CN106084102A - 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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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
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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
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
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Abstract
The invention discloses the preparation method of a kind of spherical granular lithium ion sieve, comprise the steps: step (1): dispersant and water mix, dissolve to obtain aqueous phase；Step (2): add powdery lithium ion sieve in the aqueous phase of step (1), stirring adds, after heating up, the oil phase comprising monomer and initiator and carries out suspension polymerization；Described monomer comprises styrene；Step (3): after step (2) has been reacted, continues to heat up, and makes the spherical particle hardening that suspension polymerization prepares, the granule after hardening successively through washing, be dried, pickling, washing and dried ball-shaped lithium-ion sieve.The spherical granular lithium ion sieve epigranular that the present invention prepares, intensity is high；The oil phase response rate is more than 95%, and the powdery ion sieve response rate is 100%.
Description
Technical field
The invention belongs to the preparation field of ion sieve adsorbent, be specifically related to the preparation side of a kind of spherical granular lithium ion sieve
Method.
Background technology
Lithium is the metal that a kind of electro-chemical activity is high, and application is extensive, lithium battery, controllable nuclear fusion reactor,
Aero-Space, glass, pottery, 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 the most exhausted, can not meet the market demand.And salt lake bittern, sea water, well halogen etc. are huge liquid lithium
Mineral reserve, in recent years, attach great importance to extraction lithium from these liquid ore deposits both at home and abroad, and the lithium salts having nearly 80% at present is that salt carries lithium
Product, comprehensive exploitation and utilize salt lithium resource to become the main flow of lithium industrial development.China western part has abundant salt lithium
Resource, but owing in the most of salt lake bittern of China, Li content is low, Mg/Li ratio is high, traditional " precipitation-crystallization process " is not appropriate for
Carrying lithium in this type of salt lake, and absorption method is a kind of effective ways extracting lithium from low concentration lithium-containing solution, 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, it being superfine powder, mobility and permeability the most poor, molten loss rate is higher, and when absorption-desorption, bed easily collapses
Collapse to such an extent as to complete block fluid, so being not used to industrialized production.Only prepare granular adsorbent, could realize inhaling
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 emphasis of this area scientist concern.
People also studied and take different methods, it is intended to be prepared as preparing granulated sorbent or membranaceous adsorbent.At present
Go out, report for powder body ion sieve adsorbent prilling process be broadly divided into two big classes: one is direct molding bonded,
Another kind is organic polymer molding.
The method that direct molding bonded produces granulated sorbent has: (1) utilizes polrvinyl chloride and ion sieve powder mixture
Dissolve with organic solvent (such as DMF or NMP), then instill molding in water and prepare granular ion sieve (CN101898113A)；(2) with
Water-soluble salt such as KCl is pore creating material, adds DMF or NMP, size mixing, be pressed in PVC, KCl and powdery ion sieve mixture
Lamellar, crushed after being dried becomes graininess, dissolves away KCl through water logging and is referred to as granular ion sieve adsorbant；(3) polysaccharide is added with solvent
Heat of solution mixes, then is added in solution by ion sieve presoma, is uniformly mixing to obtain viscous solution, then viscous solution is instilled stone
In the oil phases such as oil ether, obtain solid spherical adsorbent (CN103316623A) etc. that particle diameter is 2～5mm.
With having of organic polymer molding: (1) forms crosslinking polymer process with acrylic monomer inverse suspension polymerization
Middle lithium ion sieve powder body is coated on polymer in and obtain granular lithium ion sieve (CN 101955210A)；(2) with acrylamide
For polymerization forming monomer, ion sieve powder body is suspended in monomer solution, adds initiator and cross-linking agent, cause cross-linked polymeric anti-
Should, prepare pelletized polypropylene amide-lithium ion sieve (CN1511963).
The preparation method of these granular lithium ion sieve adsorbants reported at present also exists some as not enough in intensity, granularity difficulties
To control, or the granulated sorbent obtained is not spherical morphology, the poor fluidity of solution, and bed resistance is big, therefore, it is difficult to full
The requirement of foot industrial applications.
Summary of the invention
For solving the technical problem that existing lithium ion sieve intensity is not enough, exterior appearance is poor, the invention provides a kind of suspension
Polymerization prepares the method for spherical granular lithium ion sieve, the method prepare lithium ion sieve intensity height, epigranular, be suitable for work
The lithium adsorbent prilling process of industry production application.
The preparation method of a kind of spherical granular lithium ion sieve, comprises the steps:
Step (1): dispersant and water mix, dissolve to obtain aqueous phase；
Step (2): add modified powdery lithium ion sieve in the aqueous phase of step (1), stirring adds after heating up and comprises
The oil phase of monomer and initiator carries out suspension polymerization；Described monomer comprises styrene；
Step (3): after step (2) has been reacted, continues to heat up, and makes the spherical particle hardening that suspension polymerization prepares,
Granule after hardening successively through washing, be dried, pickling, washing and dried ball-shaped lithium-ion sieve.
In the present invention, by powdery lithium ion sieve bag during employing styrene monomer suspension polymerisation formation crosslinking polymer
Spherical granular lithium ion sieve is obtained in overlaying on polymer；Contribute to preparing product by styrene monomer and suspension polymerisation mode
Intensity height, epigranular, the ball-shaped lithium-ion sieve of good fluidity, beneficially industrialized repeatedly cycle applications, and the method
Reaction system is easily controlled, and oil phase and the powdery ion sieve response rate are high.
The feature of the present invention is exactly: during polymerizing styrene sill is polymerized, and allows lithium ion sieve powder body and organic
Thing copolymerization, forms granular lithium ion sieve adsorbant spherical, that intensity is high.The lithium ion sieve adsorbant prepared in this way
Granule is to have product strength height, epigranular, the sphere material of good fluidity.
In step (1), described dispersant is selected from sodium chloride, magnesium hydroxide, sodium hydroxide, magnesium chloride, potassium chloride, water glass
In glass, sodium hexameta phosphate, gelatin, sodium lignin sulfonate, polyvinyl alcohol, dodecylbenzene sodium sulfonate, calcium phosphate at least one.
As preferably, in aqueous phase, the w/v of dispersant and water is less than 10g/100mL water.
The aqueous phase of step (1) adds powdery lithium ion sieve after having prepared.
As preferably, powdery ion sieve add weight and oil phase volume ratio for 10-100g: 100mL.
Existing lithium ion sieve all can apply the inventive method to make spheroidal particle, and as preferably, described lithium ion screens
From LiMn2O4、Li4Mn5O12、Li1.6Mn1.6O4、Li2Mn3O7、Li4Mn5O12Or Li2TiO3。
Powdery ion sieve, before adding, first carries out surface modification treatment to powdery lithium ion sieve adsorbant.At modification
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.Described surfactant is but is not limited to coupling agent, fatty acid.
As preferably, described surfactant be silane coupler, titanate coupling agent, hexadecylic acid, palmate, ten
At least one in eight acid, octadecanoate.
Further preferably, described surfactant is stearic acid.
During surface modification treatment, powdery lithium ion sieve to be modified is soaked in stearic ethanol solution.Molten at this
In liquid, stearic concentration does not affect surface modification treatment effect.
Powdery lithium ion sieve after being processed on surface adds to the aqueous phase of step (1), under agitation heats up；Add subsequently
Oil phase, carries out suspension polymerization.
In suspension polymerization, oil phase and aqueous phase volume ratio are 1～10: 10.
In step (2), temperature when oil phase adds, stir speed (S.S.) in polymerization process and polymeric reaction temperature and monomer class
Types etc. all can affect intensity and the granularity of prepared spheroidal particle.
As preferably, in step (2), it is warming up at 40 DEG C～75 DEG C add described oil after adding powdery lithium ion sieve
Phase, is warming up to 80 DEG C-85 DEG C and carries out suspension polymerization after having fed intake；The stir speed (S.S.) of suspension polymerization is 100-
500r/min；Time is 1h-5h.
In the present invention, described oil phase comprises styrene monomer and initiator.
Existing oil-soluble initiator all can be as initiator of the present invention.
As preferably, described initiator is azo-initiator and/or peroxide initiator.
Azo-initiator has azodiisobutyronitrile (AIBN), 2,2'-Azobis(2,4-dimethylvaleronitrile) (ABVN) etc.；Peroxide initiator
For example, benzoyl peroxide, the benzoyl peroxide tert-butyl ester, methyl ethyl ketone peroxide etc..
Further preferably, described initiator be azodiisobutyronitrile, 2,2'-Azobis(2,4-dimethylvaleronitrile), azo dicyclohexyl formonitrile HCN,
In benzoyl peroxide at least one.
The weight ratio of initiator and monomer is 1%-8%.
In suspension polymerization, described monomer can be styrene single monomer；In order to improve suspension polymerisation system further
The intensity of ball-shaped lithium-ion sieve, particle size uniformity, described monomer is in addition to comprising styrene, and going back selectivity, to comprise other single
Body, such as alternative comprise other vinyl monomers, acrylic monomer.
As preferably, described monomer also comprises that divinylbenzene, propylene be fine, vinyl chloride, vinylidene chloride, methyl methacrylate
One or more in ester.
As preferably, in described monomer, cinnamic weight is the 20-100% of total monomer weight.
In the present invention, going back selectivity and comprise perforating agent in described oil phase, described perforating agent is selected from toluene, hexane, heptan
At least one in alkane, octane, normal heptane, 12 carbon alkane, fatty acid, polystyrene, polyvinylacetate.
Further preferably, in step (2), the temperature that adds of described oil phase is 40 DEG C～75 DEG C, carries out after having fed 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 suspension polymerisation completes, being continuously heating to 85 DEG C～100 DEG C, the spherical particle preparing suspension polymerization is carried out
Cure process；The cure process time is more than or equal to 0.5h.
In step (3), after cure process completes, filter, obtain spherical granular lithium ion sieve presoma, this spherical granular lithium
Ion sieve presoma sequentially passes through 80 DEG C of warm water washings, oven for drying, mordant pickling, wash and dry after obtain object i.e.
Spherical granular lithium ion sieve.
The granule of granularity 20-80 mesh of the lithium ion sieve prepared by the suspension polymerization of the present invention accounts for more than 95%,
Granule strength is high, mobility is preferable, can preferably recycle.
The spherical granular lithium ion sieve epigranular that the present invention prepares, intensity is high；The oil phase response rate be more than 95%, powdery from
The son sieve response rate is 100%.Additionally, this method technical process is simple, granulation time is short, production efficiency is high and with low cost.
Accompanying drawing explanation
Fig. 1 is the preparation technology flow chart of spherical granular lithium ion sieve of the present invention；
Fig. 2 is the SEM figure of the spherical granular lithium ion sieve particle surface that embodiment 1 prepares；
Fig. 3 is the spherical granular lithium ion sieve granule photo of the granularity 20-40 mesh that embodiment 4 prepares；
Fig. 4 is the spherical granular lithium ion sieve granule photo of the granularity 40-80 mesh that embodiment 4 prepares.
Detailed description of the invention
Following example are pressed aforesaid operations method and are implemented:
Technical scheme is described in detail by the specific embodiment below in conjunction with the present invention, certainly, is retouched
The embodiment stated is only a portion embodiment of the present invention rather than whole.
Following example prepare spherical granular lithium ion sieve by Fig. 1 preparation technology flow process.
Embodiment 1
Weigh sodium chloride 2.5g, polyvinyl alcohol 0.05g, gelatin 0.25g, be dissolved in 50mL pure water and be configured to aqueous phase.Measure
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 aqueous phase being added in the there-necked flask of band reflux condenser, stirring is to being completely dissolved；In stirring
It is slowly added to the powdery ion sieve after 5g surface modification (modified through stearic acid alcohol solution dipping) under state, begins to warm up, etc.
After temperature rises to 60 DEG C, add oil phase.It is to slowly warm up to 80 DEG C, constant temperature polyreaction 3h；Then heat to 90 DEG C, boil ball 2h.
Filter the ion sieve spheroid obtaining pelletize, with hot wash 2-3 time of 80 DEG C, wash away Granular gelatin.Then spheroid is placed in rope
In family name's extractor, remove the normal heptane in granule, before then granule is dried to obtain the spherical granular ion sieve of porous at 60 DEG C
Drive body.
Granular lithium ion sieve presoma is put in a certain amount of 0.5mol/l hydrochloric acid solution, low rate mixing at 30 DEG C, instead
Answer 1.5-2h, obtain spherical granular lithium ion sieve adsorbant.
The oil phase response rate is 95%, and the powdery ion sieve response rate is 100%.The granular lithium ion sieve adsorbant prepared
For spherical, grain graininess is uniform, and 20-80 mesh granule accounts for 95.5%.
Fig. 2 is the SEM photograph of the granular lithium ion sieve adsorbant that embodiment 1 prepares；Fig. 2 (a) part be this lithium from
Son sieve granule SEM photograph, it can be seen that granule is spheroidal particle；Fig. 2 (b) part is granule table after amplifying 1000 times
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 is separately added into 50ml deionized water dissolving, then is mixed by this two solution
Close；Weighing gelatin 0.5g, polyvinyl alcohol 0.1g again, adding above-mentioned is in mixed liquor, and heating for dissolving obtains aqueous phase.Measure styrene
9mL, methyl methacrylate 1mL, benzoyl peroxide 0.45g, obtain oil phase after mixed dissolution.First aqueous phase is added band backflow
In the there-necked flask of condenser, stir and heat, after temperature rises to 60 DEG C, under stirring, being slowly added to 6g surface modification
After powdery ion sieve (modified through stearic acid alcohol solution dipping), be then slowly added into oil phase.It is to slowly warm up to 80 DEG C, constant temperature
Polyreaction 3h；Then heat to 90 DEG C, boil ball 1h.Filter the ion sieve spheroid obtaining pelletize, with the hot wash 2-3 of 80 DEG C
Time, wash away Granular gelatin.Then granule is dried to obtain spherical granular ion sieve presoma at 60 DEG C, obtains spherical grain after pickling
Shape lithium ion sieve adsorbant.
The oil phase response rate is 98%, and the powdery ion sieve response rate is 100%.The granular lithium ion sieve adsorbant prepared
For spherical, grain graininess is uniform, and 20-80 mesh granule accounts for 96%.
Embodiment 3
Weigh sodium chloride 3g, polyvinyl alcohol 0.2g, gelatin 0.5g, be dissolved in 100mL pure water and be configured to aqueous phase.Measure benzene second
Alkene 10mL, benzoyl peroxide 0.45g, obtain oil phase after mixed dissolution.First aqueous phase is added three mouthfuls of burnings of band reflux condenser
In Ping, stir and heat, after temperature rises to 70 DEG C, under stirring, being slowly added to the powdery ion sieve after 6g surface modification
(modified through stearic acid alcohol solution dipping), is then slowly added into oil phase.It is to slowly warm up to 80 DEG C, constant temperature polyreaction 3h；So
After be warming up to 90 DEG C, boil ball 1h.Filter the ion sieve spheroid obtaining pelletize, with hot wash 2-3 time of 80 DEG C, wash away granule bright
Glue.Then granule is dried to obtain spherical granular ion sieve presoma at 60 DEG C, obtains spherical granular lithium ion sieve and inhale after pickling
Attached dose.
The oil phase response rate is 97.5%, and the powdery ion sieve response rate is 100%.The granular lithium ion sieve absorption prepared
Agent is spherical, and grain graininess is uniform, and 20-80 mesh granule accounts for 83.5%.
Embodiment 4
Weigh NaOH 0.416g, MgCl2·6H2O 1.03g is dissolved in 250mL pure water respectively, successively by NaOH solution and
MgCl2Solution adds in the there-necked flask of band reflux condenser.Weigh gelatin 2.5g, polyvinyl alcohol 0.45g, add there-necked flask
In, stirring, heating for dissolving.After being warming up to 75 DEG C, weigh the powdery lithium ion sieve after 10g surface modification (molten through stearic acid ethanol
Immersion bubble modification), it is slowly added in there-necked flask.Then in there-necked flask, add the 50mL dissolved with 4.5g benzoyl peroxide
Styrene, adds 5ml methyl methacrylate.It is continuously heating to 90 DEG C after reaction 3h, after hardening 1h, just prepares spherical lithium
Ion sieve precursor granule.Then granule is carried out sucking filtration, put in drying baker (60 DEG C) after pure water 2-3 time of 80 DEG C
Obtain spherical granular lithium ion sieve presoma after drying, obtain granular lithium ion sieve adsorbant through pickling.
The oil phase response rate is 98%, and the powdery ion sieve response rate is 100%.The granular lithium ion sieve adsorbant prepared
For spherical, grain graininess is uniform, and the granule of 20-40 mesh accounts for 62%, and the granule of 40-80 mesh accounts for 33.5%.
Fig. 3 and Fig. 4 is the photo of the granular lithium ion sieve adsorbant that embodiment 4 prepares；Wherein Fig. 3 is that granularity is
The photo of the granule of 20-40 mesh, Fig. 4 is the photo for the granule that granularity is 40-80 mesh.It can be seen that granule is ball
Shape granule.
Comparative example 1
Weigh NaOH 0.1g, MgCl2·6H2O 0.25g is separately added into 50ml deionized water dissolving, then is mixed by this two solution
Close；Weighing gelatin 0.5g, polyvinyl alcohol 0.1g again, adding above-mentioned is in mixed liquor, and heating for dissolving obtains aqueous phase.Measure styrene
9mL, methyl methacrylate 1mL, benzoyl peroxide 0.45g, obtain oil phase after mixed dissolution.First aqueous phase is added band backflow
In the there-necked flask of condenser, stir and heat, after temperature rises to 60 DEG C, under stirring, being slowly added to the unmodified place of 6g
The powdery ion sieve of reason (modified without stearic acid alcohol solution dipping), is then slowly added into oil phase.It is to slowly warm up to 80 DEG C, permanent
Temperature polymerization；Polyreaction 3h；Then heat to 90 DEG C, boil ball 1h.Filter and obtain spherical polymer beads, with the hot water of 80 DEG C
Wash 2-3 time, wash away Granular gelatin.Then granule is dried to obtain polymer beads at 60 DEG C.
When using the lithium ion sieve powder body not carrying out surface modification to carry out pelletize, the polymer beads obtained is for being translucent
Spheroidal particle, the most a small amount of powdery lithium ion sieve has been aggregated in spheroidal particle, and great majority remain in aqueous phase.Oil phase
The response rate is 98%, and powdery ion sieve pelletize combination rate is less than 15%.
Claims (10)
1. the preparation method of a spherical granular lithium ion sieve, it is characterised in that comprise the steps:
Step (1): dispersant and water mix, dissolve to obtain aqueous phase；
Step (2): add modified powdery lithium ion sieve in the aqueous phase of step (1), stirring adds after heating up and comprises monomer
Suspension polymerization is carried out with the oil phase of initiator；Described monomer comprises styrene；
Step (3): after step (2) has been reacted, continues to heat up, and makes the spherical particle hardening that suspension polymerization prepares, hardening
After granule successively through washing, be dried, pickling, washing and dried ball-shaped lithium-ion sieve.
2. the preparation method of spherical granular lithium ion sieve as claimed in claim 1, it is characterised in that described monomer also comprises
Divinylbenzene, propylene are fine, one or more in vinyl chloride, vinylidene chloride, methyl methacrylate.
3. the preparation method of spherical granular lithium ion sieve as claimed in claim 2, it is characterised in that in described 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, it is characterised in that described dispersant
Selected from sodium chloride, magnesium hydroxide, sodium hydroxide, magnesium chloride, potassium chloride, waterglass, sodium hexameta phosphate, gelatin, lignin sulfonic acid
In sodium, polyvinyl alcohol, dodecylbenzene sodium sulfonate, calcium phosphate at least one.
5. the preparation method of spherical granular lithium ion sieve as claimed in claim 4, it is characterised in that in aqueous phase, dispersant and
The w/v of water is less than 10g/100mL water.
6. the preparation method of spherical granular lithium ion sieve as claimed in claim 1, it is characterised in that in step (2), powdery from
What son sieved adds weight and oil phase volume ratio for 10-100g: 100mL.
7. the preparation method of spherical granular lithium ion sieve as claimed in claim 1, it is characterised in that described initiator is even
Nitrogen class initiator and/or peroxide initiator.
8. the preparation method of spherical granular lithium ion sieve as claimed in claim 1, it is characterised in that in suspension polymerization,
Oil phase and aqueous phase volume ratio are 1～10: 10.
9. the preparation method of spherical granular lithium ion sieve as claimed in claim 1, it is characterised in that in step (2), add powder
It is warming up to after shape lithium ion sieve at 40 DEG C～75 DEG C add described oil phase, is warming up to 80 DEG C-85 DEG C after having fed intake and hangs
Floating polyreaction；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, it is characterised in that in step (3), suspend
After being polymerized, being continuously heating to 85 DEG C～100 DEG C, the spherical particle preparing suspension polymerization carries out cure process；Firmly
Change processes the time more than or equal to 0.5h.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108435142A (en) * | 2018-04-23 | 2018-08-24 | 陕西省膜分离技术研究院有限公司 | A kind of granular ion crossover adsorbent, preparation and the application of absorption rubidium or lithium |
| CN108435143A (en) * | 2018-04-23 | 2018-08-24 | 陕西省膜分离技术研究院有限公司 | A kind of high-hydrophilic adsorbent, preparation and the application of absorption rubidium ion or lithium ion |
| CN116020397A (en) * | 2023-02-06 | 2023-04-28 | 湖南卓亚科技发展有限责任公司 | Preparation method of manganese-titanium composite lithium ion sieve adsorbent |
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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 |
| CN108435142B (en) * | 2018-04-23 | 2020-11-13 | 陕西省膜分离技术研究院有限公司 | Granular ion exchange type adsorbent, preparation and application of granular ion exchange type adsorbent in adsorbing rubidium or lithium |
| CN116020397A (en) * | 2023-02-06 | 2023-04-28 | 湖南卓亚科技发展有限责任公司 | Preparation method of manganese-titanium composite lithium ion sieve adsorbent |
| CN116020397B (en) * | 2023-02-06 | 2023-09-19 | 湖南卓亚科技发展有限责任公司 | Preparation method of manganese-titanium composite lithium ion sieve adsorbent |
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