CN117258747B - Lithium adsorbent particles, and preparation method and application thereof - Google Patents

Lithium adsorbent particles, and preparation method and application thereof Download PDF

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CN117258747B
CN117258747B CN202311561325.2A CN202311561325A CN117258747B CN 117258747 B CN117258747 B CN 117258747B CN 202311561325 A CN202311561325 A CN 202311561325A CN 117258747 B CN117258747 B CN 117258747B
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particles
lithium adsorbent
extruder
lithium
active component
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CN117258747A (en
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董冰洋
翟振强
关锋
欧洋
魏汉辉
赵伟国
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Wanhua Chemical Group Co Ltd
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    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
    • B01J20/0248—Compounds of B, Al, Ga, In, Tl
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    • B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
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    • 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
    • B01J20/28002—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 physical properties
    • B01J20/28004—Sorbent size or size distribution, e.g. particle size
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    • B01J20/2803—Sorbents comprising a binder, e.g. for forming aggregated, agglomerated or granulated products
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D15/00—Lithium compounds
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Abstract

The invention belongs to the technical field of lithium adsorbents, and particularly relates to a lithium adsorbent particle, a preparation method and application thereof, wherein the lithium adsorbent particle comprises an inorganic active component and a binder, and the proportion of the inorganic active component is 60-95wt%; the interior of the lithium adsorbent particles is in a porous structure, and the wet water content is 30-60%; the adsorbent particles are spherical or ellipsoidal, the average particle diameter is 0.3-1.2mm, the length-diameter ratio is less than or equal to 1.5, the span is less than or equal to 0.5, and the circularity is more than or equal to 0.88. The lithium adsorbent particles are spherical or spheroid-like, and the lithium adsorbent is regular in appearance, small and uniform in particle size, low in loss in the use process and high in adsorption quantity.

Description

Lithium adsorbent particles, and preparation method and application thereof
Technical Field
The invention belongs to the technical field of lithium adsorbents, and particularly relates to lithium adsorbent particles, and a preparation method and application thereof.
Background
Aiming at low-grade lithium-containing brine, an adsorption+membrane method is the most competitive lithium extraction process, and the core of the method is the preparation of a lithium adsorbent. At present, more researches are carried out: however, the active ingredients of lithium adsorbents such as aluminum-based, manganese-based, and titanium-based are all inorganic powders, and it is difficult to use them directly, and therefore, it is necessary to granulate and mold the powders by a suitable process to prepare a granular lithium adsorbent.
Patent document CN 116099520A discloses a method for producing a flat spherical lithium adsorbent, which is to crush spherical particles having a particle diameter of 1-2mm into flat spherical particles having a thickness of 0.5mm by extrusion, but the adsorption amount is limited and the production efficiency is low.
Patent document CN 115445587B discloses an adsorbent of hollow structure and a preparation method thereof, the method is to extrude spinning solution into hollow fibers by a spinning machine and then cut the hollow fibers into small particles, but the prepared granular adsorbent has irregular morphology, and the risk of excessive loss is still caused in the long-period use process.
Therefore, further research and improvement of the processing and preparation process of lithium adsorbent particles are directions worthy of research.
Disclosure of Invention
In order to solve the problems of irregular shape, large particle size, complex preparation process and the like of the existing lithium adsorbent particles, the invention aims to provide the lithium adsorbent particles and the preparation method thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
in a first aspect, there is provided a lithium adsorbent particle comprising an inorganic active component and a binder, the inorganic active component being present in a proportion of 60 to 95wt% (e.g. 62wt%, 65wt%, 70wt%, 75wt%, 80wt%, 85wt%, 90wt%, 94 wt%), preferably 80 to 90wt%, based on 100wt% of the total amount of the lithium adsorbent particle; the balance being binder;
the interior of the lithium adsorbent particles is porous, and the wet water content is 30-60% (for example, 32%, 35%, 40%, 45%, 50%, 55%);
the lithium adsorbent particles are spherical or ellipsoidal, and the average particle diameter of the particles (average particle diameter of the particles measured by an image particle sizer) is 0.3 to 1.2mm (e.g., 0.4mm, 0.45mm, 0.55mm, 0.6mm, 0.8mm, 0.9mm, 1.1 mm), preferably 0.5 to 1.0mm; the aspect ratio of the particles is less than or equal to 1.5 (e.g., 1.4, 1.2, 1.0, 0.8, 0.6, 0.5, 0.3, 0.2, 0.1); the span of the particles is less than or equal to 0.5 (e.g., 0.45, 0.4, 0.3, 0.2, 0.1); the circularity of the particles is ≡0.88 (e.g.0.89, 0.92, 0.94, 0.95, 0.96, 0.98), preferably ≡0.90.
In some embodiments, the lithium sorbent particles have a attrition rate of 2% or less (e.g., 1.5%, 1.2%, 1%, 0.8%, 0.6%, 0.5%, 0.4%, 0.2%, 0.1%).
In the invention, parameters such as average particle diameter, length-diameter ratio, span, circularity and the like of particles can be measured by using an image particle sizer. The smaller the aspect ratio and span of the adsorbent particles, the more uniform the particle size; the closer the circularity is to 1, the more nearly spherical the particles are. The lithium adsorbent particles are in porous structures and are spherical or ellipsoidal in appearance. The particles have the characteristics of sphere or ellipsoid-like shape, small and uniform particle size, so that the volume adsorption capacity is large, the surfaces of the particles are curved surfaces and have no edges and corners, and further the abrasion in the adsorption process is low.
In some embodiments, the inorganic active component is an inorganic powder having selective adsorption of lithium ions, preferably any one selected from the group consisting of an aluminum-based lithium adsorbent, a titanium-based lithium adsorbent, and a manganese-based lithium adsorbent.
In some embodiments, the particle size of the inorganic active component is 0.01 to 100 μm (e.g., 0.02 μm, 0.05 μm, 0.08 μm, 0.1 μm, 0.2 μm, 0.4 μm, 0.5 μm, 1.0 μm, 5.0 μm, 10 μm, 20 μm, 40 μm, 60 μm, 80 μm, 90 μm), preferably 0.1 to 50 μm.
In the present invention, the aluminum-based lithium adsorbent may be selected from xLiCl 2Al (OH) 3 ·nH 2 O (x=0.4-1.0, n=0-3); manganese-based lithium adsorbents, e.g. selected from Li (H) Mn 2 O 4 、Li(H) 1.6 Mn 1.6 O 4 、Li(H) 1.33 Mn 1.67 O 4 The method comprises the steps of carrying out a first treatment on the surface of the Titanium-based lithium adsorbents, e.g. selected from Li (H) 2 TiO 3 、Li(H) 4 Ti 5 O 12 The method comprises the steps of carrying out a first treatment on the surface of the Or may be selected from any one of the corresponding doping compounds of the titanium-based lithium adsorbent or the manganese-based lithium adsorbent.
In some embodiments, the binder is selected from one or more of polyvinyl chloride, chlorinated polyvinyl chloride, polyvinylidene fluoride, polysulfone, polyethersulfone, polyacrylonitrile, polymethyl methacrylate, and cellulose acetate.
In a second aspect, there is provided a method of preparing lithium adsorbent particles comprising the steps of:
(1) Contacting and mixing (at a temperature) the inorganic active component, binder and solvent to form a viscous mixture or a homogeneous soft mass;
(2) Extruding the obtained viscous mixed solution or uniform soft material through an extruder, and immediately cutting the extruded material into particles by a rotary fly cutter which is tightly attached to the die surface of the extruder die when the extruded material appears on the extruder die;
(3) And removing the solvent in the particles by water washing, and collecting the obtained particles to obtain the lithium adsorbent particles.
According to some embodiments of the preparation methods provided herein, the solvent of step (1) is a polar solvent that is soluble in the binder and miscible with water.
In some embodiments, the solvent of step (1) is selected from one or more of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, and dimethylsulfoxide.
In the preparation method of the lithium adsorbent particles, common thermoplastic polymers which are soluble in the solvent can be used as a binder for granulation. For example, the binder is selected from one or more of polyvinyl chloride, chlorinated polyvinyl chloride, polyvinylidene fluoride, polysulfone, polyethersulfone, polyacrylonitrile, polymethyl methacrylate, and cellulose acetate.
In some embodiments, in step (1), the mass ratio of inorganic active component, binder and solvent is (1.5-19): 1: (1-10); namely: the mass of the inorganic active component can be 2 parts, 4 parts, 5 parts, 8 parts, 10 parts, 12 parts, 14 parts, 15 parts and 18 parts by mass of the binder, and the mass of the solvent can be 2 parts, 4 parts, 5 parts, 8 parts and 9 parts by mass; alternatively, the mass ratio of inorganic active component, binder, and solvent may be, for example, 2:1:1, 4:1:1, 2:1:2, 4:1:2, 5:1:2, 8:1:2, 2:1:4, 4:1:4, 5:1:4, 8:1:4, 10:1:4, 15:1:4, 18:1:4, 4:1:5, 5:1:5, 8:1:5, 10:1:5, 15:1:5, 18:1:5, 4:1:8, 5:1:8, 8:1:8, 10:1:8, 15:1:8, 18:1:8).
In some embodiments, in step (1), the temperature of the mixing is from 15 ℃ to 150 ℃ (e.g., 20 ℃, 30 ℃, 50 ℃, 80 ℃, 100 ℃, 130 ℃, 140 ℃), preferably from 40 ℃ to 120 ℃.
In some embodiments, the means of mixing is selected from mechanical agitation mixing, kneader mixing, or in-extruder barrel mixing.
In some embodiments, the extruder of step (2) is selected from any one of a single screw extruder, a twin screw extruder, and a ram extruder.
In some embodiments, step (2) extrudes the resulting viscous mixture or homogeneous soft mass through an extruder at a temperature within the extruder barrel of 15 ℃ -150 ℃ (e.g., 20 ℃, 30 ℃, 50 ℃, 80 ℃, 100 ℃, 130 ℃, 140 ℃), preferably 40-120 ℃.
In some embodiments, in step (2), a rotating fly knife against the die face of the extruder die is immersed in flowing water as the pellets are cut, and the cut pellets are carried away by the flowing water. In the process of dicing in the step (2), the solvent in the particles may be removed by washing with water at the same time.
In some embodiments, the extruder die has a size of 0.5 to 2.0mm (e.g., 0.55mm, 0.6mm, 0.8mm, 0.9mm, 1.2mm, 1.4mm, 1.5mm, 1.8 mm), preferably 0.5 to 1.0mm.
In some embodiments, the rotational speed of the rotating fly is 1000-5000rpm (e.g., 1100rpm, 1400rpm, 1500rpm, 2000rpm, 2500rpm, 3000rpm, 3500rpm, 4000rpm, 4500 rpm).
In the invention, the spherical or ellipsoidal morphology of the granular lithium adsorbent particles can be realized by immersing a rotating fly cutter which is closely attached to the die surface of the extruder die in flowing water during the granulation. In the underwater extrusion granulation process, water can displace the solvent in the cut particles to harden by phase separation, so that the obtained granular lithium adsorbent particles can take the shape of spheres or spheroids, and the particles have small and uniform particle sizes. When extruding the uniformly mixed viscous liquid or soft material through the extrusion equipment, the extruded material is cut into particles and soaked in flowing water, the two ends of the extruded strip-shaped material shrink into curved surfaces due to the action of surface tension at the moment of being cut into particles, and then the extruded strip-shaped material is separated and hardened in water (rather than being cooled and hardened in water); by selecting a polar solvent which can dissolve the binder and is miscible with water before extrusion, not only can the inorganic active component and the binder be uniformly mixed, but also preconditions can be provided for the formation of spherical or ellipsoidal morphology of subsequent particles.
In the present invention, in the case where the amount of the binder is fixed, in general, the more the amount of the inorganic active component is, the more the amount of the solvent is required; or by means of raising the mixing temperature, the raw materials are mixed into a suitable, viscous mixed solution or soft material. If the mixed materials are too hard, the extrusion temperature can be increased during extrusion; if the mixed materials have good fluidity, the extrusion temperature can be properly reduced, and the energy consumption is reduced while the extrusion and the granulating are convenient.
In the present invention, the size of the adsorbent particles can be achieved by common control of the material conditions and the operating parameters of the apparatus. The larger the die size of the extruder, the larger the lithium adsorbent particles are, and conversely, the smaller the particle size is; through cooperative control of the size of the die and the rotating speed of the fly cutter, the formation of the regular and uniform-particle-size morphological features of the adsorbent can be promoted.
In a third aspect, there is provided the use of a lithium adsorbent particle as described above or a lithium adsorbent particle prepared by a preparation method as described above for the adsorptive extraction of lithium ions in a lithium containing solution.
The technical scheme of the invention has the following beneficial effects:
(1) The lithium adsorbent particles provided by the invention are spherical or ellipsoidal, regular in shape, uniform in particle size and small in particle size, so that the lithium adsorbent particles have high adsorption capacity in adsorption application, low wear rate and low loss; (2) The invention has simple granulation process and cheap raw materials, and can be used for mass production.
Detailed Description
So that the technical features and content of the present invention can be understood in detail, preferred embodiments of the present invention will be described in more detail below. While the preferred embodiments of the present invention have been described in the examples, it should be understood that the present invention may be embodied in various forms and should not be limited to the embodiments set forth herein. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer.
< source of raw materials >
In each of the following examples and comparative examples, the source of some of the reagents or raw materials used, if not noted for the manufacturer, were conventional products commercially available.
< test method >
1. The relevant parameters such as the particle size, the length-diameter ratio, the particle size span, the circularity and the like of the adsorbent particles are measured by a BT-2900 dynamic image particle size shape analysis system;
2. loss rate test: the testing method refers to the operation steps of the cationic resin after grinding ball rate in national standard GB/T12598-2001, wherein the difference is that the ground sample passes through a 0.1mm screen, and after the sample on the screen and the sample under the screen are dried, the mass of the sample is m1 and m2 respectively, and the loss rate is =m2/(m1+m2) x 100%;
3. and (3) water content testing: measuring a certain amount of water-containing adsorbent particles to be measured in a centrifugal filter pipe, and centrifuging in a centrifugal machine at 2000rpm/min for 5min to remove free water; then 1g of the treated adsorbent particles was weighed and tested for water content by a Metrehler HC103/02 halogen moisture meter, wherein the instrument drying temperature was 105℃and the shutdown mode was 3 (1 mg/50 seconds).
Example 1
Inorganic active component xLiCl 2Al (OH) 3 ·nH 2 O (x=0.4 to 1.0, n=0 to 3) can be prepared by referring to the method disclosed in "aluminum salt lithium adsorbent preparation Process and adsorption Performance study".
Weighing 30kg AlCl 3 ·6H 2 O and 3.0kg of LiCl are dissolved in 40kg of deionized water and mixed to prepare acid liquor; dripping 32% NaOH aqueous solution into the prepared acid solution at a flow rate of 0.5L/min at room temperature, stirring to react, stopping dripping when the pH value of the reaction system is stably maintained at 6.0, and then addingThe system is heated to 70 ℃ and stirred and aged for 1h to obtain slurry. The obtained slurry is filtered, washed, dried and crushed to obtain active component with average grain size of 5 mu m, namely LiCl 2Al (OH) 3 ·H 2 O powder.
The preparation method of the lithium adsorbent particles comprises the following steps:
(1) Weighing 5kg of LiCl 2Al (OH) prepared as above 3 ·H 2 O powder, 1kg of polyvinylidene fluoride and 6kg of N, N-dimethylacetamide, and then mixing them at 80 ℃ through a twin screw extruder to obtain a uniformly viscous mixed solution;
(2) Extruding the obtained viscous mixed solution through a plunger type extruder at 40 ℃, immediately granulating the extruded material under water by a rotary fly cutter tightly attached to the die surface of the extruder die when the extruded material appears on the extruder die, and simultaneously washing the obtained granules to remove the solvent;
wherein: the size of the extruder die is 0.9mm, and the rotating speed of the rotary fly cutter is 5000rpm;
(3) The resulting particles were collected to obtain a granular lithium adsorbent in which the inorganic active component was 83wt%.
Example 2
Inorganic active component (i.e. LiCl. 2Al (OH) 3 ·H 2 O powder) was prepared in the same manner as in example 1.
The preparation method of the lithium adsorbent particles comprises the following steps:
(1) Weighing 6kg of LiCl 2Al (OH) prepared as above 3 ·H 2 O powder, 3kg of polyvinyl chloride and 9kg of N, N-dimethylformamide, and then kneading them at 40℃by a kneader to give a uniformly viscous mixture;
(2) Extruding the obtained viscous mixed solution through a plunger type extruder at 70 ℃, immediately granulating the extruded material under water by a rotary fly cutter tightly attached to the die surface of the extruder die when the extruded material appears on the extruder die, and washing the obtained granules to remove the solvent;
wherein: the size of the extruder die is 0.7mm, and the rotating speed of the rotary fly cutter is 3000rpm;
(3) The resulting particles were collected to obtain a granular lithium adsorbent in which the inorganic active component was 67wt%.
Example 3
Inorganic active component (i.e. LiCl. 2Al (OH) 3 ·H 2 O powder) was prepared in the same manner as in example 1.
The preparation method of the lithium adsorbent particles comprises the following steps:
(1) 9kg of LiCl 2Al (OH) prepared as described above were weighed out 3 ·H 2 O powder, 1kg polysulfone and 6kg N-methylpyrrolidone, which are then mixed by a kneader at 120℃to give a homogeneous soft mass;
(2) Extruding the obtained soft material at 120 ℃ through a double-screw extruder, immediately granulating the extruded material under water by a rotary fly cutter tightly attached to the die surface of the extruder die when the extruded material appears on the extruder die, and simultaneously washing the obtained granules to remove the solvent;
wherein: the size of the extruder die is 1.0mm, and the rotating speed of the rotary fly cutter is 1000rpm;
(3) The resulting particles were collected to obtain a granular lithium adsorbent in which the inorganic active component was 90wt%.
Example 4
Inorganic active component (i.e. LiCl. 2Al (OH) 3 ·H 2 O powder) was prepared in the same manner as in example 1.
The preparation method of the lithium adsorbent particles comprises the following steps:
(1) Weighing 4kg of LiCl 2Al (OH) prepared as above 3 ·H 2 O powder, 1kg of cellulose acetate and 7kg of N, N-dimethylacetamide, and then mixing them into a uniformly viscous mixed solution by mechanical stirring at 75 ℃;
(2) Extruding the obtained viscous mixed solution through a single screw extruder at 75 ℃, immediately granulating the extruded material under water by a rotary fly cutter tightly attached to the die surface of the extruder die when the extruded material appears on the extruder die, and simultaneously washing the obtained granules to remove the solvent;
wherein: the size of the extruder die is 0.6mm, and the rotating speed of the rotary fly cutter is 2800rpm;
(3) The resulting particles were collected to obtain a granular lithium adsorbent in which the inorganic active component was 80wt%.
Example 5
The doped titanium-based inorganic active component can be prepared by a method disclosed in a patent document CN 113274971A.
Weighing 10kg of titanium dioxide, 10.29kg of lithium carbonate and 1.72kg of nano zirconium dioxide, uniformly mixing the titanium dioxide, the lithium carbonate, the nano zirconium dioxide and the nano zirconium dioxide by a high mixer, heating to 700 ℃ at a heating rate of 5 ℃/min under an air atmosphere, and sintering for 6 hours to obtain the zirconium-doped titanium inorganic active component Li with the particle size of 0.3 mu m 2 Zr 0.1 Ti 0.9 O 3 。
The preparation method of the lithium adsorbent particles comprises the following steps:
(1) Weighing 6kg of Li prepared above 2 Zr 0.1 Ti 0.9 O 3 Powder, 1kg of polyvinyl chloride and 5kg of N-methylpyrrolidone, which are then kneaded into a homogeneous soft mass by means of a kneader at 60 ℃;
(2) Extruding the obtained soft material through a single screw extruder at 60 ℃, immediately cutting the extruded material into granules under water by a rotary fly cutter tightly attached to the die surface of the extruder die when the extruded material appears on the extruder die, and simultaneously washing the obtained granules to remove the solvent;
wherein: the size of the extruder die is 0.8mm, and the rotating speed of the rotary fly cutter is 3000rpm;
(3) The resulting particles were collected to obtain a granular lithium adsorbent in which the inorganic active component was 86wt%.
Comparative example 1
Inorganic active component (i.e. LiCl. 2Al (OH) 3 ·H 2 O powder) was prepared in the same manner as in example 1.
The preparation method of the lithium adsorbent particles comprises the following steps:
(1) Weighing 5kg of LiCl 2Al (OH) prepared as above 3 ·H 2 O powder, 1kg of polyvinylidene fluoride and 6kg of N, N-dimethylacetamide, and then mixing them at 80 ℃ through a twin screw extruder to obtain a uniformly viscous mixed solution;
(2) Extruding the viscous mixture through a ram extruder at 40 ℃ into a bar, wherein: the size of the die of the plunger type extruder is 0.9mm;
(3) The strip is immersed in water to harden, then is subjected to hob dicing, and finally is washed with water to remove the solvent, so as to obtain the cylindrical lithium adsorbent, wherein the inorganic active component accounts for 83wt%.
Comparative example 2
The preparation method described in example 1 disclosed with reference to patent document CN 115445587B is used for preparing hollow fiber structured lithium adsorbent particles, which differ only in that: the inorganic active component H is used 2 TiO 3 Replaced with LiCl 2Al (OH) prepared by the preparation method described in example 1 of the present invention 3 ·H 2 O powder;
the hollow fiber structured lithium adsorbent particles were produced, in which the inorganic active component was 74wt%.
Comparative example 3
The preparation method described in example 1 disclosed with reference to patent document CN 116351384A is used for preparing cylindrical lithium adsorbent particles, and the only difference is that: the inorganic active component LiCl 2Al (OH) 3 ·nH 2 O is LiCl 2Al (OH) prepared according to the preparation method of example 1 of the present invention 3 ·H 2 O powder;
cylindrical lithium adsorbent particles were produced in which the inorganic active component was 91wt%.
Comparative example 4
Inorganic active component (i.e., li 2 Zr 0.1 Ti 0.9 O 3 Powder) was prepared in the same manner as in example 5.
The preparation method of the lithium adsorbent particles comprises the following steps:
(1) Weighing 6kg of Li prepared above 2 Zr 0.1 Ti 0.9 O 3 Powder, 1kg of polyvinyl chloride and 5kg of N-methylpyrrolidone, which are then kneaded into a homogeneous soft mass by means of a kneader at 60 ℃;
(2) Extruding the resulting soft mass into a strand at 60 ℃ through a single screw extruder, wherein: the size of the extruder die is 0.8mm;
(3) And immersing the obtained strips in water for hardening, then granulating by a hob, and finally washing with water to remove the solvent to obtain the cylindrical lithium adsorbent, wherein the inorganic active component accounts for 86 weight percent.
Performance test experiment of lithium adsorbent:
measuring 55mL of the wet samples prepared in each example and comparative example by using a measuring cylinder, loading into a chromatographic column with an inner diameter of 26mm, adsorbing salt lake brine at room temperature for 4h at a flow rate of 3Bv/h, and washing the wet samples with deionized water at a flow rate of 20Bv/h for 5min; wherein: for the aluminum-based lithium adsorbent, desorption was performed with deionized water at 35 ℃ at a flow rate of 6Bv/h for 1 hour; the titanium-based lithium adsorbent was desorbed at room temperature with a 0.2M aqueous HCl solution at a flow rate of 3Bv/h for 2h. And collecting adsorption effluent, measuring the mass and the lithium concentration of the adsorption effluent, and calculating the adsorption quantity. The cycle is thus performed for a plurality of adsorption cycles.
Wherein the lithium adsorption amount q= (C 0 -C A ) M/v, wherein C 0 C is the initial concentration of lithium in salt lake brine A For the concentration of lithium in the brine after adsorption, m is the mass of adsorption effluent, and v is the volume of the column-packed adsorbent.
TABLE 1 composition of main components in salt lake brine
Table 2 shows the test parameters of the products obtained in each example and comparative example. Wherein examples 1 to 4 and comparative examples 1 to 3 are aluminum-based lithium adsorbents; example 5 and comparative example 4 are titanium-based lithium adsorbents.
TABLE 2 test results for products obtained in examples and comparative examples
As is clear from Table 2, the average aspect ratio of the aluminum-based lithium adsorbents prepared in examples 1 to 4 is not more than 1.45, the average circularity is not less than 0.88, and the aluminum-based lithium adsorbents are more spherical, so that the loss rate is lower, the packing in the adsorption column is more compact, the ineffective volume is small, and the adsorption amount is higher. In contrast to comparative examples 1 to 3, the adsorbent has a sharp corner due to irregular morphology, and has a high loss rate due to a large aspect ratio, and has a large average particle diameter, a large column-packed ineffective volume, and a low adsorption capacity. The titanium-based lithium adsorbent prepared in example 5 was compared with comparative example 4, and had similar results.
The foregoing description of embodiments of the invention has been presented for purposes of illustration and description, and is not intended to be exhaustive or limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the spirit of the invention.

Claims (13)

1. A lithium adsorbent particle comprising an inorganic active component and a binder, characterized in that the inorganic active component is present in a ratio of 60 to 95wt%, based on 100wt% of the total amount of the lithium adsorbent particle;
the interior of the lithium adsorbent particles is in a porous structure, and the wet water content is 30-60%;
the lithium adsorbent particles are spherical or ellipsoidal, and the average particle diameter of the particles is 0.3-1.0mm; the length-diameter ratio of the particles is less than or equal to 1.5; the span of the particles is less than or equal to 0.5; the circularity of the particles is more than or equal to 0.88;
the preparation method of the lithium adsorbent particles comprises the following steps: the inorganic active component, the binder and the solvent are contacted and mixed, the obtained viscous mixed solution or uniform soft material is extruded by an extruder, and the extruded material is immediately cut into particles by a rotary fly cutter which is tightly attached to the die surface of the extruder die when the extruded material appears on the extruder die; the rotary fly cutter which is tightly attached to the die surface of the die of the extruder is soaked in flowing water when the particles are cut, and the cut particles are taken away by the flowing water; and removing the solvent in the particles by water washing, and collecting the obtained particles to obtain the lithium adsorbent particles.
2. The lithium adsorbent particles according to claim 1, characterized in that the average particle diameter of the lithium adsorbent is 0.5-1.0mm; the length-diameter ratio of the particles is less than or equal to 1.5; the span of the particles is less than or equal to 0.5; the circularity of the particles is more than or equal to 0.90.
3. The lithium adsorbent particle according to claim 1, characterized in that the attrition rate of the lithium adsorbent particle is 2% or less.
4. The lithium adsorbent particles according to claim 1, wherein the inorganic active component is an inorganic powder having selective adsorption of lithium ions; and/or
The binder is one or more selected from polyvinyl chloride, chlorinated polyvinyl chloride, polyvinylidene fluoride, polysulfone, polyether sulfone, polyacrylonitrile, polymethyl methacrylate and cellulose acetate.
5. The lithium adsorbent particles according to claim 4, wherein the inorganic active component is selected from any one of an aluminum-based lithium adsorbent, a titanium-based lithium adsorbent, and a manganese-based lithium adsorbent;
the particle size of the inorganic active component is 0.01-100 mu m.
6. A method of preparing the lithium adsorbent particles of any one of claims 1-5, comprising the steps of:
(1) Contacting and mixing the inorganic active component, the binder and the solvent to form a viscous mixed solution or a uniform soft material;
(2) Extruding the obtained viscous mixed solution or uniform soft material through an extruder, and immediately cutting the extruded material into particles by a rotary fly cutter which is tightly attached to the die surface of the extruder die when the extruded material appears on the extruder die; the rotary fly cutter which is tightly attached to the die surface of the die of the extruder is soaked in flowing water when the particles are cut, and the cut particles are taken away by the flowing water;
(3) And removing the solvent in the particles by water washing, and collecting the obtained particles to obtain the lithium adsorbent particles.
7. The method according to claim 6, wherein the solvent in the step (1) is a polar solvent which dissolves the binder and is miscible with water.
8. The method according to claim 7, wherein the solvent is one or more selected from the group consisting of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone and dimethylsulfoxide.
9. The method according to claim 6, wherein in the step (1), the mass ratio of the inorganic active component, the binder and the solvent is (1.5 to 19): 1: (1-10); and/or
In the step (1), the temperature of the mixing is 15-150 ℃.
10. The method according to claim 6, wherein the extruder in the step (2) is selected from any one of a single screw extruder, a twin screw extruder and a ram extruder.
11. The process according to claim 6, wherein the temperature in the extruder barrel is 15℃to 150℃when the viscous mixed solution or the homogeneous soft material obtained in the step (2) is extruded through the extruder.
12. The method according to claim 6, wherein in the step (2), the size of the die of the extruder is 0.5 to 2.0mm;
the rotating speed of the rotary fly cutter is 1000-5000rpm.
13. Use of the lithium adsorbent particles according to any one of claims 1-5 or the lithium adsorbent particles produced by the production process according to any one of claims 6-12 for the adsorptive extraction of lithium ions in a lithium-containing solution.
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Publication number Priority date Publication date Assignee Title
CN108722372A (en) * 2017-04-25 2018-11-02 比亚迪股份有限公司 Lithium adsorbent composite particles and preparation method thereof
CN108722341A (en) * 2017-04-25 2018-11-02 比亚迪股份有限公司 Lithium adsorbent composite particles and preparation method thereof
KR20190072996A (en) * 2017-12-18 2019-06-26 주식회사 포스코 Method for preparing aluminum based lithium adsorbent
WO2022152256A1 (en) * 2021-01-18 2022-07-21 江苏特丰新材料科技有限公司 Preparation method for high-porosity lithium ion sieve particles
CN115106013A (en) * 2022-06-14 2022-09-27 华东理工大学 Reverse extrusion type granulation forming method

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108722372A (en) * 2017-04-25 2018-11-02 比亚迪股份有限公司 Lithium adsorbent composite particles and preparation method thereof
CN108722341A (en) * 2017-04-25 2018-11-02 比亚迪股份有限公司 Lithium adsorbent composite particles and preparation method thereof
KR20190072996A (en) * 2017-12-18 2019-06-26 주식회사 포스코 Method for preparing aluminum based lithium adsorbent
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