CN106006749B - Useless LiMn2O4 cooperates with the method for administering and reclaiming manganese lithium with relieving haperacidity tail gas - Google Patents
Useless LiMn2O4 cooperates with the method for administering and reclaiming manganese lithium with relieving haperacidity tail gas Download PDFInfo
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- C01G45/12—Manganates manganites or permanganates
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- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
- B01D53/1456—Removing acid components
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- C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
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Abstract
Useless LiMn2O4 cooperates with the method for administering and reclaiming manganese lithium, its step to be with relieving haperacidity tail gas：Used Li ion cell is discharged, the useless positive plate of acquisition is disassembled, the fired positive plate that gives up, water dissolves, filtering are obtained useless LiMn2O4；Useless LiMn2O4 mix with potassium sulfate after ball milling, ball milling product loading absorption plant；Relieving haperacidity tail gas is passed through absorption plant again after first passing through conversion, the absorption plant gas for meeting discharge standard out drains into air, mixture taking-up in absorption plant is gone out with water logging, filtered after addition solution of potassium carbonate in solution again, ball milling, compression, roasting after lithium carbonate are supplemented in filter residue, the good manganate cathode material for lithium of chemical property is regained.Potassium sulfate is obtained after the crystallized treatment of filtrate.
Description
Technical field
The present invention relates to a kind of useless LiMn2O4 the method for administering and reclaiming manganese lithium is cooperateed with relieving haperacidity tail gas.
Background technology
Sulfuric acid is widely used in the life of chemical fertilizer industry, metallurgical industry, petroleum industry, mechanical industry, medical industry, detergent
Product, war industry, atomic energy industry and aerospace industry etc..But sulfuric acid industry is also the chemical industry of high pollution, gas washing in SA production
During produce tail gas in contain sulfur dioxide, sulfuric acid mist.The relieving haperacidity tail gas of sulfuric acid industry is annual substantial amounts of to airborne release
The gas pollutants such as sulfur dioxide, severe contamination environment.China issued on December 30th, 2010《Sulfuric acid industry pollutant
Discharge standard》(GB26132-2010), the discharge to relieving haperacidity tail gas is clearly required, i.e.,：After 2013 it is all newly-built and
The content of the relieving haperacidity sulfur dioxide in tail gas of existing sulphuric acid production enterprises discharge have to be lower than 400mg/m3, sulfuric acid mist must be low
In 30 mg/m3.And SO in the tail gas that current sulfuric acid industry is discharged through double-absorption production procedure2Content it is general 600 ~ 1400
mg/m3Left and right, it is impossible to directly to airborne release.
Relieving haperacidity tail gas will be by removing sulfuric acid mist and making SO2Content reach standard after could be vented.The disclosed system of reporting for work
The method of sour treating tail gas has：Sodium carbonate absorption process, NaOH absorption process, lime absorption, magnesia absorption process, ammonia absorb
Method, ammonia ammonium sulphate process, ammonia-ammonium sulfite, ammonia-ammonium hydrogen sulfate method, sulfurous acid-potassium bisulfite method, peroxy-disulfuric acid conversion
Method, basic aluminum sulfate solution absorption method, Citrate Buffer, Exchange Resin by Adsorption, charcoal absorption and conversion method etc..Its
In, sodium carbonate absorption process is to SO in relieving haperacidity tail gas2Absorptivity it is higher and obtain sodium sulfite product, but sodium sulfite market
It is limited, and also need to be continuously added antioxidant in absorption process and prevent sodium sulfite from being oxidized to sodium sulphate, when the valency of sodium carbonate
When lattice are higher than sodium sulfite, this method is just uneconomical.Lime absorption process is using limewash or milk of lime washing relieving haperacidity tail gas, the party
Law technology is ripe, low production cost, but SO2Absorption rate is slow, absorbability is small, the CaSO of generation3And CaSO4Easily block pipe
Road and equipment, in addition the method produce substantial amounts of waste residue, these waste residues to cause serious secondary pollution to environment.Ammonia absorption process is used
, used as absorbent, absorption efficiency is high, desulfurization is thorough, but ammonia is volatile for liquefied ammonia or ammoniacal liquor, the consumption of absorbent is big, in addition ammonia
Originate limited by regions larger.NaOH absorption process is to use NaOH to administer relieving haperacidity tail gas, SO2Absorbability is big,
Absorption rate is fast, efficiency high, but the problem of maximum is that raw material NaOH is more expensive, the high cost of relieving haperacidity treating tail gas.Additionally, its
The problem of its relieving haperacidity method for treating tail gas several general character of all generally existings:1) raw materials used price is high, invests larger, Operation and Maintenance
It is relatively costly；2) the byproduct added value for being obtained after relieving haperacidity treating tail gas is low.
Lithium ion battery is the secondary cell of new generation that the nineties in 20th century develops rapidly, is widely used in miniature portable
Formula electronic communication product and electric vehicle.LiMn2O4 (LiMn2O4) positive electrode due to price it is low, current potential is high, environment
It is friendly, the advantages of security performance is high, part substitution cobalt acid lithium is in compact lithium cell positive electrode and lithium-ion-power cell
Field is widely used.Because the service life of lithium ion battery is generally 2-3, therefore, scrap lithium ion battery band
The environmental pollution and resource reutilization problem for coming are increasingly subject to pay attention to.
The current recovery method on valuable metal in lithium cell anode material lithium manganate waste material has:Patent
[CN201410280343] discloses a kind of method that utilization waste lithium manganese oxide battery prepares nickel ion doped, by with sulfuric acid and mistake
Hydrogen oxide mixed solution carries out leaching process to useless LiMn2O4, obtains and contains lithium ion, the solution of manganese ion, then adds in solution
Enter nickel salt, lithium salts and precipitating reagent, sediment obtains nickel ion doped (LiNi after calcining again0.5Mn1.5O4).Patent
A kind of [CN201410246379] reclaims manganese and copper resource method in reporting waste and old lithium ion battery from manganese systems, continues with
Acid extracting, alkali solution technique, the precipitation method, Vibration Screen point-score, flotation partition method or sonic oscillation method are obtained containing Cu2+、Mn2+Solution,
Electrolysis procedure is carried out again, obtains MnO2And Cu.Patent [CN201310646706] discloses one kind and prepares nickel by useless electrokinetic cell
The method of manganese hydroxide.Obtained by with the useless nickel lithium manganate cathode material of at least one dissolving in hydrochloric acid, sulfuric acid and nitric acid
Nickeliferous, manganese mixed solution, added toward the solution after dissolving nickel acetate or nickel chloride or nickel sulfate, manganese chloride or manganese sulfate or
Manganese acetate, glycerine or ethylene glycol or BT or 1,2-PD or 1,3-PD, then use hydroxide respectively
Sodium and ammoniacal liquor adjust the pH value of solution, then obtain nickel manganese hydrogen after heating for dissolving-microwave reaction cooling-filtering-washing-is dried
Oxide.Patent [CN201310630619] discloses one kind and prepares manganate cathode material for lithium by raw material of waste and old lithium ion battery
Method, successively dissolve the LiMn2O4 that is obtained from waste and old lithium ion battery using citric acid solution, hydrogenperoxide steam generator, it is then past
Lithium nitrate or lithium acetate or lithium sulfate are added in solution, in manganese nitrate or manganese acetate or manganese sulfate regulation solution Li and Mn mole
Than, the pH value for adjusting solution with ammoniacal liquor obtains gel, then by obtaining lithium manganate cathode material after ageing-drying-pre-burning-calcining
Material.Patent [CN201310630768] reports a kind of method for dissolving waste lithium ion cell anode material, successively uses apple
The manganate cathode material for lithium that tartaric acid solution and hydrogenperoxide steam generator dissolving are obtained from waste and old lithium ion battery, that is, complete useless manganese
The course of dissolution of sour lithium anode material.Patent [CN201210017163] discloses one kind and utilizes mangaic acid using pyrometallurgy technology
Lithium waste and old lithium ion battery and scrap iron are the method that raw material manufactures manganeisen.Patent [CN201010141128] discloses one kind
The method that valuable metal is reclaimed from waste lithium manganese oxide battery.After refuse battery is broken, with DMF, N- methyl pyrroles
One or more mixed solvent immersion battery core in pyrrolidone, tetrahydrofuran obtains useless LiMn2O4, with the nothing that with the addition of hydrogen peroxide
Machine acid (one or more mixed acid solution in the hydrochloric acid of 36wt%, the nitric acid of 68wt%, the sulfuric acid of 98wt%) mixes molten
The useless LiMn2O4 of liquid dissolving, solution ph is adjusted with NaOH and ammoniacal liquor twice, obtains MnO2, sodium carbonate liquor is added through precipitation operation
After obtain lithium carbonate.Patent [CN200910116656] reports one kind and MnO is reclaimed from anode material of wasted lithium manganate battery2
Method and its application, obtain λ-MnO with the useless manganate cathode material for lithium of sulfuric acid, hydrochloric acid, nitric acid or normal pressure acidleach2, or hydro-thermal acid
The useless manganate cathode material for lithium of leaching obtains α -/β -/γ-MnO2.An Hongli etc. exists《Peking University's journal (natural science edition)》
The waste and old power lithium-ion battery of LiMn2O4 is reported in Vol.42, Special Issue, Dec. 2006,83-86 mainly to change
The recovery research of element is learned, with the HNO of 2mol/L3The H of+1 mol/L2O2The molten treatment LiMn2O4 (LiMn of mixed solution acid2O4) effect
Fruit is optimal, and the dissolution rate of LiMn2O4 is 100%.Yang Ze it is identical《Journal of Chemical Industry and Engineering》Vol.62,No.1,November 2011,
Reported in 3276-3281 based on waste lithium ion cell anode material LiMn2O4Prepare MnO2And its research of chemical property
Achievement, at normal temperatures and pressures, using the H of 0.5mol/L2SO4Acidleach is given up LiMn2O4 3h prepares λ-MnO2Nano particle；140
Under DEG C hydrothermal condition, using the H of 2 mol/L2SO4Acidleach is given up LiMn2O4 24h is obtained β-MnO2Nanometer rods.Peng Shantang etc. exists《It is military
Chinese Polytechnics journal》Vol.24, No.12, Dec.2002,27-29 report secondary oxidation-precipitation method and separate LiMn2O4
(LiMn2O4) in lithium and manganese achievement in research, with add hydrogen peroxide nitric acid or hydrochloric acid or sulfuric acid mixed solution dissolve manganese
Sour lithium, then it is separately added into a certain amount of (NH4)2S2O8(NH4)2CO3, MnO is prepared using secondary oxidation-precipitation method2And carbonic acid
Lithium.
It has been reported that the method that valuable metal is reclaimed from useless LiMn2O4, recovery technology still has to largely use correlationization
Learn reagent, such as sulfuric acid, hydrogen peroxide, citric acid, malic acid, hydrochloric acid, nitric acid, niter cake, sodium pyrosulfate, this cause it is current from
The technology cost recovery that valuable metal is reclaimed in useless LiMn2O4 is difficult to reduce.
The content of the invention
The method for administering and reclaiming manganese lithium is cooperateed with relieving haperacidity tail gas it is an object of the invention to provide a kind of useless LiMn2O4.
The present invention is that useless LiMn2O4 cooperates with the method for administering and reclaiming manganese lithium, its step to be with relieving haperacidity tail gas：
Step（1）：The scrap lithium ion battery of positive electrode is done in collection with LiMn2O4, and NaOH is positioned at room temperature
The discharge process of 1-3h is carried out in the aqueous solution；After discharge process, the lithium ion battery that will be scrapped is disassembled, and obtains positive plate；
The positive pole leftover pieces that the lithium ion battery manufacturing process for doing positive electrode with LiMn2O4 is produced are collected, positive plate is obtained；To obtain
Positive plate be fitted into ceramic crucible, be subsequently placed in resistance furnace makes furnace temperature liter since room temperature with the heating rate of 5 DEG C/min
To 550 DEG C of insulation 0.5-1h, room temperature is then naturally cooled to；The positive plate by roasting is taken out, positive plate is put into equipped with Sheng
Have in the container of water and stir 5-30min, the mixture in container is sieved with screen cloth, oversize is aluminium foil, screenings
It is the solution containing positive active material；Screenings carries out suction filtration, and thing is cleaned 1-3 times with water in filter, obtains positive active material；
The positive active material for obtaining is fitted into ceramic crucible, be subsequently placed in resistance furnace makes furnace temperature with the heating rate of 5 DEG C/min
It is raised to 500-700 DEG C and is incubated 0.5-3h, obtains useless LiMn2O4；
Step（2）：Useless LiMn2O4 is mixed with potassium sulfate, then the ball milling in ball mill, by the mixture dress after ball milling
In entering absorption plant；Mixture after loading ball milling in another identical absorption plant is as standby absorption plant
In step（3）In use；In this step, the source of potassium sulfate is the potassium sulfate chemical products or step of purchase（5）Middle acquisition
Potassium sulfate or the two mixture being mixed to form with arbitrary proportion；
Step（3）：From gas washing in SA production double-absorption system relieving haperacidity tail gas out, after first passing through heating, then it is passed through
Conversion operation is carried out in conversion system equipped with vanadium catalyst, the condition of conversion operation is：400-405 DEG C of gasinlet temperature,
Flow velocity 0.23-1.2m/s, the filling of vanadium catalyst is rated in conversion system：0.3-0.6m3Catalyst/(1000m3Relieving haperacidity tail
Gas h)；Step is passed through from conversion system gas out（2）Described in have been charged into after ball milling in the absorption plant of mixture
Absorption operation is carried out, the condition of absorption operation is：350-500 DEG C of temperature, inlet gas flow velocity 0.2-1.2m/s；Monitoring absorbs dress
Put SO in exit gas2Content whether be less than 400mg/m3And whether the content of sulfuric acid mist is less than 30mg/m3, requirement is such as reached,
It is emitted into air after the gas cooling that absorption plant is exported；Such as monitor SO in absorption plant exit gas2Content reach
To 400mg/m3Or the content of sulfuric acid mist reaches 30mg/m3, then no longer to the gas being passed through in the absorption plant from conversion system out
Body, while the gas from conversion system out is passed through into step（2）Carried out under the same terms in described standby absorption plant
SO in absorption operation and exit gas2Content, the monitoring of the content of sulfuric acid mist；Take out and be no longer passed through conversion system in this step
Mixture in the absorption plant of exit gas, the absorption plant then returns to step（2）In be again loaded into the mixing after ball milling
Thing is used in this step as standby absorption plant；
Step（4）：By step（3）In be no longer passed through mixture in the absorption plant of conversion system exit gas in stirring
Under conditions of leached with 20-50 DEG C of water, extraction time 5-30min, solid-to-liquid ratio g/mL be 1:10-1:50；Then leaching
Go out liquid and be warmed up to 95-98 DEG C, solution of potassium carbonate is slowly added to leachate, then filter, wash filter residue and dry, analyze filter residue
The content of middle Li, Mn, is 0.525 according to the mol ratio of lithium and manganese:1 requirement supplements lithium carbonate toward filter residue, then in ball mill
Middle ball milling, then it is being used into pressure compaction, it is put into clean ceramic crucible, in 450 DEG C of constant temperature 4-7h in air atmosphere,
It is slowly cooled to room temperature after being incubated 20h at being warming up to 750 DEG C again, sample comminution, grinding after firing cross 400 mesh sieves, obtain electricity
The good manganate cathode material for lithium of chemical property；
Step（5）：By step（4）The solution being filtrated to get is crystallized in crystallizing evaporator, and cerium sulphate crystal condition is vacuum
Degree 0.012-0.015MPa, 120-140 DEG C of temperature, crystal are dried under 50-80 DEG C and 0.2-3h and obtain potassium sulfate, acquisition
Potassium sulfate return to step（2）In use.
The present invention has what the good low cost of effect easy to operate, relieving haperacidity tail gas clean-up, manganese lithium were reclaimed compared with prior art
The advantage that low cost, purification process non-secondary pollution thing are produced.
Brief description of the drawings
Fig. 1 is process chart of the invention.
Specific embodiment
As shown in figure 1, the present invention is useless LiMn2O4 cooperates with the method for administering and reclaiming manganese lithium, its step with relieving haperacidity tail gas
For：
Step（1）：The scrap lithium ion battery of positive electrode is done in collection with LiMn2O4, and NaOH is positioned at room temperature
The discharge process of 1-3h is carried out in the aqueous solution；After discharge process, the lithium ion battery that will be scrapped is disassembled, and obtains positive plate；
The positive pole leftover pieces that the lithium ion battery manufacturing process for doing positive electrode with LiMn2O4 is produced are collected, positive plate is obtained；To obtain
Positive plate be fitted into ceramic crucible, be subsequently placed in resistance furnace makes furnace temperature liter since room temperature with the heating rate of 5 DEG C/min
To 550 DEG C of insulation 0.5-1h, room temperature is then naturally cooled to；The positive plate by roasting is taken out, positive plate is put into equipped with Sheng
Have in the container of water and stir 5-30min, the mixture in container is sieved with screen cloth, oversize is aluminium foil, screenings
It is the solution containing positive active material；Screenings carries out suction filtration, and thing is cleaned 1-3 times with water in filter, obtains positive active material；
The positive active material for obtaining is fitted into ceramic crucible, be subsequently placed in resistance furnace makes furnace temperature with the heating rate of 5 DEG C/min
It is raised to 500-700 DEG C and is incubated 0.5-3h, obtains useless LiMn2O4；
Step（2）：Useless LiMn2O4 is mixed with potassium sulfate, then the ball milling in ball mill, by the mixture dress after ball milling
In entering absorption plant；Mixture after loading ball milling in another identical absorption plant is as standby absorption plant
In step（3）In use；In this step, the source of potassium sulfate is the potassium sulfate chemical products or step of purchase（5）Middle acquisition
Potassium sulfate or the two mixture being mixed to form with arbitrary proportion；
Step（3）：From gas washing in SA production double-absorption system relieving haperacidity tail gas out, after first passing through heating, then it is passed through
Conversion operation is carried out in conversion system equipped with vanadium catalyst, the condition of conversion operation is：400-405 DEG C of gasinlet temperature,
Flow velocity 0.23-1.2m/s, the filling of vanadium catalyst is rated in conversion system：0.3-0.6m3Catalyst/(1000m3Relieving haperacidity tail
Gas h)；Step is passed through from conversion system gas out（2）Described in have been charged into after ball milling in the absorption plant of mixture
Absorption operation is carried out, the condition of absorption operation is：350-500 DEG C of temperature, inlet gas flow velocity 0.2-1.2m/s；Monitoring absorbs dress
Put SO in exit gas2Content whether be less than 400mg/m3And whether the content of sulfuric acid mist is less than 30mg/m3, requirement is such as reached,
It is emitted into air after the gas cooling that absorption plant is exported；Such as monitor SO in absorption plant exit gas2Content reach
To 400mg/m3Or the content of sulfuric acid mist reaches 30mg/m3, then no longer to the gas being passed through in the absorption plant from conversion system out
Body, while the gas from conversion system out is passed through into step（2）Carried out under the same terms in described standby absorption plant
SO in absorption operation and exit gas2Content, the monitoring of the content of sulfuric acid mist；Take out and be no longer passed through conversion system in this step
Mixture in the absorption plant of exit gas, the absorption plant then returns to step（2）In be again loaded into the mixing after ball milling
Thing is used in this step as standby absorption plant；
Step（4）：By step（3）In be no longer passed through mixture in the absorption plant of conversion system exit gas in stirring
Under conditions of leached with 20-50 DEG C of water, extraction time 5-30min, solid-to-liquid ratio g/mL be 1:10-1:50；Then leaching
Go out liquid and be warmed up to 95-98 DEG C, solution of potassium carbonate is slowly added to leachate, then filter, wash filter residue and dry, analyze filter residue
The content of middle Li, Mn, is 0.525 according to the mol ratio of lithium and manganese:1 requirement supplements lithium carbonate toward filter residue, then in ball mill
Middle ball milling, then it is being used into pressure compaction, it is put into clean ceramic crucible, in 450 DEG C of constant temperature 4-7h in air atmosphere,
It is slowly cooled to room temperature after being incubated 20h at being warming up to 750 DEG C again, sample comminution, grinding after firing cross 400 mesh sieves, obtain electricity
The good manganate cathode material for lithium of chemical property；
Step（5）：By step（4）The solution being filtrated to get is crystallized in crystallizing evaporator, and cerium sulphate crystal condition is vacuum
Degree 0.012-0.015MPa, 120-140 DEG C of temperature, crystal are dried under 50-80 DEG C and 0.2-3h and obtain potassium sulfate, acquisition
Potassium sulfate return to step（2）In use.
The step of approach described above（1）In sodium hydrate aqueous solution concentration be 0.1-1.0mol/L.
The step of approach described above（1）It is middle that the positive plate for obtaining is pressed into the quality of positive plate and the volume of ceramic crucible
Ratio g/mL is 1:10-1:15.
The step of approach described above（1）According to positive plate quality and water volume ratio g/mL be 1:40-1:
70, positive plate is put into and is equipped with the container for filling water and is stirred 5-30min, the temperature of whipping process reclaimed water with electric mixer
It it is 20-50 DEG C, mixing speed is 10-200r/min.
The step of approach described above（1）In screen cloth for 10-20 mesh screen cloth.
The step of approach described above（2）The middle useless LiMn2O4 that will be obtained is 1 with potassium sulfate g/g in mass ratio:0.01-
2.4 ratio mixes, then the ball milling in ball mill, and Ball-milling Time is 0.1-1.0 h, and rotating speed is 200-500 r/min.
The step of approach described above（4）The concentration of middle solution of potassium carbonate is 1.0-3.0mol/L.
The step of approach described above（4）In Ball-milling Time be 0.5-2h, rotating speed is 200-500r/min, the pressure of compression
Power is 0.1-100MPa.
The step of approach described above（3）In vanadium catalyst be S108 type vanadium catalysts.
Below the present invention is further spread out with embodiment.Only it is to better embodiment of the invention described in embodiment
, not make any formal limitation to the present invention, it is every according to technical spirit of the invention to the implementation method of embodiment
Any simple modification made, equivalent variations and modification, belong in the range of technical solution of the present invention.
Embodiment 1：
The scrap lithium ion battery of positive electrode is done in collection with LiMn2O4, and the hydroxide of 0.5mol/L is positioned at room temperature
The discharge process of 2h is carried out in sodium water solution；After discharge process, the lithium ion battery that will be scrapped is disassembled, and obtains positive plate；
The positive plate that will be obtained is 1 in the ratio (g/mL) of the volume of the quality and ceramic crucible of positive plate:10 ratio is by positive plate
It is fitted into ceramic crucible, be subsequently placed in chamber type electric resistance furnace makes furnace temperature be raised to 550 since room temperature with the heating rate of 5 DEG C/min
DEG C insulation 0.5h, room temperature is naturally cooled to after power-off；The positive plate by roasting is taken out, according to the quality and the body of water of positive plate
Long-pending ratio (g/mL) is 1:50 are put into equipped with 20min is stirred in the container for filling water and with electric mixer positive plate, stir
The temperature of process reclaimed water is mixed for 25 DEG C, mixing speed is 100r/min；After stopping stirring, by 10 purposes of the mixture in container
Screen cloth is sieved, and oversize is aluminium foil, and screenings is the solution containing positive active material；Screenings carries out suction filtration, in filter
Thing is cleaned 3 times with water, obtains positive active material；The positive active material for obtaining is fitted into ceramic crucible, case is subsequently placed in
Furnace temperature is raised to 550 DEG C and be incubated 1h with the heating rate of 5 DEG C/min in formula resistance furnace, obtain useless LiMn2O4；By useless LiMn2O4
It is 1 with potassium sulfate (g/g) in mass ratio:0.05 ratio mixes, then the ball milling in planetary ball mill, and Ball-milling Time is
0.5 h, rotating speed is 300 r/min；Mixture after ball milling is fitted into absorption plant；From gas washing in SA production double-absorption system out
Relieving haperacidity tail gas, after first passing through heating, then be passed through conversion operation carried out in the conversion system equipped with S108 type vanadium catalysts,
The condition of conversion operation is：400 DEG C of gasinlet temperature, flow velocity 0.3m/s, the filling of S108 types vanadium catalyst in conversion system
It is rated for：0.5m3Catalyst/(1000m3Relieving haperacidity tail gas h)；It is passed through from conversion system gas out after having been charged into ball milling and is mixed
Absorption operation is carried out in the absorption plant of compound, the condition of absorption operation is：450 DEG C of temperature, inlet gas flow velocity 0.3m/s；Inspection
Measure SO in absorption plant exit gas2Content be less than 400mg/m3And whether the content of sulfuric acid mist is less than 30mg/m3, will inhale
It is emitted into air after the gas cooling of receiving apparatus outlet；It is mixed in the absorption plant of conversion system exit gas by being no longer passed through
Compound under conditions of stirring with 50 DEG C of water with solid-to-liquid ratio (g/mL) be 1:20 leach 30min；Then leachate is warmed up to
98 DEG C, the solution of potassium carbonate of 3.0mol/L is slowly added to leachate and produces sediment, gained sediment is through filtering, washing, do
After dry, the content of Li, Mn in analysis sediment, is 0.525 according to the mol ratio of lithium and manganese:1 requirement supplements one toward sediment
Quantitative lithium carbonate, then with the abundant ball milling 2h of the speed of 400r/min in planetary ball mill, then by its 5MPa pressure
Compressed under power, be put into clean ceramic crucible, in 450 DEG C of constant temperature 6h in air atmosphere, then be warming up to 750 DEG C of insulation 20h
After be slowly cooled to room temperature, 400 mesh sieves are crossed in sample comminution after firing, grinding, obtain manganate cathode material for lithium；By above-mentioned step
The solution being filtrated to get in rapid crystallize in crystallizing evaporator, and cerium sulphate crystal condition is vacuum 0.015MPa, 120 DEG C of temperature,
Crystal is dried under 80 DEG C and 2h and obtains potassium sulfate.
Embodiment 2：
The scrap lithium ion battery of positive electrode is done in collection with LiMn2O4, and the hydroxide of 0.5mol/L is positioned at room temperature
The discharge process of 2h is carried out in sodium water solution；After discharge process, the lithium ion battery that will be scrapped is disassembled, and obtains positive plate；
The positive plate that will be obtained is 1 in the ratio (g/mL) of the volume of the quality and ceramic crucible of positive plate:10 ratio is by positive plate
It is fitted into ceramic crucible, be subsequently placed in chamber type electric resistance furnace makes furnace temperature be raised to 550 since room temperature with the heating rate of 5 DEG C/min
DEG C insulation 0.5h, room temperature is naturally cooled to after power-off；The positive plate by roasting is taken out, according to the quality and the body of water of positive plate
Long-pending ratio (g/mL) is 1:50 are put into equipped with 20min is stirred in the container for filling water and with electric mixer positive plate, stir
The temperature of process reclaimed water is mixed for 25 DEG C, mixing speed is 100r/min；After stopping stirring, by 10 purposes of the mixture in container
Screen cloth is sieved, and oversize is aluminium foil, and screenings is the solution containing positive active material；Screenings carries out suction filtration, in filter
Thing is cleaned 3 times with water, obtains positive active material；The positive active material for obtaining is fitted into ceramic crucible, case is subsequently placed in
Furnace temperature is raised to 550 DEG C and be incubated 1h with the heating rate of 5 DEG C/min in formula resistance furnace, obtain useless LiMn2O4；By useless LiMn2O4
It is 1 with potassium sulfate (g/g) in mass ratio:0.2 ratio mixes, then the ball milling in planetary ball mill, and Ball-milling Time is 0.5
H, rotating speed is 300 r/min；Mixture after ball milling is fitted into absorption plant；From gas washing in SA production double-absorption system system out
Sour tail gas, after first passing through heating, then is passed through conversion operation is carried out in the conversion system equipped with S108 type vanadium catalysts, converts
The condition of operation is：400 DEG C of gasinlet temperature, flow velocity 0.3m/s, the filling of S108 types vanadium catalyst is by norm in conversion system
For：0.5m3Catalyst/(1000m3Relieving haperacidity tail gas h)；It is passed through from conversion system gas out and has been charged into mixture after ball milling
Absorption plant in carry out absorption operation, the condition of absorption operation is：410 DEG C of temperature, inlet gas flow velocity 0.3m/s；Detect
SO in absorption plant exit gas2Content be less than 400mg/m3And whether the content of sulfuric acid mist is less than 30mg/m3, filled absorbing
It is emitted into air after the gas cooling for putting outlet；The mixture in the absorption plant of conversion system exit gas will be no longer passed through
Under conditions of stirring with 50 DEG C of water with solid-to-liquid ratio (g/mL) be 1:20 leach 30min；Then leachate is warmed up to 98 DEG C,
The solution of potassium carbonate of 3.0mol/L is slowly added to leachate and produces sediment, after gained sediment is through filtering, washing, drying,
The content of Li, Mn in analysis sediment, is 0.525 according to the mol ratio of lithium and manganese:1 requirement supplements a certain amount of toward sediment
Lithium carbonate, then with the abundant ball milling 2h of the speed of 400r/min in planetary ball mill, then its pressure in 5MPa is pushed
Tightly, it is put into clean ceramic crucible, in 450 DEG C of constant temperature 6h in air atmosphere, then is warming up to slow after 750 DEG C of insulation 20h
Room temperature is cooled to, sample comminution, grinding after firing cross 400 mesh sieves, obtain manganate cathode material for lithium；By mistake in above-mentioned steps
The solution that filter is obtained is crystallized in crystallizing evaporator, and cerium sulphate crystal condition is vacuum 0.015MPa, 120 DEG C of temperature, crystal
Dried under 80 DEG C and 2h and obtain potassium sulfate.
Embodiment 3：
The scrap lithium ion battery of positive electrode is done in collection with LiMn2O4, and the hydroxide of 0.5mol/L is positioned at room temperature
The discharge process of 2h is carried out in sodium water solution；After discharge process, the lithium ion battery that will be scrapped is disassembled, and obtains positive plate；
The positive plate that will be obtained is 1 in the ratio (g/mL) of the volume of the quality and ceramic crucible of positive plate:10 ratio is by positive plate
It is fitted into ceramic crucible, be subsequently placed in chamber type electric resistance furnace makes furnace temperature be raised to 550 since room temperature with the heating rate of 5 DEG C/min
DEG C insulation 0.5h, room temperature is naturally cooled to after power-off；The positive plate by roasting is taken out, according to the quality and the body of water of positive plate
Long-pending ratio (g/mL) is 1:50 are put into equipped with 20min is stirred in the container for filling water and with electric mixer positive plate, stir
The temperature of process reclaimed water is mixed for 25 DEG C, mixing speed is 100r/min；After stopping stirring, by 10 purposes of the mixture in container
Screen cloth is sieved, and oversize is aluminium foil, and screenings is the solution containing positive active material；Screenings carries out suction filtration, in filter
Thing is cleaned 3 times with water, obtains positive active material；The positive active material for obtaining is fitted into ceramic crucible, case is subsequently placed in
Furnace temperature is raised to 550 DEG C and be incubated 1h with the heating rate of 5 DEG C/min in formula resistance furnace, obtain useless LiMn2O4；By useless LiMn2O4
It is 1 with potassium sulfate (g/g) in mass ratio:0.3 ratio mixes, then the ball milling in planetary ball mill, and Ball-milling Time is 0.5
H, rotating speed is 300 r/min；Mixture after ball milling is fitted into absorption plant；From gas washing in SA production double-absorption system system out
Sour tail gas, after first passing through heating, then is passed through conversion operation is carried out in the conversion system equipped with S108 type vanadium catalysts, converts
The condition of operation is：400 DEG C of gasinlet temperature, flow velocity 0.3m/s, the filling of S108 types vanadium catalyst is by norm in conversion system
For：0.5m3Catalyst/(1000m3Relieving haperacidity tail gas h)；It is passed through from conversion system gas out and has been charged into mixture after ball milling
Absorption plant in carry out absorption operation, the condition of absorption operation is：390 DEG C of temperature, inlet gas flow velocity 0.3m/s；Detect
SO in absorption plant exit gas2Content be less than 400mg/m3And whether the content of sulfuric acid mist is less than 30mg/m3, filled absorbing
It is emitted into air after the gas cooling for putting outlet；The mixture in the absorption plant of conversion system exit gas will be no longer passed through
Under conditions of stirring with 50 DEG C of water with solid-to-liquid ratio (g/mL) be 1:20 leach 30min；Then leachate is warmed up to 98 DEG C,
The solution of potassium carbonate of 3.0mol/L is slowly added to leachate and produces sediment, after gained sediment is through filtering, washing, drying,
The content of Li, Mn in analysis sediment, is 0.525 according to the mol ratio of lithium and manganese:1 requirement supplements a certain amount of toward sediment
Lithium carbonate, then with the abundant ball milling 2h of the speed of 400r/min in planetary ball mill, then its pressure in 5MPa is pushed
Tightly, it is put into clean ceramic crucible, in 450 DEG C of constant temperature 6h in air atmosphere, then is warming up to slow after 750 DEG C of insulation 20h
Room temperature is cooled to, sample comminution, grinding after firing cross 400 mesh sieves, obtain manganate cathode material for lithium；By mistake in above-mentioned steps
The solution that filter is obtained is crystallized in crystallizing evaporator, and cerium sulphate crystal condition is vacuum 0.015MPa, 120 DEG C of temperature, crystal
Dried under 80 DEG C and 2h and obtain potassium sulfate.
Embodiment 4：
The scrap lithium ion battery of positive electrode is done in collection with LiMn2O4, and the hydroxide of 0.5mol/L is positioned at room temperature
The discharge process of 2h is carried out in sodium water solution；After discharge process, the lithium ion battery that will be scrapped is disassembled, and obtains positive plate；
The positive plate that will be obtained is 1 in the ratio (g/mL) of the volume of the quality and ceramic crucible of positive plate:10 ratio is by positive plate
It is fitted into ceramic crucible, be subsequently placed in chamber type electric resistance furnace makes furnace temperature be raised to 550 since room temperature with the heating rate of 5 DEG C/min
DEG C insulation 0.5h, room temperature is naturally cooled to after power-off；The positive plate by roasting is taken out, according to the quality and the body of water of positive plate
Long-pending ratio (g/mL) is 1:50 are put into equipped with 20min is stirred in the container for filling water and with electric mixer positive plate, stir
The temperature of process reclaimed water is mixed for 25 DEG C, mixing speed is 100r/min；After stopping stirring, by 10 purposes of the mixture in container
Screen cloth is sieved, and oversize is aluminium foil, and screenings is the solution containing positive active material；Screenings carries out suction filtration, in filter
Thing is cleaned 3 times with water, obtains positive active material；The positive active material for obtaining is fitted into ceramic crucible, case is subsequently placed in
Furnace temperature is raised to 550 DEG C and be incubated 1h with the heating rate of 5 DEG C/min in formula resistance furnace, obtain useless LiMn2O4；By useless LiMn2O4
It is 1 with potassium sulfate (g/g) in mass ratio:0.4 ratio mixes, then the ball milling in planetary ball mill, and Ball-milling Time is 0.5
H, rotating speed is 300 r/min；Mixture after ball milling is fitted into absorption plant；From gas washing in SA production double-absorption system system out
Sour tail gas, after first passing through heating, then is passed through conversion operation is carried out in the conversion system equipped with S108 type vanadium catalysts, converts
The condition of operation is：400 DEG C of gasinlet temperature, flow velocity 0.3m/s, the filling of S108 types vanadium catalyst is by norm in conversion system
For：0.5m3Catalyst/(1000m3Relieving haperacidity tail gas h)；It is passed through from conversion system gas out and has been charged into mixture after ball milling
Absorption plant in carry out absorption operation, the condition of absorption operation is：400 DEG C of temperature, inlet gas flow velocity 0.3m/s；Detect
SO in absorption plant exit gas2Content be less than 400mg/m3And whether the content of sulfuric acid mist is less than 30mg/m3, filled absorbing
It is emitted into air after the gas cooling for putting outlet；The mixture in the absorption plant of conversion system exit gas will be no longer passed through
Under conditions of stirring with 50 DEG C of water with solid-to-liquid ratio (g/mL) be 1:20 leach 30min；Then leachate is warmed up to 98 DEG C,
The solution of potassium carbonate of 3.0mol/L is slowly added to leachate and produces sediment, after gained sediment is through filtering, washing, drying,
The content of Li, Mn in analysis sediment, is 0.525 according to the mol ratio of lithium and manganese:1 requirement supplements a certain amount of toward sediment
Lithium carbonate, then with the abundant ball milling 2h of the speed of 400r/min in planetary ball mill, then its pressure in 5MPa is pushed
Tightly, it is put into clean ceramic crucible, in 450 DEG C of constant temperature 6h in air atmosphere, then is warming up to slow after 750 DEG C of insulation 20h
Room temperature is cooled to, sample comminution, grinding after firing cross 400 mesh sieves, obtain manganate cathode material for lithium；By mistake in above-mentioned steps
The solution that filter is obtained is crystallized in crystallizing evaporator, and cerium sulphate crystal condition is vacuum 0.015MPa, 120 DEG C of temperature, crystal
Dried under 80 DEG C and 2h and obtain potassium sulfate.
Embodiment 5：
The scrap lithium ion battery of positive electrode is done in collection with LiMn2O4, and the hydroxide of 0.5mol/L is positioned at room temperature
The discharge process of 2h is carried out in sodium water solution；After discharge process, the lithium ion battery that will be scrapped is disassembled, and obtains positive plate；
The positive plate that will be obtained is 1 in the ratio (g/mL) of the volume of the quality and ceramic crucible of positive plate:10 ratio is by positive plate
It is fitted into ceramic crucible, be subsequently placed in chamber type electric resistance furnace makes furnace temperature be raised to 550 since room temperature with the heating rate of 5 DEG C/min
DEG C insulation 0.5h, room temperature is naturally cooled to after power-off；The positive plate by roasting is taken out, according to the quality and the body of water of positive plate
Long-pending ratio (g/mL) is 1:50 are put into equipped with 20min is stirred in the container for filling water and with electric mixer positive plate, stir
The temperature of process reclaimed water is mixed for 25 DEG C, mixing speed is 100r/min；After stopping stirring, by 10 purposes of the mixture in container
Screen cloth is sieved, and oversize is aluminium foil, and screenings is the solution containing positive active material；Screenings carries out suction filtration, in filter
Thing is cleaned 3 times with water, obtains positive active material；The positive active material for obtaining is fitted into ceramic crucible, case is subsequently placed in
Furnace temperature is raised to 550 DEG C and be incubated 1h with the heating rate of 5 DEG C/min in formula resistance furnace, obtain useless LiMn2O4；By useless LiMn2O4
It is 1 with potassium sulfate (g/g) in mass ratio:0.5 ratio mixes, then the ball milling in planetary ball mill, and Ball-milling Time is 0.5
H, rotating speed is 300 r/min；Mixture after ball milling is fitted into absorption plant；From gas washing in SA production double-absorption system system out
Sour tail gas, after first passing through heating, then is passed through conversion operation is carried out in the conversion system equipped with S108 type vanadium catalysts, converts
The condition of operation is：400 DEG C of gasinlet temperature, flow velocity 0.3m/s, the filling of S108 types vanadium catalyst is by norm in conversion system
For：0.5m3Catalyst/(1000m3Relieving haperacidity tail gas h)；It is passed through from conversion system gas out and has been charged into mixture after ball milling
Absorption plant in carry out absorption operation, the condition of absorption operation is：415 DEG C of temperature, inlet gas flow velocity 0.3m/s；Detect
SO in absorption plant exit gas2Content be less than 400mg/m3And whether the content of sulfuric acid mist is less than 30mg/m3, filled absorbing
It is emitted into air after the gas cooling for putting outlet；The mixture in the absorption plant of conversion system exit gas will be no longer passed through
Under conditions of stirring with 50 DEG C of water with solid-to-liquid ratio (g/mL) be 1:20 leach 30min；Then leachate is warmed up to 98 DEG C,
The solution of potassium carbonate of 3.0mol/L is slowly added to leachate and produces sediment, after gained sediment is through filtering, washing, drying,
The content of Li, Mn in analysis sediment, is 0.525 according to the mol ratio of lithium and manganese:1 requirement supplements a certain amount of toward sediment
Lithium carbonate, then with the abundant ball milling 2h of the speed of 400r/min in planetary ball mill, then its pressure in 5MPa is pushed
Tightly, it is put into clean ceramic crucible, in 450 DEG C of constant temperature 6h in air atmosphere, then is warming up to slow after 750 DEG C of insulation 20h
Room temperature is cooled to, sample comminution, grinding after firing cross 400 mesh sieves, obtain manganate cathode material for lithium；By mistake in above-mentioned steps
The solution that filter is obtained is crystallized in crystallizing evaporator, and cerium sulphate crystal condition is vacuum 0.015MPa, 120 DEG C of temperature, crystal
Dried under 80 DEG C and 2h and obtain potassium sulfate.
Embodiment 6：
The scrap lithium ion battery of positive electrode is done in collection with LiMn2O4, and the hydroxide of 0.5mol/L is positioned at room temperature
The discharge process of 2h is carried out in sodium water solution；After discharge process, the lithium ion battery that will be scrapped is disassembled, and obtains positive plate；
The positive plate that will be obtained is 1 in the ratio (g/mL) of the volume of the quality and ceramic crucible of positive plate:10 ratio is by positive plate
It is fitted into ceramic crucible, be subsequently placed in chamber type electric resistance furnace makes furnace temperature be raised to 550 since room temperature with the heating rate of 5 DEG C/min
DEG C insulation 0.5h, room temperature is naturally cooled to after power-off；The positive plate by roasting is taken out, according to the quality and the body of water of positive plate
Long-pending ratio (g/mL) is 1:50 are put into equipped with 20min is stirred in the container for filling water and with electric mixer positive plate, stir
The temperature of process reclaimed water is mixed for 25 DEG C, mixing speed is 100r/min；After stopping stirring, by 10 purposes of the mixture in container
Screen cloth is sieved, and oversize is aluminium foil, and screenings is the solution containing positive active material；Screenings carries out suction filtration, in filter
Thing is cleaned 3 times with water, obtains positive active material；The positive active material for obtaining is fitted into ceramic crucible, case is subsequently placed in
Furnace temperature is raised to 550 DEG C and be incubated 1h with the heating rate of 5 DEG C/min in formula resistance furnace, obtain useless LiMn2O4；By useless LiMn2O4
It is 1 with potassium sulfate (g/g) in mass ratio:0.6 ratio mixes, then the ball milling in planetary ball mill, and Ball-milling Time is 0.5
H, rotating speed is 300 r/min；Mixture after ball milling is fitted into absorption plant；From gas washing in SA production double-absorption system system out
Sour tail gas, after first passing through heating, then is passed through conversion operation is carried out in the conversion system equipped with S108 type vanadium catalysts, converts
The condition of operation is：400 DEG C of gasinlet temperature, flow velocity 0.3m/s, the filling of S108 types vanadium catalyst is by norm in conversion system
For：0.5m3Catalyst/(1000m3Relieving haperacidity tail gas h)；It is passed through from conversion system gas out and has been charged into mixture after ball milling
Absorption plant in carry out absorption operation, the condition of absorption operation is：395 DEG C of temperature, inlet gas flow velocity 0.3m/s；Detect
SO in absorption plant exit gas2Content be less than 400mg/m3And whether the content of sulfuric acid mist is less than 30mg/m3, filled absorbing
It is emitted into air after the gas cooling for putting outlet；The mixture in the absorption plant of conversion system exit gas will be no longer passed through
Under conditions of stirring with 50 DEG C of water with solid-to-liquid ratio (g/mL) be 1:20 leach 30min；Then leachate is warmed up to 98 DEG C,
The solution of potassium carbonate of 3.0mol/L is slowly added to leachate and produces sediment, after gained sediment is through filtering, washing, drying,
The content of Li, Mn in analysis sediment, is 0.525 according to the mol ratio of lithium and manganese:1 requirement supplements a certain amount of toward sediment
Lithium carbonate, then with the abundant ball milling 2h of the speed of 400r/min in planetary ball mill, then its pressure in 5MPa is pushed
Tightly, it is put into clean ceramic crucible, in 450 DEG C of constant temperature 6h in air atmosphere, then is warming up to slow after 750 DEG C of insulation 20h
Room temperature is cooled to, sample comminution, grinding after firing cross 400 mesh sieves, obtain manganate cathode material for lithium；By mistake in above-mentioned steps
The solution that filter is obtained is crystallized in crystallizing evaporator, and cerium sulphate crystal condition is vacuum 0.015MPa, 120 DEG C of temperature, crystal
Dried under 80 DEG C and 2h and obtain potassium sulfate.
Embodiment 7：
The scrap lithium ion battery of positive electrode is done in collection with LiMn2O4, and the hydroxide of 0.5mol/L is positioned at room temperature
The discharge process of 2h is carried out in sodium water solution；After discharge process, the lithium ion battery that will be scrapped is disassembled, and obtains positive plate；
The positive plate that will be obtained is 1 in the ratio (g/mL) of the volume of the quality and ceramic crucible of positive plate:10 ratio is by positive plate
It is fitted into ceramic crucible, be subsequently placed in chamber type electric resistance furnace makes furnace temperature be raised to 550 since room temperature with the heating rate of 5 DEG C/min
DEG C insulation 0.5h, room temperature is naturally cooled to after power-off；The positive plate by roasting is taken out, according to the quality and the body of water of positive plate
Long-pending ratio (g/mL) is 1:50 are put into equipped with 20min is stirred in the container for filling water and with electric mixer positive plate, stir
The temperature of process reclaimed water is mixed for 25 DEG C, mixing speed is 100r/min；After stopping stirring, by 10 purposes of the mixture in container
Screen cloth is sieved, and oversize is aluminium foil, and screenings is the solution containing positive active material；Screenings carries out suction filtration, in filter
Thing is cleaned 3 times with water, obtains positive active material；The positive active material for obtaining is fitted into ceramic crucible, case is subsequently placed in
Furnace temperature is raised to 550 DEG C and be incubated 1h with the heating rate of 5 DEG C/min in formula resistance furnace, obtain useless LiMn2O4；By useless LiMn2O4
It is 1 with potassium sulfate (g/g) in mass ratio:0.7 ratio mixes, then the ball milling in planetary ball mill, and Ball-milling Time is 0.5
H, rotating speed is 300 r/min；Mixture after ball milling is fitted into absorption plant；From gas washing in SA production double-absorption system system out
Sour tail gas, after first passing through heating, then is passed through conversion operation is carried out in the conversion system equipped with S108 type vanadium catalysts, converts
The condition of operation is：400 DEG C of gasinlet temperature, flow velocity 0.3m/s, the filling of S108 types vanadium catalyst is by norm in conversion system
For：0.5m3Catalyst/(1000m3Relieving haperacidity tail gas h)；It is passed through from conversion system gas out and has been charged into mixture after ball milling
Absorption plant in carry out absorption operation, the condition of absorption operation is：420 DEG C of temperature, inlet gas flow velocity 0.3m/s；Detect
SO in absorption plant exit gas2Content be less than 400mg/m3And whether the content of sulfuric acid mist is less than 30mg/m3, filled absorbing
It is emitted into air after the gas cooling for putting outlet；The mixture in the absorption plant of conversion system exit gas will be no longer passed through
Under conditions of stirring with 50 DEG C of water with solid-to-liquid ratio (g/mL) be 1:20 leach 30min；Then leachate is warmed up to 98 DEG C,
The solution of potassium carbonate of 3.0mol/L is slowly added to leachate and produces sediment, after gained sediment is through filtering, washing, drying,
The content of Li, Mn in analysis sediment, is 0.525 according to the mol ratio of lithium and manganese:1 requirement supplements a certain amount of toward sediment
Lithium carbonate, then with the abundant ball milling 2h of the speed of 400r/min in planetary ball mill, then its pressure in 5MPa is pushed
Tightly, it is put into clean ceramic crucible, in 450 DEG C of constant temperature 6h in air atmosphere, then is warming up to slow after 750 DEG C of insulation 20h
Room temperature is cooled to, sample comminution, grinding after firing cross 400 mesh sieves, obtain manganate cathode material for lithium；By mistake in above-mentioned steps
The solution that filter is obtained is crystallized in crystallizing evaporator, and cerium sulphate crystal condition is vacuum 0.015MPa, 120 DEG C of temperature, crystal
Dried under 80 DEG C and 2h and obtain potassium sulfate.
Embodiment 8：
The scrap lithium ion battery of positive electrode is done in collection with LiMn2O4, and the hydroxide of 0.5mol/L is positioned at room temperature
The discharge process of 2h is carried out in sodium water solution；After discharge process, the lithium ion battery that will be scrapped is disassembled, and obtains positive plate；
The positive plate that will be obtained is 1 in the ratio (g/mL) of the volume of the quality and ceramic crucible of positive plate:10 ratio is by positive plate
It is fitted into ceramic crucible, be subsequently placed in chamber type electric resistance furnace makes furnace temperature be raised to 550 since room temperature with the heating rate of 5 DEG C/min
DEG C insulation 0.5h, room temperature is naturally cooled to after power-off；The positive plate by roasting is taken out, according to the quality and the body of water of positive plate
Long-pending ratio (g/mL) is 1:50 are put into equipped with 20min is stirred in the container for filling water and with electric mixer positive plate, stir
The temperature of process reclaimed water is mixed for 25 DEG C, mixing speed is 100r/min；After stopping stirring, by 10 purposes of the mixture in container
Screen cloth is sieved, and oversize is aluminium foil, and screenings is the solution containing positive active material；Screenings carries out suction filtration, in filter
Thing is cleaned 3 times with water, obtains positive active material；The positive active material for obtaining is fitted into ceramic crucible, case is subsequently placed in
Furnace temperature is raised to 550 DEG C and be incubated 1h with the heating rate of 5 DEG C/min in formula resistance furnace, obtain useless LiMn2O4；By useless LiMn2O4
It is 1 with potassium sulfate (g/g) in mass ratio:0.8 ratio mixes, then the ball milling in planetary ball mill, and Ball-milling Time is 0.5
H, rotating speed is 300 r/min；Mixture after ball milling is fitted into absorption plant；From gas washing in SA production double-absorption system system out
Sour tail gas, after first passing through heating, then is passed through conversion operation is carried out in the conversion system equipped with S108 type vanadium catalysts, converts
The condition of operation is：400 DEG C of gasinlet temperature, flow velocity 0.3m/s, the filling of S108 types vanadium catalyst is by norm in conversion system
For：0.5m3Catalyst/(1000m3Relieving haperacidity tail gas h)；It is passed through from conversion system gas out and has been charged into mixture after ball milling
Absorption plant in carry out absorption operation, the condition of absorption operation is：415 DEG C of temperature, inlet gas flow velocity 0.3m/s；Detect
SO in absorption plant exit gas2Content be less than 400mg/m3And whether the content of sulfuric acid mist is less than 30mg/m3, filled absorbing
It is emitted into air after the gas cooling for putting outlet；The mixture in the absorption plant of conversion system exit gas will be no longer passed through
Under conditions of stirring with 50 DEG C of water with solid-to-liquid ratio (g/mL) be 1:20 leach 30min；Then leachate is warmed up to 98 DEG C,
The solution of potassium carbonate of 3.0mol/L is slowly added to leachate and produces sediment, after gained sediment is through filtering, washing, drying,
The content of Li, Mn in analysis sediment, is 0.525 according to the mol ratio of lithium and manganese:1 requirement supplements a certain amount of toward sediment
Lithium carbonate, then with the abundant ball milling 2h of the speed of 400r/min in planetary ball mill, then its pressure in 5MPa is pushed
Tightly, it is put into clean ceramic crucible, in 450 DEG C of constant temperature 6h in air atmosphere, then is warming up to slow after 750 DEG C of insulation 20h
Room temperature is cooled to, sample comminution, grinding after firing cross 400 mesh sieves, obtain manganate cathode material for lithium；By mistake in above-mentioned steps
The solution that filter is obtained is crystallized in crystallizing evaporator, and cerium sulphate crystal condition is vacuum 0.015MPa, 120 DEG C of temperature, crystal
Dried under 80 DEG C and 2h and obtain potassium sulfate.
Embodiment 9：
The scrap lithium ion battery of positive electrode is done in collection with LiMn2O4, and the hydroxide of 0.5mol/L is positioned at room temperature
The discharge process of 2h is carried out in sodium water solution；After discharge process, the lithium ion battery that will be scrapped is disassembled, and obtains positive plate；
The positive plate that will be obtained is 1 in the ratio (g/mL) of the volume of the quality and ceramic crucible of positive plate:10 ratio is by positive plate
It is fitted into ceramic crucible, be subsequently placed in chamber type electric resistance furnace makes furnace temperature be raised to 550 since room temperature with the heating rate of 5 DEG C/min
DEG C insulation 0.5h, room temperature is naturally cooled to after power-off；The positive plate by roasting is taken out, according to the quality and the body of water of positive plate
Long-pending ratio (g/mL) is 1:50 are put into equipped with 20min is stirred in the container for filling water and with electric mixer positive plate, stir
The temperature of process reclaimed water is mixed for 25 DEG C, mixing speed is 100r/min；After stopping stirring, by 10 purposes of the mixture in container
Screen cloth is sieved, and oversize is aluminium foil, and screenings is the solution containing positive active material；Screenings carries out suction filtration, in filter
Thing is cleaned 3 times with water, obtains positive active material；The positive active material for obtaining is fitted into ceramic crucible, case is subsequently placed in
Furnace temperature is raised to 550 DEG C and be incubated 1h with the heating rate of 5 DEG C/min in formula resistance furnace, obtain useless LiMn2O4；By useless LiMn2O4
It is 1 with potassium sulfate (g/g) in mass ratio:0.9 ratio mixes, then the ball milling in planetary ball mill, and Ball-milling Time is 0.5
H, rotating speed is 300 r/min；Mixture after ball milling is fitted into absorption plant；From gas washing in SA production double-absorption system system out
Sour tail gas, after first passing through heating, then is passed through conversion operation is carried out in the conversion system equipped with S108 type vanadium catalysts, converts
The condition of operation is：400 DEG C of gasinlet temperature, flow velocity 0.3m/s, the filling of S108 types vanadium catalyst is by norm in conversion system
For：0.5m3Catalyst/(1000m3Relieving haperacidity tail gas h)；It is passed through from conversion system gas out and has been charged into mixture after ball milling
Absorption plant in carry out absorption operation, the condition of absorption operation is：380 DEG C of temperature, inlet gas flow velocity 0.3m/s；Detect
SO in absorption plant exit gas2Content be less than 400mg/m3And whether the content of sulfuric acid mist is less than 30mg/m3, filled absorbing
It is emitted into air after the gas cooling for putting outlet；The mixture in the absorption plant of conversion system exit gas will be no longer passed through
Under conditions of stirring with 50 DEG C of water with solid-to-liquid ratio (g/mL) be 1:20 leach 30min；Then leachate is warmed up to 98 DEG C,
The solution of potassium carbonate of 3.0mol/L is slowly added to leachate and produces sediment, after gained sediment is through filtering, washing, drying,
The content of Li, Mn in analysis sediment, is 0.525 according to the mol ratio of lithium and manganese:1 requirement supplements a certain amount of toward sediment
Lithium carbonate, then with the abundant ball milling 2h of the speed of 400r/min in planetary ball mill, then its pressure in 5MPa is pushed
Tightly, it is put into clean ceramic crucible, in 450 DEG C of constant temperature 6h in air atmosphere, then is warming up to slow after 750 DEG C of insulation 20h
Room temperature is cooled to, sample comminution, grinding after firing cross 400 mesh sieves, obtain manganate cathode material for lithium；By mistake in above-mentioned steps
The solution that filter is obtained is crystallized in crystallizing evaporator, and cerium sulphate crystal condition is vacuum 0.015MPa, 120 DEG C of temperature, crystal
Dried under 80 DEG C and 2h and obtain potassium sulfate.
Embodiment 10：
The scrap lithium ion battery of positive electrode is done in collection with LiMn2O4, and the hydroxide of 0.5mol/L is positioned at room temperature
The discharge process of 2h is carried out in sodium water solution；After discharge process, the lithium ion battery that will be scrapped is disassembled, and obtains positive plate；
The positive plate that will be obtained is 1 in the ratio (g/mL) of the volume of the quality and ceramic crucible of positive plate:10 ratio is by positive plate
It is fitted into ceramic crucible, be subsequently placed in chamber type electric resistance furnace makes furnace temperature be raised to 550 since room temperature with the heating rate of 5 DEG C/min
DEG C insulation 0.5h, room temperature is naturally cooled to after power-off；The positive plate by roasting is taken out, according to the quality and the body of water of positive plate
Long-pending ratio (g/mL) is 1:50 are put into equipped with 20min is stirred in the container for filling water and with electric mixer positive plate, stir
The temperature of process reclaimed water is mixed for 25 DEG C, mixing speed is 100r/min；After stopping stirring, by 10 purposes of the mixture in container
Screen cloth is sieved, and oversize is aluminium foil, and screenings is the solution containing positive active material；Screenings carries out suction filtration, in filter
Thing is cleaned 3 times with water, obtains positive active material；The positive active material for obtaining is fitted into ceramic crucible, case is subsequently placed in
Furnace temperature is raised to 550 DEG C and be incubated 1h with the heating rate of 5 DEG C/min in formula resistance furnace, obtain useless LiMn2O4；By useless LiMn2O4
It is 1 with potassium sulfate (g/g) in mass ratio:1.0 ratio mixes, then the ball milling in planetary ball mill, and Ball-milling Time is 0.5
H, rotating speed is 300 r/min；Mixture after ball milling is fitted into absorption plant；From gas washing in SA production double-absorption system system out
Sour tail gas, after first passing through heating, then is passed through conversion operation is carried out in the conversion system equipped with S108 type vanadium catalysts, converts
The condition of operation is：400 DEG C of gasinlet temperature, flow velocity 0.3m/s, the filling of S108 types vanadium catalyst is by norm in conversion system
For：0.5m3Catalyst/(1000m3Relieving haperacidity tail gas h)；It is passed through from conversion system gas out and has been charged into mixture after ball milling
Absorption plant in carry out absorption operation, the condition of absorption operation is：420 DEG C of temperature, inlet gas flow velocity 0.3m/s；Detect
SO in absorption plant exit gas2Content be less than 400mg/m3And whether the content of sulfuric acid mist is less than 30mg/m3, filled absorbing
It is emitted into air after the gas cooling for putting outlet；The mixture in the absorption plant of conversion system exit gas will be no longer passed through
Under conditions of stirring with 50 DEG C of water with solid-to-liquid ratio (g/mL) be 1:20 leach 30min；Then leachate is warmed up to 98 DEG C,
The solution of potassium carbonate of 3.0mol/L is slowly added to leachate and produces sediment, after gained sediment is through filtering, washing, drying,
The content of Li, Mn in analysis sediment, is 0.525 according to the mol ratio of lithium and manganese:1 requirement supplements a certain amount of toward sediment
Lithium carbonate, then with the abundant ball milling 2h of the speed of 400r/min in planetary ball mill, then its pressure in 5MPa is pushed
Tightly, it is put into clean ceramic crucible, in 450 DEG C of constant temperature 6h in air atmosphere, then is warming up to slow after 750 DEG C of insulation 20h
Room temperature is cooled to, sample comminution, grinding after firing cross 400 mesh sieves, obtain manganate cathode material for lithium；By mistake in above-mentioned steps
The solution that filter is obtained is crystallized in crystallizing evaporator, and cerium sulphate crystal condition is vacuum 0.015MPa, 120 DEG C of temperature, crystal
Dried under 80 DEG C and 2h and obtain potassium sulfate.
Embodiment 11：
The positive pole leftover pieces that the lithium ion battery manufacturing process for doing positive electrode with LiMn2O4 is produced are collected, positive pole is obtained
Piece；Ratio (g/mL) in the volume of the quality and ceramic crucible of positive plate is 1:Positive plate is loaded ceramic crucible by 10 ratio
In, be subsequently placed in chamber type electric resistance furnace makes furnace temperature be raised to 550 DEG C of insulation 0.5h since room temperature with the heating rate of 5 DEG C/min,
Room temperature is naturally cooled to after power-off；The positive plate by roasting is taken out, according to the ratio (g/ of the volume of the quality and water of positive plate
ML it is) 1:50 are put into equipped with filling in the container of water and with electric mixer stir 20min positive plate, whipping process reclaimed water
Temperature is 25 DEG C, and mixing speed is 100r/min；After stopping stirring, the mixture in container is sieved with the screen cloth of 10 mesh
Point, oversize is aluminium foil, and screenings is the solution containing positive active material；Screenings carries out suction filtration, and thing cleans 3 with water in filter
It is secondary, obtain positive active material；By obtain positive active material be fitted into ceramic crucible, be subsequently placed in chamber type electric resistance furnace with
The heating rate of 5 DEG C/min makes furnace temperature be raised to 550 DEG C and is incubated 1h, obtains useless LiMn2O4；Useless LiMn2O4 and potassium sulfate are pressed into matter
Amount is 1 than (g/g):1.3 ratio mixes, then the ball milling in planetary ball mill, and Ball-milling Time is 0.5 h, and rotating speed is 300
r/min；Mixture after ball milling is fitted into absorption plant；From gas washing in SA production double-absorption system relieving haperacidity tail gas out, first pass through
After crossing heating, then it is passed through conversion operation, the condition of conversion operation is carried out in the conversion system equipped with S108 type vanadium catalysts
For：400 DEG C of gasinlet temperature, flow velocity 0.3m/s, the filling of S108 types vanadium catalyst is rated in conversion system：0.5m3Urge
Agent/(1000m3Relieving haperacidity tail gas h)；The absorption plant for having been charged into mixture after ball milling is passed through from conversion system gas out
In carry out absorption operation, the condition of absorption operation is：410 DEG C of temperature, inlet gas flow velocity 0.3m/s；Absorption plant is detected to go out
SO in gas2Content be less than 400mg/m3And whether the content of sulfuric acid mist is less than 30mg/m3, the gas that absorption plant is exported
It is emitted into air after body cooling；Bar of the mixture that will be no longer passed through in the absorption plant of conversion system exit gas in stirring
Under part with 50 DEG C of water with solid-to-liquid ratio (g/mL) be 1:20 leach 30min；Then leachate is warmed up to 98 DEG C, by 3.0mol/L
Solution of potassium carbonate be slowly added to leachate produce sediment, gained sediment through filtering, washing, dry after, analyze sediment
The content of middle Li, Mn, is 0.525 according to the mol ratio of lithium and manganese:1 requirement supplements a certain amount of lithium carbonate toward sediment, so
Afterwards with the abundant ball milling 2h of the speed of 400r/min in planetary ball mill, then it is compressed under the pressure of 5MPa, be put into dry
In net ceramic crucible, in 450 DEG C of constant temperature 6h in air atmosphere, then be warming up to 750 DEG C insulation 20h after slowly cool to room
Temperature, sample comminution, grinding after firing, crosses 400 mesh sieves, obtains manganate cathode material for lithium；By what is be filtrated to get in above-mentioned steps
Solution is crystallized in crystallizing evaporator, cerium sulphate crystal condition be vacuum 0.015MPa, 120 DEG C of temperature, crystal 80 DEG C with
And acquisition potassium sulfate is dried under 2h.
Embodiment 12：
The positive pole leftover pieces that the lithium ion battery manufacturing process for doing positive electrode with LiMn2O4 is produced are collected, positive pole is obtained
Piece；Ratio (g/mL) in the volume of the quality and ceramic crucible of positive plate is 1:Positive plate is loaded ceramic crucible by 10 ratio
In, be subsequently placed in chamber type electric resistance furnace makes furnace temperature be raised to 550 DEG C of insulation 0.5h since room temperature with the heating rate of 5 DEG C/min,
Room temperature is naturally cooled to after power-off；The positive plate by roasting is taken out, according to the ratio (g/ of the volume of the quality and water of positive plate
ML it is) 1:50 are put into equipped with filling in the container of water and with electric mixer stir 20min positive plate, whipping process reclaimed water
Temperature is 25 DEG C, and mixing speed is 100r/min；After stopping stirring, the mixture in container is sieved with the screen cloth of 10 mesh
Point, oversize is aluminium foil, and screenings is the solution containing positive active material；Screenings carries out suction filtration, and thing cleans 3 with water in filter
It is secondary, obtain positive active material；By obtain positive active material be fitted into ceramic crucible, be subsequently placed in chamber type electric resistance furnace with
The heating rate of 5 DEG C/min makes furnace temperature be raised to 550 DEG C and is incubated 1h, obtains useless LiMn2O4；Useless LiMn2O4 and potassium sulfate are pressed into matter
Amount is 1 than (g/g):1.5 ratio mixes, then the ball milling in planetary ball mill, and Ball-milling Time is 0.5 h, and rotating speed is 300
r/min；Mixture after ball milling is fitted into absorption plant；From gas washing in SA production double-absorption system relieving haperacidity tail gas out, first pass through
After crossing heating, then it is passed through conversion operation, the condition of conversion operation is carried out in the conversion system equipped with S108 type vanadium catalysts
For：400 DEG C of gasinlet temperature, flow velocity 0.3m/s, the filling of S108 types vanadium catalyst is rated in conversion system：0.5m3Urge
Agent/(1000m3Relieving haperacidity tail gas h)；The absorption plant for having been charged into mixture after ball milling is passed through from conversion system gas out
In carry out absorption operation, the condition of absorption operation is：405 DEG C of temperature, inlet gas flow velocity 0.3m/s；Absorption plant is detected to go out
SO in gas2Content be less than 400mg/m3And whether the content of sulfuric acid mist is less than 30mg/m3, the gas that absorption plant is exported
It is emitted into air after body cooling；Bar of the mixture that will be no longer passed through in the absorption plant of conversion system exit gas in stirring
Under part with 50 DEG C of water with solid-to-liquid ratio (g/mL) be 1:20 leach 30min；Then leachate is warmed up to 98 DEG C, by 3.0mol/L
Solution of potassium carbonate be slowly added to leachate produce sediment, gained sediment through filtering, washing, dry after, analyze sediment
The content of middle Li, Mn, is 0.525 according to the mol ratio of lithium and manganese:1 requirement supplements a certain amount of lithium carbonate toward sediment, so
Afterwards with the abundant ball milling 2h of the speed of 400r/min in planetary ball mill, then it is compressed under the pressure of 5MPa, be put into dry
In net ceramic crucible, in 450 DEG C of constant temperature 6h in air atmosphere, then be warming up to 750 DEG C insulation 20h after slowly cool to room
Temperature, sample comminution, grinding after firing, crosses 400 mesh sieves, obtains manganate cathode material for lithium；By what is be filtrated to get in above-mentioned steps
Solution is crystallized in crystallizing evaporator, cerium sulphate crystal condition be vacuum 0.015MPa, 120 DEG C of temperature, crystal 80 DEG C with
And acquisition potassium sulfate is dried under 2h.
Embodiment 13：
The positive pole leftover pieces that the lithium ion battery manufacturing process for doing positive electrode with LiMn2O4 is produced are collected, positive pole is obtained
Piece；Ratio (g/mL) in the volume of the quality and ceramic crucible of positive plate is 1:Positive plate is loaded ceramic crucible by 10 ratio
In, be subsequently placed in chamber type electric resistance furnace makes furnace temperature be raised to 550 DEG C of insulation 0.5h since room temperature with the heating rate of 5 DEG C/min,
Room temperature is naturally cooled to after power-off；The positive plate by roasting is taken out, according to the ratio (g/ of the volume of the quality and water of positive plate
ML it is) 1:50 are put into equipped with filling in the container of water and with electric mixer stir 20min positive plate, whipping process reclaimed water
Temperature is 25 DEG C, and mixing speed is 100r/min；After stopping stirring, the mixture in container is sieved with the screen cloth of 10 mesh
Point, oversize is aluminium foil, and screenings is the solution containing positive active material；Screenings carries out suction filtration, and thing cleans 3 with water in filter
It is secondary, obtain positive active material；By obtain positive active material be fitted into ceramic crucible, be subsequently placed in chamber type electric resistance furnace with
The heating rate of 5 DEG C/min makes furnace temperature be raised to 550 DEG C and is incubated 1h, obtains useless LiMn2O4；Useless LiMn2O4 and potassium sulfate are pressed into matter
Amount is 1 than (g/g):1.7 ratio mixes, then the ball milling in planetary ball mill, and Ball-milling Time is 0.5 h, and rotating speed is 300
r/min；Mixture after ball milling is fitted into absorption plant；From gas washing in SA production double-absorption system relieving haperacidity tail gas out, first pass through
After crossing heating, then it is passed through conversion operation, the condition of conversion operation is carried out in the conversion system equipped with S108 type vanadium catalysts
For：400 DEG C of gasinlet temperature, flow velocity 0.3m/s, the filling of S108 types vanadium catalyst is rated in conversion system：0.5m3Urge
Agent/(1000m3Relieving haperacidity tail gas h)；The absorption plant for having been charged into mixture after ball milling is passed through from conversion system gas out
In carry out absorption operation, the condition of absorption operation is：395 DEG C of temperature, inlet gas flow velocity 0.3m/s；Absorption plant is detected to go out
SO in gas2Content be less than 400mg/m3And whether the content of sulfuric acid mist is less than 30mg/m3, the gas that absorption plant is exported
It is emitted into air after body cooling；Bar of the mixture that will be no longer passed through in the absorption plant of conversion system exit gas in stirring
Under part with 50 DEG C of water with solid-to-liquid ratio (g/mL) be 1:20 leach 30min；Then leachate is warmed up to 98 DEG C, by 3.0mol/L
Solution of potassium carbonate be slowly added to leachate produce sediment, gained sediment through filtering, washing, dry after, analyze sediment
The content of middle Li, Mn, is 0.525 according to the mol ratio of lithium and manganese:1 requirement supplements a certain amount of lithium carbonate toward sediment, so
Afterwards with the abundant ball milling 2h of the speed of 400r/min in planetary ball mill, then it is compressed under the pressure of 5MPa, be put into dry
In net ceramic crucible, in 450 DEG C of constant temperature 6h in air atmosphere, then be warming up to 750 DEG C insulation 20h after slowly cool to room
Temperature, sample comminution, grinding after firing, crosses 400 mesh sieves, obtains manganate cathode material for lithium；By what is be filtrated to get in above-mentioned steps
Solution is crystallized in crystallizing evaporator, cerium sulphate crystal condition be vacuum 0.015MPa, 120 DEG C of temperature, crystal 80 DEG C with
And acquisition potassium sulfate is dried under 2h.
Embodiment 14：
The positive pole leftover pieces that the lithium ion battery manufacturing process for doing positive electrode with LiMn2O4 is produced are collected, positive pole is obtained
Piece；Ratio (g/mL) in the volume of the quality and ceramic crucible of positive plate is 1:Positive plate is loaded ceramic crucible by 10 ratio
In, be subsequently placed in chamber type electric resistance furnace makes furnace temperature be raised to 550 DEG C of insulation 0.5h since room temperature with the heating rate of 5 DEG C/min,
Room temperature is naturally cooled to after power-off；The positive plate by roasting is taken out, according to the ratio (g/ of the volume of the quality and water of positive plate
ML it is) 1:50 are put into equipped with filling in the container of water and with electric mixer stir 20min positive plate, whipping process reclaimed water
Temperature is 25 DEG C, and mixing speed is 100r/min；After stopping stirring, the mixture in container is sieved with the screen cloth of 10 mesh
Point, oversize is aluminium foil, and screenings is the solution containing positive active material；Screenings carries out suction filtration, and thing cleans 3 with water in filter
It is secondary, obtain positive active material；By obtain positive active material be fitted into ceramic crucible, be subsequently placed in chamber type electric resistance furnace with
The heating rate of 5 DEG C/min makes furnace temperature be raised to 550 DEG C and is incubated 1h, obtains useless LiMn2O4；Useless LiMn2O4 and potassium sulfate are pressed into matter
Amount is 1 than (g/g):1.8 ratio mixes, then the ball milling in planetary ball mill, and Ball-milling Time is 0.5 h, and rotating speed is 300
r/min；Mixture after ball milling is fitted into absorption plant；From gas washing in SA production double-absorption system relieving haperacidity tail gas out, first pass through
After crossing heating, then it is passed through conversion operation, the condition of conversion operation is carried out in the conversion system equipped with S108 type vanadium catalysts
For：400 DEG C of gasinlet temperature, flow velocity 0.3m/s, the filling of S108 types vanadium catalyst is rated in conversion system：0.5m3Urge
Agent/(1000m3Relieving haperacidity tail gas h)；The absorption plant for having been charged into mixture after ball milling is passed through from conversion system gas out
In carry out absorption operation, the condition of absorption operation is：430 DEG C of temperature, inlet gas flow velocity 0.3m/s；Absorption plant is detected to go out
SO in gas2Content be less than 400mg/m3And whether the content of sulfuric acid mist is less than 30mg/m3, the gas that absorption plant is exported
It is emitted into air after body cooling；Bar of the mixture that will be no longer passed through in the absorption plant of conversion system exit gas in stirring
Under part with 50 DEG C of water with solid-to-liquid ratio (g/mL) be 1:20 leach 30min；Then leachate is warmed up to 98 DEG C, by 3.0mol/L
Solution of potassium carbonate be slowly added to leachate produce sediment, gained sediment through filtering, washing, dry after, analyze sediment
The content of middle Li, Mn, is 0.525 according to the mol ratio of lithium and manganese:1 requirement supplements a certain amount of lithium carbonate toward sediment, so
Afterwards with the abundant ball milling 2h of the speed of 400r/min in planetary ball mill, then it is compressed under the pressure of 5MPa, be put into dry
In net ceramic crucible, in 450 DEG C of constant temperature 6h in air atmosphere, then be warming up to 750 DEG C insulation 20h after slowly cool to room
Temperature, sample comminution, grinding after firing, crosses 400 mesh sieves, obtains manganate cathode material for lithium；By what is be filtrated to get in above-mentioned steps
Solution is crystallized in crystallizing evaporator, cerium sulphate crystal condition be vacuum 0.015MPa, 120 DEG C of temperature, crystal 80 DEG C with
And acquisition potassium sulfate is dried under 2h.
Embodiment 15：
The positive pole leftover pieces that the lithium ion battery manufacturing process for doing positive electrode with LiMn2O4 is produced are collected, positive pole is obtained
Piece；Ratio (g/mL) in the volume of the quality and ceramic crucible of positive plate is 1:Positive plate is loaded ceramic crucible by 10 ratio
In, be subsequently placed in chamber type electric resistance furnace makes furnace temperature be raised to 550 DEG C of insulation 0.5h since room temperature with the heating rate of 5 DEG C/min,
Room temperature is naturally cooled to after power-off；The positive plate by roasting is taken out, according to the ratio (g/ of the volume of the quality and water of positive plate
ML it is) 1:50 are put into equipped with filling in the container of water and with electric mixer stir 20min positive plate, whipping process reclaimed water
Temperature is 25 DEG C, and mixing speed is 100r/min；After stopping stirring, the mixture in container is sieved with the screen cloth of 10 mesh
Point, oversize is aluminium foil, and screenings is the solution containing positive active material；Screenings carries out suction filtration, and thing cleans 3 with water in filter
It is secondary, obtain positive active material；By obtain positive active material be fitted into ceramic crucible, be subsequently placed in chamber type electric resistance furnace with
The heating rate of 5 DEG C/min makes furnace temperature be raised to 550 DEG C and is incubated 1h, obtains useless LiMn2O4；Useless LiMn2O4 and potassium sulfate are pressed into matter
Amount is 1 than (g/g):2.0 ratio mixes, then the ball milling in planetary ball mill, and Ball-milling Time is 0.5 h, and rotating speed is 300
r/min；Mixture after ball milling is fitted into absorption plant；From gas washing in SA production double-absorption system relieving haperacidity tail gas out, first pass through
After crossing heating, then it is passed through conversion operation, the condition of conversion operation is carried out in the conversion system equipped with S108 type vanadium catalysts
For：405 DEG C of gasinlet temperature, flow velocity 0.3m/s, the filling of S108 types vanadium catalyst is rated in conversion system：0.5m3Urge
Agent/(1000m3Relieving haperacidity tail gas h)；The absorption plant for having been charged into mixture after ball milling is passed through from conversion system gas out
In carry out absorption operation, the condition of absorption operation is：400 DEG C of temperature, inlet gas flow velocity 0.3m/s；Absorption plant is detected to go out
SO in gas2Content be less than 400mg/m3And whether the content of sulfuric acid mist is less than 30mg/m3, the gas that absorption plant is exported
It is emitted into air after body cooling；Bar of the mixture that will be no longer passed through in the absorption plant of conversion system exit gas in stirring
Under part with 50 DEG C of water with solid-to-liquid ratio (g/mL) be 1:20 leach 30min；Then leachate is warmed up to 98 DEG C, by 3.0mol/L
Solution of potassium carbonate be slowly added to leachate produce sediment, gained sediment through filtering, washing, dry after, analyze sediment
The content of middle Li, Mn, is 0.525 according to the mol ratio of lithium and manganese:1 requirement supplements a certain amount of lithium carbonate toward sediment, so
Afterwards with the abundant ball milling 2h of the speed of 400r/min in planetary ball mill, then it is compressed under the pressure of 5MPa, be put into dry
In net ceramic crucible, in 450 DEG C of constant temperature 6h in air atmosphere, then be warming up to 750 DEG C insulation 20h after slowly cool to room
Temperature, sample comminution, grinding after firing, crosses 400 mesh sieves, obtains manganate cathode material for lithium；By what is be filtrated to get in above-mentioned steps
Solution is crystallized in crystallizing evaporator, cerium sulphate crystal condition be vacuum 0.015MPa, 120 DEG C of temperature, crystal 80 DEG C with
And acquisition potassium sulfate is dried under 2h.
Claims (9)
1. the LiMn2O4 that gives up cooperates with the method for administering and reclaiming manganese lithium with relieving haperacidity tail gas, it is characterised in that its step is：
Step（1）：The scrap lithium ion battery of positive electrode is done in collection with LiMn2O4, NaOH is positioned at room temperature water-soluble
The discharge process of 1-3h is carried out in liquid；After discharge process, the lithium ion battery that will be scrapped is disassembled, and obtains positive plate；Collect
The positive pole leftover pieces that the lithium ion battery manufacturing process for doing positive electrode with LiMn2O4 is produced, obtain positive plate；To obtain just
Pole piece is fitted into ceramic crucible, and be subsequently placed in resistance furnace makes furnace temperature be raised to 550 since room temperature with the heating rate of 5 DEG C/min
DEG C insulation 0.5-1h, then naturally cool to room temperature；The positive plate by roasting is taken out, positive plate is put into equipped with filling water
In container and stir 5-30min, the mixture in container sieved with screen cloth, oversize is aluminium foil, screenings be containing
The solution of positive active material；Screenings carries out suction filtration, and thing is cleaned 1-3 times with water in filter, obtains positive active material；To obtain
Positive active material be fitted into ceramic crucible, be subsequently placed in resistance furnace is raised to furnace temperature with the heating rate of 5 DEG C/min
500-700 DEG C and 0.5-3h is incubated, obtains useless LiMn2O4；
Step（2）：Useless LiMn2O4 is mixed with potassium sulfate, then the ball milling in ball mill, the mixture after ball milling is loaded and is inhaled
In receiving apparatus；Mixture after loading ball milling in another identical absorption plant is as standby absorption plant in step
Suddenly（3）In use；In this step, the source of potassium sulfate is the potassium sulfate chemical products or step of purchase（5）The sulphur of middle acquisition
Sour potassium or the two mixture being mixed to form with arbitrary proportion；
Step（3）：From gas washing in SA production double-absorption system relieving haperacidity tail gas out, after first passing through heating, then it is passed through and is equipped with
Conversion operation is carried out in the conversion system of vanadium catalyst, the condition of conversion operation is：400-405 DEG C of gasinlet temperature, flow velocity
0.23-1.2m/s, the filling of vanadium catalyst is rated in conversion system：0.3-0.6m3Catalyst/(1000m3Relieving haperacidity tail gas
h)；Step is passed through from conversion system gas out（2）Described in have been charged into carried out in the absorption plant of mixture after ball milling
Absorption operation, the condition of absorption operation is：350-500 DEG C of temperature, inlet gas flow velocity 0.2-1.2m/s；Monitoring absorption plant goes out
SO in gas2Content whether be less than 400mg/m3And whether the content of sulfuric acid mist is less than 30mg/m3, requirement is such as reached, will inhale
It is emitted into air after the gas cooling of receiving apparatus outlet；Such as monitor SO in absorption plant exit gas2Content reach
400mg/m3Or the content of sulfuric acid mist reaches 30mg/m3, then no longer to the gas being passed through in the absorption plant from conversion system out
Body, while the gas from conversion system out is passed through into step（2）Carried out under the same terms in described standby absorption plant
SO in absorption operation and exit gas2Content, the monitoring of the content of sulfuric acid mist；Take out and be no longer passed through conversion system in this step
Mixture in the absorption plant of exit gas, the absorption plant then returns to step（2）In be again loaded into the mixing after ball milling
Thing is used in this step as standby absorption plant；
Step（4）：By step（3）In be no longer passed through the bar of mixture in the absorption plant of conversion system exit gas in stirring
Leached with 20-50 DEG C of water under part, extraction time 5-30min, solid-to-liquid ratio g/mL is 1:10-1:50；Then leachate
95-98 DEG C is warmed up to, solution of potassium carbonate is slowly added to leachate, then filtered, washed filter residue and dry, in analysis filter residue
The content of Li, Mn, is 0.525 according to the mol ratio of lithium and manganese:1 requirement supplements lithium carbonate toward filter residue, then in ball mill
Ball milling, then it is being used into pressure compaction, it is put into clean ceramic crucible, in 450 DEG C of constant temperature 4-7h in air atmosphere, then
It is slowly cooled to room temperature after being incubated 20h at being warming up to 750 DEG C, sample comminution, grinding after firing cross 400 mesh sieves, obtain electrification
Learn manganate cathode material for lithium of good performance；
Step（5）：By step（4）The solution being filtrated to get is crystallized in crystallizing evaporator, and cerium sulphate crystal condition is vacuum
120-140 DEG C of 0.012-0.015MPa, temperature, crystal is dried under 50-80 DEG C and 0.2-3h and obtains potassium sulfate, the sulphur of acquisition
Sour potassium return to step（2）In use.
2. useless LiMn2O4 according to claim 1 cooperates with the method for administering and reclaiming manganese lithium, its feature to exist with relieving haperacidity tail gas
In：Step（1）In sodium hydrate aqueous solution concentration be 0.1-1.0mol/L.
3. useless LiMn2O4 according to claim 1 cooperates with the method for administering and reclaiming manganese lithium, its feature to exist with relieving haperacidity tail gas
In：Step（1）The ratio g/mL of the middle volume by the positive plate for obtaining in the quality and ceramic crucible of positive plate is 1:10-1:
15。
4. useless LiMn2O4 according to claim 1 cooperates with the method for administering and reclaiming manganese lithium, its feature to exist with relieving haperacidity tail gas
In：Step（1）According to positive plate quality and water volume ratio g/mL be 1:40-1:70, positive plate is put into and is equipped with
Fill in the container of water and stir 5-30min with electric mixer, the temperature of whipping process reclaimed water is 20-50 DEG C, mixing speed
It is 10-200r/min.
5. useless LiMn2O4 according to claim 1 cooperates with the method for administering and reclaiming manganese lithium, its feature to exist with relieving haperacidity tail gas
In：Step（1）In screen cloth for 10-20 mesh screen cloth.
6. useless LiMn2O4 according to claim 1 cooperates with the method for administering and reclaiming manganese lithium, its feature to exist with relieving haperacidity tail gas
In：Step（2）The middle useless LiMn2O4 that will be obtained is 1 with potassium sulfate g/g in mass ratio:The ratio mixing of 0.01-2.4, Ran Hou
Ball milling in ball mill, Ball-milling Time is 0.1-1.0 h, and rotating speed is 200-500 r/min.
7. useless LiMn2O4 according to claim 1 cooperates with the method for administering and reclaiming manganese lithium, its feature to exist with relieving haperacidity tail gas
In：Step（4）The concentration of middle solution of potassium carbonate is 1.0-3.0mol/L.
8. useless LiMn2O4 according to claim 1 cooperates with the method for administering and reclaiming manganese lithium, its feature to exist with relieving haperacidity tail gas
In：Step（4）In Ball-milling Time be 0.5-2h, rotating speed is 200-500r/min, and the pressure of compression is 0.1-100MPa.
9. useless LiMn2O4 according to claim 1 cooperates with the method for administering and reclaiming manganese lithium, its feature to exist with relieving haperacidity tail gas
In：Step（3）In vanadium catalyst be S108 type vanadium catalysts.
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| CN104577104A (en) * | 2015-01-15 | 2015-04-29 | 兰州理工大学 | Regeneration method of positive material lithium manganate waste of lithium ion battery |
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