CN116553689A - Electrochemical coupling membrane distillation device, waste lithium battery wet recycling distillation system adopting same and use method - Google Patents
Electrochemical coupling membrane distillation device, waste lithium battery wet recycling distillation system adopting same and use method Download PDFInfo
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- 238000004821 distillation Methods 0.000 title claims abstract description 145
- 239000012528 membrane Substances 0.000 title claims abstract description 96
- 230000008878 coupling Effects 0.000 title claims abstract description 52
- 238000010168 coupling process Methods 0.000 title claims abstract description 52
- 238000005859 coupling reaction Methods 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims abstract description 34
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 29
- 239000002699 waste material Substances 0.000 title claims abstract description 13
- 238000004064 recycling Methods 0.000 title claims description 9
- 239000002994 raw material Substances 0.000 claims abstract description 161
- 239000007788 liquid Substances 0.000 claims abstract description 144
- 230000007246 mechanism Effects 0.000 claims abstract description 134
- 238000006243 chemical reaction Methods 0.000 claims abstract description 118
- 239000007789 gas Substances 0.000 claims abstract description 36
- 238000005273 aeration Methods 0.000 claims abstract description 33
- 238000011084 recovery Methods 0.000 claims abstract description 29
- 238000010521 absorption reaction Methods 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 84
- 239000000460 chlorine Substances 0.000 claims description 48
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical class [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 35
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 30
- 239000003546 flue gas Substances 0.000 claims description 30
- 229910052801 chlorine Inorganic materials 0.000 claims description 22
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 21
- 239000000463 material Substances 0.000 claims description 19
- 239000003011 anion exchange membrane Substances 0.000 claims description 13
- 230000008569 process Effects 0.000 claims description 11
- 238000001354 calcination Methods 0.000 claims description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- 239000006260 foam Substances 0.000 claims description 5
- 239000010936 titanium Substances 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims description 4
- 238000003487 electrochemical reaction Methods 0.000 abstract description 17
- 239000002440 industrial waste Substances 0.000 abstract description 14
- 238000011065 in-situ storage Methods 0.000 abstract description 10
- 238000010438 heat treatment Methods 0.000 abstract description 9
- 239000007787 solid Substances 0.000 abstract description 7
- 239000002918 waste heat Substances 0.000 abstract description 7
- 239000000243 solution Substances 0.000 description 44
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 18
- 230000009471 action Effects 0.000 description 17
- 238000004519 manufacturing process Methods 0.000 description 12
- 229910001416 lithium ion Inorganic materials 0.000 description 11
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 10
- 239000001569 carbon dioxide Substances 0.000 description 9
- 229910002092 carbon dioxide Inorganic materials 0.000 description 9
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 8
- 230000004907 flux Effects 0.000 description 8
- 238000013461 design Methods 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000005684 electric field Effects 0.000 description 6
- 239000002912 waste gas Substances 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
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- 239000007774 positive electrode material Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000006276 transfer reaction Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
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- 238000000605 extraction Methods 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000010979 pH adjustment Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000009827 uniform distribution Methods 0.000 description 2
- 239000010926 waste battery Substances 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000002042 Silver nanowire Substances 0.000 description 1
- 238000005349 anion exchange Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
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- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- CJTCBBYSPFAVFL-UHFFFAOYSA-N iridium ruthenium Chemical compound [Ru].[Ir] CJTCBBYSPFAVFL-UHFFFAOYSA-N 0.000 description 1
- 238000009285 membrane fouling Methods 0.000 description 1
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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
- C02F1/4698—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis electro-osmosis
-
- 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
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
- C02F1/10—Treatment of water, waste water, or sewage by heating by distillation or evaporation by direct contact with a particulate solid or with a fluid, as a heat transfer medium
-
- 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
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
- C02F1/16—Treatment of water, waste water, or sewage by heating by distillation or evaporation using waste heat from other processes
-
- 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
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/447—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by membrane distillation
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Abstract
The invention relates to the technical field of waste lithium battery recovery, in particular to an electrochemical coupling membrane distillation device, a waste lithium battery wet recovery distillation system adopting the membrane distillation device and a use method, wherein the system comprises a reaction mechanism, a conductive mechanism, a cover plate mechanism and an aeration mechanism; the reaction mechanism comprises a raw material reaction plate, an anode reaction plate and a permeation plate; the electrochemical coupling membrane distillation device disclosed by the invention can perform in-situ electrochemical reaction on the surface of the conductive distillation membrane, improves the concentration rate of the solution, creates an alkaline environment, and introduces high-temperature CO into the raw material reaction plate 2 Gas realization raw materialIn-situ heating of liquid and utilization of industrial waste heat, and CO is trapped by alkaline environment absorption of the liquid 2 Gas and produce high quality Li 2 CO 3 A solid; that is, the electrochemical coupling membrane distillation device disclosed by the invention not only can produce high-quality Li at the site 2 CO 3 A solid; but also can absorb and trap industrial waste gas and waste heat.
Description
Technical Field
The invention relates to the technical field of waste lithium batteries, in particular to an electrochemical coupling membrane distillation device, a waste lithium battery wet recycling distillation system adopting the membrane distillation device and a use method.
Background
Global climate change has been exacerbated in the last decades, which has led to the search for efficient, environmentally friendly energy production and CO reduction 2 The discharge becomes urgent.
Lithium batteries are widely used in electric vehicles and energy storage systems, and play an important role in the field of renewable energy sources.
However, the total amount of lithium ore resources is limited, and significant carbon emissions (e.g., li) still occur during the production of lithium batteries 2 CO 3 And FePO 4 Will produce a large amount of CO during calcination 2 )。
In summary, the efficient recovery technology of the waste lithium battery and the CO in the lithium battery production process are developed 2 Trapping technology is becoming an important point of future research and development.
In the acid release process of the positive electrode material recovered from the retired battery, a large amount of LiCl solution with medium and low concentration is often obtained, and the concentration, pH adjustment and Na addition are needed 2 CO 3 Recovering Li from the mixture by means of 2 CO 3 。
For example, patent: 201580049244.1-methods of recovering positive electrode materials for lithium ion batteries.
The energy consumption, the chemical reagent dosage and the like in the process do not meet the current environmental protection targets.
Therefore, in order to improve or solve the above problems, an optimization design is required for the existing recovery method, process or equipment of lithium ions of the waste battery.
Disclosure of Invention
The invention aims to provide an electrochemical coupling membrane distillation device which can reduce industrial carbon emission and can realize lithium ion recovery of waste batteries.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
an electrochemical coupling membrane distillation device comprises a reaction mechanism, a conductive mechanism, a cover plate mechanism and an aeration mechanism;
the reaction mechanism comprises a raw material reaction plate, an anode reaction plate and a permeation plate;
a raw material liquid channel is arranged on the raw material reaction plate;
an anode water flow channel is arranged on the anode reaction plate;
the permeation plate is provided with a permeation side channel;
the cover plate mechanism comprises an anode side cover plate and a permeation side cover plate;
the anode side cover plate, the anode reaction plate, the raw material reaction plate, the permeation plate and the permeation side cover plate are sequentially distributed;
the conductive mechanism comprises a conductive distillation film and an electrode plate;
the conductive distillation membrane is arranged in a region between the permeation plate and the raw material reaction plate; the electrode plate is arranged in a region between the anode side cover plate and the anode reaction plate;
an anion exchange membrane is arranged between the anode reaction plate and the raw material reaction plate;
the aeration mechanism comprises an aeration plate arranged in the raw material liquid channel, and the aeration plate is connected with an air supply part.
The air supply part comprises an air supply pipeline connected with the aeration plate, and CO is supplied in the air supply pipeline 2 Is a high temperature industrial flue gas.
The high-temperature industrial flue gas is Li 2 CO 3 High temperature industrial flue gas generated in the process of preparing LFP by calcination.
The aeration plate is made of foam titanium; the high-temperature industrial flue gas is high-temperature CO 2 The gas temperature is 90-200 ℃, and the flow rate of the high-temperature industrial flue gas and the area of the conductive distillation membrane are set in proportion.
A distillation system comprising an electrochemically coupled membrane distillation apparatus; the electrochemical coupling membrane distillation device is connected with a material system and a power supply mechanism;
the material system comprises a raw material supply mechanism, an anode liquid supply mechanism, a chlorine treatment mechanism and a water liquid recovery mechanism;
the raw material supply mechanism, the anolyte supply mechanism, the chlorine treatment mechanism and the water liquid recovery mechanism are respectively connected with the electrochemical coupling membrane distillation device through pipeline mechanisms.
The power supply mechanism comprises a programmable power supply which is connected with a conductive mechanism in the electrochemical coupling film distillation device; the positive electrode of the programmable power supply is connected with the electrode plate, and the negative electrode of the programmable power supply is connected with the conductive distillation film.
The raw material supply mechanism comprises a raw material liquid pump and a raw material liquid pool; the raw material liquid pump is connected with the raw material liquid pool; the raw material liquid pump is connected with the raw material liquid pool through a pipeline mechanism and a raw material reaction plate in the electrochemical coupling membrane distillation device;
the anolyte supply mechanism comprises an anolyte tank and an anolyte water pump, and the anolyte tank is connected with the anolyte water pump; the anolyte water pump and the anode pool are respectively connected with an anode reaction plate in the electrochemical coupling membrane distillation device through a pipeline mechanism;
the chlorine treatment mechanism comprises a chlorine gas absorption tank; the chlorine absorption tank is connected with the anode reaction plate through a pipeline mechanism;
the water liquid recovery mechanism; the water liquid recovery mechanism comprises a water liquid pool; the water pond is connected with the osmosis plate through a pipeline mechanism.
The raw material liquid pump is connected with the raw material liquid pool in series; and a solid-liquid separator is arranged between the raw material liquid pump and the raw material liquid pool.
And saturated LiCl solution is arranged in the anode pool.
A method of using the distillation system, the method comprising the steps of:
step 1: assembling the whole distillation system; and ensure that each mechanism can be used normally;
step 2: after the step 1 is completed, the raw material liquid to be treated is supplied into the raw material reaction plate through a raw material supply mechanism; supplying a saturated LiCl solution into the anode reaction plate through an anolyte supply mechanism; the power supply mechanism is started and supplies power to the guide motor mechanism; the aeration component continuously supplies air into the raw material reaction plate;
step 3: continuously carrying out the step 2 to realize the treatment of the raw material liquid; until the set requirement is reached.
The invention has the advantages that:
the invention discloses an electrochemical coupling membrane distillation device, a distillation system with the distillation device and a use method of the distillation system.
The electrochemical coupling membrane distillation device disclosed by the invention can perform in-situ electrochemical reaction on the surface of the conductive distillation membrane, improves the concentration rate of the solution, creates an alkaline environment, and introduces high-temperature CO into the raw material reaction plate 2 The gas realizes the in-situ heating of the raw material liquid and the utilization of industrial waste heat, and the alkaline environment of the solution absorbs and traps CO 2 Gas and produce high quality Li 2 CO 3 A solid; in other words; namely, the electrochemical coupling membrane distillation device disclosed by the invention not only can produce high-quality Li at the position 2 CO 3 A solid; but also can absorb and trap industrial waste gas and waste heat.
The distillation system can circularly treat raw material liquid, and in addition, the invention utilizes the catalyst rich in CO 2 The raw material liquid of the membrane distillation system is heated by the high-temperature flue gas, and the CO is absorbed under the condition of no additional chemical reagent by means of electrochemical reaction of the surface of the conductive membrane material 2 Concentrating LiCl raw material liquid to produce battery grade Li 2 CO 3 The method comprises the steps of carrying out a first treatment on the surface of the Synchronously realize the utilization of industrial waste heat and CO 2 The method is used for capturing lithium resources in wastewater and recovering lithium resources in wastewater, and solves the problem that the membrane flux of a membrane distillation system is reduced along with the increase of concentration multiple.
Drawings
The contents of the drawings and the marks in the drawings of the present specification are briefly described as follows:
FIG. 1 is a system block diagram of a distillation system of the present invention;
FIG. 2 is a schematic diagram of an electrochemical coupled membrane distillation assembly;
FIG. 3 is a cross-sectional view of an electrochemically coupled membrane distillation assembly;
the labels in the above figures are:
wherein, the device comprises a 01-electrochemical coupling membrane distillation component, a 02-aeration component, a 03-raw material liquid pool, a 04-solid-liquid separator, a 05-raw material liquid water pump, a 06-anode pool, a 07-anode liquid water pump, a 08-chlorine absorption pool, a 09-condenser, a 10-water pool, a 11-vacuum pump and a 12-programmable power supply.
01-1-raw material reaction plate, 01-2-conductive distillation film, 01-3-permeation plate, 01-4-permeation side cover plate, 01-5-anion exchange film, 01-6-anode reaction plate, 01-7-electrode, 01-8-anode side cover plate, 01-9-anode side water pipe, 01-10-raw material liquid water pipe, 01-11-gas supply pipe and 01-12-permeation side pipe.
Detailed Description
The following detailed description of the invention refers to the accompanying drawings, which illustrate preferred embodiments of the invention in further detail.
An electrochemical coupling membrane distillation device 01 comprises a reaction mechanism, a conductive mechanism, a cover plate mechanism and an aeration mechanism 02; the electrochemical coupling membrane distillation device 01 disclosed by the invention can perform in-situ electrochemical reaction on the surface of the conductive distillation membrane 01-2, improve the concentration rate of the solution, create an alkaline environment, and introduce high-temperature CO into the raw material reaction plate 01-1 2 The gas realizes the in-situ heating of the raw material liquid and the utilization of industrial waste heat, and the alkaline environment of the solution absorbs and traps CO 2 Gas and produce high quality Li 2 CO 3 A solid; that is, the electrochemical coupling membrane distillation apparatus 01 disclosed by the invention not only can produce high-quality Li at the site 2 CO 3 A solid; but also can absorb and trap industrial waste gas and waste heat.
The electrochemical coupling membrane distillation device 01 disclosed by the invention can realize CO through electrochemical reaction 2 The gas is trapped, and meanwhile, li ions in LiCl solution formed after acid release and extraction of the anode material of the lithium ion battery can be separated; formation of Li 2 CO 3 And (5) precipitation.
Specifically, the reaction mechanism disclosed by the invention comprises a raw material reaction plate 01-1, an anode reaction plate 01-6 and a permeation plate 01-3; in the invention, the raw material reaction plate 01-1 is used for raw material liquid and CO 2 Gas enters and the two are reacted subsequently; while the anode reaction plate 01-6 is used for anode water inflow, which is convenient for subsequent Cl - The water flows to the anode water flow channel 01-61 by crossing the anion exchange membrane 01-5 under the action of an electric field; finally, cl is formed in the anode reaction plate 01-6 2 Discharging, and then realizing Cl in LiCl raw material liquid - By Cl 2 Is removed and recovered; in addition, the arrangement of the permeation plate 01-3 mainly facilitates the evaporation and discharge of water liquid in the distillation process of Eilen, so that the remarkable increase of the ion concentration of the raw material liquid in actual production is avoided, and meanwhile, the membrane flux of the membrane material can be kept in a higher state all the time.
In addition, a raw material liquid channel 01-12 is arranged on the raw material reaction plate 01-1; the anode reaction plate 01-6 is provided with an anode water flow channel 01-61; the permeation plate 01-3 is provided with a permeation side channel 01-3; the invention adopts the raw material liquid channel 01-12, the raw material liquid channel 01-12 is an internal cavity structure of the raw material reaction plate 01-1, mainly provides an internal reaction space, is convenient for raw material liquid and is rich in CO 2 The high-temperature industrial flue gas is collected and reacted in a raw material reaction plate 01-1; and the anode reaction plate 01-6 is provided with an anode water flow channel 01-61, and the anode water flow channel 01-61 enables the inner side of the anode reaction plate 01-6 to form a cavity structure, thereby facilitating the flow of the anode water flow channel 01-61 and the subsequent Cl 2 Is arranged outside the reactor; the permeation side channel 01-3 is also of a plate inner cavity structure, is mainly used for discharging water vapor, accelerates concentration of solution, and simultaneously discharges water vapor, and in addition, in the actual production process; because the electrolytic water reaction and the evaporation of water in the membrane distillation process do not cause the remarkable increase of the ion concentration of the raw material liquid, the membrane flux of the membrane material can be always maintained in a high state so as to avoid the influence of the water vapor collecting in the distillation device.
In addition, the cover plate mechanism comprises an anode side cover plate 01-8 and a permeation side cover plate 01-4; the anode side cover plate 01-8, the anode reaction plate 01-6, the raw material reaction plate 01-1, the permeation plate 01-3 and the permeation side cover plate 01-4 are distributed in sequence; the invention facilitates the integral assembly and fixation of the distillation device through the arrangement of the anode side cover plate 01-8 and the permeation side cover plate 01-4, and the anode side cover plate 01-8, the anode reaction plate 01-6, the raw material reaction plate 01-1, the permeation plate 01-3 and the permeation side cover plate 01-4 are connected through bolts when the distillation device is actually assembled, and other connection modes can be selected according to the needs for connection when the distillation device is actually assembled.
Meanwhile, in the invention, the conductive mechanism comprises a conductive distillation film 01-2 and an electrode plate 01-7; according to the invention, through the design, the basic purpose is to realize connection between the distillation device and the power supply mechanism, so that the subsequent electrifying operation during use is convenient, and then the electrolytic operation on the solution is realized.
In the actual arrangement, it is required that the conductive distillation membrane 01-2 is arranged in the region between the permeation plate 01-3 and the raw material reaction plate 01-1; the electrode plate 01-7 is arranged in the area between the anode side cover plate 01-8 and the anode reaction plate 01-6; through the arrangement mode, the electrolysis operation of anode water and raw material liquid can be realized; meanwhile, an anion exchange membrane 01-5 is arranged between the anode reaction plate 01-6 and the raw material reaction plate 01-1; anion exchange membranes 01-5 are used herein; can realize Cl in the raw material liquid - Because of Cl under the action of electrochemical reaction - Conversion to Cl 2 And enter a chlorine absorption tank 08 to be recovered, and Cl in the solution in the anode water flow channel 01-61 is recovered - Reduced concentration of Cl - The concentration is reduced, and Cl in the raw material liquid channel 01-12 is reduced under the action of an electric field - Supplementing the anode water flow channel 01-61 through the anion exchange membrane 01-5.
Meanwhile, the aeration mechanism 02 in the present invention includes a liquid passage 0 provided in the raw material1-12, wherein the aeration plate is connected with an air supply part; the aeration mechanism 02 disclosed by the invention is mainly used for carrying out air supply operation on the raw material reaction plate 01-1, the supplied air is high-temperature carbon dioxide, one function of the high-temperature carbon dioxide is to heat raw material liquid, the other function is to supply carbonate ions, and the subsequent combination with lithium ions is convenient to form Li 2 CO 3 And (5) precipitation.
In sum, through the arrangement of the distillation device, the collection and separation of lithium ions in the raw material liquid can be realized, and meanwhile, the high-temperature waste gas formed by industrial production can be secondarily utilized, so that the influence of the industrial waste gas on air can be reduced, and the waste heat of the industrial waste gas can be utilized, thereby realizing the secondary utilization of waste heat; in other words, the distillation device disclosed by the invention is not only beneficial to improving the efficiency of the lithium battery recovery process, but also greatly reduces CO in the lithium battery production process 2 Emissions, contribute to global management of climate change.
Further, in the invention, the air supply part comprises an air supply pipeline 01-11 connected with the aeration plate, and the air supply part is mainly used for carrying out air supply operation on the aeration plate, and in actual design, the air supply part comprises the air supply pipeline 01-11 connected with the aeration plate, and the air supply pipeline 01-11 can be directly connected with an industrial waste gas exhaust pipeline or can be connected with the industrial waste gas exhaust pipeline through an air supply pump or other air supply equipment; the main purpose is that the required gas can be supplied to the aeration plate; in addition, in the specific implementation, the gas supply pipes 01 to 11 are required to be supplied with a gas containing CO 2 High temperature industrial flue gas; where CO is contained 2 The high-temperature industrial flue gas is rich in CO 2 High temperature industrial flue gas; because the distillation device disclosed by the invention mainly avoids CO in the waste gas besides utilizing the waste heat of the waste gas 2 Is discharged by CO 2 Form carbonate ions, which facilitate subsequent combination with lithium ions to form Li 2 CO 3 And (5) precipitation.
Further, in the invention, the high-temperature industrial flue gas is Li 2 CO 3 Produced during the calcination of LFPHigh temperature industrial flue gas; the secondary utilization of waste heat of waste gas during lithium battery production can be realized, and the greenhouse effect caused by the discharge of a large amount of generated carbon dioxide is avoided; in other words, the present invention is achieved by the above method for preparing Li 2 CO 3 The utilization of high-temperature industrial flue gas generated in the process of preparing the LFP through calcination can obviously reduce carbon emission in the process of producing the lithium battery, can reduce the subsequent waste gas treatment cost, and is also beneficial to improving the efficiency of the lithium battery recovery process; and also contributes to global management of climate change; has excellent social popularization significance.
Of course, in actual production, it is preferable to ensure the carbon dioxide content in the high-temperature industrial flue gas and reduce the gas existence as much as possible, so that the method can be used together with an actual gas treatment device, so that the treated waste gas is rich in more carbon dioxide and other gases are reduced or avoided.
Further, in the invention, the aeration plate is made of foam titanium; the high-temperature industrial flue gas is high-temperature CO 2 The gas temperature is 90-200 ℃, and the flow rate of the high-temperature industrial flue gas and the area of the conductive distillation membrane 01-2 are set according to the proportion; in the invention, microporous structural materials such as foam titanium are used for realizing micron-sized bubble generation and uniform distribution, and the bubble size range is 20-100 mu m. The industrial flue gas introduced into the flue gas is high-temperature CO 2 The gas temperature is 90-200deg.C, the flow rate is related to the area of the conductive distillation membrane 01-2, and is set to 0.1-5m 3 Carbon dioxide /(m 2 Film material Min); by adopting the design proportion, high-temperature CO is avoided 2 The gas is excessively supplied or excessively supplied in the raw material reaction plate 01-1; thereby avoiding the collection of excessive ions in the raw material liquid; and meanwhile, the influence on the separation of lithium ions caused by the existence of too little carbonate ions is avoided.
A distillation system, comprising an electrochemical coupling membrane distillation device 01; the electrochemical coupling membrane distillation device 01 is connected with a material system and a power supply mechanism; in addition, the distillation system disclosed by the invention can circularly realize the treatment of raw material liquid, and in addition, the invention utilizes the catalyst rich in CO 2 Is heated by high-temperature flue gas of a membrane distillation systemThe raw material liquid is subjected to electrochemical reaction on the surface of the conductive film material to absorb CO without adding any chemical reagent 2 Concentrating LiCl raw material liquid to produce battery grade Li 2 CO 3 The method comprises the steps of carrying out a first treatment on the surface of the Synchronously realize the utilization of industrial waste heat and CO 2 The method is used for capturing lithium resources in wastewater and recovering lithium resources in wastewater, and solves the problem that the membrane flux of a membrane distillation system is reduced along with the increase of concentration multiple.
Specifically, the material system comprises a raw material supply mechanism, an anode liquid supply mechanism, a chlorine gas treatment mechanism and a water liquid recovery mechanism; in the invention, the raw material supply mechanism mainly supplies raw material liquid, so that the raw material liquid continuously flows in the raw material reaction plate 01-1; meanwhile, the anolyte supply mechanism mainly supplies anolyte so that the anolyte is continuously supplied in the anode reaction plate 01-6 in a flowing way; the chlorine treatment mechanism is mainly used for collecting chlorine discharged from the anode plate to avoid the overflow of the chlorine, and the water liquid recovery mechanism is mainly used for collecting water vapor discharged from the permeation plate 01-3 to avoid the overflow of the water vapor.
Meanwhile, in the invention, the raw material supply mechanism, the anolyte supply mechanism, the chlorine treatment mechanism and the water liquid recovery mechanism are respectively connected with the electrochemical coupling membrane distillation device 01 through pipeline mechanisms; the arrangement of the pipeline mechanism is convenient for the connection between each mechanism and the electrochemical coupling membrane distillation device 01, the pipeline mechanism is mainly a pipeline structure, a valve body can be arranged on the pipeline structure, the valve body can be an electromagnetic valve or other control valve body structures, the valve body mainly controls the on-off of the pipeline mechanism, and meanwhile, the length and the size of the pipeline mechanism are selected according to the needs; the arrangement of the pipeline mechanism facilitates the dispersion arrangement of each mechanism, and a plurality of distillation devices can conveniently share one set of material system in actual production.
Further, in the invention, the power supply mechanism comprises a programmable power supply 12, and the programmable power supply 12 is connected with the conductive mechanism in the electrochemical coupling film distillation device 01; the positive electrode of the programmable power supply 12 is connected with the electrode plate 01-7, and the negative electrode of the programmable power supply 12 is connected with the conductive distillation film 01-2; the inventionA clear use programmable power supply 12; the output voltage can be intelligently regulated and controlled between 1.2 and 30V according to the parameters of system current density, solution conductivity, solution pH and the like, thereby ensuring good concentration rate and Li 2 CO 3 Yield and H2 purity; particularly excellent practical use effect.
Further, in the present invention, the raw material supply means includes a raw material liquid pump 05 and a raw material liquid pool 03; the raw material liquid pump 05 is connected with the raw material liquid pool 03; the raw material liquid pump 05 and the raw material liquid pool 03 are connected with a raw material reaction plate 01-1 in the electrochemical coupling membrane distillation device 01 through a pipeline mechanism; through the design, the raw material liquid pump 05 pumps the raw material liquid in the raw material liquid pool 03 during subsequent use, so that the raw material liquid enters or is discharged from the raw material reaction plate 01-1.
And the same is done; the anolyte supply mechanism comprises an anolyte pool 06 and an anolyte water pump 07, and the anolyte pool 06 is connected with the anolyte water pump 07; the anolyte water pump 07 and the anode pool 06 are respectively connected with anode reaction plates 01-6 in the electrochemical coupling film distillation device 01 through pipeline mechanisms; through the design, the invention is convenient for the subsequent use or the control of the anolyte in the anode pool 06 by the anolyte pump 07, and is convenient for the entry or the discharge of the anolyte in the anode reaction plate 01-6.
And the chlorine treatment mechanism comprises a chlorine gas absorption basin 08; the chlorine absorption tank 08 is connected with the anode reaction plate 01-6 through a pipeline mechanism; the chlorine absorption tank 08 is mainly used for storing dichloromethane or sodium hydroxide; the subsequent absorption and recovery of chlorine are convenient.
The water liquid recovery mechanism in the invention; the water recovery mechanism comprises a water pond 10; the water pond 10 is connected with the permeation plate 01-3 through a pipeline mechanism; the water tank 10 is used for recovering water vapor, and a condenser 09 is provided in front of the water tank 10 for ensuring recovery effect.
Further, in the present invention, the raw material liquid pump 05 is connected in series with the raw material liquid pool 03; a solid-liquid separator 04 is arranged between the raw material liquid pump 05 and the raw material liquid pool 03; the invention can lead Li to be formed by arranging the solid-liquid separator 04 2 CO 3 Separating the precipitate; the liquid continues to enter the raw material liquid pool 03 for the next electrochemical distillation treatment operation.
Further, in the invention, the anode pool 06 is filled with saturated LiCl solution; the solution can prevent Cl generated by electrode plates 01-7 2 Redissolved in solution to facilitate the reaction to Cl 2 Is used for the recovery of the anion exchange membrane 01-5.
A method of using the distillation system, the method comprising the steps of:
step 1: assembling the whole distillation system; and ensure that each mechanism can be used normally;
step 2: after the step 1 is completed, the raw material liquid to be treated is supplied into the raw material reaction plate 01-1 through a raw material supply mechanism; supplying a saturated LiCl solution into the anode reaction plate 01-6 through an anolyte supply mechanism; the power supply mechanism is started and supplies power to the guide motor mechanism; the aeration mechanism 02 continuously supplies air into the raw material reaction plate 01-1;
step 3: continuously carrying out the step 2 to realize the treatment of the raw material liquid; until the set requirement is reached.
According to the invention, through the disclosure of the using method and the continuous operation of the step 2, repeated treatment of the raw material liquid can be realized, and the sufficient separation operation of lithium ions in the raw material liquid is ensured.
Specifically:
in the acid release process of the positive electrode material recovered from the retired battery, a large amount of LiCl solution with medium and low concentration is often obtained, and the concentration, pH adjustment and Na addition are needed 2 CO 3 Recovering Li from the mixture by means of 2 CO 3 。
The energy consumption, the chemical reagent dosage and the like of the normal treatment process do not meet the current environmental protection targets.
The invention discloses a novel separation device and a separation method based on a membrane distillation technology, and has the advantages of high concentration multiple, low-grade energy availability, simple device structure, difficult membrane fouling occurrence and the like.
At the same time, the invention is generalInstalling a conductive distillation membrane 01-2 and performing in-situ coupling electrochemical reaction; can overcome the problems that a membrane distillation system can not realize the conversion of chemical components, flux is reduced after high-power concentration and the like, and can also overcome the problems that the membrane distillation system can not realize the conversion of chemical components, the flux is reduced after high-power concentration and the like by utilizing industrial flue gas (such as high-temperature CO generated by calcination in the production process of lithium batteries) 2 ) In-situ heating is carried out, and CO is realized while the energy utilization efficiency is improved 2 Is included in the collection of the liquid.
Therefore, the device is not only beneficial to improving the efficiency of the lithium battery recovery process, but also greatly reduces CO in the lithium battery production process 2 Emissions, contribute to global management of climate change.
In the present invention; aiming at the problems existing in the prior art, the invention prepares a high-quality conductive distillation membrane 01-2, and designs an electrochemical coupling membrane distillation device 01 and an operation mode for synchronously realizing the output of lithium carbonate and the capture of carbon dioxide.
In-situ electrochemical reaction on the surface of the conductive distillation membrane 01-2 improves the concentration rate of the solution, creates an alkaline environment, and introduces high-temperature CO into the membrane distillation assembly 2 The gas realizes the in-situ heating of the raw material liquid and the utilization of industrial waste heat, and simultaneously, the alkaline environment of the solution absorbs and captures CO 2 Gas and produce high quality Li 2 CO 3 A solid.
The specific technical scheme is as follows:
an electrochemical coupling membrane distillation device 01 and a distillation system.
The distillation device mainly comprises a reaction mechanism, a conductive mechanism, a cover plate mechanism and an aeration mechanism 02; the reaction mechanism comprises a raw material reaction plate 01-1, an anode reaction plate 01-6 and a permeation plate 01-3; the raw material reaction plate 01-1 is provided with a raw material liquid channel 01-12; the anode reaction plate 01-6 is provided with an anode water flow channel 01-61; the permeation plate 01-3 is provided with a permeation side channel 01-3; the cover plate mechanism comprises an anode side cover plate 01-8 and a permeation side cover plate 01-4; the anode side cover plate 01-8, the anode reaction plate 01-6, the raw material reaction plate 01-1, the permeation plate 01-3 and the permeation side cover plate 01-4 are distributed in sequence; the conductive mechanism comprises a conductive distillation film 01-2 and an electrode plate 01-7; the conductive distillation membrane 01-2 is arranged in the area between the permeation plate 01-3 and the raw material reaction plate 01-1; the electrode plate 01-7 is arranged in the area between the anode side cover plate 01-8 and the anode reaction plate 01-6; an anion exchange membrane 01-5 is arranged between the anode reaction plate 01-6 and the raw material reaction plate 01-1; the aeration mechanism 02 comprises an aeration plate arranged in the raw material liquid channel 01-12, and the aeration plate is connected with an air supply part.
Specifically, the method comprises the following steps;
the distillation system comprises an electrochemical coupling membrane distillation device 01, an aeration mechanism 02, a raw material liquid pool 03, a solid-liquid separator 04, a raw material liquid pump 05, an anode pool 06, an anode liquid pump 07, a chlorine absorption pool 08, a condenser 09, a water liquid pool 10, a vacuum pump 11 and a programmable power supply 12.
As shown in fig. 2 and 3, the electrochemical coupling membrane distillation apparatus 01 comprises a raw material liquid channel 01-12, a conductive distillation membrane 01-2, a vacuum permeation side channel 01-3, a permeation side cover plate 01-4, an anion exchange membrane 01-5, an anode water flow channel 01-61, an electrode plate 01-7 and an anode side cover plate 01-8.
The pipeline mechanism connected with the anode reaction plate 01-6 mainly comprises an anode side water pipe 01-9; for the supply of anolyte; the pipeline mechanism connected with the raw material reaction plate 01-1 mainly comprises a raw material liquid water pipe 01-10; the device is mainly used for supplying raw material liquid of a raw material reaction plate; the gas supply pipeline 01-11 is mainly used for supplying high-temperature industrial gas in the raw material reaction plate, and the pipeline mechanism connected to the permeation plate 01-3 comprises a permeation side pipeline 01-12.
The preparation method of the conductive distillation film 01-2 comprises the following steps: the conductive coating is loaded on the surface of the hydrophobic PTFE membrane in a vacuum-driven self-assembly mode, so that the conductive distillation membrane 01-2 can be obtained.
Specifically, a PTFE hydrophobic membrane is wetted by ethanol, and then an aqueous solution containing graphene, silver nanowires, metal organic framework particles and a polyvinyl alcohol cross-linking agent is subjected to suction filtration under the negative pressure of 0.1-0.4Bar, so that components in water are trapped on the surface of a membrane material and self-assembled into a conductive layer with the thickness of 50-200 nm.
The electrode plate 01-7 is selected from titanium electrode plate 01-7, ruthenium iridium electrode plate 01-7 or platinum electrode plate 01-7.
The aeration mechanism 02 uses a microporous structure such as foam titaniumThe material realizes micron-sized bubble generation and uniform distribution, and the bubble size range is 20-100 mu m. The industrial flue gas introduced into the flue gas is high-temperature CO 2 The gas temperature is 90-200deg.C, the flow rate is related to the area of the conductive distillation membrane 01-2, and is set to 0.1-5m 3 Carbon dioxide /(m 2 Film material ·min)。
LiCl solution with lower concentration is prepared from the anode material of the lithium ion battery after acid release and extraction, and the concentration range is 20-400mmol/L.
The anode pool 06 is filled with saturated LiCl solution which can prevent Cl generated by the electrode plates 01-7 2 Redissolved in solution to facilitate the reaction to Cl 2 Is used for the recovery of the anion exchange membrane 01-5.
Dichloromethane or sodium hydroxide is filled in the chlorine absorption tank 08 to realize Cl 2 Is absorbed and recovered.
The positive electrode of the programmable power supply 12 is connected with an electrode plate 01-7 in the electrochemical coupling film distillation device 01, the negative electrode is connected with a conductive distillation film 01-2 in the electrochemical coupling film distillation device 01, and the output voltage of the programmable power supply can be intelligently regulated and controlled between 1.2 and 30V according to parameters such as the current density of the system, the conductivity of the solution, the pH value of the solution and the like, so that good concentration rate and Li are ensured 2 CO 3 Yield and H 2 Purity of the product.
The device comprises three mass transfer reactions of channels, wherein the three reactions are carried out simultaneously, and the mass transfer reactions are as follows:
anode channel reaction R1: the saturated LiCl solution in the anode pool 06 flows into the anode water flow channel 01-61 of the electrochemical coupling film distillation device 01 under the action of the anode liquid pump 07, and Cl is reacted under the action of electrochemistry - Conversion to Cl 2 And enter a chlorine absorption tank 08 to be recovered, and Cl in the solution in the anode water flow channel 01-61 is recovered - The concentration is reduced, and Cl in the raw material liquid channel 01-12 is reduced under the action of an electric field - The solution is supplemented to the anode water flow channel 01-61 through the anion exchange membrane 01-5, the saturated state of LiCl is maintained, and finally the solution flows back to the anode pool 06.
Raw material liquid channel 01-12 reaction R2. Medium and low concentration LiCl solution in raw material liquid pool 03 is pumped in raw material liquid pump05 into a raw material liquid channel 01-12 of an electrochemical coupling membrane distillation device 01 under the action of the catalyst, and forming LiOH solution under the action of electrochemical reaction; the solution is subjected to high temperature CO 2 Heating, wherein liquid water is evaporated into water vapor, and enters into a vacuum permeation side channel 01-3 under the action of negative pressure; at the same time LiOH and CO 2 Reaction to form Li 2 CO 3 The sediment flows out of the electrochemical coupling membrane distillation device 01 along with water flow, enters the solid-liquid separator 04 and is recovered, and the rest solution returns to the raw material liquid pool 03.
Permeation side channel 01-3 reaction R3 by vacuum pump 11, vapor evaporated from raw material liquid channel 01-12 and unreacted CO 2 H generated by electrochemical reaction on surface of conductive distillation film 01-2 2 All penetrate through the conductive distillation membrane 01-2 and enter the vacuum permeation side channel 01-3 for recovery.
In principle, the distillation system of the invention has electrochemical reaction and membrane distillation reaction simultaneously in the operation process; the method comprises the following steps:
electrochemical reaction part: under the driving of electrochemical reaction and electric field, cl is generated on the surface of the electrode plate 01-7 2 And reduce Cl in the anode water flow channel 01-61 - Concentration of Cl in raw material liquid channel 01-12 - The water flows to the anode water flow channel 01-61 by crossing the anion exchange membrane 01-5 under the action of an electric field; h is generated on the surface of the conductive distillation film 01-2 2 OH production on the film material surface - An alkaline environment is formed. Meanwhile, the electrolytic water reaction consumes liquid water in the raw material liquid, and the concentration of the solution is accelerated to a certain extent.
Membrane distillation reaction part: the membrane distillation reaction takes the temperature difference as the driving force, wherein the higher water temperature in the raw material liquid channel 01-12 is derived from the combined action of the heat release of electrolyzed water and the heating of industrial flue gas; the aeration mechanism 02 can enrich CO 2 High temperature industrial flue gas (e.g. using Li) 2 CO 3 CO generated in the process of preparing LFP by calcination 2 ) Heating the solution in the water flow channel in situ; meanwhile, as the solution is concentrated, CO is generated in alkaline environment 2 Is soluble in liquid and is compatible with Li + Bonding to form Li 2 CO 3 Precipitating, andli is realized by a solid-liquid separator 04 2 CO 3 Is separated from the (a); in addition, cl in LiCl raw material liquid - By Cl 2 Is removed and recovered, li + By Li 2 CO 3 The form of (c) is separated, so that the electrolysis water reaction and the evaporation of water in the membrane distillation process do not cause the concentration of the raw material liquid ions to be significantly increased, and the membrane flux of the membrane material can be always maintained in a high state.
The device comprises three mass transfer reactions of channels, wherein the three reactions are carried out simultaneously, and the specific implementation modes are as follows:
anode channel reaction R1: the saturated LiCl solution in the anode pool 06 flows into the anode water flow channel 01-61 of the electrochemical coupling film distillation device 01 under the action of the anode liquid pump 07, and Cl is reacted under the action of electrochemistry - Conversion to Cl 2 And enter a chlorine absorption tank 08 to be recovered, and Cl in the solution in the anode water flow channel 01-61 is recovered - The concentration is reduced, and Cl in the raw material liquid channel 01-12 is reduced under the action of an electric field - The solution is supplemented to the anode water flow channel 01-61 through the anion exchange membrane 01-5, the saturated state of LiCl is maintained, and finally the solution flows back to the anode pool 06.
Raw material liquid channel 01-12 reaction R2, wherein the medium-low concentration LiCl solution in the raw material liquid pond 03 flows into the raw material liquid channel 01-12 of the electrochemical coupling film distillation device 01 under the action of the raw material liquid pump 05, and forms LiOH solution under the action of electrochemical reaction; the solution is subjected to high temperature CO 2 Heating, wherein liquid water is evaporated into water vapor, and enters into a vacuum permeation side channel 01-3 under the action of negative pressure; at the same time LiOH and CO 2 Reaction to form Li 2 CO 3 The sediment flows out of the electrochemical coupling membrane distillation device 01 along with water flow, enters the solid-liquid separator 04 and is recovered, and the rest solution returns to the raw material liquid pool 03.
Permeation side channel 01-3 reaction R3 by vacuum pump 11, vapor evaporated from raw material liquid channel 01-12 and unreacted CO 2 H generated by electrochemical reaction on surface of conductive distillation film 01-2 2 All penetrate through the conductive distillation membrane 01-2 and enter the vacuum permeation side channel 01-3 for recovery.
The invention discloses an electrochemical coupling membrane distillation device 01 and a distillation system; the distillation system disclosed by the invention can synchronously realize the output of lithium carbonate and the capture of carbon dioxide.
The invention utilizes the CO-enriched 2 The raw material liquid of the membrane distillation system is heated by the high-temperature flue gas, and the CO is absorbed under the condition of no additional chemical reagent by means of electrochemical reaction of the surface of the conductive membrane material 2 Concentrating LiCl raw material liquid to produce battery grade Li 2 CO 3 。
Simultaneously, the technology synchronously realizes the utilization of industrial waste heat and CO 2 The problems that the membrane flux of a membrane distillation system is reduced along with the increase of concentration multiple are solved; particularly excellent in use effect.
It is obvious that the specific implementation of the present invention is not limited by the above-mentioned modes, and that it is within the scope of protection of the present invention only to adopt various insubstantial modifications made by the method conception and technical scheme of the present invention.
Claims (10)
1. An electrochemical coupling membrane distillation device is characterized by comprising a reaction mechanism, a conductive mechanism, a cover plate mechanism and an aeration mechanism;
the reaction mechanism comprises a raw material reaction plate, an anode reaction plate and a permeation plate;
a raw material liquid channel is arranged on the raw material reaction plate;
an anode water flow channel is arranged on the anode reaction plate;
the permeation plate is provided with a permeation side channel;
the cover plate mechanism comprises an anode side cover plate and a permeation side cover plate;
the anode side cover plate, the anode reaction plate, the raw material reaction plate, the permeation plate and the permeation side cover plate are sequentially distributed;
the conductive mechanism comprises a conductive distillation film and an electrode plate;
the conductive distillation membrane is arranged in a region between the permeation plate and the raw material reaction plate; the electrode plate is arranged in a region between the anode side cover plate and the anode reaction plate;
an anion exchange membrane is arranged between the anode reaction plate and the raw material reaction plate;
the aeration mechanism comprises an aeration plate arranged in the raw material liquid channel, and the aeration plate is connected with an air supply part.
2. An electrochemical coupling membrane distillation apparatus according to claim 1, wherein the gas supply means comprises a gas supply pipe connected to an aeration plate, the gas supply pipe being supplied with a gas containing CO 2 Is a high temperature industrial flue gas.
3. An electrochemical coupling membrane distillation apparatus according to claim 2, wherein the high temperature industrial flue gas is Li 2 CO 3 High temperature industrial flue gas generated in the process of preparing LFP by calcination.
4. An electrochemical coupling membrane distillation apparatus according to claim 2, wherein the aeration plate is made of titanium foam; the high-temperature industrial flue gas is high-temperature CO 2 The gas temperature is 90-200 ℃, and the flow rate of the high-temperature industrial flue gas and the area of the conductive distillation membrane are set in proportion.
5. A wet recovery distillation system for waste lithium batteries, which is characterized by comprising the electrochemical coupling membrane distillation device according to any one of claims 1-4; the electrochemical coupling membrane distillation device is connected with a material system and a power supply mechanism;
the material system comprises a raw material supply mechanism, an anode liquid supply mechanism, a chlorine treatment mechanism and a water liquid recovery mechanism;
the raw material supply mechanism, the anolyte supply mechanism, the chlorine treatment mechanism and the water liquid recovery mechanism are respectively connected with the electrochemical coupling membrane distillation device through pipeline mechanisms.
6. The wet recycling distillation system for waste lithium batteries according to claim 5, wherein the power supply mechanism comprises a programmable power supply, and the programmable power supply is connected with a conductive mechanism in the electrochemical coupling membrane distillation device; the positive electrode of the programmable power supply is connected with the electrode plate, and the negative electrode of the programmable power supply is connected with the conductive distillation film.
7. The wet recycling distillation system for waste lithium batteries according to claim 5, wherein the raw material supply mechanism comprises a raw material liquid pump and a raw material liquid pool; the raw material liquid pump is connected with the raw material liquid pool; the raw material liquid pump is connected with the raw material liquid pool through a pipeline mechanism and a raw material reaction plate in the electrochemical coupling membrane distillation device;
the anolyte supply mechanism comprises an anolyte tank and an anolyte water pump, and the anolyte tank is connected with the anolyte water pump; the anolyte water pump and the anode pool are respectively connected with an anode reaction plate in the electrochemical coupling membrane distillation device through a pipeline mechanism;
the chlorine treatment mechanism comprises a chlorine gas absorption tank; the chlorine absorption tank is connected with the anode reaction plate through a pipeline mechanism;
the water liquid recovery mechanism; the water liquid recovery mechanism comprises a water liquid pool; the water pond is connected with the osmosis plate through a pipeline mechanism.
8. The wet recycling distillation system for waste lithium batteries according to claim 7, wherein the wet recycling distillation system is characterized in that; the raw material liquid pump is connected with the raw material liquid pool in series; and a solid-liquid separator is arranged between the raw material liquid pump and the raw material liquid pool.
9. The wet recycling distillation system for waste lithium batteries according to claim 7, wherein the wet recycling distillation system is characterized in that; and saturated LiCl solution is arranged in the anode pool.
10. A method of using a distillation system according to any one of claims 5 to 9, wherein the method of using comprises the steps of:
step 1: assembling a whole wet recovery distillation system of the waste lithium battery; and ensure that each mechanism can be used normally;
step 2: after the step 1 is completed, the raw material liquid to be treated is supplied into the raw material reaction plate through a raw material supply mechanism; supplying a saturated LiCl solution into the anode reaction plate through an anolyte supply mechanism; the power supply mechanism is started and supplies power to the guide motor mechanism; the aeration component continuously supplies air into the raw material reaction plate;
step 3: continuously carrying out the step 2 to realize the treatment of the raw material liquid; until the set requirement is reached.
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