CN110508057A - Exhaust gas purifying method and system in a kind of lithium battery removal process - Google Patents
Exhaust gas purifying method and system in a kind of lithium battery removal process Download PDFInfo
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- CN110508057A CN110508057A CN201910866458.8A CN201910866458A CN110508057A CN 110508057 A CN110508057 A CN 110508057A CN 201910866458 A CN201910866458 A CN 201910866458A CN 110508057 A CN110508057 A CN 110508057A
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- exhaust gas
- gas
- heat
- fluorine
- waste
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- 238000000034 method Methods 0.000 title claims abstract description 80
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 68
- 230000008569 process Effects 0.000 title claims abstract description 57
- 239000007789 gas Substances 0.000 claims abstract description 172
- 239000007788 liquid Substances 0.000 claims abstract description 101
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 97
- 239000011737 fluorine Substances 0.000 claims abstract description 97
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 96
- 238000010521 absorption reaction Methods 0.000 claims abstract description 91
- 239000003513 alkali Substances 0.000 claims abstract description 60
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 45
- 238000001179 sorption measurement Methods 0.000 claims abstract description 41
- 239000002918 waste heat Substances 0.000 claims abstract description 40
- 239000005416 organic matter Substances 0.000 claims abstract description 36
- 238000000746 purification Methods 0.000 claims abstract description 34
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 33
- 238000002485 combustion reaction Methods 0.000 claims abstract description 32
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims abstract description 29
- 238000000605 extraction Methods 0.000 claims abstract description 28
- 239000002912 waste gas Substances 0.000 claims abstract description 25
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 24
- 239000011574 phosphorus Substances 0.000 claims abstract description 24
- 239000000463 material Substances 0.000 claims abstract description 21
- -1 and dirt Substances 0.000 claims abstract description 19
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 239000002699 waste material Substances 0.000 claims abstract description 14
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 9
- 239000001506 calcium phosphate Substances 0.000 claims abstract description 7
- 229910000389 calcium phosphate Inorganic materials 0.000 claims abstract description 7
- 235000011010 calcium phosphates Nutrition 0.000 claims abstract description 7
- 230000008676 import Effects 0.000 claims abstract description 7
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims abstract description 7
- 239000013618 particulate matter Substances 0.000 claims abstract description 6
- 230000018044 dehydration Effects 0.000 claims abstract description 5
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 5
- 238000007711 solidification Methods 0.000 claims abstract description 4
- 230000008023 solidification Effects 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 49
- 239000002253 acid Substances 0.000 claims description 47
- 239000000243 solution Substances 0.000 claims description 42
- 238000011084 recovery Methods 0.000 claims description 40
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 34
- 239000003546 flue gas Substances 0.000 claims description 34
- 239000000428 dust Substances 0.000 claims description 26
- 238000009825 accumulation Methods 0.000 claims description 18
- 238000005260 corrosion Methods 0.000 claims description 15
- OBCUTHMOOONNBS-UHFFFAOYSA-N phosphorus pentafluoride Chemical compound FP(F)(F)(F)F OBCUTHMOOONNBS-UHFFFAOYSA-N 0.000 claims description 15
- 230000007797 corrosion Effects 0.000 claims description 14
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 13
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 12
- 230000003197 catalytic effect Effects 0.000 claims description 12
- 238000004140 cleaning Methods 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 12
- 239000000945 filler Substances 0.000 claims description 12
- 239000002351 wastewater Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 10
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 10
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 10
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 9
- 230000005611 electricity Effects 0.000 claims description 8
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 238000005070 sampling Methods 0.000 claims description 7
- 239000012855 volatile organic compound Substances 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 239000004743 Polypropylene Substances 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 6
- 239000001569 carbon dioxide Substances 0.000 claims description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 229930195733 hydrocarbon Natural products 0.000 claims description 6
- 150000002430 hydrocarbons Chemical class 0.000 claims description 6
- 239000007791 liquid phase Substances 0.000 claims description 6
- 229920001155 polypropylene Polymers 0.000 claims description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 6
- 239000006096 absorbing agent Substances 0.000 claims description 5
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 claims description 5
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 claims description 5
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 5
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000013049 sediment Substances 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 125000004122 cyclic group Chemical group 0.000 claims description 3
- 239000007792 gaseous phase Substances 0.000 claims description 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 3
- 239000000347 magnesium hydroxide Substances 0.000 claims description 3
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 3
- 239000012071 phase Substances 0.000 claims description 3
- 238000004064 recycling Methods 0.000 claims description 3
- 239000007770 graphite material Substances 0.000 claims description 2
- ZHQXROVTUTVPGO-UHFFFAOYSA-N [F].[P] Chemical compound [F].[P] ZHQXROVTUTVPGO-UHFFFAOYSA-N 0.000 claims 1
- 238000001914 filtration Methods 0.000 claims 1
- 238000003825 pressing Methods 0.000 claims 1
- 230000009102 absorption Effects 0.000 description 70
- 239000003054 catalyst Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 238000007084 catalytic combustion reaction Methods 0.000 description 5
- 238000013015 e-cracking Methods 0.000 description 5
- 238000005338 heat storage Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000012774 insulation material Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 231100000572 poisoning Toxicity 0.000 description 3
- 230000000607 poisoning effect Effects 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000003682 fluorination reaction Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 230000000415 inactivating effect Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000006303 photolysis reaction Methods 0.000 description 2
- 230000015843 photosynthesis, light reaction Effects 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 description 1
- HMWVNKJRYWXJGS-UHFFFAOYSA-N C(C)(=O)OC=C.[C] Chemical compound C(C)(=O)OC=C.[C] HMWVNKJRYWXJGS-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 230000003694 hair properties Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010079 rubber tapping Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D45/00—Separating dispersed particles from gases or vapours by gravity, inertia, or centrifugal forces
- B01D45/12—Separating dispersed particles from gases or vapours by gravity, inertia, or centrifugal forces by centrifugal forces
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
- B01D46/02—Particle separators, e.g. dust precipitators, having hollow filters made of flexible material
-
- 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
-
- 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
- B01D53/73—After-treatment of removed 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
- B01D53/74—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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/96—Regeneration, reactivation or recycling of reactants
-
- 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
-
- 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
- F23G7/061—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases with supplementary heating
- F23G7/065—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases with supplementary heating using gaseous or liquid fuel
- F23G7/066—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases with supplementary heating using gaseous or liquid fuel preheating the waste gas by the heat of the combustion, e.g. recuperation type incinerator
-
- 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
- F23G7/07—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases in which combustion takes place in the presence of catalytic material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/20—Halogens or halogen compounds
- B01D2257/204—Inorganic halogen compounds
- B01D2257/2047—Hydrofluoric acid
-
- 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
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
-
- 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
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/30—Capture or disposal of greenhouse gases of perfluorocarbons [PFC], hydrofluorocarbons [HFC] or sulfur hexafluoride [SF6]
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Biomedical Technology (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Treating Waste Gases (AREA)
Abstract
The present invention relates to exhaust gas purifying method and systems in a kind of lithium battery removal process, the exhaust gas generated in lithium battery removal process first removes dust-laden particulate matter therein through dust-extraction unit, then through most fluorine component in two sections of circulating absorption tower removing exhaust gas, exhaust gas after removing fluorine component removes volatile organic matter therein by high-temp combustion or medium temperature catalysis burning, then enters the remaining micro hydrogen fluoride of alkali adsorption tower removal after waste heat recycles；The waste liquid that is generated in the above process import in neutralization chamber with neutralize alkaline reaction, form harmless solidfied material calcirm-fluoride and calcium phosphate after making fluorine therein, phosphorus solidification dehydration.The present invention can remove most fluorine component in exhaust gas, and dirt, fluorine and volatile organic matter removal efficiency meet or exceed relevant criterion in exhaust gas after processing, fluorine in exhaust gas and P elements are converted to harmless solidfied material simultaneously, both achieved the purpose that waste gas purification was administered, while having realized comprehensive utilization of resources.
Description
Technical field
The present invention relates to waste gas purification sides in waste gas purification processing technology field more particularly to a kind of lithium battery removal process
Method and system.
Background technique
In recent years, new-energy automobile industry in China's is flourished, and dynamic lithium battery production capacity rapidly increases therewith, there is report
Road shows that the year two thousand twenty country new-energy automobile total output is expected to reach 2,000,000, and corresponding power battery demand reaches 120.8GWh,
Power battery demand speedup compound every year is about 54.9%, and automobile power cell is mainly based on lithium battery at present.
Lithium ion battery generally uses dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, ethylene carbonate and hexafluoro phosphorus
The mixed solvents such as sour lithium are as electrolyte, compared to lead-acid battery, nickel-cadmium cell, although the lithium battery on service life and service life
Performance it is very superior, but its service life is generally 3 to 5 years, and with the growth of dynamic lithium battery service life, replacement is eliminated
Multiple is measured into increase.Containing a large amount of non-renewable metal resources, such as cobalt, lithium, nickel, copper, aluminium in discarded lithium battery, if energy
Effectively waste lithium cell is recycled, environmental pollution caused by waste lithium cell can not only be mitigated, while can also create
More rich economic benefit is made, to realize lithium electricity green circulation economy.
In waste lithium cell removal process, waste lithium cell will by dismantling, broken, nitrogen protection heating, drying, sorting,
The processes such as the preparation of battery powder, metal recovery.Waste lithium cell generates a large amount of dust in dismantling shattering process, and electric cracking was dried
A large amount of organic solvents evaporate in the electrolyte generated in journey, such as dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, carbon
Vinyl acetate etc., lithium hexafluoro phosphate cracking and with fluorine-containing group of a large amount of hydrogen fluoride, phosphorus pentafluoride etc. can be generated after reaction of moisture
Point, it, but will serious pollution environment if exhaust gas not only endangers the health of surrounding people without direct outlet is handled.
Therefore, the waste gas purification generated in waste lithium cell removal process, mainly to dedusting, fluorine-containing harmful constituent and
Volatile organic matter is purified, and the discharge of removal process exhaust gas is made to reach corresponding country and professional standard.
However, fluorine component has susceptibility-to-corrosion and removal since useless old lithium removal process exhaust gas organic component is complicated
The features such as slow, existing waste gas purification apparatus and system, not only cannot achieve waste gas purification discharge index, but also unavoidable
Fluoro-gas is corrosion-damaged to cleaning equipment bring.
The Chinese patent of Patent No. CN207950933U discloses a kind of " organic exhaust gas generated in lithium battery removal process
Processing system ", the system use sack cleaner, catalytic combustion device and alkali pool, filter progress to remove solia particle,
Catalytic combustion device contains a large amount of fluorine component to remove the volatile organic matters such as carbonates in exhaust gas, without
Processing, which is directly entered in catalytic combustion device, to be caused to corrode to processing, while making catalyst for catalytic combustion poison deactivation, in turn
Greatly shorten a whole set of processing equipment service life.Mainly exist in the form of phosphorus pentafluoride in fluorine component, phosphorus pentafluoride exists
It can decompose in alkaline aqueous solution, but decomposition rate is slow, inefficiency, alkali pool can not be such that the removal efficiency of fluorine component reaches
To effluent standard.In addition, drying volatile organic matter concentration range in exhaust gas in lithium electricity recycling pyrolysis furnace process and being up to
150g/m3, this also has exceeded the opereating specification of catalytic combustion device.
The Chinese patent of Patent No. CN108096977A disclose it is a kind of " exhaust gas generated in lithium battery removal process
Processing method and system ", which is dehumidified using nitrogen protection, adsorbent, although the generation of hydrogen fluoride can be reduced, in exhaust gas
Part fluorine component is reacted acutely with water, is unavoidably had moisture in cell classification screening shattering process and is introduced, halogen acid is made
At equipment corrosion phenomenon it is inevitable, while the processing method is not provided with the removal methods of fluorine component, in cleaning of off-gas
Fluorine component discharge beyond standards not can avoid.
The Chinese patent of Patent No. CN110124432A discloses a kind of " flue gas in waste lithium cell recovery processing technique
Purification device ", the device further remove dust particles substance, lye eluting column by bag filter dedusting, water eluting column
Purifying inorganic halogen acid, activated carbon adsorption device remove volatile organic matter, and ultraviolet photolysis is further degraded the volatilization not removed
Property organic matter；Although the device is provided with caustic wash tower, the hydrogen fluoride in fluorine component can be removed, other fluorine components can not
Removing up to standard, especially phosphorus pentafluoride.In addition, the volatile organic content in exhaust gas is high, it is living using activated carbon adsorption device
Property charcoal adsorption saturation within the short time will lead to replacement frequently to inactivating, operating cost is high.Ultraviolet photolysis device is suitable for
The improvement of smell, and the removing to esters, need greater energy consumption to can be only achieved certain removal effect, and there are the wind of secondary pollution
Danger.
The Chinese patent of Patent No. CN108128953A discloses a kind of " exhaust gas of waste lithium cell recycling cracking and useless
Electric cracking furnace is arranged in water treatment facilities and method ", the device, and lithium electricity recycles exhaust gas and mixes through gas sampling pipe, surge tank, air
Electric cracking furnace is directly entered after device, because there are a large amount of fluorine components in lithium electricity removal process, fluorine component is after electric cracking furnace
High concentration hydrogen fluoride gas is generated, serious corrosion can be caused, to electric cracking furnace apparatus so as to shorten equipment life；In addition, should
Device can be collected in pyrolysis furnace without cleaner, direct waste gas from incinerator, a large amount of dust, influence the operation of processing unit.
By the description and analysis to the above prior art: realizing waste gas purification needs pair in lithium battery removal process
Dust, fluorine component and volatile organic matter are removed respectively, and the removing of fluorine component is committed step therein, this is just
It is required that the exhaust gas that waste lithium cell removal process generates is after dedusting, Ying Shouxian removes fluorine component as efficiently as possible,
Fluorine component is preferably removed completely or fluorine component concentration in exhaust gas is removed to≤10ppm, and then the property of will volatilize is organic again
Object is removed to qualified discharge requirement, it is generally recognized that: in exhaust gas when the molar content < 0.2% of fluorine, fluorine-containing mixing organic exhaust gas exists
When being purified using direct combustion system, fluoride will not cause serious corrosion to equipment.
In conclusion in order to overcome above-mentioned defect in the prior art, and make to generate in waste lithium cell removal process
Exhaust gas can reach complete purification standard discharge, and there is an urgent need to above-mentioned existing purification device and method are improved and created
Newly, corrosion of the fluorine component to emission-control equipment ontology, thermal insulation material or heat storage is prevented, or catalyst fluorine poisoning is avoided to lose
It is living, effectively extend the service life of exhaust gas apparatus, guarantees that exhaust gas purification and treatment device system is safe and stable and reliability service, make
Dirt, fluorine and volatile organic matter removal efficiency meet or exceed relevant criterion in exhaust gas.
Summary of the invention
The present invention provides exhaust gas purifying method and systems in a kind of lithium battery removal process, for lithium battery removal process
The exhaust gas of middle generation has the characteristics that high concentration dirt, fluorine and volatile organic matter, and each functional element is rationally arranged, and can remove useless
Most fluorine component in gas, prevents fluorine component to TREATMENT OF VOCs device noumenon, thermal insulation material or heat storage
Corrosion, avoid catalyst fluorine poisoning inactivate, effectively extend exhaust treating purifier service life, guarantee waste gas purification at
Manage safety, stability and the reliability of equipment operation；Dirt, fluorine and volatile organic matter removal efficiency in exhaust gas after processing
Relevant criterion is met or exceeded, while fluorine in exhaust gas and P elements are converted to harmless solidfied material, has both reached waste gas purification
The purpose of improvement, while realizing comprehensive utilization of resources.
In order to achieve the above object, the present invention is implemented with the following technical solutions:
Exhaust gas purifying method in a kind of lithium battery removal process, the exhaust gas generated in lithium battery removal process are first filled through dedusting
Removal dust-laden particulate matter therein is set, then through most fluorine component in two sections of circulating absorption tower removing exhaust gas, removing contains
Exhaust gas after fluorine component removes volatile organic matter therein by high-temp combustion or medium temperature catalysis burning, then after waste heat recycles
Into the remaining micro hydrogen fluoride of alkali adsorption tower removal；The waste liquid generated in the above process imports anti-with neutralization lye in neutralization chamber
It answers, forms harmless solidfied material calcirm-fluoride and calcium phosphate after making fluorine therein, phosphorus solidification dehydration.
Exhaust gas purifying method in a kind of lithium battery removal process, specifically comprises the following steps:
1) exhaust gas generated in lithium electricity removal process enters dust removing units through gas sampling pipeline, the dust-laden particle in exhaust gas
Object send temporary to grey library exhaust gas dustiness < 10mg/m after dedusting by ash conveying device after being filtered off3；
2) exhaust gas after dust separation is sent into fluorine removal unit, through gas-liquid heat-exchange and the suction from two sections of circulating absorption towers
Liquid heat exchange cooling is received, subsequently into two sections of circulating absorption towers；The lower section of two sections of circulating absorption towers is passed through acid absorbing liquid, exhaust gas
In most phosphorus pentafluoride and hydrogen fluoride be removed；Wherein it is fluorine-containing with acid absorbing liquid react generation for the phosphorus pentafluoride in exhaust gas
Phosphorus complex, for the mixed solution after reaction after gas-liquid heat-exchange heats, fluorine-containing phosphorus complex is respectively formed hydrofluoric acid and phosphorus
Acid；The upper section of two sections of circulating absorption towers is passed through alkaline absorption solution, further absorbs the phosphorus pentafluoride escaped from lower section and fluorination
Hydrogen；Molar content through fluorine in the purified exhaust gas of fluorine removal unit is in 100ppm or less；
3) enter the incinerator in volatile organic matter removal unit through dedusting, the purified exhaust gas of defluorinate and carry out 850 DEG C
~1000 DEG C of high-temp combustions or 250 DEG C~350 DEG C catalysis burnings；Dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate in exhaust gas
Ester, ethylene carbonate and micro fluorine-containing phosphorus compound are fully oxidized in the case where high-temp combustion acts on or is catalyzed combustion, raw
At carbon dioxide, water and micro hydrogen fluoride and phosphorus pentoxide, non-methane total hydrocarbons in the exhaust gas after removing volatile organic matter
Content is less than 80mg/m3, VOCs purification efficiency is greater than 95%；
4) high-temperature flue gas that exhaust gas generates after high-temp combustion in step 3) enters waste heat recovery unit, is recycled and is filled by waste heat
It sets and generates low middle pressure steam；Enter alkali adsorption tower after waste heat flue gas after the recovery passes through heat exchange cooling again；Or exhaust gas is through urging
Change the medium temperature flue gas generated after burning and enters alkali adsorption tower after heat exchange cooling；
5) in alkali adsorption tower, flue gas and alkaline absorption solution counter current contacting, remaining micro hydrogen fluoride is absorbed in flue gas,
Hydrogen fluoride content is less than 3mg/m in purified flue gas3；
6) row of the solution after gas-liquid heat-exchange heat resolve, the relief liquor of two sections of circulating absorption tower upper sections and alkali adsorption tower
Tapping imports in neutralization chamber respectively, and with neutralization alkaline reaction, fluorine therein and phosphorus are cured to form sediment, de- by filter press
After water, the calcirm-fluoride and calcium phosphate of formation are harmless solidfied material.
The gas-liquid heat-exchange heats acid absorbing liquid by heat source of the exhaust gas after dedusting, and acid absorbing liquid is in gas-liquid heat exchange
Heating dwell times in device are 60~600min, and the flow channel of acid absorbing liquid uses corrosion-resistant graphite in gas-liquid heat-exchange
Material is made.
The acidity absorbing liquid is one of sulfuric acid, phosphoric acid, hydrofluoric acid, hydrochloric acid or a variety of any mixing；Acidity absorbs
The mass fraction of liquid is 1%~10%.
The alkaline absorption solution is the sodium hydroxide solution that mass fraction is 5%~20%.
The incinerator is using one in direct-combustion furnace, box accumulation of heat incinerator, rotation accumulation of heat incinerator, catalytic burning furnace
Kind；Wherein ignition temperature of the exhaust gas in direct-combustion furnace, box accumulation of heat incinerator, rotation accumulation of heat incinerator is 850 DEG C~1000 DEG C,
Reaction temperature of the exhaust gas in catalytic burning furnace is 250 DEG C~350 DEG C, air speed 15000h-1~25000h-1；Exhaust gas is in incinerator
The interior residence time is 0.2s~5s.
The lye that neutralizes is the calcium hydroxide solution or magnesium hydroxide solution that mass concentration is 5%~20%.
Waste gas cleaning system in a kind of lithium battery removal process, including dust removing units, fluorine removal unit, volatile organic matter
Removal unit, waste heat recovery unit, Alkali absorption unit and treatment unit for waste water；The dust removing units at least set dust-extraction unit, fluorine
Removal unit at least sets gas-liquid heat-exchange and two sections of circulating absorption towers；Volatile organic matter removal unit at least sets incinerator；It is remaining
Heat recovery units are at least provided with heat exchanger or waste-heat recovery device and heat exchanger；Alkali absorption unit at least sets alkali adsorption tower, waste water
Processing unit at least sets neutralization chamber and filter press；
The gas sampling pipeline of the dusty gas entrance connection lithium battery recovery system of dust-extraction unit, the purification of dust-extraction unit
Gas vent connects the gas phase entrance of gas-liquid heat-exchange, and the gaseous phase outlet of gas-liquid heat-exchange connects two sections of circulating absorption tower lower parts
Exhaust gas entrance；The lower section of two sections of circulating absorption towers is acid absorber portion, is equipped with acid absorbing liquid entrance, is equipped with acidity outside tower body
Absorbing liquid circulating line sets absorbing liquid cooler on acid absorbing liquid circulating line；In addition acid absorbing liquid circulating line connects
The liquid-phase outlet of the liquid phase entrance of gas-liquid heat-exchange, gas-liquid heat-exchange connects neutralization chamber；The upper section of two sections of circulating absorption towers is alkali
Property absorber portion, be equipped with alkaline absorption solution entrance, alkaline absorption solution circulating line, alkaline absorption solution circulating line be equipped with outside tower body
In addition neutralization chamber is connected；The exhaust gas entrance connection of the clean gas outlet and incinerator of two sections of cyclic absorption column overheads, incinerator
Exhanst gas outlet connects the exhaust gas entrance of alkali adsorption tower bottom, alkali adsorption tower after heat exchanger or waste-heat recovery device and heat exchanger
Top set Alkali absorption liquid entrance, the outside of alkali adsorption tower sets lye circulating line, in addition lye circulating line connects neutralization chamber,
Clean gas outlet is set at the top of alkali adsorption tower；It is set on neutralization chamber and neutralizes alkali liquor inlet and mixture export, mixture export connection
Filter press.
The dust-extraction unit is sack cleaner, cyclone dust collectors or multicyclone, and dust-extraction unit inner wall is equipped with
Corrosion-resistant and wear-resistant material liner.
Upper section, the lower section of two sections of circulating absorption towers set filler respectively, filler using polyhedron empty ball, Taylor's garland,
Rectangular saddle ring, Pall ring, Raschig ring or regular corrugation plate filler, filler material are polypropylene, reinforced polypropylene or polytetrafluoroethylene (PTFE).
Compared with prior art, the beneficial effects of the present invention are:
Have the characteristics that high concentration dirt, fluorine and volatile organic matter for the exhaust gas generated in lithium battery removal process, closes
Each functional element is arranged in reason, can remove most fluorine component in exhaust gas, prevent fluorine component to volatile organic matter at
The corrosion for managing device noumenon, thermal insulation material or heat storage avoids catalyst fluorine poisoning from inactivating, and effectively extends waste gas purification processing and sets
Standby service life guarantees safety, stability and the reliability of exhaust treating purifier operation；In exhaust gas after processing
Dirt, fluorine and volatile organic matter removal efficiency meet or exceed relevant criterion, while fluorine in exhaust gas and P elements being converted to
Harmless solidfied material had both achieved the purpose that waste gas purification was administered, while having realized comprehensive utilization of resources.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of waste gas cleaning system in lithium battery removal process described in the embodiment of the present invention 1.
Fig. 2 is the structural schematic diagram of waste gas cleaning system in lithium battery removal process described in the embodiment of the present invention 2.
Fig. 3 is the structural schematic diagram of waste gas cleaning system in lithium battery removal process described in the embodiment of the present invention 3.
In figure: the box accumulation of heat of 1. dust-extraction unit, 2. gas-liquid heat-exchange, 3. 2 sections of circulating absorption towers, 41. direct-combustion furnace 42. is burnt
It is defeated to burn 43. catalytic burning furnace of furnace, 5. waste-heat recovery device, 6. heat exchanger, 7. alkali adsorption tower, 8. neutralization chamber, 9. filter presses 10.
The acid 14. alkaline absorption solution device for supplying of absorbing liquid device for supplying of 11. absorbing liquid cooler of apparatus for ash, 12. circulating pump 13.
15. 16. blower of fire arrester
Specific embodiment
Specific embodiments of the present invention will be further explained with reference to the accompanying drawing:
As shown in Figure 1-Figure 3, exhaust gas purifying method in a kind of lithium battery removal process of the present invention, lithium battery recycled
The exhaust gas generated in journey first removes dust-laden particulate matter therein through dust-extraction unit 1, then removes exhaust gas through two sections of circulating absorption towers 3
In most fluorine component, the exhaust gas after removing fluorine component therein waved by high-temp combustion or medium temperature catalysis burning removal
Hair property organic matter, then enter alkali adsorption tower 7 after waste heat recycles and remove remaining micro hydrogen fluoride；What is generated in the above process is useless
Liquid import in neutralization chamber 8 with neutralize alkaline reaction, form harmless solidfied material calcirm-fluoride and phosphorus after making fluorine therein, phosphorus solidification dehydration
Sour calcium.
Exhaust gas purifying method in a kind of lithium battery removal process, specifically comprises the following steps:
1) exhaust gas generated in lithium electricity removal process enters dust removing units through gas sampling pipeline, the dust-laden particle in exhaust gas
Object send temporary to grey library exhaust gas dustiness < 10mg/m after dedusting by ash conveying device 10 after being filtered off3；
2) exhaust gas after dust separation is sent into fluorine removal unit, through gas-liquid heat-exchange 2 with from two sections of circulating absorption towers 3
Absorbing liquid heat exchange cooling, subsequently into two sections of circulating absorption towers 3；The lower section of two sections of circulating absorption towers 3 is passed through acid absorbing liquid,
Most phosphorus pentafluoride and hydrogen fluoride are removed in exhaust gas；Wherein the phosphorus pentafluoride in exhaust gas reacts generation with acid absorbing liquid
Fluorine-containing phosphorus complex, for the mixed solution after reaction after the heating of gas-liquid heat-exchange 2, fluorine-containing phosphorus complex is respectively formed hydrofluoric acid
With phosphoric acid；The upper section of two sections of circulating absorption towers 3 is passed through alkaline absorption solution, further absorb phosphorus pentafluoride escape from lower section with
Hydrogen fluoride；Molar content through fluorine in the purified exhaust gas of fluorine removal unit is in 100ppm or less；
3) enter the incinerator in volatile organic matter removal unit through dedusting, the purified exhaust gas of defluorinate and carry out 850 DEG C
~1000 DEG C of high-temp combustions or 250 DEG C~350 DEG C catalysis burnings；Dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate in exhaust gas
Ester, ethylene carbonate and micro fluorine-containing phosphorus compound are fully oxidized in the case where high-temp combustion acts on or is catalyzed combustion, raw
At carbon dioxide, water and micro hydrogen fluoride and phosphorus pentoxide, non-methane total hydrocarbons in the exhaust gas after removing volatile organic matter
Content is less than 80mg/m3, VOCs purification efficiency is greater than 95%；
4) high-temperature flue gas that exhaust gas generates after high-temp combustion in step 3) enters waste heat recovery unit, is recycled and is filled by waste heat
Set the low middle pressure steam of 5 generations；Enter alkali adsorption tower 7 after waste heat flue gas after the recovery passes through heat exchange cooling again；Or exhaust gas warp
The medium temperature flue gas generated after catalysis burning enters alkali adsorption tower 7 after heat exchange cooling；
5) in alkali adsorption tower 7, flue gas and alkaline absorption solution counter current contacting, remaining micro hydrogen fluoride is inhaled in flue gas
It receives, hydrogen fluoride content is less than 3mg/m in purified flue gas3；
6) relief liquor and alkali adsorption tower 7 of the solution after 2 heat resolve of gas-liquid heat-exchange, two sections of 3 upper sections of circulating absorption tower
Relief liquor imported in neutralization chamber 8 respectively, and neutralize alkaline reaction, fluorine therein and phosphorus are cured to form sediment, pass through pressure
After filter 9 is dehydrated, the calcirm-fluoride and calcium phosphate of formation are harmless solidfied material.
The gas-liquid heat-exchange 2 heats acid absorbing liquid by heat source of the exhaust gas after dedusting, and acid absorbing liquid is changed in gas-liquid
Heating dwell times in hot device 2 are 60~600min, and the flow channel of acid absorbing liquid is using corrosion-resistant in gas-liquid heat-exchange 2
Graphite material is made.
The acidity absorbing liquid is one of sulfuric acid, phosphoric acid, hydrofluoric acid, hydrochloric acid or a variety of any mixing；Acidity absorbs
The mass fraction of liquid is 1%~10%.
The alkaline absorption solution is the sodium hydroxide solution that mass fraction is 5%~20%.
The incinerator is using in direct-combustion furnace 41, box accumulation of heat incinerator, rotation accumulation of heat incinerator, catalytic burning furnace 43
It is a kind of；Wherein exhaust gas direct-combustion furnace 41, box accumulation of heat incinerator, rotation accumulation of heat incinerator in ignition temperature be 850 DEG C~
1000 DEG C, reaction temperature of the exhaust gas in catalytic burning furnace 43 is 250 DEG C~350 DEG C, air speed 15000h-1~25000h-1；It is useless
Residence time of the gas in incinerator is 0.2s~5s.
The lye that neutralizes is the calcium hydroxide solution or magnesium hydroxide solution that mass concentration is 5%~20%.
Waste gas cleaning system in a kind of lithium battery removal process, including dust removing units, fluorine removal unit, volatile organic matter
Removal unit, waste heat recovery unit, Alkali absorption unit and treatment unit for waste water；The dust removing units at least set dust-extraction unit 1, fluorine
Removal unit at least sets gas-liquid heat-exchange 2 and two sections of circulating absorption towers 3；Volatile organic matter removal unit at least sets incinerator；
Waste heat recovery unit is at least provided with heat exchanger 6 or waste-heat recovery device 5 and heat exchanger 6；Alkali absorption unit at least sets alkali adsorption tower
7, treatment unit for waste water at least sets neutralization chamber 8 and filter press 9；
Dust-extraction unit 1 dusty gas entrance connection lithium battery recovery system gas sampling pipeline, dust-extraction unit 1 it is net
Change the gas phase entrance of gas vent connection gas-liquid heat-exchange 2, the gaseous phase outlet of gas-liquid heat-exchange 2 connects two sections of circulating absorption towers 3
The exhaust gas entrance of lower part；The lower section of two sections of circulating absorption towers 3 is acid absorber portion, is equipped with acid absorbing liquid entrance, outside tower body
Equipped with acid absorbing liquid circulating line, absorbing liquid cooler 11 is set on acid absorbing liquid circulating line；Acid absorbing liquid circulation pipe
In addition road connects the liquid phase entrance of gas-liquid heat-exchange 2, the liquid-phase outlet of gas-liquid heat-exchange 2 connects neutralization chamber 8；Two sections of cyclic absorptions
The upper section of tower 3 is alkaline absorber portion, is equipped with alkaline absorption solution entrance, alkaline absorption solution circulating line, alkalinity are equipped with outside tower body
In addition absorbing liquid circulating line connects neutralization chamber 8；The clean gas outlet of two sections of 3 tower tops of circulating absorption tower and the exhaust gas of incinerator enter
Mouth connection, the exhanst gas outlet of incinerator connect 7 bottom of alkali adsorption tower after heat exchanger 6 or waste-heat recovery device 5 and heat exchanger 6
Exhaust gas entrance, the top of alkali adsorption tower 7 sets Alkali absorption liquid entrance, and the outside of alkali adsorption tower 7 sets lye circulating line, and lye follows
In addition endless tube road connects neutralization chamber 8, the top of alkali adsorption tower 7 sets clean gas outlet；It is set on neutralization chamber 8 and neutralizes alkali liquor inlet and mix
Liquid outlet is closed, mixture export connects filter press 9.
The dust-extraction unit 1 is sack cleaner, cyclone dust collectors or multicyclone, and the inner wall of dust-extraction unit is set
There is corrosion-resistant and wear-resistant material liner.
Upper section, the lower section of two sections of circulating absorption towers 3 set filler respectively, filler using polyhedron empty ball, Taylor's garland,
Rectangular saddle ring, Pall ring, Raschig ring or regular corrugation plate filler, filler material are polypropylene, reinforced polypropylene or polytetrafluoroethylene (PTFE).
Following embodiment is implemented under the premise of the technical scheme of the present invention, gives detailed embodiment and tool
The operating process of body, but protection scope of the present invention is not limited to following embodiments.Method therefor is such as without spy in following embodiments
Not mentionleting alone bright is conventional method.
[embodiment 1]
As shown in Figure 1, in the present embodiment, waste gas purification apparatus system includes dedusting list in a kind of lithium battery removal process
Member, fluorine removal unit, volatile organic matter removal unit, waste heat recovery unit, treatment unit for waste water and Alkali absorption unit.Its
In:
Dust removing units are made of dust-extraction unit 1, ash conveying device 10 and grey library, and the exhaust gas generated in lithium electricity removal process is through useless
Gas collection conduit enters dust-extraction unit 1, and 1 inner wall of dust-extraction unit sets corrosion-resistant and wear-resistant material liner, such as polytetrafluoro material liner.
The preferred sack cleaner of dust-extraction unit 1.On exhaust gas particulate matter attachment cloth bag contained therein after dust-extraction unit 1, through nitrogen
After blowback, dirt is collected in the ash bucket of dust-extraction unit 1, is sent by ash conveying device 10 to grey library and is kept in.After dust removing units purify
Exhaust gas dustiness be less than 10mg/m3, exhaust gas after dust separation is sent into fluorine removal unit, can be avoided a large amount of dust in this way and draw
Enter subsequent processing device, to prevent equipment from blocking, it is ensured that safe, the continuous and stable operation of aftertreatment systems.
Fluorine removal unit is by 2, two sections of circulating absorption towers 3 of gas-liquid heat-exchange, alkaline absorption solution device for supplying 14, acid absorption
Liquid device for supplying 13 forms, and the exhaust gas after dedusting enters gas-liquid heat-exchange 2, absorbs with from two sections of the acid of circulating absorption tower 3
Liquid heat exchange, the exhaust gas after cooling enter in two sections of circulating absorption towers 3, and the fluorine component in exhaust gas is largely removed.Two sections are followed
Circulating pump 12 is set respectively on the alkaline absorption solution circulating line of 3 upper section of ring absorption tower and the acid absorbing liquid circulating line of lower section.
Exhaust gas after removing fluorine component is delivered to volatile organic matter removal unit through blower 16.By acid absorbing liquid device for supplying 13
The acid absorbing liquid of conveying be mass fraction 5% hydrofluoric acid, phosphorus pentafluoride with acidity absorbing liquid react to be formed it is corresponding fluorine-containing
Phosphorus complex, for the mixed solution after reaction after the heating of gas-liquid heat-exchange 2, fluorine-containing phosphorus complex is respectively formed hydrofluoric acid and phosphorus
Acid.It is the sodium hydroxide solution that mass fraction is 10% by the alkaline absorption solution that alkaline absorption solution device for supplying 14 conveys, two
The upper section of section circulating absorption tower 3 further absorbs phosphorus pentafluoride and hydrogen fluoride from lower section escape.It is purified through fluorine removal unit
Afterwards, in exhaust gas the molar content of fluorine in 100ppm hereinafter, the fluorochemical in exhaust gas obtains high-efficient purification, alleviate it to rear
The corrosion of continuous device, extends waste gas cleaning system service life, guarantees system reliability of operation and safety.
Volatile organic matter removal unit is made of fire arrester 15, direct-combustion furnace 41 (being equipped with burner and combustion fan), is hindered
Firearm 15 is set on the exhaust piping between heat exchanger 6 and direct-combustion furnace 41；Dedusting, the purified exhaust gas of defluorinate, send through blower 16
Enter volatile organic matter removal unit, the ignition temperature in direct-combustion furnace 41 is controlled at 900 DEG C, exhaust gas residence time 2.8s, is given up
Dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, ethylene carbonate and micro fluorine-containing phosphorus compound in gas are at high temperature
It is fully oxidized, generates carbon dioxide, water and micro hydrogen fluoride and phosphorus pentoxide, the non-methane total hydrocarbons after purification in exhaust gas
Content is less than 80mg/m3, VOCs purification efficiency reaches 99%.
Waste heat recovery unit is made of waste-heat recovery device 5 and heat exchanger 6 (gas-gas heat exchanger), in lithium battery removal process
Contain large amount of organic component in the exhaust gas of generation, such as dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate and ethylene carbonate
Ester, after direct-combustion furnace burns, high-temperature flue gas produces low middle pressure steam through waste-heat recovery device 5, logical through waste heat flue gas after the recovery
It crosses heat exchanger 6 and preheats the exhaust gas after dedusting, to further increase the waste heat recovery efficiency of flue gas, reduce the fuel of direct-combustion furnace 41
Consumption, energy saving reduce the operating cost of exhaust treatment system.
Alkali absorption unit is made of alkali adsorption tower 7, and the flue gas after the heat exchange cooling of heat exchanger 6 enters in alkali adsorption tower 7, with
The sodium hydroxide solution counter current contacting that mass concentration is 10%, micro hydrogen fluoride is absorbed in flue gas, the fluorination in neat stress
Hydrogen content is less than 3mg/m3, can be directly discharged into atmosphere.
Treatment unit for waste water is made of neutralization chamber 8 and filter press 9, solution after 2 heat resolve of gas-liquid heat-exchange, two sections follow
The relief liquor of relief liquor and alkali adsorption tower 7 after the absorption of 3 upper section of ring absorption tower, imports in neutralization chamber 8 respectively, leads in neutralization chamber 8
Enter the calcium hydroxide solution that mass fraction is 10% and carry out neutralization reaction, fluorine and phosphorus are cured to form sediment, pass through filter press 9
Calcirm-fluoride is formed after dehydration and calcium phosphate, the two are harmless solidfied material, can be used for mining area place landfill etc., it is same in waste gas pollution control and treatment
When, accomplish environmental-friendly, waste utilization.
[embodiment 2]
As shown in Fig. 2, in the present embodiment, waste gas purification apparatus system includes dedusting list in a kind of lithium battery removal process
Member, fluorine removal unit, volatile organic matter removal unit, waste heat recovery unit, treatment unit for waste water and Alkali absorption unit.Its
In:
Dust removing units are made of dust-extraction unit 1, ash conveying device 10 and grey library, and dust-extraction unit 1 selects sack cleaner, work
It is same as Example 1 to make principle.The dustiness of exhaust gas is less than 10mg/m after purification3。
Fluorine removal unit is by 2, two sections of circulating absorption towers 3 of gas-liquid heat-exchange, alkaline absorption solution device for supplying 14, acid absorption
Liquid device for supplying 13 form, working principle is substantially the same manner as Example 1, acid absorbing liquid use mass fraction for 5% salt
Acid, alkaline absorption solution use mass fraction for 10% sodium hydroxide solution, after the purification of fluorine removal unit in exhaust gas fluorine mole
Content is in 100ppm or less.
By fire arrester 15, box accumulation of heat incinerator 42, (RTO furnace equipped with burner and helps volatile organic matter removal unit
Fire blower) composition, fire arrester 15 is on the exhaust piping between two sections of circulating absorption towers 3 and blower 16；Dedusting, defluorinate purification
Exhaust gas afterwards is sent into box accumulation of heat incinerator 42 through blower 16, and the ignition temperature in box accumulation of heat incinerator 42 is controlled at 950 DEG C,
Exhaust gas residence time is 2s, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, ethylene carbonate in exhaust gas and micro
Fluorine-containing phosphorus compound is fully oxidized at high temperature, generates carbon dioxide, water and micro hydrogen fluoride and phosphorus pentoxide, purification
The content of non-methane total hydrocarbons is less than 60mg/m in exhaust gas afterwards3, VOCs purification efficiency is 95%.
Waste heat recovery unit is made of waste-heat recovery device 5 and heat exchanger 6 (air-water heat exchanger), in lithium battery removal process
Contain large amount of organic component in the exhaust gas of generation, such as dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate and ethylene carbonate
Ester, after the burning of box accumulation of heat incinerator 42, a part of high-temperature flue gas enters in waste-heat recovery device 5 from furnace body side line for pair
Low middle pressure steam is produced, another part high-temperature flue gas is used to heat the heat storage in box accumulation of heat incinerator 42, and waste heat is after the recovery
Flue gas, which enters in heat exchanger 6, heats tap water, it is possible to provide hot water for life, so that waste heat recovery efficiency is further increased, energy conservation
Consumption reduction.
Alkali absorption unit is made of alkali adsorption tower 7, is entered in alkali adsorption tower 7 by the flue gas after the heat exchange cooling of heat exchanger 6,
The sodium hydroxide solution counter current contacting for being 10% with mass concentration, micro hydrogen fluoride is absorbed in flue gas, the fluorine in neat stress
Change hydrogen content and is less than 3mg/m3, can be directly discharged into atmosphere.
Treatment unit for waste water is made of neutralization chamber 8 and filter press 9, and working principle is same as Example 1.
[embodiment 3]
As shown in figure 3, in the present embodiment, waste gas cleaning system includes dust removing units, fluorine in a kind of lithium battery removal process
Removal unit, volatile organic matter removal unit, waste heat recovery unit, treatment unit for waste water and Alkali absorption unit.Wherein:
Dust removing units are made of dust-extraction unit 1, ash conveying device 10 and grey library, and dust-extraction unit 1 selects sack cleaner, work
It is same as Example 1 to make principle.The dustiness of exhaust gas is less than 10mg/m after purification3。
Fluorine removal unit is by 2, two sections of circulating absorption towers 3 of gas-liquid heat-exchange, alkaline absorption solution device for supplying 14, acid absorption
Liquid device for supplying 13 form, working principle is substantially the same manner as Example 1, acid absorbing liquid use mass fraction for 5% salt
The mixed liquor for the phosphoric acid that acid is 5% with mass fraction, alkaline absorption solution use mass fraction for 15% sodium hydroxide solution, pass through
After the purification of fluorine removal unit in exhaust gas the molar content of fluorine in 100ppm or less.
Volatile organic matter removal unit is by fire arrester 15, catalytic burning furnace 43 (being equipped with burner and combustion fan) group
At dedusting, the purified exhaust gas of defluorinate are sent into catalytic burning furnace 43 through blower 16, the ignition temperature control in catalytic burning furnace 43
At 300 DEG C, catalyst space velocities 20000h-1, select noble metal catalyst, dimethyl carbonate, diethyl carbonate, carbonic acid in exhaust gas
Methyl ethyl ester, ethylene carbonate are fully oxidized under hot-air and catalyst collective effect, carbon dioxide, water are generated, after purification
Non-methane total hydrocarbons content in exhaust gas is less than 20mg/m3, VOCs purification efficiency is 96%.
Waste heat recovery unit is made of heat exchanger 6 (gas-gas heat exchanger), and the medium temperature flue gas that catalytic burning furnace 43 generates passes through
Heat exchanger 6 preheats the exhaust gas after dedusting, to further increase the waste heat recovery efficiency of flue gas, reduces the combustion of catalytic burning furnace 43
Material consumption, energy saving reduce the operating cost of exhaust treatment system.
Alkali absorption unit is made of alkali adsorption tower 7, and the flue gas after the heat exchange of heat exchanger 6 enters in alkali adsorption tower 7, with quality
The sodium hydroxide solution counter current contacting that concentration is 10%, micro hydrogen fluoride is absorbed in flue gas, and the hydrogen fluoride in neat stress contains
Amount is less than 3mg/m3, atmosphere can be directly discharged into.
Treatment unit for waste water is made of neutralization chamber 8 and filter press 9, and working principle is same as Example 1.
Term used in this specification and form of presentation are merely used as term descriptive, and not restrictive and statement side
Formula is not intended to have indicated and any equivalent of the feature described or its component part when using these terms and form of presentation
Exclusion.
The above embodiment is only the preferred embodiment of the present invention, and the scope of protection of the present invention is not limited thereto,
Those of ordinary skill in the art are it should be recognized that can be to these embodiments in the case where not departing from principle of the present invention and spirit
Any flexible and improvement, protection scope of the present invention is carried out to be determined by the attached claims and its equivalent.
Claims (10)
1. exhaust gas purifying method in a kind of lithium battery removal process, which is characterized in that the exhaust gas generated in lithium battery removal process
Dust-laden particulate matter therein first is removed through dust-extraction unit, then through most fluorine-containing group in two sections of circulating absorption tower removing exhaust gas
Point, the exhaust gas after removing fluorine component removes volatile organic matter therein by high-temp combustion or medium temperature catalysis burning, then passes through
Enter the remaining micro hydrogen fluoride of alkali adsorption tower removal after waste heat recycling；The waste liquid that is generated in the above process import in neutralization chamber with
Alkaline reaction is neutralized, forms harmless solidfied material calcirm-fluoride and calcium phosphate after making fluorine therein, phosphorus solidification dehydration.
2. exhaust gas purifying method in a kind of lithium battery removal process according to claim 1, which is characterized in that specifically include
Following steps:
1) exhaust gas generated in lithium electricity removal process enters dust removing units through gas sampling pipeline, the dust-laden particulate matter quilt in exhaust gas
Temporary to grey library exhaust gas dustiness < 10mg/m after dedusting is sent after filtering out by ash conveying device3；
2) exhaust gas after dust separation is sent into fluorine removal unit, through gas-liquid heat-exchange and the absorbing liquid from two sections of circulating absorption towers
Heat exchange cooling, subsequently into two sections of circulating absorption towers；The lower section of two sections of circulating absorption towers is passed through acid absorbing liquid, big in exhaust gas
Partial phosphorus pentafluoride and hydrogen fluoride is removed；Wherein the phosphorus pentafluoride in exhaust gas is reacted with acid absorbing liquid generates containing fluorine phosphorus network
Object is closed, for the mixed solution after reaction after gas-liquid heat-exchange heats, fluorine-containing phosphorus complex is respectively formed hydrofluoric acid and phosphoric acid；Two
The upper section of section circulating absorption tower is passed through alkaline absorption solution, further absorbs the phosphorus pentafluoride and hydrogen fluoride escaped from lower section；Through
The molar content of fluorine is in 100ppm or less in the purified exhaust gas of fluorine removal unit；
3) through dedusting, the purified exhaust gas of defluorinate enter the incinerator in volatile organic matter removal unit carry out 850 DEG C~
1000 DEG C of high-temp combustions or 250 DEG C~350 DEG C catalysis burnings；Dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate in exhaust gas
Ester, ethylene carbonate and micro fluorine-containing phosphorus compound act on or are catalyzed combustion in high-temp combustion and be fully oxidized, and generate
Carbon dioxide, water and micro hydrogen fluoride and phosphorus pentoxide, remove volatile organic matter after exhaust gas in non-methane total hydrocarbons contain
Amount is less than 80mg/m3, VOCs purification efficiency is greater than 95%；
4) high-temperature flue gas that exhaust gas generates after high-temp combustion in step 3) enters waste heat recovery unit, is produced by waste-heat recovery device
Raw low middle pressure steam；Enter alkali adsorption tower after waste heat flue gas after the recovery passes through heat exchange cooling again；Or exhaust gas is fired through catalysis
The medium temperature flue gas generated after burning enters alkali adsorption tower after heat exchange cooling；
5) in alkali adsorption tower, flue gas and alkaline absorption solution counter current contacting, remaining micro hydrogen fluoride is absorbed in flue gas, is purified
Hydrogen fluoride content is less than 3mg/m in flue gas afterwards3；
6) relief liquor of the solution after gas-liquid heat-exchange heat resolve, the relief liquor of two sections of circulating absorption tower upper sections and alkali adsorption tower
It imports in neutralization chamber respectively, with neutralization alkaline reaction, fluorine therein and phosphorus are cured to form sediment, is dehydrated by filter press
Afterwards, the calcirm-fluoride and calcium phosphate of formation are harmless solidfied material.
3. exhaust gas purifying method in a kind of lithium battery removal process according to claim 2, which is characterized in that the gas-liquid
Heat exchanger heats acid absorbing liquid using the exhaust gas after dedusting as heat source, when heating dwell of the acid absorbing liquid in gas-liquid heat-exchange
Between be 60~600min, the flow channel of acid absorbing liquid is made of corrosion-resistant graphite material in gas-liquid heat-exchange.
4. exhaust gas purifying method in a kind of lithium battery removal process according to claim 2, which is characterized in that the acidity
Absorbing liquid is one of sulfuric acid, phosphoric acid, hydrofluoric acid, hydrochloric acid or a variety of any mixing；The mass fraction of acid absorbing liquid is 1%
~10%.
5. exhaust gas purifying method in a kind of lithium battery removal process according to claim 2, which is characterized in that the alkalinity
Absorbing liquid is the sodium hydroxide solution that mass fraction is 5%~20%.
6. exhaust gas purifying method in a kind of lithium battery removal process according to claim 2, which is characterized in that the burning
Furnace is using one of direct-combustion furnace, box accumulation of heat incinerator, rotation accumulation of heat incinerator, catalytic burning furnace；Wherein exhaust gas is in direct combustion
Furnace, box accumulation of heat incinerator, the ignition temperature rotated in accumulation of heat incinerator are 850 DEG C~1000 DEG C, and exhaust gas is in catalytic burning furnace
In reaction temperature be 250 DEG C~350 DEG C, air speed 15000h-1~25000h-1；Residence time of the exhaust gas in incinerator be
0.2s~5s.
7. exhaust gas purifying method in a kind of lithium battery removal process according to claim 2, which is characterized in that the neutralization
Lye is the calcium hydroxide solution that mass concentration is 5%~20% or magnesium hydroxide solution.
8. waste gas cleaning system in a kind of lithium battery removal process for realizing claim 2 the method, which is characterized in that
At dust removing units, fluorine removal unit, volatile organic matter removal unit, waste heat recovery unit, Alkali absorption unit and waste water
Manage unit；The dust removing units at least set dust-extraction unit, and fluorine removal unit at least sets gas-liquid heat-exchange and two sections of circulating absorption towers；
Volatile organic matter removal unit at least sets incinerator；Waste heat recovery unit is at least provided with heat exchanger or waste-heat recovery device and changes
Hot device；Alkali absorption unit at least sets alkali adsorption tower, and treatment unit for waste water at least sets neutralization chamber and filter press；
The gas sampling pipeline of the dusty gas entrance connection lithium battery recovery system of dust-extraction unit, the purification gas of dust-extraction unit
The gas phase entrance of outlet connection gas-liquid heat-exchange, the gaseous phase outlet of gas-liquid heat-exchange connect the exhaust gas of two sections of circulating absorption tower lower parts
Entrance；The lower section of two sections of circulating absorption towers is acid absorber portion, is equipped with acid absorbing liquid entrance, acid absorb is equipped with outside tower body
Liquid circulating line sets absorbing liquid cooler on acid absorbing liquid circulating line；In addition acid absorbing liquid circulating line connects gas-liquid
The liquid-phase outlet of the liquid phase entrance of heat exchanger, gas-liquid heat-exchange connects neutralization chamber；The upper section of two sections of circulating absorption towers is that alkalinity is inhaled
Section is received, alkaline absorption solution entrance is equipped with, is equipped with alkaline absorption solution circulating line outside tower body, alkaline absorption solution circulating line is in addition
Connect neutralization chamber；The exhaust gas entrance connection of the clean gas outlet and incinerator of two sections of cyclic absorption column overheads, the flue gas of incinerator
Export after heat exchanger or waste-heat recovery device and heat exchanger connect alkali adsorption tower bottom exhaust gas entrance, alkali adsorption tower it is upper
Portion sets Alkali absorption liquid entrance, and the outside of alkali adsorption tower sets lye circulating line, and in addition lye circulating line connects neutralization chamber, alkali is inhaled
It receives and sets clean gas outlet at the top of tower；It is set on neutralization chamber and neutralizes alkali liquor inlet and mixture export, mixture export connects filters pressing
Machine.
9. waste gas cleaning system in a kind of lithium battery removal process according to claim 8, which is characterized in that the dedusting
Device is sack cleaner, cyclone dust collectors or multicyclone, and dust-extraction unit inner wall is equipped with corrosion-resistant and wear-resistant material
Liner.
10. waste gas cleaning system in a kind of lithium battery removal process according to claim 8, which is characterized in that described two
Upper section, the lower section of section circulating absorption tower set filler respectively, filler using polyhedron empty ball, Taylor's garland, rectangular saddle ring, Pall ring,
Raschig ring or regular corrugation plate filler, filler material are polypropylene, reinforced polypropylene or polytetrafluoroethylene (PTFE).
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| CN110961432A (en) * | 2019-12-18 | 2020-04-07 | 晶科能源有限公司 | Photovoltaic module recovery method and device |
| CN111320154A (en) * | 2020-03-31 | 2020-06-23 | 福建省龙德新能源股份有限公司 | Method for recycling phosphorus pentafluoride in lithium hexafluorophosphate synthesis tail gas by utilizing ester and derivatives thereof |
| CN111939679A (en) * | 2020-07-06 | 2020-11-17 | 浙江天能新材料有限公司 | Flue gas dry purification treatment system and method in lithium battery recycling treatment process |
| CN112403235A (en) * | 2020-08-27 | 2021-02-26 | 万向一二三股份公司 | Multi-point source lithium ion battery electrolyte waste gas treatment device and method |
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| CN115041008A (en) * | 2022-06-30 | 2022-09-13 | 江苏泰瑞联腾材料科技有限公司 | Lithium hexafluorophosphate tail gas treatment process and device thereof |
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