Patent Grant
12233401
This application claims priority to Chinese Application 202310980240.1 filed Aug. 4, 2023, the contents of which are incorporated herein by reference.
The present disclosure relates to the field of lithium extraction by adsorption, and in particular to a lithium adsorbent and a preparation method therefor.
Lithium, as the lightest metal element in the periodic table of elements, is widely used in the fields of aviation and navigation, new energy materials, ceramics, lithium batteries, nuclear industry, etc. due to its unique physicochemical properties. In particular, the explosion of the new energy automobile industry in recent years, which brings a super-large cycle to the market of lithium resources, is also an important reason for industry-wide competition for lithium mines today. Lithium resources in China are mainly found in solid lithium ores and salt lake brines. A method for extracting lithium from a salt lake mainly includes an adsorption method, a precipitation method, a solvent extraction method, a calcination method, a membrane separation method, etc., among which the adsorption method is considered as an economical and efficient method for extracting lithium from the salt lake brine due to the advantages of low cost, high selectivity, stable cycle and no pollution. Currently lithium adsorbents are mostly in a powder form, have a high dissolution rate during preparation and regeneration, and are not suitable for widespread use.
For this purpose, a patent CN115845825A provides a lithium adsorbent molding method. Polyvinyl chloride, polyurethane TPU and chlorinated polyvinyl chloride which are used as a binder, and polyvinylpyrrolidone, polyethylene glycol 8000 and polyethylene glycol 400 which are used as a pore-forming agent are mixed with a lithium adsorbent in a specific ratio, and the mixture is extruded, solidified, washed and dried to achieve granulation molding of a powdered lithium adsorbent. However, the lithium adsorbent prepared by this method has the problems of a slow adsorption rate and low adsorption capacity.
Therefore, the technical problem to be solved by the present disclosure is to overcome the defects of a slow adsorption rate and low adsorption capacity of a lithium adsorbent existing in the prior art, thereby providing a novel lithium adsorbent and a preparation method therefor.
The present disclosure provides a lithium adsorbent, and a raw material for preparing the lithium adsorbent includes a lithium adsorbent active material, a hydrophilic binder and reinforcing fibers.
The term lithium adsorbent active material refers to an adsorbent having an adsorbing function on lithium ions, and adsorbents conventional in the art may be employed, such as an aluminum salt lithium adsorbent.
Further, the hydrophilic binder includes at least one of an inorganic binder and an organic binder.
Further, the inorganic binder is any one or a combination of two or more selected from silica sol, alumina sol, potassium silicate, lithium silicate, sodium silicate, and polyaluminum chloride: preferably the silica sol; and
Further, a mass percentage of a dry matter in the hydrophilic binder is 5-30% based on a dry weight of the lithium adsorbent active material being 100%.
Further, the reinforcing fibers are selected from any one or a combination of two or more of glass fibers, polyacrylonitrile fibers, polypropylene fibers, polyethylene fibers, polyvinyl chloride fibers, polyamide fibers, and polyester fibers:
Further, a mass of the reinforcing fibers is 1-20% of the dry weight of the lithium adsorbent active material, preferably 1-5% of the dry weight of the lithium adsorbent active material.
Further, the lithium adsorbent active material is an aluminum salt lithium adsorbent, preferably dry powder or wet powder having a water content of less than 60% of an aluminum salt lithium adsorbent.
Further, the lithium adsorbent active material is prepared from lithium hydroxide and alumina sol by gelling, aging and heating in the presence of water.
Further, a mass ratio of the lithium hydroxide to the alumina sol is (2-10): 100; and/or, sealed heating is performed at a temperature of 80-180° C.; and/or, the heating is performed for 2-24 h.
Further, the raw material for preparing the lithium adsorbent further includes other adjuvants, wherein preferably the other adjuvants are selected from one or a combination of more of a pore-forming agent, a thickener, and a pH regulator.
Further, the pore-forming agent is one or a combination of more selected from butylene glycol, glycerol, and sodium chloride; and/or, the thickener is one or a combination of more selected from guar gum, sesbania powder, starch, and glucose; and/or, the pH regulator is one or a combination of more selected from calcium carbonate, sodium bicarbonate, ammonium chloride, calcium hydroxide, sodium carbonate, and aqueous ammonia; and/or, a mass of the pore-forming agent is 10-100% of the dry weight of the lithium adsorbent active material; and/or, a mass of the thickener is 0.1-2% of the dry weight of the lithium adsorbent active material; and/or, a mass of the pH regulator is 1-20% of the dry weight of the lithium adsorbent active material.
Further, the raw material for preparing the lithium adsorbent consists of an aluminum salt lithium adsorbent, silica sol, guar gum and glass fibers, wherein based on a dry weight of the aluminum salt lithium adsorbent being 100%, a mass percentage of a dry matter in the silica sol is 9%, a mass percentage of the guar gum is 1%, and a mass percentage of the glass fibers is 2%; or,
The present disclosure further provides a method for preparing any one lithium adsorbent described above, including the following steps of mixing the raw material for preparing the lithium adsorbent, and performing extruding, curing and drying to prepare the lithium adsorbent.
Further, the curing is performed at a temperature ranging from room temperature to 80° C.
Further, the drying is performed at a temperature ranging from 80° C. to 150° C., preferably ranging from 80° C. to 120° C.
Optionally, the curing time ranges from 12 h to 36 h and the drying time ranges from 2 h to 10 h.
Further, the prepared lithium adsorbent is in the form of a strip, and preferably, the strip has a width ranging from 0.1 mm to 2 mm and a length ranging from 1 mm to 10 mm.
The technical solution of the present disclosure has the following advantages:
The following examples are provided for a better further understanding of the present disclosure, are not limited to the best embodiments, and do not limit the content and scope of protection of the present disclosure. Any product identical to or similar to the present disclosure obtained by anyone under the inspiration of the present disclosure or by combining the present disclosure with other features in the prior art falls within the scope of protection of the present disclosure.
Specific experimental steps or conditions are not specified in the examples, they can be performed according to the operations or conditions of conventional experimental steps described in the literature in the field. The used reagents or instruments of which a manufacturer is not indicated are conventional commercially available reagent products.
The polyacrylonitrile fibers are manufactured by a manufacturer: Shandong Oude Chemical Fiber Products Co., Ltd., and have a model of PD650. The polyethylene fibers are manufactured by a manufacturer: Shandong New Power Engineering Materials Co., Ltd., and are customized to have a diameter of 10 μm and a length of 2 mm. The polyvinyl alcohol is manufactured by a manufacturer: Guangzhou Suixin Chemical Co., Ltd., has a model of 0588 and 2499. The urea-formaldehyde resin is manufactured by a manufacturer: Leixiang Chemical Firm in Erqi District, Zhengzhou City, and has a model of 681, and a solid content of 50%. The silica sol is manufactured by a manufacturer: Guangzhou Suize Environmental Protection Technology Co., Ltd., its specification is neutral silica sol, and the silica sol has a particle size of 10-30 nm, and a solid content of 30%. The glass fibers are manufactured by a manufacturer: Wuhe County Weijia Composite Materials Co., Ltd., and have a model of WJ03, a diameter of 12 μm, and a length of 2 mm. The glass fibers are manufactured by a manufacturer: Taishan Glass Fiber Co., Ltd., and have a model of T435N, having a diameter of 10 μm, and a length of 2 mm; and have a model of T435TM, having a diameter of 8 μm, and a length of 2 mm. The sesbania powder is manufactured by a manufacturer: Shandong Taihecheng Bioengineering Co., Ltd., and its specification is food-grade.
The aluminum salt lithium adsorbents in the Examples and Comparative examples of the present disclosure are prepared by the following method:
This example provides a lithium adsorbent, and a raw material for preparing the lithium adsorbent is shown in the table below.
A method for preparing the above lithium adsorbent includes: weighing raw materials according to the usage amounts in the above table, adding the weighed raw materials into a mixing kettle, and uniformly stirring the raw materials at normal temperature to obtain a cemented premix: transferring the premix to a storage tank, and removing bubbles: extruding the premix through a die of a twin screw extruder to extrude filaments onto a conveyor belt to be collected to obtain a filamentous material; storing for curing the filamentous material at room temperature for 24 h, then cutting the cured filamentous material through a cutter, and drying the cut material at 100° C. for 2 h to finally obtain a lithium adsorbent having a diameter of 0.6 mm and a length of 2 mm.
This example provides a lithium adsorbent, and a raw material for preparing the lithium adsorbent is shown in the table below.
A method for preparing the above lithium adsorbent includes: weighing raw materials according to the usage amounts in the above table, adding the weighed raw materials into a mixing kettle, and uniformly stirring the raw materials at normal temperature to obtain a cemented premix; transferring the premix to a storage tank, and removing bubbles; extruding the premix through a die of a twin screw extruder to extrude filaments onto a conveyor belt to be collected to obtain a filamentous material; storing for curing the filamentous material at 80° C. for 24 h, then cutting the cured filamentous material through a cutter, and drying the cut material at 120° C. for 2 h to finally obtain a lithium adsorbent having a diameter of 0.6 mm and a length of 2 mm.
This example provides a lithium adsorbent, and a raw material for preparing the lithium adsorbent is shown in the table below.
A method for preparing the above lithium adsorbent is basically the same as that in Example 2 except that the drying time is adjusted to 4 h.
This example provides a lithium adsorbent, and a raw material for preparing the lithium adsorbent is shown in the table below.
A method for preparing the above lithium adsorbent is the same as that in Example 2.
This example provides a lithium adsorbent, and a raw material for preparing the lithium adsorbent is shown in the table below.
A method for preparing the above lithium adsorbent is the same as that in Example 1.
This example provides a lithium adsorbent, and a raw material for preparing the lithium adsorbent is shown in the table below.
A method for preparing the above lithium adsorbent is basically the same as that in Example 1 except that the drying temperature is adjusted to 90° C. and the drying time is 6 h.
This example provides a lithium adsorbent, and a raw material for preparing the lithium adsorbent is shown in the table below.
A method for preparing the above lithium adsorbent is basically the same as that in Example 1 except that the drying temperature is adjusted to 90° C. and the drying time is 2 h.
This example provides a lithium adsorbent, and a raw material for preparing the lithium adsorbent is shown in the table below.
A method for preparing the above lithium adsorbent is the same as that in Example 2.
This example provides a lithium adsorbent, and a raw material for preparing the lithium adsorbent is shown in the table below.
A method for preparing the above lithium adsorbent is the same as that in Example 2.
This example provides a lithium adsorbent, and a raw material for preparing the lithium adsorbent is shown in the table below.
A method for preparing the above lithium adsorbent is the same as that in Example 1.
This example provides a lithium adsorbent, and a raw material for preparing the lithium adsorbent is shown in the table below.
A method for preparing the above lithium adsorbent is the same as that in Example 2.
This example provides a lithium adsorbent, and a raw material for preparing the lithium adsorbent is shown in the table below.
A method for preparing the above lithium adsorbent is the same as that in Example 2.
This example provides a lithium adsorbent, and a raw material and a method for preparing the lithium adsorbent are substantially the same as those in Example 2 except that the drying temperature is adjusted to 70° C. and the drying time is 5 h.
This example provides a lithium adsorbent, and a raw material and a method for preparing the lithium adsorbent are substantially the same as those in Example 2 except that the drying temperature is adjusted to 150° C. and the drying time is 2 h.
Lithium adsorbent composite particles are prepared by using the steps of a method in Example 1 of a patent CN108722372A.
This Comparative example provides a lithium adsorbent, and a raw material for preparing the lithium adsorbent is shown in the table below.
A method for preparing the above lithium adsorbent is the same as that in Example 2.
This Comparative example provides a lithium adsorbent, and a raw material for preparing the lithium adsorbent is shown in the table below.
A method for preparing the above lithium adsorbent is the same as that in Example 2.
The adsorption performance of the lithium adsorbents prepared in the Examples and Comparative Example 1 was tested by using a salt lake brine, including adsorption capacities at 2 h and 12 h. Its specific surface area and pore volume were tested with a Geminni V2380 specific surface area and porosity analyzer.
An adsorption performance test method was a static adsorption method. 20 g of deionized water and 2 g of the lithium adsorbent were mixed, the mixture was placed in a shaker for desorption at room temperature at 150 rpm for 15 min, centrifuging was performed to remove free water, deionized water was added again for desorption again, and the above operations were repeatedly performed for 5 times to obtain a lithium deintercalation treated lithium adsorbent, the lithium deintercalation treated lithium adsorbent was added to 200 ml of salt lake brine (with a lithium content of 300 ppm, a magnesium content of 110 g/L, a chlorine content of 300 g/L, and a pH of 5.5), adsorption was performed in a shaker at room temperature at 150 rpm for 2 h, sampling was performed, and re-sampling was performed after an interval of 12 h. A sample to be tested was filtered and the lithium content of the filtrate was tested.
The adsorption capacity of an adsorbent is:
Q=V(C0−C)/m
The test results are shown below:
As can be seen from the above results, compared with Comparative example 1, the lithium adsorbent products provided in the examples of the present disclosure are almost in a saturated adsorption state when adsorption is performed for 2h, and have a higher adsorption capacity and adsorption rate. Compared with the other examples, Examples 7, 9 and 12 of the present disclosure have significantly improved adsorption capacity when adsorption is performed for 2h, especially Example 12.
The stability of the lithium adsorbents prepared in the Examples and Comparative examples 2-3 was tested by using a shaker experiment and a periodic adsorption and desorption experiment on a chromatographic column.
The specific operation of the shaker experiment was as follows: 2 g of a lithium adsorbent and 100 ml of water were charged in a 250 ml ground triangular flask, and the ground triangular flask was placed in a shaker, and shaken continuously at 160 rpm for 24 h, and lithium adsorbent fracture was observed.
The specific operation of the periodic adsorption and desorption experiment on the chromatographic column was as follows: 30 g of a lithium adsorbent was soaked in 300 ml of pure water for half an hour. 30 ml of the lithium adsorbent in a lower layer was measured, and loaded into a 50 ml chromatographic column, and a peristaltic pump was used to control a flow rate to pump 300 ml of brine in Experimental example 1 in the chromatographic column in a forward direction for 1 hour (an adsorption step), and then pump 300 ml of pure water for 1 hour (a desorption step), so that one adsorption and desorption cycle was completed, and the adsorption step and the desorption step were repeatedly and alternately performed to 20 cycles.
The results showed that the lithium adsorbents prepared in the Examples of the present disclosure did not exhibit fracture and powder dropping phenomena within 24 hours during the shaker experiment, and no fracture and powder dropping phenomena were found after 20 cycles of adsorption and desorption, and the cycle life is 20 cycles or more, satisfying the practical requirements.
The lithium adsorbents prepared in Comparative examples 2 and 3 showed partial fracture during the shaker experiment after being soaked in water for 2 min and 5 min, respectively. 90% or more of the lithium adsorbents were fractured after being used for a first adsorption and desorption cycle, affecting the use, and the service life is less than one cycle.
Obviously, the above examples are merely instances for clarity of illustration and are not intended to limit the embodiments. Other variations or changes in different forms may be made on the basis of the above description for those of ordinary skill in the art. There is no need and cannot be an exhaustive list of all embodiments here. The obvious variations or changes derived therefrom are still within the scope of protection of the present disclosure.
| Number | Date | Country | Kind |
|---|---|---|---|
| 202310980240.1 | Aug 2023 | CN | national |
| Number | Date | Country |
|---|---|---|
| 102631897 | Aug 2012 | CN |
| 108114693 | Jun 2018 | CN |
| 110102273 | Aug 2019 | CN |
| 110215896 | Sep 2019 | CN |
| 110961070 | Apr 2020 | CN |
| 111036169 | Apr 2020 | CN |
| 108043358 | Jul 2020 | CN |
| 115155528 | Oct 2022 | CN |
| 115845825 | Mar 2023 | CN |
| 4134159 | Feb 2023 | EP |
| 2021074782 | Jun 2021 | KR |
| 2722839 | Jun 2020 | RU |
| WO-2023276697 | Jan 2023 | WO |
| 2023124974 | Jul 2023 | WO |
| Entry |
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| Office Action of Corresponding Canadian Application No. 3,216,007 Dated Nov. 6, 2024, 3 pages. |
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