CN117258744A - Granular lithium adsorbent and preparation method and application thereof - Google Patents
Granular lithium adsorbent and preparation method and application thereof Download PDFInfo
- Publication number
- CN117258744A CN117258744A CN202210675632.2A CN202210675632A CN117258744A CN 117258744 A CN117258744 A CN 117258744A CN 202210675632 A CN202210675632 A CN 202210675632A CN 117258744 A CN117258744 A CN 117258744A
- Authority
- CN
- China
- Prior art keywords
- lithium
- mixture
- adsorbent
- solvent
- ion sieve
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003463 adsorbent Substances 0.000 title claims abstract description 116
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 88
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 88
- 238000002360 preparation method Methods 0.000 title abstract description 17
- 239000000203 mixture Substances 0.000 claims abstract description 78
- 239000002904 solvent Substances 0.000 claims abstract description 67
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 50
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 50
- 238000000034 method Methods 0.000 claims abstract description 48
- 238000001179 sorption measurement Methods 0.000 claims abstract description 47
- 239000007788 liquid Substances 0.000 claims abstract description 24
- 229920000642 polymer Polymers 0.000 claims abstract description 24
- 230000008569 process Effects 0.000 claims abstract description 20
- 238000002156 mixing Methods 0.000 claims abstract description 15
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 23
- 239000012267 brine Substances 0.000 claims description 20
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims description 20
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 14
- 229910052719 titanium Inorganic materials 0.000 claims description 14
- 239000010936 titanium Substances 0.000 claims description 14
- 238000000498 ball milling Methods 0.000 claims description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 235000002639 sodium chloride Nutrition 0.000 claims description 12
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 11
- 238000000605 extraction Methods 0.000 claims description 10
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 10
- 238000011282 treatment Methods 0.000 claims description 10
- 235000019441 ethanol Nutrition 0.000 claims description 8
- -1 polyethylene Polymers 0.000 claims description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 239000002033 PVDF binder Substances 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 6
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- 239000002270 dispersing agent Substances 0.000 claims description 6
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 6
- 150000007522 mineralic acids Chemical class 0.000 claims description 6
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 6
- 229920001223 polyethylene glycol Polymers 0.000 claims description 6
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 6
- 239000004800 polyvinyl chloride Substances 0.000 claims description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 6
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- 239000004695 Polyether sulfone Substances 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 4
- 239000004743 Polypropylene Substances 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 238000002386 leaching Methods 0.000 claims description 4
- 229920006393 polyether sulfone Polymers 0.000 claims description 4
- 229920000573 polyethylene Polymers 0.000 claims description 4
- 229920001155 polypropylene Polymers 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- 239000013535 sea water Substances 0.000 claims description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 4
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 3
- 239000001103 potassium chloride Substances 0.000 claims description 3
- 235000011164 potassium chloride Nutrition 0.000 claims description 3
- 235000010333 potassium nitrate Nutrition 0.000 claims description 3
- 239000004323 potassium nitrate Substances 0.000 claims description 3
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 3
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 3
- 235000011151 potassium sulphates Nutrition 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- 239000002910 solid waste Substances 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- 235000010344 sodium nitrate Nutrition 0.000 claims description 2
- 239000004317 sodium nitrate Substances 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 235000011152 sodium sulphate Nutrition 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims 1
- 239000002245 particle Substances 0.000 description 25
- 238000000889 atomisation Methods 0.000 description 23
- 238000005191 phase separation Methods 0.000 description 18
- 239000007787 solid Substances 0.000 description 16
- 238000001035 drying Methods 0.000 description 13
- 238000002474 experimental method Methods 0.000 description 13
- 238000000227 grinding Methods 0.000 description 13
- 230000002572 peristaltic effect Effects 0.000 description 11
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 229910001220 stainless steel Inorganic materials 0.000 description 10
- 239000010935 stainless steel Substances 0.000 description 10
- 239000011363 dried mixture Substances 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- DUEPRVBVGDRKAG-UHFFFAOYSA-N carbofuran Chemical compound CNC(=O)OC1=CC=CC2=C1OC(C)(C)C2 DUEPRVBVGDRKAG-UHFFFAOYSA-N 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 238000004364 calculation method Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- 239000008240 homogeneous mixture Substances 0.000 description 2
- GCICAPWZNUIIDV-UHFFFAOYSA-N lithium magnesium Chemical compound [Li].[Mg] GCICAPWZNUIIDV-UHFFFAOYSA-N 0.000 description 2
- 239000003595 mist Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 229910013553 LiNO Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000004378 air conditioning Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000005008 domestic process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000010438 granite Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- LPUQAYUQRXPFSQ-DFWYDOINSA-M monosodium L-glutamate Chemical compound [Na+].[O-]C(=O)[C@@H](N)CCC(O)=O LPUQAYUQRXPFSQ-DFWYDOINSA-M 0.000 description 1
- 239000004223 monosodium glutamate Substances 0.000 description 1
- 235000013923 monosodium glutamate Nutrition 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- 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
- B01J20/04—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
-
- 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
- B01J20/04—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
-
- 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
- B01J20/04—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
- B01J20/043—Carbonates or bicarbonates, e.g. limestone, dolomite, aragonite
-
- 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
- B01J20/04—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
- B01J20/046—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 containing halogens, e.g. halides
-
- 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
- B01J20/28—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
- B01J20/28016—Particle form
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention relates to a granular lithium adsorbent, and a preparation method and application thereof. The method comprises the following steps: s1, mixing a polymer, a pore-forming agent and a first solvent to obtain a first mixture; s2, mixing the first mixture with a lithium ion sieve adsorbent to obtain a second mixture; s3, enabling the second mixture to be in contact with a second solvent under the atmosphere of atomized liquid drops, and obtaining the mixture containing the granular lithium adsorbent. The method has simple process and easy operation, and can improve the adsorption capacity and the adsorption rate of the granular lithium adsorbent.
Description
Technical Field
The invention belongs to the technical field of lithium extraction, and particularly relates to a granular lithium adsorbent and a preparation method thereof.
Background
Lithium is the metal with the smallest density in nature, and is widely applied to the fields of energy, electrons, medical treatment, aviation and the like at present, and is known as industrial monosodium glutamate.
Lithium resources in nature are mainly present in sea water, salt lake brine, granite pegmatite deposits and geothermal water. Therefore, the lithium extraction process is mainly divided into two methods of extracting lithium from brine and extracting lithium from ores. Since the beginning of the 20 th century, ore extraction of lithium is the main method for extracting lithium resources, and high-quality ore sources are almost exhausted through long-term and accumulated mining. The salt lake brine has abundant lithium resources, simple lithium extraction process and lower cost, so the current brine lithium extraction process becomes the mainstream research process.
Although China is a large country of lithium resources, china is also a large country of lithium consumption. Most of domestic salt lake brine has the characteristics of low lithium content and high magnesium-lithium ratio, and great difficulty is brought to the extraction of lithium from the salt lake brine. The current domestic method for extracting lithium from salt lake mainly comprises an adsorption method, a precipitation method, an extraction method, a membrane separation method and the like, wherein the adsorption method is simple in process, energy-saving and environment-friendly, low in cost, suitable for separating and extracting lithium ions from salt lake brine with high magnesium-lithium ratio, and wide in application prospect. The key point of the adsorption method for extracting lithium is to prepare the adsorbent with high selectivity and high adsorption capacity, which mainly comprises an ion sieve adsorbent and an aluminum adsorbent. However, since these adsorbents are all in powder state after synthesis, they cannot be directly applied to conventional equipment such as fixed bed for adsorption-desorption lithium extraction. Therefore, the development of the granular porous adsorbent with commercial application value has important significance for the development of future lithium resources.
Disclosure of Invention
In view of the above background, the present invention aims to solve at least one of the disadvantages of the prior art, in order to overcome the problems of poor permeability and fluidity of the powdery lithium ion adsorbent and small pores of the existing granular adsorbent. For example, one of the objects of the present invention is to provide a method for preparing a granular lithium adsorbent, which has a simple process and easy operation, and can increase the adsorption capacity and adsorption rate of the granular lithium adsorbent. For another example, another object of the present invention is to provide a granular lithium adsorbent corresponding to the above preparation method, where the granular lithium adsorbent has high strength and good toughness, and is not easy to break and pulverize when being loaded into an adsorption tower.
In order to achieve the above object, a first aspect of the present invention provides a method for preparing a granular lithium adsorbent, comprising the steps of:
s1, mixing a polymer, a pore-forming agent and a first solvent to obtain a first mixture;
s2, mixing the first mixture with a lithium ion sieve adsorbent to obtain a second mixture;
s3, enabling the second mixture to be in contact with a second solvent under the atmosphere of atomized liquid drops, and obtaining the mixture containing the granular lithium adsorbent.
In some embodiments of the invention, the polymer is selected from one or more of polyethylene, polypropylene, polyacrylonitrile, polyvinylidene fluoride, polyvinyl alcohol, polyvinyl chloride, polyethylene glycol, and polyethersulfone.
In some embodiments of the invention, the pore-forming agent is selected from one or more of sodium chloride, potassium chloride, sodium sulfate, potassium sulfate, sodium nitrate, and potassium nitrate.
In some embodiments of the invention, the first solvent is selected from one or more of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide and tetrahydrofuran.
In the present invention, the materials defined for the polymer, pore-forming agent and first solvent are all commercially available via the carbofuran technology. It will be appreciated that other sources of raw materials from which the particulate lithium adsorbent of the present invention can be made are also suitable.
In some embodiments of the invention, the mass ratio of the polymer to the first solvent is (0.01 to 5): 1, preferably (0.1 to 1): 1.
In some embodiments of the invention, the mass ratio of the pore former to the first solvent is (0.05 to 0.3): 1, preferably (0.1 to 0.2): 1.
In some embodiments of the invention, when the lithium ion sieve adsorbent is added in step S2, the mass ratio of the lithium ion sieve adsorbent to the first organic solvent is (0.1 to 1): 1, preferably (0.2 to 0.5): 1.
According to the invention, in both step S1 and step S2, the temperature at which the mixing is carried out may be between 10 and 100 ℃.
In some embodiments of the invention, the atomized droplet atmosphere is formed by a poor solvent for the polymer; preferably, the poor solvent is one or both of water and ethanol.
According to the present invention, the atomized droplet atmosphere may be formed by a cold mist humidifier or an ultrasonic humidifier.
In some embodiments of the invention, the second solvent is a poor solvent for the polymer; preferably, the second solvent is one or more of water, ethanol, propanol, ethylene glycol and acetone.
In some embodiments of the invention, the mass ratio of the second mixture to the second solvent is (0.01 to 0.3): 1, preferably (0.10 to 0.15): 1.
In some embodiments of the invention, in step S3, the contacting is by dropping the second mixture into the second solvent; preferably, the rate of addition is 0.1 to 1.0ml/min, i.e., 3 to 30 drops/min. The dropping speed defined by the invention can lead the second mixture to be contacted with the second solvent in the form of liquid drops and to be subjected to non-solvent induced phase separation, and ensures that the second mixture is contacted with atomized liquid drops for 2-20 seconds in the processes of condensation and dropping out of the tail end of the hose.
The above-mentioned non-solvent phase separation of the present invention means that the atomized second mixture contains the first solvent, the first solvent in the formed granular adsorbent is not removed, and at this time, the granular adsorbent is placed in a reagent which is more miscible with the first solvent therein and is a poor solvent for the polymer, the first solvent is extracted, the solvent remaining in the granular adsorbent is removed, and the granular adsorbent is solidified.
According to the invention, the second mixture may be added dropwise to the second solvent by means of a peristaltic pump. Wherein the peristaltic pump has a flow rate of 0.1-1 ml/min, preferably 0.18-0.25 ml/min, and the contact time between the second mixture and the atomized liquid drops in the coagulation and dripping process is 2-20 s; the inner diameter of the hose used for the peristaltic pump is 1.6 or 2.4mm, preferably 1.6mm; the second mixture is added dropwise into the second solvent for non-solvent induced phase separation for 30 min-4 h, preferably 30 min-1 h.
In the present invention, the non-solvent induced phase separation time is the time of dropping the second mixture droplets into the second solvent (i.e., poor solvent of the polymer) to remove the first solvent and solidify after the second mixture droplets are contacted with the atomized droplets, i.e., the time of immersing the atomized pretreated second mixture in the second solvent.
In the invention, the time for atomization pretreatment is the time when a certain droplet of the second mixture is contacted with atomized droplets in the process of starting to agglomerate and drop out at the tail end of a peristaltic pump hose. In the present invention, the consumption of atomized droplets was 20g/h.
According to the present invention, the poor solvent of the polymer means a solvent having weak dissolving ability for the polymer solute, and having an interaction parameter with the polymer solute close to or greater than 0.5.
In the invention, after the second mixture is contacted with the second solvent (for example, the second mixture is dripped into the second solvent) in the atomized liquid drop atmosphere in the step S3, the pores on the surface of the granular adsorbent can be effectively enlarged, the lithium ion sieve wrapped by the polymer is fully exposed, the specific surface area of the adsorbent is increased, and the granular adsorbent is ensured to have higher adsorption capacity and adsorption rate. In the atomized liquid drop atmosphere, the second mixture liquid drop fully contacts with the atomized liquid drop in the dropping process, and holes are formed on the surface of the adsorbent, so that the specific surface area is further increased. And taking out the granular matters subjected to non-solvent induced phase separation in the second solvent, and drying (such as 20-60 ℃) to obtain the granular lithium adsorbent.
According to the invention, the particle size of the granular lithium adsorbent obtained by the preparation method is uniform, and the average particle size can be about 4 mm. It is understood that the particle size of the particulate lithium adsorbent is not limited thereto.
The principle of the preparation method is that the lithium ion sieve adsorbent is mixed with the first mixture to obtain a second mixture, the second mixture is dripped into a second solvent (poor solvent of the polymer) under an atomization atmosphere to perform non-solvent induced phase separation to remove the first solvent and solidify the particle adsorbent, so as to obtain the granular lithium adsorbent.
According to the preparation method, an atomization pretreatment process is added on the basis of a traditional granulation process, and the peristaltic pump is used for controlling the flow rate and further controlling the atomization time in the dripping process, so that the surface adsorbent sites of the prepared granular lithium adsorbent are exposed, the specific surface area is increased, the hydrophilicity is enhanced, and the adsorption capacity and the adsorption rate of the prepared granular lithium adsorbent can be improved.
In some embodiments of the invention, a method of preparing the lithium ion sieve adsorbent comprises the steps of:
A. ball milling is carried out on a titanium source, a lithium source and a dispersing agent to obtain a ball-milled mixture;
B. roasting the mixture after ball milling to obtain a lithium ion sieve adsorbent precursor;
C. and leaching the precursor of the lithium ion sieve adsorbent by using an inorganic acid solution to obtain the lithium ion sieve adsorbent.
In some embodiments of the invention, the titanium source is selected from one or more of anatase titanium dioxide, rutile titanium dioxide, and titanium platelet titanium dioxide.
According to the present invention, anatase titania, rutile titania and titanium dioxide platelet are commercially available through the carboline technology.
In some embodiments of the invention, the lithium source is selected from one or more of lithium nitrate, lithium carbonate, lithium acetate, lithium chloride, and lithium hydroxide.
According to the invention, lithium nitrate, lithium carbonate, lithium acetate, lithium chloride and lithium hydroxide are all commercially available by the carbofuran technology.
In some embodiments of the invention, the dispersant is selected from one or more of ethanol and acetone.
In some embodiments of the invention, the molar ratio of titanium in the titanium source to lithium in the lithium source is 1 (2-2.5), preferably 1 (2-2.125).
In some embodiments of the invention, the mass ratio of the dispersant to the total mass of the titanium source and the lithium source is (1-4): 1, preferably (1-2): 1.
According to the present invention, the ball milling treatment of step A may be performed in a ball milling pot in which stainless steel balls are placed. The diameter of the stainless steel balls used is 1-5 mm, preferably 3.5mm. The mass of the stainless steel balls placed in the ball milling tank is 10-40 times, preferably 20 times, the total mass of the titanium source and the lithium source.
In some embodiments of the present invention, the conditions under which the ball milling process is performed in step a include: the rotation speed of the ball milling is 200-400 rpm, preferably 300rpm; the ball milling time is 1 to 8 hours, preferably 4 to 5 hours.
In the present invention, after the ball milling treatment of step a is completed, the resultant ball milled mixture may be subjected to a drying treatment at a temperature of 10 to 100 c, preferably 40 to 60 c. And (C) drying the ball-milled mixture, and then roasting in the step (B).
In some embodiments of the invention, the conditions under which the firing process is performed include: the roasting temperature is 600-900 ℃ and the roasting time is 3-8 h.
According to the invention, the roasting treatment is carried out in air atmosphere, and the lithium ion sieve adsorbent precursor Li is obtained after the roasting is completed 2 TiO 3 。
In some embodiments of the invention, the mineral acid solution is selected from one or more of hydrochloric acid solution, sulfuric acid solution and nitric acid solution, preferably hydrochloric acid solution; preferably, the molar concentration of the inorganic acid solution is 0.1 to 1mol/L, preferably 0.2 to 0.5mol/L.
According to the invention, the lithium in the lithium ion sieve adsorbent precursor is leached by using an inorganic acid solution to finish leachingAfter the treatment, filtering, washing, drying and grinding treatment can be carried out to obtain the powdery lithium ion sieve adsorbent H 2 TiO 3 。
In the present invention, the filtration, washing, drying and grinding treatments are not particularly limited, and may be determined by those skilled in the art according to the actual circumstances.
In a second aspect the present invention provides a particulate lithium adsorbent prepared by a process as described in the first aspect above.
According to the invention, the obtained granular lithium adsorbent takes the polymer as a binder, and the lithium adsorbent powder is molded and granulated to obtain the granular lithium adsorbent with uniform particle size, and the average particle size can be controlled to be about 4 mm.
In a third aspect, the present invention provides an application of the granular lithium adsorbent prepared by the method according to the first aspect in lithium extraction, especially in adsorption of salt lake brine, seawater, geothermal water and solid waste leaching liquor.
Compared with the prior art, the invention has at least one of the following beneficial effects:
(1) According to the preparation method provided by the invention, an atomization pretreatment process is added on the basis of a traditional granulation process, so that the surface adsorbent sites of the prepared granular lithium adsorbent are exposed, the specific surface area is increased, the hydrophilicity is enhanced, and the adsorption capacity and adsorption rate of the prepared granular lithium adsorbent can be improved;
(2) The preparation method provided by the invention has the advantages of simple preparation process, low cost and little environmental pollution, and is suitable for industrial application;
(3) The granular lithium adsorbent prepared by the preparation method has high particle strength, good toughness, uniform particle size and stable performance, and is loaded into an adsorption column for multiple (more than 15 times) adsorption-desorption cycles without crushing and pulverization;
(4) The granular lithium adsorbent prepared by the preparation method is suitable for adsorbing lithium in lithium-containing solutions such as salt lake brine, seawater, geothermal water, solid waste leaching solution and the like, and has uniform particle size and stable performance.
Drawings
The invention will be described in further detail with reference to the accompanying drawings.
FIG. 1 is a particulate porous lithium adsorbent prepared in example 1.
FIG. 2 is a surface morphology of the granular porous lithium adsorbent prepared in example 1.
FIG. 3 is a graph showing the adsorption capacity of the granular porous lithium adsorbent prepared in example 1 according to the number of cycles.
Detailed Description
In order that the invention may be more readily understood, the invention will be described in detail below with reference to the following examples and the accompanying drawings, which are given by way of illustration only and are not limiting the scope of application of the invention.
The granular porous lithium adsorbent prepared by the invention is used for lithium adsorption, and the adsorption capacity is an important parameter for evaluating the lithium adsorption material. An important index for measuring the adsorption performance of the adsorbent is the adsorption capacity Q, namely the mass of the granular porous lithium adsorbent for adsorbing lithium ions from a solution when the adsorption reaches an equilibrium, and the calculation formula is as follows:
wherein: q is the adsorption capacity at a certain temperature, unit: mg/g; c (C) 0 And C is the concentration of the solution at the time of ion initiation and adsorption saturation, respectively, in mg/L; v is the volume of adsorption solution, unit: l is; m is the mass of the granular adsorbent, and the unit is: g.
the time t of atomization pretreatment can be controlled by adjusting the flow rate of a peristaltic pump, and the calculation formula is as follows:
wherein: t is the atomization pretreatment time of each mixture droplet, and the unit is s; v is the flow rate of the peristaltic pump in units of: ml/min; r is the radius of the drop of the second mixture in units of: cm.
In the examples below, the chemicals used were all commercially available products, and no particular purification treatment was carried out unless stated separately. Wherein the weight average molecular weight of the polyethylene, the polypropylene, the polyacrylonitrile, the polyvinylidene fluoride, the polyvinyl alcohol, the polyvinyl chloride, the polyethylene glycol and the polyethersulfone is 4000-120000g/mol, and the polyethylene, the polypropylene, the polyacrylonitrile, the polyvinylidene fluoride, the polyvinyl alcohol, the polyvinyl chloride, the polyethylene glycol and the polyethersulfone are commercially available through the carbofuran technology or the enokava technology. In the examples described below, the polyvinyl chloride (product number: 189588; brand: aldrich), polyvinylidene fluoride (product number: 427144; brand: aldrich), polyacrylonitrile (product number: 226749; brand: J & K), polyethylene glycol (product number: 939758; brand: J & K) were all purchased in the carbofuran technology.
In the following examples, simulated brines were prepared from lithium chloride and magnesium chloride, wherein Li + The concentration is 0.15g/L, mg 2+ The concentration was 4g/L and the pH of the simulated brine was adjusted to 9.5 using ammonia water and ammonium chloride.
Example 1
Preparation of lithium ion sieve adsorbent:
weighing anatase TiO according to the mol ratio of 1:1.05 2 And Li (lithium) 2 CO 3 Adding the mixture into a stainless steel ball grinding tank, adding ethanol which is 2 times of the solid mass and stainless steel balls which are 3.5mm and are 20 times of the solid mass into the ball grinding tank, ball-milling the mixture for 4 hours at a speed of 200rpm by using a planetary ball mill, drying the mixture at 40 ℃, then placing the mixture into a muffle furnace, and roasting the mixture for 6 hours in an air atmosphere at 800 ℃; and (3) eluting with 0.5mol/L HCl for 24 hours after cooling to obtain the lithium ion sieve.
Atomizing pretreatment to obtain a granular lithium adsorbent:
mixing and dissolving polyvinyl chloride, N-methylpyrrolidone and sodium chloride according to a mass ratio of 2:10:1 to obtain a polymer solution; adding a lithium ion sieve accounting for 30% of the mass percentage of the N-methyl pyrrolidone, and uniformly mixing to obtain a uniform mixture; adding deionized water into an ultrasonic humidifier to prepare an atomization atmosphere (the consumption of atomization liquid drops is 20 g/h), dropwise adding the uniform mixture into the deionized water under the atomization liquid drop atmosphere by using a peristaltic pump provided with a hose with the inner diameter of 1.6mm (the mass ratio of the deionized water to the uniform mixture is 10:1) to perform non-solvent induced phase separation to form solid particles, wherein the flow rate of the uniform mixture in the hose is 0.2ml/min, the atomization time of the mixture liquid drops is about 10 seconds, and the non-solvent induced phase separation time is 30 minutes; and after the non-solvent phase separation is finished, taking out the solid particles, and drying at 40 ℃ to obtain the granular lithium adsorbent A1 with the particle size of about 4 mm.
The adsorption experiment of lithium ions in simulated brine was performed using the obtained granular lithium adsorbent A1, and the results are shown in table 1.
Example 2
Preparation of lithium ion sieve adsorbent:
weighing rutile type TiO according to the mol ratio of 1:2 2 And LiNO 3 Adding the mixture into a stainless steel ball grinding tank, adding acetone which is 2.5 times of the solid mass and stainless steel balls which are 4mm of the solid mass into a ball grinding tank, ball-milling the mixture for 4 hours at a speed of 300rpm by using a planetary ball mill, drying the mixture at 40 ℃, putting the dried mixture into a muffle furnace, roasting the dried mixture for 6 hours in an air atmosphere at 750 ℃, cooling the dried mixture, and eluting the dried mixture by using 0.5mol/L HCl for 24 hours to obtain the lithium ion sieve adsorbent.
Atomizing pretreatment to obtain a granular lithium adsorbent:
mixing and dissolving polyvinylidene fluoride, N-N dimethylformamide and potassium chloride according to a mass ratio of 2.5:10:0.5 to obtain a polymer solution; adding a lithium ion sieve adsorbent accounting for 28% of the mass percentage of the N-N dimethylformamide, and uniformly mixing to obtain a uniform mixture; adding deionized water into an ultrasonic humidifier to prepare an atomized liquid drop atmosphere (the consumption of atomized liquid drops is 20 g/h), dropwise adding the uniform mixture into the deionized water (the mass ratio of the deionized water to the uniform mixture is 10:1) under the atomized liquid drop atmosphere by using a peristaltic pump provided with a hose with the inner diameter of 1.6mm to perform non-solvent induced phase separation to form solid particles, wherein the flow rate of the uniform mixture in the hose is 0.4ml/min, the atomization time of the mixture liquid drops is about 5 seconds, and the non-solvent induced phase separation time is 30min; and after the non-solvent induced phase separation process is finished, taking out the solid particles, and drying at 40 ℃ to obtain the granular lithium adsorbent A2 with the particle size of about 4 mm.
The adsorption experiment of lithium ions in simulated brine was performed using the obtained granular lithium adsorbent A2, and the results are shown in table 1.
Example 3
Preparation of lithium ion sieve adsorbent:
weighing titanium plate TiO according to a molar ratio of 1:2 2 And LiCl, adding the mixture into a stainless steel ball grinding tank, adding ethanol which is 2 times of the solid mass and stainless steel balls which are 2.5mm of the solid mass into a ball grinding tank, ball-grinding the mixture for 3 hours at a speed of 300rpm by using a planetary ball mill, drying the mixture at 40 ℃, putting the dried mixture into a muffle furnace, roasting the dried mixture for 7 hours in an air atmosphere at 800 ℃, and eluting the dried mixture for 24 hours by using 0.2mol/L HCl to obtain the lithium ion sieve adsorbent.
Atomizing pretreatment to obtain a granular lithium adsorbent:
mixing and dissolving polyacrylonitrile, N-N dimethylacetamide and potassium sulfate according to a mass ratio of 2:10:1 to obtain a polymer solution; adding a lithium ion sieve adsorbent accounting for 30% of the mass percentage of the N-N dimethylacetamide, and uniformly mixing to obtain a uniform mixture; adding deionized water into an ultrasonic humidifier to prepare an atomized liquid drop atmosphere (the consumption of atomized liquid drops is 20 g/h), and dropwise adding the uniform mixture into absolute ethyl alcohol (the mass ratio of the absolute ethyl alcohol to the uniform mixture is 10:1) in the atomized liquid drop atmosphere by using a peristaltic pump with a hose with the inner diameter of 2.4mm to perform non-solvent induced phase separation to form solid particles; wherein the flow rate of the uniform mixture in the hose is 0.2ml/min, the atomization time of the mixture liquid drops is about 10 seconds, and the time of non-solvent induced phase separation is 30min; and after the non-solvent induced phase separation process is finished, taking out the solid particles, and drying at 40 ℃ to obtain the granular lithium adsorbent A3 with the particle size of about 4 mm.
The adsorption experiment of lithium ions in simulated brine was performed with the obtained granular lithium adsorbent A3, and the results are shown in table 1.
Example 4
Preparation of lithium ion sieve adsorbent:
weighing rutile TiO according to the mol ratio of 1:2.1 2 And LiOH, adding into a stainless steel ball grinding tank, adding acetone 1.5 times the solid mass and ball-grinding steel balls 4mm 25 times the solid mass into a ball-grinding tank, ball-grinding for 3 hours at 400rpm by using a planetary ball mill, drying at 50 ℃, putting into a muffle furnace, and air-conditioning at 850 DEG CRoasting for 6 hours in atmosphere, cooling, and eluting for 24 hours by using 0.1mol/L HCl to obtain a lithium ion sieve adsorbent;
atomizing pretreatment to obtain a granular lithium adsorbent:
mixing and dissolving polyethylene glycol, N-N dimethylacetamide and potassium nitrate according to a mass ratio of 2:10:1 to obtain a polymer solution; adding a lithium ion sieve adsorbent accounting for 28% of the mass percentage of the N-N dimethylacetamide, and uniformly mixing to obtain a uniform mixture; adding deionized water into a cold mist humidifier to prepare an atomized liquid drop atmosphere (the consumption of atomized liquid drops is 20 g/h), and dropwise adding the uniform mixture into the deionized water (the mass ratio of the deionized water to the uniform mixture is 10:1) under the atomized liquid drop atmosphere by using a peristaltic pump with a hose with the inner diameter of 1.6mm to perform non-solvent induced phase separation to form solid particles; wherein the flow rate of the uniform mixture in the hose is 0.2ml/min; the atomization time of the mixture droplets is about 10 seconds, and the time of non-solvent induced phase separation is 30 minutes; and after the non-solvent induced phase separation process is finished, taking out the solid particles, and drying at 40 ℃ to obtain the granular lithium adsorbent A4 with the particle size of about 4 mm.
The adsorption experiment of lithium ions in simulated brine was performed using the obtained granular lithium adsorbent A4, and the results are shown in table 1.
Example 5
The procedure was the same as in example 1 except that the flow rate of the uniform mixture in the hose was set to 0.4ml/min, the atomization time of the mixture droplets was about 5 seconds, and a lithium ion sieve adsorbent A5 having a particle diameter of about 4mm was obtained. The obtained lithium ion sieve adsorbent was used for simulating the adsorption experiment of lithium ions in brine, and the adsorption experiment results are shown in table 1.
Example 6
The procedure of example 1 was repeated except that the flow rate of the uniform mixture in the hose was set to 0.7ml/min and the atomization time of the mixture droplets was about 3 seconds, to obtain a lithium ion sieve adsorbent A6 having a particle diameter of about 4 mm. The obtained lithium ion sieve adsorbent was used for simulating the adsorption experiment of lithium ions in brine, and the adsorption experiment results are shown in table 1.
Comparative example 1
Except that the atomization pretreatment was not performed, the procedure was the same as in example 1, to obtain a lithium ion sieve adsorbent B1 having a particle diameter of about 4 mm. The obtained lithium ion sieve adsorbent was used for simulating the adsorption experiment of lithium ions in brine, and the adsorption experiment results are shown in table 1.
Comparative example 2
Except that the atomization pretreatment was not performed, the procedure was the same as in example 2, to obtain a lithium ion sieve adsorbent B2 having a particle diameter of about 4 mm. An adsorption experiment simulating lithium ions in brine was performed with the obtained lithium ion sieve adsorbent B2, and the adsorption experiment results are shown in table 1.
The adsorbent products prepared in examples 1-4 and comparative examples 1-2 were put into simulated brine for adsorption experiments, and the adsorption capacity Q was calculated according to the adsorption capacity calculation formula, and the results are shown in Table 1.
According to table 1, comparing the adsorption performance results of the adsorbent products A1 and B1 and the adsorbent products A2 and B2, it can be seen that the adsorption effect of the granular ion adsorbent without atomization pretreatment is poor, and the adsorption effect of lithium after atomization is significantly increased; comparing the adsorbent products A1, A5 and A6, it can be seen that the adsorption effect of the particulate ion adsorbent increases stepwise as the flow rate of the homogeneous mixture is lower, i.e. the atomization pretreatment time increases.
The adsorbent products prepared in examples 1 to 4 and comparative examples 1 to 2 were tested for specific surface area and the results are shown in Table 2.
From table 2, the specific surface area test results of the comparative adsorbent products A1 and B1 and the adsorbent products A2 and B2 show that the specific surface area of the granular ion adsorbent without the atomization pretreatment is smaller, and the specific surface area of the granular ion adsorbent after the atomization is greatly improved. It can be seen by comparing the specific surface areas of A1, A5, A6 that the specific surface area is greater as the flow rate of the homogeneous mixture is lower, i.e. the atomizing pretreatment time is longer.
It should be noted that the above-described embodiments are only for explaining the present invention and do not constitute any limitation of the present invention. The invention has been described with reference to exemplary embodiments, but it is understood that the words which have been used are words of description and illustration, rather than words of limitation. Modifications may be made to the invention as defined in the appended claims, and the invention may be modified without departing from the scope and spirit of the invention. Although the invention is described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, as the invention extends to all other means and applications which perform the same function.
Claims (12)
1. A method of preparing a particulate lithium adsorbent comprising the steps of:
s1, mixing a polymer, a pore-forming agent and a first solvent to obtain a first mixture;
s2, mixing the first mixture with a lithium ion sieve adsorbent to obtain a second mixture;
s3, contacting the second mixture with a second solvent under the atmosphere of atomized liquid drops to obtain a mixture containing the granular lithium adsorbent,
wherein the polymer is selected from one or more of polyethylene, polypropylene, polyacrylonitrile, polyvinylidene fluoride, polyvinyl alcohol, polyvinyl chloride, polyethylene glycol and polyethersulfone.
2. The method of claim 1, wherein the pore-forming agent is selected from one or more of sodium chloride, potassium chloride, sodium sulfate, potassium sulfate, sodium nitrate, and potassium nitrate; and/or
The first solvent is selected from one or more of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide and tetrahydrofuran.
3. The method according to claim 1 or 2, characterized in that the mass ratio of the polymer to the first solvent is (0.01-5): 1, preferably (0.1-1): 1; and/or
The mass ratio of the pore-forming agent to the first solvent is (0.05-0.3) 1, preferably (0.1-0.2) 1; and/or
The mass ratio of the lithium ion sieve adsorbent to the first solvent is (0.1-1): 1, preferably (0.2-0.5): 1.
4. A method according to any one of claims 1-3, wherein the atomized droplet atmosphere is formed by a poor solvent for the polymer; preferably, the poor solvent is one or both of water and ethanol; and/or
The second solvent is a poor solvent for the polymer; preferably, the second solvent is one or more of water, ethanol, propanol, ethylene glycol and acetone.
5. The method according to any one of claims 1 to 4, wherein the mass ratio of the second mixture to the second solvent is (0.01 to 0.3): 1, preferably (0.10 to 0.15): 1.
6. The method of any one of claims 1-5, wherein the contacting is by dropping the second mixture into the second solvent; preferably, the dropping speed is 0.1 to 1.0ml/min.
7. The method of any one of claims 1-6, wherein the method of preparing the lithium ion sieve adsorbent comprises the steps of:
A. ball milling is carried out on a titanium source, a lithium source and a dispersing agent to obtain a ball-milled mixture;
B. roasting the mixture after ball milling to obtain a lithium ion sieve adsorbent precursor;
C. and leaching the precursor of the lithium ion sieve adsorbent by using an inorganic acid solution to obtain the lithium ion sieve adsorbent.
8. The method of claim 7, wherein the titanium source is selected from one or more of anatase titanium dioxide, rutile titanium dioxide, and titanium platelet titanium dioxide; and/or
The lithium source is selected from one or more of lithium nitrate, lithium carbonate, lithium acetate, lithium chloride and lithium hydroxide; and/or
The dispersing agent is selected from one or more of ethanol and acetone.
9. The method according to claim 7 or 8, characterized in that the molar ratio of titanium in the titanium source to lithium in the lithium source is 1 (2-2.5), preferably 1 (2-2.125); and/or
The mass ratio of the dispersant to the total mass of the titanium source and the lithium source is (1-4): 1, preferably (1-2): 1.
10. The method according to any one of claims 7 to 9, wherein the conditions under which the calcination treatment is performed include: the roasting temperature is 600-900 ℃ and the roasting time is 3-8 h; and/or
The inorganic acid solution is selected from one or more of hydrochloric acid solution, sulfuric acid solution and nitric acid solution, preferably hydrochloric acid solution; preferably, the molar concentration of the inorganic acid solution is 0.1 to 1mol/L, preferably 0.2 to 0.5mol/L.
11. A particulate lithium adsorbent prepared by the method of any one of claims 1-10.
12. Use of a particulate lithium adsorbent prepared by a process according to any one of claims 1 to 10 in lithium extraction, in particular in adsorption of salt lake brine, seawater, geothermal water, solid waste leachate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210675632.2A CN117258744A (en) | 2022-06-15 | 2022-06-15 | Granular lithium adsorbent and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210675632.2A CN117258744A (en) | 2022-06-15 | 2022-06-15 | Granular lithium adsorbent and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117258744A true CN117258744A (en) | 2023-12-22 |
Family
ID=89204978
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210675632.2A Pending CN117258744A (en) | 2022-06-15 | 2022-06-15 | Granular lithium adsorbent and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117258744A (en) |
-
2022
- 2022-06-15 CN CN202210675632.2A patent/CN117258744A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP4306667A1 (en) | Method for preparing granular titanium-based lithium ion sieve adsorbent having high adsorption capacity | |
| Wei et al. | Porous lithium ion sieves nanofibers: General synthesis strategy and highly selective recovery of lithium from brine water | |
| Wang et al. | Selective recovery of lithium from geothermal water by EGDE cross-linked spherical CTS/LMO | |
| CN112871127B (en) | Preparation method of high-porosity lithium ion sieve particles | |
| CN111905700B (en) | Resin-based inorganic nanoparticle composite lithium extraction particle | |
| Zhao et al. | Synthesis of porous fiber-supported lithium ion-sieve adsorbent for lithium recovery from geothermal water | |
| CN106311190A (en) | Preparation method of porous manganese-based lithium ion sieve adsorbent | |
| CN108525636B (en) | Adsorbent for rapid adsorption and desorption, preparation and application in lithium/rubidium adsorption | |
| CN108126651B (en) | Fly ash floating bead loaded lithium ion sieve sheet and preparation method thereof | |
| CN114288983B (en) | Titanium-based lithium ion exchanger and preparation method thereof | |
| Tian et al. | Lithium extraction from shale gas flowback and produced water using H1. 33Mn1. 67O4 adsorbent | |
| CN115155528A (en) | Preparation method of granular aluminum salt lithium extraction adsorbent with high adsorption capacity | |
| CN109078602B (en) | Magnetic microporous lithium adsorbent and preparation method and application thereof | |
| CN115970661A (en) | Preparation method of high-adsorption-capacity lithium ion imprinted nano composite particles | |
| CN112079346B (en) | Metal organic framework in-situ activated hollow carbon sphere and preparation method and application thereof | |
| CN105032203A (en) | Preparation method of membrane adsorbent for removing ammonia nitrogen in wastewater | |
| Ding et al. | Fabrication of polyacrylonitrile-Li1. 6Mn1. 6O4 composite nanofiber flat-sheet membranes via electrospinning method as effective adsorbents for Li+ recovery from salt-lake brine | |
| CN108435143A (en) | A kind of high-hydrophilic adsorbent, preparation and the application of absorption rubidium ion or lithium ion | |
| Li et al. | Novel lithium ion-sieve spinning fiber composite of PVDF-HMO for lithium recovery from geothermal water | |
| CN108046368B (en) | Lithium ion sieve filler loaded by open-cell foam glass and preparation method thereof | |
| CN112316928B (en) | Cellulose lithium ion sieve composite membrane and preparation method and application thereof | |
| Zhao et al. | One-pot granulation of cross-linked PVA/LMO for efficient lithium recovery from gas field brine | |
| CN116159531A (en) | Preparation method of hollow fiber membrane lithium ion adsorbent | |
| CN116328713A (en) | Method for preparing lithium ion sieve adsorbent particles and application thereof | |
| CN117258744A (en) | Granular lithium adsorbent and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |