CN106902774A - The preparation method and stratiform aluminum salt adsorbent of a kind of stratiform aluminum salt adsorbent - Google Patents
The preparation method and stratiform aluminum salt adsorbent of a kind of stratiform aluminum salt adsorbent Download PDFInfo
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Abstract
The invention discloses the preparation method and stratiform aluminum salt adsorbent of a kind of stratiform aluminum salt adsorbent, the method of the present invention can be used for preparing the aluminum salt adsorbent with double-decker, the outer layer of layered aluminum salt adsorbent is high molecular polymer, the skeleton of polysaccharide is enclosed with the high molecular polymer, aluminum salt adsorbent is enclosed between the skeleton of the polysaccharide, the aluminum salt adsorbent composition is [xMg (OH)2(2‑x)Al(OH)3]·nH2O's, the aluminum salt adsorbent has the hole that size is 10 500nm.Stratiform aluminum salt adsorbent of the invention can be used for the absorption of lithium ion.
Description
Technical field
The invention belongs to Salt Lake Chemistry field, and in particular to a kind of stratiform aluminum salt adsorbent and using it from the low lithium halogen in salt lake
The method that lithium is extracted in water.
Background technology
Lithium and its compound are significant strategic materials in national economy and national defense construction, are also and people's life
The closely bound up new green power material of work.With the continuous improvement of scientific and technological level, resource and environment problem becomes increasingly conspicuous,
In particular with the fast development of portable electric appts and new-energy automobile, the reserves of ore lithium are far from meeting city in the world
Field demand, and solid mineral resources is constantly exhausted, and the peat utilization of lithium ore resources also faces turnover.
China is salt lake country distributed more widely, and saline lake lithium resource relatively enriches, and only in the Yanhu District in Qinghai, is just stored up
The lithium chloride of up to ten million tons is deposited, the half of national lithium resource is accounted for.With continually developing for saline lake lithium resource, salt lake mining area is opened
Adopt and will produce the poor lithium brine deposit in substantial amounts of salt lake, i.e. Li after rich lithium ore deposit+Concentration will gradually reduce, it is existing to put forward lithium work
Exploitation is not suitable with after skill technology at last.Particularly with lithium resource total amount is big, Li+The low poor mining area-Cha Er Han Salt Lake of content,
Its lithium resource reserves accounts for the 60% of the whole province.Micro Li in salt lake+Coexisted with substantial amounts of alkali metal, alkaline-earth metal ions, and
The chemical property of lithium magnesium is again very close so that carry that lithium is very difficult, especially in the environment of High Contents of Magnesium ion.
From the point of view of long term growth, the technology how research and development carry lithium from low-grade salt lake lithium ore deposit is extremely urgent, and this is not only
The exploitation time limit of China's saline lake lithium resource can be extended, increase lithium salts yield, also there is actively weight in terms of economic and technical deposit
The realistic meaning and scientific meaning wanted.Therefore, a kind of low cost, process is simple, the environment-friendly lithium that carries is researched and developed to produce
Method is imperative.
In the relatively low bittern containing lithium of grade or lake water, absorption method has an obvious advantage, and from long-range protection ring
Border and actual production angle considered, be especially preferred with aluminum salt adsorbent, wash-out to adsorbent, is regenerated without substantial amounts of acid
Alkali, directly can just be achieved the goal with fresh water, so using aluminum salt adsorbent selective absorption Li+It is that a kind of application prospect is preferable
The method that lithium is carried from the bittern containing lithium of salt lake.
Patent US4221767 is disclosed and AlCl is successively added in anion exchange resin3Solution and NH4OH solution, then use
The treatment of LiCl solution, synthesizes aluminum salt adsorbent LiCl2Al (OH)3·nH2O, after it is dispersed in the space of resin, should
The adsorbent optionally separation and Extraction lithium from salt lake bittern of method synthesis, and experiment shows alternately to be flowed through bittern, follows
Using after 140 cycles, resin does not reduce significantly ring to the adsorption capacity of lithium.The aluminium synthesized in patent US4221767
Salt adsorbent LiCl2Al (OH)3·nH2O, cycle performance is more stable, but because resin price is higher, adds easily by halogen
Other ionic soils in water, cause its regeneration expensive, thus are difficult to expanding production.
Patent US6280693 discloses a kind of fairly simple synthetic method, and it is by Al that mesh number is between 10 to 140
(OH)3Particle is positioned in LiOH solution, LiOH is entered into Al (OH)3In the space of particle, granular LiOH/Al is formed
(OH)3, then with HCl treatment, make LiOH/Al (OH)3Change into LiCl2Al (OH)3·nH2O.The aluminium prepared using the method
Salt lithium adsorbent is difficult to be contaminated, be difficult to be destroyed, service life is more long.Patent US6280693 provides synthesis LiCl2Al
(OH)3·nH2Although the method for O is easy, through laboratory and industrial pillar experiment prove its work adsorption capacity there was only 2~
3mg/g, 40% or so of only powdered aluminium salt lithium adsorbent adsorption capacity, and also molten loss rate is larger during adsorbent reactivation.
Chinese patent application ZL02145583.X old halogen containing lithium, hair for high Mg/Li ratio lake bittern water containing lithium salts and salt pan concentration
Understand aluminium salt lithium adsorbent LiCl2Al (OH)3·nH2O.It is that LiCl is inserted into Al (OH)3Reaction generation plug-in type LiCl
2Al(OH)3·nH2O compounds, powder is generated after filtering, washing, dry.Polyethylene is dissolved in cyclohexanone again, is added
LiCl·2Al(OH)3·nH2O powder is tuned into pasty state and is granulated, and the aluminium salt lithium adsorbent that will have been granulated loads absorption-desorption dress
The absorption for carrying out salt lake bittern lithium is put, the lithium ion that will be adsorbed with water elutes desorption, eluent is refined, concentration, that is, meet and produce
Acceptable material needed for lithium carbonate or lithium chloride, lithium yield is up to 92%.The absorbing process that Chinese patent ZL02145583.X is provided
Flow is simple, and cost is relatively low, available and environmentally friendly, but because work adsorption capacity only has 2-3mg/g, it is relatively more relatively low, lead
Prospects for commercial application is caused to be obstructed.
Dong Qian (《Aluminum salt adsorbent adsorbs research [J] of lithium from salt lake bittern》, rare metal, 2007,31 (3):
Aluminum salt adsorbent 357-361.) etc. is prepared for aluminium hydroxide and lithium hydroxide, first by Al (OH)3Added water with LiOH and mixed,
Watery hydrochloric acid is added after reaction certain hour and is stirred, the pH value of mixture supernatant liquor is maintained between 5-7.Then pickling 3-
After 5h, the middle LiCl of mixture is removed with water, obtain the Al (OH) containing specific hole3Crystallization, i.e. Li+Adsorbent.And explore
Influence a series of conditions of its absorption property.Although the adsorbent absorption property of the preparations such as Dong Qian it is highly stable and also to lithium from
Sub- selectivity is higher, but its adsorbance only has 0.6~0.9mg/g.
Li Jie (《Aluminium salt lithium adsorbent preparation technology and Study on adsorption properties [D]》, Chengdu:Chengdu University of Technology,
2011.) for the salt lake bittern that lithium concentration is higher, by controlling NaOH, LiCl and AlCl3The dropwise addition mode of solution, obtains
Arrive aluminium salt lithium adsorbent, and absorption property to its adsorbent is studied.It is by a certain proportion of AlCl3·6H2O and
LiCl is dissolved in distilled water, is vibrated with thermostatic ultrasonic well mixed.Then mixed liquor is added dropwise to sodium hydroxide solution, controls water
The factors such as bath temperature, feed time, endpoint pH, mixing speed, washing and drying can obtain aluminium salt lithium adsorbent after agitated ageing,
Aluminium salt lithium adsorbent the best conditions of preparation pr ocess is also drawn simultaneously.Although the aluminum salt adsorbent that Li Jie develops is to Li+Have
Good Selective adsorption, is disturbed smaller by extraneous factor, and absorption property is preferable, but the adsorption capacity of lithium only has 5mg/g, parsing
Rate is also than relatively low.And, the sorbent circulation periodic inequality, after three circulations, adsorbance drops to 2.3mg/g.
In order that aluminum salt adsorbent be easy to operate and reduce the loss of adsorbent, it is necessary to by adsorbent be fixed on carrier it
It is upper --- granulation.But it is the polymeric materials such as PVC to be typically chosen carrier material, can be formed after certain method is granulated
Micropore, but because bad hydraulic permeability, adsorption process are slower, it is limited by very large the application of adsorbent.
The aluminum salt adsorbent that other different synthetic methods are obtained can selectively isolate Li from salt lake bittern+,
But because regenerating that expensive, adsorption capacity is low, desorption is relatively slow or because granulation reduce further before adsorption capacity causes practical application
Scape allows of no optimist.
The content of the invention
Contain it is an object of the invention to be directed to trend that lithium content in salt lake in future gradually reduces and low-grade salt lake
Lithium bittern, there is provided a kind of method that selective absorption carries lithium.The present invention is inhaled by synthesizing a kind of stratiform aluminium salt of efficient absorption lithium
Attached dose, by carrying out selective absorption to the low lithium bittern in salt lake after granulation, impurity content is obtained through washing after adsorbent saturation
Relatively low lithium-containing solution, it is concentrated or add soda ash conversion to can obtain corresponding lithium salts product by after removal of impurities.
The method that the present invention prepares efficient stratiform aluminum salt adsorbent is specifically included：
Will magnesium salts, lithium chloride and aluminium salt dissolve after obtain mixing salt solution, by aqueous slkali add mixing salt solution in, 20
Reacted at~80 DEG C, after be filtrated to get plug-in type compound L iCl [xMg (OH)2(2-x)Al(OH)3]·nH2O, then
By LiCl [xMg (OH)2(2-x)Al(OH)3]·nH2O is added in the aqueous solution of the compound of polysaccharide that concentration is 1~4%,
Added it to again after well mixed in the organic solution of polymer, granulated after fully mixing, obtain absorbent particles, used
The lithium salts that washing is gone in the absorbent particles, forms the room of lithium salts, obtains stratiform aluminum salt adsorbent.
The process that a kind of typical case of the present invention prepares stratiform aluminum salt adsorbent is as follows：
By MgCl2·6H2O, AlCl3·6H2After O and LiCl dissolvings, at ambient temperature, aqueous slkali is added and is acutely stirred
In the mixing salt solution mixed, reacted at 20~80 DEG C, after be cooled to room temperature, be filtrated to get shortcoming type disordered structure insert
Enter formula compound L iCl [xMg (OH)2(2-x)Al(OH)3]·nH2O.Then by LiCl [xMg (OH)2(2-x)Al
(OH)3]·nH2O is added in the aqueous solution of the compound of polysaccharide that concentration is 1~4%, and stirring is well mixed the two, will mix
Liquid is added to 1~10% CaCl2In the aqueous solution, the aluminum salt adsorbent containing compound of polysaccharide is prepared, then add it to
It is mixed with the organic solution of high molecular polymer binder, is granulated after fully mixing, obtains absorbent particles.Rushed using water
Adsorbent is washed, LiCl therein is washed away, the room of LiCl is formed, so as to obtain granular stratiform aluminum salt adsorbent.
Used as a kind of preferably selection of above-mentioned technical proposal, the magnesium salts is magnesium nitrate, magnesium chloride or magnesium sulfate.
Used as a kind of preferably selection of above-mentioned technical proposal, the aluminium salt is aluminum nitrate, aluminium chloride or aluminum sulfate.
Used as a kind of preferably selection of above-mentioned technical proposal, the aqueous slkali is potassium hydroxide, NaOH and/or ammonia
Water.
Used as a kind of preferably selection of above-mentioned technical proposal, the concentration of the aqueous slkali is 0.2-10M, more preferably 0.2-
0.5M, 0.5-1M, 1-3M, 3-6M, 6-10M.
Used as a kind of preferably selection of above-mentioned technical proposal, the temperature of aqueous slkali and the reaction of magnesium salts, lithium salts and aluminium salt is 20-
35 degrees Celsius.
Used as a kind of preferably selection of above-mentioned technical proposal, the temperature of aqueous slkali and the reaction of magnesium salts, lithium salts and aluminium salt is 35-
60 degrees Celsius.
Used as a kind of preferably selection of above-mentioned technical proposal, the temperature of aqueous slkali and the reaction of magnesium salts, lithium salts and aluminium salt is 60-
80 degrees Celsius.
Used as a kind of preferably selection of above-mentioned technical proposal, the compound of polysaccharide is alginate, can specifically be selected
Alginate can be sodium alginate or potassium alginate.Those skilled in the art can be by adding calcium salt or others side
Formula forms calcium alginate or other salt fix polysaccharide skeleton.
Preferably selected as one of above-mentioned technical proposal, chemical combination during by the aqueous solution to compound of polysaccharide and insertion
The mode of calcium chloride is added to form calcium alginate in the mixed liquor of thing.
As above-mentioned technical proposal a kind of preferably selection, the MgCl2·6H2O, AlCl3·6H2O and LiCl mole
Than being 0.01-0.20：1.99-1.80：0.90-2.00.
As above-mentioned technical proposal a kind of preferably selection, the MgCl2·6H2O, AlCl3·6H2O and LiCl mole
Than being 0.01-0.10：1.99-1.80：1.20-1.50.
Used as a kind of preferably selection of above-mentioned technical proposal, the x values are 0.01-0.20.
Used as a kind of preferably selection of above-mentioned technical proposal, the x values are 0.01-0.10.
Used as a kind of preferably selection of above-mentioned technical proposal, the organic polymer is PVC, PE or PP.
Present invention also offers the stratiform aluminum salt adsorbent prepared using the above method.
Present invention also offers the stratiform aluminum salt adsorbent prepared using the above method, layered aluminum salt adsorbent
Outer layer be polymer, the polymeric inner is enclosed with the skeleton of polysaccharide, aluminium salt included in the space of the polysaccharide skeleton
Adsorbent, the composition of the aluminum salt adsorbent is [xMg (OH)2(2-x)Al(OH)3]·nH2The adsorbent of O, the aluminium salt absorption
Agent surface has the hole that size is 10-500nm.
Stratiform aluminum salt adsorbent of the invention has tertiary structure, and its first level structure is to be wrapped in outermost polymerization
Thing, its second level structure is that, by the polysaccharide skeleton of polymer wrapped, its third level structure is the aluminium being distributed between polysaccharide skeleton
Salt absorbent particles.
Used as a kind of preferably selection of previous technical scheme, the compound of polysaccharide is alginate.
Used as a kind of preferably selection of previous technical scheme, the polymer is PVC, PE or PP.
Used as a kind of preferably selection of above-mentioned technical proposal, the aluminum salt adsorbent skeleton is part aluminium in lithium aluminum hydrotalcite
For magnesium replaces, and the structure that removal lithium ion is formed.
Used as a kind of preferably selection of previous technical scheme, the aluminium of 1-20% is partially substituted by magnesium in the lithium aluminum hydrotalcite.
Used as a kind of preferably selection of previous technical scheme, the aluminium of 1-10% is partially substituted by magnesium in the lithium aluminum hydrotalcite.
Used as a kind of preferably selection of above-mentioned technical proposal, it is 10-20nm's that the aluminum salt adsorbent surface has size
Hole.
Used as a kind of preferably selection of above-mentioned technical proposal, it is 20-50nm's that the aluminum salt adsorbent surface has size
Hole.
Used as a kind of preferably selection of above-mentioned technical proposal, it is 50-100nm's that the aluminum salt adsorbent surface has size
Hole.
Used as a kind of preferably selection of above-mentioned technical proposal, it is 100-200nm that the aluminum salt adsorbent surface has size
Hole.
Used as a kind of preferably selection of above-mentioned technical proposal, it is 200-500nm that the aluminum salt adsorbent surface has size
Hole.
There is directly influence in the aperture of adsorbent for the adsorption capacity of aluminum salt adsorbent, and those skilled in the art can be with
A pore diameter range for rational stratiform aluminum salt adsorbent is selected and designed as needed.
As general knowledge, by sieving and control the size of sieve aperture can to obtain the absorbent particles with specific dimensions.
Used as a kind of preferably selection of above-mentioned technical proposal, the thickness of layered aluminum salt adsorbent outer layer copolymer is
0.5-50nm, more preferably may range from 0.5-5,5-10,10-20,20-35,35-50nm.
The adsorption process for carrying out lithium ion using adsorbent of the invention is as follows：
The stratiform aluminum salt adsorbent that will be prepared loads in absorption-desorption post, according to certain bed volume by salt lake halogen containing lithium
Water is desorbed by adsorbent post after adsorption capacity reaches saturation with the water of certain bed volume, desorption obtain containing lithium
Solution also has a small amount of magnesium and other foreign ions, and lithium-containing solution can make impurity content be reduced to lithium salts product institute by after refined
The requirement for needing.It is concentrated to give lithium chloride solution or lithium carbonate product can be formed to itself plus alkali conversion.
The adsorption capacity of stratiform aluminum salt adsorbent prepared by the present invention reaches more than 10mg/g, is circulated through multiple adsorption/desorption
Afterwards, adsorption capacity is held essentially constant.The present invention solves the trend that lithium content in salt lake in future gradually reduces and low-grade
The difficult problem of salt lake brine mining containing lithium, it is possible to decrease carry lithium cost, shortening puies forward lithium technique, simplifies the removal of impurities in subtractive process
Method.The present invention has synthesized Layered Lithium absorbent particles by complex carrier of calcium alginate and PVC, and successfully realizes it
To the quick adsorption of lithium under low consistency conditions, and adsorbent shows the selective absorption performance to lithium, it is ensured that inhale
Attached dose of molten damage, and increased the intensity of aluminum salt adsorbent.
The present invention has following beneficial effect：
(1) synthesis material is cheap and easy to get, and synthesis technique is simple, low cost；
(2) whole flow process from synthesis step to adsorption process does not introduce other poisonous and hazardous reagents, to environmental hazard
It is small；
(3) by the introducing of magnesium, the supporting role played in the structure, so as in reducing elution process, easily cause
Structural collapse and the problem of adsorbent failure.
(4) adsorbent is used directly for the absorption of Lithium from Salt Lake Brine, without adjusting acid-base property；
(5) can directly be washed with water when adsorbent is desorbed, it is not necessary to pickling, it is to avoid corrosion of the acid to equipment；
(6) the spherical lithium adsorbent with the polymer such as calcium alginate and PVC as mixed carrier has synthesized, increased intensity, protect
The small molten damage of adsorbent is demonstrate,proved.And it is successfully realized under low consistency conditions to the quick adsorption of lithium, and adsorbent
Show the selective absorption performance to lithium.
Brief description of the drawings
The XRD of the adsorbent that Fig. 1, the present invention are prepared.
The XRD of the adsorbent that Fig. 2, one embodiment of the invention are prepared.
The XRD of the adsorbent that Fig. 3, another embodiment of the present invention are prepared.
The crystal model figure (side-looking chart-pattern) of Fig. 4, intermediate of the present invention.
The crystal model figure (top view chart-pattern) of Fig. 5, intermediate of the present invention.
The artwork of Fig. 6, adsorption treatment lithium chloride of the present invention.
Specific embodiment
Low-grade salt lake bittern containing lithium after carrying lithium with Qinghai as follows is utilized by instantiation as raw material to the present invention
Stratiform aluminum salt adsorbent absorption lithium is described further.
The present invention prepare aluminum salt adsorbent and carry out lithium chloride absorption using it process referring to Fig. 6.
The main composition of the bittern that the present invention is used is (g/L)：Li 0.511, Mg 50, Na 0.3, other example bags
The common ion such as chlorion, nitrate ion, sulfate ion and calcium ion is included, the bittern of other concentration can also be using this
The adsorbent of invention is enriched with.
Embodiment one
The preparation of stratiform aluminum salt adsorbent and compound are carried out as follows：
By Mg：Al：The amount ratio of Li materials is 0.05:1.95:1.5 proportioning weighs MgCl2·6H2O、AlCl3·6H2O and
LiCl, plus after suitable quantity of water makes it fully dissolve, at ambient temperature, by OH-：(Al3++Mg2+) be 2.5 proportioning weigh NaOH simultaneously
It is made into the mixing salt solution that the addition of 5%~15% solution is stirred vigorously.Reacted at 80 DEG C afterwards.40~60min of reaction
Afterwards, it is cooled to room temperature.Filtering can obtain the plug-in type compound L iCl [0.05Mg (OH) of shortcoming type disordered structure2·
1.95Al(OH)3]·nH2O.Then by LiCl [0.05Mg (OH)2·1.95Al(OH)3]·nH2O is added to 1~2% sea
In alginic acid sodium water solution, then stirring is well mixed the two, and mixed liquor is added to 3~5% CaCl2In the aqueous solution, system
It is standby go out calcium alginate aluminum salt adsorbent.Calcium alginate aluminum salt adsorbent is added to again is mixed with high molecular polymerization matter PVC binding agent
Organic solution in, fully mix after granulated, obtain absorbent particles.Using fresh water flush adsorbent, wash away therein
LiCl, forms the room of LiCl, and so as to obtain granular stratiform aluminum salt adsorbent, wherein aluminum salt adsorbent is distributed in many saccharification
In the skeleton gap of compound.Wherein adsorbent is more than 2 with the mass ratio of carrier, and its XRD is referring to Fig. 1.
Adsorption and desorption and conversion：The stratiform aluminum salt adsorbent that will be prepared loads in absorption-desorption post, according to per hour 3~
10 times of bed volume flow velocitys will contain Li+Concentration be the salt lake bittern of 0.4~1.0g/L by adsorbent post, when adsorption capacity reach it is full
Desorbed with water with rear, the lithium-containing solution that desorption is obtained also has a small amount of magnesium and other foreign ions, impurity is made by refined
Content be reduced to lithium salts product needed for requirement.Concentrate eluant obtains lithium chloride solution or itself plus alkali is converted to form lithium carbonate
Product.
Now, [0.05Mg (OH)2·1.95Al(OH)3]·nH2O adsorbents to Li+Static capacity be 13~
15mg/g, work adsorption capacity is 11~13mg/g, and after repeatedly circulation, work adsorption capacity is kept approximately constant.
In order to ensure being normally carried out for reaction in said process, reaction system should maintain preferably stirring, and must
Intensification can be taken to promote reaction when wanting.
Embodiment two
The preparation of stratiform aluminum salt adsorbent and compound：Mg：Al：The amount ratio of Li materials is 0.10:1.9:1.5 proportioning
Weigh MgCl2·6H2O、AlCl3·6H2O and LiCl, plus after suitable quantity of water makes it fully dissolve, at ambient temperature, by OH-：
(Al3++Mg2+) it is that 2.8 proportioning weighs KOH and is made into during 5%~15% solution adds the mixing salt solution that is stirred vigorously.Afterwards
Reacted at 80 DEG C.After 40~60min of reaction, room temperature is cooled to.Filtering can obtain the plug-in type of shortcoming type disordered structure
Compound L iCl [0.10Mg (OH)2·1.90Al(OH)3]·nH2O.Then by LiCl [0.10Mg (OH)2·1.90Al
(OH)3]·nH2O is added in 1~3% sodium alginate aqueous solution, and then stirring is well mixed the two, and mixed liquor is added
To 3~5% CaCl2In the aqueous solution, calcium alginate aluminum salt adsorbent is prepared.Calcium alginate aluminum salt adsorbent is added to again
Being mixed with the organic solution of high molecular polymer PP binding agents for certain content, is granulated after fully mixing, and obtains adsorbent
Particle.Using fresh water flush adsorbent, LiCl therein is washed away, the room of LiCl is formed, so as to obtain granular aluminum laminate
Salt adsorbent, wherein aluminum salt adsorbent are distributed in the skeleton gap of compound of polysaccharide.The wherein mass ratio of adsorbent and carrier
More than 2, its XRD is referring to Fig. 2.
Adsorption and desorption and conversion：The stratiform aluminum salt adsorbent that will be prepared loads in absorption-desorption post, according to per hour 3~
10 times of bed volume flow velocitys will contain Li+Concentration be the salt lake bittern of 0.1~0.5g/L by adsorbent post, when adsorption capacity reach it is full
Desorbed with water with rear, the lithium-containing solution that desorption is obtained also has a small amount of magnesium and other foreign ions, impurity is made by refined
Content be reduced to lithium salts product needed for requirement.Concentrate eluant obtains lithium chloride solution or itself plus alkali is converted to form lithium carbonate
Product.
Now, [0.10Mg (OH)2·1.90Al(OH)3]·nH2O adsorbents to Li+Static capacity be 10~
13mg/g, work adsorption capacity is 8~12mg/g, and after repeatedly circulation, work adsorption capacity is kept approximately constant.
Embodiment three
The preparation of stratiform aluminum salt adsorbent and compound：Mg：Al：The amount ratio of Li materials is 0.05:1.95:1.5 match somebody with somebody
Than weighing MgCl2·6H2O、AlCl3·6H2O and LiCl, plus after suitable quantity of water makes it fully dissolve, at ambient temperature, by OH-：
(Al3++Mg2+) it is that 3 proportioning weighs ammoniacal liquor and is made into during 10%~15% solution adds the mixing salt solution that is stirred vigorously.Afterwards
Reacted at 80 DEG C.After reaction 1h, room temperature is cooled to.Filtering can obtain the plug-in type compound of shortcoming type disordered structure
LiCl·[0.05Mg(OH)2·1.95Al(OH)3]·nH2O.Then by LiCl [0.05Mg (OH)2·1.95Al(OH)3]·
nH2O is added in 2~3% sodium alginate aqueous solution, and then stirring is well mixed the two, mixed liquor is added to 2~
4% CaCl2In the aqueous solution, calcium alginate aluminum salt adsorbent is prepared.Calcium alginate aluminum salt adsorbent is added to necessarily again
Being mixed with the organic solution of high molecular polymer such as PVC binding agents for content, is granulated after fully mixing, and obtains adsorbent
Grain.Using fresh water flush aluminum salt adsorbent, LiCl therein is washed away, the room of LiCl is formed, so as to obtain granular stratiform
Aluminum salt adsorbent.Wherein adsorbent is more than 2 with the mass ratio of carrier, and its XRD is referring to Fig. 3.
Adsorption and desorption and conversion：The stratiform aluminum salt adsorbent that will be prepared loads in absorption-desorption post, according to per hour 3~
10 times of bed volume flow velocitys will contain Li+Concentration be the salt lake bittern of 0.1~0.5g/L by adsorbent post, when adsorption capacity reach it is full
Desorbed with water with rear, the lithium-containing solution that desorption is obtained also has a small amount of magnesium and other foreign ions, impurity is made by refined
Content be reduced to lithium salts product needed for requirement.Concentrate eluant obtains lithium chloride solution or itself plus alkali is converted to form lithium carbonate
Product.
Now, [0.05Mg (OH)2·1.95Al(OH)3]·nH2O adsorbents to Li+Static capacity be 11~
14mg/g, work adsorption capacity is 8~10mg/g, and after repeatedly circulation, work adsorption capacity is kept approximately constant.
In the above embodiments, magnesium chloride may also be magnesium sulfate or magnesium nitrate and magnesium chloride and its mixture, and aluminium salt can
So that from aluminum sulfate or aluminum nitrate and aluminium chloride and its mixture, for the concentration of alkali, those skilled in the art can basis
Needs are adjusted.
The stratiform aluminum salt adsorbent prepared using the above method is provided with tertiary structure, and its first level structure is parcel
In outermost polymer, its second level structure is that, by the polysaccharide skeleton of polymer wrapped, its third level structure is more to be distributed in
Aluminum salt adsorbent particle between sugared skeleton, the aluminum salt adsorbent has the hole that size is 10-500nm.The polymerization of its outer layer
Thing thickness can have differences according to the method and addition that prepare.
Referring to Fig. 4 and Fig. 5, the adsorbent skeleton is that part aluminium is magnesium substitution in lithium aluminum hydrotalcite, and removal lithium ion
The structure of formation.
Other slaines in the present invention in addition to lithium chloride can be substituted using other water miscible salt, as long as it can expire
Foot forms corresponding hydroxide under alkaline environment.
Other embodiments of the invention are referring to following table：
After repeatedly circulation, work adsorption capacity is kept approximately constant.
Detailed displaying and explanation have been carried out to the present invention above by accompanying drawing and preferred embodiment, but the invention is not restricted to
These embodiments having revealed that, other schemes that those skilled in the art therefrom derive also protection scope of the present invention it
It is interior.
Claims (10)
1. a kind of preparation method of stratiform aluminum salt adsorbent, including：
Will magnesium salts, lithium chloride and aluminium salt dissolve after obtain mixing salt solution, by aqueous slkali add mixing salt solution in, 20~80
Reacted at DEG C, after be filtrated to get plug-in type compound L iCl [xMg (OH)2(2-x)Al(OH)3]·nH2O, then will
LiCl·[xMg(OH)2(2-x)Al(OH)3]·nH2O is added in the aqueous solution of the compound of polysaccharide that concentration is 1~4%, is mixed
Added it to again after closing uniformly in the organic solution of polymer, granulated after fully mixing, obtain absorbent particles, use water
The lithium salts in the absorbent particles is washed away, the room of lithium salts is formed, stratiform aluminum salt adsorbent is obtained.
2. method according to claim 1, it is characterised in that the compound of polysaccharide is alginate.
3. method according to claim 1, it is characterised in that the organic polymer is PVC, PE or PP.
4. the stratiform aluminum salt adsorbent for being prepared according to claim 1-3 either method.
5. a kind of stratiform aluminum salt adsorbent, it is characterised in that
The outer layer of layered aluminum salt adsorbent is polymer, and the polymeric inner is enclosed with the skeleton of polysaccharide, the polysaccharide
Stratiform aluminum salt adsorbent is included in the space of skeleton, the composition of the aluminum salt adsorbent is [xMg (OH)2(2-x)Al
(OH)3]·nH2O, the surface of the aluminum salt adsorbent has the hole that size is 10-500nm.
6. stratiform aluminum salt adsorbent according to claim 6, it is characterised in that：The skeleton of the aluminum salt adsorbent is lithium aluminium
Part aluminium is magnesium substitution in hydrotalcite, and removes the structure that lithium ion is formed.
7. stratiform aluminum salt adsorbent according to claim 5, it is characterised in that：The aluminium of 1-20% in the lithium aluminum hydrotalcite
It is partially substituted by magnesium.
8. stratiform aluminum salt adsorbent according to claim 5, it is characterised in that the polysaccharide is alginate.
9. stratiform aluminum salt adsorbent according to claim 5, it is characterised in that the polymer is PVC, PE or PP.
10. stratiform aluminum salt adsorbent according to claim 5, it is characterised in that the outer strata of layered aluminum salt adsorbent
The thickness of compound is 0.5-50nm.
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