CN108525636A - A kind of adsorbent, preparation and the application adsorbed in lithium/rubidium of quick adsorption parsing - Google Patents
A kind of adsorbent, preparation and the application adsorbed in lithium/rubidium of quick adsorption parsing Download PDFInfo
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
- B01J20/041—Oxides or hydroxides
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- 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
- B01J20/0218—Compounds of Cr, Mo, W
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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
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
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Abstract
The invention discloses a kind of adsorbent of quick adsorption parsing, the applications for preparing and being adsorbed in lithium/rubidium, powder adsorbent is mixed with hydrophilic polymer and water, it is thick liquid-solid mixture to dissolve by heating, it is added dropwise in phase transformation agent with drops, spherical nascent state adsorbent is formed by solution inversion of phases；After nascent state adsorbent low-temperature reduced-pressure is dried, it is added to cross-linking reaction in the solution containing chemical cross-linking agent, obtains high-hydrophilic adsorbent.With method operating procedure provided by the present invention simplicity, low in raw material price is easy to get.The high-hydrophilic adsorbent of preparation, property are stablized, and molten loss rate is low, and absorption and parsing rate are fast.
Description
Technical field
The invention belongs to adsorbent preparing technical fields, and in particular to a kind of adsorbent of quick adsorption parsing, prepare and
In the application of lithium/rubidium absorption.
Background technology
Lithium metal and its compound play an increasingly important role in national economy and national defense construction, 80% or more
Lithium resource is stored in salt lake bittern and seawater, and therefore, the research that salt lake bittern extracts lithium has the utilization of lithium resource
There is great strategic significance.Ion sieve absorption method, which extracts lithium, has the spies such as stable circulation, high selectivity, adsorbance etc., at low cost
Point has become one of the method that lithium most industrial prospect is extracted in China's salt lake bittern.However since ion sieve adsorbant is more
For powder, mobility and permeability are poor, are directly used in ADSORPTION IN A FIXED BED extraction lithium there are certain difficulty, therefore ion sieve powder
The molding of body is to realize the ion sieve extraction industrialized key of lithium.
The hydrophobic polymers such as forming agent more PVC or PVDF in current ion sieve adsorbant, such hydrophobic polymerizable
On the one hand affinity is small between inorganic adsorbent powder for object, and powder is easy to fall off.On the other hand, moisture due to polymer hydrophobicity is strong
Son is not portable to enter adsorbent content by exchange ion, leads to the ion sieve or ion-exchanger of absorbent interior, Bu Nengyou
Effect is contacted with water phase and is exchanged so that the adsorbance of adsorbent is low, and the rate of adsorption and parsing rate are slower.Production effect is seriously affected
Rate.Therefore, how to be kept in forming process the performance of powder ion sieve have become be placed in ion sieve extraction lithium it is industrialized
Critical issue.
The method for preparing spherical lithium ion sieve adsorbent in the prior art is usually prepared by ball processed and crosslinking, but
The adsorbent that will appear in crosslinking cannot be repeatedly use, and the reaction process time is long.Such as " CN103212388A gel balls
Type rubidium/cesium ion adsorbent, preparation method and application " provide one kind using hydrophilic polymer such as alginic acid as embedding medium,
The forming technique for preparing rubidium ion adsorbent is prepared by calcium ion network in sodium alginate and calcium chloride solution and the precipitation method
It obtains.But decomplexing can occur after encountering strong acid or carbonate, sulfate radical due to calcium alginate, absorption prepared by this method
Agent, acid decomposition, therefore may not apply to parse the preparation of the lithium ion adsorbent of lithium by acid.Meanwhile prepared by this method
Rubidium ion adsorbent can not be applied to the solution containing carbonate or sulfate radical, as to carry lithium raffinate, lithium carbonate heavy for lepidolite stone
In shallow lake raffinate etc., rubidium or lithium ion are extracted.
Invention content
For the defect and deficiency of existing technology of preparing, the object of the present invention is to provide a kind of quick adsorption agent, preparation sides
Method and application for adsorbing rubidium ion or lithium ion, solve existing adsorbent absorption and resolution speed is slow, and adsorbance is low, absorption
Agent reuse in molten damage the problems such as.
To achieve the goals above, the present invention is realised by adopting the following technical scheme：
A kind of preparation method of quick adsorption agent mixes powder adsorbent with hydrophilic polymer and water, dissolves by heating
It for thick liquid-solid mixture, is added dropwise in phase transformation agent with drops, forming spherical nascent state by solution inversion of phases inhales
Attached dose；After nascent state adsorbent low-temperature reduced-pressure is dried, it is added to cross-linking reaction in the solution containing chemical cross-linking agent, is obtained fast
Fast adsorbent.
Optionally, the hydrophilic polymer is hydroxyethyl cellulose or sodium carboxymethylcellulose；
The powder adsorbent is lithium ion sieve or rubidium ion exchanger, wherein powder adsorbent and hydrophilic polymer
Mass ratio be 1~2/1, water-solid ratio be 100/20~50.
Optionally, the lithium ion sieve is LixMn3-xO4Manganese oxysome lithium ion sieve, wherein x=1.6,1.33 or 1；Institute
The rubidium ion exchanger stated is ammonium phosphomolybdate or tungsten ammonium molybdate.
Optionally, the organic solvent that the phase transformation agent can dissolve each other with water；The pressure of the described low-temperature reduced-pressure drying is
0.1MPa, temperature are 30~60 DEG C.
Optionally, the solution of the chemical cross-linking agent is the quality for the epoxychloropropane that mass concentration is 5%~10%
The temperature of a concentration of 10% sodium hydrate aqueous solution, cross-linking reaction is 30~60 DEG C.
A kind of adsorbent, preparation method of the adsorbent through the quick adsorption agent are prepared.
The adsorbent that the preparation method of the quick adsorption agent is prepared is for brine, seawater and rubidium mica miberal powder acid
The application of adsorbing and extracting lithium ion and/or rubidium ion in immersion liquid.
Optionally, the adsorbing and extracting lithium ion condition be pH=8~10 lithium-containing solution, analysis condition be 0.3~
The hydrochloric acid solution of 0.5mol/L.
Optionally, the absorption of the adsorbing and extracting rubidium ion is in neutral solution containing rubidium, and analysis condition is that mass concentration is
20% ammonium chloride solution.
Compared with prior art, the beneficial effects of the invention are as follows：
(1) powder shaped lithium ion sieve or rubidium ion exchanger being embedded using hydrophilic polymer the present invention provides a kind of
Method efficiently solves the problems, such as the molten damage of powdery lithium ion or rubidium ion sorbing material during absorption carries lithium or rubidium.
(2) lithium/rubidium ion adsorbent resulting product being prepared using hydrophilic polymer the present invention provides a kind of, effectively
It avoids in the prior art, ion sieve is coated by hydrophobic polymers such as PVC or PVDF, cause ion sieve effectively same
Ion exchange occurs for water phase contact, and the problem of influence the absorption property of adsorbent；
(3) hydroxyl in the alkaline solution and hydrophilic polymer chain provided by the invention using epoxychloropropane contracts
Reaction is closed, polyethers cross-linking reaction method is formed, can be stabilized in faintly acid or weakly alkaline solution, and be resistant to containing sulphur
The solution environmental of acid group, carbonate is widely portable to precipitate from seawater, brine, lepidolite stone acidleach raffinate and lithium carbonate
Lithium/rubidium ion is extracted in raffinate, produces strong applicability.
(4) adsorbent prepared by the method for the present invention makes because that can generate good hydrogen bond action with water containing the water-soluble of lithium/rubidium
Effectively with the adsorbent of absorbent interior ion exchange occurs for liquid energy, and therefore, the rate of adsorption is fast, and parsing rate is fast.It is a kind of high
Performance extracts the product of lithium, rubidium.
(5) simple production process of the present invention, operating condition are mild；Production efficiency is high, at low cost.For another example,
CN103316623A " a method of preparing spherical lithium ion sieve adsorbent " in, including：Polysaccharide and solvent are dissolved by heating
Mixing, then ion sieve presoma is added in solution, it is uniformly mixing to obtain viscous solution；By viscous solution at 50~100 DEG C
It instills in oil phase, obtains the solid spherical adsorbent that grain size is 2~5mm；Above-mentioned spherical adsorbent is placed in crosslinking agent, in 20
~80 DEG C of 10~30h of crosslinking, filtration washing obtain crosslinked spherical shape MnO2 absorbent particles；Absorbent particles are molten in de- lithium
It is eluted in agent, spherical lithium ion sieve adsorbent is finally made.It can be seen that selection in this preparation method is polysaccharide, reacted
Time length (10~30h of crosslinking) in journey, reaction temperature height " instilling oil phase at 50~100 DEG C ", and the method reaction of the present invention
Quickly (30min), and can complete inversion of phases process at normal temperatures illustrates the type, each for each raw material that the present invention selects
Proportion relation between reaction condition is all where creating point, and the adsorbent being prepared through the invention can not only be repeatedly
Crosslinking reuse, while also ensuring the efficient absorption of adsorbent, the process of adsorption and desorption is all fast quickly.
In addition, being given in " a kind of preparation methods of spherical granular lithium ion sieve of CN106084102A " including walking as follows
Suddenly：Step (1)：Water phase is dissolved to obtain in dispersant and water mixing；Step (2)：Powdery lithium ion is added into the water phase of step (1)
Sieve is added the oil phase comprising monomer and initiator after stirring heating and carries out suspension polymerization；The monomer includes styrene；
Step (3)：After the completion of step (2) reaction, continue to heat up, so that spherical particle made from suspension polymerization is hardened, after hardening
Particle obtains ball-shaped lithium-ion sieve after washing, drying, pickling, washing and drying successively.It can be seen that current molding ion sieve absorption
The hydrophobic polymers such as the more PVC, PVDF of forming agent, styrene in agent cause ion sieve that cannot effectively be contacted with water phase and exchange,
So that the rate of adsorption and adsorbance of adsorbent decline, and the powder embedded is easy to fall off.Therefore, how to be protected in forming process
Hold powder ion sieve performance have become be placed in ion sieve extraction the industrialized critical issue of lithium；The present invention is exactly based on original
The adsorbent that the adjustment of the factors such as material, dosage, preparation parameter is prepared has the function of the reuse of crosslinking repeatedly, ensures
The process of the efficient absorption of adsorbent, adsorption and desorption is all fast quickly.
One kind is given in " a kind of modified cellulose class adsorbents of CN102671634A and its preparation method and application " to change
Property Cellulose-based Adsorbents and its preparation method and application, include the following steps：(1) pre-treatment：Cellulosic material is washed
Only it, air-dries, be sliced, pulverization process；(2) it pre-processes：Lye-ultrasonication is carried out to cellulose powder；(3) it reacts：It is added
Epoxychloropropane reacts 1h under conditions of 100-110 DEG C of temperature, mixing speed 150-200r/min, then adds propylene
Acid the reaction was continued under the above-described reaction conditions 2-3h；(4) finished product：Then the feed liquid cooling after reaction is washed with water to solution
It is in neutrality, filters, dry to get target affinity agent.Preparation method disclosed in the document and the present invention are also different, and it is prepared
Be adsorbent using fibrous material as raw material, it is different from the technical problem to be solved in the present invention.
Description of the drawings
Attached drawing is for providing further understanding of the disclosure, and a part for constitution instruction, with following tool
Body embodiment is used to explain the disclosure together, but does not constitute the limitation to the disclosure.In the accompanying drawings：
The shape appearance figure for the adsorbent that Fig. 1 is prepared for embodiment 1,500 times of (a), (b) 1000 times；
The shape appearance figure for the adsorbent that Fig. 2 is prepared for embodiment 2,500 times of (a), (b) 1000 times；
The present invention is illustrated below in conjunction with specification drawings and specific embodiments.
Specific implementation mode
The invention discloses a kind of preparation methods of quick adsorption agent, specifically include：Powder adsorbent is (such as powdered
Lithium ion adsorbent or rubidium ion adsorbent) directly mixed with hydrophilic polymer, water, it is solid that heating for dissolving forms uniform liquid
Mixture, and instilled in phase transformation agent with drops, spherical nascent state adsorbent is formed by solution inversion of phases；By nascent state
Adsorbent, which is added in the alkaline solution of epoxychloropropane, carries out chemical crosslink reaction, obtains quick adsorption agent.
The quick adsorption agent that the present invention is prepared is mainly used for carrying lithium raffinate, carbonic acid from seawater, brine, lepidolite acidleach
Lithium precipitation carries lithium raffinate etc., adsorbing and extracting rubidium ion or lithium ion.
Specific embodiments of the present invention are given below, it should be noted that the invention is not limited in following specific examples
In, all equivalent transformations made on the basis of the technical solutions of the present application each falls within protection scope of the present invention.
Embodiment 1:
By 10g hydroxyethyl celluloses and 10g manganese systems lithium ion sieve adsorbant presomas Li1.6Mn1.6O4Mixing, then with 50g
Water is heated to stirring at 100 DEG C and forms uniformly sticky liquid solid solution, is extruded manually with syringe and is added dropwise to phase transformation agent four
In hydrogen tetrahydrofuran solution, becomes spherical solid particles after phase conversion reaction 3min, obtain the lithium ion spherical adsorbent of nascent state.
By the nascent state spherical adsorbent under 60 DEG C, 0.1MPa negative pressure after drying, it is added to the ring that mass concentration is 5%
In the sodium hydrate aqueous solution that the mass concentration of oxygen chloropropane is 10%, 30min is reacted in heating at 50 DEG C, is obtained after taking-up spherical
High-hydrophilic lithium ion adsorbent.
As shown in Figure 1, Fig. 1 (a) is the adsorbent surface shape appearance figure for amplifying 500 times, Fig. 1 (b) is the pattern of the adsorbent
The adsorbent surface shape appearance figure of 1000 times of amplification.
Separation and recovery by spherical lithium ion adsorbent obtained for lithium ion in brine.Various ions in practical brine
Content is：Li+A concentration of 200mg/L, Mg2+A concentration of 23g/L, K+A concentration of 15g/L, Na+A concentration of 110g/L is (wet with 3g
Weight, it is 0.615g that powder, which adsorbs agent content) spherical adsorbent, is adsorbed, efflux after 60min in the case where flow velocity is 2mL/min flow velocitys
In lithium content it is same with initial phase, show absorption reached balance, according to adsorb Mother liquor in Material calculation, obtain adsorbent
Average adsorption amount to lithium is 6.8mg/g (in terms of powder adsorbent mass).In the same stream of hydrochloric acid solution of 0.3mol/L
Under the conditions of speed, after parsing 30min, lithium ion has not been detected in efflux, shows that parsing has reached balance.Obtained desorbed solution
In K/Li ratios be 4/1, Na/Li ratios be 17/1, Mg/Li 6/1.Resolution factor is 92%.When the adsorbent is reused four times
The equilibrium adsorption capacity of lithium is still stablized in 6.5mg/g.
Embodiment 2:
By 10g sodium carboxymethylcelluloses and 10g manganese systems lithium ion sieve adsorbant presomas LiMn2O4Mixing, then with 50g water
It is heated to stirring at 80 DEG C and forms uniformly sticky liquid solid solution, extruded manually with syringe and be added dropwise to phase transformation agent tetrahydrochysene furan
It mutters in solution, becomes spherical solid particles after phase conversion reaction 3min, obtain the lithium ion spherical adsorbent of nascent state.
After drying, it is a concentration of to be added to mass volume ratio under 60 DEG C, 0.1MPa negative pressure for the nascent state spherical adsorbent
In 10% sodium hydrate aqueous solution of 5% epoxychloropropane, 60min is reacted in heating at 50 DEG C, and spherical height is obtained after taking-up
Hydrophily lithium ion adsorbent.
As shown in Fig. 2, Fig. 2 (a) is the adsorbent surface shape appearance figure for amplifying 500 times, Fig. 2 (b) is the pattern of the adsorbent
The adsorbent surface shape appearance figure of 1000 times of amplification.
Separation and recovery by spherical lithium ion adsorbent obtained for lithium ion in brine.Practical brine composition and example
1 is identical, and with 3g adsorbents (weight in wet base, it is 0.615g that powder, which adsorbs agent content) dress column, flow velocity is set as 2mL/min.120min inhales
It is attached up to after balance, according to the Material calculation in absorption Mother liquor, obtain adsorbent to the average adsorption amount of lithium be 4.6mg/g (with
Powder adsorbent mass meter).It is balanced, is surveyed under same flow conditions, parsing 120min reaches in the hydrochloric acid solution of 0.5mol/L
It is 90% to obtain resolution factor.The equilibrium adsorption capacity of lithium is stablized in 4.5mg/g when the adsorbent is reused four times.
Embodiment 3：
By 10g hydroxyethyl celluloses and 12.3g manganese systems lithium ion sieve adsorbant presomas Li4Mn5O12Mixing, with 50g water
It is heated to stirring at 100 DEG C and forms uniformly sticky liquid solid solution, extruded manually with syringe and be added dropwise to phase transformation agent tetrahydrochysene
Become spherical solid particles in tetrahydrofuran solution, after phase conversion reaction 30min after drying, to be added under 60 DEG C, 0.1MPa negative pressure
In the sodium hydrate aqueous solution that the mass concentration for the epoxychloropropane that mass concentration is 5% is 10%, heating is reacted at 40 DEG C
30min obtains spherical high-hydrophilic lithium ion adsorbent after taking-up.
Spherical lithium ion adsorbent obtained is taken into dress column (amount of filling out is 65g, and weight in wet base, it is 12.3g that powder, which adsorbs agent content),
Flow velocity is set as 2mL/min, is adsorbed with brine identical with example 1, up to balance, measuring adsorbance is for absorption after 4h
12mg/g (in terms of powder adsorbent mass).3h is parsed under the flow velocity of 3mL/min with 0.5M hydrochloric acid solutions, resolution factor reaches
92%, it reuses four times, adsorbance is stablized in 10mg/g or so.
The preferred embodiment of the disclosure is described in detail above in association with attached drawing, still, the disclosure is not limited to above-mentioned reality
The detail in mode is applied, in the range of the technology design of the disclosure, a variety of letters can be carried out to the technical solution of the disclosure
Monotropic type, these simple variants belong to the protection domain of the disclosure.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the disclosure to it is various can
The combination of energy no longer separately illustrates.
In addition, arbitrary combination can also be carried out between a variety of different embodiments of the disclosure, as long as it is without prejudice to originally
Disclosed thought equally should be considered as disclosure disclosure of that.
Claims (9)
1. a kind of preparation method of quick adsorption agent, which is characterized in that powder adsorbent is mixed with hydrophilic polymer and water,
It is thick liquid-solid mixture to dissolve by heating, and is added dropwise in phase transformation agent, is formed by solution inversion of phases spherical with drops
Nascent state adsorbent；After nascent state adsorbent low-temperature reduced-pressure is dried, it is added in the solution containing chemical cross-linking agent and is crosslinked instead
It answers, obtains quick adsorption agent.
2. the preparation method of quick adsorption agent as described in claim 1, which is characterized in that the hydrophilic polymer is hydroxyl
Ethyl cellulose or sodium carboxymethylcellulose；
The powder adsorbent is lithium ion sieve or rubidium ion exchanger, the wherein matter of powder adsorbent and hydrophilic polymer
For amount than being 1~2/1, water-solid ratio is 100/20~50.
3. the preparation method of quick adsorption agent as described in claim 1, which is characterized in that the lithium ion sieve is LixMn3- xO4Manganese oxysome lithium ion sieve, wherein x=1.6,1.33 or 1；The rubidium ion exchanger is ammonium phosphomolybdate or tungsten ammonium molybdate.
4. the preparation method of quick adsorption agent as described in claim 1, which is characterized in that the phase transformation agent can be mutually with water
Molten organic solvent；The pressure of the low-temperature reduced-pressure drying is 0.1MPa, and temperature is 30~60 DEG C.
5. the preparation method of quick adsorption agent as described in claim 1, which is characterized in that the solution of the chemical cross-linking agent
For mass concentration be 5%~10% epoxychloropropane mass concentration be 10% sodium hydrate aqueous solution, cross-linking reaction
Temperature is 30~60 DEG C.
6. a kind of adsorbent, which is characterized in that preparation side of the adsorbent through any quick adsorption agent of claim 1-5
Method is prepared.
7. the adsorbent that the preparation method of any quick adsorption agent of claim 1-5 is prepared is for brine, seawater
And in rubidium mica miberal powder pickle liquor adsorbing and extracting lithium ion and/or rubidium ion application.
8. application as claimed in claim 7, which is characterized in that the adsorbing and extracting lithium ion condition is pH=8~10
Lithium-containing solution, analysis condition be 0.3~0.5mol/L hydrochloric acid solution.
9. application as claimed in claim 7, which is characterized in that the absorption of the adsorbing and extracting rubidium ion is to contain rubidium in neutrality
Solution, analysis condition are the ammonium chloride solution that mass concentration is 20%.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110804120A (en) * | 2019-11-15 | 2020-02-18 | 四川大学 | Gel microsphere with ultrahigh cleaning capability on positively charged toxins and preparation method thereof |
| CN111085176A (en) * | 2018-10-23 | 2020-05-01 | 南京化学工业园环保产业协同创新有限公司 | Selective adsorbent and preparation method thereof |
| CN113509918A (en) * | 2020-11-25 | 2021-10-19 | 中国科学院青海盐湖研究所 | Preparation method of heteropolyacid salt ion sieve adsorbent particles for extracting liquid rubidium and cesium resources |
| CN115738892A (en) * | 2022-11-30 | 2023-03-07 | 中国科学院青海盐湖研究所 | Spherical combined lithium adsorbent and granulation method thereof |
| 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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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103316623A (en) * | 2013-07-10 | 2013-09-25 | 华东理工大学 | Method for preparing spherical lithium ion sieve adsorbent |
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2018
- 2018-04-23 CN CN201810368191.5A patent/CN108525636B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103316623A (en) * | 2013-07-10 | 2013-09-25 | 华东理工大学 | Method for preparing spherical lithium ion sieve adsorbent |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111085176A (en) * | 2018-10-23 | 2020-05-01 | 南京化学工业园环保产业协同创新有限公司 | Selective adsorbent and preparation method thereof |
| CN110804120A (en) * | 2019-11-15 | 2020-02-18 | 四川大学 | Gel microsphere with ultrahigh cleaning capability on positively charged toxins and preparation method thereof |
| CN110804120B (en) * | 2019-11-15 | 2021-02-26 | 四川大学 | Gel microsphere with ultrahigh cleaning capability on positively charged toxins and preparation method thereof |
| CN113509918A (en) * | 2020-11-25 | 2021-10-19 | 中国科学院青海盐湖研究所 | Preparation method of heteropolyacid salt ion sieve adsorbent particles for extracting liquid rubidium and cesium resources |
| CN115738892A (en) * | 2022-11-30 | 2023-03-07 | 中国科学院青海盐湖研究所 | Spherical combined lithium adsorbent and granulation method thereof |
| CN115738892B (en) * | 2022-11-30 | 2023-06-02 | 中国科学院青海盐湖研究所 | Spherical combined lithium adsorbent and granulating method thereof |
| 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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