CN212327906U - Lithium battery waste liquid recycling environmental protection processing system - Google Patents
Lithium battery waste liquid recycling environmental protection processing system Download PDFInfo
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- CN212327906U CN212327906U CN202020924608.4U CN202020924608U CN212327906U CN 212327906 U CN212327906 U CN 212327906U CN 202020924608 U CN202020924608 U CN 202020924608U CN 212327906 U CN212327906 U CN 212327906U
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The utility model discloses a lithium cell waste liquid resourceful environmental protection processing system relates to industrial waste environmental protection processing and resourceful technical field, including burning furnace, half-dry deacidification reactor, quench tower, one-level, second grade deacidification tower, gas heater, dust remover, gas heater, denitration equipment, chimney and sediment liquid holding vessel, waste liquid treatment tank, useless solid salt solution adds hydrochloric acid treatment tank, useless solid salt solution adds LiOH treatment tank, the rotary drum, main equipment such as evaporimeter and drying furnace, utilize techniques such as burning and chemical reaction with the Na in the lithium cell waste liquid+、Ca2+、F‑、Cl‑、Li+Etc. into solid LiF, anhydrous calcium chloride. The utility model discloses fully realized the purpose that lithium cell waste liquid innoxious, minimizing, resourceization. Outstanding environmental protection effect, full resource utilization and obvious energy-saving and consumption-reducing effects. The system and the equipment have reasonable integral design, compact structure and flexible treatment mode, and are suitable for popularization and use.
Description
Technical Field
The utility model relates to an industrial waste handles recovery technical field, specifically is a lithium cell waste liquid resourceful environmental protection processing system.
Background
The current chemical industry is more and more developed, and waste liquid waste gas production volume is more and more, and the national requirement to the environmental protection also is more and more high, along with the development of production, chemical production device is large-scale to build rapidly, and the output of harmful waste is more and more.
For example, the lithium battery is one of the most popular batteries in the 21 st century, and is widely applied to cameras, mobile phones, notebook computers, portable measuring instruments, electric vehicles and the like, along with the popularization of the policy of oil-free vehicles, the usage amount of the lithium battery is increased, more and more lithium battery manufacturers are provided, and the waste liquid generated in the production of the lithium battery is increased. And lithium cell can produce a large amount of washing waste water in process of production, and washing waste water contains a large amount of organic pollutants, and has the hypertoxic, belongs to hazardous waste, can not directly discharge, can discharge after needing to administer, therefore the treatment process of lithium cell waste liquid also should be transported to take place. The prior art generally adopts electrochemical flocculation precipitation for treatment.
For example, the waste lithium battery electrolyte and the electrolyte wastewater treatment method with the patent number of CN201610057373.1 based on MBR and A2/O, and the waste lithium battery liquid treatment process and the treatment system with the patent number of CN201710015803.8 adopt electrochemical methods for treatment, so that the process requirement is high, the reaction time is too long, the efficiency is low, the requirement on operators is also high, the final waste is not well utilized, the precious Li resource is wasted, and the subsequent treatment is still needed.
The national treatment technology for harmful wastes is higher and higher, the incineration technology has the advantages of thorough treatment, high efficiency, investment saving, small occupied area and the like, and becomes an important technology in the chemical industry, the incineration device also becomes an important component of the chemical device, the incineration method for treating organic wastes is an effective means for treating organic matters in waste liquid by utilizing air deep oxidation under the high-temperature condition, and the wastes of organic compounds are generally incinerated at high temperature to be converted into CO2And H2After O, the reaction mixture is discharged to the atmosphere. As long as the temperature in the incinerator is more than 1100 ℃, and the waste has enough residence time in the high-temperature zone in the incinerator, the waste can be basically and completely decomposed, and the environmental-friendly standard reaching or ultra-clean emission can be realized through flue gas purification treatment means such as dust removal, deacidification, denitration and the like. Meanwhile, the useful components in the waste are recovered by adopting an advanced technology in the incineration process, so that the resource utilization of the waste can be realized.
Therefore, how to realize the standard discharge of the waste and reasonably use the waste, and the realization of the treatment mode of the one-stone two-bird is an important subject before the engineering design workers and is also the main purpose of the patent.
Disclosure of Invention
An object of the utility model is to provide a lithium cell waste liquid resourceful environmental protection processing system to solve the problem that proposes in the above-mentioned background art.
In order to achieve the above object, the utility model provides a following technical scheme: a lithium battery waste liquid recycling environment-friendly treatment system comprises an incinerator, a semi-dry deacidification reactor, a primary deacidification tower, a secondary deacidification tower, a flue gas heat exchanger, a bag-type dust collector, denitration equipment, a chimney, a drying furnace and an evaporator, wherein a waste liquid atomization spray gun arranged on the wall of the incinerator is connected with a waste liquid storage tank and two screw conveying pumps for one use and the other use through pipelines, an auxiliary combustion-supporting burner is arranged on the wall of the incinerator, a flue gas outlet of the incinerator is sequentially connected with the semi-dry deacidification reactor, a quench water tower, the primary deacidification tower, the secondary deacidification tower, the flue gas heat exchanger, the bag-type dust collector, the denitration equipment and the chimney through flues, a flue gas outlet of the denitration equipment is connected to a flue gas inlet of the flue gas heat exchanger, an induced draft fan is arranged at the flue gas outlet of the flue gas heat, the waste liquid treatment tank is sequentially connected with a waste liquid conveying pump, a rotary drum A and a waste solid salt dissolving liquid and hydrochloric acid treatment tank through pipelines, the waste solid salt dissolving liquid and hydrochloric acid treatment tank is connected with a waste solid salt dissolving liquid first-stage conveying pump for one use through pipelines and a waste solid salt dissolving liquid and LiOH treatment tank, the waste solid salt dissolving liquid and LiOH treatment tank is sequentially connected with a waste solid salt dissolving liquid second-stage conveying pump, a rotary drum B, an evaporator and a drying furnace through pipelines, the lower ends of a first-stage deacidification tower and a second-stage deacidification tower are sequentially connected with a circulating alkali liquid return tank through pipelines, the right side of the circulating alkali liquid return tank is connected with a circulating alkali liquid neutralization tank through pipelines, the circulating alkali liquid neutralization tank is respectively connected with a semi-dry deacidification reactor, a quench water tower, a first-stage deacidification tower and a second-stage deacidification tower through pipelines, and a semi-dry reactor alkali liquid spray pump is arranged on the pipeline between the circulating alkali liquid neutralization tank and the semi-dry, the circulating alkali liquor neutralizing tank is characterized in that a quenching pump is arranged on a pipeline between the circulating alkali liquor neutralizing tank and the quenching water tower, and a primary deacidification spray pump and a secondary deacidification spray pump are respectively arranged on the pipeline between the circulating alkali liquor neutralizing tank and the two deacidification towers.
Further: the semi-dry deacidification reactor and the quenching water tower both belong to quenching equipment, the quenching equipment adopts two forms, one belongs to a wet method and the other belongs to a semi-dry method, and the wet method comprises the semi-dry deacidification reactor and the quenching water tower and is connected in sequence through a flue; the semidry method comprises a semidry deacidification reactor, a high-temperature ceramic film deduster and a quenching water tower which are sequentially connected through a flue; the semi-dry deacidification reactor is characterized in that flue gas passes through an alkali liquor spray pump of the semi-dry deacidification reactor, circulating alkali liquor is returned to a tank, alkali liquor is pumped and sent to an alkali liquor spray atomization spray gun A, the alkali liquor is atomized and sprayed into the semi-dry deacidification reactor through the alkali liquor spray atomization spray gun A, the flue gas passes through a quench pump, the circulating alkali liquor is returned to the tank, the alkali liquor is pumped and sent to an alkali liquor spray atomization spray gun B, the alkali liquor is atomized and sprayed into a quench water tower through the alkali liquor spray atomization spray gun B, and the alkali liquor is neutralized with acid gas in the flue gas to realize further deacidification, a slaked lime pipeline is connected at a flue outlet of the semi-dry deacidification reactor, the lowest end of the quench water tower is connected to a slag liquor collecting tank through a pipeline, one side of an ash hopper at the lower end of a high-temperature, and the left side of the residue liquid collecting tank is connected with an additional hydrochloric acid pipeline.
Further: the device comprises a first-stage deacidification tower, a second-stage deacidification tower, a demister, desalted water cleaning atomization spray guns and desalted water cleaning spray guns, wherein the first-stage deacidification tower and the second-stage deacidification tower are internally provided with three layers of alkali liquor atomization spray guns, the uppermost end in the second-stage deacidification tower is provided with the demister, the upper end and the lower end of the demister are respectively provided with the desalted.
Further: denitration equipment is equipped with flue gas heater, flue gas heating combustor, denitration tower, flue gas heater has arranged on upper portion flue gas heater flue gas heating combustor, the flue gas heater lower extreme is connected with the denitration tower, the denitration tower upper end is equipped with the denitration and spouts ammonia atomizing spray gun, the denitration is spouted ammonia atomizing spray gun and is connected with the ammonia pipeline, arrange multilayer low temperature denitration catalyst in the denitration tower.
Further: one side of an ash bucket on the lower part of the bag-type dust collector is connected with a desalted water pipeline, the lowest end of the ash bucket is connected with a wastewater tank through a pipeline, the wastewater tank is sequentially connected with a wastewater delivery pump, and the wastewater delivery pump is connected onto a slag liquid collecting tank through a pipeline.
Further: the right side of the waste liquid treatment tank is connected with an external calcium chloride and lime milk pipeline.
Further: the rotary drum A and the rotary drum B both belong to solid-liquid separation devices, wastewater separated by the rotary drum A is sent to a sewage treatment plant through a pipeline for retreatment, separated solid salts are sent to a waste solid salt dissolving solution and hydrochloric acid treatment tank, the waste solid salt dissolving solution and hydrochloric acid treatment tank is provided with an additional hydrochloric acid pipeline and a stirrer, a solution prepared in the waste solid salt dissolving solution and hydrochloric acid treatment tank is sent to a waste solid salt dissolving solution and LiOH treatment tank through a waste solid salt dissolving solution primary conveying pump, and then is conveyed to the rotary drum B through a waste solid salt dissolving solution secondary conveying pump; the waste solid salt solution and LiOH treatment tank is provided with an additional LiOH solution pipeline and a stirrer, the solution separated by the rotary drum B enters an evaporator, the separated solid salt is sent to a packing workshop for recycling, and the solution separated by the rotary drum B enters the evaporator for evaporation and then is crystallized to form solid crystals, and the solid crystals are sent to a drying furnace for drying.
Further: the temperature of the drying furnace is controlled to be 260-300 ℃ according to the property of the solid crystal, a partition wall heat exchange mode is adopted, the purity of the solid and the purity of hot air after heat exchange are ensured, and the purity of the hot air after heat exchange can be used as primary air to be sent into the incinerator to save energy.
Firstly, an incinerator:
according to the requirement of GB18484 hazardous waste incineration pollution control Standard (2019 edition promulgated manuscript), the material incineration temperature of the hazardous waste is more than or equal to 1100 ℃. The incineration temperature of the incinerator is controlled to be about 1200 ℃, and the retention time is 2 s.
Solid Li produced in an incinerator2And O and molten NaF pass through a slag discharge pipe at the bottom of the incinerator and are collected into a slag liquid collecting tank for centralized treatment.
Drying CaCl in air required by incineration in incinerator by drying furnace2·2H2And the cooled hot air after O realizes energy conservation.
Considering the strong corrosiveness of hydrogen fluoride gas, incinerator materials are selected to take full account of the corrosiveness of hydrogen fluoride. Hydrogen fluoride is very active and reacts with Fe and Si at any temperature, so that a high-purity white corundum brick refractory material and a heat-insulating material without Fe and Si are required to be selected, and a special high-temperature-resistant and hydrogen fluoride corrosion-resistant coating is adopted on the fire surface.
Considering that the fluorine content in the waste is large, in order to ensure that the fluorine element is converted into hydrogen fluoride in the incineration process as much as possible and prevent hydrogen deficiency in the hydrogen fluoride generation process, water vapor is reserved for supplementing hydrogen to the hearth.
Two forms, wet and semi-dry:
a wet method, namely a semi-dry deacidification reactor (namely a first-stage quenching tower) and a second-stage quenching tower, and a semi-dry method, namely a semi-dry deacidification reactor (namely a first-stage quenching tower) and a high-temperature ceramic dust remover
Semi-dry type deacidification reactor
The temperature of the flue gas discharged from the hearth of the incinerator is about 1200 ℃, and in order to meet the use requirements of subsequent process equipment, the flue gas needs to be cooled. According to the GB18484 latest hazardous waste incineration control standard (2014 quotation for opinions), HJT176-2005 hazardous waste centralized incineration disposal engineering construction technical specification and other standards, a waste heat boiler is not required to be adopted for cooling a hazardous waste incineration system for treating hazardous waste with high fluorine content or more than 5% chlorine content. In the process, the temperature of the flue gas is reduced from 1200 ℃ to about 550 ℃ by spraying alkali liquor into the reactor. Meanwhile, partial HF gas in the flue gas can be removed through the alkali liquor.
Considering the corrosivity of hydrogen fluoride gas, the reactor is filled with high-temperature flue gas, the material selection is the same as that of the incinerator, namely, a high-purity white corundum brick refractory material and a Fe-Si-free heat-insulating material are selected, and special high-temperature-resistant and hydrogen fluoride corrosion-resistant coating is adopted on the flue gas side.
Introduction of a quenching system of a semi-dry deacidification reactor: the flue gas is quickly cooled by spraying alkali liquor into the high-temperature flue gas at about 1200 ℃ from the incinerator, so that the temperature of the flue gas is reduced from 1200 ℃ to about 550 ℃, and meanwhile, part of HF gas in the flue gas can be removed through the alkali liquor.
The flue gas cooled from 1200 ℃ to about 550 ℃ can be treated by one of the following two methods:
the first treatment method adopts a second-stage quenching tower
In order to achieve the purposes of reducing the temperature of the flue gas and preventing the flue gas from generating dioxin substances in the cooling process and removing part of HF, the system is provided with a second-stage quenching mode, alkali liquor is sprayed, the flue gas with the temperature of about 550 ℃ coming out of a quenching system of a semi-dry deacidification reactor is further reduced to be below 80 ℃ within 1s, and then the flue gas is sent into a first-stage deacidification tower for continuous treatment.
Introducing 550 deg.C high temperature flue gas from the upper part of quenching tower, rapidly cooling the flue gas by spraying atomized quenching circulating alkali liquor into the flue gas to rapidly cool the flue gas to about 80 deg.C within 1s, and allowing part of HF and Ca (OH)2Neutralization reaction occurs to generate calcium fluoride.
The quenching spraying alkali liquor coming from the bottom of the quenching water tower mainly contains Na2HPO4、NaF、LiF、CaF2And collecting the components in a slag liquid collecting tank for centralized treatment.
The second treatment method adopts a high-temperature ceramic dust remover
And cooling the incinerator flue gas through a semi-dry deacidification reactor, and then entering a high-temperature ceramic film deduster for dedusting and purifying.
Because the flue gas of the incinerator contains Na4P2O7、NaF、Li2O, especially Na4P2O7Has high content of Na in the smoke when the temperature of the smoke is reduced from 1200 ℃ to about 550 DEG C4P2O7Changing the gas state into solid particles, passing through a high-temperature ceramic dust collector, and then obtaining Na in the flue gas4P2O7、NaF、Li2And O and other components are filtered, so that gas-solid separation is performed on the flue gas, and preliminary purification treatment is realized.
The high-temperature ceramic film dust remover is a high-temperature gas-solid separation device taking a high-performance high-temperature ceramic film element as a core, and mainly comprises the high-temperature ceramic film element, a high-temperature dust remover shell, a pulse back-blowing system, an automatic control system and the like.
The ash bucket of the high-temperature ceramic film dust remover is provided with a desalted water interface, and the desalted water is sprayed into the ash bucket to scour and collect dust and particulate matters in the ash bucket into a slag liquid collecting tank for centralized treatment.
Third, deacidify the tower
The temperature of the flue gas from the quenching water tower is about 80 ℃, and a two-stage deacidification tower is arranged to remove the hydrogen fluoride gas from the flue gas.
If the waste liquid of the lithium battery to be incinerated contains F-、Cl-When the amount of the acid radical ions is higher, more than two stages of deacidification towers are needed to realize F pairs-、Cl-Removing the acid radical ions by neutralization reaction; if the waste liquid of the lithium battery to be incinerated contains F-、Cl-When the amount of the acid radical ions is lower, a first-stage deacidification tower can be adopted, and the F can be treated-、Cl-The acid radical ions are neutralized and removed.
Fourth, flue gas heat exchanger
The flue gas heat exchanger comprises a shell, a frame, a heat exchange pipe, an external heat preservation, a flue gas measuring point and the like. The heating surface of the flue gas heat exchanger is arranged in a flue formed by the shell and the frame, and the clean flue gas with higher temperature after denitration treatment exchanges heat with the flue gas with lower temperature from the secondary deacidification tower through the heat exchange tube. The method comprises the following steps that high-temperature clean flue gas after denitration treatment passes through a shell pass, low-temperature flue gas from a secondary deacidification tower passes through a tube pass, the low-temperature flue gas from the secondary deacidification tower enters a bag-type dust remover after heat exchange and temperature rise, the flue gas enters a flue gas reheating furnace for heating after dust removal, the flue gas enters a denitration device for denitration after reaching the activation temperature of a denitration catalyst, the denitrated flue gas serves as a heat source, and the low-temperature flue gas from the secondary deacidification tower is heated in a flue gas heat exchanger. And a smoke temperature measuring and pressure measuring point is arranged at a reasonable position of the smoke heat exchanger module.
Selecting materials of the flue gas heat exchanger: the shell and the carbon steel inner coating of the heat exchange tube are KN22 temperature-resistant and corrosion-resistant coating. The outer layer of the shell is welded with a frame for supporting and reinforcing, and the frame is a combined beam made of Q235B. And laying heat insulation materials on the outer layer of the shell steel plate to ensure that the temperature of the outer wall of the flue gas heat exchanger is less than or equal to 60 ℃ in normal operation.
Bag dust collector
Selecting materials of a bag-type dust collector: the filter bag is made of PTFE material, and the checkered plate, the bag cage and the inner side of the box body are made of carbon steel KN22 temperature-resistant corrosion-resistant paint.
The ash bucket of the bag-type dust collector is provided with a desalted water interface, and the desalted water is sprayed into the ash bucket to wash out dust and particles in the ash bucket, and the dust and the particles are collected in a waste water tank and sent into a slag liquid collecting tank by a water pump to be treated in a centralized manner.
Sixthly, denitration equipment: adopts a combination mode of a heater and an SCR denitration tower
Flue gas discharged by gas-solid separation of the bag-type dust collector enters a flue gas heater, and the flue gas is reheated to the activation temperature of a denitration catalyst of a denitration device by burning natural gas and then enters the denitration device to remove NOx in the flue gas.
The SCR denitration device mainly comprises an external steel frame, an outer protective steel plate, a lining protective furnace wall, a catalyst bracket and an SCR denitration catalyst, wherein the SCR denitration catalyst is a medium-low temperature catalyst, the operation temperature is 260-400 ℃, and the service life is more than or equal to 5 years. Material selection of the SCR deacidification device: the material of the contact part of the inside of the denitration device and the flue gas is carbon steel internal coating KN22 temperature-resistant corrosion-resistant coating.
Seventh, the flue gas is discharged
The purified flue gas after deacidification and denitration is cooled by a flue gas heat exchanger and then is sent into a chimney by a draught fan for evacuation. The material of the contact part of the induced draft fan and the flue gas is carbon steel internal coating KN22 temperature-resistant corrosion-resistant coating. The main material of the chimney is carbon steel internal coating KN22 temperature-resistant corrosion-resistant coating.
Eighthly, recovery treatment of salt:
1. the recovery materials generated by the incinerator, the quench water tower, the deacidification tower and the bag-type dust remover are all collected into a slag liquid collecting tank for centralized treatment, and the main components are as follows: na (Na)2HPO4、NaF、LiF、CaF2And the like.
2. Firstly, hydrochloric acid is added into a slag liquid collecting tank to ensure that the pH value of the solution in the tank is adjusted<3, converting it into NaCl, CaF2、LiF、Na2HPO4And the like.
3. The adjusted solution flows into a waste liquid treatment tank from a slag liquid collection tank.
4. Adding calcium chloride aqueous solution and lime milk into the waste liquid treatment tank, wherein Ca is contained2+And F-Reaction to CaF2，CaF2Is insoluble in water. Meanwhile, Li+And F-The reaction produces LiF, which is also a water insoluble substance.
Ca2++2F-→CaF2↓
Li++F-→LiF↓
5. The slurry at the bottom of the waste liquid treatment tank is led out by a slurry pump, and is dehydrated by a rotary drum, so that waste solid salt (CaF) is separated2LiF, etc.). And returning a part of the wastewater separated by the rotary drum to the circulating alkali liquor return tank, and discharging a part of the wastewater to a wastewater treatment plant.
6. Separating the waste solid salt (CaF)2LiF) is sent into a waste solid salt treatment tank 1, a hydrochloric acid solution is added into the tank for mixing, and the temperature of the solution is ensured to be lower than 10 ℃. Under these conditions, CaF2Dissolving in hydrochloric acid solution, and converting into CaCl2Whereas LiF is insoluble in hydrochloric acid solution. And (3) leading out the solution in the waste solid salt treatment tank 1 by using a slurry pump, and sending the solution into a waste solid salt treatment tank 2. LiOH, Li in LiOH is added into the waste solid salt treatment tank 2+Will react with F in solution-The reaction produces LiF. The reaction process is as follows:
CaF2+2HCl→CaCl2+HF
LiOH+ HF→LiF↓+H2O
extracting the solution in the waste solid salt treatment tank 2 by a slurry pump, dehydrating by a rotary drum, and separating LiF solid, wherein the aqueous solution only contains CaCl2And (3) components. CaCl separated by a rotary drum2Recovery of CaCl from aqueous solutions by evaporation2·2H2And O, and drying to recover anhydrous calcium chloride.
The utility model has the advantages that: carry out further refinement and optimization through the compound mode of existing equipment between to equipment, the good waste liquid of more reasonable processing carries out rationalization maximize's processing with the waste liquid and utilizes, and concrete effect is as follows:
1. the incinerator has sufficient combustion and good effect, thoroughly burns organic matters in the lithium battery waste liquid, and converts alkali metal contained in the organic matters into Na4P2O7、NaF、Li2O and the like;
2. the double-stage cooling instantly reduces the temperature of the flue gas to 80 ℃ in less than 1s, and simultaneously adopts circulating alkali liquor to reduce the temperature, thereby effectively inhibiting the formation of dioxin;
3. the flue gas heat exchanger is arranged to reasonably utilize the temperature of the flue gas in the system, so that the aims of saving energy and reducing consumption are fulfilled;
4. changes waste into valuable by adopting scientific means, recycles LiF and anhydrous calcium chloride with high market price, and realizes resource utilization of waste.
The utility model relates to a rationally, compact structure, the flue gas after the processing accords with national environmental protection requirement completely, selects wet process processing mode or dry process processing mode by enterprise's comprehensive consideration, and nimble flexible is fit for using widely.
Drawings
FIG. 1 is a schematic view of the wet process of the present invention;
FIG. 2 is a schematic diagram of the semi-dry process of the present invention;
FIG. 3 is an enlarged view of a portion of the wet combination;
fig. 4 is a partially enlarged view of a semi-dry combination.
In the figure: 1. incinerator, 2, semi-dry deacidification reactor, 3, primary deacidification tower, 4, secondary deacidification tower, 5, flue gas heat exchanger, 6, bag-type dust remover, 7, denitration equipment, 8, chimney, 9, drying furnace, 10, rotary drum A, 11, waste liquid storage tank, 12, slag liquid collection tank, 13, waste liquid treatment tank, 14, circulating alkali liquor return tank, 15, circulating alkali liquor neutralization tank, 16, waste water tank, 17, evaporator, 18, waste solid salt solution and LiOH treatment tank, 19, quench pump, 20, primary deacidification spray pump, 21, secondary deacidification spray pump, 22, semi-dry deacidification reactor alkali liquor spray pump, 23, circulating alkali liquor delivery pump, 24, waste water delivery pump, 25, waste liquid delivery pump, 26, draught fan, 27, screw rod delivery pump, 28, waste liquid atomization spray gun, 29, auxiliary burner, 30, alkali liquor atomization spray gun A, 31, flue gas heat exchanger, 6, cloth bag dust collector, 7, denitration equipment, 8, chimney, Alkali liquor spraying atomizing spray gun B, 32, desalted water cleaning atomizing spray gun, 33, demister, 34, flue gas heater, 35, denitration ammonia spraying atomizing spray gun, 36, denitration tower, 37, flue gas heating burner, 38, rotary drum B, 39, waste solid salt dissolving liquid primary conveying pump, 40, waste solid salt dissolving liquid secondary conveying pump, 41, waste solid salt dissolving liquid hydrochloric acid treatment tank, 42, high-temperature ceramic film dust remover, 43, quenching water tower, 44 and low-temperature denitration catalyst.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely with reference to the accompanying drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only some embodiments of the present invention, not all embodiments. Based on the embodiments in the present invention, all other embodiments obtained by a person skilled in the art without creative work belong to the protection scope of the present invention.
Referring to fig. 1-4, the present invention provides a technical solution: the system comprises an incinerator 1, a semi-dry deacidification reactor 2, a primary deacidification tower 3, a secondary deacidification tower 4, a flue gas heat exchanger 5, a bag-type dust remover 6, a denitration device 7, a chimney 8, a drying furnace 9 and an evaporator 17, wherein a waste liquid atomization spray gun 28 arranged on the wall of the incinerator 1 is connected with a waste liquid storage tank 11 and two screw conveying pumps 27 for one use by one through pipelines, an auxiliary combustion-supporting burner 29 is arranged on the wall of the incinerator 1, a flue gas outlet of the incinerator 1 is sequentially connected with the semi-dry deacidification reactor 2, a quenching water tower 43, the primary deacidification tower 3, the secondary deacidification tower 4, the flue gas heat exchanger 5, the bag-type dust remover 6, the denitration device 7 and the chimney 8 through flues, a flue gas outlet flue of the denitration device 7 is connected with a flue gas inlet of the flue gas heat exchanger 5, a draught fan, the lower side of the incinerator 1 is sequentially connected with a slag liquid collecting tank 12 and a waste liquid treatment tank 13 through pipelines, the waste liquid treatment tank 13 is sequentially connected with a waste liquid conveying pump 25, a rotary drum A10, a waste solid salt solution and hydrochloric acid treatment tank 41 through pipelines, the waste solid salt solution and hydrochloric acid treatment tank 41 connects 2 waste solid salt solution primary conveying pumps 39 for one use with a waste solid salt solution and LiOH treatment tank 18 through pipelines, the waste solid salt solution and LiOH treatment tank 18 is sequentially connected with a waste solid salt solution secondary conveying pump 40, a rotary drum B38, an evaporator 17 and a drying furnace 9 through pipelines, the lower ends of a primary deacidification tower 3 and a secondary deacidification tower 4 are sequentially connected with a circulating alkali liquid return tank 14 through pipelines, the right side of the circulating alkali liquid return tank 14 is connected with a circulating alkali liquid neutralization tank 15 through pipelines, and the circulating alkali liquid neutralization tank 15 is respectively connected with a semi-dry deacidification reactor 2, a semi-dry deacidification reactor, a rotary drum A rotary, The system comprises a quenching water tower 43, a primary deacidification tower 3 and a secondary deacidification tower 4, wherein a pipeline between a circulating alkali liquor neutralization tank 15 and a semi-dry deacidification reactor 2 is provided with a semi-dry deacidification reactor alkali liquor spray pump 22, a pipeline between the circulating alkali liquor neutralization tank 15 and the quenching water tower 43 is provided with a quenching pump 19, and a pipeline between the circulating alkali liquor neutralization tank 15 and the two deacidification towers is respectively provided with a primary deacidification spray pump 20 and a secondary deacidification spray pump 21.
The semi-dry deacidification reactor 2 and the quenching water tower 43 both belong to quenching equipment, and the quenching equipment adopts two forms, one belongs to a wet method. The wet process comprises a semi-dry deacidification reactor 2 and a quenching water tower 43 which are connected in sequence through a flue; the semidry method comprises a semidry deacidification reactor 2, a high-temperature ceramic film deduster 42 and a quenching water tower 43 which are connected in sequence through a flue; the semi-dry deacidification reactor 2 is characterized in that high-temperature flue gas with the temperature of more than 1100 ℃ passes through an alkali liquor spraying pump 22 of the semi-dry deacidification reactor, alkali liquor in a circulating alkali liquor returning tank 14 is pumped and sent into an alkali liquor spraying and atomizing spray gun A30, the alkali liquor is atomized and sprayed into the semi-dry deacidification reactor 2 through an alkali liquor spraying and atomizing spray gun A30, the temperature of the flue gas is rapidly reduced to about 550 ℃, and the flue gas and acid gas in the flue gas are subjected to neutralization reaction to realize deacidification. The quenching water tower 43 is characterized in that high-temperature flue gas with the temperature of 550 ℃ passes through a quenching pump 19, alkali liquor in a circulating alkali liquor returning tank 14 is pumped and sent into an alkali liquor spraying and atomizing spray gun B31, the alkali liquor is atomized and sprayed into the quenching water tower 43 through an alkali liquor spraying and atomizing spray gun B31, the temperature of the flue gas is rapidly reduced to about less than 200 ℃, and the flue gas and acid gas in the flue gas are subjected to neutralization reaction to realize further deacidification. 2 flue exits of half-dry deacidification reactor are connected with the slaked lime pipeline, quench water tower 19 passes through the pipe connection at slag liquid collecting vessel 12 bottom, 42 lower extreme ash buckets one side of high temperature ceramic film dust remover are connected with the desalination water pipeline and the ash bucket export passes through the pipe connection at slag liquid collecting vessel 12, slag liquid collecting vessel 12 left side is connected with plus hydrochloric acid pipeline.
Three layers of alkali liquor spraying spray guns are arranged inside the first-stage deacidification tower 3 and the second-stage deacidification tower 4, a demister 33 is arranged at the uppermost end inside the second-stage deacidification tower 4, desalted water cleaning atomizing spray guns 32 are arranged at the upper end and the lower end of the demister 33 respectively, and desalted water is adopted to spray and clean the demister 33.
Denitration equipment 7 is equipped with flue gas heater 34, flue gas heating combustor 37, denitration tower 36, flue gas heating combustor 37 has been arranged on flue gas heater 34 upper portion, flue gas heater 34 lower extreme is connected with denitration tower 36, denitration tower 36 upper end is equipped with the denitration and spouts ammonia atomizing spray gun 35, the denitration spouts ammonia atomizing spray gun 35 and is connected with the ammonia pipeline, arrange multilayer low temperature denitration catalyst 44 in the denitration tower 36.
6 lower part ash bucket one side of sack cleaner is connected with the desalination water pipe, and the ash bucket has waste water tank 16 through the pipe connection in the lower extreme, waste water tank 16 still has connected gradually waste water delivery pump 24, waste water delivery pump 24 is through pipe connection to the sediment liquid collection tank 12 on.
The right side of the waste liquid treatment tank 13 is connected with an external calcium chloride and lime milk pipeline.
The drum A10 and the drum B38 both belong to solid-liquid separation devices, wastewater separated by the drum A10 is sent to a sewage treatment plant through a pipeline for retreatment, separated solid salts are sent to a waste solid salt solution and hydrochloric acid treatment tank 41, the waste solid salt solution and hydrochloric acid treatment tank 41 is provided with an additional hydrochloric acid pipeline and a stirrer device, the additional hydrochloric acid amount is adjusted according to the requirement of the pH value of the solution in the waste solid salt solution and hydrochloric acid treatment tank 41, meanwhile, the stirrer is adopted for stirring to ensure the uniformity of the solution in the waste solid salt solution and hydrochloric acid treatment tank 41, and the solution prepared in the waste solid salt solution and hydrochloric acid treatment tank 41 according to the requirement of the pH value is conveyed through the primary conveying of the waste solid salt solutionThe waste solid salt solution is added into the LiOH treatment tank 18 by a pump 39, LiF and CaCl are formed by adding LiOH and stirring2The aqueous solution is conveyed to a rotary drum B38 by a secondary conveying pump 40 of waste solid salt dissolving solution; the waste solid salt solution and LiOH treatment tank 18 is provided with an additional LiOH solution pipeline and a stirrer device, the solution separated by the rotary drum B38 enters the evaporator 17, the separated solid salt LiF is sent to a packing workshop for recycling, and CaCl separated by the rotary drum B382The solution is evaporated in an evaporator 17 and crystallized to form solid CaCl2.2H2O crystal is sent into a drying furnace 9 for drying, and then the anhydrous CaCl can be packed and recovered2；
The drying furnace 9 is based on solid CaCl2.2H2The requirement of the physical property of the O crystal is 260 ℃ to 300 ℃ in the furnace, and a partition wall heat exchange mode is adopted to ensure that anhydrous CaCl is2The purity of the solid and the hot air after heat exchange are pure, and the pure hot air after heat exchange can be used as primary air to be sent into the incinerator 1 so as to save energy.
In using the utility model discloses the time, at first the composition of analysis waste liquid, this patent is established and is developed successfully on the composition basis of following lithium cell waste liquid, and the main composition of lithium cell waste liquid is: carbonate, PVDF, phosphate, fluoride salt, carbon, water, etc., and the relevant physical properties are as follows:
1. carbonate ester: the analysis of the relevant physical properties was carried out using ethyl carbonate as a representative.
The molecular formula of the ethyl carbonate is C5H10O3Molecular weight 118, colorless liquid. Melting point-43 deg.C, boiling point 125.8 deg.C, water-insoluble, and miscible in most organic solvents such as alcohol, ketone, and ester.
Ethyl carbonate is flammable and the products of combustion (decomposition) are carbon monoxide and carbon dioxide.
2. PVDF: PVDF is the English abbreviation of Polyvinylidene fluoride (PVDF), mainly refers to vinylidene fluoride homopolymer or copolymer of vinylidene fluoride and other small amount of fluorine-containing vinyl monomer, and has a molecular formula of- (CH)2-CF2)n-。
Through related data inquiry, PVDF can be treated by adopting an incineration mode, but HF gas is generated after PVDF is heated and decomposed, so that related equipment and measures are required to treat the HF gas subsequently.
3. The phosphate is mainly disodium hydrogen phosphate, and has a molecular formula of Na2HPO4And a molecular weight of 142. The appearance is white powder, flake or granular, and the sodium pyrophosphate is dissolved in water and decomposed into sodium pyrophosphate at 250 ℃.
The molecular formula of the sodium pyrophosphate is Na4P2O7Molecular weight 266, white powder or crystalline in appearance. Melting point 880 deg.C, boiling point 938 deg.C, water-soluble, stable aqueous solution below 70 deg.C, and hydrolyzing to disodium hydrogen phosphate when boiling.
4. The fluoride salts are mainly lithium and sodium salts
Sodium fluoride: molecular formula is NaF, molecular weight 42. Melting point 993 deg.C, boiling point 1695 deg.C, and dissolving in water. Sodium fluoride is toxic.
Lithium fluoride: the molecular formula is LiF, and the molecular weight is 26. Is white crystal at room temperature, is slightly soluble in water, and is easily soluble in acid at room temperature. Melting point 848 deg.C, boiling point 1681 deg.C. It is toxic. Decomposed in high temperature to produce hydrogen fluoride and lithium oxide.
The two treatment methods are as follows:
1. semi-dry method treatment process: the incinerator 1 → the semi-dry type deacidification reactor 2 → the high temperature ceramic dust remover 42 → the quenching water tower 43 → the primary deacidification tower 3 → the secondary deacidification tower 4 → the heat exchanger 5 → the bag-type dust collector 6 → the flue gas heater 34 → the denitration device 7 → the flue gas heat exchanger 5 → the induced draft fan 26 → the chimney 8;
liquid and solid salt generated by incineration in the incinerator 1 + solid salt collected by the high-temperature ceramic dust collector 42 → a slag liquid collection tank (hydrochloric acid is added to match a PH <3 acid solution) → a waste liquid treatment tank (calcium chloride aqueous solution is added to the waste liquid treatment tank and lime milk solution is added to the waste liquid treatment tank for neutralization treatment) → a rotary drum (solid-liquid separation, liquid is sent to a sewage treatment plant for treatment) → solid salt is sent to the waste solid salt treatment tank 1 (hydrochloric acid is added to the waste liquid treatment tank, and the solution is stirred and cooled to <10 ℃) → solid salt is sent to the waste solid salt treatment tank 2 (LiOH is added to the waste liquid treatment tank, and the solution is stirred and cooled to <10 ℃) → a rotary drum (solid-liquid separation, solid LiF is recovered) → an evaporator → a drying furnace.
2. And (3) wet processing flow: the incinerator 1 → the semi-dry deacidification reactor 2 → the quench tower 43 → the primary deacidification tower 3 → the secondary deacidification tower 4 → the heat exchanger 5 → the bag-type dust collector 6 → the flue gas heater 34 → the denitrating equipment 7 → the flue gas heat exchanger 5 → the induced draft fan 26 → the chimney 8;
liquid and solid salt generated by incineration in the incinerator 1 + liquid and solid salt collected by the quench water tower 43 → a slag liquid collection tank (hydrochloric acid is added to match a PH <3 acid solution) → a waste liquid treatment tank (calcium chloride aqueous solution is added to add, lime milk solution is added to neutralize treatment) → a rotary drum (solid-liquid separation, liquid is sent to a sewage treatment plant to treat) → solid salt is sent to the waste solid salt treatment tank 1 (hydrochloric acid is added to the waste solid salt treatment tank 1, and the solution is stirred and cooled to <10 ℃) → solid salt is sent to the waste solid salt treatment tank 2 (LiOH is added to the waste solid salt treatment tank, and the solution is stirred and cooled to <10 ℃) → a rotary drum (solid-liquid separation, solid LiF is recovered) → an evaporator → a drying furnace → anhydrous calcium chloride is recovered.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (8)
1. The utility model provides a lithium cell waste liquid resourceful environmental protection processing system, includes incinerator (1), semi-dry deacidification reactor (2), one-level deacidification tower (3), second grade deacidification tower (4), gas heater (5), sack cleaner (6), denitration device (7), chimney (8), drying furnace (9) and evaporimeter (17), its characterized in that: the waste liquid atomization spray gun (28) arranged on the wall of the incinerator (1) is connected with a waste liquid storage tank (11) and two screw delivery pumps (27) for one standby, an auxiliary combustion-supporting burner (29) is arranged on the wall of the incinerator (1), a flue gas outlet of the incinerator (1) is sequentially connected with a semi-dry deacidification reactor (2), a quench water tower (43), a primary deacidification tower (3), a secondary deacidification tower (4), a flue gas heat exchanger (5), a cloth bag dust remover (6), a denitration device (7) and a chimney (8) through a flue, a flue gas outlet flue of the denitration device (7) is connected with a flue gas inlet of the flue gas heat exchanger (5), a draught fan (26) is arranged at the flue gas outlet of the flue gas heat exchanger (5) and connected with the lower end of the chimney (8), a slag liquid collection tank (12) and a waste liquid treatment tank (13) are sequentially connected, the waste liquid treatment tank (13) is sequentially connected with a waste liquid conveying pump (25), a rotary drum A (10), a waste solid salt dissolving liquid and hydrochloric acid treatment tank (41) through pipelines, the waste solid salt dissolving liquid and hydrochloric acid treatment tank (41) is connected with two waste solid salt dissolving liquid primary conveying pumps (39) for one use and a waste solid salt dissolving liquid and LiOH treatment tank (18) through pipelines, the waste solid salt dissolving liquid and LiOH treatment tank (18) is sequentially connected with a waste solid salt dissolving liquid secondary conveying pump (40), a rotary drum B (38), an evaporator (17) and a drying furnace (9) through pipelines, the lower ends of a primary deacidification tower (3) and a secondary deacidification tower (4) are sequentially connected with a circulating alkali liquid return tank (14) through pipelines, the right side of the circulating alkali liquid return tank (14) is connected with a circulating alkali liquid neutralization tank (15) through pipelines, and the circulating alkali liquid neutralization tank (15) is respectively connected with a semi-dry deacidification reactor (2) through pipelines, Quench water tower (43), one-level deacidification tower (3) and second grade deacidification tower (4) are connected, be equipped with half-dry deacidification reactor alkali liquor spray pump (22) on the pipeline between circulation alkali liquor neutralization tank (15) and half-dry deacidification reactor (2), be equipped with quench pump (19) on the pipeline between circulation alkali liquor neutralization tank (15) and quench water tower (43), be equipped with one-level deacidification spray pump (20) and second grade deacidification spray pump (21) on the pipeline between circulation alkali liquor neutralization tank (15) and two deacidification towers respectively.
2. The lithium battery waste liquid recycling and environment-friendly treatment system as claimed in claim 1, wherein: the semi-dry deacidification reactor (2) and the quenching water tower (43) both belong to quenching equipment, the quenching equipment adopts two forms, one belongs to a wet method and the other belongs to a semi-dry method, and the wet method comprises the semi-dry deacidification reactor (2) and the quenching water tower (43) and is connected in sequence through a flue; the semi-dry method comprises a semi-dry deacidification reactor (2), a high-temperature ceramic film deduster (42) and a quenching water tower (43), which are sequentially connected through a flue; the semi-dry deacidification reactor (2) is characterized in that flue gas passes through an alkali liquor spray pump (22) of the semi-dry deacidification reactor, alkali liquor in a circulating alkali liquor return tank (14) is pumped and sent into an alkali liquor spray atomization spray gun A (30), the alkali liquor is atomized and sprayed into the semi-dry deacidification reactor (2) through the alkali liquor spray atomization spray gun A (30), the flue gas passes through a quenching pump (19) by a quenching water tower (43), the alkali liquor in the circulating alkali liquor return tank (14) is pumped and sent into an alkali liquor spray atomization spray gun B (31), the alkali liquor is atomized and sprayed into the quenching water tower (43) through the alkali liquor spray atomization spray gun B (31) and is subjected to neutralization reaction with acid gas in the flue gas to realize further deacidification, a slaked lime pipeline is connected at a flue outlet of the semi-dry deacidification reactor (2), and the lowest end of the quenching water tower (43) is connected with a slag liquor collection, one side of an ash bucket at the lower end of the high-temperature ceramic film dust collector (42) is connected with a desalted water pipeline, an outlet of the ash bucket is connected to the slag liquid collecting tank (12) through a pipeline, and the left side of the slag liquid collecting tank (12) is connected with an external hydrochloric acid pipeline.
3. The lithium battery waste liquid recycling and environment-friendly treatment system as claimed in claim 1, wherein: the three-layer alkali liquor atomization spray gun is arranged inside the first-stage deacidification tower (3) and the second-stage deacidification tower (4), the demister (33) is arranged at the uppermost end inside the second-stage deacidification tower (4), the upper end and the lower end of the demister (33) are respectively provided with a desalted water cleaning atomization spray gun (32), and desalted water is adopted to spray and clean the demister (33).
4. The lithium battery waste liquid recycling and environment-friendly treatment system as claimed in claim 1, wherein: denitration equipment (7) are equipped with flue gas heater (34), flue gas heating combustor (37), denitration tower (36), flue gas heating combustor (37) have been arranged on flue gas heater (34) upper portion, flue gas heater (34) lower extreme is connected with denitration tower (36), denitration tower (36) upper end is equipped with the denitration and spouts ammonia spray gun (35), the denitration is spouted ammonia spray gun (35) and is connected with the ammonia pipeline, arrange multilayer low temperature denitration catalyst (44) in denitration tower (36).
5. The lithium battery waste liquid recycling and environment-friendly treatment system as claimed in claim 1, wherein: one side of an ash bucket on the lower part of the bag-type dust collector (6) is connected with a desalting water pipeline, the lowest end of the ash bucket is connected with a waste water tank (16) through a pipeline, the waste water tank (16) is sequentially connected with a waste water delivery pump (24), and the waste water delivery pump (24) is connected to a slag liquid collecting tank (12) through a pipeline.
6. The lithium battery waste liquid recycling and environment-friendly treatment system as claimed in claim 1, wherein: the right side of the waste liquid treatment tank (13) is connected with an external calcium chloride and lime milk pipeline.
7. The lithium battery waste liquid recycling and environment-friendly treatment system as claimed in claim 1, wherein: the drum A (10) and the drum B (38) both belong to solid-liquid separation devices, wastewater separated by the drum A (10) is sent to a sewage treatment plant through a pipeline for retreatment, separated solid salts are sent to a waste solid salt dissolving liquid and hydrochloric acid treatment tank (41), the waste solid salt dissolving liquid and hydrochloric acid treatment tank (41) is provided with an additional hydrochloric acid pipeline and a stirrer, a solution prepared in the waste solid salt dissolving liquid and hydrochloric acid treatment tank (41) is sent to a waste solid salt dissolving liquid and LiOH treatment tank (18) through a waste solid salt dissolving liquid primary conveying pump (39), and then is conveyed to the drum B (38) through a waste solid salt dissolving liquid secondary conveying pump (40); the waste solid salt solution and LiOH treatment tank (18) is provided with an additional LiOH solution pipeline and a stirrer, the solution separated by the rotary drum B (38) enters the evaporator (17), the separated solid salt is sent to a packing workshop for recycling, the solution separated by the rotary drum B (38) enters the evaporator (17) for evaporation and then is crystallized to form solid crystals, and the solid crystals are sent to the drying furnace (9) for drying.
8. The lithium battery waste liquid recycling and environment-friendly treatment system as claimed in claim 1, wherein: the temperature of the drying furnace (9) is controlled to be 260-300 ℃ according to the property of the solid crystal, a partition wall heat exchange mode is adopted to ensure the purity of the solid and the purity of hot air after heat exchange, and the purity of the hot air after heat exchange can be used as primary air to be sent into the incinerator (1) to save energy.
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| CN114130275A (en) * | 2021-11-26 | 2022-03-04 | 广东长信精密设备有限公司 | Cadmium chloride mixed crystal hydrate solution production system |
| CN114130275B (en) * | 2021-11-26 | 2024-03-26 | 广东长信精密设备有限公司 | Cadmium chloride mixed crystal hydrate solution production system |
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