CN211513756U - Waste gas purification system in lithium battery recovery process - Google Patents
Waste gas purification system in lithium battery recovery process Download PDFInfo
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Abstract
The utility model relates to a waste gas purification system in the lithium battery recovery process, which comprises a dust removal unit, a fluorine removal unit, a volatile organic compound removal unit, a waste heat recovery unit, an alkali absorption unit and a waste water treatment unit; the dust removal unit is at least provided with a dust removal device, and the fluorine removal unit is at least provided with a gas-liquid heat exchanger and a two-section circulating absorption tower; the volatile organic compound removing unit is at least provided with an incinerator; the waste heat recovery unit is at least provided with a heat exchanger or a waste heat recovery device and a heat exchanger; the alkali absorption unit is at least provided with an alkali absorption tower, and the wastewater treatment unit is at least provided with a neutralization tank and a filter press; the utility model discloses most fluorine-containing component in the desorption waste gas, and through handling in the waste gas dirt, fluorine and volatile organic compounds desorption efficiency reach or even exceed relevant standard, change into harmless condensate with fluorine and phosphorus element in the waste gas simultaneously, both reached the purpose that exhaust purification administered, realized resource comprehensive utilization simultaneously.
Description
Technical Field
The utility model relates to a waste gas purification handles technical field, especially relates to a lithium cell recovery in-process exhaust gas purification system.
Background
In recent years, the new energy automobile industry in China is developed vigorously, the capacity of power lithium batteries is increased rapidly, reports show that the total yield of new energy automobiles in China is expected to reach 200 thousands in 2020, the corresponding power battery requirement reaches 120.8GWH, the annual composite acceleration of the power battery requirement is about 54.9%, and the current automobile power batteries mainly use lithium batteries.
The lithium ion battery generally uses a mixed solvent of dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, ethylene carbonate, lithium hexafluorophosphate and the like as an electrolyte, and compared with a lead-acid battery and a nickel-cadmium battery, the lithium ion battery has very superior performance in service life and service life, but the service life of the lithium ion battery is generally 3 to 5 years, and the replacement elimination quantity of the lithium ion battery is multiplied along with the increase of the service life of a power lithium battery. The waste lithium batteries contain a large amount of nonrenewable metal resources, such as cobalt, lithium, nickel, copper, aluminum and the like, and if the waste lithium batteries can be effectively recycled, the environmental pollution caused by the waste lithium batteries can be reduced, and meanwhile, abundant economic benefits can be created, so that the green circular economy of the lithium batteries is realized.
In the waste lithium battery recovery process, the waste lithium battery is subjected to the working procedures of disassembly, crushing, nitrogen protection, heating and drying, sorting, battery powder preparation, metal recovery and the like. Waste lithium battery produces a large amount of dusts in the crushing process of disassembling, and a large amount of organic solvents volatilize in the electrolyte that the electricity schizolysis stoving in-process produced, such as dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, ethylene carbonate etc. lithium hexafluorophosphate can produce fluorine-containing component such as a large amount of hydrogen fluoride, phosphorus pentafluoride after the schizolysis reaches and reacts with moisture, if waste gas is directly discharged outside not handling, not only endanger personnel's in the periphery healthy, more can serious polluted environment.
Therefore, the waste gas generated in the waste lithium battery recovery process is mainly used for purifying dust removal, fluorine-containing harmful components and volatile organic compounds, so that the waste gas emission in the recovery process reaches the corresponding national and industrial standards.
However, because the organic components of the waste gas in the waste lithium battery recovery process are complex, and the fluorine-containing components have the characteristics of easy corrosion, slow removal and the like, the existing waste gas purification device and system cannot realize the waste gas purification emission index, and can not avoid the corrosion damage of the fluorine-containing gas to the purification equipment.
Chinese patent No. CN207950933U discloses "an organic waste gas treatment system produced in the lithium battery recovery process", which adopts a bag type dust collector, a catalytic combustion device and an alkali pool, the filtering process is used to remove solid particles, the catalytic combustion device is used to remove volatile organic compounds such as carbonates, but the waste gas contains a large amount of fluorine-containing components, the waste gas directly enters the catalytic combustion device without being treated to corrode the treatment, and the catalytic combustion catalyst is poisoned and ineffective at the same time, thereby greatly shortening the service life of the whole set of treatment device. The fluorine-containing component mainly exists in the form of phosphorus pentafluoride, the phosphorus pentafluoride can be decomposed in an alkaline aqueous solution, but the decomposition speed is slow, the efficiency is low, and the alkali pool can not enable the removal efficiency of the fluorine-containing component to reach the standard and discharge. In addition, in the working procedure of the lithium battery recovery cracking furnace, baking is carried outThe concentration range of volatile organic compounds in the dry waste gas is as high as 150g/m3This also exceeds the operating range of catalytic combustion devices.
Chinese patent No. CN108096977A discloses a method and a system for treating waste gas generated during the recovery of lithium batteries, in which the system employs nitrogen protection and adsorbent to remove moisture, although the generation of hydrogen fluoride can be reduced, part of fluorine-containing components in the waste gas reacts violently with water, and the introduction of water can not be avoided during the classification, screening and crushing of batteries, and the corrosion of equipment caused by halogen acid can not be avoided.
Chinese patent No. CN110124432A discloses "a flue gas purification device in waste lithium battery recycling process", which removes dust by a bag-type dust remover, further removes dust particulate matter by a water leaching tower, purifies inorganic halogen acid by an alkali liquor leaching tower, removes volatile organic compounds by an activated carbon adsorption device, and further degrades unremoved volatile organic compounds by ultraviolet photolysis; although the device is provided with the alkaline washing tower, the hydrogen fluoride in the fluorine-containing components can be removed, but other fluorine-containing components cannot reach the standard, especially phosphorus pentafluoride. In addition, the content of volatile organic compounds in the waste gas is high, and an activated carbon adsorption device is adopted, so that activated carbon is subjected to adsorption saturation within a short time and is inactivated, the replacement is frequent, and the operation cost is high. The ultraviolet photolysis device is suitable for treating odor and peculiar smell, and can achieve certain removal effect only by higher energy consumption for removing esters, and has the risk of secondary pollution.
Chinese patent No. CN108128953A discloses "a waste gas and wastewater treatment apparatus and method for recycling and cracking waste lithium batteries", the apparatus is provided with an electric cracking furnace, the waste gas recovered by lithium batteries directly enters the electric cracking furnace after passing through a waste gas collecting pipe, a buffer tank and an air mixer, because a large amount of fluorine-containing components exist in the lithium battery recycling process, the fluorine-containing components generate high-concentration hydrogen fluoride gas after passing through the electric cracking furnace, which can cause serious corrosion to the electric cracking furnace equipment, thereby shortening the service life of the equipment; in addition, the device directly burns waste gas without a dust removal device, and a large amount of dust can be gathered in the cracking furnace to influence the operation of the treatment device.
As can be seen from the above description and analysis of the prior art: the method for purifying the waste gas in the lithium battery recovery process needs to remove dust, fluorine-containing components and volatile organic compounds respectively, and the removal of the fluorine-containing components is a key step in the process, so that the waste gas generated in the waste lithium battery recovery process needs to remove the fluorine-containing components as efficiently as possible after dedusting, preferably completely remove the fluorine-containing components or remove the concentration of the fluorine-containing components in the waste gas to be less than or equal to 10ppm, and then remove the volatile organic compounds to meet the emission standard, and generally considered that: when the molar content of fluorine in the waste gas is less than 0.2 percent, the fluoride can not cause serious corrosion to equipment when the fluorine-containing mixed organic waste gas is purified by adopting a direct combustion mode.
In summary, in order to overcome the defects in the prior art and enable the exhaust gas generated in the waste lithium battery recovery process to reach the complete purification standard emission, it is urgently needed to improve and innovate the existing purification device and method, prevent the fluorine-containing component from corroding the body of the exhaust gas treatment device, the heat insulation material or the heat storage body, or avoid the catalyst from being poisoned and inactivated by fluorine, effectively prolong the service life of the exhaust gas equipment, ensure the safe, stable and reliable operation of the exhaust gas purification treatment device system, and enable the removal efficiency of dust, fluorine and volatile organic compounds in the exhaust gas to reach or even exceed the relevant standards.
Disclosure of Invention
The utility model provides a waste gas purification system in lithium cell recovery process, to the waste gas that produces in the lithium cell recovery process have high concentration dirt, fluorine and the characteristics of volatile organic compounds, rationally set up each functional unit, can desorption most fluorine-containing component in the waste gas, prevent the corrosion of fluorine-containing component to volatile organic compounds processing apparatus body, insulation material or heat accumulator, avoid catalyst fluorine poisoning deactivation, effectively prolong the life of waste gas purification treatment equipment, guarantee the security, stability and the reliability of waste gas purification treatment equipment operation; the removal efficiency of dust, fluorine and volatile organic compounds in the treated waste gas reaches or even exceeds the relevant standard, and simultaneously, fluorine and phosphorus elements in the waste gas are converted into harmless condensate, thereby achieving the purpose of waste gas purification and treatment and realizing the comprehensive utilization of resources.
In order to achieve the above purpose, the utility model adopts the following technical scheme:
a waste gas purification system in a lithium battery recovery process comprises a dust removal unit, a fluorine removal unit, a volatile organic compound removal unit, a waste heat recovery unit, an alkali absorption unit and a wastewater treatment unit; the dust removal unit is at least provided with a dust removal device, and the fluorine removal unit is at least provided with a gas-liquid heat exchanger and a two-section circulating absorption tower; the volatile organic compound removing unit is at least provided with an incinerator; the waste heat recovery unit is at least provided with a heat exchanger or a waste heat recovery device and a heat exchanger; the alkali absorption unit is at least provided with an alkali absorption tower, and the wastewater treatment unit is at least provided with a neutralization tank and a filter press; the dust removal unit, the fluorine removal unit, the volatile organic compound removal unit, the waste heat recovery unit and the alkali absorption unit are sequentially connected, and the fluorine removal unit and the alkali absorption unit are additionally connected with the wastewater treatment unit through wastewater pipelines.
A dust-containing gas inlet of the dust removal device is connected with a waste gas collecting pipeline of the lithium battery recovery system, a purified gas outlet of the dust removal device is connected with a gas phase inlet of the gas-liquid heat exchanger, and a gas phase outlet of the gas-liquid heat exchanger is connected with a waste gas inlet at the lower part of the two-section circulating absorption tower; the lower section of the second-section circulating absorption tower is an acidic absorption section and is provided with an acidic absorption liquid inlet, the outside of the tower body is provided with an acidic absorption liquid circulating pipeline, and an absorption liquid cooler is arranged on the acidic absorption liquid circulating pipeline; the acid absorption liquid circulating pipeline is additionally connected with a liquid phase inlet of the gas-liquid heat exchanger, and a liquid phase outlet of the gas-liquid heat exchanger is connected with the neutralizing tank; the upper section of the second-section circulating absorption tower is an alkaline absorption section and is provided with an alkaline absorption liquid inlet, and an alkaline absorption liquid circulating pipeline is arranged outside the tower body and is additionally connected with a neutralization tank; a purified gas outlet at the top of the second-section circulating absorption tower is connected with a waste gas inlet of the incinerator, a flue gas outlet of the incinerator is connected with a waste gas inlet at the bottom of the alkali absorption tower after passing through a heat exchanger or a waste heat recovery device and the heat exchanger, an alkali absorption liquid inlet is arranged at the upper part of the alkali absorption tower, an alkali liquor circulating pipeline is arranged outside the alkali absorption tower, the alkali liquor circulating pipeline is additionally connected with a neutralizing tank, and a purified gas outlet is arranged at the top of the alkali absorption tower; the neutralizing tank is provided with a neutralizing alkali liquor inlet and a mixed liquor outlet, and the mixed liquor outlet is connected with a filter press.
The dust removal device is a bag type dust remover, a cyclone dust remover or a multi-pipe cyclone dust remover, and the inner wall of the dust removal device is provided with a corrosion-resistant and wear-resistant material lining.
The upper section and the lower section of the two-section circulating absorption tower are respectively provided with a filler, the filler adopts polyhedral hollow spheres, Taylor rosettes, rectangular saddle rings, pall rings, Raschig rings or regular corrugated plate fillers, and the filler is made of polypropylene, reinforced polypropylene or polytetrafluoroethylene.
The incinerator adopts one of a direct-fired furnace, a box-type heat accumulation incinerator, a rotary heat accumulation incinerator and a catalytic incinerator.
Compared with the prior art, the beneficial effects of the utility model are that:
aiming at the characteristics that waste gas generated in the lithium battery recovery process has high-concentration dust, fluorine and volatile organic compounds, all functional units are reasonably arranged, most of fluorine-containing components in the waste gas can be removed, the fluorine-containing components are prevented from corroding a volatile organic compound treatment device body, a heat insulation material or a heat accumulator, the catalyst is prevented from being inactivated by fluorosis, the service life of waste gas purification treatment equipment is effectively prolonged, and the safety, the stability and the reliability of the operation of the waste gas purification treatment equipment are ensured; the removal efficiency of dust, fluorine and volatile organic compounds in the treated waste gas reaches or even exceeds the relevant standard, and simultaneously, fluorine and phosphorus elements in the waste gas are converted into harmless condensate, thereby achieving the purpose of waste gas purification and treatment and realizing the comprehensive utilization of resources.
Drawings
Fig. 1 is a schematic structural diagram of a waste gas purification system in the lithium battery recovery process in embodiment 1 of the present invention.
Fig. 2 is a schematic structural diagram of a waste gas purification system in the lithium battery recovery process in embodiment 2 of the present invention.
Fig. 3 is a schematic structural diagram of a waste gas purification system in the lithium battery recovery process in embodiment 3 of the present invention.
In the figure: 1. dust removal device 2, gas-liquid heat exchanger 3, two-stage circulating absorption tower 41, direct combustion furnace 42, box type regenerative incinerator 43, catalytic incinerator 5, waste heat recovery device 6, heat exchanger 7, alkali absorption tower 8, neutralization tank 9, filter press 10, ash conveying device 11, absorption liquid cooler 12, circulating pump 13, acid absorption liquid supply device 14, alkali absorption liquid supply device 15, flame arrester 16 and fan
Detailed Description
The following description of the embodiments of the present invention will be made with reference to the accompanying drawings:
as shown in fig. 1-3, the system for purifying waste gas generated in the lithium battery recovery process of the present invention comprises a dust removal unit, a fluorine removal unit, a volatile organic compound removal unit, a waste heat recovery unit, an alkali absorption unit and a wastewater treatment unit; the dust removal unit is at least provided with a dust removal device 1, and the fluorine removal unit is at least provided with a gas-liquid heat exchanger 2 and a two-section circulating absorption tower 3; the volatile organic compound removing unit is at least provided with an incinerator; the waste heat recovery unit is at least provided with a heat exchanger 6 or a waste heat recovery device 5 and a heat exchanger 6; the alkali absorption unit is at least provided with an alkali absorption tower 7, and the wastewater treatment unit is at least provided with a neutralization tank 8 and a filter press 9; the dust removal unit, the fluorine removal unit, the volatile organic compound removal unit, the waste heat recovery unit and the alkali absorption unit are sequentially connected, and the fluorine removal unit and the alkali absorption unit are additionally connected with the wastewater treatment unit through wastewater pipelines.
A dust-containing gas inlet of the dust removal device 1 is connected with a waste gas collecting pipeline of a lithium battery recovery system, a purified gas outlet of the dust removal device 1 is connected with a gas phase inlet of the gas-liquid heat exchanger 2, and a gas phase outlet of the gas-liquid heat exchanger 2 is connected with a waste gas inlet at the lower part of the two-section circulating absorption tower 3; the lower section of the second-section circulating absorption tower 3 is an acidic absorption section which is provided with an acidic absorption liquid inlet, the outside of the tower body is provided with an acidic absorption liquid circulating pipeline, and an absorption liquid cooler 11 is arranged on the acidic absorption liquid circulating pipeline; the acid absorption liquid circulating pipeline is additionally connected with a liquid phase inlet of the gas-liquid heat exchanger 2, and a liquid phase outlet of the gas-liquid heat exchanger 2 is connected with the neutralizing tank 8; the upper section of the second-section circulating absorption tower 3 is an alkaline absorption section and is provided with an alkaline absorption liquid inlet, and the outside of the tower body is provided with an alkaline absorption liquid circulating pipeline which is additionally connected with a neutralizing tank 8; a purified gas outlet at the top of the second-section circulating absorption tower 3 is connected with a waste gas inlet of an incinerator, a flue gas outlet of the incinerator is connected with a waste gas inlet at the bottom of an alkali absorption tower 7 after passing through a heat exchanger 6 or a waste heat recovery device 5 and the heat exchanger 6, an alkali absorption liquid inlet is arranged at the upper part of the alkali absorption tower 7, an alkali liquor circulating pipeline is arranged outside the alkali absorption tower 7, the alkali liquor circulating pipeline is additionally connected with a neutralizing tank 8, and a purified gas outlet is arranged at the top of the alkali absorption tower 7; the neutralizing tank 8 is provided with a neutralizing alkali liquor inlet and a mixed liquor outlet, and the mixed liquor outlet is connected with a filter press 9.
The dust removing device 1 is a bag type dust remover, a cyclone dust remover or a multi-pipe cyclone dust remover, and the inner wall of the dust removing device is provided with a corrosion-resistant and wear-resistant material lining.
The upper section and the lower section of the two-section circulating absorption tower 3 are respectively provided with a filler, the filler adopts polyhedral hollow spheres, Taylor rosettes, rectangular saddle rings, pall rings, Raschig rings or regular corrugated plate fillers, and the filler is made of polypropylene, reinforced polypropylene or polytetrafluoroethylene.
A lithium cell recovery in-process exhaust gas purification system's theory of operation is: the waste gas generated in the lithium battery recovery process is firstly subjected to dust removal device 1 to remove dust-containing particles, then is subjected to secondary circulating absorption tower 3 to remove most of fluorine-containing components in the waste gas, the waste gas after the removal of the fluorine-containing components is subjected to high-temperature combustion or medium-temperature catalytic combustion to remove volatile organic compounds, and then is subjected to waste heat recovery and enters alkali absorption tower 7 to remove residual trace hydrogen fluoride; the waste liquid generated in the process is converged into the neutralizing tank 8 to react with the neutralizing alkali liquor, so that the fluorine and the phosphorus in the waste liquid are solidified and dehydrated to form harmless condensate calcium fluoride and calcium phosphate.
Lithium cell recovery in-process exhaust gas purification system's concrete working process as follows:
1) waste gas generated in the lithium battery recovery process enters the dust removal unit through the waste gas collection pipeline, dust-containing particles in the waste gas are filtered out and then are conveyed to the ash storehouse for temporary storage through the ash conveying device 10, and the dust content of the waste gas after dust removal is less than 10mg/m3；
2) The waste gas after dust removal and purification is sent into a fluorine removal unit, exchanges heat with absorption liquid from a second-stage circulating absorption tower 3 through a gas-liquid heat exchanger 2 to reduce the temperature, and then enters the second-stage circulating absorption tower 3; introducing an acidic absorption liquid into the lower section of the second-stage circulating absorption tower 3, and removing most of phosphorus pentafluoride and hydrogen fluoride in the waste gas; phosphorus pentafluoride in the waste gas reacts with the acidic absorption liquid to generate a fluorine-containing phosphorus complex, and the fluorine-containing phosphorus complex forms hydrofluoric acid and phosphoric acid respectively after the mixed solution after the reaction is heated by the gas-liquid heat exchanger 2; alkaline absorption liquid is introduced into the upper section of the second-section circulating absorption tower 3 to further absorb phosphorus pentafluoride and hydrogen fluoride escaping from the lower section; the molar content of fluorine in the waste gas purified by the fluorine removal unit is below 100 ppm;
3) the waste gas after dust removal and defluorination purification enters an incinerator in a volatile organic compound removal unit to be burnt at the high temperature of 850-1000 ℃ or catalytic combustion at the temperature of 250-350 ℃; dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, ethylene carbonate and a trace amount of fluorine-containing phosphorus compounds in the waste gas are completely oxidized under the action of high-temperature combustion or catalytic combustion to generate carbon dioxide, water and trace amounts of hydrogen fluoride and phosphorus pentoxide, and the content of non-methane total hydrocarbons in the waste gas after volatile organic compounds are removed is less than 80mg/m3The purification efficiency of VOCs is more than 95%;
4) high-temperature flue gas generated after the waste gas is subjected to high-temperature combustion in the step 3) enters a waste heat recovery unit, and low-medium pressure steam is generated by a waste heat recovery device 5; the flue gas after waste heat recovery enters an alkali absorption tower 7 after heat exchange and temperature reduction; or the medium-temperature flue gas generated after catalytic combustion of the waste gas enters the alkali absorption tower 7 after heat exchange and temperature reduction;
5) in the alkali absorption tower 7, the flue gas is in countercurrent contact with the alkali absorption liquid, the residual trace hydrogen fluoride in the flue gas is absorbed, and the content of the hydrogen fluoride in the purified flue gas is less than 3mg/m3；
6) The solution heated and decomposed by the gas-liquid heat exchanger 2, the discharge liquid at the upper section of the two-section circulating absorption tower 3 and the discharge liquid of the alkali absorption tower 7 are respectively merged into a neutralization tank 8 to react with a neutralization alkali liquor, wherein fluorine and phosphorus are solidified to form precipitates, and calcium fluoride and calcium phosphate are formed as harmless condensate after dehydration through a filter press 9.
The gas-liquid heat exchanger 2 uses the dedusted waste gas as a heat source to heat the acidic absorption liquid, the heating retention time of the acidic absorption liquid in the gas-liquid heat exchanger 2 is 60-600 min, and a flow channel of the acidic absorption liquid in the gas-liquid heat exchanger 2 is made of a corrosion-resistant graphite material.
The acidic absorption liquid is one or a mixture of sulfuric acid, phosphoric acid, hydrofluoric acid and hydrochloric acid; the mass fraction of the acidic absorption liquid is 1-10%.
The alkaline absorption liquid is a sodium hydroxide solution with the mass fraction of 5-20%.
The combustion temperature of the waste gas in the direct-fired furnace 41, the box-type heat accumulation incinerator and the rotary heat accumulation incinerator is 850-1000 ℃, the reaction temperature of the waste gas in the catalytic incinerator 43 is 250-350 ℃, and the airspeed is 15000h-1～25000h-1(ii) a The residence time of the waste gas in the incinerator is 0.2 s-5 s.
The neutralized alkali liquor is calcium hydroxide solution or magnesium hydroxide solution with the mass concentration of 5-20%.
The following examples are carried out on the premise of the technical solution of the present invention, and detailed embodiments and specific operation procedures are given, but the scope of the present invention is not limited to the following examples. The methods used in the following examples are conventional methods unless otherwise specified.
[ example 1 ]
As shown in fig. 1, in this embodiment, a waste gas purification device system in a lithium battery recovery process includes a dust removal unit, a fluorine removal unit, a volatile organic compound removal unit, a waste heat recovery unit, a wastewater treatment unit, and an alkali absorption unit. Wherein:
the dust removal unit comprises dust collector 1, defeated grey device 10 and ash storehouse, and the waste gas that produces among the lithium electricity recovery process gets into dust collector 1 through waste gas collection pipeline, and corrosion-resistant and wear-resisting material inside lining is established to dust collector 1 inner wall, for example the polytetrafluoroethylene material inside lining. The dust removing device 1 is preferably a bag filter. The particles contained in the waste gas after passing through the dust removing device 1 are attached to the cloth bag, and after being back blown by nitrogen, the dust is collected in the dust hopper of the dust removing device 1 and is sent by the dust conveying device 10And storing in an ash warehouse. The dust content of the waste gas purified by the dust removal unit is less than 10mg/m3And the waste gas after dust removal and purification is sent into the fluorine removal unit, so that a large amount of dust can be prevented from being introduced into subsequent treatment equipment, the equipment is prevented from being blocked, and the safe, continuous and stable operation of a subsequent treatment system is ensured.
The fluorine removal unit consists of a gas-liquid heat exchanger 2, a second-stage circulating absorption tower 3, an alkaline absorption liquid supply device 14 and an acidic absorption liquid supply device 13, the dedusted waste gas enters the gas-liquid heat exchanger 2 to exchange heat with the acidic absorption liquid from the second-stage circulating absorption tower 3, the cooled waste gas enters the second-stage circulating absorption tower 3, and most of fluorine-containing components in the waste gas are removed. The alkaline absorption liquid circulating pipeline at the upper section of the two-section circulating absorption tower 3 and the acidic absorption liquid circulating pipeline at the lower section are respectively provided with a circulating pump 12. The exhaust gas from which the fluorine-containing component is removed is sent to a volatile organic compound removal unit by a fan 16. The acid absorption liquid conveyed by the acid absorption liquid supply device 13 is hydrofluoric acid with the mass fraction of 5%, phosphorus pentafluoride reacts with the acid absorption liquid to form a corresponding fluorine-containing phosphorus complex, and the fluorine-containing phosphorus complex forms hydrofluoric acid and phosphoric acid respectively after the mixed solution after the reaction is heated by the gas-liquid heat exchanger 2. The alkaline absorption liquid delivered by the alkaline absorption liquid supply device 14 is a sodium hydroxide solution with a mass fraction of 10%, and phosphorus pentafluoride and hydrogen fluoride escaping from the lower stage are further absorbed at the upper stage of the second-stage circulating absorption tower 3. After the waste gas is purified by the fluorine removal unit, the molar content of fluorine in the waste gas is below 100ppm, the fluorine-containing compound in the waste gas is efficiently purified, the corrosion of the waste gas to subsequent devices is reduced, the service life of a waste gas purification system is prolonged, and the reliability and the safety of the operation of the system are ensured.
The volatile organic compound removing unit consists of a flame arrester 15 and a direct-fired furnace 41 (provided with a burner and a combustion-supporting fan), wherein the flame arrester 15 is arranged on a waste gas pipeline between the heat exchanger 6 and the direct-fired furnace 41; the waste gas after dust removal and defluorination purification is sent to a volatile organic compound removal unit through a fan 16, the combustion temperature in a direct combustion furnace 41 is controlled at 900 ℃, the retention time of the waste gas is 2.8s, and dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, ethylene carbonate and trace fluorine-containing phosphorus compounds in the waste gas are highIs completely oxidized at the temperature to generate carbon dioxide, water and trace hydrogen fluoride and phosphorus pentoxide, and the content of non-methane total hydrocarbon in the purified waste gas is less than 80mg/m3And the purification efficiency of VOCs reaches 99%.
The waste heat recovery unit is composed of a waste heat recovery device 5 and a heat exchanger 6 (a gas-gas heat exchanger), waste gas generated in the lithium battery recovery process contains a large amount of organic matter components, such as dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate and ethylene carbonate, after being incinerated by the direct-fired furnace, high-temperature smoke is used for producing low-medium pressure steam through the waste heat recovery device 5, and the waste gas after dust removal is preheated by the waste gas after waste heat recovery through the heat exchanger 6, so that the waste heat recovery efficiency of the smoke is further improved, the fuel consumption of the direct-fired furnace 41 is reduced, the energy consumption is saved, and the operation cost of a waste gas treatment system is reduced.
The alkali absorption unit consists of an alkali absorption tower 7, the flue gas subjected to heat exchange and temperature reduction by the heat exchanger 6 enters the alkali absorption tower 7 and is in countercurrent contact with a sodium hydroxide solution with the mass concentration of 10%, trace hydrogen fluoride in the flue gas is absorbed, and the content of the hydrogen fluoride in the clean flue gas is less than 3mg/m3And can be directly discharged into the atmosphere.
The waste water treatment unit consists of a neutralization tank 8 and a filter press 9, a solution obtained after heating decomposition of the gas-liquid heat exchanger 2, a discharge liquid obtained after absorption of the upper section of the two-section circulating absorption tower 3 and a discharge liquid obtained after absorption of the alkali absorption tower 7 are respectively converged into the neutralization tank 8, a calcium hydroxide solution with the mass fraction of 10% is introduced into the neutralization tank 8 for neutralization reaction, fluorine and phosphorus are solidified to form precipitates, calcium phosphate fluoride is formed after dehydration through the filter press 9, both the fluorine and the phosphorus are harmless condensate and can be used for landfill of mining area sites and the like, and the waste gas treatment and waste utilization are environment-friendly and waste utilization are realized.
[ example 2 ]
As shown in fig. 2, in this embodiment, a waste gas purification device system in a lithium battery recovery process includes a dust removal unit, a fluorine removal unit, a volatile organic compound removal unit, a waste heat recovery unit, a wastewater treatment unit, and an alkali absorption unit. Wherein:
the dust removal unit consists of a dust removal device 1, an ash conveying device 10 and an ash storehouse, wherein the dust removal device 1 selects a bag type dust removal deviceThe working principle of the device is the same as that of embodiment 1. The dust content of the purified waste gas is less than 10mg/m3。
The fluorine removal unit is composed of a gas-liquid heat exchanger 2, a two-stage circulating absorption tower 3, an alkaline absorption liquid supply device 14 and an acidic absorption liquid supply device 13, the working principle of the fluorine removal unit is basically the same as that of the embodiment 1, the acidic absorption liquid adopts hydrochloric acid with the mass fraction of 5%, the alkaline absorption liquid adopts sodium hydroxide solution with the mass fraction of 10%, and the molar content of fluorine in the waste gas purified by the fluorine removal unit is below 100 ppm.
The volatile organic compound removing unit consists of a flame arrester 15 and a box-type regenerative thermal oxidizer 42(RTO furnace, provided with a burner and a combustion fan), wherein the flame arrester 15 is arranged on a waste gas pipeline between the two-section circulating absorption tower 3 and the fan 16; the waste gas after dust removal and defluorination purification is sent into a box type heat accumulation incinerator 42 by a fan 16, the combustion temperature in the box type heat accumulation incinerator 42 is controlled at 950 ℃, the retention time of the waste gas is 2s, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, ethylene carbonate and a trace amount of fluorine-containing phosphorus compounds in the waste gas are completely oxidized at high temperature to generate carbon dioxide, water and a trace amount of hydrogen fluoride and phosphorus pentoxide, and the content of non-methane total hydrocarbon in the purified waste gas is less than 60mg/m3And the purification efficiency of VOCs is 95%.
The waste heat recovery unit consists of a waste heat recovery device 5 and a heat exchanger 6 (a gas-water heat exchanger), waste gas generated in the lithium battery recovery process contains a large amount of organic matter components such as dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate and ethylene carbonate, after the waste gas is incinerated in the box type heat accumulation incinerator 42, a part of high-temperature flue gas enters the waste heat recovery device 5 from the side line of the furnace body for producing low and medium pressure steam as a byproduct, the other part of high-temperature flue gas is used for heating a heat accumulator in the box type heat accumulation incinerator 42, and the flue gas after waste heat recovery enters the heat exchanger 6 for heating tap water to provide domestic hot water, so that the waste heat recovery efficiency is further improved, and energy.
The alkali absorption unit consists of an alkali absorption tower 7, the flue gas which is subjected to heat exchange and temperature reduction through a heat exchanger 6 enters the alkali absorption tower 7 and is in countercurrent contact with a sodium hydroxide solution with the mass concentration of 10 percent, trace hydrogen fluoride in the flue gas is absorbed,the content of hydrogen fluoride in the clean smoke is less than 3mg/m3And can be directly discharged into the atmosphere.
The wastewater treatment unit consists of a neutralization tank 8 and a filter press 9, and the working principle is the same as that of example 1.
[ example 3 ]
As shown in fig. 3, in this embodiment, a waste gas purification system in a lithium battery recovery process includes a dust removal unit, a fluorine removal unit, a volatile organic compound removal unit, a waste heat recovery unit, a wastewater treatment unit, and an alkali absorption unit. Wherein:
the dust removal unit consists of a dust removal device 1, an ash conveying device 10 and an ash warehouse, wherein the dust removal device 1 adopts a bag type dust remover, and the working principle of the dust removal device is the same as that of the embodiment 1. The dust content of the purified waste gas is less than 10mg/m3。
The fluorine removal unit is composed of a gas-liquid heat exchanger 2, a two-stage circulating absorption tower 3, an alkaline absorption liquid supply device 14 and an acidic absorption liquid supply device 13, the working principle of the fluorine removal unit is basically the same as that of the embodiment 1, the acidic absorption liquid adopts a mixed solution of hydrochloric acid with the mass fraction of 5% and phosphoric acid with the mass fraction of 5%, the alkaline absorption liquid adopts a sodium hydroxide solution with the mass fraction of 15%, and the molar content of fluorine in the waste gas purified by the fluorine removal unit is below 100 ppm.
The volatile organic compound removing unit consists of a flame arrester 15 and a catalytic incinerator 43 (provided with a burner and a combustion-supporting fan), the waste gas after dust removal and defluorination purification is sent into the catalytic incinerator 43 through a fan 16, the combustion temperature in the catalytic incinerator 43 is controlled at 300 ℃, and the catalyst airspeed is 20000h-1Selecting noble metal catalyst, fully oxidizing dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate and ethylene carbonate in the waste gas under the combined action of hot air and catalyst to produce carbon dioxide and water, and purifying the waste gas to obtain the purified waste gas with total hydrocarbon content of non-methane less than 20mg/m3The purification efficiency of VOCs is 96%.
The waste heat recovery unit is composed of a heat exchanger 6 (a gas-gas heat exchanger), and the medium-temperature flue gas generated by the catalytic incinerator 43 is preheated by the heat exchanger 6 to remove dust, so that the waste heat recovery efficiency of the flue gas is further improved, the fuel consumption of the catalytic incinerator 43 is reduced, the energy consumption is saved, and the operation cost of a waste gas treatment system is reduced.
The alkali absorption unit consists of an alkali absorption tower 7, the flue gas after heat exchange by the heat exchanger 6 enters the alkali absorption tower 7 and is in countercurrent contact with a sodium hydroxide solution with the mass concentration of 10%, trace hydrogen fluoride in the flue gas is absorbed, and the content of the hydrogen fluoride in the clean flue gas is less than 3mg/m3And can be directly discharged into the atmosphere.
The wastewater treatment unit consists of a neutralization tank 8 and a filter press 9, and the working principle is the same as that of example 1.
The terms and expressions which have been employed in the specification are used as terms of description and not of limitation, and there is no intention in the use of such terms and expressions of excluding any equivalents of the features shown and described or portions thereof.
The above-described embodiments are only preferred embodiments of the present invention, and the protection scope of the present invention should not be limited thereby, and it should be appreciated by those skilled in the art that changes and modifications may be made in these embodiments without departing from the principles and spirit of the present invention, the protection scope of which is defined in the appended claims and their equivalents.
Claims (5)
1. A waste gas purification system in a lithium battery recovery process is characterized by comprising a dust removal unit, a fluorine removal unit, a volatile organic compound removal unit, a waste heat recovery unit, an alkali absorption unit and a wastewater treatment unit; the dust removal unit is at least provided with a dust removal device, and the fluorine removal unit is at least provided with a gas-liquid heat exchanger and a two-section circulating absorption tower; the volatile organic compound removing unit is at least provided with an incinerator; the waste heat recovery unit is at least provided with a heat exchanger or a waste heat recovery device and a heat exchanger; the alkali absorption unit is at least provided with an alkali absorption tower, and the wastewater treatment unit is at least provided with a neutralization tank and a filter press; the dust removal unit, the fluorine removal unit, the volatile organic compound removal unit, the waste heat recovery unit and the alkali absorption unit are sequentially connected, and the fluorine removal unit and the alkali absorption unit are additionally connected with the wastewater treatment unit through wastewater pipelines.
2. The system for purifying the waste gas generated in the lithium battery recovery process according to claim 1, wherein a dust-containing gas inlet of the dust removal device is connected with a waste gas collecting pipeline of the lithium battery recovery system, a purified gas outlet of the dust removal device is connected with a gas phase inlet of the gas-liquid heat exchanger, and a gas phase outlet of the gas-liquid heat exchanger is connected with a waste gas inlet at the lower part of the two-stage circulating absorption tower; the lower section of the second-section circulating absorption tower is an acidic absorption section and is provided with an acidic absorption liquid inlet, the outside of the tower body is provided with an acidic absorption liquid circulating pipeline, and an absorption liquid cooler is arranged on the acidic absorption liquid circulating pipeline; the acid absorption liquid circulating pipeline is additionally connected with a liquid phase inlet of the gas-liquid heat exchanger, and a liquid phase outlet of the gas-liquid heat exchanger is connected with the neutralizing tank; the upper section of the second-section circulating absorption tower is an alkaline absorption section and is provided with an alkaline absorption liquid inlet, and an alkaline absorption liquid circulating pipeline is arranged outside the tower body and is additionally connected with a neutralization tank; a purified gas outlet at the top of the second-section circulating absorption tower is connected with a waste gas inlet of the incinerator, a flue gas outlet of the incinerator is connected with a waste gas inlet at the bottom of the alkali absorption tower after passing through a heat exchanger or a waste heat recovery device and the heat exchanger, an alkali absorption liquid inlet is arranged at the upper part of the alkali absorption tower, an alkali liquor circulating pipeline is arranged outside the alkali absorption tower, the alkali liquor circulating pipeline is additionally connected with a neutralizing tank, and a purified gas outlet is arranged at the top of the alkali absorption tower; the neutralizing tank is provided with a neutralizing alkali liquor inlet and a mixed liquor outlet, and the mixed liquor outlet is connected with a filter press.
3. The system for purifying the waste gas generated in the lithium battery recycling process as claimed in claim 1 or 2, wherein the dust removing device is a bag type dust remover, a cyclone dust remover or a multi-tube cyclone dust remover, and the inner wall of the dust removing device is provided with a lining made of corrosion-resistant and wear-resistant materials.
4. The system for purifying the waste gas generated in the lithium battery recovery process according to claim 1 or 2, wherein the upper section and the lower section of the two-section circulating absorption tower are respectively provided with a filler, the filler is a polyhedral hollow sphere, a Taylor flower ring, a rectangular saddle ring, a pall ring, a Raschig ring or a regular corrugated plate, and the filler is made of polypropylene, reinforced polypropylene or polytetrafluoroethylene.
5. The system for purifying waste gas generated in the lithium battery recycling process according to claim 1 or 2, wherein the incinerator is one of a direct-fired furnace, a box-type regenerative incinerator, a rotary regenerative incinerator and a catalytic incinerator.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110508057A (en) * | 2019-09-12 | 2019-11-29 | 鞍钢(上海)环境工程技术有限公司 | Exhaust gas purifying method and system in a kind of lithium battery removal process |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110508057A (en) * | 2019-09-12 | 2019-11-29 | 鞍钢(上海)环境工程技术有限公司 | Exhaust gas purifying method and system in a kind of lithium battery removal process |
| CN110508057B (en) * | 2019-09-12 | 2024-05-03 | 鞍钢(上海)环境工程技术有限公司 | Waste gas purification method and system in lithium battery recovery process |
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