CN117845275A - Continuous lithium extraction unit and application thereof - Google Patents
Continuous lithium extraction unit and application thereof Download PDFInfo
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- CN117845275A CN117845275A CN202211222060.9A CN202211222060A CN117845275A CN 117845275 A CN117845275 A CN 117845275A CN 202211222060 A CN202211222060 A CN 202211222060A CN 117845275 A CN117845275 A CN 117845275A
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 217
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 217
- 238000000605 extraction Methods 0.000 title claims abstract description 138
- 230000005540 biological transmission Effects 0.000 claims abstract description 18
- 239000012528 membrane Substances 0.000 claims abstract description 18
- 150000001450 anions Chemical class 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 8
- 238000003860 storage Methods 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims description 77
- 239000002994 raw material Substances 0.000 claims description 41
- 238000007789 sealing Methods 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 11
- 125000000129 anionic group Chemical group 0.000 claims description 8
- 238000002336 sorption--desorption measurement Methods 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 abstract description 6
- 238000004064 recycling Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 15
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 11
- 229910001416 lithium ion Inorganic materials 0.000 description 11
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 8
- 238000000926 separation method Methods 0.000 description 8
- 239000012267 brine Substances 0.000 description 7
- 238000010586 diagram Methods 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 7
- 238000001179 sorption measurement Methods 0.000 description 7
- 230000009286 beneficial effect Effects 0.000 description 5
- 238000003795 desorption Methods 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 239000011810 insulating material Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052596 spinel Inorganic materials 0.000 description 4
- 239000011029 spinel Substances 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 239000013535 sea water Substances 0.000 description 3
- 230000008093 supporting effect Effects 0.000 description 3
- 229910010710 LiFePO Inorganic materials 0.000 description 2
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 2
- 229910013716 LiNi Inorganic materials 0.000 description 2
- 229910018584 Mn 2-x O 4 Inorganic materials 0.000 description 2
- 229910003251 Na K Inorganic materials 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012527 feed solution Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 150000002642 lithium compounds Chemical class 0.000 description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 2
- FRMOHNDAXZZWQI-UHFFFAOYSA-N lithium manganese(2+) nickel(2+) oxygen(2-) Chemical compound [O-2].[Mn+2].[Ni+2].[Li+] FRMOHNDAXZZWQI-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000011550 stock solution Substances 0.000 description 2
- 239000011232 storage material Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 1
- 239000003011 anion exchange membrane Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005265 energy consumption 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
- 239000012535 impurity Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- GCICAPWZNUIIDV-UHFFFAOYSA-N lithium magnesium Chemical compound [Li].[Mg] GCICAPWZNUIIDV-UHFFFAOYSA-N 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
- C22B26/12—Obtaining lithium
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/02—Electrolytic production, recovery or refining of metals by electrolysis of solutions of light metals
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
- C25C7/02—Electrodes; Connections thereof
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
- C25C7/06—Operating or servicing
Abstract
The invention discloses a continuous lithium extraction unit and application thereof, which are used for continuously recycling and enriching lithium in aqueous solution, wherein the continuous lithium extraction unit comprises: a cylindrical chamber; an anion membrane, wherein the anion membrane is movably contacted with the side wall of the cylindrical chamber and divides the cylindrical chamber into a first chamber and a second chamber; the sidewall of the first chamber includes a first electrode; the sidewall of the second chamber includes a second electrode; the first electrode and the second electrode include a lithium storage substance therein; and the transmission rod controls the rotation of the cylindrical cavity. The invention also discloses application of the continuous lithium extraction unit.
Description
Technical Field
The invention relates to the technical field of extraction metallurgy, in particular to a continuous lithium extraction unit and application thereof.
Background
Lithium and lithium compounds such as lithium chloride, lithium carbonate, lithium hydroxide and organic lithium compounds are widely used in the fields of high-energy batteries, aerospace, nuclear power generation and the like, and have important significance for the development of economy. For example, with the rapid development of technology and the straight rise of energy demand, the challenges facing the supply of energy are great, the use of clean energy such as nuclear energy and solar energy is urgent, and in the process of using clean energy, the assistance of an energy storage battery is required, among various energy storage batteries, lithium (ion) batteries are outstanding because of their excellent performance. Lithium is the main material (positive electrode, electrolyte) of lithium (ion) batteries, thus realizing extraction/repetition of lithium and contributing to the development of the high-energy battery field and the new energy application field.
The lithium resource of the salt lake accounts for more than 69% of the industrial reserves of the lithium resource in the world, and the extraction of lithium from the brine of the salt lake is one of the methods competing for energy resources. Methods for extracting lithium from brine are mainly evaporation crystallization, precipitation, extraction, adsorption, calcination, membrane separation, electrochemical extraction and the like. The electrochemical lithium extraction technology is used as a novel lithium separation and extraction technology, has the advantages of environmental protection, high lithium extraction efficiency, good impurity separation effect and the like, and is more and more concerned and researched. However, current research on electrochemical lithium extraction devices and methods is relatively small. For example, a salt lake brine magnesium-lithium separation and enrichment device based on an anion exchange membrane is realized in the prior art, however, the device is composed of a lithium desorption tank and a lithium adsorption tank separated by an anion membrane, after one lithium extraction period is completed, the feeding direction of raw material liquid and lithium-rich liquid, namely, the raw lithium desorption tank is switched to the lithium adsorption tank, the lithium adsorption tank is switched to the lithium desorption tank, and in the switching process, the separation and extraction efficiency of lithium is low and the water consumption is high because the separation and extraction of lithium are required to be stopped for washing the separation and adsorption tanks. The continuous electrochemical element extraction is realized by the technology, but the lithium extraction system is complex, and only one electrode is transferred from the extraction tank to the recovery tank at a time, so that the lithium extraction efficiency is lower and the energy consumption is higher.
In order to be suitable for continuous, stable and efficient electrochemical separation and extraction of lithium in solutions with different lithium concentrations, a continuous electrochemical lithium extraction device which has simple structure and operation and is easy to realize industrial application needs to be developed.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems existing in the prior art. Therefore, the invention provides a continuous lithium extraction unit, which can realize continuous electrolytic lithium extraction and improve the lithium extraction efficiency.
The invention also provides a continuous lithium extraction system comprising the continuous lithium extraction unit.
The invention also provides a lithium extraction method adopting the continuous lithium extraction unit or the continuous lithium extraction system.
The invention also provides application of the lithium extraction method in seawater lithium extraction and post-treatment of a lithium ion battery.
According to an embodiment of the first aspect of the present invention, there is provided a continuous lithium extraction unit including:
a cylindrical chamber;
an anionic membrane, which is in movable contact with a side wall of the cylindrical chamber and divides the cylindrical chamber into a first chamber and a second chamber; the sidewall of the first chamber includes a first electrode; the sidewall of the second chamber includes a second electrode; the first electrode and the second electrode comprise lithium storage substances;
and the transmission rod is used for controlling the rotation of the cylindrical cavity.
The continuous lithium extraction unit provided by the embodiment of the invention has at least the following beneficial effects:
(1) In the continuous lithium extraction unit provided by the invention, the contact mode between the anion membrane and the side wall of the cylindrical cavity is matched with the transmission rod, so that the relative positions of the first electrode, the second electrode and the first cavity and the second cavity are changed;
the existence of the lithium storage substance can meet the requirement of the adsorption or desorption of lithium in the first electrode or the second electrode;
in the use process of the continuous lithium extraction unit, after the adsorption of lithium in one chamber (for example, the first chamber) of one electrode (for example, the first electrode) is completed, the electrode can be transferred to the other chamber to desorb lithium through the rotation of the cylindrical chamber, and meanwhile, the other electrode is moved to adsorb lithium; and the continuous extraction of lithium is realized only by rotating the side wall of the cylindrical cavity, so that the operation steps are simplified, and meanwhile, the extraction efficiency of lithium is remarkably improved.
(2) The continuous lithium extraction unit provided by the invention does not need to comprise a liquid path switching device in the continuous operation process, so that the structure of the continuous lithium extraction unit is simplified, and the continuous lithium extraction unit is more convenient for commercial expansion.
According to some embodiments of the invention, the lithium storage substance is capable of accommodating deintercalation of lithium ions.
According to some embodiments of the invention, the lithium storage substance comprises at least one of a common lithium ion battery positive electrode material and negative electrode material.
According to some embodiments of the invention, the lithium storage substance comprises olivine structured lithium iron phosphate (LiFePO) 4 LFP), spinel structured lithium manganate (LiMn 2 O 4 LMO), spinel structured lithium nickel manganese oxide (LiNi x Mn 2-x O 4 LNMO), and layered cathode materials (LCO, LNO, or NCM).
According to some embodiments of the invention, the first electrode is an arc electrode forming a sidewall of the first chamber.
According to some embodiments of the invention, the first electrode occupies a portion of a side wall of the first chamber.
According to some embodiments of the invention, the second electrode is an arc electrode forming a sidewall of the second chamber.
According to some embodiments of the invention, the second electrode occupies a portion of the sidewall of the second chamber.
According to some embodiments of the invention, the continuous lithium extraction unit further comprises an insulating member provided on a side wall of the cylindrical chamber and provided between the first electrode and the second electrode. Thereby, a short circuit between the first electrode and the second electrode can be avoided.
When the first electrode is a side wall of the first chamber and the second electrode is a side wall of the second chamber, the insulating member also serves to connect the first electrode and the second electrode so as to constitute the cylindrical chamber.
According to some embodiments of the invention, the anionic membrane passes through the axis of the cylindrical chamber. Thus, the first chamber and the second chamber are both semi-cylindrical chambers.
According to some embodiments of the invention, the continuous lithium extraction unit further comprises a sealing member disposed between a side wall of the cylindrical chamber and the anionic membrane. Thereby, the mutual contamination of the contents in the first chamber and the second chamber (both chambers are not leaked) during the rotation of the cylindrical chamber can be avoided.
According to some embodiments of the invention, the sealing member connects the insulating member of the cylindrical chamber and the anionic membrane.
According to some embodiments of the invention, the continuous lithium extraction unit further comprises a sealing plate sealing the cylindrical chamber.
The sealing plate enables the first chamber and the second chamber to form two closed spaces.
In order to avoid short circuit between the first electrode and the second electrode, the sealing plate is made of insulating materials.
According to some embodiments of the invention, a sealing plate at one side of the cylindrical chamber is provided with a lithium-rich liquid inlet communicated with the second chamber; a raw material liquid outlet communicated with the first chamber is arranged.
According to some embodiments of the invention, a sealing plate at the other side of the cylindrical chamber is provided with a lithium-rich liquid outlet communicated with the second chamber; a raw material liquid inlet communicated with the first chamber is arranged.
According to some embodiments of the invention, in the continuous lithium extraction unit, the number of the transmission rods is not less than 1.
According to some embodiments of the invention, the connection between the drive rod and the cylindrical chamber is at least one of a gear engagement or a screw engagement. Thus, the transmission can be better realized.
According to some embodiments of the invention, the drive rod is integrally at least one of a cylindrical screw or a quasi-cylindrical screw.
According to some embodiments of the invention, the transmission rod is made of an insulating material. Thereby, an influence on the first electrode or the second electrode can be avoided.
According to some embodiments of the invention, the continuous lithium extraction unit further comprises a power supply system, a cathode and an anode of the power supply system being connected to the first electrode or the second electrode, respectively.
In the running process of the continuous lithium extraction unit, the first electrode and the second electrode need to be converted into anodes and cathodes, so that the power supply system is movably connected with the first electrode and the second electrode;
or the power supply system is provided with a change-over switch to realize the conversion of the power supply electrode.
According to an embodiment of the second aspect of the present invention, there is provided a continuous lithium extraction system comprising at least one continuous lithium extraction unit as described, and an insulating housing accommodating the continuous lithium extraction unit.
The continuous lithium extraction system provided by the embodiment of the invention has at least the following beneficial effects:
the continuous lithium extraction system adopts all the technical schemes of the continuous lithium extraction unit of the embodiment, so that the continuous lithium extraction system has at least all the beneficial effects brought by the technical schemes of the embodiment.
The insulating housing is a supporting structure for the continuous lithium extraction system, wherein insulation ensures that it is not affected by external circuitry.
According to some embodiments of the invention, the insulating housing is cylindrical. Thereby facilitating the rotation of the cylindrical chamber driven by the drive rod.
According to some embodiments of the invention, the two sections of the insulating housing are provided with covers to avoid external substances affecting the movement of the cylindrical chamber, for example to avoid mechanical jamming caused by external debris.
According to some embodiments of the invention, the drive rod passes through the cover, whereby the drive rod may be driven by an external circuit, while the cover may also form a support for the drive rod.
According to some embodiments of the invention, the cylindrical chamber passes through the cover, whereby the cover may form a supporting effect for the cylindrical chamber.
According to some embodiments of the invention, there is no contact between the sidewalls of the cylindrical chambers of the plurality of continuous lithium extraction units. Thereby avoiding the influence of the electrodes in different consecutive lithium extraction units on each other.
According to some embodiments of the invention, in the continuous lithium extraction system, the number of the continuous lithium extraction units is 10-25.
The connection mode of the plurality of continuous lithium extraction units comprises at least one of parallel connection and series connection.
Specifically, if the extraction is easier and the processing capacity is larger, a parallel connection mode can be adopted; conversely, if it is desired to increase the extraction efficiency of lithium as much as possible, a plurality of continuous lithium extraction units may be connected in series. Meanwhile, a serial and parallel mixed connection mode can be performed according to the needs.
According to some embodiments of the invention, the continuous lithium extraction system further comprises an external raw material liquid buffer tank and a lithium-rich liquid buffer tank; so as to realize the circulating flow of the raw material liquid and the lithium-rich liquid.
Under the buffer action of the raw material liquid buffer tank and the lithium-rich liquid buffer tank, the hydraulic retention time of the raw material liquid and the lithium-rich liquid in the continuous lithium extraction system is 3-5 h, and preferably, the hydraulic retention time is about 4h.
According to an embodiment of the third aspect of the present invention, there is provided a lithium extraction method, using the continuous lithium extraction unit, or the continuous lithium extraction system;
the lithium extraction method comprises the following steps:
s1, injecting a raw material solution into the first chamber, injecting a lithium-rich solution into the second chamber, and performing electrochemical adsorption-desorption lithium extraction operation by taking the first electrode as a cathode and the second electrode as an anode;
s2, maintaining the anion membrane fixed, driving the side wall of the cylindrical cavity to rotate through the transmission rod, enabling the first electrode to be an anode and to be in contact with the lithium-rich liquid, enabling the second electrode to be a cathode and to be in contact with the raw material liquid, and continuing electrochemical adsorption-desorption lithium extraction operation.
The lithium extraction method has the following mechanism:
when the first electrode is a cathode, lithium ions in the raw material liquid are inserted into the cathode, and lithium ions in the second electrode are released into the lithium-rich liquid.
After the above process is completed, the lithium ions intercalated into the first electrode are released into the lithium-rich solution due to the rotation and electrode conversion, and the released second electrode is contacted with the raw material solution to perform the lithium-absorbing step.
In this way, the lithium content in the raw material liquid is reduced, and the lithium content in the lithium-rich liquid is increased.
The lithium extraction method provided by the embodiment of the invention has at least the following beneficial effects:
the continuous lithium extraction system or the continuous lithium extraction unit is adopted in the lithium extraction method, so that continuous lithium extraction can be realized through simple rotation and electrode switching, and the production efficiency is improved. Meanwhile, the raw material liquid and the lithium-rich liquid are not contacted all the time, and no pollution is caused between the raw material liquid and the lithium-rich liquid, so that the first chamber or the second chamber does not need to be cleaned, the operation steps of lithium extraction treatment are simplified, and the water consumption is reduced; is convenient for realizing industrialization.
According to some embodiments of the invention, the feed solution and the lithium-rich solution are injected continuously.
According to some embodiments of the invention, the feed solution is selected from at least one of lithium salt lake brine, underground brine, or other lithium-containing solutions.
According to some embodiments of the invention, the content of lithium ions in the raw material liquid is more than or equal to 0.2g/L; preferably, the content of lithium ions in the raw material liquid is more than or equal to 0.4g/L.
According to some embodiments of the invention, in step S1, the introduced lithium-rich liquid is selected from aqueous lithium chloride solutions. Preferably, the concentration of the lithium chloride aqueous solution is more than or equal to 0.1g/L. Preferably, the concentration of the lithium chloride aqueous solution is less than or equal to 1g/L.
According to some embodiments of the invention, in step S2, the angle of rotation is 180 °.
According to an embodiment of the fourth aspect of the present invention, there is provided the use of the lithium extraction method in extracting lithium from a lithium-containing solution.
The application adopts all the technical schemes of the lithium extraction method of the embodiment, so that the lithium extraction method has at least all the beneficial effects brought by the technical schemes of the embodiment.
According to some embodiments of the invention, the lithium-containing solution comprises at least one of seawater, lithium ion battery leachate.
The term "about" as used herein, unless otherwise specified, means that the tolerance is within + -2%, for example, about 100 is actually 100 + -2%. Times.100.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.
Drawings
The foregoing and/or additional aspects and advantages of the invention will become apparent and may be better understood from the following description of embodiments taken in conjunction with the accompanying drawings in which:
fig. 1 is a schematic side view of a continuous lithium extraction unit in example 1 of the present invention.
Fig. 2 is a schematic top view of the components of the continuous lithium extraction unit of embodiment 1 of the present invention except for the transmission rod.
Fig. 3 is a schematic side view of the continuous lithium extraction system of example 2 of the present invention.
FIG. 4 is a schematic diagram of the operation mechanism of the serial continuous lithium extraction system in example 2 of the present invention;
fig. 5 is a schematic diagram of the operation mechanism of the parallel continuous lithium extraction system in example 2 of the present invention.
Reference numerals:
a cylindrical chamber 100; a first electrode 111; a first chamber 112; a raw material liquid inlet 113; a raw material liquid outlet 114; a second electrode 121; a second chamber 122; a lithium-rich liquid outlet 123; a lithium-rich liquid inlet 124; an insulating member 130; a sealing plate 140;
an anionic membrane 200;
a transmission rod 300;
a sealing member 400;
an insulating housing 500.
Detailed Description
Embodiments of the present invention are described in detail below, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to like or similar elements or elements having like or similar functions throughout. The embodiments described below by referring to the drawings are illustrative only and are not to be construed as limiting the invention.
In the description of the present invention, the description of first, second, etc. is for the purpose of distinguishing between technical features only and should not be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated or implicitly indicating the precedence of the technical features indicated.
In the description of the present invention, it should be understood that the direction or positional relationship indicated with respect to the description of the orientation, such as up, down, etc., is based on the direction or positional relationship shown in the drawings, is merely for convenience of describing the present invention and simplifying the description, and does not indicate or imply that the apparatus or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and thus should not be construed as limiting the present invention.
In the description of the present invention, unless explicitly defined otherwise, terms such as arrangement, installation, connection, etc. should be construed broadly and the specific meaning of the terms in the present invention can be determined reasonably by a person skilled in the art in combination with the specific content of the technical solution.
Example 1
The embodiment provides a continuous lithium extraction unit, the structural schematic diagram of which is shown in fig. 1-2, and the structure is specific to the following:
the continuous lithium extraction unit includes:
a cylindrical chamber 100, wherein an arc-shaped first electrode 111 and an arc-shaped second electrode 121 are connected via an insulating member 130 to constitute a side wall of the cylindrical chamber 100;
the arc-shaped first electrode 111 and the arc-shaped second electrode 121 include lithium storage materials capable of desorbing lithium ions therein, and it is understood that the lithium storage materials may be olivine-structured lithium iron phosphate (LiFePO) 4 LFP), spinel structured lithium manganate (LiMn 2 O 4 LMO), spinel structured lithium nickel manganese oxide (LiNi x Mn 2-x O 4 LNMO), and a layered cathode material (LCO, LNO, or NCM); the present embodiment selects LFP.
Sealing plates 140 are arranged at the openings at the two ends of the cylindrical chamber 100, so that the cylindrical chamber 100 forms a closed space; the sealing plate 140 is made of insulating material;
the anion membrane 200 is disposed inside the cylindrical chamber 100, passes through the axis of the cylindrical chamber 100, and is movably connected with the insulating member 130 via the sealing member 400;
the anion membrane 200 divides the cylindrical chamber 100 into a first chamber 112 and a second chamber 122;
the sealing plate 140 on the cylindrical chamber 100 side is provided with: a lithium-rich liquid inlet 124 in communication with the second chamber 122 and a feed liquid outlet 114 in communication with the first chamber 112. The sealing plate 140 on the other side of the cylindrical chamber 100 is provided with: a lithium-rich liquid outlet 123 communicating with the second chamber 122 communicates with the raw material liquid inlet 113 of the first chamber 112.
The transmission rod 300 of insulating material, the transmission rod 300 and the cylindrical chamber 100 are engaged by screw threads, and the rotation of the latter is controlled by screw transmission.
Example 2
The embodiment provides a continuous lithium extraction system integrated by the continuous lithium extraction unit provided by the embodiment, a schematic structural diagram is shown in fig. 3, and specifically, the continuous lithium extraction system includes:
a plurality of continuous lithium extraction units and an insulating housing for accommodating the continuous lithium extraction units;
the insulating shell is cylindrical with a cover, a hole is arranged on the cylindrical cover, and a transmission rod and a cylindrical cavity of the continuous lithium lifting unit penetrate through the hole to form positioning and supporting and are connected with an external liquid path and a circuit.
It can be understood that the liquid paths of the plurality of continuous lithium extraction units are connected in parallel, and the specific schematic diagram is shown in fig. 4; i.e. all the raw material liquid passes through only one continuous lithium extraction unit.
It can be understood that the liquid paths of the plurality of continuous lithium extraction units are connected in series, and the specific schematic diagram is shown in fig. 5; namely, the raw material liquid passes through all continuous lithium extraction units in the continuous lithium extraction system.
It is understood that the continuous lithium extraction system further comprises an external raw material liquid buffer tank and a lithium-rich liquid buffer tank (not shown in the figure), wherein the raw material liquid buffer tank can buffer and store the raw material liquid discharged from the continuous lithium extraction system, and the buffered and stored raw material liquid is re-conveyed into the continuous lithium extraction system for processing.
Example 3
In this embodiment, the parallel continuous lithium extraction system (9 continuous lithium extraction units are shown in fig. 4 only in schematic diagram) in embodiment 2 is adopted to perform the lithium extraction operation of the salt lake brine with high lithium concentration, and the specific steps are as follows:
s1, continuously injecting a raw material liquid into a first chamber 112, continuously injecting a lithium-rich liquid into a second chamber 122, and performing electrochemical adsorption-desorption lithium extraction operation by taking a first electrode 111 as a cathode and a second electrode 121 as an anode; in the process, lithium in the raw material liquid is adsorbed into the cathode;
s2, after the adsorption-desorption lithium extraction operation of the step S1 is performed for 4 hours, the anion membrane 200 is kept fixed, the side wall of the cylindrical chamber 100 is driven by the transmission rod 300 to rotate 180 degrees, meanwhile, the electrode of the power supply is switched, the first electrode 111 is made to be an anode and contacted with lithium-rich liquid, the second electrode 121 is made to be a cathode and contacted with raw material liquid, and electrochemical adsorption-desorption lithium extraction operation is continued.
S3, after the adsorption-desorption lithium extraction operation of the step S2 is carried out for 4 hours, the steps S1-S2 are circularly carried out, and the produced raw material liquid and the lithium-rich liquid are collected.
In this example, the hydraulic retention time of the raw material liquid and the lithium-rich liquid in the continuous lithium extraction system is about 4 hours, and the flow states of the two solutions are turbulent.
In this example, the raw material liquid and the lithium-rich liquid used, and the components of the raw material liquid and the lithium-rich liquid produced are shown in Table 1.
TABLE 1 partial composition (g/L) of the starting materials and products in example 3
| Material name | Li | Na | K | Mg | Ca | S | B |
| Feed stock solution | 1.056 | 74.490 | 7.346 | 2.798 | 0.024 | 0.799 | 0.389 |
| Feed lithium-rich liquid | 0.330 | ||||||
| Discharging raw material liquid | 0.020 | 72.272 | 6.850 | 2.538 | 2.190 | 0.775 | 0.341 |
| Discharging lithium-rich liquid | 4.210 | 4.163 | 0.483 | 0.150 | 0.057 | 0.104 | 0.035 |
Therefore, according to the lithium extraction method provided by the invention, when a serial continuous lithium extraction system is adopted, lithium in the aqueous solution can be effectively enriched and extracted, and other components can be reduced as much as possible from entering the lithium-enriched solution.
Example 4
The embodiment performs lithium extraction operation of salt lake brine with medium and low lithium concentration, and the specific difference from embodiment 3 is that:
a serial continuous lithium extraction system of example 2 (9 continuous lithium extraction units in total, only schematic in fig. 4) was used.
In this example, the raw material liquid and the lithium-rich liquid used, and the components of the raw material liquid and the lithium-rich liquid produced are shown in Table 2.
TABLE 2 partial composition (g/L) of the starting materials and products in example 4
| Material name | Li | Na | K | Mg | Ca | S | B |
| Feed stock solution | 0.565 | 78.771 | 6.160 | 2.821 | 0.778 | 1.560 | 0.221 |
| Feed lithium-rich liquid | 0.552 | ||||||
| Discharging raw material liquid | 0.138 | 77.011 | 5.985 | 2.760 | 0.819 | 1.503 | 0.026 |
| Discharging lithium-rich liquid | 2.933 | 3.851 | 0.503 | 0.169 | 0.055 | 0.033 | 0.028 |
Therefore, according to the lithium extraction method provided by the invention, when a parallel continuous lithium extraction system is adopted, lithium in the aqueous solution can be effectively enriched and extracted, and other components can be reduced as much as possible from entering the lithium-enriched solution. In conclusion, the continuous lithium extraction unit and the continuous lithium extraction system provided by the invention can effectively separate lithium from other components in the aqueous solution to realize enrichment and recovery no matter for the raw material liquid with high lithium concentration or the raw material liquid with low lithium concentration, have wide application prospects in the aspect of extracting lithium from seawater, and are also expected to recover lithium in the lithium ion battery reclaimed material leaching solution.
The embodiments of the present invention have been described in detail with reference to the accompanying drawings, but the present invention is not limited to the above embodiments, and various changes can be made within the knowledge of one of ordinary skill in the art without departing from the spirit of the present invention.
Claims (10)
1. A continuous lithium extraction unit, characterized in that the continuous lithium extraction unit comprises:
a cylindrical chamber (100);
an anionic membrane (200), the anionic membrane (200) being in movable contact with a side wall of the cylindrical chamber (100) and dividing the cylindrical chamber into a first chamber (112) and a second chamber (122); the side wall of the first chamber (112) comprises a first electrode (111); the side wall of the second chamber (122) comprises a second electrode (121); -the first electrode (111) and the second electrode (121) comprise a lithium storage substance therein;
-a transmission rod (300), said transmission rod (300) controlling the rotation of said cylindrical chamber (100).
2. The continuous lithium extraction unit according to claim 1, further comprising a sealing plate (140) sealing the cylindrical chamber (100).
3. The continuous lithium extraction unit according to claim 1, wherein the number of the transmission rods (300) in the continuous lithium extraction unit is not less than 1.
4. The continuous lithium extraction unit according to claim 1, further comprising a sealing member (400) provided between a side wall of the cylindrical chamber (100) and the anionic membrane (200).
5. The continuous lithium extraction unit according to claim 1, further comprising an insulating member (130) provided on a side wall of the cylindrical chamber (100) and provided between the first electrode (111) and the second electrode (121).
6. The continuous lithium extraction unit according to any one of claims 1 to 5, further comprising a power supply system, the cathode and anode of which are connected to the first electrode (111) or the second electrode (121), respectively.
7. Continuous lithium extraction system, characterized in that it comprises at least one continuous lithium extraction unit according to any one of claims 1 to 6, and an insulating casing (500) containing said continuous lithium extraction unit.
8. A lithium extraction method characterized in that the continuous lithium extraction unit according to any one of claims 1 to 6 or the continuous lithium extraction system according to claim 7 is used;
the lithium extraction method comprises the following steps:
s1, injecting a raw material liquid into the first chamber (112), injecting a lithium-rich liquid into the second chamber (122), and performing electrochemical adsorption-desorption lithium extraction operation by taking the first electrode (111) as a cathode and the second electrode (121) as an anode;
s2, maintaining the anion membrane (200) fixed, driving the side wall of the cylindrical chamber (100) to rotate through the transmission rod (300), enabling the first electrode (111) to be an anode and to be in contact with the lithium-rich liquid, enabling the second electrode (121) to be a cathode and to be in contact with the raw material liquid, and continuing electrochemical adsorption-desorption lithium extraction operation.
9. The method according to claim 8, wherein the raw material liquid and the lithium-rich liquid are continuously injected.
10. Use of the lithium extraction method according to claim 8 or 9 for extracting lithium from lithium-containing solutions.
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| PCT/CN2023/078477 WO2024074007A1 (en) | 2022-10-08 | 2023-02-27 | Continuous lithium extraction unit and use thereof |
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| JP2002167628A (en) * | 2000-11-28 | 2002-06-11 | National Institute Of Advanced Industrial & Technology | Apparatus and method for recovering lithium |
| WO2012065361A1 (en) * | 2010-11-19 | 2012-05-24 | 中南大学 | Method and device for separating lithium from magnesium and enriching lithium in salt lake brine |
| CN104587835B (en) * | 2015-01-12 | 2016-04-13 | 太原理工大学 | A kind of continuous synchronization Selective Separation reclaims the device and method of anions and canons in weak solution |
| CN205653516U (en) * | 2016-03-03 | 2016-10-19 | 中南大学 | Electricity chemical approach retrieves device of lithium |
| CN105948188B (en) * | 2016-06-29 | 2018-12-18 | 太原理工大学 | A kind of continuously automatically controlled ion fractionation device and technique |
| CN106732239B (en) * | 2017-01-18 | 2018-12-18 | 太原理工大学 | The device and its application method of zwitterion continuity separation in a kind of solution |
| CN109264835B (en) * | 2018-10-09 | 2021-08-06 | 天津科技大学 | Continuous electrochemical element extraction system |
| CN110724832B (en) * | 2019-09-29 | 2021-09-10 | 天津科技大学 | Continuous ion pump lithium extraction device and lithium extraction method thereof |
| CN113999979A (en) * | 2021-11-26 | 2022-02-01 | 西安热工研究院有限公司 | Continuous operation electrochemical lithium extraction system and method |
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