CN108128953A - The exhaust gas and wastewater treatment equipment and method of a kind of waste lithium cell recycling cracking - Google Patents

The exhaust gas and wastewater treatment equipment and method of a kind of waste lithium cell recycling cracking Download PDF

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Publication number
CN108128953A
CN108128953A CN201711434854.0A CN201711434854A CN108128953A CN 108128953 A CN108128953 A CN 108128953A CN 201711434854 A CN201711434854 A CN 201711434854A CN 108128953 A CN108128953 A CN 108128953A
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water
exhaust gas
waste
tank
pump
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CN108128953B (en
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季宏飞
陈金明
李争
潘成程
杜润生
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Hefei Hengli Equipment Co Ltd
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Hefei Hengli Equipment Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
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    • 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
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    • 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
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    • B01D53/14—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 absorption
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    • 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
    • B01D53/14—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 absorption
    • B01D53/1425—Regeneration of liquid absorbents
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    • 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
    • B01D53/48—Sulfur compounds
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    • B01D53/46—Removing components of defined structure
    • B01D53/68—Halogens or halogen compounds
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    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00—Multistage treatment of water, waste water or sewage
    • 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
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/30—Alkali metal compounds
    • B01D2251/304—Alkali metal compounds of sodium
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
    • B01D2252/10—Inorganic absorbents
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
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    • B01D2253/102—Carbon
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    • C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
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    • C02F1/24—Treatment of water, waste water, or sewage by flotation
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    • C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
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    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
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    • C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
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Abstract

The present invention relates to the exhaust gas and wastewater treatment equipment and method of a kind of recycling cracking of waste lithium cell, and including exhaust gas treatment unit and treatment unit for waste water, method is：A. it by after burned waste gas, into lye spray absorber, is handled with sodium hydroxide solution spray-absorption, then the high altitude discharge after active carbon adsorber adsorption treatment；B. waste water is adjusted into pH value, reaction generation Na3AlF6Precipitation；C. fluorine removal waste water microelectrolysis processing removes clear organic matter subsequently into Fenton oxidation tower and reduces its COD；D. sandfiltration pot, absorbent charcoal adsorption tank and cation exchange resin column are sequentially entered and removes suspended matter, COD, calcium and magnesium ion；E. it is evaporated concentration into single effect evaporator；It realizes that exhaust-gas treatment meets the recycling water zero discharge after discharge standard, wastewater treatment and avoids nozzle, filler caused by recycling water to block, pump and pipeline blockage phenomenon.

Description

The exhaust gas and wastewater treatment equipment and method of a kind of waste lithium cell recycling cracking
Technical field
The present invention relates to exhaust gas field of wastewater, the more particularly to a kind of exhaust gas and wastewater treatment of waste lithium cell recycling cracking Method.
Background technology
The toxic heavy metal elements such as lithium battery is not mercurous, cadmium, lead, are referred to as " green battery ", but its positive and negative pole material, six The substances such as lithium fluophosphate electrolyte solution can cause seriously to pollute to environment and the ecosystem, while contain in discarded lithium battery A large amount of non-renewable and high economic value metals resources, such as cobalt, lithium, nickel, copper, aluminium, if can effectively be recycled useless It abandons or underproof lithium battery, pressure of the old and useless battery to environment can not only be mitigated, can also avoid that the metals such as cobalt, nickel is caused to provide The waste in source to reducing pollution, alleviating the problems such as scarcity of resources, has important social and economic significance.
It is put into 440 DEG C~500 DEG C of high temperature nitrogen protective atmosphere pyrolysis furnace and is sintered after the Dismantlement of waste lithium cell, Electrolyte, PP/PE battery diaphragms during 25-30min in waste lithium cell generate Pintsch process, and battery diaphragm PP/PE diaphragms are split Solution generates toxic waste gas containing fluoride, organic exhaust gas, nitrogen, CO, CO into tar, electrolyte pyrolysis2Wait harmful exhausts, organic exhaust gas Complicated component, main component and accounting are 2.07%, 1,3,5- trifluoro-benzene 0.49% of ethyl chloride, cyclohexene 0.08%, ring Hexyl isocyanates 0.25%, ethylene carbonate 71.4%, 1,2- dimethyl -4- tertiary butyl -6- cyclopenta benzene 0.56%, 1,3- Propane sultone 3.16%, fluorine-containing 10.09%, CO and CO211.9%, wherein ethyl chloride chance water resolves into ethylsulfonic acid Water is dissolved in, cyclohexyl isocyanate is reacted with water, and ethylene carbonate is dissolved in water, 160 DEG C of ethylene carbonate flash-point；Ethyl sulphonyl Burning can be cracked under chlorine, cyclohexyl isocyanate high temperature or is ignited.Different cultivars or the lithium battery electrolysis of different manufacturers production Liquid ingredient and formula are different, and the exhaust gas constituents and accounting that waste lithium cell is discharged when cracking are different.Using the single of routine Absorption process, oxidizing process, absorption method, bioanalysis, low-temperature plasma method etc. and single common process are such as：Burn oxygen Change method, absorption method, photocatalytic method, bioanalysis, low-temperature plasma ruling by law reason VOCs organic exhaust gas, bioxin processing are extremely difficult to GB9078-1996《Industrial furnace atmosphere pollutants emission standards》、GB30484-2013《Battery industry pollutant emission standard》、 GB18485-2014《Domestic waste incineration emission standard》And GB14554-1993《Emission standard for odor pollutants》 Primary standard.
Waste gas containing fluoride severe corrosion to equipment invests the waste gas containing fluoride processing equipment of high temperature high corrosion big, processing hardly possible, Conventional stage lye spray process tower purified treatment emission limit is extremely difficult to GB9078-1996《Industrial furnace atmosphere pollution Discharge standard》And GB30484-2013《Battery industry pollutant emission standard》5 standard of table；Inlet concentrations (in terms of fluorine) 180~200g/m3；Using in calcium hydroxide circulated sprinkling and absorbing, reservoir solution easily forms sludge, and when circulated sprinkling easily makes Into nozzle, filler blocking and pump and pipeline blockage, while the ultrafiltration membrane of water Treatment for Reuse can be caused to block, influence ultrafiltration membrane use Service life.
Wastewater treatment after exhaust-gas treatment makes heavy metal ion, at COD using Conventional waste water processing by materializing strategy Up to standard, then water reuse after ultrafiltration or reverse-osmosis treated is managed, but reusing rate is low, generally between 60%~80%, after reuse Water salinity is more and more denseer, returns in exhaust-gas treatment lye spray absorber and makees lye spray-water, nozzle, filler can be caused to block up It fills in, salinity crystallization is precipitated in solution in pump and pipeline, causes pump and pipeline blockage；Purified treatment film is caused to block simultaneously, equipment It is not normally functioning, maintenance cost is high.Organic wastewater, COD are under the conditions of no biochemical treatment in electrolyte, and COD processing is not up to To GB30484-2013《Battery industry pollutant emission standard》2 standard of table, the water COD after reuse is higher and higher, causes to purify Process film and recycle-water cannot use.
Invention content
Meet the recycling water zero-emission after discharge standard, wastewater treatment the purpose of the present invention is to provide a kind of exhaust-gas treatment It puts and avoids nozzle, filler caused by recycling water and block, the waste lithium cell recycling of pump and pipeline blockage is given up when cracking Gas and wastewater treatment equipment and method.
In order to achieve the above object, the technical solution adopted by the present invention is：A kind of exhaust gas of waste lithium cell recycling cracking and Wastewater treatment equipment, including exhaust gas treatment unit and treatment unit for waste water, the exhaust gas treatment unit includes being sequentially communicated useless Gas collecting pipe, surge tank, air mixer, organic exhaust gas electric cracking stove, cooling jacket, lye spray absorber I, lye spray Absorption tower II, exhaust blower and active carbon adsorber, the treatment unit for waste water includes the wastewater regulation tank being sequentially communicated, waste water carries Rise pump, coagulating slot, sloping plate deposition tower, intermediate pool, intermediate pool elevator pump, iron-carbon micro-electrolysis tower, Fenton oxidation tower, gas Floating pond, clear water reserviors, clear water reserviors elevator pump, sandfiltration pot, absorbent charcoal adsorption tank, cation exchange resin column, ultrafiltrate pump, ultrafiltration dress It puts, concentrate flow container I, concentrate elevator pump, single effect evaporator and condenser, the lye spray absorber I and lye spray are inhaled Tower II is received to connect with the wastewater regulation tank by discharge pipe.
The gas sampling pipe and surge tank lowermost end are respectively arranged with tar emission pipe plug I and tar emission pipe plug II, The coagulating slot has been respectively communicated with sulfuric acid automatic medicine adding apparatus, alum automatic stirring chemicals dosing plant.
The sloping plate deposition tower, Fenton oxidation tower and air supporting bottom of pond portion connect respectively with sludge pump I, and the sludge pump I goes out Mouth has been respectively communicated with sludge-tank, sludge pump II and filter press, and the filter press water outlet is connected with the wastewater regulation tank.
The Fenton oxidation tower has been respectively communicated with H2O2Automatic medicine adding apparatus, sulfuric acid automatic medicine adding apparatus and NaOH automatic stirrings Mix chemicals dosing plant.
Flowmeter is provided between the clear water reserviors elevator pump and sandfiltration pot, the ultrafiltration apparatus water outlet is communicated with light Water pot I, the fresh water tank I are connected by fresh water transfer pump with lye spray absorber I, lye spray absorber II.
The cation exchange resin column concentrated water outlet is connected with the concentration flow container I, the single effect evaporator concentrate Outlet has centrifuge, and the condenser condensation-water drain is sprayed by condensed water delivery pump and lye spray absorber I, lye Leaching absorption tower II connects.
A kind of exhaust gas and wastewater treatment method of waste lithium cell recycling cracking, include the following steps：
A. exhaust gas through gas sampling pipe and surge tank and is passed through air mixer and is mixed into fresh air to keep organic waste O in pneumoelectric pyrolysis furnace2Concentration be in 6%~10% after enter in organic exhaust gas electric cracking stove and carry out 2s~5s and fully crack and burn Burning-off tar removing, CO and volatile organic matter, the exhaust gas after burning are decomposed into water vapour and carbonated, the mixing of fluorine, sulphur Exhaust gas, water vapour and mix waste gas are quickly cooled to 150 DEG C through cooling jacket 0.5min~2min, reduce organic exhaust gas cracking and burn The generation of Hou bioxin is burnt, exhaust gas after cooling sequentially enters lye spray absorber I and lye spray absorber II, with spray Water is handled for the sodium hydroxide solution spray-absorption of mass concentration 3.5%~6%, removes the mixed gas of fluorine and sulphur through air draft High altitude discharge after machine, active carbon adsorber Adsorption bioxin, fluorine and sulphur content do not react generation fluorine with sodium hydroxide in exhaust gas The organic exhaust gas that change sodium and sodium hydrogensulfite and minute quantity are not easy to be ignited, burn, which is dissolved into shower water, forms waste water；
B. waste water enters wastewater regulation tank through lye spray absorber I and lye spray absorber II, then through waste water lifting Pump enters coagulating slot, while sulfuric acid automatic medicine adding apparatus and alum automatic stirring chemicals dosing plant respectively add sulfuric acid and alum Enter coagulating slot, adjust pH value to 6~8, react 30min~40min, generate Na3AlF6Precipitation, is treated after completion of the reaction, waste water Precipitation is carried out in into sloping plate deposition tower and forms fluorine removal waste water and sludge I, fluorine removal waste water enters intermediate pool；
C. fluorine removal waste water enters iron-carbon micro-electrolysis tower progress microelectrolysis processing through intermediate pool elevator pump, while micro- to iron carbon Air is passed through in electrolysis tower, air capacity is 3-5 times of fluorine removal wastewater flow rate, and subsequently into Fenton oxidation tower, while sulfuric acid adds automatically Medicine device and H2O2Automatic medicine adding apparatus is respectively by sulfuric acid and H2O2It adds in the progress pH adjustings of Fenton oxidation tower and oxidation processes is formed Sludge II and clear water I, then clear water I enter flotation tank, NaOH automatic stirrings chemicals dosing plant by NaOH add in flotation tank adjust pH Value is to 8.5~9, then is passed through air and carries out air-flotation process, removes the organic matter in clear water I and forms III He of sludge with its COD is reduced Clear water II, clear water II enter clear water reserviors；
D. clear water II sequentially enters sandfiltration pot, absorbent charcoal adsorption tank and cation through flowmeter by clear water reserviors elevator pump and sets Ester exchange column forms clear water III and concentrated water I after removing suspended matter, COD, calcium and magnesium ion, and clear water III enters ultrafiltration through ultrafiltrate pump and fills It puts to form permeate and concentrated water II；
E. concentrated water I and I concentrated liquid elevator pump of the entrance concentrated water of concentrated water II tank enter single effect evaporator and are evaporated concentration shape Into concentrate and steam, steam enters lye spray absorber I through condensed water delivery pump after entering condenser condensation and lye sprays Drench II reuse of absorption tower.
Sludge I, sludge II and sludge III in the sloping plate deposition tower, Fenton oxidation tower and flotation tank are beaten through sludge pump I Enter sludge-tank, then filter press press filtration is squeezed into mud cake through sludge pump II, mud cake outward transport is handed at the solid waste company that environmental protection administration specifies Reason, filter press water outlet enter wastewater regulation tank and reprocess, and the permeate enters after fresh water tank I is delivered to alkali through fresh water transfer pump II reuse of liquid spray absorber I and lye spray absorber, the concentrate enter centrifuge and are centrifuged to form sludge IV, sludge The solid waste company processing that environmental protection administration specifies is handed in IV outward transport.
It being burned in the step a and includes three phases, first stage organic exhaust gas electric cracking furnace temperature maintains 160~ 300 DEG C, second stage organic exhaust gas electric cracking furnace temperature maintains 300~730 DEG C, phase III organic exhaust gas electric cracking furnace temperature Degree maintains 730~870 DEG C.
By the device of the invention and method, exhaust gas enters organic exhaust gas through gas sampling pipe, surge tank, air mixer Electric cracking stove, which burn, removes tar removing, CO, volatile organic matter (VOCs), and the exhaust gas after burning is decomposed into water vapour and containing two Carbonoxide, fluorine, sulphur mix waste gas, water vapour and mix waste gas sequentially enter lye spray absorber I and alkali through cooling jacket Liquid spray absorber II is that the sodium hydroxide solution spray-absorption that mass concentration is 3.5%~6% is handled with shower water, removes The mixed gas of fluorine and sulphur high altitude discharge after exhaust blower, active carbon adsorber Adsorption bioxin meet discharge standard, spray Water drenching uses sodium hydroxide solution, avoids using Ca (OH)2Solution causes nozzle, filler blocking and pump and pipeline blockage to show As, extend ultrafiltration membrane service life, in exhaust gas fluorine and sulphur content react with sodium hydroxide generate sodium fluoride and sodium hydrogensulfite with And the minute quantity organic exhaust gas that is not easy to be ignited, burn is dissolved into shower water and forms waste water, waste water is through lye spray-absorption Tower I and lye spray absorber II enter wastewater regulation tank, then enter coagulating slot, while sulfuric acid is automatic through waste water lifting pump Sulfuric acid and alum are added in coagulating slot by chemicals dosing plant and alum automatic stirring chemicals dosing plant respectively, generate Na3AlF6Precipitation, It treats after completion of the reaction, waste water, which enters in sloping plate deposition tower precipitate, forms fluorine removal waste water and sludge I, and fluorine removal waste water enters centre Pond, fluorine removal waste water enter iron-carbon micro-electrolysis tower through intermediate pool elevator pump and carry out microelectrolysis processing, while to iron-carbon micro-electrolysis Air is passed through in tower, subsequently into Fenton oxidation tower, while sulfuric acid automatic medicine adding apparatus and H2O2Automatic medicine adding apparatus is respectively by sulphur Acid and H2O2It adds in Fenton oxidation tower and pH and oxidation processes formation sludge II and clear water I is adjusted, then clear water I enters air supporting NaOH is added in flotation tank and adjusts pH by pond, NaOH automatic stirrings chemicals dosing plant, then is passed through air and is carried out air-flotation process, removes clear water Organic matter and its COD of reduction formation sludge III and clear water II, clear water II in I enter clear water reserviors, and clear water II is carried by clear water reserviors Rise pump sequentially enters sandfiltration pot through flowmeter, absorbent charcoal adsorption tank and cation exchange resin column remove suspended matter, COD, calcium and Clear water III and concentrated water I are formed after magnesium ion, clear water III enters ultrafiltration apparatus through ultrafiltrate pump and forms permeate and concentrated water II, concentrated water I Enter I concentrated liquid elevator pump of concentrated water tank with concentrated water II and enter single effect evaporator and be evaporated concentration and form concentrate and steam, Steam enters after condenser condensation and enters II reuse of lye spray absorber I and lye spray absorber through condensed water delivery pump, Meet the recycling water zero discharge after discharge standard, wastewater treatment so as to fulfill exhaust-gas treatment and avoid caused by recycling water Nozzle, filler block, pump and pipeline blockage phenomenon.
Description of the drawings
Fig. 1 is the structure chart of the present invention.
Specific embodiment
With reference to Fig. 1, the present invention is described in further detail.
A kind of exhaust gas and wastewater treatment equipment of waste lithium cell recycling cracking, including exhaust gas treatment unit and wastewater treatment Unit, the exhaust gas treatment unit include the gas sampling pipe 1, surge tank 2, air mixer 3, the organic waste pneumoelectric that are sequentially communicated Pyrolysis furnace 4, cooling jacket 5, lye spray absorber I 6, lye spray absorber II 7, exhaust blower 8 and active carbon adsorber 39, The treatment unit for waste water includes the wastewater regulation tank 9 being sequentially communicated, waste water lifting pump 10, coagulating slot 11, sloping plate deposition Tower 12, intermediate pool 13, intermediate pool elevator pump 14, iron-carbon micro-electrolysis tower 15, Fenton oxidation tower 16, flotation tank 17, clear water reserviors 18th, clear water reserviors elevator pump 19, sandfiltration pot 20, absorbent charcoal adsorption tank 21, cation exchange resin column 22, ultrafiltrate pump 23, ultrafiltration dress Put 24, concentration flow container I 25, concentrate elevator pump 26, single effect evaporator 27 and condenser 28, I 6 He of lye spray absorber Lye spray absorber II 7 is connected by discharge pipe with the wastewater regulation tank 9.
The gas sampling pipe 1 and 2 lowermost end of surge tank are respectively arranged with tar emission pipe plug I and tar emission pipe plug II, the coagulating slot 11 has been respectively communicated with sulfuric acid automatic medicine adding apparatus 29, alum automatic stirring chemicals dosing plant 30.
The sloping plate deposition tower 12, Fenton oxidation tower 16 and 17 bottom of flotation tank connect respectively with sludge pump I 31, the dirt The outlet of dredge pump I 31 has been respectively communicated with sludge-tank 32, sludge pump II 33 and filter press 34, and 34 water outlet of filter press gives up with described Water regulating tank 9 connects.
The Fenton oxidation tower 16 has been respectively communicated with H2O2Automatic medicine adding apparatus 35, sulfuric acid automatic medicine adding apparatus 36 and NaOH Automatic stirring chemicals dosing plant 37.
Flowmeter is provided between the clear water reserviors elevator pump 19 and sandfiltration pot 20,24 water outlet of ultrafiltration apparatus connects Fresh water tank I 38 is connected with, the fresh water tank I 38 passes through fresh water transfer pump and lye spray absorber I 6 and lye spray absorber II 7 connections.
22 concentrated water of the cation exchange resin column outlet is connected with the concentration flow container I 25, the single effect evaporator 27 Concentrated solution outlet is communicated with centrifuge, and 28 condensation-water drain of condenser passes through condensed water delivery pump and lye spray absorber I 6 connect with lye spray absorber II 7.
Embodiment 1 based on above device, includes the following steps：
A. exhaust gas through gas sampling pipe and surge tank and is passed through air mixer and is mixed into fresh air to keep organic waste O in pneumoelectric pyrolysis furnace2Concentration be in 6% after enter in organic exhaust gas electric cracking stove and carry out 2s and fully crack burning and go to devoke Oil, CO, volatile organic matter (VOCs), the exhaust gas after burning is decomposed into water vapour and carbonated, the mixing of fluorine, sulphur are given up Gas, water vapour and mix waste gas are quickly cooled to 150 DEG C through cooling jacket 2min, reduce organic exhaust gas cracking and burn Hou bioxin Generation, exhaust gas after cooling sequentially enters lye spray absorber I and lye spray absorber II, is that quality is dense with shower water The sodium hydroxide solution spray-absorption processing for 3.5% is spent, removes the mixed gas of fluorine and sulphur through exhaust blower, active carbon adsorber High altitude discharge after Adsorption bioxin, fluorine and sulphur content do not react generation sodium fluoride and sodium hydrogensulfite with sodium hydroxide in exhaust gas And the minute quantity organic exhaust gas that is not easy to be ignited, burn is dissolved into shower water and forms waste water；
B. waste water enters wastewater regulation tank through lye spray absorber I and lye spray absorber II, then through waste water lifting Pump enters coagulating slot, while sulfuric acid automatic medicine adding apparatus and alum automatic stirring chemicals dosing plant respectively add sulfuric acid and alum Enter coagulating slot, adjust pH value to 6, react 30min, generate Na3AlF6Precipitation, is treated after completion of the reaction, waste water enters inclined plate and sinks Precipitation is carried out in the tower of shallow lake and forms fluorine removal waste water and sludge I, fluorine removal waste water enters intermediate pool；
C. fluorine removal waste water enters iron-carbon micro-electrolysis tower progress microelectrolysis processing through intermediate pool elevator pump, while micro- to iron carbon Air is passed through in electrolysis tower, air capacity is 3 times of fluorine removal wastewater flow rate, subsequently into Fenton oxidation tower, while sulfuric acid Automatic Dosing Device and H2O2Automatic medicine adding apparatus is respectively by sulfuric acid and H2O2It adds in the progress pH adjustings of Fenton oxidation tower and oxidation processes forms dirt Mud II and clear water I, then clear water I enter flotation tank, NaOH automatic stirrings chemicals dosing plant by NaOH add in flotation tank adjust pH value It to 8.5, then is passed through air and carries out air-flotation process, remove the organic matter in clear water I and reduce its COD formation sludge III and clear water II, clear water II enters clear water reserviors；
D. clear water II sequentially enters sandfiltration pot, absorbent charcoal adsorption tank and cation through flowmeter by clear water reserviors elevator pump and sets Ester exchange column forms clear water III and concentrated water I after removing suspended matter, COD, calcium and magnesium ion, and clear water III enters ultrafiltration through ultrafiltrate pump and fills It puts to form permeate and concentrated water II；
E. concentrated water I and I concentrated liquid elevator pump of the entrance concentrated water of concentrated water II tank enter single effect evaporator and are evaporated concentration shape Into concentrate and steam, steam enters lye spray absorber I through condensed water delivery pump after entering condenser condensation and lye sprays Drench II reuse of absorption tower.
Sludge I, sludge II and sludge III in the sloping plate deposition tower, Fenton oxidation tower and flotation tank are beaten through sludge pump I Enter sludge-tank, then filter press press filtration is squeezed into mud cake through sludge pump II, mud cake outward transport is handed at the solid waste company that environmental protection administration specifies Reason, filter press water outlet enter wastewater regulation tank and reprocess, and the permeate enters after fresh water tank I is delivered to alkali through fresh water transfer pump II reuse of liquid spray absorber I and lye spray absorber, the concentrate enter centrifuge and are centrifuged to form sludge IV, sludge The solid waste company processing that environmental protection administration specifies is handed in IV outward transport.
It being burned in the step a and includes three phases, first stage organic exhaust gas electric cracking furnace temperature maintains 160 DEG C, Second stage organic exhaust gas electric cracking furnace temperature maintains 300 DEG C, and phase III organic exhaust gas electric cracking furnace temperature maintains 730 ℃。
Non-methane total hydrocarbons is 30mg/m from the exhaust gas of exhaust blower waste discharge mouth detection high altitude discharge3, fluorine content 5mg/m3、 Dioxin 0.07ngITEQ/Nm3, sulphur-containing exhaust gas be detected as 0mg/m3, the fluorine content from intermediate pool detection fluorine removal waste water is 6mg/ L takes clear water III to detect COD contents and is 55mg/L, is accorded with so as to fulfill exhaust-gas treatment from cation exchange resin column supernatant outlet It closes the recycling water zero discharge after discharge standard, wastewater treatment and avoids nozzle, filler caused by recycling water and block, pump And pipeline blockage phenomenon.
Embodiment 2 based on above device, includes the following steps：
A. exhaust gas through gas sampling pipe and surge tank and is passed through air mixer and is mixed into fresh air to keep organic waste O in pneumoelectric pyrolysis furnace2Concentration be in 8% after enter in organic exhaust gas electric cracking stove and carry out 3.5s and fully crack burning and go to devoke Oil, CO, volatile organic matter (VOCs), the exhaust gas after burning is decomposed into water vapour and carbonated, the mixing of fluorine, sulphur are given up Gas, water vapour and mix waste gas are quickly cooled to 150 DEG C through cooling jacket 1.25min, reduce two after organic exhaust gas cracking is burned Evil English generates, and exhaust gas after cooling sequentially enters lye spray absorber I and lye spray absorber II, is matter with shower water A concentration of 4.75% sodium hydroxide solution spray-absorption processing is measured, removes the mixed gas of fluorine and sulphur through exhaust blower, activated carbon High altitude discharge after absorber Adsorption bioxin, fluorine and sulphur content do not react generation sodium fluoride and sulfurous with sodium hydroxide in exhaust gas The organic exhaust gas that sour hydrogen sodium and minute quantity are not easy to be ignited, burn, which is dissolved into shower water, forms waste water；
B. waste water enters wastewater regulation tank through lye spray absorber I and lye spray absorber II, then through waste water lifting Pump enters coagulating slot, while sulfuric acid automatic medicine adding apparatus and alum automatic stirring chemicals dosing plant respectively add sulfuric acid and alum Enter coagulating slot, adjust pH value to 7, react 35min, generate Na3AlF6Precipitation, is treated after completion of the reaction, waste water enters inclined plate and sinks Precipitation is carried out in the tower of shallow lake and forms fluorine removal waste water and sludge I, fluorine removal waste water enters intermediate pool；
C. fluorine removal waste water enters iron-carbon micro-electrolysis tower progress microelectrolysis processing through intermediate pool elevator pump, while micro- to iron carbon Air is passed through in electrolysis tower, air capacity is 4 times of fluorine removal wastewater flow rate, subsequently into Fenton oxidation tower, while sulfuric acid Automatic Dosing Device and H2O2Automatic medicine adding apparatus is respectively by sulfuric acid and H2O2It adds in the progress pH adjustings of Fenton oxidation tower and oxidation processes forms dirt Mud II and clear water I, then clear water I enter flotation tank, NaOH automatic stirrings chemicals dosing plant by NaOH add in flotation tank adjust pH value It to 8.7, then is passed through air and carries out air-flotation process, remove the organic matter in clear water I and reduce its COD formation sludge III and clear water II, clear water II enters clear water reserviors；
D. clear water II sequentially enters sandfiltration pot, absorbent charcoal adsorption tank and cation through flowmeter by clear water reserviors elevator pump and sets Ester exchange column forms clear water III and concentrated water I after removing suspended matter, COD, calcium and magnesium ion, and clear water III enters ultrafiltration through ultrafiltrate pump and fills It puts to form permeate and concentrated water II；
E. concentrated water I and I concentrated liquid elevator pump of the entrance concentrated water of concentrated water II tank enter single effect evaporator and are evaporated concentration shape Into concentrate and steam, steam enters lye spray absorber I through condensed water delivery pump after entering condenser condensation and lye sprays Drench II reuse of absorption tower.
Sludge I, sludge II and sludge III in the sloping plate deposition tower, Fenton oxidation tower and flotation tank are beaten through sludge pump I Enter sludge-tank, then filter press press filtration is squeezed into mud cake through sludge pump II, mud cake outward transport is handed at the solid waste company that environmental protection administration specifies Reason, filter press water outlet enter wastewater regulation tank and reprocess, and the permeate enters after fresh water tank I is delivered to alkali through fresh water transfer pump II reuse of liquid spray absorber I and lye spray absorber, the concentrate enter centrifuge and are centrifuged to form sludge IV, sludge The solid waste company processing that environmental protection administration specifies is handed in IV outward transport.
It being burned in the step a and includes three phases, first stage organic exhaust gas electric cracking furnace temperature maintains 230 DEG C, Second stage organic exhaust gas electric cracking furnace temperature maintains 515 DEG C, and phase III organic exhaust gas electric cracking furnace temperature maintains 800 ℃。
Non-methane total hydrocarbons is 16mg/m from the exhaust gas of exhaust blower waste discharge mouth detection high altitude discharge3, fluorine content 4mg/m3、 Dioxin 0.05ngITEQ/Nm3, sulphur-containing exhaust gas be detected as 0mg/m3, from intermediate pool detection fluorine removal waste water fluorine content be 4.6mg/L, it is 51mg/L clear water III to be taken to detect COD contents from cation exchange resin column supernatant outlet, so as to fulfill exhaust gas It handles the recycling water zero discharge after meeting discharge standard, wastewater treatment and avoids nozzle, filler caused by recycling water It blocks, pump and pipeline blockage phenomenon.
Embodiment 3 based on above device, includes the following steps：
A. exhaust gas through gas sampling pipe and surge tank and is passed through air mixer and is mixed into fresh air to keep organic waste O in pneumoelectric pyrolysis furnace2Concentration be in 10% after enter in organic exhaust gas electric cracking stove and carry out 5s and fully crack burning and go to devoke Oil, CO, volatile organic matter (VOCs), the exhaust gas after burning is decomposed into water vapour and carbonated, the mixing of fluorine, sulphur are given up Gas, water vapour and mix waste gas are quickly cooled to 150 DEG C through cooling jacket 0.5min, reduce organic exhaust gas cracking and burn Hou bis- Evil English generates, and exhaust gas after cooling sequentially enters lye spray absorber I and lye spray absorber II, is quality with shower water A concentration of 6% sodium hydroxide solution spray-absorption processing, removes the mixed gas of fluorine and sulphur through exhaust blower, active carbon adsorber High altitude discharge after Adsorption bioxin, fluorine and sulphur content do not react generation sodium fluoride and sodium hydrogensulfite with sodium hydroxide in exhaust gas And the minute quantity organic exhaust gas that is not easy to be ignited, burn is dissolved into shower water and forms waste water；
B. waste water enters wastewater regulation tank through lye spray absorber I and lye spray absorber II, then through waste water lifting Pump enters coagulating slot, while sulfuric acid automatic medicine adding apparatus and alum automatic stirring chemicals dosing plant respectively add sulfuric acid and alum Enter coagulating slot, adjust pH value to 8, react 40min, generate Na3AlF6Precipitation, is treated after completion of the reaction, waste water enters inclined plate and sinks Precipitation is carried out in the tower of shallow lake and forms fluorine removal waste water and sludge I, fluorine removal waste water enters intermediate pool；
C. fluorine removal waste water enters iron-carbon micro-electrolysis tower progress microelectrolysis processing through intermediate pool elevator pump, while micro- to iron carbon Air is passed through in electrolysis tower, air capacity is 5 times of fluorine removal wastewater flow rate, subsequently into Fenton oxidation tower, while sulfuric acid Automatic Dosing Device and H2O2Automatic medicine adding apparatus is respectively by sulfuric acid and H2O2It adds in the progress pH adjustings of Fenton oxidation tower and oxidation processes forms dirt Mud II and clear water I, then clear water I enter flotation tank, NaOH automatic stirrings chemicals dosing plant by NaOH add in flotation tank adjust pH value It to 9, then is passed through air and carries out air-flotation process, remove the organic matter in clear water I and reduce its COD formation sludge III and clear water II, Clear water II enters clear water reserviors；
D. clear water II sequentially enters sandfiltration pot, absorbent charcoal adsorption tank and cation through flowmeter by clear water reserviors elevator pump and sets Ester exchange column forms clear water III and concentrated water I after removing suspended matter, COD, calcium and magnesium ion, and clear water III enters ultrafiltration through ultrafiltrate pump and fills It puts to form permeate and concentrated water II；
E. concentrated water I and I concentrated liquid elevator pump of the entrance concentrated water of concentrated water II tank enter single effect evaporator and are evaporated concentration shape Into concentrate and steam, steam enters lye spray absorber I through condensed water delivery pump after entering condenser condensation and lye sprays Drench II reuse of absorption tower.
Sludge I, sludge II and sludge III in the sloping plate deposition tower, Fenton oxidation tower and flotation tank are beaten through sludge pump I Enter sludge-tank, then filter press press filtration is squeezed into mud cake through sludge pump II, mud cake outward transport is handed at the solid waste company that environmental protection administration specifies Reason, filter press water outlet enter wastewater regulation tank and reprocess, and the permeate enters after fresh water tank I is delivered to alkali through fresh water transfer pump II reuse of liquid spray absorber I and lye spray absorber, the concentrate enter centrifuge and are centrifuged to form sludge IV, sludge The solid waste company processing that environmental protection administration specifies is handed in IV outward transport.
It being burned in the step a and includes three phases, first stage organic exhaust gas electric cracking furnace temperature maintains 300 DEG C, Second stage organic exhaust gas electric cracking furnace temperature maintains 730 DEG C, and phase III organic exhaust gas electric cracking furnace temperature maintains 870 ℃。
Non-methane total hydrocarbons is 4mg/m from the exhaust gas of exhaust blower waste discharge mouth detection high altitude discharge3, fluorine content 1.1mg/m3、 Dioxin 0.02ngITEQ/Nm3, sulphur-containing exhaust gas be detected as 0mg/m3, from intermediate pool detection fluorine removal waste water fluorine content be 3.8mg/L, it is 46mg/L clear water III to be taken to detect COD contents from cation exchange resin column supernatant outlet, so as to fulfill exhaust gas It handles the recycling water zero discharge after meeting discharge standard, wastewater treatment and avoids nozzle, filler caused by recycling water It blocks, pump and pipeline blockage phenomenon.
Embodiment described above is only that the preferred embodiment of the present invention is described, not to the model of the present invention It encloses and is defined, under the premise of design spirit of the present invention is not departed from, those of ordinary skill in the art are to the technical side of the present invention The various modifications and improvement that case is made should all be fallen into the protection domain that claims of the present invention determines.

Claims (9)

1. a kind of exhaust gas and wastewater treatment equipment of waste lithium cell recycling cracking, it is characterised in that：Including exhaust gas treatment unit And treatment unit for waste water, the exhaust gas treatment unit include the gas sampling pipe being sequentially communicated（1）, surge tank（2）, air mixing Device（3）, organic exhaust gas electric cracking stove（4）, cooling jacket（5）, lye spray absorber I（6）, lye spray absorber II（7）、 Exhaust blower（8）With active carbon adsorber (39), the treatment unit for waste water includes the wastewater regulation tank being sequentially communicated（9）, waste water Elevator pump（10）, coagulating slot（11）, sloping plate deposition tower（12）, intermediate pool（13）, intermediate pool elevator pump（14）, iron carbon Light electrolysis tower（15）, Fenton oxidation tower（16）, flotation tank（17）, clear water reserviors（18）, clear water reserviors elevator pump（19）, sandfiltration pot （20）, absorbent charcoal adsorption tank（21）, cation exchange resin column（22）, ultrafiltrate pump（23）, ultrafiltration apparatus（24）, concentration flow container I （25）, concentrate elevator pump（26）, single effect evaporator（27）And condenser（28）, the lye spray absorber I（6）And lye Spray absorber II（7）Pass through discharge pipe and the wastewater regulation tank（9）Connection.
2. the exhaust gas and wastewater treatment equipment of a kind of waste lithium cell recycling cracking according to claim 1, feature exist In：The gas sampling pipe（1）And surge tank（2）Lowermost end is respectively arranged with tar emission pipe plug I and tar emission pipe plug II, The coagulating slot（11）It has been respectively communicated with sulfuric acid automatic medicine adding apparatus（29）, alum automatic stirring chemicals dosing plant（30）.
3. the exhaust gas and wastewater treatment equipment of a kind of waste lithium cell recycling cracking according to claim 1, feature exist In：The sloping plate deposition tower（12）, Fenton oxidation tower（16）And flotation tank（17）Bottom respectively with sludge pump I（31）Connection, institute State sludge pump I（31）Outlet has been respectively communicated with sludge-tank（32）, sludge pump II（33）And filter press（34）, the filter press（34） Water outlet and the wastewater regulation tank（9）Connection.
4. the exhaust gas and wastewater treatment equipment of a kind of waste lithium cell recycling cracking according to claim 1, feature exist In：The Fenton oxidation tower（16）It has been respectively communicated with H2O2Automatic medicine adding apparatus（35）, sulfuric acid automatic medicine adding apparatus（36）And NaOH Automatic stirring chemicals dosing plant（37）.
5. the exhaust gas and wastewater treatment equipment of a kind of waste lithium cell recycling cracking according to claim 1, feature exist In：The clear water reserviors elevator pump（19）With sandfiltration pot（20）Between be provided with flowmeter, the ultrafiltration apparatus（24）Water outlet It is communicated with fresh water tank I（38）, the fresh water tank I（38）Pass through fresh water transfer pump and lye spray absorber I（6）It is sprayed with lye Absorption tower II（7）Connection.
6. the exhaust gas and wastewater treatment equipment of a kind of waste lithium cell recycling cracking according to claim 1, feature exist In：The cation exchange resin column（22）Concentrated water exports and the concentration flow container I（25）Connection, the single effect evaporator（27） Concentrated solution outlet is communicated with centrifuge, the condenser（28）Condensation-water drain passes through condensed water delivery pump and lye spray-absorption Tower I（6）With lye spray absorber II（7）Connection.
7. a kind of exhaust gas and wastewater treatment method of waste lithium cell recycling cracking, it is characterised in that include the following steps：
A. exhaust gas through gas sampling pipe and surge tank and is passed through air mixer and is mixed into fresh air to keep organic exhaust gas electric O in pyrolysis furnace2Concentration be in 6%~10% after enter organic exhaust gas electric cracking stove in carry out 2s~5s fully crack burning removal Tar, CO and volatile organic matter, the exhaust gas after burning are decomposed into the mix waste gas of water vapour and carbonated, fluorine, sulphur, water Steam and mix waste gas are quickly cooled to 150 DEG C through cooling jacket 0.5min~2min, reduce two after organic exhaust gas cracking is burned Evil English generates, and exhaust gas after cooling sequentially enters lye spray absorber I and lye spray absorber II, is matter with shower water The sodium hydroxide solution spray-absorption processing of concentration 3.5%~6% is measured, removes the mixed gas of fluorine and sulphur through exhaust blower, activated carbon High altitude discharge after absorber Adsorption bioxin, fluorine and sulphur content do not react generation sodium fluoride and sulfurous with sodium hydroxide in exhaust gas The organic exhaust gas that sour hydrogen sodium and minute quantity are not easy to be ignited, burn, which is dissolved into shower water, forms waste water；
B. waste water enters wastewater regulation tank through lye spray absorber I and lye spray absorber II, then through waste water lifting pump into Enter coagulating slot, while sulfuric acid and alum are added in mix respectively by sulfuric acid automatic medicine adding apparatus and alum automatic stirring chemicals dosing plant Solidifying reactive tank adjusts pH value to 6~8, reacts 30min~40min, generate Na3AlF6Precipitation, is treated after completion of the reaction, and waste water enters Precipitation is carried out in sloping plate deposition tower and forms fluorine removal waste water and sludge I, fluorine removal waste water enters intermediate pool；
C. fluorine removal waste water enters iron-carbon micro-electrolysis tower through intermediate pool elevator pump and carries out microelectrolysis processing, while to iron-carbon micro-electrolysis Air is passed through in tower, air capacity is 3-5 times of fluorine removal wastewater flow rate, and subsequently into Fenton oxidation tower, while sulfuric acid Automatic Dosing fills It puts and H2O2Automatic medicine adding apparatus is respectively by sulfuric acid and H2O2It adds in Fenton oxidation tower and carries out pH adjustings and oxidation processes formation sludge II and clear water I, then clear water I enter flotation tank, NaOH automatic stirrings chemicals dosing plant by NaOH add in flotation tank adjust pH value to 8.5~9, then be passed through air and carry out air-flotation process, remove the organic matter in clear water I and reduce its COD formation sludge III and clear water II, clear water II enters clear water reserviors；
D. clear water II sequentially enters sandfiltration pot, absorbent charcoal adsorption tank and resin cation through flowmeter by clear water reserviors elevator pump and hands over Clear water III is formed after changing column removing suspended matter, COD, calcium and magnesium ion and concentrated water I, clear water III enter ultrafiltration apparatus shape through ultrafiltrate pump Into permeate and concentrated water II；
E. concentrated water I and concentrated water II enter I concentrated liquid elevator pump of concentrated water tank enter single effect evaporator be evaporated concentration formed it is dense Contracting liquid and steam, steam enters lye spray absorber I through condensed water delivery pump after entering condenser condensation and lye spray is inhaled Receive II reuse of tower.
8. the exhaust gas and wastewater treatment method of a kind of waste lithium cell recycling cracking according to claim 7, feature exist In：Sludge I, sludge II and sludge III in the sloping plate deposition tower, Fenton oxidation tower and flotation tank squeeze into sludge through sludge pump I Pond, then filter press press filtration is squeezed into mud cake through sludge pump II, the solid waste company processing that environmental protection administration specifies, press filtration are handed in mud cake outward transport Machine water outlet enters wastewater regulation tank and reprocesses, and the permeate enters after fresh water tank I is delivered to lye spray through fresh water transfer pump II reuse of absorption tower I and lye spray absorber, the concentrate enter centrifuge and are centrifuged to form sludge IV, and sludge IV is transported outward Hand over the solid waste company processing that environmental protection administration specifies.
9. the exhaust gas and wastewater treatment method of a kind of waste lithium cell recycling cracking according to claim 7, feature exist In：It being burned in the step a and includes three phases, first stage organic exhaust gas electric cracking furnace temperature maintains 160~300 DEG C, Second stage organic exhaust gas electric cracking furnace temperature maintains 300~730 DEG C, and phase III organic exhaust gas electric cracking furnace temperature maintains At 730~870 DEG C.
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