Content, filtered Cake S6As Hydrogen adsorbent, the Hydrogen adsorbent can be recycled.Measurement result is shown in Table 4, table 5.
The lithium carbonate sinker mother liquor composition that 3 embodiment 3 of table uses
Component Li+ Ca2+ Na+ K+ CO3 2- Cl- SO4 2-
Content (g/L) 1.55 0.01 76.56 9.13 20.67 100.86 10.45
The separating magnesium and lithium situation of the adsorption process of 4 embodiment 1-3 of table
Adsorb mother liquor Content of magnesium/g Magnesium removal efficiency/% Lithium content/mg Lithium adsorption rate/%
L1 19.11 99.5 44.8 75.1
L3 - - 62.6 82.6
L5 - - 21.1 93.2
The lithium recovering state of 5 embodiment 1-3 desorption process of table
Stripping liquid Content of magnesium/mg Magnesium desorption efficiency/% Lithium content/mg Lithium desorption efficiency/% Molten loss rate/the % of titanium Lithium enrichment times
L2 99.6 99.6 134.5 99.5 0.004 6.2
L4 - - 296.5 99.7 0.003 3.7
L6 - - 286.6 99.2 0.005 1.0

Claims (7)

1. a kind of doped titanic acid lithium adsorbent, which is characterized in that the doped titanic acid lithium adsorbent HxLi4-xMyTi5-yO12It is by M It is incorporated into Li4Ti5O12Lattice in formed presoma Li4MyTi5-yO3, then through pickling take off what lithium obtained, wherein M be Ce, Sn, One or more of mixing of Nb, Zr, Mo, Ta, W, Mn, Hf, x value range 0.0~4.0, y value range 0.0~2.0.This M element described in invention replaces Li4Ti5O12The position of middle titanium elements be it is random, do not have the restriction of specific position.
2. the preparation method of doped titanic acid lithium adsorbent described in claim 1, which is characterized in that mix titanium source, lithium source and M salt Uniformly, dry, cake of press is calcined, and cooling, pickling synthesizes doped lithium titanate adsorbent material HxLi4-xMyTi5-yO12。
3. method according to claim 2, titanium source is titanium dioxide (rutile-type or anatase titanium dioxide) or metatitanic acid；Lithium source is vinegar Sour lithium, lithium hydroxide or lithium carbonate, M salt are the solubility of several metals of one of Ce, Sn, Nb, Zr, Mo, Ta, W, Mn, Hf Salt or insolubility salt, preferably soluble-salt mix these types of raw material such as carbonate, acetate or nitrate.
4. method according to claim 2, lithium source and titanium source additional amount are added by the molar ratio of Li:Ti=4.0~4.2:5.0 Enter, for M salt by chemical reaction metering than addition, the value range of y is 0.0~2.0, and when M is Determination of multiple metal elements, y is every kind The sum of metallic element atomicity；The doped lithium titanate sorbent precursor body forms Hydrogen metatitanic acid lithium adsorbent after pickling takes off lithium HxLi4-xMyTi5-yO12, wherein the value range of x is 0.0~4.0；Solid titanium source, lithium source and M salt and water or acetum are mixed It closes, solid-to-liquid ratio is 1:0.3-7 (mass ratio), is dried in 10~95 DEG C of 0.5~10h of stirring, then by the material.
5. method according to claim 2, drying process be by spray drying, vacuum drying and forced air drying at least A kind of progress, 80 DEG C~300 DEG C of drying temperature, drying time 1h~for 24 hours.
6. method according to claim 2, calcination process be above-mentioned dry feedstock calcined to 10 at 450~850 DEG C~ 70h, preferably 12~50h are to get doped lithium titanate sorbent precursor body.
7. method according to claim 2, acid cleaning process be by doped lithium titanate sorbent precursor body 0.1mol/L~ The HCl or H of 3.0mol/L2SO4, impregnate, 0.5~12h of stirring, remodel to obtain Hydrogen doped titanic acid lithium adsorbent HxLi4- xMyTi5-yO12。
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