CN114086006A - Lithium extraction process for coupling powdery lithium adsorbent with hollow fiber membrane - Google Patents
Lithium extraction process for coupling powdery lithium adsorbent with hollow fiber membrane Download PDFInfo
- Publication number
- CN114086006A CN114086006A CN202111388808.8A CN202111388808A CN114086006A CN 114086006 A CN114086006 A CN 114086006A CN 202111388808 A CN202111388808 A CN 202111388808A CN 114086006 A CN114086006 A CN 114086006A
- Authority
- CN
- China
- Prior art keywords
- lithium
- adsorbent
- liquid
- membrane separation
- solid
- 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.)
- Granted
Links
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 344
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 344
- 239000003463 adsorbent Substances 0.000 title claims abstract description 296
- 239000012528 membrane Substances 0.000 title claims abstract description 217
- 238000000605 extraction Methods 0.000 title claims abstract description 57
- 239000012510 hollow fiber Substances 0.000 title claims abstract description 20
- 230000008878 coupling Effects 0.000 title claims description 6
- 238000010168 coupling process Methods 0.000 title claims description 6
- 238000005859 coupling reaction Methods 0.000 title claims description 6
- 239000007788 liquid Substances 0.000 claims abstract description 261
- 238000001179 sorption measurement Methods 0.000 claims abstract description 148
- 238000000926 separation method Methods 0.000 claims abstract description 147
- 239000012267 brine Substances 0.000 claims abstract description 130
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims abstract description 127
- 238000003795 desorption Methods 0.000 claims abstract description 110
- 238000005406 washing Methods 0.000 claims abstract description 55
- 239000000203 mixture Substances 0.000 claims abstract description 49
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 40
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 39
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000002351 wastewater Substances 0.000 claims abstract description 16
- 239000012670 alkaline solution Substances 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims description 57
- 239000002245 particle Substances 0.000 claims description 30
- 150000002500 ions Chemical class 0.000 claims description 22
- 238000011010 flushing procedure Methods 0.000 claims description 19
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 17
- 239000000843 powder Substances 0.000 claims description 12
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 7
- 150000002678 macrocyclic compounds Chemical class 0.000 claims description 7
- 239000011707 mineral Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 5
- 238000000034 method Methods 0.000 abstract description 45
- 230000008901 benefit Effects 0.000 abstract description 4
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 32
- 229910001437 manganese ion Inorganic materials 0.000 description 32
- 239000000243 solution Substances 0.000 description 31
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 description 29
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 24
- 230000008569 process Effects 0.000 description 23
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 20
- 230000000694 effects Effects 0.000 description 16
- 238000012360 testing method Methods 0.000 description 16
- 238000001914 filtration Methods 0.000 description 14
- 238000002360 preparation method Methods 0.000 description 13
- 238000007599 discharging Methods 0.000 description 9
- 239000002243 precursor Substances 0.000 description 8
- 238000000746 purification Methods 0.000 description 8
- 230000003068 static effect Effects 0.000 description 7
- 239000002033 PVDF binder Substances 0.000 description 6
- 229910010252 TiO3 Inorganic materials 0.000 description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 6
- 239000000872 buffer Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 6
- GCICAPWZNUIIDV-UHFFFAOYSA-N lithium magnesium Chemical compound [Li].[Mg] GCICAPWZNUIIDV-UHFFFAOYSA-N 0.000 description 6
- 238000003760 magnetic stirring Methods 0.000 description 6
- 239000011572 manganese Substances 0.000 description 6
- 235000010755 mineral Nutrition 0.000 description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 5
- 229910052748 manganese Inorganic materials 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000000967 suction filtration Methods 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 4
- 239000004480 active ingredient Substances 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000005469 granulation Methods 0.000 description 4
- 230000003179 granulation Effects 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 4
- 229910052808 lithium carbonate Inorganic materials 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000005457 optimization Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 230000005484 gravity Effects 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000011812 mixed powder Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 230000000717 retained effect Effects 0.000 description 3
- 238000004062 sedimentation Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 238000000108 ultra-filtration Methods 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical class O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- SWAIALBIBWIKKQ-UHFFFAOYSA-N lithium titanium Chemical compound [Li].[Ti] SWAIALBIBWIKKQ-UHFFFAOYSA-N 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- ALIMWUQMDCBYFM-UHFFFAOYSA-N manganese(2+);dinitrate;tetrahydrate Chemical compound O.O.O.O.[Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ALIMWUQMDCBYFM-UHFFFAOYSA-N 0.000 description 2
- 239000004005 microsphere Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- 229910003890 H2TiO3 Inorganic materials 0.000 description 1
- 229910007848 Li2TiO3 Inorganic materials 0.000 description 1
- 229910015645 LiMn Inorganic materials 0.000 description 1
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229920012266 Poly(ether sulfone) PES Polymers 0.000 description 1
- 229910009866 Ti5O12 Inorganic materials 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- -1 calixarene macrocyclic compound Chemical class 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000003983 crown ethers Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical class O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000000909 electrodialysis Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000001891 gel spinning Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical class O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 238000001471 micro-filtration Methods 0.000 description 1
- 239000000178 monomer Substances 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
- 235000013923 monosodium glutamate Nutrition 0.000 description 1
- 239000004223 monosodium glutamate Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000001728 nano-filtration Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000002572 peristaltic effect Effects 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- XZPVPNZTYPUODG-UHFFFAOYSA-M sodium;chloride;dihydrate Chemical compound O.O.[Na+].[Cl-] XZPVPNZTYPUODG-UHFFFAOYSA-M 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
- C22B26/12—Obtaining lithium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/005—Separation by a physical processing technique only, e.g. by mechanical breaking
-
- 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
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Geology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Water Treatment By Sorption (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention provides a lithium extraction process for a powdery lithium adsorbent coupled hollow fiber membrane, which comprises the following steps: (1) adjusting the pH value of the lithium-containing brine by using an alkaline solution to obtain alkaline lithium-containing brine; (2) carrying out cyclic dynamic adsorption on alkaline lithium-containing brine by using a powdery lithium adsorbent to obtain an adsorbed solid-liquid mixture, and carrying out first solid-liquid membrane separation to obtain a lithium-containing adsorbent I and lithium-removing brine; (3) carrying out cyclic dynamic washing on the lithium-containing adsorbent I by using pure water to obtain a washing solid-liquid mixture containing the lithium-containing adsorbent, and carrying out second solid-liquid membrane separation to obtain a lithium-containing adsorbent II and washing wastewater; (4) and (3) carrying out cyclic dynamic desorption on the lithium-containing adsorbent II by using desorption liquid to obtain a desorbed solid-liquid mixture, and carrying out third solid-liquid membrane separation to obtain a regenerated powdery lithium adsorbent and a lithium-rich liquid. The method has the characteristics of novelty, high efficiency and low cost, greatly improves the lithium extraction efficiency of the brine and the lithium ion yield, and has remarkable economic and social benefits.
Description
Technical Field
The invention belongs to the technical field of lithium resource extraction, and particularly relates to a lithium extraction process for a powdery lithium adsorbent coupled hollow fiber membrane.
Background
Lithium is called industrial monosodium glutamate, an important element for promoting world progress and an energy element in the 21 st century, and is widely applied to industries of new energy, ceramic glass manufacturing, chemical industry, metallurgy, medical treatment and the like.
In global lithium resources, the lithium ore and the lithium brine respectively account for 38.2 percent and 61.8 percent of the total amount, the lithium storage amount in the brine is huge, and the lithium extraction from the brine becomes a main lithium extraction way along with the continuous increase of the demand of lithium resources. China is a large lithium resource reserve country, wherein the proven reserve of the salt lake brine lithium resource accounts for about 80 percent of the total amount, and the ascertained reserve of the salt lake brine lithium resource accounts for 1/3 percent of the salt lake brine lithium resource in the world, and the salt lake brine lithium resource is mainly distributed in high-altitude areas such as Qinghai and Tibet, and the reserve of the Qinghai salt lake brine lithium resource is the largest and accounts for more than half of the reserve of the lithium resource in China. However, most of the salt lake brine in China has the characteristics of low lithium content and high magnesium-lithium ratio, and the difficulty in extracting lithium from the salt lake brine is brought.
At present, methods for extracting lithium from brine mainly comprise an adsorption method, a precipitation method, an extraction method, a membrane method, a calcination leaching method and the like, wherein the adsorption method for extracting lithium from brine is one of the current research hotspots, especially the field of extracting lithium from brine with high magnesium-lithium ratio, and the method is to utilize a lithium adsorbent for extracting Li in brine+Adsorbing, and desorbing Li+And (5) desorbing, further purifying the obtained lithium-rich liquid, and preparing the required lithium product.
In the prior art of extracting lithium, patent CN201410555213.0 adopts an adsorption method to extract lithium, and static Li is carried out in an adsorption tank+After adsorption, separating the adsorbent by using a ceramic membrane and a plate-and-frame filter press, adding the adsorbent into a desorption tank for static desorption, and performing nanofiltration, ion exchange, RO, mass transfer and mass transfer on the obtained desorption solution,Electrodialysis, precipitation and impurity removal and other processes are carried out to prepare battery grade Li2CO3. In patent CN201810981694.X, an ion sieve adsorbent and polyacrylonitrile are mixed and cast into a hollow fiber membrane through dry-wet spinning, and a membrane module is built for brine circulation adsorption and lithium extraction. In patent CN201910212673.6, a monomer containing a polymer is introduced into a manganese-based lithium ion sieve by ultrasound, an intercalation polymer @ manganese-based lithium ion sieve composite material is prepared through a polymerization reaction, and the composite material and PVDF are dissolved in DMF to finally prepare an intercalation polymer lithium ion sieve/PVDF membrane, wherein the prepared membrane has high lithium ion adsorption capacity and selectivity. The patent technologies have the problems of large reduction of the actual adsorption capacity of the lithium adsorbent, complex membrane preparation process, long time consumption of static adsorption and desorption, large consumption of pure water and desorption liquid and the like, and the development of a high-efficiency and high-selectivity lithium extraction process and device is urgently needed.
Disclosure of Invention
In order to solve the problems, the invention provides a lithium extraction process for coupling a powdery lithium adsorbent with a hollow fiber membrane, which comprises the following steps:
(1) in an adsorption tank, adjusting the pH value of lithium-containing brine by using an alkaline solution to obtain alkaline lithium-containing brine; the pH value of the alkaline lithium-containing brine is specifically 7.5-9.5;
(2) carrying out cyclic dynamic adsorption on alkaline lithium-containing brine by using a powdery lithium adsorbent to obtain an adsorbed solid-liquid mixture, and carrying out first solid-liquid membrane separation on the adsorbed solid-liquid mixture to obtain a lithium-containing adsorbent I and lithium-removing brine;
(3) carrying out circulating dynamic washing on the lithium-containing adsorbent I by using pure water to obtain a washing solid-liquid mixture containing the lithium-containing adsorbent after the dynamic washing is finished, and carrying out second solid-liquid membrane separation on the washing solid-liquid mixture to obtain a lithium-containing adsorbent II and washing wastewater;
(4) and (3) carrying out cyclic dynamic desorption on the lithium-containing adsorbent II by using desorption liquid to obtain a desorbed solid-liquid mixture, and carrying out third solid-liquid membrane separation on the desorbed solid-liquid mixture to obtain a regenerated powdery lithium adsorbent and a lithium-rich liquid.
Wherein the powdery lithium adsorbent is one or a mixture of several of ion sieve type adsorbent, aluminum salt adsorbent, modified mineral adsorbent, macrocyclic compound type adsorbent and hydroxide type adsorbent.
Aiming at different types of powdery lithium adsorbents, the alkaline lithium-containing brine needs to be in different pH value ranges so as to promote the adsorption capacity of the adsorbents to the maximum extent, and when the ion sieve type adsorbents are adopted, the pH value of the alkaline lithium-containing brine is preferably 8.5-9.5; when an aluminum salt adsorbent and a hydroxide adsorbent are adopted, the pH value of the alkaline lithium-containing brine is preferably 7.5-8.0; when the modified mineral adsorbent is adopted, the pH value of the alkaline lithium-containing brine is preferably 7.0-8.0; when the macrocyclic compound adsorbent is adopted, the pH value of the alkaline lithium-containing brine is preferably 7.0-8.5. When the adsorbents are used in combination, it is preferable to conduct experiments to determine the optimum pH range.
The alkaline solution is one or a mixture of more of a sodium hydroxide solution, a sodium carbonate solution and a sodium bicarbonate solution, and the concentration of the solution is 10-40 wt%.
And keeping stirring in the process of adjusting the pH value, wherein the stirring speed is controlled to be 50-120 r/min, and preferably 60-90 r/min. According to the lithium-containing brine in the adsorption tank, the stirring effect is ensured, the stirring speed is prevented from being too high, and the electric energy consumption is reduced.
In the application, firstly, the pH value of the lithium-containing brine is adjusted, and after the pH value is adjusted, the lithium adsorbent can play a role in promoting the lithium ion adsorption process; then, lithium ion adsorption is carried out by utilizing the powdery lithium adsorbent, and a better adsorption effect can be obtained by virtue of larger adsorption capacity and specific surface area. At present, in order to separate lithium adsorbents in a lithium extraction process, the lithium adsorbents are generally granulated to form particles with the particle size of 0.5-5 mm or mixed casting films of the particles, 20-50% of adsorption sites of the two types of lithium adsorbents are sacrificed due to the fact that the two types of lithium adsorbents are adhered to corresponding carriers, the adsorption capacity of the lithium adsorbents to lithium ions is obviously reduced, meanwhile, due to the limitation of mechanical strength of the carriers, the meeting probability of the lithium adsorbents and the lithium ions in lithium-containing brine cannot be increased by using external forces such as stirring and the like, most of the lithium adsorbents can only adopt static adsorption, static washing and static desorption, the lithium extraction efficiency is low, and the time consumption is long. In this application, powdered lithium adsorbent has been adopted, these powdered lithium adsorbents need not to carry out granulation or cast membrane and handle, have reduced the process on the one hand, have practiced thrift the energy, have reduced manufacturing cost, and on the other hand is because the original structure of lithium adsorbent has been remain completely, and is more to lithium ion's adsorption site, and adsorption capacity is also bigger, and powdered lithium adsorbent mechanical strength is high, does not receive external force restriction such as stirring, can realize the abundant contact of whole adsorption process lithium ion and powdered lithium adsorbent.
In the embodiment of the application, the adsorption performance difference of the same ion sieve type lithium adsorbent under different appearance forms is compared, wherein the adsorption capacity of the powdery ion sieve type lithium adsorbent can reach 30-37 mg/g according to the lithium extraction process of the application, and the adsorption capacity of the granular ion sieve type lithium adsorbent can only reach 15.7mg/g according to the existing process. As can be seen from the comparison of the data, the powdered lithium adsorbent has a significant advantage in adsorption capacity over the granular lithium adsorbent.
Further, in order to ensure the adsorption effect of the lithium adsorbent and the solid-liquid separation effect of the hollow fiber membrane, the particle size range of the powdery lithium adsorbent is selected to be 200-600 nm. When the particle size of the lithium adsorbent is too small, the hollow fiber membrane pores are easy to block, the solid-liquid membrane separation effect is influenced, the backflushing frequency is increased, the equipment loss is accelerated, and the operation investment is increased; when the particle size of the lithium adsorbent is too large, the specific surface area of the lithium adsorbent is reduced, corresponding lithium adsorbent adsorption sites are also reduced, the adsorption capacity of the lithium adsorbent is unfavorable, and the particle size is too large, so that the sedimentation tendency of the lithium adsorbent is easily increased, and the stable cycle is not favorable.
Specifically, in the step (1), the lithium-containing brine is salt lake brine or underground brine; mg in lithium-containing brine2+With Li+The mass ratio of (A) to (B) is 1: 1-1500: 1; li in lithium-containing brine+The mass percentage concentration is 0.002-2%.
The lithium extraction process adopts the powdery lithium adsorbent, avoids the adsorption site loss caused by granulation or membrane casting treatment, has higher adsorption performance, effectively promotes the adsorption process of the lithium adsorbent to lithium ions by utilizing a circulating dynamic adsorption system, has wider applicable brine water quality conditions compared with other methods, and is particularly suitable for extracting lithium from brine with high magnesium-lithium ratio and low lithium content.
Specifically, in the step (2), the cyclic dynamic adsorption is to add a powdery lithium adsorbent into the alkaline lithium-containing brine, stir the mixture uniformly to form a first cyclic liquid, so that the first cyclic liquid flows in a first cycle between the adsorption tank and the membrane separation device, and the powdery lithium adsorbent dynamically adsorbs lithium ions; and after the dynamic adsorption is finished, forming an adsorption solid-liquid mixture, and performing first solid-liquid membrane separation on the adsorption solid-liquid mixture by using the membrane separation device to obtain a lithium-containing adsorbent I and lithium-removing brine.
In the application, dynamic adsorption and first solid-liquid membrane separation are carried out in the same device, wherein the membrane separation device is used as different equipment at different stages, and during dynamic adsorption, the membrane separation device does not start a membrane separation unit and is only used as an adsorption container, so that the first circulating liquid can smoothly complete circulating flow, and the smooth implementation of circulating dynamic adsorption is ensured. In the first solid-liquid membrane separation process, the membrane separation device recovers the filtering function thereof to obtain the lithium-containing adsorbent I. In the process of carrying out first solid-liquid membrane separation, continuous flow of first circulating liquid needs to be ensured, so that the concentration of the adsorbent in the first circulating liquid can be gradually reduced, and a large amount of adsorbent is prevented from being retained in a membrane separation device to form a thick filter layer, thereby influencing the filtration efficiency.
Above-mentioned design, make full use of carries lithium technology in-system device, need not additionally to add the circulation and adsorb the buffer tank, makes each material concentration of upper and lower floor in the adsorption tank even, avoids powdered lithium adsorbent to subside, increases the meeting probability of powdered lithium adsorbent and lithium ion simultaneously, realizes the dynamic adsorption of the two.
Further, the addition amount of the powdery lithium adsorbent in the alkaline lithium-containing brine is 0.5-8 g/L, and the preferred addition amount is 1-5 g/L; and adding alkaline lithium-containing brine into the powdery lithium adsorbent, performing first stirring, and stirring for 10-30 min to form a first circulating liquid, wherein the stirring speed of the first stirring is 60-120 r/min. The first stirring time is preferably 15-20 min, and the stirring speed of the first stirring is preferably 70-90 r/min.
When the addition amount of the powdery lithium adsorbent is too small, the adsorption efficiency of the powdery lithium adsorbent on lithium ions in lithium-containing brine is low, the adsorption time is long, the content of residual lithium ions in the lithium-removing brine is high, and the lithium extraction effect is poor; when the addition amount is too large, the lithium extraction cost is increased, the difficulty of solid-liquid membrane separation is also increased, and the comprehensive efficiency of the lithium extraction process is influenced. The first stirring aims at fully wetting and uniformly mixing the powdery lithium adsorbent and the alkaline lithium-containing brine, and due to the fact that the powdery lithium adsorbent is large in stacking specific gravity and strong in sedimentation tendency, reasonable stirring time and stirring speed must be guaranteed to avoid sedimentation or overhigh local concentration of the powdery lithium adsorbent, and the use effect of the powdery lithium adsorbent can be influenced by too short time or too low stirring speed.
Further, when the cyclic dynamic adsorption is carried out, the temperature of the first circulating liquid is-5-45 ℃, the further optimization is 10-35 ℃, and the cyclic dynamic adsorption time is 1-4 h, the further optimization is 2-3 h;
and in the circulating dynamic adsorption, keeping the first circulating liquid in the adsorption tank to be subjected to second stirring, wherein the stirring speed of the second stirring is 30-80 r/min, and more preferably 40-60 r/min.
The salt lake or underground lithium-containing brine has high salt content and low freezing point, and the lithium extraction process has low requirement on the temperature of the brine and can be practically produced for a long time every year. However, the temperature is too low or too high, which easily causes unnecessary abnormal problems of the hollow fiber membrane separation device and influences the stability of the lithium extraction process system. The circulating dynamic adsorption can effectively improve the lithium extraction efficiency of the lithium adsorbent, shorten the lithium extraction time and reduce the concentration of residual lithium ions in the lithium removal brine, but the short adsorption time can cause the lithium ions not to be fully adsorbed, cause the waste of the adsorbent and possibly cause the reworking and re-adsorption of the lithium-containing brine; the adsorption time is too long, and although the lithium extraction yield can be improved by a small amount, the cost performance is lower compared with the input energy and time.
Further, the membrane separation device is a hollow fiber membrane separation device, negative pressure suction is adopted when first solid-liquid membrane separation is carried out, the suction pressure is-0.4 to-0.8 MPa, more preferably-0.5 to-0.7 MPa, the membrane passing temperature is 0 to 80 ℃, more preferably 10 to 60 ℃, and the membrane surface flow rate is 1 to 3 m/s.
The membrane separation device is a hollow fiber membrane separation device and comprises a microfiltration membrane and an ultrafiltration membrane, wherein the ultrafiltration membrane is preferably adopted, the average pore diameter of the membrane is 15-150 nm, and the porosity is 35-50%; the membrane separation mode comprises an external pressure type and an internal pressure type; the membrane material comprises an inorganic membrane and an organic membrane, and preferably comprises a ceramic membrane, a polyvinylidene fluoride (PVDF) membrane and a polyether sulfone (PES) membrane; the membrane separation device module includes a single-stage type and a combined type.
In the first solid-liquid membrane separation process, the suction pressure is recommended to be within a recommended range, particularly recommended to be within a preferable range, when the suction pressure is too low, the membrane separation effect is poor, and the solid-liquid membrane separation time is long; when the suction pressure is too high, the requirement on the membrane separation device is high on one hand, the corresponding cost is increased, and on the other hand, the lithium adsorbent is too fast to block the membrane surface, so that the discharge of the lithium removal brine is influenced. When the flow rate of the membrane surface is too low, the lithium adsorbent is easy to deposit, the back-flushing frequency is increased, and the membrane separation efficiency is influenced; when the flow velocity of the membrane surface is too high, the requirement on a delivery pump is high, the energy consumption is high, and meanwhile, the lithium-containing adsorbent I can be suspended and circulated for a long time, which is not beneficial to solid-liquid membrane separation.
Further, in the step (3), in the step of cyclic dynamic washing, pure water is added into the lithium-containing adsorbent I to form second cyclic liquid, then the second cyclic liquid is subjected to second cyclic flow between the membrane separation device and the cyclic tank to dynamically wash the lithium-containing adsorbent I, after the dynamic washing is completed, a washing solid-liquid mixture is formed, and the membrane separation device is used for performing second solid-liquid membrane separation on the washing solid-liquid mixture to obtain a lithium-containing adsorbent II and washing wastewater;
when dynamic washing is carried out, the temperature of the second circulating liquid is 5-60 ℃, the further optimization is 10-35 ℃, and the washing time is 5-20 min, the further optimization is 10-20 min; the flushing time is the duration of the second circulation flow;
the membrane separation device is a hollow fiber membrane separation device, negative pressure suction is adopted when second solid-liquid membrane separation is carried out, the suction pressure is-0.4 to-0.8 MPa, the further preferable pressure is-0.5 to-0.6 MPa, the membrane passing temperature is 5 to 70 ℃, the further preferable pressure is 10 to 50 ℃, and the membrane surface flow rate is 1 to 3 m/s.
In the application, dynamic washing and second solid-liquid membrane separation are both carried out in the same device, wherein the membrane separation device is used as different equipment in different stages, and when the dynamic washing is carried out, the membrane separation device does not start a membrane separation unit and is only used as an overflowing container, so that the second circulating liquid can smoothly complete circulating flow, and in the circulating flow, the lithium-containing adsorbent II is washed, so that the washing is smoothly carried out. In the second solid-liquid membrane separation process, the membrane separation device recovers the filtering function of the device to obtain the lithium-containing adsorbent II. In the process of performing the second solid-liquid membrane separation, the continuous flow of the second circulating liquid needs to be ensured, so that the concentration of the adsorbent in the second circulating liquid can be gradually reduced, and a large amount of adsorbent is prevented from being retained in the membrane separation device to form a thick filter layer, which affects the filtration efficiency.
When the dynamic washing time is too short, the washing effect is poor, more impurity ions exist on the surface of the obtained lithium-containing adsorbent II, and the impurity ions enter the lithium-rich liquid along with the desorption process, so that the purification of the final lithium product is difficult; the washing time is too long, which causes energy waste and small amount of lithium ions to be separated out, and affects the lithium ion yield of the lithium adsorbent.
Further, in the step (4), in the cyclic dynamic desorption, desorption liquid is added into the lithium-containing adsorbent II to form third circulation liquid, then the third circulation liquid is subjected to third circulation flow between the membrane separation device and the second circulation tank, dynamic desorption is performed on the lithium-containing adsorbent II, after the dynamic desorption is completed, a desorption solid-liquid mixture is formed, and the membrane separation device is used for performing third solid-liquid membrane separation on the desorption solid-liquid mixture to obtain a regenerated powder lithium adsorbent and a lithium-rich liquid;
when dynamic desorption is carried out, the temperature of the third circulating liquid is 5-60 ℃, the preferred temperature is 10-40 ℃, and the desorption time is 1-3 h, the preferred time is 2-3 h;
the membrane separation device is a hollow fiber membrane separation device, negative pressure suction is adopted when third solid-liquid membrane separation is carried out, the suction pressure is-0.4 to-0.8 MPa, more preferably-0.5 to-0.7 MPa, the membrane passing temperature is 5 to 70 ℃, more preferably 10 to 50 ℃, and the membrane surface flow rate is 1 to 3 m/s.
In the application, dynamic desorption and third solid-liquid membrane separation are carried out in the same device, wherein the membrane separation device is used as different equipment at different stages, and during dynamic desorption, the membrane separation device does not start a membrane separation unit and is only used as a desorption container, so that the third circulating liquid can smoothly complete circulating flow, and the smooth desorption is ensured. In the third solid-liquid membrane separation process, the membrane separation device recovers the filtering function of the device to obtain a regenerated powdery lithium adsorbent and a lithium-rich liquid. In the process of carrying out the third solid-liquid membrane separation, the continuous flow of the third circulating liquid needs to be ensured, so that the concentration of the adsorbent in the third circulating liquid can be gradually reduced, and the phenomenon that a large amount of adsorbent is retained in the membrane separation device to form a thick filter layer to influence the filtration efficiency is avoided.
In the present application, in order to avoid excessive equipment purchase cost and maintenance cost due to repeated installation of equipment, it is preferable that the first circulation tank and the second circulation tank be the same circulation tank.
When the desorption time is too short, lithium ions adsorbed in the lithium-containing adsorbent II are not fully desorbed, and the desorption rate of the lithium ions and the actual lithium ion yield are influenced; when the desorption time is too long, the desorption rate of the desorption solution to the lithium-containing adsorbent II tends to be stable, the desorbed lithium ions are less, and the cost performance is not high.
Further, in order to improve the utilization rate of equipment, the same membrane separation device is adopted for carrying out first solid-liquid membrane separation, second solid-liquid membrane separation and third solid-liquid membrane separation; when the cyclic dynamic adsorption, the cyclic dynamic flushing and the cyclic dynamic desorption are carried out, the first circulating liquid during the cyclic dynamic adsorption, the second circulating liquid during the cyclic dynamic flushing and the third circulating liquid during the cyclic dynamic desorption are all carried out by the membrane separation device. And when the circulating dynamic adsorption, the circulating dynamic flushing and the circulating dynamic desorption are carried out, the same circulating pump is adopted as a circulating power device.
The design not only can improve the utilization rate of the equipment and reduce the purchase cost and the maintenance cost of the equipment, but also can avoid the transfer of the lithium adsorbent, and because the lithium adsorbent is always in a controllable space, the use amounts of the washing pure water and the desorption liquid can be obviously reduced.
In the lithium extraction process, the lithium adsorbent undergoes the steps of adsorption, cleaning and desorption, and is respectively formed into three stages of a lithium-containing adsorbent I, a lithium-containing adsorbent II and a regenerated powdery lithium adsorbent.
The application also has the following overall effects:
1. the lithium extraction process of coupling the powdery lithium adsorbent with the hollow fiber membrane effectively solves the bottleneck problem that the powdery lithium adsorbent is difficult to industrially apply;
2. the adopted powdery lithium adsorbent avoids the loss of adsorption sites and the reduction of adsorption capacity, structural strength and service life of the powdery lithium adsorbent caused by molding treatment, and retains the original adsorption performance advantage of the powdery lithium adsorbent to the maximum extent;
3. by circulating the dynamic adsorption, flushing and desorption processes, the solid-liquid mixture in each step is circulated, the adsorption, flushing and desorption efficiency and the lithium ion yield of the process are greatly improved, and the time for the adsorption, flushing and desorption processes is obviously shortened;
4. because the circulating flushing loop and the circulating desorption loop which do not pass through the adsorption tank are adopted, the addition amount of the flushing pure water and the desorption liquid can be controlled as required, and the consumption amount of the pure water and the desorption liquid is effectively reduced.
5. The selection range of the powdery lithium adsorbent in the lithium extraction process is wide, and the process can be applied to all self-grinding or commercially available ion sieve type adsorbents, aluminum salt adsorbents, modified mineral adsorbents, macrocyclic compound adsorbents, hydroxide adsorbents and mixtures of the above materials with the powder particle size of 200-600 nm.
6. The lithium extraction process has wide application range, is suitable for most of lithium extraction occasions of brine at home and abroad, and is particularly suitable for extracting lithium from brine with high magnesium-lithium ratio and low lithium content.
In conclusion, the application provides a novel, efficient and low-cost brine lithium extraction process, the brine lithium extraction efficiency and the lithium ion yield are greatly improved, and the economic and social benefits are remarkable.
Drawings
FIG. 1 is a process flow diagram of the present application.
Fig. 2 is a schematic view of a lithium extraction device for use in the present application.
FIG. 3 is a layout of the apparatus involved in the cyclic dynamic adsorption and the first solid-liquid membrane separation.
FIG. 4 is a layout of the equipment involved in circulating dynamic washing and performing the second solid-liquid membrane separation.
FIG. 5 is a layout of the apparatus involved in the cyclic dynamic desorption and the performance of the third solid-liquid membrane separation.
Detailed Description
First, a lithium extraction device used in the present application will be described below, with reference to fig. 2, the lithium extraction device includes an adsorption tank 10, a circulation pump 20, a membrane separation device 30, and a buffer tank 40, a stirrer 11 is installed in the adsorption tank, a motor 12 for driving the stirrer 11 to rotate is installed on the top of the adsorption tank, a feed pipe 13 and a circulation feed mouthpiece 15 are installed on the upper portion of the adsorption tank 10, a circulation discharge mouthpiece 14 is installed on the lower portion of the adsorption tank 10, a drain pipe 19 is installed on the bottom of the adsorption tank 10, a drain valve 191 is installed on the drain pipe 19, and an alkali inlet pipe 181 and an adsorbent inlet pipe 182 are installed on the top of the adsorption tank.
The inlet of the circulating pump is connected with two liquid inlet pipes, which are a first liquid inlet pipe 21 and a second liquid inlet pipe 22 respectively, wherein the first liquid inlet pipe 21 is connected to the circulating discharge interface pipe 14, the first liquid inlet pipe is provided with a first liquid inlet switching valve 16, the second liquid inlet pipe 22 is connected to a circulating liquid outlet connecting pipe 42 at the bottom of the buffer tank 40, and the second liquid inlet pipe 22 is provided with a second liquid inlet switching valve 43.
The outlet of the circulation pump is connected to the feed inlet 31 of the membrane separation device 30. A concentrated solution outlet 32 of the membrane separation device 30 is connected with a first liquid outlet pipe 34 and a second liquid outlet pipe 35, wherein the first liquid outlet pipe 34 is communicated with the circulating feeding interface pipe 15, and a first liquid outlet switching valve 17 is arranged on the first liquid outlet pipe; the second liquid outlet pipe 35 is communicated with a circulating liquid inlet connecting pipe 41 at the upper part of the buffer tank 40, and a second liquid outlet switching valve 44 is arranged on the second liquid outlet pipe 35.
The vacuum outlet of the vacuum device 50 is connected to the clean liquid outlet 33 of the membrane separation device 30 via the intermediate tank 51, and the clean liquid outlet 33 is provided with a shut-off valve 53. A waste water outlet 54 is provided at the bottom of the intermediate tub 51, and a waste water valve 55 is mounted on the waste water outlet 54. In the present embodiment, the vacuum device 50 is a roots vacuum pump, and it is understood that in other embodiments, the vacuum device may also be other vacuum devices, such as a rotary-vane vacuum pump or a water-ring vacuum pump.
For convenience of operation, in this embodiment, the lithium extraction device is further provided with a water tank 61 and a desorption liquid tank 62, wherein the water tank 61 is used for containing pure water, and the desorption liquid tank 62 is used for containing desorption liquid. It can be understood that when the consumption of pure water and desorption liquid can in time satisfy the needs, water pitcher 61 and desorption liquid jar 62 all can cancel, in process of production, directly add pure water and desorption liquid respectively to the circulating tank as required.
The membrane separation device is a hollow fiber membrane separation device, and specifically in the embodiment, an ultrafiltration membrane is adopted, the average pore diameter of the membrane is 50nm, and the porosity is 35-45%; membrane separation modes include external pressure type; the membrane material is polyvinylidene fluoride (PVDF); the membrane separation device is of a single-stage type.
The following describes a lithium extraction process of coupling a powdery lithium adsorbent to a hollow fiber membrane, and referring to fig. 1, the lithium extraction process is performed by using the above-mentioned lithium extraction device. The lithium extraction process is first generally described as follows, and comprises the following steps:
(1) and introducing lithium-containing brine into the adsorption tank 10 through the feed pipe 13, and then introducing an alkaline solution into the adsorption tank 10 through the alkali inlet pipe 181 until the pH value is set, so as to obtain the lithium-containing brine.
(2) The second liquid outlet switching valve 44, the second liquid inlet pipe 22 and the cut-off valve 33 are closed, and the first liquid outlet switching valve 17 and the first liquid inlet switching valve 16 are opened.
Putting a powdery lithium adsorbent into the adsorption tank 10 through the adsorbent inlet pipe 182, uniformly stirring to form a first circulating liquid, starting the circulating pump 20 to make the first circulating liquid perform first circulating flow between the adsorption tank and the membrane separation device, and dynamically adsorbing lithium ions by the powdery lithium adsorbent; after the dynamic adsorption is finished, an adsorption solid-liquid mixture is formed. And opening a cut-off valve 53, starting a vacuum device 50, carrying out first solid-liquid membrane separation on the adsorbed solid-liquid mixture, feeding the lithium-removed brine into a middle barrel 51, discharging the lithium-removed brine to a wastewater treatment system periodically, and keeping a lithium-containing adsorbent I in a membrane separation device 30.
In the first solid-liquid membrane separation, the circulation pump 20 is kept in operation, and the adsorbed solid-liquid mixture in the adsorption tank and the pipeline is returned to the membrane separation apparatus 30 as much as possible until the solid-liquid separation is completed, and the circulation pump is turned off. Alternatively, the adsorption tank is disposed above the membrane separation device 30, and the adsorbed solid-liquid mixture in the adsorption tank and the pipeline is introduced into the membrane separation device 30 by gravity.
Referring to fig. 3, fig. 3 is a layout diagram of the devices involved in step (2).
(3) The first liquid outlet switching valve 17, the first liquid inlet switching valve 16 and the cut-off valve 33 are closed, the second liquid outlet switching valve 44 and the second liquid inlet pipe 22 are opened, and pure water in the water tank 61 is added into the buffer tank 40 until the volume is set. And mixing the pure water with the lithium-containing adsorbent I to form a second circulating liquid.
And starting the circulating pump 20 to enable the second circulating liquid to flow between the membrane separation device and the circulating tank 40 in a second circulating mode, dynamically washing the lithium-containing adsorbent I, and forming a washing solid-liquid mixture after the dynamic washing is finished.
And opening the cut-off valve 53, starting the vacuum device 50, performing second solid-liquid membrane separation on the washing solid-liquid mixture, introducing the washing wastewater into the intermediate barrel 51, periodically discharging the washing wastewater into a wastewater treatment system, and retaining the lithium-containing adsorbent II in the membrane separation device 30.
In the second solid-liquid membrane separation, the circulation pump 20 is kept in operation, and the circulation tank and the pipe are returned to the membrane separation device 30 as much as possible until the solid-liquid separation is completed, and the circulation pump is turned off. Or the circulation tank is arranged above the membrane separation device 30, and the flushing solid-liquid mixture in the adsorption tank and the pipeline enters the membrane separation device 30 by utilizing gravity.
Referring to fig. 4, fig. 4 is a layout diagram of the apparatus involved in step (3).
(4) The first effluent switching valve 17, the first liquid inlet switching valve 16 and the shut-off valve 33 are closed, the second effluent switching valve 44 and the second liquid inlet pipe 22 are opened, and the desorption liquid in the desorption liquid tank 62 is added into the buffer tank 40 until the volume is set. And mixing the desorption solution with a lithium-containing adsorbent II to form a third circulating solution.
And starting the circulating pump 20 to make the third circulating liquid flow in a third circulating mode between the membrane separation device and the circulating tank 40, and performing dynamic desorption on the lithium-containing adsorbent II to form a desorbed solid-liquid mixture after the dynamic desorption is completed.
Opening a cut-off valve 53, starting a vacuum device 50, carrying out third solid-liquid membrane separation on the desorbed solid-liquid mixture, allowing the lithium-rich liquid to enter an intermediate barrel 51, periodically discharging the lithium-rich liquid to a lithium ion purification system, and finally preparing the lithium-rich liquid into a required lithium product; the regenerated powdered lithium sorbent remains within the membrane separation device 30. The next round of production is performed.
Referring to fig. 5, fig. 5 is a layout diagram of the apparatus involved in the step (4).
In the present embodiment, the second circulation liquid and the third circulation liquid are circulated through the same circulation tank when the second circulation flow and the third circulation flow are performed, and it is understood that, in another embodiment, the second circulation flow and the third circulation flow are circulated using different circulation tanks, respectively, for example, between the membrane separation apparatus and the first circulation tank when the second circulation flow is performed; in the third circulation flow, the flow proceeds between the membrane separation device and the second circulation tank.
In the following specific examples, the khaki salt lake brine, which is characterized by low lithium content, high magnesium-lithium ratio and great difficulty in extracting lithium, was used as the test object, and the mass percentage concentrations of the ions and the magnesium-lithium ratio in the brine are shown in table 1:
TABLE 1 composition of Carr's salt lake brine (wt%)
| Na+ | K+ | Mg2+ | Li+ | Ca2+ | SO4 2- | Cl- | B3+ | Mg2+/Li+ |
| 0.224 | 0.056 | 10.0602 | 0.0094 | 0.096 | 0.02 | 22.78 | 0.012 | 1070.2：1 |
The powdery lithium adsorbent in the application can be one or a mixture of several of self-grinding or commercially available ion sieve type adsorbents, aluminum salt adsorbents, modified mineral adsorbents, macrocyclic compound type adsorbents and hydroxide adsorbents, the particle size of the powdery lithium adsorbent is 200-600 nm, and the powdery lithium adsorbent meeting the requirements can be used in the lithium extraction process.
Wherein the ion sieve adsorbent comprises manganese ion sieve adsorbent (such as HMn)2O4、H1.33Mn1.67O4、 H1.6Mn1.6O4Etc.), titanium-based ion sieve adsorbent (e.g., H)2TiO3、H4Ti5O12Etc.), antimony-based ion sieve adsorbent [ e.g., HSb (OH) ]6Etc. of]And various doped modified ion sieve adsorbents of the three, wherein after lithium ions are adsorbed by the adsorbent, pure water is generally used for washing, an acid solution is used for desorption, and a lithium-rich liquid and a regenerated manganese ion sieve adsorbent are obtained through filtration and separation. Aluminum salt adsorbents have the general formula LiX 2Al (OH)3·nH2O, wherein X represents an anion (e.g. Cl)-And Br-) And n represents the number of crystal water, the adsorbent of the type generally has small adsorption capacity, and pure water is used for flushing and desorption.
The hydroxide-type adsorbents are generally amorphous structures, in which amorphous aluminum hydroxide [ structure Al (OH) ]is used3]Most commonly, pure water is used for this type of adsorbent rinse and desorption. The modified mineral adsorbent comprises a modified kaolin adsorbent, a modified zeolite adsorbent, a modified montmorillonite adsorbent and the like, and the modified montmorillonite adsorbent is generally washed by pure water after adsorbing lithium ions, desorbed by an acid solution, filtered and separated after desorption to obtain a lithium-rich liquid and a regenerated modified mineral adsorbent.
The macrocyclic compound type adsorbent is formed by more than 12 or 12 atoms in a ring shape, wherein more than 3 coordination atoms are contained, a special cavity structure can selectively adsorb lithium ions, and the macrocyclic compound type adsorbent is typically a calixarene macrocyclic compound type adsorbent and a crown ether type adsorbent.
In some embodiments of the present application, an ion sieve type adsorbent is used, including a titanium-based ion sieve adsorbent and a manganese-based ion sieve adsorbent, and in other embodiments, an aluminum salt adsorbent is used, wherein the titanium-based ion sieve adsorbent contains powder and particles, and the other adsorbents are in powder form. The aluminum salt adsorbent, the titanium ion sieve adsorbent and the manganese ion sieve adsorbent related in each embodiment of the application are self-made products of the team, and the specific preparation methods are respectively as follows:
the preparation method of the aluminum salt adsorbent comprises the following steps: 100g of aluminum chloride and 27.2g of lithium chloride are weighed, mixed, dissolved and fixed in a 1000mL volumetric flask for standby. 500mL of mixed solution of lithium chloride and aluminum chloride is put in an open crystallizer, the reaction temperature is controlled to be 80 ℃, the stirring speed is controlled to be 200r/min, the rotational speed of a peristaltic pump is controlled to adjust the dropping speed to be 3mL/min, and 5mol/L of sodium hydroxide solution is slowly dropped into the mixed solution of lithium chloride and aluminum chloride for coprecipitation reaction. And controlling the pH value of the end point to be 6-7, washing, centrifuging, carrying out solid-liquid separation, drying and grinding the obtained solid in a blast oven at the temperature of 60 ℃ to obtain the aluminum salt adsorbent product. The aluminum salt adsorbent prepared by the method is uniform powder, the particle size of the adsorbent is 250-550 nm, and the method is suitable for the application example 2.
The preparation method of the powdery titanium ion sieve adsorbent comprises the following steps: dissolving 25g of lithium carbonate in 100mL of absolute ethyl alcohol at room temperature, and adding TiO according to the molar ratio of lithium to titanium of 2:1 under magnetic stirring2Continuously stirring for 24h, carrying out spray drying on the obtained slurry at 90 ℃ at a feeding rate of 5ml/min under magnetic stirring to obtain lithium source titanium source mixed powder, uniformly spreading the mixed powder on a ceramic calcining plate for 4.5g/(200mm multiplied by 200mm), heating to 650 ℃ at 2 ℃/min in a muffle furnace, preserving heat for 18h, and naturally cooling to room temperature to obtain a precursor Li2TiO3. Under the condition of magnetic stirring, taking the precursor Li according to the solid-to-liquid ratio of 2g/L2TiO3Added to 1mol/LAcid treatment in hydrochloric acid solution for 24H, then filtering, washing and drying to obtain titanium ion sieve adsorbent (structural formula is H)2TiO3). The titanium ion sieve adsorbent prepared by the method is in a uniform powder shape, the particle size of the adsorbent is 250-450 nm, and the method is suitable for the application example 1.
The preparation method of the granular titanium ion sieve adsorbent comprises the following steps: the granular titanium ion sieve adsorbent is prepared by mixing and granulating a precursor of the powdery titanium ion sieve adsorbent and a carrier material to prepare granules, wherein the particle size of the prepared adsorbent granules is 1-3 mm, and the content of active ingredients is 42 wt%. Specifically, 36ml of NMP was placed in a 500ml beaker and 5.5g of PVC was added slowly with magnetic stirring. After the PVC is completely dissolved, 7.1g of PEG and 1.2gCA are added for dissolution, and then 10g of Li which is a precursor of the powdery titanium ion sieve adsorbent is slowly added2TiO3Mixing, and stirring for 30 min. Dropping the mixture into a 500ml beaker filled with 350ml of deionized water at the speed of 1 drop/second by using a dropping device to obtain the microsphere particles. And (3) after complete dropwise addition, standing for 60min, washing the microsphere particles with deionized water for multiple times, filtering, and drying in a 50 ℃ oven for 24h to obtain precursor particles. Adding precursor particles into 0.5mol/L hydrochloric acid according to the proportion of 2g/120ml, washing to remove lithium and activate, stirring for 6H at 85 ℃, filtering, washing to be neutral, and drying to obtain porous-hydrophilic H2TiO3And (4) sieving the particles with ions. The granular titanium ion sieve adsorbent prepared by the method has the particle size of 1-3 mm, and is suitable for the comparative example 1 of the application.
The preparation method of the manganese ion sieve adsorbent comprises the following steps: 50g of lithium carbonate was added to 150mL of anhydrous ethanol under magnetic stirring to obtain an ethanol solution of lithium carbonate. And (3) according to the molar ratio of lithium to manganese of 1:2, metering manganese nitrate tetrahydrate into the solution, and continuously stirring until the manganese nitrate tetrahydrate is dissolved. And (3) drying the obtained mixed solution at 90 ℃ in vacuum to obtain a brownish red solid, and fully grinding the brownish red solid to obtain the lithium source manganese source mixed powder with high dispersity. Transferring the ground powder to a muffle furnace, heating to 700 ℃ and reacting for 20h to obtain a precursor LiMn2O4. Under the magnetic stirring, taking the LiMn precursor according to the solid-to-liquid ratio of 2g/L2O4Adding 1mol ofAcid treatment in hydrochloric acid solution for 24h, and then filtering, washing and drying to obtain manganese ion sieve adsorbent (with the structural formula of HMn)2O4). The manganese ion sieve adsorbent prepared by the method is in a uniform powder shape, has the particle size of 200-500 nm, and is suitable for the application of example 3, example 4 and example 5.
Example 1
(1) Injecting 100L of brine into the adsorption tank, wherein the temperature of the brine is 15 ℃, starting a stirrer 11 of the adsorption tank, and keeping the stirring speed at 80 r/min; and (3) adjusting the pH of the brine by using a 30 wt% sodium hydroxide solution, and adjusting the pH of the brine to 9.0-9.5 by adopting a pH online detector for real-time test to obtain the alkaline lithium-containing brine.
(2) 300g of powdery titanium ion sieve adsorbent (structural formula H) is metered2TiO3) Adding into alkaline lithium-containing brine, keeping the stirring speed at 80r/min, and continuously stirring for 20min to uniformly disperse the powdery titanium ion sieve adsorbent into the alkaline lithium-containing brine to form a first circulating liquid; starting the circulating pump 20, keeping the vacuum device in a closed state, reducing the stirring speed to 50r/min, and starting circulating dynamic adsorption for 2 h; testing Li in the first circulating liquid after adsorption+The adsorption capacity of the powdery titanium ion sieve adsorbent is calculated to be 30.3mg/g according to the mass percentage concentration.
Starting a vacuum device, and carrying out first solid-liquid membrane separation by negative pressure suction, wherein the suction pressure is-0.6 MPa, the membrane passing temperature is 35 ℃, and the membrane surface flow rate is 2 m/s; discharging the lithium-removed brine through a permeation side, and intercepting to obtain the lithium-containing adsorbent I.
The powdery titanium ion sieve adsorbent in the embodiment has uniform and fine appearance, and the particle size of the adsorbent is 250-450 nm.
(3) Closing the vacuum device, metering and adding 20L of pure water to form a second circulating liquid, and starting to circularly and dynamically wash for 15 min; and starting a vacuum device, performing second solid-liquid membrane separation, wherein the suction pressure is-0.5 MPa, the membrane passing temperature is 35 ℃, the membrane surface flow rate is 1.5m/s, performing suction filtration to obtain flushing wastewater, and intercepting to obtain a lithium-containing adsorbent II.
(4) The vacuum device is closed, 20L of 3 wt% hydrochloric acid solution is metered in to form a third circulating liquid,the temperature of the third circulating liquid is 20 ℃, and the circulating dynamic desorption is started for 2 hours; and after the desorption is finished, starting a vacuum device to perform third solid-liquid membrane separation, wherein the suction pressure is-0.7 MPa, the membrane passing temperature is less than 50 ℃, and the membrane surface flow rate is 2 m/s. The lithium-rich liquid is pumped out from the permeation side of the membrane separation device, and Li in the lithium-rich liquid is tested+The mass percentage concentration is reduced to 93.5 percent of desorption rate of the powdery titanium ion sieve adsorbent, and the obtained lithium-rich liquid is supplied to the subsequent lithium ion purification and lithium product preparation processes; the obtained regenerated powdery titanium ion sieve adsorbent is continuously and repeatedly used for extracting lithium from subsequent lithium-containing brine.
Comparative example 1
The comparative example 1 differs from example 1 in that: although the titanium ion sieve type adsorbent belongs to the same titanium ion sieve type adsorbent, the adsorbent is granular, the particle size is 1-3 mm, and the adsorption performance and the effect of the adsorbent are different. The method comprises the following specific steps:
(1) injecting 100L of brine into the adsorption tank, wherein the temperature of the brine is 18 ℃, starting a stirrer 11 of the adsorption tank, and keeping the stirring speed at 80 r/min; and (3) adjusting the pH of the brine by using a 30 wt% sodium hydroxide solution, and adjusting the pH of the brine to 9.0-9.5 by adopting a pH online detector for real-time test to obtain the alkaline lithium-containing brine.
(2) Stopping stirring, and adding 715g of granular titanium ion sieve lithium adsorbent (active ingredient is 42 wt%, and the active ingredient is of the ionic sieve structural formula H) into the alkaline lithium-containing brine2TiO3) Standing for adsorption for 18 h; testing Li in adsorbed lithium-containing brine+The mass percentage concentration is calculated to obtain that the adsorption capacity of the granular lithium titanium ion sieve adsorbent is 9.7mg/g (test data of the granular lithium titanium ion sieve adsorbent with 42 wt% of active ingredients).
And opening a drainage valve, intercepting the lithium-containing adsorbent I by using a filter screen with 80 meshes arranged at a water outlet in the tank, and filtering and discharging the lithium-removing brine.
In this embodiment, a granular titanium ion sieve adsorbent is used, the particle size of the granular titanium ion sieve adsorbent is 1 to 3mm, and the content of the titanium ion sieve adsorbent in the granular titanium ion sieve adsorbent is 42 wt%.
(3) Adding 40L of pure water into the lithium-containing adsorbent I in a metering manner, soaking and washing for 20min, opening a drainage valve, and filtering washing water by using an 80-mesh filter screen arranged at a water outlet in the tank; and then 20L of pure water is metered and added, the mixture is soaked and washed for 10min again, the lithium-containing adsorbent II is obtained by interception through a 80-mesh filter screen arranged at a water outlet in the tank, and the filtered washing wastewater is discharged.
(4) Adding 60L of 3 wt% hydrochloric acid solution into the lithium-containing adsorbent II, soaking and desorbing for 12 h; after the desorption is finished, a drainage valve is opened, a 80-mesh filter screen arranged at a water outlet in the tank is used for intercepting to obtain a regenerated granular titanium ion sieve adsorbent, lithium-rich liquid is obtained by filtration, and Li in the lithium-rich liquid is tested+The mass percentage concentration is reduced to obtain that the desorption rate of the granular titanium ion sieve adsorbent is 72.5 percent; the obtained lithium-rich liquid is supplied to subsequent lithium product purification and preparation processes for use; the obtained regenerated granular titanium ion sieve adsorbent is continuously and repeatedly used for extracting lithium from subsequent lithium-containing brine.
Compared with a powdery titanium ion sieve adsorbent, the granular titanium ion sieve adsorbent is used for extracting lithium ions, although the lithium extraction process is simpler, the problems of complex granulation process, large addition amount of the adsorbent, long time consumption in the adsorption, washing and desorption processes, large consumption of washing pure water and desorption liquid (3 wt% hydrochloric acid solution) and the like exist, meanwhile, the adsorption capacity of the adsorbent particles is 23.1mg/g under the condition that the effective components are 100% by converting the content of the adsorbent particles into 42 wt%, compared with the adsorption capacity of the powdery titanium ion sieve adsorbent which is not subjected to granulation treatment in example 1, the adsorption capacity of the granulated titanium ion sieve adsorbent is reduced by 23.76%, in a static desorption process, the desorption rate is also low, and the lithium extraction efficiency and the lithium ion yield in the whole process are not superior.
Example 2
The difference compared to example 1 is that: different powdered lithium adsorbents are selected, and the adsorption, flushing and desorption process control is also different. The method comprises the following specific steps:
(1) injecting 100L of brine into the adsorption tank, wherein the temperature of the brine is 15 ℃, starting a stirrer 11 of the adsorption tank, and keeping the stirring speed at 80 r/min; adjusting the pH of the brine by using a 30 wt% sodium hydroxide solution, and adjusting the pH of the brine to 7.5-8.0 by adopting a pH online detector for real-time test to obtain alkaline lithium-containing brine;
(2) 450g of powdery aluminum salt adsorbent [ the general structural formula of which is LiX.2Al (OH) ]3·nH2O]Adding the mixture into the alkaline lithium-containing brine, and keeping the stirring speed of 80r/min to continue stirring for 20min so that the adsorbent is uniformly dispersed in the alkaline lithium-containing brine; forming a first circulating liquid; starting the circulating pump 20, keeping the vacuum device in a closed state, reducing the stirring speed to 50r/min, and starting circulating dynamic adsorption for 2 h; testing Li in the first circulating liquid after adsorption+The mass percentage concentration is calculated to obtain that the adsorption capacity of the powdery aluminum salt adsorbent is 10.5 mg/g.
Starting a vacuum device, and performing negative pressure suction to perform first solid-liquid membrane separation, wherein the suction pressure is-0.6 MPa, the membrane passing temperature is 35 ℃, and the membrane surface flow velocity is 2 m/s; discharging the lithium-removing brine through the permeation side, and intercepting to obtain the lithium-containing adsorbent I.
The powdered aluminum salt adsorbent in the embodiment is uniform powder, and the particle size of the adsorbent is 250-550 nm.
(3) Closing the vacuum device, metering and adding 10L of pure water to form a second circulating liquid, and starting to circularly and dynamically wash for 5 min; and starting a vacuum device, performing second solid-liquid membrane separation, wherein the suction pressure is-0.5 MPa, the membrane passing temperature is 25 ℃, the membrane surface flow rate is 1.5m/s, performing suction filtration to obtain washing wastewater, and intercepting to obtain a lithium-containing adsorbent II.
(4) Closing the vacuum device, metering and injecting 20L of pure water to form a third circulating liquid, wherein the temperature of the formed third circulating liquid is 20 ℃, and starting to perform cyclic dynamic desorption for 2 h; and after the desorption is finished, starting a vacuum device to perform third solid-liquid membrane separation, wherein the suction pressure is-0.6 MPa, the membrane passing temperature is less than 50 ℃, and the membrane surface flow rate is 2 m/s. The lithium-rich liquid is pumped out from the permeation side of the membrane separation device, and Li in the lithium-rich liquid is tested+The mass percentage concentration is reduced to 93.8 percent of desorption rate of the powdery aluminum salt adsorbent, and the obtained lithium-rich liquid is supplied to subsequent lithium product purification and preparation processes; the obtained regenerated powder aluminum salt adsorbent is continuously and repeatedly used for extracting lithium from subsequent lithium-containing brine.
Under the same process, the adsorption capacity of the powdery aluminum salt adsorbent is smaller, but the preparation process is simple, the energy consumption is less, pure water is used for desorption in the desorption process, the cost is lower, the pollution is less, and the method has a certain application space.
Example 3
The differences compared to example 1 are: although the manganese ion sieve adsorbent belongs to the ion sieve type adsorbent, the manganese ion sieve adsorbent is selected in powder form, and the manganese ion sieve adsorbent are different in structure and composition, and different in adsorption performance and effect. The method comprises the following specific steps:
(1) injecting 100L of brine into the adsorption tank, wherein the temperature of the brine is 18 ℃, starting a stirrer 11 of the adsorption tank, and keeping the stirring speed at 80 r/min; and (3) adjusting the pH of the brine by using a 30 wt% sodium hydroxide solution, and adjusting the pH of the brine to 9.0-9.5 by adopting a pH online detector for real-time test to obtain the alkaline lithium-containing brine.
(2) 300g of powdery manganese ion sieve adsorbent (structural formula HMn)2O4) Adding into alkaline lithium-containing brine, and keeping the stirring speed of 80r/min to continue stirring for 20min, so that the powdery manganese ion sieve adsorbent is uniformly dispersed in the alkaline lithium-containing brine; forming a first circulating liquid; starting the circulating pump 20, keeping the vacuum device in a closed state, reducing the stirring speed to 50r/min, and starting circulating dynamic adsorption for 2 h; testing Li in the first circulating liquid after adsorption+The adsorption capacity of the powdery manganese ion sieve adsorbent is 34.7mg/g by calculation according to the mass percentage concentration.
Starting a vacuum device, and carrying out first solid-liquid membrane separation by negative pressure suction, wherein the suction pressure is-0.6 MPa, the membrane passing temperature is 37 ℃, and the membrane surface flow rate is 2 m/s; discharging the lithium-removing brine through the permeation side, and intercepting to obtain the lithium-containing adsorbent I.
The particle size of the powdery manganese ion sieve adsorbent in the embodiment is 200-500 nm.
(3) Closing the vacuum device, metering and adding 20L of pure water to form a second circulating liquid, and starting to circularly and dynamically wash for 15 min; and starting a vacuum device, performing second solid-liquid membrane separation, wherein the suction pressure is-0.5 MPa, the membrane passing temperature is 35 ℃, the membrane surface flow rate is 1.5m/s, performing suction filtration to obtain flushing wastewater, and intercepting to obtain a lithium-containing adsorbent II.
(4) The vacuum apparatus is switched off and 3 wt.% hydrochloric acid solution is metered in20L of liquid to form third circulating liquid, wherein the temperature of the third circulating liquid is 21 ℃, the cyclic dynamic desorption is started, and the desorption time is 2 hours; and after the desorption is finished, starting a vacuum device to perform third solid-liquid membrane separation, wherein the suction pressure is-0.7 MPa, the membrane passing temperature is less than 50 ℃, and the membrane surface flow rate is 2 m/s. The lithium-rich liquid is pumped out from the permeation side of the membrane separation device, and Li in the lithium-rich liquid is tested+The mass percentage concentration is converted into the desorption rate of the powdery manganese ion sieve adsorbent of 94.7 percent; the obtained lithium-rich liquid is used in the subsequent lithium product purification and preparation processes; the obtained regenerated powdery manganese ion sieve adsorbent is continuously and repeatedly used for extracting lithium from subsequent lithium-containing brine.
The powdery manganese ion sieve adsorbent adopts the lithium extraction process, so that a good lithium extraction effect is achieved, the adsorption capacity and the desorption rate are high, the time consumption of the whole lithium extraction process is short, and the economical efficiency is good.
Example 4
The difference compared to example 3 is that: the same powdered manganese ion sieve adsorbent is adopted, but the adsorbent is adjusted to Li in the lithium-containing brine+Adsorption and desorption times of (a). The method comprises the following specific steps:
(1) injecting 100L of brine into the adsorption tank, wherein the temperature of the brine is 16 ℃, starting a stirrer 11 of the adsorption tank, and keeping the stirring speed at 80 r/min; and (3) adjusting the pH of the brine by using a 30 wt% sodium hydroxide solution, and adjusting the pH of the brine to 9.0-9.5 by adopting a pH online detector for real-time test to obtain the alkaline lithium-containing brine.
(2) 300g of powdery manganese ion sieve adsorbent (structural formula HMn) is respectively metered2O4) Adding into alkaline lithium-containing brine, and keeping the stirring speed of 80r/min to continue stirring for 20min, so that the powdery manganese ion sieve adsorbent is uniformly dispersed in the alkaline lithium-containing brine; forming a first circulating liquid; starting a circulating pump 20, keeping the vacuum device in a closed state, reducing the stirring speed to 50r/min, and starting circulating dynamic adsorption for 1h, 3h and 4h respectively; testing Li in the first circulating liquid after adsorption+And (4) calculating the adsorption capacity of the powdery manganese ion sieve adsorbent according to the mass percentage concentration.
Starting a vacuum device, and carrying out first solid-liquid membrane separation by negative pressure suction, wherein the suction pressure is-0.6 MPa, the membrane passing temperature is 35 ℃, and the membrane surface flow rate is 2 m/s; discharging the lithium-removed brine through a permeation side, and intercepting to obtain a lithium-containing adsorbent I;
the particle size of the manganese ion sieve adsorbent is 200-500 nm.
(3) Closing the vacuum device, metering and adding 20L of pure water to form a second circulating liquid, and starting to circularly and dynamically wash for 15 min; starting a vacuum device, carrying out second solid-liquid membrane separation, wherein the suction pressure is-0.5 MPa, the membrane passing temperature is 32 ℃, the membrane surface flow rate is 1.5m/s, carrying out suction filtration on the flushing wastewater, and intercepting to obtain a lithium-containing adsorbent II;
(4) closing the vacuum device, and metering and adding 20L of 3 wt% hydrochloric acid solution to form a third circulating liquid, wherein the temperature of the third circulating liquid is 20 ℃, and the circulating dynamic desorption is started, and the desorption time is respectively 1h, 2h and 3 h; and after the desorption is finished, starting a vacuum device to perform third solid-liquid membrane separation, wherein the suction pressure is-0.7 MPa, the membrane passing temperature is less than 50 ℃, and the membrane surface flow rate is 2 m/s. The lithium-rich liquid is filtered out by the permeation side of the membrane separation device, and Li in the lithium-rich liquid is tested+Converting the mass percent concentration into the desorption rate of the powdery manganese ion sieve adsorbent; the obtained lithium-rich liquid is supplied to subsequent lithium product purification and preparation processes for use; the obtained regenerated powdery manganese ion sieve adsorbent is continuously and repeatedly used for extracting lithium from subsequent lithium-containing brine. The adjusted test results are shown in table 2.
TABLE 2
By combining the relevant test data of the adsorption time of 2h and the desorption time of 2h in the embodiment 3, in the embodiment, when the adsorption time of the powdery manganese ion sieve adsorbent is 1h, the adsorption capacity value is smaller and is only 27.7mg/g, it can be seen that the adsorption time is shorter, the powdery manganese ion sieve adsorbent cannot be sufficiently adsorbed, and when the adsorption time is prolonged to 3h and 4h, the adsorption capacity is greatly improved, but the improvement rate of the adsorption capacity between the two is not large, which indicates that the lithium adsorbent is close to saturated adsorption, and the influence of the time prolongation on the adsorption capacity is small, so that the adsorption time is preferably 2-3 h, and the cost is optimal; on the other hand, the desorption rate of lithium ions in the adsorbent is in an increasing trend along with the prolonging of the desorption time, when the desorption time is prolonged to 2 hours and 3 hours, the desorption rate reaches a higher level, the operation cost and the lithium extraction efficiency are comprehensively considered, and the preferred desorption time is 2-3 hours.
Example 5
The difference compared to example 3 is that: the same powdery manganese ion sieve adsorbent is adopted, but the types and concentration parameters of desorption liquid in the lithium extraction process are adjusted. The method comprises the following specific steps:
(1) injecting 100L of brine into the adsorption tank, wherein the temperature of the brine is 17 ℃, starting a stirrer 11 of the adsorption tank, and keeping the stirring speed at 80 r/min; and (3) adjusting the pH of the brine by using a 30 wt% sodium hydroxide solution, and adjusting the pH of the brine to 9.0-9.5 by adopting a pH online detector for real-time test to obtain the alkaline lithium-containing brine.
(2) 300g of powdery manganese ion sieve adsorbent (structural formula HMn)2O4) Adding into alkaline lithium-containing brine, and keeping the stirring speed of 80r/min to continue stirring for 20min, so that the powdery manganese ion sieve adsorbent is uniformly dispersed in the alkaline lithium-containing brine; forming a first circulating liquid; starting the circulating pump 20, keeping the vacuum device in a closed state, reducing the stirring speed to 50r/min, and starting circulating dynamic adsorption for 2 h; testing Li in the first circulating liquid after adsorption+And calculating the mass percent concentration to obtain the adsorption capacity of the powdery manganese ion sieve adsorbent of 35.8 mg/g.
Starting a vacuum device, and carrying out first solid-liquid membrane separation by negative pressure suction, wherein the suction pressure is-0.6 MPa, the membrane passing temperature is 35 ℃, and the membrane surface flow rate is 2 m/s; discharging the lithium-removing brine through the permeation side, and intercepting to obtain the lithium-containing adsorbent I.
The particle size of the powdery manganese ion sieve adsorbent in the embodiment is 200-500 nm.
(3) Closing the vacuum device, metering and adding 20L of pure water to form a second circulating liquid, and starting to circularly and dynamically wash for 15 min; and starting a vacuum device, performing second solid-liquid membrane separation, wherein the suction pressure is-0.5 MPa, the membrane passing temperature is 25 ℃, the membrane surface flow rate is 1.5m/s, performing suction filtration to obtain flushing wastewater, and intercepting to obtain a lithium adsorbent II.
(4) Closing the vacuum device, and metering 20L of desorption liquid with different types and different concentrations (the type and the concentration of the desorption liquid are shown in table 3) to form third circulating liquid, wherein the temperature of the third circulating liquid is 20 ℃, the circulating dynamic desorption is started, and the desorption time is 2 h; and after the desorption is finished, starting a vacuum device to perform third solid-liquid membrane separation, wherein the suction pressure is-0.7 MPa, the membrane passing temperature is less than 50 ℃, and the membrane surface flow rate is 2 m/s. The lithium-rich liquid is pumped out from the permeation side of the membrane separation device, and Li in the lithium-rich liquid is tested+Converting the mass percent concentration into the desorption rate of the powdery manganese ion sieve adsorbent; the obtained lithium-rich liquid is supplied to subsequent lithium product purification and preparation processes for use; the obtained regenerated powdery manganese ion sieve adsorbent is continuously and repeatedly used for extracting lithium from subsequent lithium-containing brine.
The results of the influence of different desorption liquid types and concentrations on the desorption rate of the lithium adsorbent II are shown in Table 3.
TABLE 3
As can be seen from the data in table 3, the desorption effect of the nitric acid solution is the worst, and the data change is large; the desorption effect of the sulfuric acid solution is not as good as that of the hydrochloric acid solution; the hydrochloric acid solution has high desorption rate effect of lithium ions under the concentration of 1 wt%, 2 wt% and 3 wt%, and can be comprehensively selected in combination with other factors in practical application.
Claims (10)
1. A lithium extraction process for coupling a powdery lithium adsorbent with a hollow fiber membrane is characterized by comprising the following steps:
(1) in an adsorption tank, adjusting the pH value of lithium-containing brine by using an alkaline solution to obtain alkaline lithium-containing brine;
(2) carrying out cyclic dynamic adsorption on alkaline lithium-containing brine by using a powdery lithium adsorbent to obtain an adsorbed solid-liquid mixture, and carrying out first solid-liquid membrane separation on the adsorbed solid-liquid mixture to obtain a lithium-containing adsorbent I and lithium-removing brine;
(3) carrying out cyclic dynamic washing on the lithium-containing adsorbent I by using pure water to obtain a washing solid-liquid mixture including the lithium-containing adsorbent after the dynamic washing is finished, and carrying out second solid-liquid membrane separation on the washing solid-liquid mixture to obtain a lithium-containing adsorbent II and washing wastewater;
(4) and (3) carrying out cyclic dynamic desorption on the lithium-containing adsorbent II by using desorption liquid to obtain a desorbed solid-liquid mixture, and carrying out third solid-liquid membrane separation on the desorbed solid-liquid mixture to obtain a regenerated powdery lithium adsorbent and a lithium-rich liquid.
2. The lithium extraction process of claim 1,
the powdery lithium adsorbent is one or a mixture of several of an ion sieve type adsorbent, an aluminum salt adsorbent, a modified mineral adsorbent, a macrocyclic compound type adsorbent and a hydroxide adsorbent, and the particle size of the powdery lithium adsorbent is 200-600 nm.
3. The lithium extraction process of claim 1,
in the step (1), the lithium-containing brine is salt lake brine or underground brine; mg in lithium-containing brine2+With Li+The mass ratio of (A) to (B) is 1: 1-1500: 1; li in lithium-containing brine+The mass percentage concentration is 0.002-2%.
4. The lithium extraction process of claim 1,
in the step (2), the step of cyclic dynamic adsorption is to add the powdery lithium adsorbent into the alkaline lithium-containing brine, stir the mixture evenly to form a first circulating liquid, so that the first circulating liquid flows in a first cycle between the adsorption tank and the membrane separation device, and the powdery lithium adsorbent dynamically adsorbs lithium ions; and after the dynamic adsorption is finished, forming an adsorption solid-liquid mixture, and performing first solid-liquid membrane separation on the adsorption solid-liquid mixture by using the membrane separation device to obtain a lithium-containing adsorbent I and lithium-removing brine.
5. The lithium extraction process of claim 4,
the adding amount of the powdery lithium adsorbent in the alkaline lithium-containing brine is 0.5-8 g/L, after the alkaline lithium-containing brine is added into the powdery lithium adsorbent, first stirring is carried out, a first circulating liquid is formed after stirring is carried out for 10-30 min, and the stirring speed of the first stirring is 60-120 r/min.
6. The lithium extraction process of claim 4,
when the cyclic dynamic adsorption is carried out, the temperature of the first circulating liquid is-5-45 ℃, and the cyclic dynamic adsorption time is 1-4 h;
and during the circulating dynamic adsorption, keeping the first circulating liquid in the adsorption tank to be subjected to second stirring, wherein the stirring speed of the second stirring is 30-80 r/min.
7. The lithium extraction process of claim 4,
the membrane separation device is a hollow fiber membrane separation device, and negative pressure suction is adopted when first solid-liquid membrane separation is carried out, wherein the suction pressure is-0.4 to-0.8 MPa, the membrane passing temperature is 0 to 80 ℃, and the membrane surface flow rate is 1 to 3 m/s.
8. The lithium extraction process of claim 1,
in the step (3), the step of circularly and dynamically washing is to add pure water into the lithium-containing adsorbent I to form a second circulating liquid, then to make the second circulating liquid perform second circulating flow between the membrane separation device and the first circulating tank, to dynamically wash the lithium-containing adsorbent I, after the dynamic washing is completed, to form a washing solid-liquid mixture, and to perform second solid-liquid membrane separation on the washing solid-liquid mixture by using the membrane separation device to obtain a lithium-containing adsorbent II and washing wastewater;
when dynamic washing is carried out, the temperature of the second circulating liquid is 5-60 ℃, and the washing time is 5-20 min;
the membrane separation device is a hollow fiber membrane separation device, negative pressure suction is adopted when second solid-liquid membrane separation is carried out, the suction pressure is-0.4 to-0.8 MPa, and the membrane passing temperature is 5-70 ℃.
9. The lithium extraction process of claim 1,
in the step (4), in the cyclic dynamic desorption, desorption liquid is added into a lithium-containing adsorbent II to form third circulation liquid, then the third circulation liquid is subjected to third circulation flow between a membrane separation device and a second circulation tank, dynamic desorption is carried out on the lithium-containing adsorbent II, a desorption solid-liquid mixture is formed after the dynamic desorption is completed, and the membrane separation device is used for carrying out third solid-liquid membrane separation on the desorption solid-liquid mixture to obtain a regenerated powder lithium adsorbent and a lithium-rich liquid;
when dynamic desorption is carried out, the temperature of the third circulating liquid is 5-60 ℃, and the desorption time is 1-3 h;
the membrane separation device is a hollow fiber membrane separation device, negative pressure suction is adopted when third solid-liquid membrane separation is carried out, the suction pressure is-0.4 to-0.8 MPa, and the membrane passing temperature is 5-70 ℃.
10. The lithium extraction process of claim 1,
performing first solid-liquid membrane separation, second solid-liquid membrane separation and third solid-liquid membrane separation by using the same membrane separation device; when the cyclic dynamic adsorption, the cyclic dynamic flushing and the cyclic dynamic desorption are carried out, the first circulating liquid during the cyclic dynamic adsorption, the second circulating liquid during the cyclic dynamic flushing and the third circulating liquid during the cyclic dynamic desorption are all carried out by the membrane separation device.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111388808.8A CN114086006B (en) | 2021-11-22 | 2021-11-22 | Lithium extraction process for coupling powdery lithium adsorbent with hollow fiber membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111388808.8A CN114086006B (en) | 2021-11-22 | 2021-11-22 | Lithium extraction process for coupling powdery lithium adsorbent with hollow fiber membrane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114086006A true CN114086006A (en) | 2022-02-25 |
| CN114086006B CN114086006B (en) | 2023-03-21 |
Family
ID=80302853
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111388808.8A Active CN114086006B (en) | 2021-11-22 | 2021-11-22 | Lithium extraction process for coupling powdery lithium adsorbent with hollow fiber membrane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114086006B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115074526A (en) * | 2022-06-28 | 2022-09-20 | 礼思(上海)材料科技有限公司 | Device and method for reducing impurity content of desorption liquid |
| 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 |
| CN116062836A (en) * | 2022-12-05 | 2023-05-05 | 碧水源膜技术研究中心(北京)有限公司 | Adsorption and membrane coupling water treatment method and device |
| CN116240401A (en) * | 2023-03-03 | 2023-06-09 | 桂林理工大学 | Method for extracting rare-earth element lithium from Bayer process sodium aluminate solution |
| CN116751989A (en) * | 2023-06-21 | 2023-09-15 | 唐山鑫丰锂业有限公司 | Method for extracting lithium from salt lake brine |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102086521A (en) * | 2010-12-10 | 2011-06-08 | 江苏久吾高科技股份有限公司 | Adsorption and ceramic membrane coupling process for removing sulfate ions from saline water |
| CN103304063A (en) * | 2013-07-01 | 2013-09-18 | 大唐国际化工技术研究院有限公司 | Integral reactor for liquid-phase adsorption and solid-liquid separation, application thereof and water treatment method |
| CN104313348A (en) * | 2014-07-23 | 2015-01-28 | 江苏久吾高科技股份有限公司 | Method for extracting lithium from salt lake brine by using adsorption method |
| CN106435220A (en) * | 2016-09-06 | 2017-02-22 | 南京工业大学 | Method for reducing magnesium-lithium ratio of salt lake brine |
| CN109266851A (en) * | 2018-09-07 | 2019-01-25 | 中国科学院青海盐湖研究所 | A method of lithium is extracted by magnetic micropore lithium adsorbent |
| CN110106356A (en) * | 2019-05-24 | 2019-08-09 | 江苏特丰新材料科技有限公司 | A kind of method of powder-type titanium system's ion-exchanger separation Lithium from Salt Lake Brine |
| US20210077990A1 (en) * | 2018-02-28 | 2021-03-18 | Lilac Solutions, Inc. | Ion exchange reactor with particle traps for lithium extraction |
-
2021
- 2021-11-22 CN CN202111388808.8A patent/CN114086006B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102086521A (en) * | 2010-12-10 | 2011-06-08 | 江苏久吾高科技股份有限公司 | Adsorption and ceramic membrane coupling process for removing sulfate ions from saline water |
| CN103304063A (en) * | 2013-07-01 | 2013-09-18 | 大唐国际化工技术研究院有限公司 | Integral reactor for liquid-phase adsorption and solid-liquid separation, application thereof and water treatment method |
| CN104313348A (en) * | 2014-07-23 | 2015-01-28 | 江苏久吾高科技股份有限公司 | Method for extracting lithium from salt lake brine by using adsorption method |
| CN106435220A (en) * | 2016-09-06 | 2017-02-22 | 南京工业大学 | Method for reducing magnesium-lithium ratio of salt lake brine |
| US20210077990A1 (en) * | 2018-02-28 | 2021-03-18 | Lilac Solutions, Inc. | Ion exchange reactor with particle traps for lithium extraction |
| CN109266851A (en) * | 2018-09-07 | 2019-01-25 | 中国科学院青海盐湖研究所 | A method of lithium is extracted by magnetic micropore lithium adsorbent |
| CN110106356A (en) * | 2019-05-24 | 2019-08-09 | 江苏特丰新材料科技有限公司 | A kind of method of powder-type titanium system's ion-exchanger separation Lithium from Salt Lake Brine |
Non-Patent Citations (1)
| Title |
|---|
| 孟庆伟等: "《离子筛吸附与陶瓷膜耦合用于盐湖卤水提锂》", 《化工学报》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115074526A (en) * | 2022-06-28 | 2022-09-20 | 礼思(上海)材料科技有限公司 | Device and method for reducing impurity content of desorption liquid |
| CN115074526B (en) * | 2022-06-28 | 2024-05-24 | 礼思(上海)材料科技有限公司 | Device and method for reducing impurity content of desorption liquid |
| 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 |
| CN116062836A (en) * | 2022-12-05 | 2023-05-05 | 碧水源膜技术研究中心(北京)有限公司 | Adsorption and membrane coupling water treatment method and device |
| CN116240401A (en) * | 2023-03-03 | 2023-06-09 | 桂林理工大学 | Method for extracting rare-earth element lithium from Bayer process sodium aluminate solution |
| CN116751989A (en) * | 2023-06-21 | 2023-09-15 | 唐山鑫丰锂业有限公司 | Method for extracting lithium from salt lake brine |
| CN116751989B (en) * | 2023-06-21 | 2024-02-09 | 唐山鑫丰锂业有限公司 | Method for extracting lithium from salt lake brine |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114086006B (en) | 2023-03-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN114086006B (en) | Lithium extraction process for coupling powdery lithium adsorbent with hollow fiber membrane | |
| KR101047986B1 (en) | Adsorption and desorption device of litium ion using counter current decantation process and method using the same | |
| JP2021120350A (en) | System for preparing battery-grade, and high-purity-grade lithium hydroxide and lithium carbonate from high-impurity lithium source | |
| WO2015096549A1 (en) | Process and apparatus for extracting battery grade lithium from brine | |
| CN111729350B (en) | Equipment for extracting lithium from brine by adsorption method | |
| CN112808251A (en) | Adsorbent for extracting lithium from salt lake and preparation method thereof | |
| CN104229906B (en) | The method and apparatus of the nickel-containing waste water preparation plating level single nickel salt utilizing surface treatment process to produce | |
| CN113511663A (en) | Process for preparing lithium carbonate by extracting lithium from oil field underground brine | |
| WO2024027045A1 (en) | Method for preparing aluminum salt functional material for lithium extraction | |
| WO2022007662A1 (en) | Band filter and application thereof in extraction of lithium from brine using adsorption method | |
| CN108126739A (en) | Catalyst of COD and preparation method thereof in a kind of ozone heterocatalysis oxidized waste water | |
| CN113262648A (en) | Lithium ion selective permeation membrane and application thereof | |
| Chen et al. | Highly efficient and selective cesium recovery from natural brine resources using mesoporous Prussian blue analogs synthesized by ionic liquid-assisted strategy | |
| CN105363413A (en) | Multidimensional mesoporous metal organic frameworks adsorbent and application thereof | |
| CN113578287A (en) | Fluorine adsorbent and preparation and application thereof | |
| CN115069208B (en) | Porous fiber bundle-shaped titanium-based lithium adsorbent and preparation method thereof | |
| WO2024011796A1 (en) | Lithium adsorption material, and preparation method therefor and use thereof | |
| CN110106356B (en) | Method for separating lithium from salt lake brine by using powder type titanium ion exchanger | |
| CN112076717A (en) | Method for preparing lithium ion sieve through melt impregnation reaction | |
| CN109621922A (en) | A kind of monoblock type phenolic resin base lithium ion sieve and its preparation method and application | |
| CN106582513A (en) | Composite adsorption material for treatment of heavy metal wastewater and preparation method thereof | |
| CN117258744A (en) | Granular lithium adsorbent and preparation method and application thereof | |
| CN115807169A (en) | Lithium extraction method for alkaline solution | |
| CN102847507A (en) | Composite absorption material for removing sulfates in water, and preparation method thereof | |
| CN117398965B (en) | Silicon removing material 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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |