CN106084102B - A kind of preparation method of spherical granular lithium ion sieve - Google Patents
A kind of preparation method of spherical granular lithium ion sieve Download PDFInfo
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F112/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F112/02—Monomers containing only one unsaturated aliphatic radical
- C08F112/04—Monomers containing only one unsaturated aliphatic radical containing one ring
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- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
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Abstract
The invention discloses a kind of preparation methods of spherical granular lithium ion sieve, include the following steps：Step (1)：Water phase is dissolved to obtain in dispersant and water mixing；Step (2)：Powdery lithium ion sieve is added into the water phase of step (1), the oil phase comprising monomer and initiator, which is added, after stirring heating carries out suspension polymerization；The monomer includes styrene；Step (3)：After the completion of step (2) reaction, continue to heat up, spherical particle made from suspension polymerization is made to harden, the particle after hardening obtains ball-shaped lithium-ion sieve after washing, drying, pickling, washing and drying successively.Spherical granular lithium ion sieve epigranular produced by the present invention, intensity are high；The oil phase rate of recovery is more than 95%, and the powdery ion sieve rate of recovery is 100%.
Description
Technical field
The invention belongs to the preparation fields of ion sieve adsorbant, and in particular to a kind of preparation side of spherical granular lithium ion sieve
Method.
Background technology
Lithium is a kind of metal that electro-chemical activity is high, and application field is extensive, lithium battery, controllable nuclear fusion reactor,
Aerospace, glass, ceramics, medicine and other fields have important use, for the market demand rapid development of lithium.Solid in the world
The reserves of lithium ore are increasingly exhausted, can not meet the market demand.And salt lake bittern, seawater, well halogen etc. are huge liquid lithiums
Mineral reserve are attached great importance to extracting lithium from these liquid mines, the lithium salts for having nearly 80% at present is that brine carries lithium both at home and abroad in recent years
Product, comprehensive exploitation and the mainstream that lithium industrial development is had become using brine lithium resource.China western part possesses abundant brine lithium
Resource, but since Li contents are low in the most of salt lake bitterns in China, Mg/Li is than high, traditional " precipitation-crystallisation " is not appropriate for
Lithium is carried in such salt lake, and absorption method is that the effective ways of lithium are extracted in a kind of lithium-containing solution from low concentration, absorption method carries lithium
Main media is lithium ion sieve adsorbant.
Existing lithium ion sieve such as LiMn2O4、Li4Mn5O12、Li1.6Mn1.6O4、Li2Mn3O7、Li4Mn5O12Or Li2TiO3
Deng being superfine powder, mobility and permeability are all poor, and molten loss rate is higher, and in absorption-desorption, and bed is easy to collapse
It collapses so that complete block fluid, so being not used to industrialized production.Granular adsorbent is only prepared, could realize suction
Attached method puies forward the industrial applications of lithium.In view of the above reason, this superfine powder shape lithium ion sieve is made loose porous
Graininess becomes one of the emphasis of this field scientist concern.
People, which also studied, takes different methods, it is intended to be prepared into and prepare granulated sorbent or membranaceous adsorbent.At present
The prilling process for powder ion sieve adsorbant go out, reported is broadly divided into two major classes：One is direct molding bonded,
Another kind is organic polymer molding.
The method that direct molding bonded produces granulated sorbent has：(1) polyvinyl chloride and ion sieve powder mixture are utilized
It is dissolved with organic solvent (such as DMF or NMP), then instills molding in water and prepare granular ion sieve (CN101898113A)；(2) with
Water-soluble salt such as KCl is pore creating material, and DMF or NMP is added in PVC, KCl and powdery ion sieve mixture, sizes mixing, is pressed into
Sheet, crushed after being dried dissolve away KCl at graininess, through water logging and are known as granular ion sieve adsorbant；(3) polysaccharide and solvent are added
Heat of solution mixes, then ion sieve presoma is added in solution, is uniformly mixing to obtain viscous solution, then viscous solution is instilled stone
In the oil phases such as oily ether, the solid spherical adsorbent (CN103316623A) etc. that grain size is 2~5mm is obtained.
Have with organic polymer is molding：(1) acrylic monomer inverse suspension polymerization is used to form crosslinking polymer process
It is middle that lithium ion sieve powder is coated in polymer and obtains granular lithium ion sieve (CN 101955210A)；(2) with acrylamide
For polymerization forming monomer, ion sieve powder is suspended in monomer solution, initiator and crosslinking agent is added, it is anti-to cause cross-linked polymeric
It answers, pelletized polypropylene amide-lithium ion sieve (CN1511963) is made.
There is some as intensity is insufficient, granularity is difficult for the preparation method of these granular lithium ion sieve adsorbants reported at present
With control, or obtained granulated sorbent is not spherical morphology, and the poor fluidity of solution, bed resistance is big, and therefore, it is difficult to full
The requirement of sufficient industrial applications.
Invention content
To solve existing lithium ion sieve intensity deficiency, the technical problem of exterior appearance difference, the present invention provides a kind of suspensions
The method that polymerization prepares spherical granular lithium ion sieve, lithium ion sieve intensity height made from this method, are suitable for work at epigranular
The lithium adsorbent prilling process of industry production application.
A kind of preparation method of spherical granular lithium ion sieve, includes the following steps：
Step (1)：Water phase is dissolved to obtain in dispersant and water mixing；
Step (2)：Modified powdery lithium ion sieve is added into the water phase of step (1), stirring is added after heating up includes
The oil phase of monomer and initiator carries out suspension polymerization；The monomer includes styrene；
Step (3)：After the completion of step (2) reaction, continue to heat up, spherical particle made from suspension polymerization made to harden,
Particle after hardening obtains ball-shaped lithium-ion sieve after washing, drying, pickling, washing and drying successively.
In the present invention, crosslinking polymer is formed in the process by powdery lithium ion sieve packet using styrene monomer suspension polymerisation
It overlays in polymer and obtains spherical granular lithium ion sieve；Contribute to that product is made by styrene monomer and suspension polymerisation mode
Intensity height, epigranular, good fluidity, the ball-shaped lithium-ion sieve for being conducive to industrialized multiple cycle applications, and this method
Reaction system is easy to control, and oil phase and the powdery ion sieve rate of recovery are high.
The features of the present invention is exactly：During polymerizing styrene sill polymerize, lithium ion sieve powder and organic is allowed
Object is copolymerized, and forms granular lithium ion sieve adsorbant spherical, that intensity is high.The lithium ion sieve adsorbant being prepared in this way
Particle be have product strength height, epigranular, good fluidity sphere material.
In step (1), the dispersant is selected from sodium chloride, magnesium hydroxide, sodium hydroxide, magnesium chloride, potassium chloride, water glass
At least one of glass, calgon, gelatin, sodium lignin sulfonate, polyvinyl alcohol, neopelex, calcium phosphate.
Preferably, in water phase, the w/v of dispersant and water is less than 10g/100mL water.
The water phase of step (1) adds powdery lithium ion sieve after the completion of preparing.
Preferably, the add weight and oil phase volume ratio of powdery ion sieve are 10-100g: 100mL.
Spheric granules can be made using the method for the present invention in existing lithium ion sieve, preferably, the lithium ion screening
From LiMn2O4、Li4Mn5O12、Li1.6Mn1.6O4、Li2Mn3O7、Li4Mn5O12Or Li2TiO3。
Powdery ion sieve first carries out surface modification treatment before adding to powdery lithium ion sieve adsorbant.At modified
Reason makes inorganic lithium ion sieve powder surface have lipophile.
During surface modification treatment, powdery lithium ion sieve to be modified is immersed in containing the organic solution in surfactant
In.The surfactant is but is not limited to coupling agent, aliphatic acid.
Preferably, the surfactant is silane coupling agent, titanate coupling agent, hexadecylic acid, palmate, ten
At least one of eight acid, octadecanoate.
Further preferably, the surfactant is stearic acid.
During surface modification treatment, in the ethanol solution that powdery lithium ion sieve to be modified is impregnated to stearic acid.It is molten at this
In liquid, the concentration of stearic acid does not influence surface modification treatment effect.
Powdery lithium ion sieve after surface treatment is added into the water phase of step (1), is heated up under stiring；Then add
Oil phase carries out suspension polymerization.
In suspension polymerization, oil phase is 1~10: 10 with water phase volume ratio.
In step (2), temperature when oil phase adds, the stir speed (S.S.) and polymeric reaction temperature in polymerization process and monomer class
Type etc. can all influence the intensity and granularity of spheric granules obtained.
Preferably, in step (2), the oil described in being added at 40 DEG C~75 DEG C is warming up to after powdery lithium ion sieve is added
Phase is warming up to 80 DEG C of -85 DEG C of progress suspension polymerizations after the completion of feeding intake；The stir speed (S.S.) of suspension polymerization is 100-
500r/min；Time is 1h-5h.
In the present invention, the oil phase includes styrene monomer and initiator.
Existing oil-soluble initiator can be used as initiator of the present invention.
Preferably, the initiator is azo-initiator and/or peroxide initiator.
Azo-initiator has azodiisobutyronitrile (AIBN), azobisisoheptonitrile (ABVN) etc.；Peroxide initiator
For example, benzoyl peroxide, the benzoyl peroxide tert-butyl ester, methyl ethyl ketone peroxide etc..
Further preferably, the initiator be azodiisobutyronitrile, azobisisoheptonitrile, azo diisopropyl imidazoline hydrochloride,
At least one of benzoyl peroxide.
The weight ratio of initiator and monomer is 1%-8%.
In suspension polymerization, the monomer can be styrene single monomer；In order to further increase suspension polymerisation system
The intensity of the ball-shaped lithium-ion sieve obtained, particle size uniformity, the monomer is in addition to comprising styrene, and also selectivity includes other lists
Body, such as alternative includes other vinyl monomers, acrylic monomer.
Preferably, the monomer also includes divinylbenzene, acrylonitrile, vinyl chloride, vinylidene chloride, methyl methacrylate
It is one or more in ester.
Preferably, in the monomer, the weight of styrene is the 20-100% of total monomer weight.
In the present invention, also selectivity includes perforating agent in the oil phase, and the perforating agent is selected from toluene, hexane, heptan
At least one of alkane, octane, normal heptane, 12 carbon alkane, aliphatic acid, polystyrene, polyvinylacetate.
Further preferably, in step (2), the temperature that adds of the oil phase is 40 DEG C~75 DEG C, is carried out after the completion of feeding intake
Suspension polymerization temperature is 80 DEG C -85 DEG C；The stir speed (S.S.) of suspension polymerization is 100-500r/min；Time is 1h-5h.
After the completion of suspension polymerisation, 85 DEG C~100 DEG C are continuously heating to, spherical particle made from suspension polymerization is carried out
Cure process；The cure process time is greater than or equal to 0.5h.
In step (3), after the completion of cure process, filtering obtains spherical granular lithium ion sieve presoma, the spherical granular lithium
Ion sieve presoma obtains object i.e. after 80 DEG C of warm water washings, baking oven drying, mordant pickling, washing and drying successively
Spherical granular lithium ion sieve.
The particle of the granularity 20-80 mesh of lithium ion sieve made from suspension polymerization through the invention accounts for 95% or more,
Granule strength is high, mobility is preferable, can preferably recycle.
Spherical granular lithium ion sieve epigranular produced by the present invention, intensity are high；The oil phase rate of recovery be more than 95%, powdery from
The son sieve rate of recovery is 100%.In addition, this method technical process is simple, granulation time is short, production efficiency is high and of low cost.
Description of the drawings
Fig. 1 is the preparation technology flow chart of spherical granular lithium ion sieve of the present invention；
Fig. 2 is the SEM figures of spherical granular lithium ion sieve particle surface made from embodiment 1；
Fig. 3 is the spherical granular lithium ion sieve particle photo of granularity 20-40 mesh made from embodiment 4；
Fig. 4 is the spherical granular lithium ion sieve particle photo of granularity 40-80 mesh made from embodiment 4.
Specific implementation mode
Following embodiment is implemented by aforesaid operations method：
Technical scheme of the present invention is described in detail below in conjunction with specific embodiments of the present invention, certainly, is retouched
The embodiment stated is only a portion embodiment of the present invention, rather than whole.
Following embodiment prepares spherical granular lithium ion sieve by Fig. 1 preparation process flows.
Embodiment 1
Sodium chloride 2.5g, polyvinyl alcohol 0.05g, gelatin 0.25g are weighed, is dissolved in 50mL pure water and is configured to water phase.It measures
Styrene 1.65mL, divinylbenzene 5.45mL, methyl methacrylate 4.77mL, normal heptane 10mL, benzoyl peroxide 0.3g,
Oil phase is obtained after mixed dissolution.First water phase is added in the three-necked flask with reflux condenser, stirring is to being completely dissolved；It is stirring
It is slowly added to the modified powdery ion sieve in the surfaces 5g (being modified through stearic acid alcohol solution dipping) under state, begins to warm up, etc.
After temperature rises to 60 DEG C, oil phase is added.80 DEG C are to slowly warm up to, constant temperature polymerisation 3h；90 DEG C are then heated to, ball 2h is boiled.
Filtering obtains the ion sieve sphere being granulated, and is washed 2-3 times with 80 DEG C of hot water, washes away Granular gelatin.Then sphere is placed in rope
In family name's extractor, except the normal heptane in degranulation, before then particle is dried to obtain porous spherical granular ion sieve at 60 DEG C
Drive body.
Granular lithium ion sieve presoma is put in a certain amount of 0.5mol/l hydrochloric acid solutions, is mixed slowly at 30 DEG C, instead
1.5-2h is answered, spherical granular lithium ion sieve adsorbant is obtained.
The oil phase rate of recovery is 95%, and the powdery ion sieve rate of recovery is 100%.The granular lithium ion sieve adsorbant being prepared
For spherical shape, grain graininess is uniform, and 20-80 mesh particles account for 95.5%.
Fig. 2 is the SEM photograph for the granular lithium ion sieve adsorbant that embodiment 1 is prepared；Fig. 2 (a) partly be the lithium from
Son sieve particle SEM photograph, it can be seen from the figure that particle is spheric granules；Fig. 2 (b) is partly particle table after 1000 times of amplification
The photo in face, as can be seen from the figure particle surface is vesicular texture.
Embodiment 2
Weigh NaOH 0.1g, MgCl2·6H2O 0.25g are separately added into 50ml deionized water dissolvings, then this two solution is mixed
It closes；Gelatin 0.5g, polyvinyl alcohol 0.1g are weighed again, and it is in mixed liquor to be added above-mentioned, and heating for dissolving obtains water phase.Measure styrene
9mL, methyl methacrylate 1mL, benzoyl peroxide 0.45g obtain oil phase after mixed dissolution.Band reflux first is added in water phase
It in the three-necked flask of condenser, stirs and heats, after temperature rises to 60 DEG C, the modification of the surfaces 6g is slowly added under stirring
Powdery ion sieve (being modified through stearic acid alcohol solution dipping) afterwards, is then slowly added into oil phase.80 DEG C are to slowly warm up to, constant temperature
Polymerisation 3h；90 DEG C are then heated to, ball 1h is boiled.Filtering obtains the ion sieve sphere being granulated, and 2-3 is washed with 80 DEG C of hot water
Time, wash away Granular gelatin.Then particle is dried to obtain spherical granular ion sieve presoma at 60 DEG C, and spherical grain is obtained after pickling
Shape lithium ion sieve adsorbant.
The oil phase rate of recovery is 98%, and the powdery ion sieve rate of recovery is 100%.The granular lithium ion sieve adsorbant being prepared
For spherical shape, grain graininess is uniform, and 20-80 mesh particles account for 96%.
Embodiment 3
Sodium chloride 3g, polyvinyl alcohol 0.2g, gelatin 0.5g are weighed, is dissolved in 100mL pure water and is configured to water phase.Measure benzene second
Alkene 10mL, benzoyl peroxide 0.45g obtain oil phase after mixed dissolution.First water phase is added three mouthfuls of burnings with reflux condenser
In bottle, stirs and heat, after temperature rises to 70 DEG C, the modified powdery ion sieve in the surfaces 6g is slowly added under stirring
(being modified through stearic acid alcohol solution dipping), is then slowly added into oil phase.80 DEG C are to slowly warm up to, constant temperature polymerisation 3h；So
After be warming up to 90 DEG C, boil ball 1h.Filtering obtains the ion sieve sphere being granulated, and is washed 2-3 times with 80 DEG C of hot water, it is bright to wash away particle
Glue.Then particle is dried to obtain spherical granular ion sieve presoma at 60 DEG C, and the suction of spherical granular lithium ion sieve is obtained after pickling
Attached dose.
The oil phase rate of recovery is 97.5%, and the powdery ion sieve rate of recovery is 100%.The granular lithium ion sieve absorption being prepared
Agent is spherical shape, and grain graininess is uniform, and 20-80 mesh particles account for 83.5%.
Embodiment 4
Weigh NaOH 0.416g, MgCl2·6H2O 1.03g are dissolved in respectively in 250mL pure water, successively by NaOH solution and
MgCl2Solution is added in the three-necked flask with reflux condenser.Gelatin 2.5g, polyvinyl alcohol 0.45g are weighed, three-necked flask is added
In, stirring dissolves by heating.After being warming up to 75 DEG C, it is (molten through stearic acid ethyl alcohol to weigh the modified powdery lithium ion sieve in the surfaces 10g
Liquid, which impregnates, to be modified), it is slowly added in three-necked flask.Then the 50mL dissolved with 4.5g benzoyl peroxides is added into three-necked flask
Styrene adds 5ml methyl methacrylates.90 DEG C are continuously heating to after reaction 3h, spherical lithium has just been made after hardening 1h
Ion sieve precursor particle.Then particle is filtered, with being put into drying box (60 DEG C) after 80 DEG C of pure water 2-3 times
Spherical granular lithium ion sieve presoma is obtained after drying, and granular lithium ion sieve adsorbant is obtained through pickling.
The oil phase rate of recovery is 98%, and the powdery ion sieve rate of recovery is 100%.The granular lithium ion sieve adsorbant being prepared
For spherical shape, grain graininess is uniform, and the particle that the particle of 20-40 mesh accounts for 62%, 40-80 mesh accounts for 33.5%.
Fig. 3 and Fig. 4 is the photo for the granular lithium ion sieve adsorbant that embodiment 4 is prepared；Wherein Fig. 3 is that granularity is
The photo of the particle of 20-40 mesh, Fig. 4 are the photo for the particle that granularity is 40-80 mesh.It can be seen from the figure that particle is ball
Shape particle.
Comparative example 1
Weigh NaOH 0.1g, MgCl2·6H2O 0.25g are separately added into 50ml deionized water dissolvings, then this two solution is mixed
It closes；Gelatin 0.5g, polyvinyl alcohol 0.1g are weighed again, and it is in mixed liquor to be added above-mentioned, and heating for dissolving obtains water phase.Measure styrene
9mL, methyl methacrylate 1mL, benzoyl peroxide 0.45g obtain oil phase after mixed dissolution.Band reflux first is added in water phase
It in the three-necked flask of condenser, stirs and heats, after temperature rises to 60 DEG C, the unmodified places 6g are slowly added under stirring
The powdery ion sieve of reason (being modified without stearic acid alcohol solution dipping), is then slowly added into oil phase.80 DEG C are to slowly warm up to, perseverance
Temperature polymerization；Polymerisation 3h；90 DEG C are then heated to, ball 1h is boiled.Filtering obtains spherical polymer beads, with 80 DEG C of hot water
Washing 2-3 times, washes away Granular gelatin.Then particle is dried to obtain polymer beads at 60 DEG C.
When being granulated using the lithium ion sieve powder for not carrying out surface modification, obtained polymer beads are to be translucent
Spheric granules, only a small amount of powdery lithium ion sieve has been aggregated in spheric granules, most of to remain in water phase.Oil phase
The rate of recovery is 98%, and it is less than 15% that powdery ion sieve, which is granulated Percentage bound,.
Claims (10)
1. a kind of preparation method of spherical granular lithium ion sieve, which is characterized in that include the following steps：
Step (1)：Water phase is dissolved to obtain in dispersant and water mixing；
Step (2)：Surface modification treatment is carried out to powdery lithium ion sieve adsorbant, inorganic lithium ion sieve powder is made by modification
Body surface face has lipophile；
Modified powdery lithium ion sieve is added into the water phase of step (1), it includes monomer and initiator to be added after stirring heating
Oil phase carry out suspension polymerization；The monomer includes styrene；
Step (3)：After the completion of step (2) reaction, continue to heat up, spherical particle made from suspension polymerization is made to harden, hardening
Particle afterwards obtains ball-shaped lithium-ion sieve after washing, drying, pickling, washing and drying successively.
2. the preparation method of spherical granular lithium ion sieve as described in claim 1, which is characterized in that the monomer also includes
It is one or more in divinylbenzene, acrylonitrile, vinyl chloride, vinylidene chloride, methyl methacrylate.
3. the preparation method of spherical granular lithium ion sieve as claimed in claim 2, which is characterized in that in the monomer, benzene
The weight of ethylene is the 20-100% of total monomer weight.
4. the preparation method of spherical granular lithium ion sieve as claimed in claim 1 or 2, which is characterized in that the dispersant
Selected from sodium chloride, magnesium hydroxide, sodium hydroxide, magnesium chloride, potassium chloride, waterglass, calgon, gelatin, lignin sulfonic acid
At least one of sodium, polyvinyl alcohol, neopelex, calcium phosphate.
5. the preparation method of spherical granular lithium ion sieve as claimed in claim 4, which is characterized in that in water phase, dispersant and
The w/v of water is less than 10g/100mL.
6. the preparation method of spherical granular lithium ion sieve as described in claim 1, which is characterized in that in step (2), powdery from
The add weight and oil phase volume ratio of son sieve are 10-100g：100mL.
7. the preparation method of spherical granular lithium ion sieve as described in claim 1, which is characterized in that the initiator is even
Nitrogen class initiator and/or peroxide initiator.
8. the preparation method of spherical granular lithium ion sieve as described in claim 1, which is characterized in that in suspension polymerization,
Oil phase is 1~10 with water phase volume ratio：10.
9. the preparation method of spherical granular lithium ion sieve as described in claim 1, which is characterized in that in step (2), powder is added
It is warming up to after shape lithium ion sieve and adds the oil phase at 40 DEG C~75 DEG C, being warming up to 80 DEG C -85 DEG C after the completion of feeding intake is hanged
Floating polymerisation；The stir speed (S.S.) of suspension polymerization is 100-500r/min；Time is 1h-5h.
10. the preparation method of spherical granular lithium ion sieve as claimed in claim 9, which is characterized in that in step (3), suspend
After the completion of polymerization, 85 DEG C~100 DEG C are continuously heating to, cure process is carried out to spherical particle made from suspension polymerization；Firmly
Change processing time more than or equal to 0.5h.
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| CN108435143B (en) * | 2018-04-23 | 2020-11-13 | 陕西省膜分离技术研究院有限公司 | High-hydrophilicity adsorbent, preparation and application of adsorbent in adsorbing rubidium ions or lithium ions |
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