CN112354342A - Lithium ion battery electrolyte waste gas treatment device and system - Google Patents
Lithium ion battery electrolyte waste gas treatment device and system Download PDFInfo
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- CN112354342A CN112354342A CN202010693880.0A CN202010693880A CN112354342A CN 112354342 A CN112354342 A CN 112354342A CN 202010693880 A CN202010693880 A CN 202010693880A CN 112354342 A CN112354342 A CN 112354342A
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- 239000002912 waste gas Substances 0.000 title claims abstract description 71
- 239000003792 electrolyte Substances 0.000 title claims abstract description 48
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 22
- 238000002336 sorption--desorption measurement Methods 0.000 claims abstract description 105
- 239000007789 gas Substances 0.000 claims abstract description 66
- 238000001179 sorption measurement Methods 0.000 claims abstract description 60
- 238000007084 catalytic combustion reaction Methods 0.000 claims abstract description 39
- 239000002131 composite material Substances 0.000 claims abstract description 36
- 238000005507 spraying Methods 0.000 claims abstract description 30
- 238000003795 desorption Methods 0.000 claims abstract description 24
- 239000000126 substance Substances 0.000 claims abstract description 19
- 239000007788 liquid Substances 0.000 claims description 69
- 238000002485 combustion reaction Methods 0.000 claims description 44
- 239000007921 spray Substances 0.000 claims description 34
- 239000000463 material Substances 0.000 claims description 21
- 238000003860 storage Methods 0.000 claims description 18
- 239000003513 alkali Substances 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 239000002699 waste material Substances 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 11
- 239000000376 reactant Substances 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- 229920006395 saturated elastomer Polymers 0.000 claims description 8
- 238000009413 insulation Methods 0.000 claims description 3
- 238000011049 filling Methods 0.000 claims description 2
- 239000010815 organic waste Substances 0.000 abstract description 13
- 230000000694 effects Effects 0.000 abstract description 6
- 238000013461 design Methods 0.000 abstract description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- 238000000034 method Methods 0.000 description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 7
- 239000003960 organic solvent Substances 0.000 description 7
- 238000006303 photolysis reaction Methods 0.000 description 7
- 238000000746 purification Methods 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 239000012295 chemical reaction liquid Substances 0.000 description 6
- 230000015843 photosynthesis, light reaction Effects 0.000 description 5
- 239000012855 volatile organic compound Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000005485 electric heating Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 4
- 230000001502 supplementing effect Effects 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 3
- -1 lithium hexafluorophosphate Chemical compound 0.000 description 3
- 229910003002 lithium salt Inorganic materials 0.000 description 3
- 159000000002 lithium salts Chemical class 0.000 description 3
- 239000002957 persistent organic pollutant Substances 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical group [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- 239000002918 waste heat Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 229910001290 LiPF6 Inorganic materials 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 229910019256 POF3 Inorganic materials 0.000 description 2
- 101100408805 Schizosaccharomyces pombe (strain 972 / ATCC 24843) pof3 gene Proteins 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- FFUQCRZBKUBHQT-UHFFFAOYSA-N phosphoryl fluoride Chemical compound FP(F)(F)=O FFUQCRZBKUBHQT-UHFFFAOYSA-N 0.000 description 2
- 239000011775 sodium fluoride Substances 0.000 description 2
- 235000013024 sodium fluoride Nutrition 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229910019253 POF3+2HF Inorganic materials 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 229910001515 alkali metal fluoride Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- 150000004651 carbonic acid esters Chemical class 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/77—Liquid phase processes
- B01D53/78—Liquid phase processes with gas-liquid contact
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
- B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/346—Controlling the process
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/38—Removing components of undefined structure
- B01D53/44—Organic components
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/68—Halogens or halogen compounds
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G7/00—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals
- F23G7/06—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases
Abstract
The invention discloses a lithium ion battery electrolyte waste gas treatment device and a system, wherein the lithium ion battery electrolyte waste gas treatment device comprises a composite treatment tower, a two-channel switching type adsorption-desorption device and a catalytic combustion device which are sequentially communicated, wherein the composite treatment tower comprises a first treatment tower body, a second treatment tower body and a first catalytic combustion device, the first treatment tower body is provided with a first adsorption zone and a second adsorption zone, the second treatment: the composite treatment tower comprises a chemical spraying device and a demisting layer arranged at an outlet of the top of the tower; the dual-channel switching type adsorption-desorption device comprises an adsorption-desorption chamber I, an adsorption-desorption chamber II and a hot air conveying device, wherein the adsorption-desorption chamber I and the adsorption-desorption chamber II alternately perform adsorption work and perform desorption through hot air conveyed by the hot air device. The catalytic combustion device is a switching type catalytic combustion chamber with a double-bin structure. The waste gas can effectively treat HF, LiF, PF5 and most of organic waste gas by chemical spraying, and meanwhile, the design of the double-channel adsorption chamber is adopted, so that the adsorption effect can be ensured to be continuously carried out in adsorption work, and the adsorption work efficiency is improved.
Description
Technical Field
The invention relates to the technical field of waste gas treatment devices, in particular to a lithium ion battery electrolyte waste gas treatment device and system.
Background
The electrolyte of the lithium ion battery generally comprises electrolyte lithium salt, an organic solvent, a small amount of additives and the like. At present, commercial lithium ion battery electrolyte generally comprises lithium hexafluorophosphate as lithium salt and a carbonate organic solvent, wherein the carbonate organic solvent generally comprises ethylene carbonate, propylene carbonate, diethyl carbonate, dimethyl carbonate and the like. The production process of the lithium ion battery generally comprises the working procedures of homogenizing, coating, baking, injecting liquid, forming and the like, wherein electrolyte waste gas is generated in the injecting and forming working procedures. At present, the liquid injection process mainly comprises semi-automatic and automatic processes. Semi-automatically generally adopting a glove box with two openable sides, allowing a battery cell in a battery box to enter the glove box from one side under the protection of nitrogen gas and then to be injected into the glove box, rotating out from the other side, introducing the nitrogen gas from two ends of the glove box, and discharging from the middle of the box body; automatic annotate liquid and generally adopt the negative pressure to inhale the automatic liquid mode of annotating from inhaling, be about to put into the notes liquid case evacuation of battery, treat the inside negative pressure that forms of battery, be connected battery case and electrolyte through the pipeline, make and form pressure differential between the inside and electrolyte place space of battery case, utilize this pressure differential to make the automatic battery case of inhaling of electrolyte inside, accomplish automatic notes liquid, two kinds of notes liquid modes are annotating the liquid, are stood and manage to find time the in-process all have gaseous state electrolyte and volatilize. In addition, research on the formation process shows that different gases, such as H2, CO2, C2H4, CH4, C2H6 and the like, are generated at different voltage stages during formation, and direct emission causes pollution to the environment.
In addition, the electrolyte lithium salt is liable to react with water to generate corrosive hydrofluoric acid, and the main chemical reaction equation is as follows:
LiPF6+H2O→POF3+LiF+2HF
LiPF6¬→LiF+PF5
H2O+PF5→POF3+2HF
H2O+POF3→PO2F+2HF
2H2O+ PO2F→H3PO4+HF
hydrofluoric acid is very corrosive and volatile, and can react with common metals to release hydrogen and form an explosive mixture with air.
At present, in the production process of batteries, electrolyte and waste gas after formation are generally directly discharged in a negative pressure (vacuumizing) mode in a production tank body, or directly discharged to the atmosphere after being adsorbed by adding activated carbon after being vacuumized; for example, a patent CN205760465U proposes a tail gas treatment device for an electrolyte solvent purification column based on nitrogen feeding in a lithium battery electrolyte production line, in which a secondary condenser is adopted to condense and collect organic waste gas in electrolyte, and then the redundant organic waste gas is passed through an active carbon adsorption column; in patent CN206762609U, an electrolyte waste gas treatment device removes HF through a chemical spray tower, and then treats organic waste gas through a UV purifier to achieve the purpose of purification; patent CN206746260U provides an electrolyte waste gas terminal treatment equipment tower, the interior of the tower body is provided with a filtering area, a demisting area, a spraying area and a water storage area from top to bottom, the patent sprays the electrolyte waste gas through pure water, lithium hexafluorophosphate is dissolved in water, and the purified waste gas is further filtered and purified after passing through a demister; in patent CN207546208U, the electrolyte waste gas is sequentially passed through a gas-liquid separation device, condensed to recover organic solvents such as EC, DMC and DEC, residual fluorides and organic gases (C2H 4, CH4, C2H6, H2 and HF) and a saturated ca (oh)2 solution to react to generate CaF2, and residual C2H4, CH4, C2H6 and H2 are directly burned. In addition, acid and alkali neutralization is mostly adopted for acidic waste gas, and the purification methods of organic waste gas mainly comprise a thermal combustion method, a catalytic combustion method and a UV (ultraviolet) photolysis method. However, the thermal combustion and catalytic combustion methods are suitable for high-concentration organic waste gas and not suitable for low-concentration organic waste gas, the UV photolysis method is only suitable for cracking and oxidizing macromolecular organic pollutants, the technical scheme adopted in the related patents and documents for treating the electrolyte waste liquid of the existing lithium battery is that the environment is greatly polluted due to direct evacuation and discharge, and the evacuation and activated carbon adsorption method is adopted, so that the activated carbon is easy to inactivate and is frequently replaced, and secondary treatment of the activated carbon also causes environmental pollution; the problems of non-combustibility, insufficient combustion, insufficient photolysis and the like of the direct combustion, catalytic combustion and UV photolysis are also caused by low concentration of organic waste gas. For example, a "an electrolyte off-gas treatment apparatus" disclosed in chinese patent document, publication No. CN201720545459.9, includes a chemical spray tower and a UV purifier. Spray waste gas through chemical spray column, carry out the photodissociation through UV photodissociation device to remaining waste gas. The device is not suitable for solving the problems of cracking and oxidation treatment of organic pollutants with small molecular weight.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a lithium ion battery electrolyte waste gas treatment device and a lithium ion battery electrolyte waste gas treatment system, which solve the following problems in the prior art:
1. the problems that the traditional activated carbon is easy to inactivate when adsorbing organic gas (containing solid particles and water), the replacement frequency is high, and the effect of directly adsorbing small-component gas is poor are solved;
2. the problems that the UV photolysis method is not suitable for solving the cracking and oxidation treatment of organic pollutants with small molecular weight are solved;
3. solves the problem of incomplete combustion or non-combustion due to low concentration when the organic waste gas is directly combusted.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention discloses a lithium ion battery electrolyte waste gas treatment device, which comprises a composite treatment tower, a two-channel switching type adsorption-desorption device and a catalytic combustion device which are sequentially communicated, wherein the composite treatment tower comprises a main body and a main body, the two-channel switching type adsorption-desorption device comprises a main body, a main body and a main body, the two-channel switching: the composite treatment tower comprises a chemical spray device and a demisting layer arranged at an outlet of the top of the tower, wherein the chemical spray device comprises at least one group of spray headers and a waste gas reaction layer arranged below the spray headers in a sleeved mode, and the waste gas reaction layer comprises particles for increasing the gas flow stroke; the dual-channel switching type adsorption-desorption device comprises an adsorption-desorption chamber I, an adsorption-desorption chamber II and a hot air conveying device, wherein the adsorption-desorption chamber I and the adsorption-desorption chamber II alternately perform adsorption work, and when adsorption is saturated, hot air conveyed by the hot air device is used for desorption. The catalytic combustion device is a switching type catalytic combustion chamber with a double-bin structure, the switching type catalytic combustion chamber with the double-bin structure is arranged below the double-channel switching type adsorption-desorption device, and the double-bin structure is respectively arranged corresponding to the adsorption-desorption chamber I and the adsorption-desorption chamber II.
The input end of the adsorption-desorption chamber is connected with the composite structure tower, and the output end of the adsorption-desorption chamber is connected with the gas discharge port. The output end of the hot air conveying device is communicated with an adsorption-desorption chamber, the output end of the adsorption-desorption chamber is communicated with a switching type double-bin structure catalytic combustion chamber, the output end of the switching type double-bin structure catalytic combustion chamber is communicated with a gas discharge port, electrolyte waste gas is fed into the bottom of the composite treatment tower, the waste gas flows from bottom to top, a small amount of residual waste gas is adsorbed by a demisting layer to carry water vapor and part of organic waste gas, and the residual gas enters an active adsorption material for adsorption to finally obtain gas with standard emission and is discharged to the atmosphere; when the adsorption capacity of the active adsorption material is saturated, the hot air conveying device is started to input flowing hot air into the adsorption-desorption chamber to perform desorption treatment on the saturated active adsorption material, the adsorption-desorption chamber inputs the waste gas enriched after desorption into the switching type double-bin structure catalytic combustion chamber to be combusted, and carbon dioxide and water which can be directly discharged are generated after combustion.
Preferably, a liquid storage tank is further arranged at the bottom of the composite treatment tower, and a liquid level detector and an online PH meter are arranged in the liquid storage tank. After the chemical spraying device performs spraying-reaction-dissolution work, reaction liquid slowly flows into a liquid storage tank at the bottom of the reaction tower, the liquid level monitor can monitor the liquid level height of the liquid storage tank at regular time, the on-line PH meter can detect the PH value of the liquid in the liquid storage tank at regular time, and the liquid level monitor and the on-line PH meter are managed through the same processor and work in cooperation.
Preferably, a spraying circulating pump communicated with a liquid storage tank at the bottom of the tower is arranged outside the composite treatment tower, an output end of the spraying circulating pump is provided with an alkali liquor replenishing port, a waste liquid discharge port and a spraying backflow port, and the alkali liquor replenishing port and the spraying backflow port are connected with the composite treatment tower. The spraying circulating pump is matched with the spraying backflow port, so that the reaction liquid can be recycled, and the cost is saved; meanwhile, the alkali liquor replenishing port is associated with the liquid level detector, when the liquid level is reduced to a specific threshold value within a certain time, the liquid level monitor transmits a signal to the processor to start the alkali liquor replenishing port to replenish the liquid until the liquid level reaches a standard position; correspondingly, when the PH of the reaction solution exceeds the specified range, the on-line PH meter can send a signal to suspend the liquid supplementing system, the waste liquid discharge port is opened to discharge waste liquid, and then the liquid supplementing system is recovered to ensure that the subsequent work can be normally carried out.
Preferably, a limiting valve is arranged between the output end of the spraying circulating pump and the waste liquid discharge port, and a solid reactant collecting tank is arranged between the spraying circulating pump and the liquid storage tank. The limiting valve is used for controlling waste liquid discharge, and reaction liquid in the liquid storage tank needs the solid reactant collecting tank to collect and uniformly treat due to the existence of the solid reactant, so that the pipeline cannot be blocked when liquid circulation or discharge is ensured, the maintenance cost is reduced, and the service life of equipment is prolonged.
Preferably, the device also comprises an exhaust gas conveying device for conveying electrolyte exhaust gas, wherein the electrolyte exhaust gas enters the composite treatment tower through the exhaust gas conveying device; the spray header sprays by using alkali liquor; the particles are of a porous structure, and the waste gas reaction layer is formed by filling the porous structure particles in the middle of the composite treatment tower in a stacking mode. The porous particles have the characteristics of large specific surface area, good corrosion resistance and strong separation and purification capacity, hydrogen fluoride reacts with alkali liquor to generate alkali fluoride in the alkali spraying stage of electrolyte waste gas, more than 90% of carbonate organic solvent in the electrolyte waste gas is adsorbed by the porous particle filler, and the treatment work of most of the waste gas is ensured to be completed in the composite treatment tower.
Preferably, the first adsorption-desorption chamber and the second adsorption-desorption chamber are both provided with active adsorption materials. The active adsorption material is of a honeycomb molecular sieve structure, the active material of the structure has strong adsorption capacity, high purification speed and thorough desorption without residue, and can effectively adsorb impurities such as organic solvents in residual gas.
Preferably, the device also comprises a gas discharge port, and the two-channel switching type adsorption-desorption device and the catalytic combustion device are both connected with the gas discharge port; a defoaming plate is arranged between the demisting layer (21) and the spray header (23). The demister can effectively separate liquid drops entrained by gas in the tower, so that the mass transfer efficiency is ensured, the water content of the gas is reduced, the residual reaction liquid is ensured not to continuously enter the demisting layer, and the demisting effect and the service life of the demisting layer are ensured. And a VOCs detector is arranged in the gas discharge port. For discharging the treated gas and checking whether it meets the discharge standard.
Preferably, a first treatment tower exhaust valve and a second treatment tower exhaust valve are arranged at the top of the composite treatment tower, the dual-channel switching type adsorption-desorption device comprises a first adsorption-desorption chamber and a second adsorption-desorption chamber, the first treatment tower exhaust valve is connected with the first adsorption-desorption chamber, and the second treatment tower exhaust valve is connected with the second adsorption-desorption chamber; the output end of the adsorption-desorption chamber is provided with a first discharge valve; and the output end of the adsorption-desorption chamber II is provided with a discharge valve II. In order to ensure that the adsorption work of the active adsorption material can be carried out continuously, the first adsorption-desorption chamber and the second adsorption-desorption chamber are alternately carried out with adsorption-desorption work. If a first exhaust valve of the treatment tower at the top of the composite tower is opened, waste gas enters a first adsorption-desorption chamber to perform adsorption work, when a VOCs detector in a gas discharge port detects that the gas discharged from the first adsorption-desorption chamber exceeds a discharge standard, a second exhaust valve of the treatment tower is opened, the first exhaust valve of the treatment tower is closed, the waste gas enters the second adsorption-desorption chamber, and simultaneously a first combustion air inlet valve is opened and the first exhaust valve is closed; therefore, seamless switching of the adsorption work of the two adsorption-desorption chambers is realized, and the two adsorption chambers can alternately perform adsorption.
Preferably, the switching type catalytic combustion chamber with the double-bin structure is arranged below the adsorption-desorption chamber, and comprises a first combustion bin and a second combustion bin, and a heat insulation plate is arranged between the first combustion bin and the second combustion bin. When the adsorption-desorption chambers are subjected to desorption operation, the waste heat of the switching type double-bin catalytic combustion chamber can be utilized to perform auxiliary desorption on the corresponding adsorption-desorption chambers, so that the cost is saved, and the energy utilization rate is improved.
Preferably, a first heating air inlet valve is arranged between the hot air conveying device and the first adsorption-desorption chamber, and a first combustion air inlet valve is arranged between the output end of the first adsorption-desorption chamber and the switching type double-bin structure catalytic combustion chamber; and a second heating air inlet valve is arranged between the electrothermal chamber and the second adsorption-desorption chamber, and a second combustion air inlet valve is arranged between the output end of the second adsorption-desorption chamber and the switching type double-chamber catalytic combustion chamber. When the active adsorption material in the first adsorption-desorption chamber is saturated, the second adsorption-desorption chamber starts to perform adsorption work, the first adsorption-desorption chamber starts to perform desorption work, hot air is input into the first adsorption-desorption chamber through the opened first heating air inlet valve by the hot air conveying device, the active adsorption material is subjected to thermal desorption, and generated gas is input into the switching type double-bin structure catalytic combustion chamber through the first combustion air inlet valve to perform combustion; similarly, when the active adsorption material in the second adsorption-desorption chamber is saturated, the first adsorption-desorption chamber starts to perform adsorption operation, the second adsorption-desorption chamber starts to perform desorption operation, hot air is input into the second adsorption-desorption chamber through the opened second heating air inlet valve by the hot air conveying device, the active adsorption material is heated to perform desorption, and generated gas is input into the switching type double-chamber structure catalytic combustion chamber through the second combustion air inlet valve to perform combustion.
Therefore, the invention has the following beneficial effects: (1) the waste gas can effectively treat HF, LiF, PF5 and most organic waste gas through chemical spraying, and the chemical spraying device, the defoaming plate and the demisting layer are sequentially arranged to effectively remove water vapor and prolong the service life of active material molecules; (2) the concentration of the organic waste gas is increased after adsorption-desorption, the problems of low gas concentration and no combustion component are solved, and the catalytic combustion efficiency is improved; (3) by adopting the design of the double-channel adsorption-desorption chamber, the adsorption efficiency can be improved while the adsorption effect can be ensured to be continuously carried out in the adsorption work; (4) the adsorption-desorption and catalytic combustion are controlled in a modular integrated mode, the exhaust concentration of an adsorption layer is monitored, a PLC (programmable logic controller) automatically closes and switches an electromagnetic valve, and the waste gas treatment work is managed efficiently and intelligently; (5) the switching type double-bin structure is utilized to catalyze the waste heat desorption of the combustion chamber, so that the operation cost can be effectively reduced, and the aim of clean and pollution-free emission is fulfilled; (6) the composite treatment tower with a compact structure can save the floor area of equipment and reduce the cost.
Drawings
FIG. 1 is a schematic diagram of an embodiment of the present invention.
FIG. 2 is a schematic structural view of the composite treatment tower of FIG. 1.
Fig. 3 is a schematic structural view of the two-channel switching adsorption-desorption device in fig. 1.
FIG. 4 is a schematic view of another embodiment of the composite tower of FIG. 1.
Fig. 5 is a schematic view of the structure of an active adsorbent material.
In the figure: 1. A waste gas conveying device, 2, a composite treatment tower, 21, a demisting layer, 22, a chemical spray device, 23, a spray header, 24, a waste gas reaction layer, 25, a defoaming plate, 3, a two-channel switching type adsorption-desorption device, 311, a first adsorption-desorption chamber, 312, a second adsorption-desorption chamber, 32, an active adsorption material, 33, a hot air conveying device, 4, a catalytic combustion device, 41, a switching type double-chamber structure catalytic combustion chamber, 42, a first combustion chamber, 43, a second combustion chamber, 44, a heat insulation plate, 5, a gas discharge port, 6, a liquid storage tank, 61, a liquid level monitor, 62, an online PH meter, 7, a spray circulating pump, 71, an alkali liquor replenishing port, 72, a waste liquid discharge port, 73, a spray reflux port, 74, a limiting valve, 75, a solid reactant collecting tank, 81, a first treatment tower exhaust valve, a second treatment tower exhaust valve, 82, 83. the first exhaust valve 84, the second exhaust valve 91, the first heating intake valve 92, the second heating intake valve 93, the first combustion intake valve 94 and the second combustion intake valve 93.
Detailed Description
The invention is further described with reference to the following detailed description and accompanying drawings.
In the embodiment shown in fig. 1, a lithium ion battery electrolyte waste gas treatment device and system includes a waste gas conveying device 1, a composite treatment tower 2, a two-channel switching adsorption-desorption device 3 and a catalytic combustion device 4 which are sequentially communicated: the composite treatment tower 2 comprises a chemical spray device 22 and a demisting layer 21 arranged at an outlet of the top of the tower, wherein the chemical spray device 22 comprises at least one group of spray headers 23 and an exhaust gas reaction layer 24 arranged below the spray headers in a sleeved mode, and the exhaust gas reaction layer 24 comprises particles 241 for increasing a gas flow stroke; the dual-channel switching type adsorption-desorption device 3 adopts a modular integrated control mode and comprises an adsorption-desorption chamber I311, an adsorption-desorption chamber II 312 and a hot air conveying device 33, wherein the adsorption-desorption chamber I311 and the adsorption-desorption chamber II 312 alternately perform adsorption work, and when adsorption is saturated, hot air conveyed by the hot air conveying device 33 is used for desorption. The catalytic combustion device 4 is a switching type catalytic combustion chamber 41 with a double-bin structure, the switching type catalytic combustion chamber 41 with the double-bin structure is arranged below the double-channel switching type adsorption-desorption device 3, and the double-bin structure is respectively arranged corresponding to the first adsorption-desorption chamber 311 and the second adsorption-desorption chamber 312. Electrolyte waste gas is sent to the bottom of the composite treatment tower 2 through the waste gas conveying device 1, the waste gas flows from bottom to top, a small amount of residual waste gas is subjected to the spraying-reaction-dissolution process of the chemical spraying device 22, water vapor and part of organic waste gas are carried in the adsorbed gas through the defogging layer 21, and the residual gas enters the active adsorption material 32 for adsorption, so that gas with the emission standard is obtained and is discharged to the atmosphere; when the adsorption capacity of the active adsorption material 32 reaches saturation, the hot air delivery device 41 starts to input flowing hot air into the two-channel switching type adsorption-desorption device 3 to desorb the active adsorption material 32, and the two-channel switching type adsorption-desorption device 3 inputs the waste gas with relatively high concentration after desorption into the catalytic combustion device 4 to be combusted, and carbon dioxide and water which can be directly discharged are generated after the combustion.
The electrolyte waste gas is sent to a chemical spraying device 22 in the composite treatment tower 2 through a waste gas conveying device 1, as shown in fig. 2, the chemical spraying device 22 is in a double-layer spray head and waste gas reaction layer mode, a sodium hydroxide solution with the PH of 10-12 is adopted as a spraying liquid, the spraying liquid is sprayed in a circulating and reciprocating mode from top to bottom, the waste gas is ensured to flow from bottom to top, multiple times of filtering absorption and reaction are carried out, the hydrogen fluoride reacts with the alkali liquor to generate sodium fluoride and water, and the spraying effect of the composite treatment tower 2 is optimized; the waste gas reaction layer 24 adopts polypropylene porous particles with the characteristics of large specific surface area, good corrosion resistance, strong separation and purification capacity and the like, and can effectively absorb more than 90 percent of carbonic acid ester organic solvent in the electrolyte waste gas; the reactant sodium fluoride is easily dissolved in water and enters a liquid storage tank 6 at the bottom of the tower along with the spraying liquid. An online PH meter 62 and a liquid level monitor 61 are arranged in the liquid storage tank 6 at the bottom of the tower, when the PH value is lower than 8, a limiting valve 74 is opened, and a waste liquid discharge port 72 starts to discharge waste liquid; when the PH value is higher than 8, the spraying circulating pump 7 is started, and the spraying liquid passes through the spraying circulating port 73 and completes the circulating work in the tower 2 of the composite treating tower; when the liquid level is lower than the specified value, the sodium hydroxide solution is supplemented through an alkali liquor supplementing port 71, and the supplementing liquid enters the composite treatment tower 2 through a spraying circulation port 73.
Because a small amount of remaining waste gas through chemical spray device 22 is filterable owing to contain steam, so need continue upwards through removing foam sheet 25 and defogging layer 21, remove the liquid drop that foam sheet 25 can effective separation tower in the gas smugglied secretly to guarantee mass transfer efficiency, reduce gaseous water content, ensure that remaining reaction liquid can not continue upwards to get into defogging layer 21, guaranteed defogging effect and the life of defogging layer 21, the gas after removing the defogging through removing fog layer 21 does not contain steam almost, lay good basis for adsorption work on next step, avoid the condition emergence of active adsorption material 32 meeting water inactivation.
The exhaust gas continues to flow to the dual-channel switching adsorption-desorption device 3, as shown in fig. 3, the dual-channel switching adsorption-desorption device 3 adopts a dual-channel adsorption-desorption modular integrated control mode, and the continuity of gas treatment is ensured by the alternate operation of the adsorption-desorption chamber I311 and the adsorption-desorption chamber 312, in the embodiment, the active adsorption material 32 is an active carbon bed with a honeycomb molecular sieve structure, as shown in fig. 5, the structure has the characteristics of long exhaust gas treatment life, large specific surface area, high purification speed and strong adsorption, and the size can be freely customized.
The waste gas treatment process is as follows, firstly, the waste gas enters the first adsorption-desorption chamber 311 from the top of the composite treatment tower 2 through the first treatment tower exhaust valve 81, is subjected to adsorption work through the activated carbon bed 32, and flows to the gas discharge port 5 through the first discharge valve 83 for discharge. Because the gas discharge port 5 is provided with the VOCs detector, when the VOCs detector detects that the gas discharged from the first adsorption-desorption chamber 311 exceeds the discharge standard, the second treatment tower exhaust valve 82 is opened, the first treatment tower exhaust valve 81 is closed, the waste gas enters the second adsorption-desorption chamber 312 to continue the adsorption work, the second discharge valve 84 is opened, and the first discharge valve 83 is closed. Meanwhile, a first combustion air inlet valve 93 is opened, so that a first adsorption-desorption chamber 311 is communicated with a first combustion chamber 42, the hot air conveying device 41 starts to work, the hot air conveying device adopts an electric heating chamber in the embodiment, the electric heating temperature is set to be 100-150 ℃, hot air is conveyed into the first adsorption-desorption chamber 311 to carry out desorption treatment on the activated carbon bed 32, the hot air carries desorbed waste gas to enter the first combustion chamber 42, residual organic solution existing in a gas form is enriched due to adsorption of the activated carbon bed 32, the concentration of the residual organic solution is improved, the residual organic solution can be fully combusted in the first combustion chamber 42, the temperature of the first combustion chamber 42 is set to be 300-400 ℃, and CO generated by catalytic combustion is combusted2And water, which can be discharged directly through the gas discharge port 5; correspondingly, when the VOCs detector detects that the gas discharged from the second adsorption-desorption chamber 312 exceeds the discharge standard, the first treatment tower exhaust valve 81 is opened, the second treatment tower exhaust valve 82 is closed, the waste gas enters the first adsorption-desorption chamber 311 to continue the adsorption operation, the first discharge valve 83 is opened, and the second discharge valve 84 is closed. Meanwhile, the second combustion air inlet valve 92 is opened, so that the second adsorption-desorption chamber 312 is communicated with the second combustion chamber 43, the hot air conveying device 41 starts to work, hot air is sent into the first adsorption-desorption chamber 312 to carry out desorption treatment on the activated carbon bed 32, the hot air carries the desorbed waste gas to enter the second combustion chamber 43 for combustion, and then the waste gas is discharged through the gas discharge port 5, so that seamless switching of adsorption work of the two adsorption-desorption chambers is realized, and the adsorption work can be continuously carried out. It is noted that the first combustion chamber 42 is disposed in the adsorption chamberThe first desorption chamber 311 is arranged below the second combustion chamber 43, the second adsorption-desorption chamber 312 is arranged below the catalytic combustion device 4, and the catalytic combustion device 4 can utilize the combustion waste heat to assist the electric heating chamber 41 to heat and desorb the adsorption-desorption chamber which is performing desorption operation when the temperature reaches above 300 ℃ during operation, so that the energy utilization rate is effectively improved, the cost is saved, and the desorption efficiency is improved.
The waste liquid treatment apparatus of the present invention is not limited to the specific configuration shown in the drawings in the above-described embodiments, and various modifications thereof are possible within the knowledge of those skilled in the art. For example, in the embodiment, the spray liquid is a sodium hydroxide solution, or other alkali liquids may be used as the spray liquid in combination with the actual situation, if alkali metal fluoride generated by the alkali liquid and hydrogen fluoride is a solid-liquid mixture, the solid reactant may be precipitated into the liquid storage tank 6 at the bottom of the tower after being filtered by the waste gas reaction layer 24, as shown in fig. 4, a solid reactant collecting tank 75 may be additionally disposed between the spray liquid circulating pump 7 and the liquid storage tank 6, and the solid reactant insoluble in the reaction liquid is filtered, collected and centrally treated, so as to ensure that the pipeline is not blocked when the liquid is circulated or discharged, reduce the maintenance cost, and prolong the service life of the equipment; in addition, the active adsorption material 32 may be made of other adsorption materials besides activated carbon, and the main components to be adsorbed are adjusted accordingly, for example, a zeolite honeycomb molecular sieve is selected, which has hydrophobic property, can be used in a certain humidity environment, has excellent adsorption property to alcohol, ether, ester and benzene, has ozone decomposition capability, and can be used as a preferred material. In addition, the hot air delivery device may be an electric heating chamber, or may be a heat source device capable of delivering air, such as a hot air blower.
In addition to the above embodiments, the technical features of the present invention can be re-selected and combined to form new embodiments within the scope of the claims and the specification of the present invention, which are all realized by those skilled in the art without creative efforts, and thus, the embodiments of the present invention which are not described in detail should be regarded as the specific embodiments of the present invention and are within the protection scope of the present invention.
Claims (10)
1. The utility model provides a lithium ion battery electrolyte exhaust treatment device and system which characterized in that, includes exhaust gas conveyor (1), composite treatment tower (2), binary channels switching formula absorption-desorption device (3) and catalytic combustion device (4) that communicate in proper order:
the composite treatment tower (2) comprises a chemical spray device (22) and a demisting layer (21) arranged at an outlet of the top of the tower, wherein the chemical spray device (22) comprises at least one group of spray headers (23) and an exhaust gas reaction layer (24) which is arranged below the spray headers in a sleeved mode, and the exhaust gas reaction layer (24) comprises particles (241) used for increasing the gas flow stroke;
the dual-channel switching type adsorption-desorption device (3) adopts a modular integrated control mode and comprises an adsorption-desorption chamber I (311), an adsorption-desorption chamber II (312) and a hot air conveying device (33), wherein the adsorption-desorption chamber I (311) and the adsorption-desorption chamber II (312) alternately perform adsorption work, and hot air conveyed by the hot air device (33) is used for desorption when adsorption is saturated;
catalytic combustion unit (4) are two storehouse structure catalytic combustion chamber (41) of switching formula, two storehouse structure catalytic combustion chamber (41) of switching formula set up in binary channels switching formula adsorb-desorption device (3) below, two storehouse structures correspond the setting with adsorb-desorption chamber one (311) and adsorb-desorption chamber two (312) respectively.
2. The lithium ion battery electrolyte waste gas treatment device and system according to claim 1, wherein a liquid storage tank (6) is further arranged at the bottom of the composite treatment tower (2), and a liquid level monitor (61) and an online pH meter (62) are arranged inside the liquid storage tank.
3. The lithium ion battery electrolyte waste gas treatment device and system according to claim 2, characterized in that a spraying circulating pump (7) communicated with a tower bottom liquid storage tank (6) is arranged outside the composite treatment tower (2), an alkali liquor replenishing port (71), a waste liquid discharge port (72) and a spraying return port (73) are arranged at the output end of the spraying circulating pump (7), and the alkali liquor replenishing port (71) and the spraying return port (73) are connected with the composite treatment tower (2).
4. The lithium ion battery electrolyte waste gas treatment device and system according to claim 3, wherein a limiting valve (74) is arranged between the output end of the spray circulation pump (7) and the waste liquid discharge port (72), and a solid reactant collecting tank (75) is arranged between the spray circulation pump (7) and the liquid storage tank (6).
5. The lithium ion battery electrolyte waste gas treatment device and system according to claim 1, characterized by further comprising a waste gas conveying device (1) for conveying electrolyte waste gas, wherein the electrolyte waste gas enters the composite treatment tower (2) through the waste gas conveying device (1); the spray head (23) sprays by using alkali liquor; the particles (241) are of a porous structure, and the exhaust gas reaction layer (24) is formed by filling the particles (241) of the porous structure in the middle of the composite treatment tower (2) in a stacking mode.
6. The lithium ion battery electrolyte waste gas treatment device and system according to claim 1, wherein the first adsorption-desorption chamber and the second adsorption-desorption chamber are both provided with active adsorption materials (32).
7. The lithium ion battery electrolyte waste gas treatment device and system according to claim 1, further comprising a gas discharge port (5), wherein the two-channel switching adsorption-desorption device and the catalytic combustion device are both connected with the gas discharge port (5); a defoaming plate (25) is arranged between the demisting layer (21) and the spray header (23).
8. The lithium ion battery electrolyte waste gas treatment device and system according to any one of claims 1-7, characterized in that a first treatment tower exhaust valve (81) and a second treatment tower exhaust valve (82) are arranged above the top outlet of the composite treatment tower (2), the first treatment tower exhaust valve (81) is connected with the first adsorption-desorption chamber (311), and the second treatment tower exhaust valve (82) is connected with the second adsorption-desorption chamber (312); the output end of the adsorption-desorption chamber I (311) is provided with a discharge valve I (83); and a second discharge valve (84) is arranged at the output end of the second adsorption-desorption chamber (312).
9. The lithium ion battery electrolyte waste gas treatment device and system according to any one of claims 1-7, characterized in that the catalytic combustion chamber (41) comprises a first combustion chamber (42) and a second combustion chamber (43), and a heat insulation plate (44) is arranged between the first combustion chamber (42) and the second combustion chamber (43).
10. The lithium ion battery electrolyte waste gas treatment device and system according to claim 9, wherein a first heating air inlet valve (91) is arranged between the hot air delivery device (41) and a first adsorption-desorption chamber (311), and a first combustion air inlet valve (93) is arranged between the output end of the first adsorption-desorption chamber (311) and a first combustion chamber (421); a second heating air inlet valve (92) is arranged between the hot air conveying device (41) and the second adsorption-desorption chamber (312), and a second combustion air inlet valve (94) is arranged between the output end of the second adsorption-desorption chamber (312) and the second combustion bin (42).
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