CN108160023A - A kind of compound metantimonic acid lithium ion sieve filler and preparation method thereof - Google Patents
A kind of compound metantimonic acid lithium ion sieve filler and preparation method thereof Download PDFInfo
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- CN108160023A CN108160023A CN201810033248.6A CN201810033248A CN108160023A CN 108160023 A CN108160023 A CN 108160023A CN 201810033248 A CN201810033248 A CN 201810033248A CN 108160023 A CN108160023 A CN 108160023A
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- 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
- B01J20/0259—Compounds of N, P, As, Sb, Bi
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- 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
- B01J20/0248—Compounds of B, Al, Ga, In, Tl
Abstract
It the present invention relates to a kind of compound metantimonic acid lithium ion sieve filler, is particularly adulterated and disperseed with metatitanic acid, the compound metantimonic acid lithium ion sieve filler of foam glass material load, the porosity of filler is 30% 50%, and density is 500 800kg/m3, the chemical composition of compound metantimonic acid lithium ion sieve is：H1+xTixSb1‑xO3, wherein, x=0.1 0.9, compound metantimonic acid quality accounts for 70% the 80% of packing quality, and foam glass quality of materials accounts for 20% the 30% of packing quality, and the adsorption capacity of compound metantimonic acid filler is 20 25mg/g, and the presoma of compound metantimonic acid is Li1+xTixSb1‑xO3, wherein, x=0.1 0.9, compound metantimonic acid lithium is also monoclinic system.Metantimonic acid and metatitanic acid in the compound metantimonic acid lithium ion sieve of the present invention have synergistic effect, increase its adsorption capacity, improve the adsorption desorption speed of lithium ion wherein, while reduce the molten damage of antimony and improve environmental safety.
Description
Technical field
The present invention relates to a kind of compound metantimonic acid lithium ion sieve filler and preparation method thereof, particularly with metatitanic acid doping and
Dispersion, the compound metantimonic acid lithium ion sieve filler of foam glass material load belongs to new forms of energy new material field.
Technical background
World's lithium product Year's consumption far can not meet the remote of lithium with the speed sustainable growth of annual 15%-20% at present
The scape market demand.With lithium-containing materials market price continuous rise, lithium Source Study also carries lithium from traditional lithium ore and is expanded to
In the utilization of the liquid lithium resource such as salt lake bittern, seawater and GEOTHERMAL WATER.Absorption-ion-exchange is simple for process, the rate of recovery
It is high, selective good, it is particularly suitable for carrying lithium from concentration aqueous solution containing lithium, the key of this method is to prepare adsorption capacity greatly and recycle
Adsorbent of good performance.
Lithium ion sieve is by importing template Li into inorganic compound+, lithium ion sieve presoma is treated thermally to produce, so
Ore Leaching Li therein afterwards+It obtains.Lithium ion sieve is due to dimensional effect and sieve effect, to Li+There is ion specific memory to select
Selecting property, can be under polyion Coexistence Situation by Li+Ion comes with other ion isolations, and it is molten to be usually used in the rich lithium such as seawater or brine
Li in liquid+Selective extraction.Lithium ion sieve mainly has manganese systems lithium ion sieve, titanium based lithium-ion sieve and other based lithium-ions sieve
Deng.
Common titanium based lithium-ion sieve presoma mainly has the Li of monoclinic system2TiO3With spinel structure
Li4Ti5O12, compared with manganese systems lithium ion sieve, titanium based lithium-ion sieve adsorbant has low molten loss rate, stable structure and reuse
Property it is good the advantages that, but research and development starting, than later, cost of material is also higher.Adsorption capacity in other based lithium-ion sieves
Larger and higher selectivity mainly includes monoclinic system metaantimmonic acid, metaantimmonic acid tin and metaantimmonic acid titanium salt.Japan Patent JPH0283217
Hexahydroxy metaantimmonic acid lithium LiSb (OH) is initially formed using Antimony pentachloride and lithium hydroxide reaction disclosed in (1990-03-23)6,
Heat treatment forms metantimonic acid lithium LiSbO at 750-1000 DEG C3, then handled at 0-80 DEG C with the inorganic acid of 1-14mol/L, it generates
Monocline metantimonic acid HSbO3, below 500 DEG C be dried after can with high selectivity from alkali metal salt soln adsorbing separation lithium from
Son.Monocline is being prepared using antimony pentoxide and lithium carbonate reaction disclosed in Japan Patent JPH08259234 (1996-10-08)
During metantimonic acid, with potassium partial alternative lithium, the metantimonic acid lithium Li of heat treatment formation doping at 900 DEG C0.95 K0.5SbO3, other alkali
The speed that the doping of metal makes the metantimonic acid lithium adsorbent pickling of generation take off lithium improves 3 times or more.Monocline metantimonic acid lithium ion sieve
The advantages of be lithium ion selectivity it is very high, be particularly suitable for the adsorbing and extracting lithium in seawater or brine complex component, shortcoming is its knot
Brilliant very fine and close, mass transfer aretation, lithium ion adsorption desorption speed is slow, needs to take off lithium in the high-concentration inorganic acid of heat；
Since the molecular weight of metantimonic acid is larger so that lithium ion adsorption capacity is relatively low.
Lithium ion sieve commercial Application needs to be made into the filler of graininess or special shape, tower to carry out filler
Loss when continuous operation and reduction recycling.At present, the filler suitable for the graininess of tower operation or special shape is logical mostly
The crosslinked action of high-molecular organic material is crossed to prepare.Due in filler forming process organic polymer soln possibly into lithium
Ion sieve pore interior causes the blocking in mass transfer duct, makes the adsorption capacity and the rate of adsorption of lithium ion sieve filler after molding
Decline very big.The metatitanic acid hydrosol has good high temperature bond performance, can be securely fixed in metantimonic acid lithium ion sieve
On foam glass material surface, further expand its surface area, be that a kind of adsorption capacity is big, steady so as to accelerate adsorption desorption speed
High-performance lithium ion sieve filler that is qualitative good and having extended cycle life.
Invention content
The object of the present invention is to provide a kind of compound metantimonic acid lithium ion sieve fillers, are particularly adulterated and disperseed with metatitanic acid
, the compound metantimonic acid lithium ion sieve filler of foam glass material load, the porosity of filler is 30%-50%, density 500-
800kg/m3, the chemical composition of compound metantimonic acid lithium ion sieve is：H1+xTixSb1-xO3, wherein, x=0.1-0.9, compound metantimonic acid
Quality accounts for the 70%-80% of packing quality, and foam glass quality of materials accounts for the 20%-30% of packing quality, compound metantimonic acid filler
Adsorption capacity is 20-25mg/g；The presoma of the compound metantimonic acid is Li1+xTixSb1-xO3, wherein, x=0.1-0.9；Institute
The foam glass material stated is that density is less than 500kg/m3Fiberglass products, foam glass product, fly ash float or in
One of empty glass microsphere.
Compound metantimonic acid presoma Li in the present invention1+xTixSb1-xO3It is monocline metantimonic acid lithium LiSbO3With monocline metatitanic acid
Lithium Li2TiO3Compound, preferably x=0.3,0.8, compound metantimonic acid lithium is also monoclinic system.
Amorphous metantimonic acid and metatitanic acid are typical inorganic adsorbent and ion-exchanger in the present invention, but to lithium from
The adsorptive selectivity of son is not high enough.Monocline metantimonic acid lithium and monocline metatitanic acid lithium pickling take off the monocline metantimonic acid and monocline of lithium formation
Metatitanic acid is only excellent lithium ion sieve.
In the present invention the compound metantimonic acid hydrosol also as compound lithium ion sieve presoma adhesive, first by complex lithium from
Son sieve presoma is bonded on foam glass material surface, is further sintered to fix on foam glass material surface.Metantimonic acid
Gel is easily formed with metatitanic acid, it is necessary to could be uniformly mixed under hydrosol state, it is necessary to impregnate lightweight under collosol state
Glass material carrier, so that colloidal sol, which smoothly enters in the micropore of carrier surface, carries out gel.
Metatitanic acid and metantimonic acid are not simple physical mixeds in the present invention, since the doping and dispersion of metatitanic acid make inclined antimony
Acid-sol grain size becomes smaller, it is enable subsequently to react with lithium acetate to form reaction time of metantimonic acid lithium and shorten to from tens hours
Several hours；Since the inducing action of monocline metatitanic acid lithium crystallization makes amorphous state metantimonic acid lithium be converted into the heat of monocline metantimonic acid lithium
Treatment temperature is declined to a great extent from 750-1000 DEG C to 500-600 DEG C, so that the formation of monocline metantimonic acid lithium and on carrier
One step of sintering complete.Using monocline metatitanic acid adulterate and disperse monocline metantimonic acid, expand monocline metantimonic acid surface area and
Mass transfer channel improves the adsorption desorption speed of lithium ion wherein so that the de- lithium technique letter of high-concentration inorganic acid heating originally
It turns to low concentration inorganic acid and takes off lithium at room temperature, and overcome the defects of metantimonic acid lithium ion sieve desorption rate is relatively low.By molecular volume
Larger antimony atoms are doped in metatitanic acid, the defects of also improving metatitanic acid lithium ion be selectively bad in complex system,
So as to generate the synergistic effect of lithium ion absorption, the adsorption capacity of compound metantimonic acid lithium ion sieve is made to be more than the absorption of single variety
Capacity.In addition, antimony is a kind of toxic heavy-metal elements, the compound action of metatitanic acid reduces the molten damage of antimony and improves environment peace
Quan Xing, creative and practicability of the invention.
It is a further object of the present invention to provide a kind of preparation method of compound metantimonic acid lithium ion sieve filler, technical solution packets
Include prepared by the compound metantimonic acid hydrosol, prepared by compound metantimonic acid lithium filler, being sintered of compound metantimonic acid lithium filler, compound metantimonic acid
The pickling of lithium filler takes off the evaluation of lithium and compound metantimonic acid lithium ion sieve, the specific steps are：
（1）The aqueous hydrochloric acid solution of 4mol/L is added in glass reactor, under strong stirring and ice water cooling, into reaction solution
Antimony pentachloride and titanium tetrachloride solution is slowly added dropwise, control rate of addition makes the Sb (OH) of reaction generation early period5With Ti (OH)4It is heavy
Shallow lake can dissolve to form the hydrosol rapidly, and control molar ratio is：Sb：Ti：H2O=1：0.1-10：10-60, after being added dropwise to complete
Continuing stirring 1-2h makes chloride hydrolysis complete；Then the deionized water dilution of 10-15 times of quality of reaction solution is added in, is heated to reflux
Hydrosol 12-24h, distillation detach the hydrogen chloride in solution；24-36h is placed in cooling makes Sb (OH)5With Ti (OH)4Sol particles phase
Mutually polymerization doping and precipitation, detach the dilute hydrochloric acid clear liquid in colloid, and the chlorine of colloid particle absorption is cleaned multiple times using deionized water
Change hydrogen, form compound metantimonic acid hydrosol H1+xTixSb1-xO3, x=0.1-0.9, aerosol particle size 20-50nm；
（2）Under stiring by theory measurement than the lithium acetate aqueous solution of 4mol/L be slowly added to the hydrosol of compound metantimonic acid
In, continue to stir 0.5-1h after adding, generate compound metantimonic acid lithium Li1+xTixSb1-xO3The hydrosol, the hydrosol in placement process
Viscosity constantly increases；The foam glass material cleaned up is impregnated into the hydrosol, makes the Sol-gel Coated of compound metantimonic acid lithium
On foam glass material surface and enter in its surface duct, the control mass ratio that feeds intake is：Foam glass：Compound metantimonic acid lithium
=1：0.25-0.40 stirs foam glass carrier material, makes the colloidal sol of the compound metantimonic acid lithium shape on foam glass carrier material
Into gel, the acetic acid diluted aqueous solution being precipitated in gel is drained, moisture and acetic acid are dried and removed at 100-150 DEG C, is formed compound
Metantimonic acid lithium filler；
（3）Compound metantimonic acid lithium filler is put into high temperature furnace, 8-12h, compound metantimonic acid lithium are heat-treated at 500-600 DEG C
Li1+xTixSb1-xO3It is sintered and is fixed on foam glass carrier, amorphous compound metantimonic acid lithium conversion in heat treatment process
For monoclinic system metantimonic acid lithium；
（4）It is dipped in the inorganic acid aqueous solution of 0.5-1.0mol/L, cycle sprinkling inorganic acid aqueous solution makes compound metantimonic acid
Lithium ion in lithium filler completes desorption in 0.5-1h, then is cleaned with deionized water, obtains the compound metantimonic acid H of monocline1+ xTixSb1-xO3Filler, the inorganic acid are one of hydrochloric acid, nitric acid or sulfuric acid；
（5）Lithium ion sieve filler is seated in adsorption tower, circulated sprinkling contains the simulation brine 4-16h of 200mg/L lithium chlorides,
Lithium ion sieve filler is made to reach saturation absorption, measures its adsorption capacity as 20-25mg/g, adsorption capacity after adsorption desorption recycles 10 times
Also without significant change.
The adsorption capacity of lithium ion sieve filler is using in the front and rear simulation brine of ion-chromatographic determination absorption in the present invention
What lithium concentration was calculated.
Experimental raw Antimony pentachloride, titanium tetrachloride, hydrochloric acid, lithium acetate and lithium chloride used in the present invention are commercially available chemistry
Pure reagent.Foam glass material used be commercially available heat insulating refractory material glass fibre, foam glass, fly ash float or in
Empty glass microsphere.
The beneficial effects of the invention are as follows：
（1）Metantimonic acid and metatitanic acid have synergistic effect in compound metantimonic acid lithium ion sieve, its adsorption capacity is made to be more than single product
The adsorption capacity of kind, while reduce the molten damage of antimony and improve environmental safety；
（2）Compound metantimonic acid lithium ion sieve can improve the adsorption desorption speed of lithium ion wherein, make original high-concentration inorganic acid
The de- lithium process conditions of heating change into low concentration inorganic acid and complete de- lithium at room temperature；
（3）Compound synergistic effect makes the heat treatment temperature of amorphous state metantimonic acid lithium be declined to a great extent from 750-1000 DEG C to 500-600
DEG C so that the formation of monocline metantimonic acid lithium and one step of sintering on foam glass carrier are completed, and enormously simplify preparation process.
Specific embodiment
Embodiment 1
The aqueous hydrochloric acid solution 10mL of 4mol/L is added in glass reactor, under strong stirring and ice water cooling, to reaction solution
In be slowly added dropwise Antimony pentachloride solution 10.6g (0.035mol) and titanium tetrachloride solution 2.9g (0.015mol), speed is added dropwise in control
Degree makes the Sb (OH) of reaction generation early period5With Ti (OH)4Precipitation can dissolve to form the hydrosol rapidly, continue to stir after being added dropwise to complete
Mixing 2h makes chloride hydrolysis complete；Then the dilution of 350mL deionized waters is added in, is heated to reflux hydrosol 12h, distillation separation solution
In hydrogen chloride；Cooling is placed makes Sb (OH) for 24 hours5With Ti (OH)4Sol particles mutually polymerize doping and precipitation, detach in colloid
Dilute hydrochloric acid clear liquid, clean colloidal particle 3 times with 50mL deionized waters, formed containing compound metantimonic acid H1.3Ti0.3Sb0.7O3 7.4g
Colloid.
The lithium acetate aqueous solution 16.5mL of 4mol/L is slowly added in the hydrosol of compound metantimonic acid under stiring, is added
After continue to stir 1h, generation is containing compound metantimonic acid lithium Li1.3Ti0.3Sb0.7O3 The colloid of 7.8g.The glass fibre that will be cleaned up
Material 3.2g is impregnated into the hydrosol, stirs glass fiber material, makes compound metantimonic acid lithium shape on fiberglass carrier material
Into gel, the acetic acid diluted aqueous solution being precipitated in gel is drained, moisture and acetic acid are dried and removed at 100-150 DEG C, is formed compound
Metantimonic acid lithium filler 11.0g.Compound metantimonic acid lithium filler is put into high temperature furnace, 12h is heat-treated at 500-600 DEG C, it is compound
Metantimonic acid lithium is sintered to fix in fiberglass carrier.It is dipped in the inorganic acid aqueous solution of 0.5mol/L, cycle sprinkling nothing
Machine aqueous acid makes the lithium ion in compound metantimonic acid lithium filler complete desorption in 1h, then is cleaned with deionized water, obtains list
Oblique compound metantimonic acid filler.Compound metantimonic acid filler is seated in adsorption tower, circulated sprinkling contains the mould of 200mg/L lithium chlorides
Intend brine 8h, lithium ion sieve filler is made to reach saturation absorption, measure its adsorption capacity as 20mg/g, adsorption desorption is inhaled after recycling 10 times
Attached capacity is 19.7mg/g.
Embodiment 2
The aqueous hydrochloric acid solution 20mL of 4mol/L is added in glass reactor, under strong stirring and ice water cooling, to reaction solution
In be slowly added dropwise Antimony pentachloride solution 6.1g (0.02mol) and titanium tetrachloride solution 15.4g (0.08mol), control rate of addition
Make the Sb (OH) of reaction generation early period5With Ti (OH)4Precipitation can dissolve to form the hydrosol rapidly, continue to stir after being added dropwise to complete
1h makes chloride hydrolysis complete；Then the dilution of 300mL deionized waters is added in, is heated to reflux hydrosol 12h, distillation is detached in solution
Hydrogen chloride；Cooling is placed makes Sb (OH) for 24 hours5With Ti (OH)4Sol particles mutually polymerize doping and precipitation, detach in colloid
Dilute hydrochloric acid clear liquid cleans colloidal particle 3 times with 50mL deionized waters, is formed containing compound metantimonic acid H1.8Ti0.8Sb0.2O3 11.3g's
Colloid.
The lithium acetate aqueous solution 45mL of 4mol/L is slowly added in the hydrosol of compound metantimonic acid under stiring, after adding
Continue to stir 0.5h, generation is containing compound metantimonic acid lithium Li1.8Ti0.8Sb0.2O3 12.3g colloid.The hole-opening foaming that will be cleaned up
Glass material 3.5g is impregnated into the hydrosol, stirs hollow glass microballoon material, makes compound metantimonic acid lithium in hollow glass microballoon
Gel is formed on carrier material, the acetic acid diluted aqueous solution being precipitated in gel is drained, moisture and second is dried and removed at 100-150 DEG C
Acid forms compound metantimonic acid lithium filler 15.8g.Compound metantimonic acid lithium filler is put into high temperature furnace, at 500-600 DEG C at heat
8h is managed, compound metantimonic acid lithium is sintered to fix on hollow glass microballoon carrier.It is dipped in the inorganic acid aqueous solution of 0.5mol/L
In, cycle sprinkling inorganic acid aqueous solution make the lithium ion in compound metantimonic acid lithium filler is completed in 0.5h be desorbed, then spend from
Sub- water cleaning, obtains the compound metantimonic acid filler of monocline.Compound metantimonic acid filler is seated in adsorption tower, circulated sprinkling contains
The simulation brine 8h of 200mg/L lithium chlorides makes lithium ion sieve filler reach saturation absorption, measures its adsorption capacity as 25mg/g,
Adsorption capacity is 24.8mg/g after adsorption desorption recycles 10 times.
Claims (4)
1. a kind of compound metantimonic acid lithium ion sieve filler, it is characterised in that the foam glass material for being adulterated by metatitanic acid and being disperseed is born
The compound metantimonic acid lithium ion sieve composition filler carried, the porosity of filler is 30%-50%, density 500-800kg/m3, it is compound
The chemical composition of metantimonic acid lithium ion sieve is：H1+xTixSb1-xO3, wherein, x=0.1-0.9, compound metantimonic acid quality accounts for filler matter
The 70%-80% of amount, foam glass quality of materials account for the 20%-30% of packing quality, and the adsorption capacity of compound metantimonic acid filler is 20-
25mg/g；The presoma of the compound metantimonic acid is Li1+xTixSb1-xO3, wherein, x=0.1-0.9；The foam glass material
Material is that density is less than 500kg/m3One of fiberglass products, foam glass product, fly ash float or hollow glass microballoon.
2. compound metantimonic acid lithium ion sieve filler according to claim 1, it is characterised in that compound metantimonic acid lithium Li1+ xTixSb1-xO3It is monoclinic system, is monocline metantimonic acid lithium LiSbO3With monocline metatitanic acid lithium Li2TiO3Compound, preferably x=
0.3,0.8.
3. compound metantimonic acid lithium ion sieve filler according to claim 1, it is characterised in that the compound metantimonic acid hydrosol is also
As the adhesive of compound lithium ion sieve presoma, compound lithium ion sieve presoma is first bonded in foam glass material surface
On, it is further sintered to fix on foam glass material surface.
4. a kind of preparation method of compound metantimonic acid lithium ion sieve filler, it is characterised in that technical solution includes compound metantimonic acid water
Prepared by colloidal sol, prepared by compound metantimonic acid lithium filler, being sintered of compound metantimonic acid lithium filler, the pickling of compound metantimonic acid lithium filler takes off
The evaluation of lithium and compound metantimonic acid lithium ion sieve, the specific steps are：
（1）The aqueous hydrochloric acid solution of 4mol/L is added in glass reactor, under strong stirring and ice water cooling, into reaction solution
Antimony pentachloride and titanium tetrachloride solution is slowly added dropwise, control rate of addition makes the Sb (OH) of reaction generation early period5With Ti (OH)4Altogether
Precipitation can dissolve to form the hydrosol rapidly, and control molar ratio is：Sb：Ti：H2O=1：0.1-10：10-60 is added dropwise to complete
After continue to stir 1-2h and make chloride hydrolysis complete；Then the deionized water dilution of 10-15 times of quality of reaction solution is added in, is heated back
Flowing water colloidal sol 12-24h, distillation detach the hydrogen chloride in solution；24-36h is placed in cooling makes Sb (OH)5With Ti (OH)4Sol particles
Mutually polymerization doping and precipitation, detach the dilute hydrochloric acid clear liquid in colloid, and the chlorination of colloid particle absorption is cleaned multiple times in deionized water
Hydrogen forms compound metantimonic acid hydrosol H1+xTixSb1-xO3, x=0.1-0.9, aerosol particle size 20-50nm；
（2）Under stiring by theory measurement than the lithium acetate aqueous solution of 4mol/L be slowly added in the compound metantimonic acid hydrosol,
Continue to stir 0.5-1h after adding, generate compound metantimonic acid lithium Li1+xTixSb1-xO3The hydrosol, the hydrosol is viscous in placement process
Degree constantly increase；The foam glass material cleaned up is impregnated into the hydrosol, makes compound metantimonic acid lithium Sol-gel Coated light
On matter glass material surface and enter in its surface duct, the control mass ratio that feeds intake is：Foam glass：Compound metantimonic acid lithium=1：
0.25-0.40 stirs foam glass carrier material, compound metantimonic acid lithium colloidal sol is made to be formed on foam glass carrier material solidifying
Glue drains the acetic acid diluted aqueous solution being precipitated in gel, and moisture and acetic acid are dried and removed at 100-150 DEG C, forms compound inclined antimony
Sour lithium filler；
（3）Compound metantimonic acid lithium filler is put into high temperature furnace, 8-12h, compound metantimonic acid lithium are heat-treated at 500-600 DEG C
Li1+xTixSb1-xO3It is sintered and is fixed on foam glass carrier, amorphous compound metantimonic acid lithium is simultaneously in heat treatment process
It is converted into monoclinic system metantimonic acid lithium；
（4）It is dipped in the inorganic acid aqueous solution of 0.5-1.0mol/L, cycle sprinkling inorganic acid aqueous solution makes compound metantimonic acid
Lithium ion in lithium filler completes desorption in 0.5-1h, then is cleaned with deionized water, obtains the compound metantimonic acid H of monocline1+ xTixSb1-xO3Filler, the inorganic acid are one of hydrochloric acid, nitric acid or sulfuric acid；
（5）Lithium ion sieve filler is seated in adsorption tower, circulated sprinkling contains the simulation brine 4-16h of 200mg/L lithium chlorides,
Lithium ion sieve filler is made to reach saturation absorption, measures its adsorption capacity as 20-25mg/g, adsorption capacity after adsorption desorption recycles 10 times
Also without significant change.
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| CN109173976A (en) * | 2018-09-07 | 2019-01-11 | 成都理工大学 | It is a kind of to efficiently separate the synthetic method for extracting the metatitanic acid type lithium adsorbent of lithium in brine |
| CN109174068A (en) * | 2018-09-07 | 2019-01-11 | 成都理工大学 | A kind of metatitanic acid type lithium adsorbent and preparation method thereof |
| CN110028104A (en) * | 2019-03-28 | 2019-07-19 | 长沙师范学院 | A kind of preparation method of compound manganese lithium system ion sieve |
| CN110090614A (en) * | 2019-05-28 | 2019-08-06 | 湖南大学 | A kind of preparation method of lithium ion sieve adsorbant and products thereof and application |
| CN113274971A (en) * | 2021-03-12 | 2021-08-20 | 北京泰丰先行新能源科技有限公司 | Titanium type lithium ion sieve and preparation method thereof |
| CN114011407A (en) * | 2022-01-04 | 2022-02-08 | 天津市职业大学 | Photocatalytic material for treating oil field wastewater and preparation method and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1237946A (en) * | 1996-10-16 | 1999-12-08 | 旭化成工业株式会社 | Porous inorganic composite and method for separating metal elements using the same |
| CN101961634A (en) * | 2010-09-16 | 2011-02-02 | 中南大学 | Manganese series lithium ion sieve adsorbent and preparation method of precursor thereof |
| US20130186760A1 (en) * | 2010-11-19 | 2013-07-25 | Central South University | Method and device for extracting and enriching lithium |
| CN104014308A (en) * | 2014-02-25 | 2014-09-03 | 江苏海普功能材料有限公司 | Method for preparing high-performance brine lithium-extraction adsorption agent and adsorption agent prepared by method |
| CN204162442U (en) * | 2014-10-17 | 2015-02-18 | 江苏久吾高科技股份有限公司 | A kind of device being extracted battery grade lithium by bittern |
| CN106044852A (en) * | 2016-08-16 | 2016-10-26 | 海宁永欣科技咨询有限公司 | Preparation method of nano tin antimony oxide powder |
-
2018
- 2018-01-14 CN CN201810033248.6A patent/CN108160023A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1237946A (en) * | 1996-10-16 | 1999-12-08 | 旭化成工业株式会社 | Porous inorganic composite and method for separating metal elements using the same |
| CN101961634A (en) * | 2010-09-16 | 2011-02-02 | 中南大学 | Manganese series lithium ion sieve adsorbent and preparation method of precursor thereof |
| US20130186760A1 (en) * | 2010-11-19 | 2013-07-25 | Central South University | Method and device for extracting and enriching lithium |
| CN104014308A (en) * | 2014-02-25 | 2014-09-03 | 江苏海普功能材料有限公司 | Method for preparing high-performance brine lithium-extraction adsorption agent and adsorption agent prepared by method |
| CN204162442U (en) * | 2014-10-17 | 2015-02-18 | 江苏久吾高科技股份有限公司 | A kind of device being extracted battery grade lithium by bittern |
| CN106044852A (en) * | 2016-08-16 | 2016-10-26 | 海宁永欣科技咨询有限公司 | Preparation method of nano tin antimony oxide powder |
Non-Patent Citations (2)
| Title |
|---|
| 张学铭 等: "《化学小词典》", 31 August 1994, 科学技术文献出版社 * |
| 莫畏 等: "《钛合金》", 30 June 1979, 冶金工业出版社 * |
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|---|---|---|---|---|
| CN109173976A (en) * | 2018-09-07 | 2019-01-11 | 成都理工大学 | It is a kind of to efficiently separate the synthetic method for extracting the metatitanic acid type lithium adsorbent of lithium in brine |
| CN109174068A (en) * | 2018-09-07 | 2019-01-11 | 成都理工大学 | A kind of metatitanic acid type lithium adsorbent and preparation method thereof |
| CN110028104A (en) * | 2019-03-28 | 2019-07-19 | 长沙师范学院 | A kind of preparation method of compound manganese lithium system ion sieve |
| CN110090614A (en) * | 2019-05-28 | 2019-08-06 | 湖南大学 | A kind of preparation method of lithium ion sieve adsorbant and products thereof and application |
| CN110090614B (en) * | 2019-05-28 | 2021-08-27 | 湖南大学 | Preparation method of lithium ion sieve adsorbent, product and application thereof |
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