WO2022152256A1 - Preparation method for high-porosity lithium ion sieve particles - Google Patents
Preparation method for high-porosity lithium ion sieve particles Download PDFInfo
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- WO2022152256A1 WO2022152256A1 PCT/CN2022/072072 CN2022072072W WO2022152256A1 WO 2022152256 A1 WO2022152256 A1 WO 2022152256A1 CN 2022072072 W CN2022072072 W CN 2022072072W WO 2022152256 A1 WO2022152256 A1 WO 2022152256A1
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- WIPO (PCT)
- Prior art keywords
- lithium ion
- acid
- ion sieve
- preparation
- lithium
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 61
- 239000002245 particle Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000000839 emulsion Substances 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000011347 resin Substances 0.000 claims abstract description 19
- 229920005989 resin Polymers 0.000 claims abstract description 19
- 239000002253 acid Substances 0.000 claims abstract description 17
- 239000000945 filler Substances 0.000 claims abstract description 13
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 10
- 238000002386 leaching Methods 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract 2
- 239000000203 mixture Substances 0.000 claims description 20
- 239000000843 powder Substances 0.000 claims description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000008187 granular material Substances 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 4
- 239000010451 perlite Substances 0.000 claims description 4
- 235000019362 perlite Nutrition 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- 229960000892 attapulgite Drugs 0.000 claims description 3
- 239000003822 epoxy resin Substances 0.000 claims description 3
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052625 palygorskite Inorganic materials 0.000 claims description 3
- 229920000647 polyepoxide Polymers 0.000 claims description 3
- 239000007790 solid phase Substances 0.000 claims description 3
- 229920001909 styrene-acrylic polymer Polymers 0.000 claims description 3
- 239000011787 zinc oxide Substances 0.000 claims description 3
- 239000005995 Aluminium silicate Substances 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 235000012211 aluminium silicate Nutrition 0.000 claims description 2
- 239000000440 bentonite Substances 0.000 claims description 2
- 229910000278 bentonite Inorganic materials 0.000 claims description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 2
- 239000001913 cellulose Substances 0.000 claims description 2
- 229920002678 cellulose Polymers 0.000 claims description 2
- SHFGJEQAOUMGJM-UHFFFAOYSA-N dialuminum dipotassium disodium dioxosilane iron(3+) oxocalcium oxomagnesium oxygen(2-) Chemical compound [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[Na+].[Na+].[Al+3].[Al+3].[K+].[K+].[Fe+3].[Fe+3].O=[Mg].O=[Ca].O=[Si]=O SHFGJEQAOUMGJM-UHFFFAOYSA-N 0.000 claims description 2
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 claims description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 2
- 239000000347 magnesium hydroxide Substances 0.000 claims description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 229920002635 polyurethane Polymers 0.000 claims description 2
- 239000004814 polyurethane Substances 0.000 claims description 2
- 229920002050 silicone resin Polymers 0.000 claims description 2
- 235000000346 sugar Nutrition 0.000 claims description 2
- 150000008163 sugars Chemical class 0.000 claims description 2
- 239000013618 particulate matter Substances 0.000 claims 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 1
- 229910052782 aluminium Inorganic materials 0.000 claims 1
- 229910052748 manganese Inorganic materials 0.000 claims 1
- 239000011572 manganese Substances 0.000 claims 1
- 239000011812 mixed powder Substances 0.000 claims 1
- 239000010936 titanium Substances 0.000 claims 1
- 229910052719 titanium Inorganic materials 0.000 claims 1
- 229910052744 lithium Inorganic materials 0.000 abstract description 30
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 29
- 238000000034 method Methods 0.000 abstract description 24
- 238000001179 sorption measurement Methods 0.000 abstract description 18
- 239000012267 brine Substances 0.000 abstract description 14
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 abstract description 14
- 238000001125 extrusion Methods 0.000 abstract description 5
- 239000011148 porous material Substances 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 5
- 239000013535 sea water Substances 0.000 abstract description 4
- 238000000227 grinding Methods 0.000 abstract description 2
- 239000003921 oil Substances 0.000 abstract description 2
- 239000007789 gas Substances 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- 239000002351 wastewater Substances 0.000 abstract 1
- 238000000605 extraction Methods 0.000 description 12
- 239000002904 solvent Substances 0.000 description 6
- 238000001994 activation Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- 230000004913 activation Effects 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000005204 segregation Methods 0.000 description 2
- 238000010557 suspension polymerization reaction Methods 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- 239000005909 Kieselgur Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000002198 insoluble material Substances 0.000 description 1
- 238000013035 low temperature curing Methods 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000010413 mother solution Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000005185 salting out Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28016—Particle form
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Definitions
- the invention relates to a preparation method of high-porosity lithium ion sieve particles, and belongs to the technical field of lithium extraction from salt lakes.
- Lithium and its compounds are important strategic materials for national economy and national defense construction, and are widely used in many fields such as glass, ceramics, aviation, nuclear energy and new energy.
- USGS United States Geological Survey Geological Survey
- Traditional lithium extraction techniques mainly include precipitation method, salting out method, solvent extraction method, etc. Due to the complex components of salt lake brine and (concentrated) seawater, the traditional extraction method has the disadvantages of complex process flow and high energy consumption; while the ion exchange and adsorption method for lithium extraction has the advantages of good selective adsorption, simple process and high recovery rate, especially It is suitable for salt lake brine with high magnesium-to-lithium ratio in my country, and has developed into a very promising method for lithium extraction.
- the lithium ion sieve powder used in the ion exchange method has the problems of difficulty in solid-liquid separation and high dissolution rate when it is directly applied, it needs to be prepared into granules of a certain size for use.
- the current mainstream methods in the prior art mainly include the following: One is to mix the lithium ion sieve powder with the thermoplastic resin and heat it to a molten state. The main defect of this method is to maintain the high temperature fluidity of the mixture, the resin content needs to be higher than 40%, and the amount of resin is too large.
- the second method is suspension polymerization or reversed-phase suspension polymerization.
- the two methods are Lithium ion sieve particles are obtained by adding lithium ion sieve powder to the oil phase or water phase composed of polymer monomers, adjusting the size of the suspended droplets by controlling stirring and dispersing agent, and raising the temperature to a certain temperature to initiate a polymerization reaction.
- the main problems of this method are that the process control is cumbersome, the cost is high, and quality fluctuations are prone to occur, and the lithium ion sieve powder is easily transferred to another phase, causing losses, and the generated organic waste liquid will also increase environmental protection pressure; the third type The method is to dissolve the resin in an organic solvent, and then mix it with lithium ion sieve powder to granulate.
- the difficulty of this method is that the solubility of general resin in organic solvents is low. Adding too much solvent will cause the slurry to be mixed and difficult to characterize. The processing is difficult, there is a risk of solvent explosion during the drying process, and the VOC emissions are also large.
- the invention aims to solve the problems in the prior art such as difficulty in forming a lithium ion sieve, high manufacturing cost, and low adsorption efficiency after forming, and provides a high-efficiency ion sieve particle and a low-cost and environmentally friendly preparation method of the lithium ion sieve particle .
- the lithium ion sieve particles prepared by this method have been tried to extract lithium from Qinghai salt lake brine, and have achieved high lithium extraction effect, which has a very broad application prospect.
- the object of the present invention is to provide a kind of preparation method of high porosity lithium ion sieve particle, it comprises the following steps:
- the lithium ion sieve described in step (1) is a material that selectively adsorbs lithium ions, including titanium series, manganese series, aluminum series, etc., but is not limited thereto. Its grinding fineness is 50-1000 mesh, and its addition amount is 10-90% of the total mass of the substance in this step;
- the template pore-forming agent is a hot water soluble substance or a dilute acid soluble particulate substance, including one of sugars, calcium carbonate, magnesium oxide, magnesium hydroxide, aluminum oxide, zinc oxide, and iron oxide. species or a mixture of several.
- the particle size is controlled at 0.5-100 ⁇ m, preferably 5-50 ⁇ m, and the pore size created in this range is more suitable; the template pore-forming agent is added in an amount of 1%-50% of the total mass of the substance in this step, and the better is,
- the mass percentage of its addition amount is 10%-20%, which is beneficial to ensure the strength of the lithium ion sieve particles and maintain a high lithium extraction rate;
- the filler in the step (1) is a powder material with a porous structure, including, but not limited to, one or more of activated carbon, cellulose, attapulgite, kaolin, diatomite, bentonite, and perlite. More preferably, an acid-insoluble material should be used as the filler, which can ensure the support of the material inside the particles during acid leaching.
- the added amount of the filler is 0%-70% (excluding 0) of the total mass of the substance in this step, and the more optimal addition amount is 20-50%. By increasing the mass ratio of the filler, the utilization rate of the lithium ion sieve can be improved, cut costs;
- the water-based resin emulsion described in step (2) comprises one or a mixture of epoxy resin emulsion, polyurethane emulsion, acrylic emulsion, silicone resin emulsion, styrene-acrylic emulsion, ethylene-propylene emulsion, and EVA emulsion. More preferably, the water-based resin emulsion with a VOC content of less than 1% is selected, which is more environmentally friendly.
- the added amount is 10%-30%wt of the mixture powder based on the solid phase; more preferably, the added amount based on the solid phase is less than 20%, which can reduce the surface area of the lithium ion sieve wrapped by the resin, Has a higher lithium extraction rate;
- the particle size of the small particles in step (2) is 0.2-5mm, preferably 0.2-2mm, and a smaller particle size helps to improve the adsorption efficiency of lithium ions;
- the acid used for the acid leaching in the step (3) includes hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, oxalic acid, acetic acid, etc., but is not limited thereto.
- the acid concentration is 0.1-2mol/L, preferably 0.5-1mol/L hydrochloric acid. Under this concentration, the lithium ion sieve particles can be fully activated without causing a large amount of dissolution loss of the ion sieve.
- the acid leaching temperature is selected. For 40-60 °C, the activation time can be shortened.
- the present invention utilizes the inherent acid leaching step in the activation process of the lithium ion sieve to dissolve the template pore-forming agent, and the activation process is also a pore-making process, and the prepared lithium ion sieve particles have high porosity, which is conducive to improving lithium
- the contact area between the ion sieve and the brine can improve the lithium extraction rate and adsorption capacity, and the porosity and pore size of the lithium ion sieve particles can be adjusted by adjusting the particle size and amount of the template pore-forming agent for different types of brine extraction. lithium.
- the present invention selects hydrophilic porous material as the framework material to support the lithium ion sieve particles, on the one hand, to ensure the strength of the particles; on the other hand, the pores can guide the entry of brine through capillary action, which is helpful for the wetting inside the lithium ion sieve particles;
- the increased gap between the lithium ion sieves by the filler effectively improves the utilization rate of the lithium ion sieve and reduces the cost of the lithium ion sieve particles.
- the use of the water-based resin emulsion in the present invention is beneficial to reduce VOC emissions, and eliminate the potential safety hazards caused by solvent volatilization.
- There are many optional equipment for the low-temperature curing molding method the process is simple and easy to control, and it is easy to produce on a large scale.
- Water as a solvent can greatly reduce the cost.
- the resin in the emulsion is suspended droplets or particles, not dissolved in water, and is not easy to migrate with the evaporation of water, which can solve the problem of segregation of solvent-based binders.
- Fig. 1 is the sample photograph of embodiment 1
- FIG. 1 is a sample photo of Example 4.
- Example 4 Other conditions are the same as in Example 4, except that the addition amount of lithium ion sieve Li 2 TO 3 in step (1) is adjusted to 40 grams, and the addition amount of perlite is adjusted to 50 grams.
- Example 1 95.6 18.4 8.25 15.86 12 23.8
- Example 2 93.2 19.6 6.96 12.88 14 19.6
- Example 3 98.4 19.1 7.67 15.05 13 22.9
- Example 4 98.8 20.5 7.13 15.18 12 23.1
- Example 5 99.1 34.6 12.52 18.14 6 27.6
- Example 6 99.5 25.8 8.44 12.59 8 33.51 Comparative Example 1 54.3 2.6 0.98 3.61 twenty two 6.01
Abstract
The present invention relates to a preparation method for lithium ion sieve particles used for extracting lithium from salt lake brine, seawater, oil and gas field brine, underground lithium-containing brine or lithium-containing wastewater. Lithium ion particles are prepared by grinding lithium ion sieves, then mixing with a pore forming agent, a filler and a water-based resin emulsion, then performing extrusion molding, executing drying and curing processes by means of heating, and finally acid leaching and water washing. The present invention has the advantages of a simple and environmentally friendly preparation process, low costs, etc., and the prepared lithium ion sieve particles have high hardness, high porosity, high selectivity, high adsorption capacity, a fast adsorption rate and a long cycle life.
Description
本发明涉及一种高孔隙率锂离子筛颗粒的制备方法，属于盐湖提锂技术领域。The invention relates to a preparation method of high-porosity lithium ion sieve particles, and belongs to the technical field of lithium extraction from salt lakes.
锂及其化合物是国民经济和国防建设的重要战略物资,被广泛应用于玻璃、陶瓷、航空、核能和新能源等众多领域。据美国地质勘探局 (United States
Geological Survey,简称USGS)20 1 6年1月出版的年报报道,全球探明的陆上锂资源储量以金属锂计约为 1400万 t,其中盐湖卤水中的储量占70%~80%;而海水中蕴藏的量达2600亿t左右。因此,为了满足可持续发展的需求,各国学者都在积极找寻从盐湖卤水及(浓)海水中提锂的新技术。Lithium and its compounds are important strategic materials for national economy and national defense construction, and are widely used in many fields such as glass, ceramics, aviation, nuclear energy and new energy. According to the United States Geological Survey
Geological Survey (USGS) annual report published in January 2016 reported that the global proven onshore lithium resource reserves in terms of metal lithium are about 14 million tons, of which the reserves in salt lake brine account for 70% to 80%; The amount contained in seawater is about 260 billion tons. Therefore, in order to meet the needs of sustainable development, scholars from all over the world are actively looking for new technologies to extract lithium from salt lake brine and (concentrated) seawater.
传统的提锂技术主要包括沉淀法、盐析法、溶剂萃取法等。因盐湖卤水及(浓)海水的组分复杂,传统的提取方法存在工艺流程复杂、能耗高等不足;而离子交换与吸附法提锂具有选择吸附性好、工艺简单、回收率高等优点,尤其适用于我国高镁锂比的盐湖卤水,已发展成一种极具前景的提锂方法。Traditional lithium extraction techniques mainly include precipitation method, salting out method, solvent extraction method, etc. Due to the complex components of salt lake brine and (concentrated) seawater, the traditional extraction method has the disadvantages of complex process flow and high energy consumption; while the ion exchange and adsorption method for lithium extraction has the advantages of good selective adsorption, simple process and high recovery rate, especially It is suitable for salt lake brine with high magnesium-to-lithium ratio in my country, and has developed into a very promising method for lithium extraction.
由于离子交换法所用的锂离子筛粉体直接应用时有固液分离困难、溶损率高等问题，需要制备成一定尺寸的颗粒剂来使用，现有技术目前的主流方法主要有以下几种：一种是将锂离子筛粉体与热塑性树脂混合后加热至熔融状态，这种方法主要缺陷是要保持混合物的高温流动性，树脂含量须要高于40%，树脂量过大将锂离子筛粉体过分包裹，孔隙率低，并且热塑性树脂多数疏水，导致锂离子筛粉体无法与卤水充分接触，提锂效率大幅下降；第二种方法是悬浮聚合或反相悬浮聚合法，这两种方法是通过把锂离子筛粉体添加到由聚合物单体组成油相或水相中，通过控制搅拌及分散剂调节悬浮液滴的尺寸，升至一定温度后引发聚合反应，得到锂离子筛颗粒，该方法主要问题是工艺控制繁琐，成本高且极易出现质量波动，并且锂离子筛粉体易转移到另一相中，造成损失，产生的含有机物废液也会增加环保压力；第三种方法是把树脂溶于有机溶剂中，再与锂离子筛粉体混合后造粒，该方法难度在于一般树脂在有机溶剂中溶解度低，添加溶剂过多会造成混合后成浆料状不易定性，加工难度大，烘干过程中具有溶剂爆炸的风险，且VOC排放量也很大，随着溶剂挥发易造成树脂的偏析，使锂离子筛颗粒表面树脂过多，阻碍卤水渗透进内部，影响提锂效率。因此，急需开发一种低成本环保高效的锂离子筛颗粒的制备工艺。Since the lithium ion sieve powder used in the ion exchange method has the problems of difficulty in solid-liquid separation and high dissolution rate when it is directly applied, it needs to be prepared into granules of a certain size for use. The current mainstream methods in the prior art mainly include the following: One is to mix the lithium ion sieve powder with the thermoplastic resin and heat it to a molten state. The main defect of this method is to maintain the high temperature fluidity of the mixture, the resin content needs to be higher than 40%, and the amount of resin is too large. Excessive encapsulation, low porosity, and most of the thermoplastic resins are hydrophobic, so that the lithium ion sieve powder cannot be fully contacted with brine, and the lithium extraction efficiency is greatly reduced; the second method is suspension polymerization or reversed-phase suspension polymerization. The two methods are Lithium ion sieve particles are obtained by adding lithium ion sieve powder to the oil phase or water phase composed of polymer monomers, adjusting the size of the suspended droplets by controlling stirring and dispersing agent, and raising the temperature to a certain temperature to initiate a polymerization reaction. The main problems of this method are that the process control is cumbersome, the cost is high, and quality fluctuations are prone to occur, and the lithium ion sieve powder is easily transferred to another phase, causing losses, and the generated organic waste liquid will also increase environmental protection pressure; the third type The method is to dissolve the resin in an organic solvent, and then mix it with lithium ion sieve powder to granulate. The difficulty of this method is that the solubility of general resin in organic solvents is low. Adding too much solvent will cause the slurry to be mixed and difficult to characterize. The processing is difficult, there is a risk of solvent explosion during the drying process, and the VOC emissions are also large. With the volatilization of the solvent, it is easy to cause the segregation of the resin, which makes the surface of the lithium ion sieve particles too much resin, which hinders the penetration of brine into the interior and affects the extraction process. Lithium efficiency. Therefore, there is an urgent need to develop a low-cost, environmentally-friendly and efficient preparation process for lithium ion sieve particles.
本发明旨在解决现有技术中的锂离子筛成型困难、制造成本高、成型后吸附效率低等问题，提供一种高效率的离子筛颗粒以及低成本、环保的锂离子筛颗粒的制备方法。本方法制备的锂离子筛颗粒，已尝试用于青海盐湖卤水的提锂，并取得了较高的提锂效果，具有很广阔的应用前景。The invention aims to solve the problems in the prior art such as difficulty in forming a lithium ion sieve, high manufacturing cost, and low adsorption efficiency after forming, and provides a high-efficiency ion sieve particle and a low-cost and environmentally friendly preparation method of the lithium ion sieve particle . The lithium ion sieve particles prepared by this method have been tried to extract lithium from Qinghai salt lake brine, and have achieved high lithium extraction effect, which has a very broad application prospect.
本发明的目的在于提供一种高孔隙率锂离子筛颗粒的制备方法，其包括以下步骤：The object of the present invention is to provide a kind of preparation method of high porosity lithium ion sieve particle, it comprises the following steps:
（1）将锂离子筛粉体研磨至一定细度，与模板造孔剂、填料混合； (1) Grind the lithium ion sieve powder to a certain fineness, and mix it with the template pore-forming agent and filler;
（2）将水性树脂乳液加入到混合物粉末中，添加一些水，捏合成面团状，通过造粒设备制成小颗粒后送入烘箱干燥；(2) Add the water-based resin emulsion to the mixture powder, add some water, knead it into a dough shape, make small granules by granulating equipment, and then send it to an oven for drying;
（3）干燥后的颗粒进行酸浸，洗涤后即得到一种高孔隙率锂离子筛颗粒；(3) The dried particles are subjected to acid leaching, and a high-porosity lithium ion sieve particle is obtained after washing;
步骤（1）中所述锂离子筛为对锂离子有选择性吸附的材料，包含钛系、锰系、铝系等，但不限于此。其研磨细度在50-1000目，其加量为该步骤中物质总质量的10-90%；The lithium ion sieve described in step (1) is a material that selectively adsorbs lithium ions, including titanium series, manganese series, aluminum series, etc., but is not limited thereto. Its grinding fineness is 50-1000 mesh, and its addition amount is 10-90% of the total mass of the substance in this step;
步骤（1）中所述模板造孔剂为热水可溶性物质或稀酸可溶性的颗粒物质，包含：糖类、碳酸钙、氧化镁、氢氧化镁、氧化铝、氧化锌、氧化铁中的一种或几种混合。其粒径控制在0.5-100μm，更优的选用5-50μm，在此区间造出的孔径更合适；模板造孔剂加量该步骤中物质总质量的1%-50%，更优的，其添加量质量百分比为10%-20%，有利于保证锂离子筛颗粒的强度并维持较高的提锂速率；In step (1), the template pore-forming agent is a hot water soluble substance or a dilute acid soluble particulate substance, including one of sugars, calcium carbonate, magnesium oxide, magnesium hydroxide, aluminum oxide, zinc oxide, and iron oxide. species or a mixture of several. The particle size is controlled at 0.5-100 μm, preferably 5-50 μm, and the pore size created in this range is more suitable; the template pore-forming agent is added in an amount of 1%-50% of the total mass of the substance in this step, and the better is, The mass percentage of its addition amount is 10%-20%, which is beneficial to ensure the strength of the lithium ion sieve particles and maintain a high lithium extraction rate;
步骤（1）中所述填料为多孔结构粉末材料，包含：活性碳、纤维素、凹凸棒土、高岭土、硅藻土、膨润土、珍珠岩中的一种或几种混合，但不限于此。更优的应选用酸不溶性材料作为填料， 能够保证酸浸时，材料在颗粒内部的支撑作用。所述填料添加量为该步骤中物质总质量的0%-70%（不含0），更优的添加量为20-50%，通过提高填料的质量比可以提高锂离子筛的利用率，降低成本；The filler in the step (1) is a powder material with a porous structure, including, but not limited to, one or more of activated carbon, cellulose, attapulgite, kaolin, diatomite, bentonite, and perlite. More preferably, an acid-insoluble material should be used as the filler, which can ensure the support of the material inside the particles during acid leaching. The added amount of the filler is 0%-70% (excluding 0) of the total mass of the substance in this step, and the more optimal addition amount is 20-50%. By increasing the mass ratio of the filler, the utilization rate of the lithium ion sieve can be improved, cut costs;
步骤（2）中所述的水性树脂乳液包含环氧树脂乳液、聚氨酯乳液、丙烯酸乳液、有机硅树脂乳液、苯丙乳液、乙丙乳液、EVA乳液中的一种或几种混合。更优的，选用VOC含量在1%以下的水性树脂乳液，对环境更加友好。其加量按固相物计添加量为混合物粉末的10%-30%wt；更优的，按固相物计其加量在20%以下，能减少锂离子筛被树脂包裹住的表面积，具有更高的提锂速率；The water-based resin emulsion described in step (2) comprises one or a mixture of epoxy resin emulsion, polyurethane emulsion, acrylic emulsion, silicone resin emulsion, styrene-acrylic emulsion, ethylene-propylene emulsion, and EVA emulsion. More preferably, the water-based resin emulsion with a VOC content of less than 1% is selected, which is more environmentally friendly. The added amount is 10%-30%wt of the mixture powder based on the solid phase; more preferably, the added amount based on the solid phase is less than 20%, which can reduce the surface area of the lithium ion sieve wrapped by the resin, Has a higher lithium extraction rate;
步骤（2）中所述小颗粒粒径为0.2-5mm，更优的，选为0.2-2mm，较小的粒径有助于提高锂离子的吸附效率； The particle size of the small particles in step (2) is 0.2-5mm, preferably 0.2-2mm, and a smaller particle size helps to improve the adsorption efficiency of lithium ions;
步骤（3）中所述酸浸所用的酸包含盐酸、硫酸、磷酸、硝酸、草酸、醋酸等，但不限于此。酸浓度为0.1-2mol/L，更优的选用0.5-1mol/L的盐酸，在此浓度下既能保证锂离子筛颗粒活化完全，又不会引起离子筛的大量溶损，酸浸温度选为40-60℃，能够缩短活化时间。The acid used for the acid leaching in the step (3) includes hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, oxalic acid, acetic acid, etc., but is not limited thereto. The acid concentration is 0.1-2mol/L, preferably 0.5-1mol/L hydrochloric acid. Under this concentration, the lithium ion sieve particles can be fully activated without causing a large amount of dissolution loss of the ion sieve. The acid leaching temperature is selected. For 40-60 ℃, the activation time can be shortened.
本申请中涉及的百分比均为质量百分比。The percentages involved in this application are all mass percentages.
（1）本发明利用锂离子筛活化过程中本就有的酸浸步骤来溶解模板造孔剂，活化的过程也是造孔的过程，制备的锂离子筛颗粒具有高孔隙率，有利于提高锂离子筛与卤水的接触面积，提高提锂速率和吸附容量，并且可通过调整模板造孔剂的粒径和加量来调整锂离子筛颗粒的孔隙率和孔径，以用于不同类型的卤水提锂。(1) The present invention utilizes the inherent acid leaching step in the activation process of the lithium ion sieve to dissolve the template pore-forming agent, and the activation process is also a pore-making process, and the prepared lithium ion sieve particles have high porosity, which is conducive to improving lithium The contact area between the ion sieve and the brine can improve the lithium extraction rate and adsorption capacity, and the porosity and pore size of the lithium ion sieve particles can be adjusted by adjusting the particle size and amount of the template pore-forming agent for different types of brine extraction. lithium.
（2）本发明选用亲水多孔材料作为骨架材料支撑锂离子筛颗粒，一方面保证颗粒的强度；另一方面孔隙可通过毛细管作用引导卤水进入，有助于锂离子筛颗粒内部的润湿；填料增大的锂离子筛之间的间隙，有效提高锂离子筛的利用率，降低锂离子筛颗粒的成本。(2) The present invention selects hydrophilic porous material as the framework material to support the lithium ion sieve particles, on the one hand, to ensure the strength of the particles; on the other hand, the pores can guide the entry of brine through capillary action, which is helpful for the wetting inside the lithium ion sieve particles; The increased gap between the lithium ion sieves by the filler effectively improves the utilization rate of the lithium ion sieve and reduces the cost of the lithium ion sieve particles.
（3）本发明使用水性树脂乳液有利于降低VOC排放，杜绝溶剂挥发带来的安全隐患，低温固化的成型方法可选择的设备多，工艺简单易控制，易于大规模生产。水作为溶剂能够大幅降低成本，乳液中的树脂为悬浮小液滴或颗粒，并非溶解在水中，不易随水分的蒸发迁移，能够解决溶剂型粘结剂的偏析问题。(3) The use of the water-based resin emulsion in the present invention is beneficial to reduce VOC emissions, and eliminate the potential safety hazards caused by solvent volatilization. There are many optional equipment for the low-temperature curing molding method, the process is simple and easy to control, and it is easy to produce on a large scale. Water as a solvent can greatly reduce the cost. The resin in the emulsion is suspended droplets or particles, not dissolved in water, and is not easy to migrate with the evaporation of water, which can solve the problem of segregation of solvent-based binders.
图1是实施例1的样品照片Fig. 1 is the sample photograph of embodiment 1
图2是实施例4的样品照片Figure 2 is a sample photo of Example 4
实施例1Example 1
（1）将锂离子筛Li
2TO
3研磨后过325目筛，称取70克Li
2TO
3与10克氧化锌20克活性炭混合；
(1) Grind the lithium ion sieve Li 2 TO 3 and pass it through a 325 mesh sieve, weigh 70 grams of Li 2 TO 3 and mix with 10 grams of zinc oxide and 20 grams of activated carbon;
（2）将30克50%固含量的EVA乳液加入到混合物粉末中，添加5ml水，捏合成面团状，通过挤出造粒机制成直径2mm柱状小颗粒，送入烘箱80℃干燥2h；(2) Add 30 grams of EVA emulsion with a solid content of 50% to the mixture powder, add 5 ml of water, knead it into a dough shape, form small cylindrical particles with a diameter of 2 mm by an extrusion granulator, and send it to an oven for drying at 80 °C for 2 hours;
（3）干燥后的颗粒用0.5mol/L盐酸浸泡6h，维持温度60℃，洗涤后即得到一种柱状锂离子筛颗粒；(3) The dried particles are soaked in 0.5mol/L hydrochloric acid for 6 hours, and the temperature is maintained at 60 °C, and a columnar lithium ion sieve particle is obtained after washing;
实施例2Example 2
（1）将锂离子筛LiMn
2O
4研磨后过325目筛，称取70克LiMn
2O
4与10克氧化镁20克凹凸棒土混合；
(1) Grind the lithium ion sieve LiMn 2 O 4 and pass it through a 325 mesh sieve, weigh 70 grams of LiMn 2 O 4 and mix with 10 grams of magnesium oxide and 20 grams of attapulgite;
（2）将30克55%固含量的苯丙乳液加入到混合物粉末中，添加2ml水，捏合成面团状，通过挤出造粒机制成直径1.5mm柱状小颗粒，送入烘箱80℃干燥2h；(2) Add 30 grams of 55% solid content styrene-acrylic emulsion to the mixture powder, add 2 ml of water, knead it into a dough shape, use an extrusion granulator to form small columnar particles with a diameter of 1.5 mm, and send it to an oven at 80 °C for drying for 2 hours ;
（3）干燥后的颗粒用1mol/L盐酸浸泡4h，维持温度60℃，洗涤后即得到一种柱状锂离子筛颗粒；(3) The dried particles were soaked in 1 mol/L hydrochloric acid for 4 hours, and the temperature was maintained at 60 °C, and a columnar lithium ion sieve particle was obtained after washing;
实施例3Example 3
（1）将锂离子筛Li
2TO
3研磨后过325目筛，称取70克Li
2TO
3与10克三氧化二铁20克硅藻土混合；
(1) Grind the lithium ion sieve Li 2 TO 3 and pass it through a 325 mesh sieve, weigh 70 grams of Li 2 TO 3 and mix with 10 grams of ferric oxide and 20 grams of diatomaceous earth;
（2）将30克55%固含量的环氧树脂乳液加入到混合物粉末中，添加5ml水，捏合成面团状，通过挤出造粒机制成直径1.5mm柱状小颗粒，送入烘箱80℃干燥2h；(2) Add 30 grams of epoxy resin emulsion with a solid content of 55% to the mixture powder, add 5 ml of water, knead it into a dough shape, and use an extrusion granulator to form small cylindrical particles with a diameter of 1.5 mm, and send it to an oven for drying at 80 °C 2h;
（3）干燥后的颗粒用1mol/L盐酸浸泡4h，维持温度60℃，洗涤后即得到一种柱状锂离子筛颗粒；(3) The dried particles were soaked in 1 mol/L hydrochloric acid for 4 hours, and the temperature was maintained at 60 °C, and a columnar lithium ion sieve particle was obtained after washing;
实施例4Example 4
（1）将锂离子筛Li
2TO
3研磨后过325目筛，称取70克Li
2TO
3与10克碳酸钙20克珍珠岩混合；
(1) Grind the lithium ion sieve Li 2 TO 3 and pass it through a 325 mesh sieve, weigh 70 grams of Li 2 TO 3 and mix it with 10 grams of calcium carbonate and 20 grams of perlite;
（2）将30克55%固含量的丙烯酸乳液加入到混合物粉末中，添加5ml水，捏合成面团状，通过挤出造粒机制成直径1mm柱状小颗粒，再使用抛丸机抛成1.5mm直径的球状颗粒，送入烘箱80℃干燥2h；(2) Add 30 grams of 55% solid content acrylic emulsion to the mixture powder, add 5 ml of water, knead it into a dough shape, use an extrusion granulator to form small cylindrical particles with a diameter of 1mm, and then use a shot blasting machine to throw it into 1.5mm Spherical particles with a diameter, sent to an oven at 80 °C for drying for 2 hours;
（3）干燥后的颗粒用1mol/L盐酸浸泡4h，维持温度60℃，洗涤后即得到一种球状锂离子筛颗粒；(3) The dried particles were soaked in 1 mol/L hydrochloric acid for 4 hours, and the temperature was maintained at 60 °C, and a spherical lithium ion sieve particle was obtained after washing;
实施例5Example 5
其他条件与实施例4相同，不同点是步骤（1）的碳酸钙加量调整为20克。Other conditions are the same as in Example 4, the difference is that the amount of calcium carbonate added in step (1) is adjusted to 20 grams.
实施例6Example 6
其他条件与实施例4相同，不同点是步骤（1）的锂离子筛Li
2TO
3 加量调整为40克，珍珠岩的加量调整为50克。
Other conditions are the same as in Example 4, except that the addition amount of lithium ion sieve Li 2 TO 3 in step (1) is adjusted to 40 grams, and the addition amount of perlite is adjusted to 50 grams.
对比例1Comparative Example 1
（1）将锂离子筛Li
2TO
3研磨后过325目筛，称取600克Li
2TO
3与400克PE树脂混合均匀后，在180℃下用螺杆挤出机挤出造粒，制成1.5mm柱状小颗粒。
(1) Grind the lithium ion sieve Li 2 TO 3 and pass it through a 325 mesh sieve, weigh 600 grams of Li 2 TO 3 and 400 grams of PE resin and mix them evenly, then extrude and granulate with a screw extruder at 180 ° C to make Into 1.5mm columnar small particles.
（2）用1mol/L盐酸浸泡4h，维持温度60℃，洗涤后即得到一种柱状锂离子筛颗粒；(2) Soak with 1mol/L hydrochloric acid for 4 hours, maintain the temperature at 60°C, and obtain a columnar lithium ion sieve particle after washing;
吸附容量检测方法：Adsorption capacity detection method:
称取50克锂离子筛颗粒，浸泡在2L含锂量1700mg/L的沉锂母液中，2h取第一次水样，测试锂含量，之后每过1h取一次水样，检测锂含量。直到相邻两次取的样品锂含量无差异视为吸附饱和，根据水样中锂的减少值计算吸附容量，根据锂离子筛含量计算出对应纯锂离子筛的饱和吸附容量。Weigh 50 grams of lithium ion sieve particles, soak them in 2L of lithium precipitation mother solution with a lithium content of 1700mg/L, take the first water sample for 2 hours to test the lithium content, and then take a water sample every 1 hour to detect the lithium content. Until there is no difference in the lithium content of the two adjacent samples taken as the adsorption saturation, the adsorption capacity is calculated according to the reduction value of lithium in the water sample, and the saturated adsorption capacity of the corresponding pure lithium ion sieve is calculated according to the content of the lithium ion sieve.
| 样品名称sample name | 活化后锂脱除率（%）Lithium removal rate after activation (%) | 孔隙率（%）Porosity(%) | 2h吸附容量（mg/g）2h adsorption capacity (mg/g) | 饱和吸附容量（mg/g）Saturated adsorption capacity (mg/g) | 达到饱和吸附所需时间（h）Time required to reach saturation adsorption (h) | 折算成纯锂离子筛的饱和吸附容量（mg/g）Converted to the saturated adsorption capacity of pure lithium ion sieve (mg/g) |
| 实施例1Example 1 | 95.695.6 | 18.418.4 | 8.258.25 | 15.8615.86 | 1212 | 23.823.8 |
| 实施例2Example 2 | 93.293.2 | 19.619.6 | 6.966.96 | 12.8812.88 | 1414 | 19.619.6 |
| 实施例3Example 3 | 98.498.4 | 19.119.1 | 7.677.67 | 15.0515.05 | 1313 | 22.922.9 |
| 实施例4Example 4 | 98.898.8 | 20.520.5 | 7.137.13 | 15.1815.18 | 1212 | 23.123.1 |
| 实施例5Example 5 | 99.199.1 | 34.634.6 | 12.5212.52 | 18.1418.14 | 66 | 27.627.6 |
| 实施例6Example 6 | 99.599.5 | 25.825.8 | 8.448.44 | 12.5912.59 | 88 | 33.5133.51 |
| 对比例1Comparative Example 1 | 54.354.3 | 2.62.6 | 0.980.98 | 3.613.61 | 22twenty two | 6.016.01 |
从上述结果可看出：From the above results, it can be seen that:
（1）由实施例5可看出模板造孔剂量增大，孔隙率增加，吸附速率增大；(1) It can be seen from Example 5 that the template pore-forming dose increases, the porosity increases, and the adsorption rate increases;
（2）由实施例6可看出随着多孔填料量的增大，孔隙率也会增加，由于锂离子筛含量降低，饱和吸附容量也降低，但锂离子筛利用率最高，折成纯锂离子筛吸附容量最高；(2) It can be seen from Example 6 that as the amount of porous filler increases, the porosity will also increase. Due to the decrease in the content of lithium ion sieves, the saturated adsorption capacity also decreases, but the utilization rate of lithium ion sieves is the highest, which is converted into pure lithium The ion sieve has the highest adsorption capacity;
（3）由对比例1看出，由于树脂含量过多，树脂熔融后过度包裹了锂离子筛表面，颗粒孔隙率很低，卤水与锂离子筛接触面较小，活化脱锂不完全，提锂效率也很低。(3) It can be seen from Comparative Example 1 that due to the excessive resin content, the surface of the lithium ion sieve is over-wrapped after the resin is melted, the particle porosity is very low, the contact surface between the brine and the lithium ion sieve is small, and the activation and delithiation are incomplete. Lithium efficiency is also very low.
本发明并不局限于前述的具体实施方式。本发明扩展到任何在本说明书中披露的新特征或任何新的组合，以及披露的任一新的方法或过程的步骤或任何新的组合。不能以此限定本发明实施的范围，故其等同组件的置换，或依本发明专利保护范围所作的等同变化与修改，皆应仍属本发明权利要求书涵盖之范畴。The present invention is not limited to the foregoing specific embodiments. The present invention extends to any new features or any new combination disclosed in this specification, as well as any new method or process steps or any new combination disclosed. The scope of the implementation of the present invention cannot be limited by this, so the replacement of the equivalent components, or the equivalent changes and modifications made according to the scope of the patent protection of the present invention should still fall within the scope covered by the claims of the present invention.
在此处键入工业实用性描述段落。Type an industrial applicability description paragraph here.
在此处键入序列表自由内容描述段落。Type the Sequence Listing free content description paragraph here.
Claims (8)
- 一种高孔隙率锂离子筛颗粒的制备方法，其包括以下步骤：A preparation method of high-porosity lithium ion sieve particles, comprising the following steps:（1）将锂离子筛粉体研磨至细度为50-1000目，与模板造孔剂、填料混合得到混合物粉末；所述模板造孔剂为热水可溶性颗粒物质或稀酸可溶性的颗粒物质，所述填料为多孔结构粉末材料； (1) Grind the lithium ion sieve powder to a fineness of 50-1000 mesh, and mix it with a template pore-forming agent and filler to obtain a mixture powder; the template pore-forming agent is hot water soluble particulate matter or dilute acid soluble particulate matter , the filler is a porous structure powder material;（2）将水性树脂乳液加入到混合物粉末中，添加水，捏合成面团状，通过造粒设备制成小颗粒后送入烘箱干燥；(2) Add the water-based resin emulsion to the mixture powder, add water, knead it into a dough shape, make small granules by granulating equipment, and then send it to an oven for drying;（3）干燥后的颗粒进行酸浸，洗涤后即得到一种高孔隙率锂离子筛颗粒。(3) The dried particles are subjected to acid leaching, and a high-porosity lithium ion sieve particle is obtained after washing.
- 如权利要求1所述的制备方法，其特征在于，步骤（1）所述锂离子筛粉体为钛系、锰系或铝系锂离子筛，其加量为10-90% wt。The preparation method of claim 1, wherein the lithium ion sieve powder in step (1) is a titanium-based, manganese-based or aluminum-based lithium ion sieve, and the added amount is 10-90% wt.
- 如权利要求2所述的制备方法，其特征在于，步骤（1）中所述模板造孔剂为糖类、碳酸钙、氧化镁、氢氧化镁、氧化铝、氧化锌、氧化铁中的一种或几种混合，模板造孔剂粒径控制在0.5-100μm，其添加量为1 -50% wt。The preparation method according to claim 2, wherein the template pore-forming agent in step (1) is one of sugars, calcium carbonate, magnesium oxide, magnesium hydroxide, aluminum oxide, zinc oxide, and iron oxide. The particle size of the template pore-forming agent is controlled at 0.5-100 μm, and the addition amount is 1-50% wt.
- 如权利要求3所述的制备方法，其特征在于，步骤（1）中所述填料为活性碳、纤维素、凹凸棒土、高岭土、硅藻土、膨润土、珍珠岩中的一种或几种混合，所述填料添加量质量百分比为0-70% wt，不含0。The preparation method according to claim 3, wherein the filler in step (1) is one or more of activated carbon, cellulose, attapulgite, kaolin, diatomite, bentonite and perlite Mixing, the mass percentage of the filler addition amount is 0-70% wt, excluding 0.
- 如权利要求4所述的制备方法，其特征在于，步骤（2）中所述的水性树脂乳液包含丙烯酸乳液、环氧树脂乳液、有机硅树脂乳液、苯丙乳液、乙丙乳液、聚氨酯乳液、EVA乳液中的一种或几种混合，其按固相物计添加量为混合物粉末的5-30% wt。The preparation method according to claim 4, wherein the water-based resin emulsion in step (2) comprises acrylic emulsion, epoxy resin emulsion, silicone resin emulsion, styrene-acrylic emulsion, ethylene-propylene emulsion, polyurethane emulsion, One or more of the EVA emulsions are mixed, and the added amount is 5-30% wt of the mixed powder in terms of solids.
- 如权利要求5所述的制备方法，其特征在于，步骤（2）中所述小颗粒大小为0.2-5mm，所述烘干温度为50~180℃。The preparation method according to claim 5, wherein the size of the small particles in step (2) is 0.2-5mm, and the drying temperature is 50-180°C.
- 如权利要求6所述的制备方法，其特征在于，步骤（3）中所述酸浸所用的酸为盐酸、硫酸、磷酸、硝酸、草酸、醋酸中的一种或几种混合，酸浓度为0.1-2mol/L，酸浸温度为40-60℃。The preparation method according to claim 6, wherein the acid used in the acid leaching in step (3) is one or a mixture of hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, oxalic acid, and acetic acid, and the acid concentration is 0.1-2mol/L, the acid leaching temperature is 40-60℃.
- 如权利要求7所述的制备方法，其特征在于，步骤（1）中将锂离子筛研磨至细度为325目，模板造孔剂粒径控制在5-50μm；模板造孔剂加量为10-20% wt，所述填料添加量为20-50%wt，步骤（2）中所述的水性树脂乳液加量按固相物计添加量为10-20% wt；步骤（2）中所述小颗粒粒径为0.2-2mm，烘干温度为80℃；步骤（3）中所述酸为盐酸，浓度为0.5-1mol/L，酸浸温度为60℃。The preparation method according to claim 7, wherein in step (1), the lithium ion sieve is ground to a fineness of 325 mesh, and the particle size of the template pore-forming agent is controlled at 5-50 μm; 10-20% wt, the filler addition amount is 20-50% wt, and the addition amount of the water-based resin emulsion described in step (2) is 10-20% wt in terms of solid phase; in step (2) The particle size of the small particles is 0.2-2 mm, and the drying temperature is 80 °C; the acid in step (3) is hydrochloric acid, the concentration is 0.5-1 mol/L, and the acid leaching temperature is 60 °C.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004025113A (en) * | 2002-06-27 | 2004-01-29 | Ind Technol Res Inst | Method of adsorbing lithium ion from lithium-containing aqueous solution with adsorbent |
| CN101259404A (en) * | 2008-04-24 | 2008-09-10 | 郑州宇晶洁净技术咨询有限公司 | Porous active carbon composite material and manufacturing method thereof |
| CN109012600A (en) * | 2018-09-17 | 2018-12-18 | 天津市职业大学 | A kind of activated carbon supported lithium ion sieve filler and its methods for making and using same |
| CN109225124A (en) * | 2018-11-09 | 2019-01-18 | 华东理工大学 | A kind of preparation method of particle lithium adsorbent |
| CN112871127A (en) * | 2021-01-18 | 2021-06-01 | 江苏特丰新材料科技有限公司 | Preparation method of high-porosity lithium ion sieve particles |
-
2021
- 2021-01-18 CN CN202110064602.3A patent/CN112871127B/en active Active
-
2022
- 2022-01-14 WO PCT/CN2022/072072 patent/WO2022152256A1/en active Application Filing
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004025113A (en) * | 2002-06-27 | 2004-01-29 | Ind Technol Res Inst | Method of adsorbing lithium ion from lithium-containing aqueous solution with adsorbent |
| CN101259404A (en) * | 2008-04-24 | 2008-09-10 | 郑州宇晶洁净技术咨询有限公司 | Porous active carbon composite material and manufacturing method thereof |
| CN109012600A (en) * | 2018-09-17 | 2018-12-18 | 天津市职业大学 | A kind of activated carbon supported lithium ion sieve filler and its methods for making and using same |
| CN109225124A (en) * | 2018-11-09 | 2019-01-18 | 华东理工大学 | A kind of preparation method of particle lithium adsorbent |
| CN112871127A (en) * | 2021-01-18 | 2021-06-01 | 江苏特丰新材料科技有限公司 | Preparation method of high-porosity lithium ion sieve particles |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116139818A (en) * | 2023-02-13 | 2023-05-23 | 江苏苏青水处理工程集团有限公司 | Adsorbent for extracting lithium from salt lake and preparation method thereof |
| CN116139818B (en) * | 2023-02-13 | 2023-10-10 | 江苏苏青水处理工程集团有限公司 | Adsorbent for extracting lithium from salt lake and preparation method thereof |
| CN116173925A (en) * | 2023-03-31 | 2023-05-30 | 江苏海普功能材料有限公司 | High-adsorption-rate lithium extraction adsorbent and preparation method and application thereof |
| CN116173925B (en) * | 2023-03-31 | 2024-05-17 | 江苏海普功能材料有限公司 | High-adsorption-rate lithium extraction adsorbent and preparation method and application thereof |
| CN116328713A (en) * | 2023-04-24 | 2023-06-27 | 中国科学院过程工程研究所 | Method for preparing lithium ion sieve adsorbent particles and application thereof |
| CN117258747A (en) * | 2023-11-22 | 2023-12-22 | 万华化学集团股份有限公司 | Lithium adsorbent particles, and preparation method and application thereof |
| CN117258747B (en) * | 2023-11-22 | 2024-02-27 | 万华化学集团股份有限公司 | Lithium adsorbent particles, and preparation method and application thereof |
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