CN1810353A - Method for preparing lithium ion sieve adsorbent - Google Patents
Method for preparing lithium ion sieve adsorbent Download PDFInfo
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- CN1810353A CN1810353A CNA2005101345147A CN200510134514A CN1810353A CN 1810353 A CN1810353 A CN 1810353A CN A2005101345147 A CNA2005101345147 A CN A2005101345147A CN 200510134514 A CN200510134514 A CN 200510134514A CN 1810353 A CN1810353 A CN 1810353A
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- lithium
- ammonia leaching
- leaching residue
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
A method for preparing a lithium ion sieve adsorbent relates to a method for preparing an adsorbent for adsorbing lithium from lithium-containing solutions such as salt lake brine, well brine, seawater and the like, in particular to a method for preparing the lithium ion sieve adsorbent by taking ocean polymetallic nodule ammonia leaching residue as a raw material. The method is characterized in that ocean polymetallic nodule ammonia leaching residue is used as a framework material to prepare the lithium ion sieve adsorbent, and the preparation process comprises the steps of firstly mixing the polymetallic nodule ammonia leaching residue with lithium salt; calcining the mixture to obtain an ionic sieve precursor; and then performing acid treatment on the precursor, converting the dissolved lithium precursor into an H-type ion sieve, and filtering, washing with water and drying the slurry to obtain the adsorbent with the sieving effect on the lithium ions. The method of the invention uses the ammonia leaching residue produced by reduction roasting of polymetallic nodule-ammonia leaching or catalytic reduction of cuprous ions and ammonia leaching to replace expensive manganese chemical reagent to prepare the adsorbent, the process is simple, the production cost is low, and the synthesized ion sieve adsorbent has good hydrophilicity and high adsorption speed.
Description
Technical field
A kind of method for preparing lithium ion sieve adsorbant, relate to a kind of being used for from the preparation of adsorbent method of lithium-containing solutions such as salt lake bittern, well halogen, seawater absorption lithium, particularly a kind of is the method for feedstock production lithium ion sieve adsorbant with the oceanic multi-metal nodule ammonia leaching residue.
Background technology
Lithium and application of compound field thereof are extensive, in lithium battery, controlled fusion reactor, ultralight high strength lithium-aluminium alloy, glass, pottery, medicine and other fields important use are arranged all, and the market demand increases rapidly.The reserves of lithium ore do not satisfy the market demand in the world, and solid lithium ore resources is day by day exhausted, and salt lake bittern, well halogen, seawater are huge liquid lithium mineral reserve, because it is simple relatively to extract lithium technology from the liquid ore deposit, attach great importance to extract lithium from liquid ore deposits such as salt lake bittern, seawater, well halogen both at home and abroad in recent years, liquid ore deposit progressively replaces the solid ore deposit becomes main lithium source.
The method of extracting lithium from salt lake bittern, seawater, well halogen etc. mainly contains the precipitation method, solvent extraction, ion exchange adsorption.Ion exchange adsorption is adsorbed on the exchanger lithium ion in the solution according to the principle of ion exchange absorbent to cation selective absorption, reaches separation and concentration lithium purpose, can obtain lithium salt solution after the desorb.Ion-exchange absorption is suitable for various lithium-containing solutions, be particularly suitable for extracting lithium bittern low from lithium content, that calcium-magnesium content is high and the seawater, have advantages such as flow process is simple, the rate of recovery is high, selectivity is good, technology cleaning, become from seawater, bittern and put forward promising scheme the lithium technology.The exchanger that adopts divides organic ion exchanger resin and inorganic ions exchange adsorbing substance, and usually, poor selectivity, the adsorbance of organic ion exchanger resin are little, and the inorganic ions exchange adsorbing substance has very high selectivity and higher adsorption capacity.
Inorganic ions exchange adsorbing substance commonly used mainly contains oxide, hydroxide, heteropolyacid salt and composite salt.Wherein the ion sieve oxide has ion sieve effect and lithium ion " memory " function, lithium in the solution had the special efficacy selectivity, and alkali metal such as the potassium, sodium, calcium, magnesium of coexistence and alkaline-earth metal ions are had good separating effect, become the most effective lithium adsorbent in seawater, the bittern.The lithium manganese oxide ion sieve is considered to one of best lithium adsorbent of absorption property and application prospect, is generally mixed by a certain percentage by lithium compound and manganese compound, makes after sintering, pickling, and manganese compound commonly used has MnOOH, MnCO
3, electrolytic manganese dioxide etc.From application point, so far, the inorganic ions exchange adsorbing substance of the better performances of development is all manually synthetic by the reagent of costliness, and cost height, production procedure are long.
Deep sea polymetallic nodule is distributed widely in the seabed surface deposition layer in each ocean, the world, and prognostic reserves reach 3 * 10
12T, only the Pacific Ocean just has 1.7 * 10
12T, but also, estimate that the annual new growth polymetallic nodules in the whole world reach 1 * 10 in continuous growth
7T, polymetallic nodules are rich in copper, nickel, cobalt, manganese, molybdenum etc., estimate that deep sea polymetallic nodule will become human important strategic metals resources of 21 century.Deep sea polymetallic nodule belongs to low grade oxidation ore, and copper, nickel, cobalt total content are generally less than 3%, slag that output is a large amount of in the development and use.Because the moisture height of polymetallic nodules, valuable metal grade are low, ore dressing can't enrichment, is suitable for hydrometallurgical process.Ammonia leaching process has to be selected to leach, leach the advantage that medicament can recycle, and is considered to promising polymetallic nodules smelting process, and typical ammonia soaking technology has reduction roasting-ammonia leaching, cuprous ion catalytic reduction ammonia to soak.The reduction roasting-ammonia leaching method is to make reducing agent with the coal gas that is rich in carbon monoxide, under 625 ℃ of conditions polymetallic nodules is carried out reduction roasting, leaches calcining with ammonia-sal volatile then, realizes that the selection of nickel, cobalt, copper is leached.It is in ammonia-ammonium salt solution medium that cuprous ion catalytic reduction ammonia soaks, and is that catalyst, carbon monoxide are reducing agent with the cuprous ion, and directly polymetallic nodules are leached in reduction.Soak in the process at above-mentioned ammonia, the manganese in the polymetallic nodules is not all leached, and stays in the leached mud with gangue and iron mineral, and therefore, ammonia leaching process is handled polymetallic nodules will produce a large amount of ammonia leaching residues, and the slag rate is up to 90%.A large amount of slags of output are simply stored up and are not only taken a large amount of land resources, and the inspection of the dimension in mine tailing storehouse take height, also can be to the environment structure potential threat.Realize the resource of polymetallic nodules leached mud, be not only environmental protection requirement, and help the comprehensive utilization value of resource.
Ammonia leaching residue contains the required manganese of preparation lithium ion sieve adsorbant, and, the specific area of ammonia leaching residue is big, contain a large amount of micropores, possess metal ion and embed required space and good ion-exchange absorption performance, can provide ion sieve to prepare required natural skeleton, for the preparation lithium ion sieve provides advantage.
Summary of the invention
Purpose of the present invention is exactly the deficiency that exists in the above-mentioned prior art in order to overcome, and provides that a kind of preparation cost is low, production procedure is short, can realize the method for preparing lithium ion sieve adsorbant of polymetallic nodules ammonia leaching residue comprehensive utilization.
The objective of the invention is to be achieved through the following technical solutions.
A kind of method for preparing lithium ion sieve adsorbant is characterized in that with the oceanic multi-metal nodule ammonia leaching residue being that framework material prepares lithium ion sieve adsorbant, its successively preparation process be:
(1) presses Li/Mn mol ratio 0.2～1.5, the oceanic multi-metal nodule ammonia leaching residue is mixed the mixture that obtains containing lithium with lithium salts;
(2) contain mixture heating and calcining 1h-24h under 200 ℃～800 ℃ temperature of lithium, obtain the ion sieve presoma;
(3) hydrochloric acid of usefulness 0.1M～2M or sulfuric acid solution are with the lithium stripping in the presoma, and presoma is transformed into H-type ion sieve, and the slip solvent and solute weight ratio of sour molten processing is 1～20: 1, pickling time 0.5h～4h;
(4) the good slurry filtration of acid treatment, and wash with water and remove in the filter cake remaining free acid, drying promptly obtains lithium ion is had the adsorbent of screening effect.
Method of the present invention is characterized in that said lithium salts is for being selected from LiOH, LiCl, LiNO
3, Li
2SO
4, Li
2CO
3In any.
Method of the present invention is characterized in that containing the mixture of lithium at 300 ℃～600 ℃ following calcining 1h～8h.
Method of the present invention is characterized in that with the hydrochloric acid of 0.1M～1M or the lithium in the sulfuric acid solution stripping presoma.
Method of the present invention when it is characterized in that the mixing of ammonia leaching residue and lithium salts, is by Li/Mn mol ratio 0.5～1, and ammonia leaching residue and solid lithium salts are mixed.
Method of the present invention when it is characterized in that the mixing of ammonia leaching residue and lithium salts, is with the lithium salts solution that contains lithium 1M～5M that is made into soluble in water, and ammonia leaching residue is soaked 1h～24h in lithium salt solution, makes its saturated absorption lithium, obtains containing the mixture of lithium after the filtration.
The raw material that the present invention uses soaks the ammonia leaching residue of output as polymetallic nodules reduction roasting-ammonia leaching or cuprous ion catalytic reduction ammonia, is applicable to that lithium salts of the present invention can be the solid or the solution of lithium chloride, lithium sulfate, lithium hydroxide, lithium nitrate, lithium carbonate.Mode by dry type or wet type, in ammonia leaching residue, allocate a certain amount of lithium into, the mixture that will contain lithium is then calcined 1h-24h down at 200 ℃～800 ℃, and manganese mineral in the ammonia leaching residue and lithium salts reaction form the lithium manganese oxide of spinel structure, are the ion sieve presoma; Handle presoma with the hydrochloric acid of 0.1M～2M or sulfuric acid solution, the lithium stripping in the presoma and be transformed into H-type ion sieve, acid-treated slip solvent and solute weight ratio is 1～20: 1, pickling time 0.5h～4h; Filter and wash with water and remove remaining free acid, drying obtains lithium ion sieve adsorbant.
In the method for the present invention, the batching mode of lithium salts and polymetallic nodules ammonia leaching residue can be the dry type batching, also can adopt the wet type batching.When adopting the dry type batching, be manganese grade,, lithium salts and ammonia leaching residue mixed according to lithium manganese mol ratio 0.2～1.5 according to the polymetallic nodules ammonia leaching residue.When adopting the wet type batching,, ammonia leaching residue is immersed in the lithium salt solution,, makes its absorption lithium that reaches capacity through 1h～12h with the lithium salts solution that contains lithium 1M～5M that is made into soluble in water.
At a certain temperature, manganese mineral and lithium salts reaction, form the lithium manganese oxide of spinel structure, by pickling lithium ion is deviate from then, formation has the adsorbent of memory function to " lithium ion ", this adsorbent has special efficacy to the lithium in the solution such as bittern, seawater and selects adsorptivity, and alkali metal such as the potassium of coexistence, sodium, calcium, magnesium and alkaline-earth metal ions are had good separating effect.The low generation that is unfavorable for lithium manganese oxide of temperature, but too high temperature not only increase synthetic energy consumption, and because the present invention is synthesis material with the leached mud, too high temperature can cause the porosity of adsorbent to reduce, and influences adsorption effect.
Method of the present invention, the ammonia leaching residue that soaks output with the reduction roasting-ammonia leaching or the cuprous ion catalytic reduction ammonia of polymetallic nodules replaces expensive manganese reagent as the raw material for preparing adsorbent, because leached mud has microcellular structure and high-ratio surface, preparation technology is simple, production cost is low, and synthetic ion sieve adsorbent good hydrophilic property, adsorption rate are fast.The efficient utilization and the cleaner production of the resource and the polymetallic nodules resource of polymetallic nodules ammonia leaching residues have been realized.
The specific embodiment
A kind of method for preparing lithium ion sieve adsorbant, with the oceanic multi-metal nodule ammonia leaching residue is that framework material prepares lithium ion sieve adsorbant, its successively preparation process be: (1) adopts the dry type mode, press Li/Mn mol ratio 0.2～1.5, the oceanic multi-metal nodule ammonia leaching residue is mixed the mixture that obtains containing lithium with lithium salts; Or employing wet type mode, the oceanic multi-metal nodule ammonia leaching residue is mixed with lithium salts,, the oceanic multi-metal nodule ammonia leaching residue is soaked 1h～24h in lithium salt solution the lithium salts solution that contains lithium 1M～5M that is made into soluble in water, make its saturated absorption lithium, obtain containing the mixture of lithium after the filtration; (2) contain mixture heating and calcining 1h～24h under 200 ℃～800 ℃ temperature of lithium, obtain the ion sieve presoma; (3) hydrochloric acid of usefulness 0.1M-2M or sulfuric acid solution are with the lithium stripping in the presoma, and presoma is transformed into H-type ion sieve, and the slip solvent and solute weight ratio of sour molten processing is 1～20: 1, pickling time 0.5h～4h; (4) the good slurry filtration of acid treatment, and wash with water and remove in the filter cake remaining free acid, drying promptly obtains lithium ion is had the adsorbent of screening effect.
With following non-limiting embodiment method of the present invention is further described, helping understanding content of the present invention and advantage thereof, and as the qualification to protection domain of the present invention, protection scope of the present invention is determined by claims.
Embodiment 1
Getting the polymetallic nodules ammonia leaching residue that 10g contains manganese 25.4%, is 0.5 to mix with lithium hydroxide by lithium manganese mol ratio, and this mixture is 350 ℃ of calcinings after 4 hours down, and with the hydrochloric acid solution pickling of 1M 3 hours, the solvent and solute weight ratio of pickling was 5: 1; Filter then, wash, drying, obtain the ion sieve adsorbent.
The adsorbent 5g for preparing is joined 125ml contain in the bittern of lithium 0.209g/L, PH7.1, after stirring 24 hours under 25 ℃, remaining lithium 0.045g/L in the bittern, the adsorbance of ion sieve is 4.1mg/g, adsorption rate is 78.5%.
Embodiment 2
Getting the polymetallic nodules ammonia leaching residue that 10g contains manganese 25.4%, is 1 to mix with lithium hydroxide by lithium manganese mol ratio, and this mixture is 300 ℃ of calcinings after 8 hours down, and with the hydrochloric acid solution pickling of 2M 0.5 hour, the solvent and solute weight ratio of pickling was 1: 1; Filter then, wash, drying, obtain the ion sieve adsorbent.
The adsorbent 5g for preparing is joined 100ml contain in the bittern of lithium 0.209g/L, PH8, after stirring 48 hours under 25 ℃, remaining lithium 0.02g/L in the bittern, the adsorbance of ion sieve is 3.8mg/g, adsorption rate is 90.4%.
Embodiment 3
Getting the polymetallic nodules ammonia leaching residue that 10g contains manganese 25.4%, is 1.5 to mix with lithium nitrate by lithium manganese mol ratio, and this mixture is 800 ℃ of calcinings after 1 hour down, and with the sulfuric acid solution pickling of 1M 4 hours, the solvent and solute weight ratio of pickling was 20: 1; Filter then, wash, drying, obtain the ion sieve adsorbent.
The adsorbent 5g for preparing is joined 125ml contain in the bittern of lithium 0.15g/L, PH8, after stirring 24 hours under 25 ℃, remaining lithium 0.015g/L in the bittern, the adsorbance of ion sieve is 3.4mg/g, adsorption rate is 90%.
Embodiment 4
Getting the polymetallic nodules ammonia leaching residue that 10g contains manganese 25.4%, is 0.2 to mix with lithium carbonate by lithium manganese mol ratio, and this mixture is 700 ℃ of calcinings after 4 hours down, and with the sulfuric acid solution pickling of 1M 4 hours, the solvent and solute weight ratio of pickling was 20: 1; Filter then, wash, drying, obtain the ion sieve adsorbent.
The adsorbent 5g for preparing is joined 125ml contain in the bittern of lithium 0.15g/L, PH8, after stirring 24 hours under 25 ℃, remaining lithium 0.014g/L in the bittern, the adsorbance of ion sieve is 3.4mg/g, adsorption rate is 90.7%.
Embodiment 5
Get the polymetallic nodules ammonia leaching residue that 10g contains manganese 25.4%, in the lithium chloride solution of 3M, soaked 24 hours, make the saturated absorption lithium of ammonia leaching residue, filter then; Filter cake moves in the electric furnace, descends calcining after 2 hours at 600 ℃, the hydrochloric acid solution pickling of usefulness 0.1M 1 hour, and the solvent and solute weight ratio of pickling is 10: 1; Filter then, wash, drying, obtain the ion sieve adsorbent.
The adsorbent 5g for preparing is joined 150ml contain in the bittern of lithium 0.2g/L, PH7, after stirring 24 hours under 25 ℃, remaining lithium 0.065g/L in the bittern, the adsorbance of ion sieve is 4.0mg/g, adsorption rate is 67.5%.
Embodiment 6
Get the polymetallic nodules ammonia leaching residue that 10g contains manganese 25.4%, in the lithium sulfate solution of 5M, soaked 1 hour, make the saturated absorption lithium of ammonia leaching residue, filter then; Filter cake moves in the electric furnace, descends calcining after 24 hours at 200 ℃, the hydrochloric acid solution pickling of usefulness 0.4M 1 hour, and the solvent and solute weight ratio of pickling is 10: 1; Filter then, wash, drying, obtain the ion sieve adsorbent.
The adsorbent 5g for preparing is joined 100ml contain in the bittern of lithium 0.23g/L, PH7, after stirring 24 hours under 25 ℃, remaining lithium 0.045g/L in the bittern, the adsorbance of ion sieve is 3.7mg/g, adsorption rate is 80.4%.
Embodiment 7
Get the polymetallic nodules ammonia leaching residue that 10g contains manganese 25.4%, in the 1M lithium hydroxide solution, soaked 24 hours, make the saturated absorption lithium of ammonia leaching residue, filter then; Filter cake moves in the electric furnace, descends calcining after 3 hours at 350 ℃, the hydrochloric acid solution pickling of usefulness 0.4M 1 hour, and the solvent and solute weight ratio of pickling is 10; Filter then, wash, drying, obtain the ion sieve adsorbent.
The adsorbent 5g for preparing is joined 100ml contain in the bittern of lithium 0.23g/L, PH6.4, after stirring 24 hours under 25 ℃, remaining lithium 0.069g/L in the bittern, the adsorbance of ion sieve is 3.2mg/g, adsorption rate is 70%.
Claims (7)
1. a method for preparing lithium ion sieve adsorbant is characterized in that with the oceanic multi-metal nodule ammonia leaching residue being that framework material prepares lithium ion sieve adsorbant, its successively preparation process be:
(1) with the oceanic multi-metal nodule ammonia leaching residue, press Li/Mn mol ratio 0.2～1.5, mix with lithium salts;
(2) contain mixture heating and calcining 1h～24h under 200 ℃～800 ℃ temperature of lithium, obtain the ion sieve presoma;
(3) hydrochloric acid of usefulness 0.1M～2M or sulfuric acid solution are with the lithium stripping in the presoma, and presoma is transformed into H-type ion sieve, and the slip solvent and solute weight ratio of sour molten processing is 1～20: 1, pickling time 0.5h～4h
(4) the good slurry filtration of acid treatment, and wash with water and remove in the filter cake remaining free acid, drying promptly obtains lithium ion is had the adsorbent of screening effect.
2. method according to claim 1 is characterized in that said lithium salts is for being selected from LiOH, LiCl, LiNO
3, Li
2SO
4, Li
2CO
3In any.
3. method according to claim 1 is characterized in that containing the mixture of lithium at 300 ℃～600 ℃ following calcining 1h～8h.
4. method according to claim 1 is characterized in that with the hydrochloric acid of 0.1M～1M or the lithium in the sulfuric acid solution stripping presoma.
5. method according to claim 3 is by Li/Mn mol ratio 0.5～1 when it is characterized in that the mixing of ammonia leaching residue and lithium salts, and ammonia leaching residue and solid lithium salts are mixed.
6. wet-mixing mode according to claim 3, when it is characterized in that the mixing of ammonia leaching residue and lithium salts, be, ammonia leaching residue is soaked 1h～24h in lithium salt solution the lithium salts solution that contains lithium 1M～5M that is made into soluble in water, make its saturated absorption lithium, obtain containing the lithium mixture after the filtration.
7. method according to claim 1 is characterized in that it being to adopt the reduction roasting-ammonia leaching or the cuprous ion catalytic reduction ammonia of polymetallic nodules to soak the ammonia leaching residue of output.
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Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101955210A (en) * | 2010-09-14 | 2011-01-26 | 华东理工大学 | Granular lithium ion sieve |
| CN101985098A (en) * | 2010-09-16 | 2011-03-16 | 中南大学 | Method for preparing manganese series lithium-ion sieve adsorbent H4Mn5O12 and precursor thereof |
| CN102049237A (en) * | 2010-11-19 | 2011-05-11 | 中南大学 | Iron phosphate ion sieve for selectively extracting Li and application thereof |
| CN102049238A (en) * | 2010-11-19 | 2011-05-11 | 中南大学 | Ion sieve for selectively extracting lithium and application thereof |
| CN102527320A (en) * | 2010-12-30 | 2012-07-04 | 浙江海洋学院 | Magnetic nano lithium ion sieve adsorbent and preparation method thereof |
| CN102935299A (en) * | 2012-09-29 | 2013-02-20 | 上海空间电源研究所 | Method for extracting lithium ions by manganese oxide adsorbing material |
| CN103045879A (en) * | 2011-10-11 | 2013-04-17 | 浙江海洋学院 | Method and device for extracting trace lithium ions in seawater on large scale |
| CN104689858A (en) * | 2013-12-10 | 2015-06-10 | 上海空间电源研究所 | Preparation method of lithium manganate ion sieve separation membrane |
| CN106311190A (en) * | 2016-08-18 | 2017-01-11 | 佛山科学技术学院 | Preparation method of porous manganese-based lithium ion sieve adsorbent |
| CN106756106A (en) * | 2017-01-04 | 2017-05-31 | 潍坊学院 | A kind of preparation method of zinc-base lithium ion extraction material |
| US10087083B2 (en) | 2015-01-28 | 2018-10-02 | Korea Institute Of Geoscience And Mineral Resources | Underwater holding-type lithium recovering apparatus and method thererof |
| CN109761250A (en) * | 2019-04-11 | 2019-05-17 | 天齐锂业资源循环技术研发(江苏)有限公司 | A method of lithium ion sieve is prepared using waste and old lithium ion battery |
| CN110479228A (en) * | 2019-08-16 | 2019-11-22 | 黄冈师范学院 | A kind of regeneration method of the ion-sieve type manganese systems adsorbent of failure |
| CN115532219A (en) * | 2022-08-30 | 2022-12-30 | 上海交通大学 | Salt lake lithium extraction adsorbent based on garnet type solid electrolyte powder and preparation and application thereof |
| CN115595455A (en) * | 2021-06-28 | 2023-01-13 | 中石化南京化工研究院有限公司（Cn） | System and method for extracting lithium from low-grade brine and application |
| CN116282061A (en) * | 2023-02-10 | 2023-06-23 | 中国地质大学（北京） | Method for preparing lithium ion sieve from nepheline |
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2005
- 2005-12-15 CN CNA2005101345147A patent/CN1810353A/en active Pending
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| CN101955210A (en) * | 2010-09-14 | 2011-01-26 | 华东理工大学 | Granular lithium ion sieve |
| CN101985098A (en) * | 2010-09-16 | 2011-03-16 | 中南大学 | Method for preparing manganese series lithium-ion sieve adsorbent H4Mn5O12 and precursor thereof |
| CN102049237A (en) * | 2010-11-19 | 2011-05-11 | 中南大学 | Iron phosphate ion sieve for selectively extracting Li and application thereof |
| CN102049238A (en) * | 2010-11-19 | 2011-05-11 | 中南大学 | Ion sieve for selectively extracting lithium and application thereof |
| CN102049238B (en) * | 2010-11-19 | 2012-08-15 | 中南大学 | Ion sieve for selectively extracting lithium and application thereof |
| CN102527320B (en) * | 2010-12-30 | 2014-03-12 | 浙江海洋学院 | Magnetic nano lithium ion sieve adsorbent and preparation method thereof |
| CN102527320A (en) * | 2010-12-30 | 2012-07-04 | 浙江海洋学院 | Magnetic nano lithium ion sieve adsorbent and preparation method thereof |
| CN103045879B (en) * | 2011-10-11 | 2014-06-25 | 浙江海洋学院 | Method and device for extracting trace lithium ions in seawater on large scale |
| CN103045879A (en) * | 2011-10-11 | 2013-04-17 | 浙江海洋学院 | Method and device for extracting trace lithium ions in seawater on large scale |
| CN102935299B (en) * | 2012-09-29 | 2015-09-30 | 上海空间电源研究所 | A kind of method using manganese oxide sorbing material to extract lithium ion |
| CN102935299A (en) * | 2012-09-29 | 2013-02-20 | 上海空间电源研究所 | Method for extracting lithium ions by manganese oxide adsorbing material |
| CN104689858A (en) * | 2013-12-10 | 2015-06-10 | 上海空间电源研究所 | Preparation method of lithium manganate ion sieve separation membrane |
| US10087083B2 (en) | 2015-01-28 | 2018-10-02 | Korea Institute Of Geoscience And Mineral Resources | Underwater holding-type lithium recovering apparatus and method thererof |
| CN106311190A (en) * | 2016-08-18 | 2017-01-11 | 佛山科学技术学院 | Preparation method of porous manganese-based lithium ion sieve adsorbent |
| CN106311190B (en) * | 2016-08-18 | 2018-11-23 | 佛山科学技术学院 | The preparation method of porous manganese systems lithium ion sieve adsorbant |
| CN106756106A (en) * | 2017-01-04 | 2017-05-31 | 潍坊学院 | A kind of preparation method of zinc-base lithium ion extraction material |
| CN106756106B (en) * | 2017-01-04 | 2019-02-22 | 潍坊学院 | A kind of preparation method of zinc-base lithium ion extraction material |
| CN109761250A (en) * | 2019-04-11 | 2019-05-17 | 天齐锂业资源循环技术研发(江苏)有限公司 | A method of lithium ion sieve is prepared using waste and old lithium ion battery |
| CN110479228A (en) * | 2019-08-16 | 2019-11-22 | 黄冈师范学院 | A kind of regeneration method of the ion-sieve type manganese systems adsorbent of failure |
| CN115595455A (en) * | 2021-06-28 | 2023-01-13 | 中石化南京化工研究院有限公司（Cn） | System and method for extracting lithium from low-grade brine and application |
| CN115595455B (en) * | 2021-06-28 | 2023-12-19 | 中国石油化工股份有限公司 | System and method for extracting lithium from low-grade brine and application |
| CN115532219A (en) * | 2022-08-30 | 2022-12-30 | 上海交通大学 | Salt lake lithium extraction adsorbent based on garnet type solid electrolyte powder and preparation and application thereof |
| CN115532219B (en) * | 2022-08-30 | 2024-03-22 | 上海交通大学 | Salt lake lithium extraction adsorbent based on garnet type solid electrolyte powder and preparation and application thereof |
| CN116282061A (en) * | 2023-02-10 | 2023-06-23 | 中国地质大学（北京） | Method for preparing lithium ion sieve from nepheline |
| CN116282061B (en) * | 2023-02-10 | 2023-11-24 | 中国地质大学（北京） | Method for preparing lithium ion sieve from nepheline |
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