CN117096487B - Method for rapidly recycling white oil from wet lithium battery diaphragm waste - Google Patents
Method for rapidly recycling white oil from wet lithium battery diaphragm waste Download PDFInfo
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- CN117096487B CN117096487B CN202311354791.3A CN202311354791A CN117096487B CN 117096487 B CN117096487 B CN 117096487B CN 202311354791 A CN202311354791 A CN 202311354791A CN 117096487 B CN117096487 B CN 117096487B
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- 239000002699 waste material Substances 0.000 title claims abstract description 65
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 40
- 238000004064 recycling Methods 0.000 title claims abstract description 21
- 238000000605 extraction Methods 0.000 claims abstract description 76
- 239000012634 fragment Substances 0.000 claims abstract description 40
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 36
- 238000003756 stirring Methods 0.000 claims abstract description 22
- 238000001035 drying Methods 0.000 claims abstract description 11
- 238000000926 separation method Methods 0.000 claims abstract description 9
- 239000011259 mixed solution Substances 0.000 claims abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 53
- 238000003860 storage Methods 0.000 claims description 38
- 239000007788 liquid Substances 0.000 claims description 35
- 229910052757 nitrogen Inorganic materials 0.000 claims description 26
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical group CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 21
- 238000011084 recovery Methods 0.000 claims description 16
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 13
- 239000012528 membrane Substances 0.000 claims description 9
- 238000007084 catalytic combustion reaction Methods 0.000 claims description 8
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 6
- 239000007791 liquid phase Substances 0.000 claims description 5
- IIEWJVIFRVWJOD-UHFFFAOYSA-N ethyl cyclohexane Natural products CCC1CCCCC1 IIEWJVIFRVWJOD-UHFFFAOYSA-N 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 abstract description 20
- 239000011174 green composite Substances 0.000 abstract description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 9
- 229910001416 lithium ion Inorganic materials 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 6
- 239000002912 waste gas Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000004146 energy storage Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 238000003912 environmental pollution Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000001988 toxicity Effects 0.000 description 3
- 231100000419 toxicity Toxicity 0.000 description 3
- 241000699670 Mus sp. Species 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 239000002910 solid waste Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000003039 volatile agent Substances 0.000 description 2
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 241000709691 Enterovirus E Species 0.000 description 1
- 102000004310 Ion Channels Human genes 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- 241000156302 Porcine hemagglutinating encephalomyelitis virus Species 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000895 extractive distillation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- -1 n-pentane compound Chemical class 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 210000005036 nerve Anatomy 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 231100000048 toxicity data Toxicity 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/30—Destroying solid waste or transforming solid waste into something useful or harmless involving mechanical treatment
- B09B3/35—Shredding, crushing or cutting
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/30—Destroying solid waste or transforming solid waste into something useful or harmless involving mechanical treatment
- B09B3/38—Stirring or kneading
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/80—Destroying solid waste or transforming solid waste into something useful or harmless involving an extraction step
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
- B29B17/02—Separating plastics from other materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
- B29B17/04—Disintegrating plastics, e.g. by milling
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/02—Making granules by dividing preformed material
- B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B2101/00—Type of solid waste
- B09B2101/75—Plastic waste
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
- B29B17/02—Separating plastics from other materials
- B29B2017/0213—Specific separating techniques
- B29B2017/0217—Mechanical separating techniques; devices therefor
- B29B2017/0231—Centrifugating, cyclones
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Processing Of Solid Wastes (AREA)
- Secondary Cells (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a method for rapidly recycling white oil from wet lithium battery diaphragm waste, which belongs to the field of lithium battery diaphragm recycling, and comprises the following steps: crushing an oil-containing waste film; placing the crushed diaphragm in a hydraulic press to separate white oil; feeding the hydraulic diaphragm into a centrifugal machine, and centrifugally separating white oil; drying to obtain oil film fragments; and (5) carrying out extraction: the extraction tank rotates positively to drive the internal blades to rotate, oil film fragments are added into the feed inlet, the oil film fragments are carried into the tank along with the forward rotation of the extraction tank, after all the oil film fragments enter the tank, the extraction agent is introduced to submerge the oil film fragments, the extraction tank drives the extraction agent and the oil film fragments to be stirred and extracted together at normal temperature, then the mixed solution of the extraction agent and the white oil is discharged, and the oil film is left in the extraction tank; and (5) re-introducing the extractant to submerge the oil film fragments, and stirring the extractant and the oil film fragments at normal temperature. The invention develops a green composite extractant capable of replacing dichloromethane on one hand and develops an extraction separation process on the other hand so as to improve the extraction efficiency of white oil.
Description
Technical Field
The invention relates to lithium battery diaphragm recovery, in particular to a method for rapidly recovering white oil from wet lithium battery diaphragm waste.
Background
With the rapid development of science and technology, lithium ion batteries play an increasingly important role in electronic products (smart phones, notebook computers, digital cameras and the like), electric vehicles (BEVs) of pure electric vehicles, HEVs), energy storage (power storage stations, household energy storage, standby power supplies, transformer substation energy storage and the like) and the like. The main components of the lithium battery comprise a positive electrode material, a negative electrode material, a diaphragm and electrolyte, and the principle is that lithium ions are separated and intercalated between the positive electrode and the negative electrode to realize energy storage and release. However, with the widespread use of lithium ion batteries, a large number of scrapped lithium ion batteries inevitably bring about environmental pollution problems, and especially the disposal of solid wastes of lithium ion batteries is very troublesome. In view of this, the world and organizations plan, and corresponding rules and standards are established to standardize the production and handling of lithium ion batteries. Despite the promulgation of some policies and regulations, the rational disposal of lithium ion battery waste remains a sharp problem.
In lithium ion batteries, the separator has the basic function of preventing the direct contact of the positive electrode and the negative electrode from being short-circuited, and providing a sufficient electrolyte lithium ion channel. The current production process of the lithium battery diaphragm has two wet methods and dry methods, and the diaphragm manufactured by the wet method process has higher quality and becomes the mainstream gradually. Wet processes require the use of white oil mixed with polyolefin to occupy the space for pore-forming and solvent extraction removal after the stretching process. The oil-containing waste film produced in the wet process is one of solid wastes of lithium batteries, and the direct incineration can cause atmospheric pollution and secondary pollution, and the adoption of the novel and environment-friendly extractant and the extraction process can not only effectively reduce the environmental pollution, but also create economic benefits.
In the wet diaphragm production, firstly, polyolefin resin and low molecular weight white oil are mixed, melted and extruded, and the thickness and uniformity of the diaphragm are optimized through a biaxial stretching process; and then, using dichloromethane as an extracting agent to extract white oil in the holes of the diaphragm to form the lithium battery diaphragm containing micropores. In the whole process, extrusion and stretching of the diaphragm can generate a certain amount of waste oil-containing waste films. The traditional incineration method is adopted to treat the oily waste film, so that high-toxicity waste gas such as dioxin and the like is easy to generate, the environment is polluted, and the polyolefin film and the white oil cannot be reused.
Although methylene dichloride in a wet process can be used as an extracting agent for the recycling treatment process of the oily waste film, a plurality of derivative problems still exist, including damage to nerves and organs of a human body; the photo-thermal reaction produces harmful gases such as phosgene, carbon monoxide and the like, has strong damage to the atmospheric ozone layer and the like. Meanwhile, the traditional extraction process has the problems of low extraction efficiency, high volatilization of an extracting agent, incomplete oil film separation and the like (such as CN111584795A and CN207371140U, high use amount of the extracting agent, high volatility and low white oil extraction efficiency (50% -75%), thereby not only influencing the quality of the deoiled film and more easily generating the problem of environmental pollution).
Therefore, the development of the extractant which is low in toxicity and does not contain ozone-depleting substances (ODS) and the establishment of the efficient extraction and separation process have great practical significance for realizing the recycling of the oil-containing waste film.
The above background is for the convenience of understanding the present invention and is not a known art which has been disclosed to the general public before the application of the present invention.
Disclosure of Invention
Aiming at the defects, the invention provides a method for rapidly recycling white oil from wet lithium battery diaphragm waste, which is characterized in that a green composite extractant capable of replacing dichloromethane is developed on one hand, and a high-efficiency extraction separation process and equipment are developed on the other hand, so that the extraction efficiency of white oil and the quality of waste films are improved, and the recycling and recycling of the oil-containing waste films of lithium batteries are realized.
The technical proposal is as follows: a method for rapidly recycling white oil from wet lithium battery diaphragm waste comprises the following steps:
throwing an oily waste film produced by a wet method into a diaphragm crusher for crushing;
placing the crushed diaphragm in a hydraulic press to separate white oil;
feeding the hydraulic diaphragm into a centrifugal machine, and centrifugally separating white oil;
drying the membrane after centrifugal separation of white oil to obtain oil film fragments;
and (5) carrying out extraction: the extraction tank rotates positively to drive the internal blades to rotate, oil film fragments are added into the feed inlet, the oil film fragments are carried into the tank along with the forward rotation of the extraction tank, after all the oil film fragments enter the tank, the extraction agent is introduced to submerge the oil film fragments, the extraction tank drives the extraction agent and the oil film fragments to be stirred and extracted together at normal temperature, and then the mixed solution of the extraction agent and the white oil is discharged, and the oil film fragments are left in the extraction tank; re-introducing the extractant to submerge the oil film fragments, stirring the extractant and the oil film fragments at normal temperature, and repeating for more than 2 times;
recovering a gas-liquid phase;
drying the extracted oil film fragments by using gas, and reversing the extraction tank to send the oil film fragments out of the extraction tank;
granulating: the oil film fragments are granulated.
Further, the device adopted in the step (II) is a device special for removing oil from the oil-containing waste film in the wet lithium battery diaphragm, the device special for removing oil from the oil-containing waste film in the wet lithium battery diaphragm comprises a tank body, the tank body comprises a horizontal inner tank and a horizontal outer tank which is used for wrapping the horizontal inner tank, a feed inlet and a discharge outlet are respectively arranged at the head end of the horizontal inner tank, a plurality of small holes are formed in the tail part of the horizontal inner tank, the horizontal inner tank is a stirring inner tank capable of rotating around the horizontal inner tank, spiral blades are arranged in the horizontal inner tank, an extract liquid inlet is formed in the upper end of the horizontal outer tank, and a mixed liquid outlet is formed in the bottom end of the horizontal outer tank.
Further, the horizontal inner tank is wavy.
Further, the device special for removing oil from the oil-containing waste film in the wet lithium battery diaphragm further comprises a mixed liquor temporary storage tank, a rectifying tower, a white oil storage tank and an extractant recovery tank, wherein the mixed liquor temporary storage tank is respectively communicated with a mixed liquor liquid outlet and the rectifying tower, the rectifying tower is respectively communicated with the white oil storage tank and the extractant recovery tank, and a first condenser is further communicated between the rectifying tower and the extractant recovery tank.
Further, the device special for removing oil from the oil-containing waste film in the wet lithium battery diaphragm further comprises an extractant storage tank, and the extractant storage tank is communicated with the liquid inlet of the extraction liquid.
Further, the device special for removing oil from the oil-containing waste film in the wet lithium battery diaphragm further comprises a nitrogen storage tank and an online nitrogen heater, and the nitrogen storage tank is communicated with a mixed liquid outlet.
Further, the device special for removing oil from the oil-containing waste film in the wet lithium battery diaphragm also comprises a second condenser which is respectively communicated with the liquid inlet of the extracting solution and the extracting agent recovery tank.
Further, the device special for removing oil from the oil-containing waste film in the wet lithium battery diaphragm also comprises a catalytic combustion device.
Further, the extractant is ethyl acetate, cyclohexane and n-pentane, wherein ethyl acetate: cyclohexane: the volume ratio of n-pentane is 1-8:1-3:1-3.
Further, the ethyl acetate: cyclohexane: the volume ratio of n-pentane is 6:1:3.
compared with the prior art, the invention has the beneficial effects that:
aiming at the problems of large usage amount of extracting agent dichloromethane, high volatility, strong toxicity, damage to an ozone layer, low extraction rate of white oil, poor quality of a recovered diaphragm and the like in the traditional extraction method for recovering the oily waste film of the wet lithium battery, the invention develops a green composite extracting agent capable of replacing the dichloromethane on one hand, and develops an efficient extraction separation process and equipment on the other hand so as to improve the extraction efficiency of the white oil and the quality of the waste film and realize the recycling and reutilization of the oily waste film of the lithium battery.
The outer tank of the extraction tank can store liquid in a sealing way, the inner wall of the inner tank is provided with spiral blades, the inner tank can rotate forward and backward, waste materials with oil-containing diaphragms are fed into the inner tank of the double-layer stirring tank during forward rotation, and waste oil films can be fed out during reverse stirring; the barrel body at the lower half part of the inner tank of the extraction tank is wavy and provided with small holes, so that the accumulation of waste films is prevented from blocking a pore channel, the extraction agent and the white oil mixture are conveniently discharged, an oil film and the extraction agent and the white oil mixture are not required to be discharged together, and the process speed is increased; the lower end of the extraction tank is connected with a hot nitrogen blowing device, so that the waste film after extraction can be quickly dried, and the waste gas is discharged into a catalytic combustion device for treatment and evacuation after being condensed and recovered at low temperature.
Compared with the traditional dichloromethane extractant, the ethyl acetate, cyclohexane and n-pentane compound extractant selected by the invention has lower toxicity and does not contain ODS substances. Table 1 shows the toxicity data of the different extractants for half-lethal dose of mice:
TABLE 1 LD of different extractants for oral administration to mice 50
Drawings
FIG. 1 is a schematic diagram of the overall structure of a device for rapidly recycling white oil from wet lithium battery diaphragm waste;
FIG. 2 is a schematic diagram showing the overall structure of an apparatus for removing oil from an oil-containing waste film in a wet lithium battery separator of comparative examples 1 to 11;
in fig. 1: 1. a feed inlet, 2, a discharge outlet, 3, a horizontal inner tank, 4, a horizontal outer tank, 5, blades, 6, a nitrogen storage tank, 7, a mixed liquid temporary storage tank, 8, a rectifying tower, 9, a white oil storage tank, 10, a first condenser, 11, an extractant recovery tank, 12, a second condenser, 13, a catalytic combustion device, 14, an extractant feed valve, 15, an extractant storage tank, 16, an extractant liquid inlet, 17, a mixed liquid outlet, 18 and an online nitrogen heater;
in fig. 2: 19. and (3) an extraction kettle.
Detailed Description
The invention will be further described with reference to the accompanying drawings.
Example 1
Referring to fig. 1, fig. 1 is a schematic diagram of the overall structure of a device for rapidly recycling white oil from wet lithium battery separator waste according to the present invention.
The utility model provides a device that oily waste film deoiling in wet process lithium cell diaphragm is exclusively used in, the steam generator comprises a tank body, the jar body includes horizontal inner tank 3 and with horizontal outer jar 4 including horizontal inner tank cladding, the head end of horizontal inner tank 3 is provided with feed inlet 1 and discharge gate 2 respectively, afterbody is equipped with a plurality of apertures in the horizontal inner tank 3, horizontal inner tank 3 is the rotatory stirring inner tank of horizontal inner tank 3 (the accessible passes through rotation axis etc. with horizontal inner tank 3 and motor to be connected and realizes rotatablely, this is current mature technique, not drawing in the figure), install spiral blade 5 in the horizontal inner tank 3, horizontal outer jar 4 upper end is provided with extract inlet 16, horizontal outer jar 4 bottom is provided with mixed liquor liquid outlet 17.
The feed inlet 1 is used for oily waste film feeding, the discharge outlet 2 is used for extracting the back membrane ejection of compact, stir the waste oil film into horizontal inner tank 3 tail end when horizontal inner tank 3 is just stirring, can send the oil film to the head end and follow discharge outlet 2 ejection of compact when horizontal inner tank 3 is contrary stirring, horizontal outer tank 4 is used for collecting extractant and white oil mixed solution, can heat the stoving through letting in nitrogen gas to horizontal outer tank 4 when horizontal inner tank 3 is rotatory to end.
Further, in order to obtain a better extraction effect, the horizontal inner tank 3 is wavy.
Further, the horizontal inner tank 3 is provided with a detachable cover, and the feed inlet 1 is provided on the cover.
Further, the device special for removing oil from the oil-containing waste film in the wet lithium battery diaphragm further comprises a mixed liquor temporary storage tank 7, a rectifying tower 8, a white oil storage tank 9 and an extractant recovery tank 11, wherein the mixed liquor temporary storage tank 7 is respectively communicated with a mixed liquor liquid outlet 17 and the rectifying tower 8, the rectifying tower 8 is respectively communicated with the white oil storage tank 9 and the extractant recovery tank 11, and a first condenser 10 is also communicated between the rectifying tower 8 and the extractant recovery tank 11.
The mixed liquor temporary storage tank 7 is used for storing mixed liquor of white oil and extractant from the mixed liquor liquid outlet 17, the rectifying tower 8 is used for separating the white oil and the extractant, and the first condenser 10 is used for condensing and recycling the extractant gas from the rectifying tower 8.
Further, the device special for removing oil from the oil-containing waste film in the wet lithium battery diaphragm further comprises an extractant storage tank 15, wherein the extractant storage tank 15 is communicated with an extractant liquid inlet 16, and extractant feeding is controlled through an extractant feeding valve 14.
Further, the device special for removing oil from the oil-containing waste film in the wet lithium battery diaphragm further comprises a nitrogen storage tank 6 and an online nitrogen heater 18, wherein the nitrogen storage tank 6 is communicated with the mixed liquid outlet 17, the online nitrogen heater 18 is used for heating nitrogen, and the hot nitrogen is used for blowing and extracting residual extractant and drying an oil film.
Further, since heat is generated during the stirring process, the extractant volatilizes, and in order to recover the extractant, the device special for removing the oil from the oil-containing waste film in the wet lithium battery diaphragm further comprises a second condenser 12, and the second condenser 12 is respectively communicated with the extractant liquid inlet 16 and the extractant recovery tank 11.
The second condenser 12 condenses the part of the extractant volatilized in the stirring process and purged by nitrogen after the stirring is completed, and recycles the extractant.
Further, in order to reduce the pollution to the environment, the device special for removing the oil from the oil-containing waste film in the wet lithium battery diaphragm also comprises a catalytic combustion device 13, wherein the catalytic combustion device 13 is used for carrying out catalytic combustion on part of the extractant which is not condensed.
During operation, the pretreated oil film enters the horizontal inner tank 3 through the feed inlet 1, the extracting agent enters the horizontal inner tank 3 through the extracting agent feed valve 14, the oil film starts to be positively stirred after entering the horizontal inner tank 3, the oil film is stirred into the tail of the tank body through the blades 5, and the tail of the horizontal inner tank 3 is provided with small holes, the tank body of the horizontal inner tank 3 is wavy, so that the small holes are not easy to be blocked, heat is generated in the stirring process, the extracting agent volatilizes, the volatilized extracting agent is condensed by the second condenser 12, the volatile extracting agent is sent into the extracting agent recycling tank 11 for recycling, after stirring extraction is finished, the mixed liquid outlet 17 is opened, the extracting agent white oil mixture is sent into the mixed liquid temporary storage tank 7 for temporary storage, then sent into the rectifying tower 8 for separation through the mixed liquid temporary storage tank 7, the extracting agent gas is sent into the first condenser 10, the extracting agent recycling tank 11 is used for recycling the extracting agent after condensation, the white oil is sent into the white oil storage tank 9, after the extracting agent white oil mixture is discharged, the nitrogen storage tank 6 is filled with hot nitrogen for residual extracting agent and drying, the hot nitrogen is sent into the nitrogen storage tank for burning the residual extracting agent and the residual extracting agent after the hot nitrogen is burnt by the second condenser 12, and the residual nitrogen is burnt for a small amount of the extracting agent is burnt and the volatile agent is burnt, and the volatile agent is blown and a small amount is burnt and burned. After the oil film is dried, the inner tank of the stirring tank is reversely stirred, and the oil film is sent out from the discharge port 2.
When the feeding is finished, the cover is opened after the stirring is finished and hot nitrogen is introduced to dry, and the stirring tank starts to reversely send out the oil film.
Example 2
The method comprises the steps of putting an oil-containing waste film (oil content of 70 wt%) produced by a wet method into a diaphragm grinder for grinding, wherein the size of the oil-containing waste film in any direction is 10-15mm.
Placing the crushed diaphragm in a hydraulic press, maintaining the pressure at 10MPa for 30min, and separating white oil for 1 time, wherein the white oil removal rate is about 45%.
And thirdly, feeding the hydraulic diaphragm into a centrifugal machine, and centrifugally separating the white oil, wherein the white oil removal rate is about 8%.
And (3) drying the membrane after centrifugal separation of the white oil for 30min at 120 ℃ to remove surface moisture and reduce the viscosity of the white oil so as to obtain oil film fragments.
According to embodiments 3-12 of the invention, the white oil rapid recovery device for the wet method lithium battery diaphragm waste material of the embodiment 1 is adopted to recover and treat the oil-containing waste film in the wet method lithium battery diaphragm.
Examples 3 to 12
Examples 3 to 12 the oily waste films were extracted by the following methods, and examples 3 to 12 were identical except that the extractant was different.
Extracting: the horizontal inner tank 3 is powered on to rotate positively to drive the inner blades 5 to rotate, 50kg of oil film fragments in the embodiment 2 are weighed and added into the feed inlet 1, the oil film fragments are carried into the horizontal inner tank 3 along with the forward rotation of the horizontal inner tank 3, and the feed inlet 1 is closed after all the oil film fragments enter the horizontal inner tank 3. And (3) opening an extractant feeding valve 14 to introduce and submerge oil film fragments of 150L of the extractant, closing the extractant feeding valve 14 to enable the horizontal inner tank 3 to drive the extractant and the oil film fragments to be stirred together for 10 minutes at normal temperature, closing a power supply to stop stirring, and opening a mixed liquid outlet 17 to recycle the mixed liquid of the extractant and the white oil into the mixed liquid temporary storage tank 7.
And the extractant feed valve 14 is opened again to perform liquid feed re-extraction, three-stage extraction is completed altogether, and hot nitrogen is introduced into the horizontal inner tank 3 and the horizontal outer tank 4 through the mixed liquid outlet 17 after the completion of the three-stage extraction, so that waste gas in the tank can be discharged, and a drying effect can be achieved on the waste diaphragm.
After three-stage extraction, turning on a power supply to enable the horizontal inner tank 3 to reversely rotate, and taking the extracted waste diaphragm out of the horizontal inner tank 3 through reverse rotation;
the extraction results are shown in Table 2 below.
Observing the oil film fragments from the horizontal inner tank 3 after the extraction of the examples 3-12, the oil film fragments have no obvious deformation, the surface is smooth and clean and oil-free, and the quality is excellent.
And (3) recycling gas and liquid phases: and (3) introducing the mixed liquid obtained by extraction into a rectifying tower 8 for rectification, condensing the extractant into a liquid phase through a first condenser 10 in a vapor state, and flowing the liquid phase into an extractant recovery tank 11, wherein the residual liquid in the rectifying tower 8 is white oil, and opening a valve to enable the white oil to flow into a white oil storage tank 9.
The waste gas carried out by the hot nitrogen is introduced into the second condenser 12 through the extract liquid inlet 16, the extractant in the waste gas is condensed and recovered, the nitrogen is discharged through the exhaust port, and the catalytic combustion device 13 is arranged at the exhaust port to avoid pollution caused by volatilizing a small amount of extractant into the atmosphere.
Granulating: granulating the oil film after three-stage extraction.
TABLE 2 extraction efficiency of composite extractants in different proportions
As can be seen from Table 2, the device of the invention can effectively remove the white oil content in the oil-containing waste, the extraction rate can reach more than 90.0%, and the oil content in the finally prepared recovered material can be lower than 10%.
The following device for removing oil from the oil-containing waste film in the wet lithium battery diaphragm according to the comparative examples 1-11 is a conventional extractive distillation device, and an ultrasonic device and a stirring kettle are arranged in the extractive kettle 19, as shown in fig. 2.
Comparative examples 1 to 11
Comparative examples 1 to 11 oily waste films were extracted by the following method, and comparative examples 1 to 11 were identical except that the extractant was different.
50kg of the oil-containing waste film to be separated in the subsequent process of example 2 is added into an extraction kettle 19, 150L of extractant is added into the extraction kettle 19, and stirring and extraction are carried out for 10min at normal temperature.
And (5) filtering the extract and an oil film, drying at 120 ℃ for 30min, and removing the residual extractant on the surface of the oil film.
And thirdly, putting the dried oil film into the extraction kettle 19 again, repeating the process of the oil film twice, and completing three-level extraction.
The results are shown in Table 3 below.
TABLE 3 comparison of oil removal effects for different times of extractions with different extractants
The final membranes (3 times of total filtration and drying) of comparative examples 1-11 from the dry film outlet were observed, and the membranes recovered by extraction had significant deformation and a matte surface.
As can be seen from tables 2-3, under the same extraction agent, the extraction process of the device special for removing oil from the oil-containing waste film in the wet lithium battery diaphragm has improved oil removal rate compared with the existing extraction process, and under the same extraction process, the mixed extraction agent achieves synergistic extraction effect.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (3)
1. A method for rapidly recycling white oil from wet lithium battery diaphragm waste is characterized by comprising the following steps:
throwing an oily waste film produced by a wet method into a diaphragm crusher for crushing;
placing the crushed diaphragm in a hydraulic press to separate white oil;
feeding the hydraulic diaphragm into a centrifugal machine, and centrifugally separating white oil;
drying the membrane after centrifugal separation of white oil to obtain oil film fragments;
and (5) carrying out extraction: the extraction tank rotates positively to drive the internal blades to rotate, oil film fragments are added into the feed inlet, the oil film fragments are carried into the tank along with the forward rotation of the extraction tank, after all the oil film fragments enter the tank, the extraction agent is introduced to submerge the oil film fragments, the extraction tank drives the extraction agent and the oil film fragments to be stirred and extracted together at normal temperature, and then the mixed solution of the extraction agent and the white oil is discharged, and the oil film fragments are left in the extraction tank; re-introducing the extractant to submerge the oil film fragments, stirring the extractant and the oil film fragments at normal temperature, and repeating for more than 2 times;
recovering a gas-liquid phase;
drying the extracted oil film fragments by using gas, and reversing the extraction tank to send the oil film fragments out of the extraction tank;
granulating: granulating oil film fragments;
the extractant is ethyl acetate, cyclohexane and n-pentane, wherein the ethyl acetate: cyclohexane: the volume ratio of n-pentane is 1-8:1-3:1-3;
the device adopted in the step (a) is a device special for removing oil from the oil-containing waste film in the wet lithium battery diaphragm, the device special for removing oil from the oil-containing waste film in the wet lithium battery diaphragm comprises a tank body, the tank body comprises a horizontal inner tank and a horizontal outer tank which covers the horizontal inner tank, the head end of the horizontal inner tank is respectively provided with a feed inlet and a discharge outlet, the tail part of the horizontal inner tank is provided with a plurality of small holes, the horizontal inner tank is a stirring inner tank which can rotate around the horizontal inner tank, a spiral blade is arranged in the horizontal inner tank, the upper end of the horizontal outer tank is provided with an extraction liquid inlet, and the bottom end of the horizontal outer tank is provided with a mixed liquid outlet;
the horizontal inner tank is wavy;
the device special for removing the oil from the oil-containing waste film in the wet lithium battery diaphragm further comprises a mixed liquor temporary storage tank, a rectifying tower, a white oil storage tank and an extractant recovery tank, wherein the mixed liquor temporary storage tank is respectively communicated with a mixed liquor liquid outlet and the rectifying tower, the rectifying tower is respectively communicated with the white oil storage tank and the extractant recovery tank, and a first condenser is also communicated between the rectifying tower and the extractant recovery tank;
the device special for removing the oil from the oil-containing waste film in the wet lithium battery diaphragm also comprises a nitrogen storage tank and an online nitrogen heater, wherein the nitrogen storage tank is communicated with a mixed liquid outlet;
the device special for removing the oil from the oil-containing waste film in the wet lithium battery diaphragm also comprises a second condenser which is respectively communicated with the liquid inlet of the extracting solution and the extracting agent recovery tank;
the device special for removing the oil from the oil-containing waste film in the wet lithium battery diaphragm also comprises a catalytic combustion device.
2. The method for rapidly recycling white oil from waste lithium battery membrane materials by wet method according to claim 1, wherein the device special for removing oil from waste oil-containing membranes in lithium battery membranes by wet method further comprises an extractant storage tank, wherein the extractant storage tank is communicated with the liquid inlet of the extraction liquid.
3. The method for rapidly recovering white oil from lithium battery separator waste material by wet process according to any one of claims 1 or 2, wherein the ethyl acetate: cyclohexane: the volume ratio of n-pentane is 6:1:3.
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