CN108128953B - Waste gas and wastewater treatment device and method for recycling and cracking waste lithium batteries - Google Patents

Waste gas and wastewater treatment device and method for recycling and cracking waste lithium batteries Download PDF

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CN108128953B
CN108128953B CN201711434854.0A CN201711434854A CN108128953B CN 108128953 B CN108128953 B CN 108128953B CN 201711434854 A CN201711434854 A CN 201711434854A CN 108128953 B CN108128953 B CN 108128953B
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CN108128953A (en
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季宏飞
陈金明
李争
潘成程
杜润生
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Hengli Eletek Co ltd
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Abstract

The invention relates to a waste gas and wastewater treatment device and method for recycling and cracking waste lithium batteries, wherein the device comprises a waste gas treatment unit and a wastewater treatment unit, and the method comprises the following steps: a. burning the waste gas, introducing into an alkali liquor spray absorption tower, spraying and absorbing with sodium hydroxide solution, adsorbing with an activated carbon adsorber, and discharging at high altitude; b. adjusting the pH value of the wastewater, and reacting to generate Na3AlF6Precipitating; c. the defluorination wastewater is subjected to micro-electrolysis treatment and then enters a Fenton oxidation tower to remove clear organic matters and reduce COD of the clear organic matters; d. sequentially entering a sand filter tank, an activated carbon adsorption tank and a cation resin exchange column to remove suspended matters, COD, calcium and magnesium ions; e. entering a single-effect evaporator for evaporation and concentration; the waste gas treatment meets the discharge standard, the zero discharge of the recycled water after the waste water treatment is realized, and the phenomena of nozzle and filler blockage, pump and pipeline blockage caused by the recycled water are avoided.

Description

Waste gas and wastewater treatment device and method for recycling and cracking waste lithium batteries
Technical Field
The invention relates to the field of waste gas and waste water, in particular to a waste gas and waste water treatment method for recycling and cracking waste lithium batteries.
Background
The lithium battery does not contain harmful heavy metal elements such as mercury, cadmium, lead and the like, is called as a green battery, but substances such as anode and cathode materials, lithium hexafluorophosphate electrolyte solution and the like can cause serious pollution to the environment and an ecological system, meanwhile, the waste lithium battery contains a large amount of non-renewable metal resources with high economic value such as cobalt, lithium, nickel, copper, aluminum and the like, if the waste or unqualified lithium battery can be effectively recycled, the pressure of the waste battery on the environment can be relieved, the waste of metal resources such as cobalt, nickel and the like can be avoided, the problems of pollution reduction, resource shortage and the like can be relieved, and the green battery has important social and economic significance.
The waste lithium battery is recycled and disassembled and then placed into a high-temperature nitrogen protective atmosphere cracking furnace with the temperature of 440-500 ℃ for sintering, when the time of 25-30min is up to the high temperature, the electrolyte and the PP/PE battery diaphragm in the waste lithium battery are cracked, the battery diaphragm PP/PE diaphragm is cracked into tar, the electrolyte is pyrolyzed to generate toxic fluorine-containing waste gas, organic waste gas, nitrogen, CO and CO2The organic waste gas of the harmful waste gas has complex organic waste gas components, and the main components and the proportions of the main components are 2.07 percent of ethyl sulfonyl chloride, 0.49 percent of 1, 3, 5-trifluoro-benzene, 0.08 percent of cyclohexene, 0.25 percent of cyclohexyl isocyanate, 71.4 percent of ethylene carbonate, 0.56 percent of 1, 2-dimethyl-4-tert-butyl-6-cyclopentyl benzene, 3.16 percent of 1, 3-propane sultone, 10.09 percent of fluorine, CO and CO211.9 percent, wherein the ethylsulfonyl chloride is decomposed into ethylsulfonic acid in water and is also dissolved in water, the cyclohexyl isocyanate is reacted with the water, the ethylene carbonate is dissolved in the water, and the flash point of the ethylene carbonate is 160 ℃; the ethyl sulfonyl chloride and cyclohexyl isocyanate can be cracked and burnt or ignited at high temperature. Lithium battery electrolytes produced by different varieties or different manufacturers have different components and formulas, and waste gas components and proportions discharged when waste lithium batteries are cracked are different. The conventional single absorption method, oxidation method, adsorption method, biological method, low-temperature plasma method and the like are adopted, and the single common process method is as follows: the treatment of VOCs organic waste gas and dioxin by a combustion oxidation method, an adsorption method, a photocatalysis method, a biological method and a low-temperature plasma method is difficult to reach the primary standards of GB9078-1996 atmospheric pollutant emission standard of industrial furnaces, GB30484-2013 emission standard of battery industrial pollutants, GB18485-2014 pollution emission standard of domestic garbage incinerators and GB14554-1993 malodorous pollutant emission standard.
The fluorine-containing waste gas has serious corrosion to equipment, the equipment investment is large for high-temperature and high-corrosion fluorine-containing waste gas treatment equipment, the treatment is difficult, and the emission limit value of the purification treatment of a conventional primary alkali liquor spraying treatment tower is difficult to reach the standard shown in table 5 of GB9078-1996 emission standard of atmospheric pollutants for industrial furnaces and GB30484-2013 emission standard of pollutants for batteries; the concentration of the air inlet (calculated by fluorine) is 180-200 g/m3(ii) a Calcium hydroxide is adopted for circulating spraying and neutralizing absorption, sludge is easily formed in a liquid storage tank solution, a nozzle, a filler and a pump and a pipeline are easily blocked during circulating spraying, and an ultrafiltration membrane for water recycling treatment is blocked, so that the service life of the ultrafiltration membrane is influenced.
The waste water treatment after waste gas treatment adopts conventional waste water treatment, namely heavy metal ions and COD treatment reach the standard through physicochemical treatment, and water is recycled after ultrafiltration or reverse osmosis treatment, but the water recycling rate is low and is generally between 60% and 80%, the recycled water has more and more concentrated salt, and the salt returns to a waste gas treatment alkali liquor spraying absorption tower to be used as alkali liquor spraying water, so that nozzles and fillers are blocked, and salt in solution in a pump and a pipeline is crystallized and separated out, so that the pump and the pipeline are blocked; meanwhile, the purification treatment membrane is blocked, the equipment cannot normally operate, and the maintenance cost is high. Under the condition of no biochemical treatment, the COD treatment of the organic wastewater and COD in the electrolyte can not reach the standard shown in Table 2 of GB30484-2013 discharge Standard of pollutants for Battery industry, and the COD of the reclaimed water is higher and higher, so that a purification treatment membrane and the reclaimed water can not be used.
Disclosure of Invention
The invention aims to provide a device and a method for treating waste gas and waste water during waste lithium battery recycling and cracking, wherein the waste gas treatment meets the discharge standard, the zero discharge of recycled water after waste water treatment is realized, and the blockage of a nozzle and a filler and the blockage of a pump and a pipeline caused by the recycled water are avoided.
In order to realize the purpose, the invention adopts the technical scheme that: a waste gas and waste water treatment device for recycling and cracking waste lithium batteries, which comprises a waste gas treatment unit and a waste water treatment unit, the waste gas treatment unit comprises a waste gas collecting pipe, a buffer tank, an air mixer, an organic waste gas electric cracking furnace, a cooling water jacket, an alkali liquor spraying absorption tower I, an alkali liquor spraying absorption tower II, an exhaust fan and an activated carbon absorber which are sequentially communicated, the wastewater treatment unit comprises a wastewater adjusting tank, a wastewater lifting pump, a coagulation reaction tank, an inclined plate precipitation tower, an intermediate water tank lifting pump, an iron-carbon micro-electrolysis tower, a Fenton oxidation tower, an air floatation tank, a clean water tank lifting pump, a sand filter tank, an activated carbon adsorption tank, a cation resin exchange column, an ultrafiltration pump, an ultrafiltration device, a concentrated liquid tank I, a concentrated liquid lifting pump, a single-effect evaporator and a condenser which are sequentially communicated, and the alkali liquor spraying absorption tower I and the alkali liquor spraying absorption tower II are communicated with the wastewater adjusting tank through a discharge pipeline.
The tail end of the waste gas collecting pipe and the bottom end of the buffer tank are respectively provided with a tar discharging pipe plug I and a tar discharging pipe plug II, and the coagulation reaction tank is respectively communicated with an automatic sulfuric acid dosing device and an automatic alum stirring dosing device.
The inclined plate sedimentation tower, the Fenton oxidation tower and the bottom of the air flotation tank are respectively communicated with a sludge pump I, an outlet of the sludge pump I is respectively communicated with a sludge tank, a sludge pump II and a filter press, and a water outlet of the filter press is communicated with the wastewater adjusting tank.
The Fenton oxidation towers are respectively communicated with H2O2An automatic dosing device, a sulfuric acid automatic dosing device and a NaOH automatic stirring dosing device.
A flowmeter is arranged between the clean water tank lifting pump and the sand filter tank, a fresh water outlet of the ultrafiltration device is communicated with a fresh water tank I, and the fresh water tank I is communicated with an alkali liquor spraying absorption tower I and an alkali liquor spraying absorption tower II through a fresh water delivery pump.
The concentrated water outlet of the cation resin exchange column is communicated with the concentrated liquid tank I, the concentrated liquid outlet of the single-effect evaporator is communicated with a centrifugal machine, and the condensed water outlet of the condenser is communicated with the alkali liquor spraying absorption tower I and the alkali liquor spraying absorption tower II through a condensed water delivery pump.
A waste gas and wastewater treatment method for recycling and cracking waste lithium batteries comprises the following steps:
a. the waste gas is mixed with fresh air through a waste gas collecting pipe and a buffer tank and an air mixer to keep the O content in the organic waste gas electric cracking furnace2The concentration of the organic waste gas is 6 to 10 percent, then the organic waste gas enters an organic waste gas electric cracking furnace for 2 to 5 seconds to fully crack and burn to remove tar, CO and volatile organic compounds, the burned waste gas is decomposed into water vapor and mixed waste gas containing carbon dioxide, fluorine and sulfur, the water vapor and the mixed waste gas are rapidly cooled to 150 ℃ through a cooling water jacket for 0.5 to 2 minutes to reduce the cracking of the organic waste gasThe method comprises the steps of generating dioxin after incineration, enabling cooled waste gas to sequentially enter an alkali liquor spraying absorption tower I and an alkali liquor spraying absorption tower II, carrying out spraying absorption treatment by using spraying water as a sodium hydroxide solution with the mass concentration of 3.5% -6%, adsorbing and removing the dioxin by using a ventilator and an active carbon adsorber, and then discharging the dioxin at high altitude, wherein fluorine and sulfur in the waste gas respectively react with sodium hydroxide to generate sodium fluoride and sodium bisulfite and extremely small amount of organic waste gas which is difficult to ignite and incinerated are dissolved in the spraying water to form waste water;
b. wastewater enters a wastewater adjusting tank through an alkali liquor spraying absorption tower I and an alkali liquor spraying absorption tower II, then enters a coagulation reaction tank through a wastewater lifting pump, simultaneously, sulfuric acid and alum are respectively added into the coagulation reaction tank by a sulfuric acid automatic dosing device and an alum automatic stirring dosing device, the pH value is adjusted to 6-8, the reaction lasts for 30-40 min, and Na is generated3AlF6Precipitating, after the reaction is finished, the wastewater enters an inclined plate precipitation tower to be precipitated to form defluorination wastewater and sludge I, and the defluorination wastewater enters an intermediate water tank;
c. the defluorination waste water enters an iron-carbon micro-electrolysis tower for micro-electrolysis treatment through a middle water tank lifting pump, air is introduced into the iron-carbon micro-electrolysis tower at the same time, the air amount is 3-5 times of the defluorination waste water amount, and then the defluorination waste water enters a Fenton oxidation tower, and simultaneously, an automatic sulfuric acid dosing device and an H automatic sulfuric acid dosing device are arranged2O2The automatic chemical feeding device respectively feeds sulfuric acid and H2O2Adding the mixture into a Fenton oxidation tower to perform pH adjustment and oxidation treatment to form sludge II and clear water I, then enabling the clear water I to enter an air floatation tank, adding NaOH into the air floatation tank by using an automatic NaOH stirring and dosing device to adjust the pH value to 8.5-9, then introducing air to perform air floatation treatment, removing organic matters in the clear water I and reducing COD of the organic matters to form sludge III and clear water II, and enabling the clear water II to enter a clear water tank;
d. clear water II sequentially enters a sand filter tank, an activated carbon adsorption tank and a cation resin exchange column through a clear water tank lifting pump through a flowmeter to remove suspended matters, COD, calcium and magnesium ions to form clear water III and concentrated water I, and the clear water III enters an ultrafiltration device through an ultrafiltration pump to form permeate and concentrated water II;
e. concentrated water I and concentrated water II enter a concentrated water tank I, enter a single-effect evaporator through a concentrated liquid lifting pump and are evaporated and concentrated to form concentrated liquid and steam, and the steam enters a condenser and is condensed and then enters an alkali liquor spraying absorption tower I and an alkali liquor spraying absorption tower II through a condensed water conveying pump for recycling.
Sludge I, sludge II and sludge III in the inclined plate sedimentation tower, the Fenton oxidation tower and the flotation tank are pumped into the sludge tank through a sludge pump I, and then are pumped into a filter press through a sludge pump II to be filter-pressed into a mud cake, the mud cake is transported and transported to a specified solid waste company of an environmental protection department outside, the outlet water of the filter press enters a wastewater adjusting tank for reprocessing, the permeate enters a fresh water tank I and then is transported to an alkali liquor spraying absorption tower I and an alkali liquor spraying absorption tower II for recycling through a fresh water delivery pump, the concentrate enters a centrifugal machine to form sludge IV through centrifugation, and the sludge IV is transported outside to a specified solid waste company of an environmental protection department for processing.
The incineration in the step a comprises three stages, wherein the temperature of the organic waste gas electric cracking furnace in the first stage is maintained at 160-300 ℃, the temperature of the organic waste gas electric cracking furnace in the second stage is maintained at 300-730 ℃, and the temperature of the organic waste gas electric cracking furnace in the third stage is maintained at 730-870 ℃.
The waste gas enters an organic waste gas electric cracking furnace through a waste gas collecting pipe, a buffer tank and an air mixer to be burnt to remove tar, CO and Volatile Organic Compounds (VOCs), the burnt waste gas is decomposed into water vapor and mixed waste gas containing carbon dioxide, fluorine and sulfur, the water vapor and the mixed waste gas sequentially enter an alkali liquor spraying absorption tower I and an alkali liquor spraying absorption tower II through a cooling water jacket, spraying and absorption treatment is carried out by using spraying water as a sodium hydroxide solution with the mass concentration of 3.5-6%, the mixed gas after removing the fluorine and the sulfur is absorbed by an exhaust fan and an active carbon absorber to remove dioxin, meets the emission standard and is discharged at high altitude, the spraying water uses the sodium hydroxide solution, and the use of Ca (OH) is avoided2Solution causes the phenomena of nozzle, filler blockage and pump and pipeline blockage, the service life of the ultrafiltration membrane is prolonged, fluorine and sulfur in waste gas respectively react with sodium hydroxide to generate sodium fluoride and sodium bisulfite and a very small amount of organic waste gas which is not easy to ignite and burn are dissolved in spray water to form waste water, the waste water enters a waste water adjusting tank through an alkali liquor spray absorption tower I and an alkali liquor spray absorption tower II, and then is lifted by waste waterThe pump enters a coagulation reaction tank, and simultaneously, the sulfuric acid automatic dosing device and the alum automatic stirring dosing device respectively add the sulfuric acid and the alum into the coagulation reaction tank to generate Na3AlF6Precipitating, after the reaction is finished, precipitating wastewater in an inclined plate precipitation tower to form defluorination wastewater and sludge I, introducing the defluorination wastewater into an intermediate water tank, introducing the defluorination wastewater into an iron-carbon micro-electrolysis tower through an intermediate water tank lifting pump to perform micro-electrolysis treatment, introducing air into the iron-carbon micro-electrolysis tower, then introducing into a Fenton oxidation tower, and simultaneously adding an automatic sulfuric acid dosing device and H into the Fenton oxidation tower2O2The automatic chemical feeding device respectively feeds sulfuric acid and H2O2Adding the mixture into a Fenton oxidation tower to adjust the pH value and perform oxidation treatment to form sludge II and clear water I, then enabling the clear water I to enter an air flotation tank, enabling NaOH to be added into the air flotation tank by an NaOH automatic stirring and adding device to adjust the pH value, then enabling air to perform air flotation treatment, removing organic matters in the clear water I and reducing COD of the clear water I to form sludge III and clear water II, enabling the clear water II to enter a clear water tank, enabling the clear water II to sequentially enter a sand filter tank, an active carbon adsorption tank and a cation resin exchange column through a flow meter to remove suspended matters, COD, calcium and magnesium ions to form clear water III and concentrated water I, enabling the clear water III to enter an ultrafiltration device through an ultrafiltration pump to form permeate and concentrated water II, enabling the concentrated water I and the concentrated water II to enter a concentrated water tank I through a concentrated liquid lifting pump to enter a single-effect evaporator to perform evaporation concentration to form concentrated liquid and steam, enabling the steam to enter a condenser to, thereby realizing that the waste gas treatment meets the discharge standard, realizing the zero discharge of the recycled water after the waste water treatment, and avoiding the phenomena of nozzle and filler blockage, pump and pipeline blockage caused by the recycled water.
Drawings
FIG. 1 is a block diagram of the present invention.
Detailed Description
The present invention is described in further detail below with reference to fig. 1.
The utility model provides a cracked waste gas and effluent treatment plant are retrieved to old and useless lithium cell, includes exhaust-gas treatment unit and waste-water treatment unit, the exhaust-gas treatment unit is including the exhaust-gas collecting pipe 1, buffer tank 2, air mixer 3, organic waste gas electric cracking furnace 4, cooling water jacket 5, alkali lye sprays absorption tower I6, alkali lye sprays absorption tower II 7, exhaust fan 8 and active carbon adsorber 39 that communicate in proper order, the waste-water treatment unit is including the waste-water adjustment tank 9 that communicates in proper order, waste-water lift pump 10, coagulation reaction tank 11, inclined plate precipitation tower 12, middle pond 13, middle pond elevator pump 14, indisputable carbon micro electrolysis tower 15, fenton oxidation tower 16, air supporting pond 17, clean water pond 18, clean water pond elevator pump 19, sand filtration jar 20, active carbon adsorption jar 21, cation resin exchange column 22, ultrafiltration pump 23, ultrafiltration device 24, concentrated fluid reservoir I25, concentrated liquid elevator pump 26, The single-effect evaporator 27 and the condenser 28, the alkali liquor spraying absorption tower I6 and the alkali liquor spraying absorption tower II 7 are communicated with the wastewater adjusting tank 9 through a discharge pipeline.
The tail end of the waste gas collecting pipe 1 and the bottom end of the buffer tank 2 are respectively provided with a tar discharging pipe plug I and a tar discharging pipe plug II, and the coagulation reaction tank 11 is respectively communicated with an automatic sulfuric acid dosing device 29 and an automatic alum stirring and dosing device 30.
The bottom parts of the inclined plate sedimentation tower 12, the Fenton oxidation tower 16 and the air flotation tank 17 are respectively communicated with a sludge pump I31, the outlet of the sludge pump I31 is respectively communicated with a sludge tank 32, a sludge pump II 33 and a filter press 34, and the water outlet of the filter press 34 is communicated with the wastewater adjusting tank 9.
The Fenton oxidation tower 16 is respectively communicated with H2O2An automatic medicine feeding device 35, a sulfuric acid automatic medicine feeding device 36 and a NaOH automatic stirring medicine feeding device 37.
A flowmeter is arranged between the clean water tank lifting pump 19 and the sand filter tank 20, a fresh water outlet of the ultrafiltration device 24 is communicated with a fresh water tank I38, and the fresh water tank I38 is communicated with an alkali liquor spraying absorption tower I6 and an alkali liquor spraying absorption tower II 7 through a fresh water delivery pump.
The concentrated water outlet of the cation resin exchange column 22 is communicated with the concentrated solution tank I25, the concentrated solution outlet of the single-effect evaporator 27 is communicated with a centrifugal machine, and the condensed water outlet of the condenser 28 is communicated with an alkali liquor spray absorption tower I6 and an alkali liquor spray absorption tower II 7 through a condensed water delivery pump.
The embodiment 1 based on the device comprises the following steps:
a. the waste gas is mixed with fresh air through a waste gas collecting pipe and a buffer tank and an air mixer to keep the O content in the organic waste gas electric cracking furnace2The concentration of the waste gas is 6 percent, then the waste gas enters an organic waste gas electric cracking furnace for 2 seconds to be fully cracked and burned to remove tar, CO and Volatile Organic Compounds (VOCs), the burned waste gas is decomposed into water vapor, carbon dioxide and fluorine, rapidly cooling the sulfur mixed waste gas, water vapor and the mixed waste gas to 150 ℃ through a cooling water jacket for 2min, reducing the generation of dioxin after cracking and burning of the organic waste gas, enabling the cooled waste gas to sequentially enter an alkali liquor spraying absorption tower I and an alkali liquor spraying absorption tower II, carrying out spraying absorption treatment by using spraying water as a sodium hydroxide solution with the mass concentration of 3.5%, adsorbing and removing the dioxin from the mixed gas with fluorine and sulfur through an exhaust fan and an active carbon adsorber, and then discharging the mixed gas at high altitude, wherein the fluorine and the sulfur in the waste gas respectively react with the sodium hydroxide to generate sodium fluoride and sodium bisulfite and a very small amount of organic waste gas which is difficult to ignite and burn are dissolved in the spraying water to form waste water;
b. the wastewater enters a wastewater adjusting tank through an alkali liquor spraying absorption tower I and an alkali liquor spraying absorption tower II, then enters a coagulation reaction tank through a wastewater lifting pump, simultaneously, a sulfuric acid automatic dosing device and an alum automatic stirring dosing device respectively add sulfuric acid and alum into the coagulation reaction tank, the pH value is adjusted to 6, the reaction is carried out for 30min, and Na is generated3AlF6Precipitating, after the reaction is finished, the wastewater enters an inclined plate precipitation tower to be precipitated to form defluorination wastewater and sludge I, and the defluorination wastewater enters an intermediate water tank;
c. the defluorination waste water enters an iron-carbon micro-electrolysis tower through a middle water tank lifting pump for micro-electrolysis treatment, air is introduced into the iron-carbon micro-electrolysis tower, the air amount is 3 times of the defluorination waste water amount, and then the defluorination waste water enters a Fenton oxidation tower, and meanwhile, an automatic sulfuric acid dosing device and H are added2O2The automatic chemical feeding device respectively feeds sulfuric acid and H2O2Adding into a Fenton oxidation tower for pH adjustment and oxidation treatment to form sludge II and clear water I, then feeding the clear water I into an air floatation tank, adding NaOH into the air floatation tank by an automatic NaOH stirring and dosing device to adjust the pH value to 8.5, and then introducing air for air floatation treatment to remove organic matters in the clear water IReducing COD of the sewage to form sludge III and clear water II, and feeding the clear water II into a clear water tank;
d. clear water II sequentially enters a sand filter tank, an activated carbon adsorption tank and a cation resin exchange column through a clear water tank lifting pump through a flowmeter to remove suspended matters, COD, calcium and magnesium ions to form clear water III and concentrated water I, and the clear water III enters an ultrafiltration device through an ultrafiltration pump to form permeate and concentrated water II;
e. concentrated water I and concentrated water II enter a concentrated water tank I, enter a single-effect evaporator through a concentrated liquid lifting pump and are evaporated and concentrated to form concentrated liquid and steam, and the steam enters a condenser and is condensed and then enters an alkali liquor spraying absorption tower I and an alkali liquor spraying absorption tower II through a condensed water conveying pump for recycling.
Sludge I, sludge II and sludge III in the inclined plate sedimentation tower, the Fenton oxidation tower and the flotation tank are pumped into the sludge tank through a sludge pump I, and then are pumped into a filter press through a sludge pump II to be filter-pressed into a mud cake, the mud cake is transported and transported to a specified solid waste company of an environmental protection department outside, the outlet water of the filter press enters a wastewater adjusting tank for reprocessing, the permeate enters a fresh water tank I and then is transported to an alkali liquor spraying absorption tower I and an alkali liquor spraying absorption tower II for recycling through a fresh water delivery pump, the concentrate enters a centrifugal machine to form sludge IV through centrifugation, and the sludge IV is transported outside to a specified solid waste company of an environmental protection department for processing.
The incineration in the step a comprises three stages, wherein the temperature of the organic waste gas electric cracking furnace in the first stage is maintained at 160 ℃, the temperature of the organic waste gas electric cracking furnace in the second stage is maintained at 300 ℃, and the temperature of the organic waste gas electric cracking furnace in the third stage is maintained at 730 ℃.
Detecting that the total non-methane hydrocarbon in the waste gas discharged from high altitude is 30mg/m from the waste discharge port of the exhaust fan3Fluorine content of 5mg/m3Dioxin 0.07ngITEQ/Nm3The sulfur-containing waste gas is detected to be 0mg/m3The fluorine content of the defluorination wastewater detected from the middle water tank is 6mg/L, and the clear water III is taken from a supernatant outlet of the cation resin exchange column to detect the COD content of 55mg/L, so that the waste gas treatment meets the emission standard, the zero emission of the recycled water after the waste water treatment is realized, and the phenomena of nozzle and filler blockage, pump and pipeline blockage caused by the recycled water are avoided.
The embodiment 2 based on the device comprises the following steps:
a. the waste gas is mixed with fresh air through a waste gas collecting pipe and a buffer tank and an air mixer to keep the O content in the organic waste gas electric cracking furnace2The concentration of the waste gas is 8 percent, then the waste gas enters an organic waste gas electric cracking furnace for 3.5 seconds to be fully cracked and burned to remove tar, CO and Volatile Organic Compounds (VOCs), the burned waste gas is decomposed into water vapor, carbon dioxide and fluorine, the method comprises the following steps of (1) quickly cooling mixed waste gas of sulfur, water vapor and the mixed waste gas to 150 ℃ through a cooling water jacket for 1.25min, reducing generation of dioxin after cracking and burning of organic waste gas, enabling the cooled waste gas to enter an alkali liquor spraying absorption tower I and an alkali liquor spraying absorption tower II in sequence, carrying out spraying absorption treatment by using spraying water as a sodium hydroxide solution with the mass concentration of 4.75%, adsorbing and removing the dioxin from the mixed gas with fluorine and sulfur through an exhaust fan and an active carbon adsorber, discharging the mixed gas at high altitude, and enabling the fluorine and the sulfur in the waste gas to react with the sodium hydroxide respectively to generate sodium fluoride and sodium bisulfite and extremely small amount of organic waste gas which is difficult to ignite and burn to be dissolved in the spraying water to form waste;
b. the wastewater enters a wastewater adjusting tank through an alkali liquor spraying absorption tower I and an alkali liquor spraying absorption tower II, then enters a coagulation reaction tank through a wastewater lifting pump, simultaneously, a sulfuric acid automatic dosing device and an alum automatic stirring dosing device respectively add sulfuric acid and alum into the coagulation reaction tank, the pH value is adjusted to 7, the reaction is carried out for 35min, and Na is generated3AlF6Precipitating, after the reaction is finished, the wastewater enters an inclined plate precipitation tower to be precipitated to form defluorination wastewater and sludge I, and the defluorination wastewater enters an intermediate water tank;
c. the defluorination waste water enters an iron-carbon micro-electrolysis tower through a middle water tank lifting pump for micro-electrolysis treatment, air is introduced into the iron-carbon micro-electrolysis tower, the air amount is 4 times of the defluorination waste water amount, and then the defluorination waste water enters a Fenton oxidation tower, and meanwhile, an automatic sulfuric acid dosing device and H are added2O2The automatic chemical feeding device respectively feeds sulfuric acid and H2O2Adding into a Fenton oxidation tower to perform pH adjustment and oxidation treatment to form sludge II and clear water I, then feeding the clear water I into an air floatation tank, adding NaOH into the air floatation tank by using an NaOH automatic stirring and dosing device to adjust the pH value to 8.7, and then introducing air to perform air floatation treatment to remove impuritiesRemoving organic matters in the clean water I and reducing COD of the organic matters to form sludge III and clean water II, and feeding the clean water II into a clean water tank;
d. clear water II sequentially enters a sand filter tank, an activated carbon adsorption tank and a cation resin exchange column through a clear water tank lifting pump through a flowmeter to remove suspended matters, COD, calcium and magnesium ions to form clear water III and concentrated water I, and the clear water III enters an ultrafiltration device through an ultrafiltration pump to form permeate and concentrated water II;
e. concentrated water I and concentrated water II enter a concentrated water tank I, enter a single-effect evaporator through a concentrated liquid lifting pump and are evaporated and concentrated to form concentrated liquid and steam, and the steam enters a condenser and is condensed and then enters an alkali liquor spraying absorption tower I and an alkali liquor spraying absorption tower II through a condensed water conveying pump for recycling.
Sludge I, sludge II and sludge III in the inclined plate sedimentation tower, the Fenton oxidation tower and the flotation tank are pumped into the sludge tank through a sludge pump I, and then are pumped into a filter press through a sludge pump II to be filter-pressed into a mud cake, the mud cake is transported and transported to a specified solid waste company of an environmental protection department outside, the outlet water of the filter press enters a wastewater adjusting tank for reprocessing, the permeate enters a fresh water tank I and then is transported to an alkali liquor spraying absorption tower I and an alkali liquor spraying absorption tower II for recycling through a fresh water delivery pump, the concentrate enters a centrifugal machine to form sludge IV through centrifugation, and the sludge IV is transported outside to a specified solid waste company of an environmental protection department for processing.
The incineration in the step a comprises three stages, wherein the temperature of the organic waste gas electric cracking furnace in the first stage is maintained at 230 ℃, the temperature of the organic waste gas electric cracking furnace in the second stage is maintained at 515 ℃, and the temperature of the organic waste gas electric cracking furnace in the third stage is maintained at 800 ℃.
The non-methane total hydrocarbon in the waste gas discharged from high altitude is detected to be 16mg/m from the waste discharge port of the exhaust fan3Fluorine content of 4mg/m3Dioxin 0.05ngITEQ/Nm3The sulfur-containing waste gas is detected to be 0mg/m3The fluorine content of the defluorination wastewater detected from the middle water tank is 4.6mg/L, and the clear water III is taken from the supernatant outlet of the cation resin exchange column to detect the COD content of 51mg/L, so that the waste gas treatment meets the discharge standard, the zero discharge of the recycled water after the waste water treatment is realized, and the phenomena of nozzle, filler blockage, pump and pipeline blockage caused by the recycled water are avoided.
Embodiment 3 based on the above apparatus comprises the following steps:
a. the waste gas is mixed with fresh air through a waste gas collecting pipe and a buffer tank and an air mixer to keep the O content in the organic waste gas electric cracking furnace2The concentration of the waste gas is 10 percent, then the waste gas enters an organic waste gas electric cracking furnace for 5 seconds to be fully cracked and burned to remove tar, CO and Volatile Organic Compounds (VOCs), the burned waste gas is decomposed into water vapor, carbon dioxide and fluorine, rapidly cooling the sulfur mixed waste gas, water vapor and the mixed waste gas to 150 ℃ through a cooling water jacket for 0.5min, reducing the generation of dioxin after cracking and burning of the organic waste gas, enabling the cooled waste gas to sequentially enter an alkali liquor spraying absorption tower I and an alkali liquor spraying absorption tower II, carrying out spraying absorption treatment by using spraying water as a sodium hydroxide solution with the mass concentration of 6%, adsorbing and removing the dioxin from the mixed gas with fluorine and sulfur through an exhaust fan and an active carbon adsorber, and then discharging the mixed gas at high altitude, wherein the fluorine and the sulfur in the waste gas respectively react with the sodium hydroxide to generate sodium fluoride and sodium bisulfite and a very small amount of organic waste gas which is difficult to ignite and burn are dissolved in the spraying water to form waste water;
b. the wastewater enters a wastewater adjusting tank through an alkali liquor spraying absorption tower I and an alkali liquor spraying absorption tower II, then enters a coagulation reaction tank through a wastewater lifting pump, simultaneously, a sulfuric acid automatic dosing device and an alum automatic stirring dosing device respectively add sulfuric acid and alum into the coagulation reaction tank, the pH value is adjusted to 8, the reaction is carried out for 40min, and Na is generated3AlF6Precipitating, after the reaction is finished, the wastewater enters an inclined plate precipitation tower to be precipitated to form defluorination wastewater and sludge I, and the defluorination wastewater enters an intermediate water tank;
c. the defluorination waste water enters an iron-carbon micro-electrolysis tower through a middle water tank lifting pump for micro-electrolysis treatment, air is introduced into the iron-carbon micro-electrolysis tower, the air amount is 5 times of the defluorination waste water amount, and then the defluorination waste water enters a Fenton oxidation tower, and meanwhile, an automatic sulfuric acid dosing device and an H are added2O2The automatic chemical feeding device respectively feeds sulfuric acid and H2O2Adding into a Fenton oxidation tower to perform pH adjustment and oxidation treatment to form sludge II and clear water I, then feeding the clear water I into an air floatation tank, adding NaOH into the air floatation tank by using an NaOH automatic stirring and dosing device to adjust the pH value to 9, and then introducing airPerforming air floatation treatment to remove organic matters in the clean water I and reduce COD of the organic matters to form sludge III and clean water II, and feeding the clean water II into a clean water pool;
d. clear water II sequentially enters a sand filter tank, an activated carbon adsorption tank and a cation resin exchange column through a clear water tank lifting pump through a flowmeter to remove suspended matters, COD, calcium and magnesium ions to form clear water III and concentrated water I, and the clear water III enters an ultrafiltration device through an ultrafiltration pump to form permeate and concentrated water II;
e. concentrated water I and concentrated water II enter a concentrated water tank I, enter a single-effect evaporator through a concentrated liquid lifting pump and are evaporated and concentrated to form concentrated liquid and steam, and the steam enters a condenser and is condensed and then enters an alkali liquor spraying absorption tower I and an alkali liquor spraying absorption tower II through a condensed water conveying pump for recycling.
Sludge I, sludge II and sludge III in the inclined plate sedimentation tower, the Fenton oxidation tower and the flotation tank are pumped into the sludge tank through a sludge pump I, and then are pumped into a filter press through a sludge pump II to be filter-pressed into a mud cake, the mud cake is transported and transported to a specified solid waste company of an environmental protection department outside, the outlet water of the filter press enters a wastewater adjusting tank for reprocessing, the permeate enters a fresh water tank I and then is transported to an alkali liquor spraying absorption tower I and an alkali liquor spraying absorption tower II for recycling through a fresh water delivery pump, the concentrate enters a centrifugal machine to form sludge IV through centrifugation, and the sludge IV is transported outside to a specified solid waste company of an environmental protection department for processing.
The incineration in the step a comprises three stages, wherein the temperature of the organic waste gas electric cracking furnace in the first stage is maintained at 300 ℃, the temperature of the organic waste gas electric cracking furnace in the second stage is maintained at 730 ℃, and the temperature of the organic waste gas electric cracking furnace in the third stage is maintained at 870 ℃.
Detecting 4mg/m of non-methane total hydrocarbon in high-altitude exhaust waste gas from exhaust outlet of exhaust fan3Fluorine content of 1.1mg/m3Dioxin 0.02ngITEQ/Nm3The sulfur-containing waste gas is detected to be 0mg/m3The fluorine content of the defluorination wastewater detected from the middle water tank is 3.8mg/L, and the clear water III is taken from the supernatant outlet of the cation resin exchange column to detect the COD content of 46mg/L, thereby realizing that the waste gas treatment meets the discharge standard, the zero discharge of the recycled water after the waste water treatment is realized, and the blockage of a nozzle and a filler, the blockage of a pump and a pipeline caused by the recycled water is avoidedA phenomenon.
The above-mentioned embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements made to the technical solution of the present invention by those skilled in the art without departing from the spirit of the present invention should fall within the protection scope defined by the claims of the present invention.

Claims (9)

1. The utility model provides a waste gas and effluent treatment plant of schizolysis are retrieved to old and useless lithium cell which characterized in that: including exhaust-gas treatment unit and waste water treatment unit, the exhaust-gas treatment unit is including exhaust-gas collection pipe (1), buffer tank (2), air mixer (3), organic waste gas electric cracking furnace (4), cooling water jacket (5), alkali lye spray absorption tower I (6), alkali lye spray absorption tower II (7), exhaust fan (8) and active carbon adsorber (39) that communicate in proper order, the waste water treatment unit is including waste water adjustment tank (9), waste water elevator pump (10), coagulation reaction tank (11), inclined plate precipitation tower (12), middle pond (13), middle pond elevator pump (14), little electrolysis tower (15) of iron carbon, fenton oxidation tower (16), air supporting pond (17), clean water pond (18), clean water pond elevator pump (19), sand filtration jar (20), active carbon adsorption jar (21), cation resin exchange column (22) that communicate in proper order, The device comprises an ultrafiltration pump (23), an ultrafiltration device (24), a concentrated liquid tank I (25), a concentrated liquid lift pump (26), a single-effect evaporator (27) and a condenser (28), wherein an alkali liquor spraying absorption tower I (6) and an alkali liquor spraying absorption tower II (7) are communicated with a wastewater adjusting tank (9) through a discharge pipeline.
2. The waste gas and wastewater treatment device for recycling and cracking waste lithium batteries according to claim 1, which is characterized in that: the tail end of the waste gas collecting pipe (1) and the bottom end of the buffer tank (2) are respectively provided with a tar discharge pipe plug I and a tar discharge pipe plug II, and the coagulation reaction tank (11) is respectively communicated with an automatic sulfuric acid dosing device (29) and an automatic alum stirring and dosing device (30).
3. The waste gas and wastewater treatment device for recycling and cracking waste lithium batteries according to claim 1, which is characterized in that: the bottom parts of the inclined plate sedimentation tower (12), the Fenton oxidation tower (16) and the air flotation tank (17) are respectively communicated with a sludge pump I (31), the outlet of the sludge pump I (31) is respectively communicated with a sludge tank (32), a sludge pump II (33) and a filter press (34), and the water outlet of the filter press (34) is communicated with the wastewater adjusting tank (9).
4. The waste gas and wastewater treatment device for recycling and cracking waste lithium batteries according to claim 1, which is characterized in that: the Fenton oxidation tower (16) is respectively communicated with H2O2An automatic medicine feeding device (35), a sulfuric acid automatic medicine feeding device (36) and an NaOH automatic stirring medicine feeding device (37).
5. The waste gas and wastewater treatment device for recycling and cracking waste lithium batteries according to claim 1, which is characterized in that: a flowmeter is arranged between the clean water tank lifting pump (19) and the sand filter tank (20), a fresh water outlet of the ultrafiltration device (24) is communicated with a fresh water tank I (38), and the fresh water tank I (38) is communicated with an alkali liquor spraying absorption tower I (6) and an alkali liquor spraying absorption tower II (7) through a fresh water delivery pump.
6. The waste gas and wastewater treatment device for recycling and cracking waste lithium batteries according to claim 1, which is characterized in that: the concentrated water outlet of the cation resin exchange column (22) is communicated with the concentrated liquid tank I (25), the concentrated liquid outlet of the single-effect evaporator (27) is communicated with a centrifugal machine, and the condensed water outlet of the condenser (28) is communicated with the alkali liquor spraying absorption tower I (6) and the alkali liquor spraying absorption tower II (7) through a condensed water delivery pump.
7. A waste gas and wastewater treatment method for recycling and cracking waste lithium batteries is characterized by comprising the following steps:
a. waste gas is collected by a waste gas collecting pipeAnd a buffer tank for mixing fresh air through an air mixer to maintain the O content in the organic waste gas electric cracking furnace2The concentration of the organic waste gas is 6 to 10 percent, then the organic waste gas enters an organic waste gas electric cracking furnace for 2 to 5 seconds to be fully cracked and burned to remove tar, CO and volatile organic compounds, the burned waste gas is decomposed into water vapor, carbon dioxide and fluorine, the method comprises the following steps of (1) quickly cooling sulfur mixed waste gas, water vapor and the mixed waste gas to 150 ℃ through a cooling water jacket for 0.5-2 min, reducing dioxin generation after organic waste gas cracking and burning, enabling the cooled waste gas to enter an alkali liquor spraying absorption tower I and an alkali liquor spraying absorption tower II in sequence, carrying out spraying absorption treatment by using spraying water as a sodium hydroxide solution with the mass concentration of 3.5-6%, adsorbing and removing dioxin in an exhaust fan and an active carbon adsorber by using mixed gas with fluorine and sulfur, discharging the mixed gas with high altitude, enabling the fluorine and the sulfur in the waste gas to react with the sodium hydroxide respectively to generate sodium fluoride and sodium bisulfite and extremely small amount of organic waste gas which is difficult to ignite and burn to be dissolved in the spraying water to form waste water;
b. wastewater enters a wastewater adjusting tank through an alkali liquor spraying absorption tower I and an alkali liquor spraying absorption tower II, then enters a coagulation reaction tank through a wastewater lifting pump, simultaneously, sulfuric acid and alum are respectively added into the coagulation reaction tank by a sulfuric acid automatic dosing device and an alum automatic stirring dosing device, the pH value is adjusted to 6-8, the reaction lasts for 30-40 min, and Na is generated3AlF6Precipitating, after the reaction is finished, the wastewater enters an inclined plate precipitation tower to be precipitated to form defluorination wastewater and sludge I, and the defluorination wastewater enters an intermediate water tank;
c. the defluorination waste water enters an iron-carbon micro-electrolysis tower for micro-electrolysis treatment through a middle water tank lifting pump, air is introduced into the iron-carbon micro-electrolysis tower at the same time, the air amount is 3-5 times of the defluorination waste water amount, and then the defluorination waste water enters a Fenton oxidation tower, and simultaneously, an automatic sulfuric acid dosing device and an H automatic sulfuric acid dosing device are arranged2O2The automatic chemical feeding device respectively feeds sulfuric acid and H2O2Adding the mixture into a Fenton oxidation tower to perform pH adjustment and oxidation treatment to form sludge II and clear water I, then enabling the clear water I to enter an air floatation tank, adding NaOH into the air floatation tank by using an automatic NaOH stirring and adding agent device to adjust the pH value to 8.5-9, then introducing air to perform air floatation treatment, removing organic matters in the clear water I and reducing COD of the organic matters to form sludge III and clear water II, and enabling the clear water II to enter the clear water IA pool;
d. clear water II sequentially enters a sand filter tank, an activated carbon adsorption tank and a cation resin exchange column through a clear water tank lifting pump through a flowmeter to remove suspended matters, COD, calcium and magnesium ions to form clear water III and concentrated water I, and the clear water III enters an ultrafiltration device through an ultrafiltration pump to form permeate and concentrated water II;
e. concentrated water I and concentrated water II enter a concentrated water tank I, enter a single-effect evaporator through a concentrated liquid lifting pump and are evaporated and concentrated to form concentrated liquid and steam, and the steam enters a condenser and is condensed and then enters an alkali liquor spraying absorption tower I and an alkali liquor spraying absorption tower II through a condensed water conveying pump for recycling.
8. The method for treating the waste gas and the waste water generated by the recycling and cracking of the waste lithium battery as claimed in claim 7, wherein the method comprises the following steps: sludge I, sludge II and sludge III in the inclined plate sedimentation tower, the Fenton oxidation tower and the flotation tank are pumped into the sludge tank through a sludge pump I, and then are pumped into a filter press through a sludge pump II to be filter-pressed into a mud cake, the mud cake is transported and transported to a specified solid waste company of an environmental protection department outside, the outlet water of the filter press enters a wastewater adjusting tank for reprocessing, the permeate enters a fresh water tank I and then is transported to an alkali liquor spraying absorption tower I and an alkali liquor spraying absorption tower II for recycling through a fresh water delivery pump, the concentrate enters a centrifugal machine to form sludge IV through centrifugation, and the sludge IV is transported outside to a specified solid waste company of an environmental protection department for processing.
9. The method for treating the waste gas and the waste water generated by the recycling and cracking of the waste lithium battery as claimed in claim 7, wherein the method comprises the following steps: the incineration in the step a comprises three stages, wherein the temperature of the organic waste gas electric cracking furnace in the first stage is maintained at 160-300 ℃, the temperature of the organic waste gas electric cracking furnace in the second stage is maintained at 300-730 ℃, and the temperature of the organic waste gas electric cracking furnace in the third stage is maintained at 730-870 ℃.
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