CN105821445B - A kind of method that charcoal and electrolyte are reclaimed in cathode carbon pieces from aluminum cell waste - Google Patents
A kind of method that charcoal and electrolyte are reclaimed in cathode carbon pieces from aluminum cell waste Download PDFInfo
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- CN105821445B CN105821445B CN201610362843.5A CN201610362843A CN105821445B CN 105821445 B CN105821445 B CN 105821445B CN 201610362843 A CN201610362843 A CN 201610362843A CN 105821445 B CN105821445 B CN 105821445B
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
- C25C3/06—Electrolytic production, recovery or refining of metals by electrolysis of melts of aluminium
- C25C3/08—Cell construction, e.g. bottoms, walls, cathodes
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/20—Halides
- C01F11/22—Fluorides
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B15/00—Operating or servicing cells
- C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes
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Abstract
The invention discloses a kind of method that charcoal and electrolyte are reclaimed in cathode carbon pieces from aluminum cell waste, comprise the following steps：Step (1)：Cathode carbon pieces are crushed, grinding；Step (2)：The negative electrode powdered carbon obtained after step (1) processing is stirred in alkali lye, leached, is then filtrated to get filter cake A1 and liquor B 1；Precipitating reagent is added into liquor B 1, is filtrated to get filter cake A2 and liquor B 2；Step (3)：Filter cake A1 and filter cake A2, flotation medium and floating agent are mixed and sized mixing, flotation, isolated charcoal and electrolyte；Described floating agent includes collecting agent, foaming agent and conditioning agent, and described collecting agent is made up of the collecting agent C1 and collecting agent C2 that mass ratio is 0.65 0.75: 0.25 0.35；Collecting agent C1 is selected from least one of coal tar, heavy oil, kerosene, diesel oil, and collecting agent C2 is selected from least one of lauryl amine, neopelex, enuatrol, dodecyl sodium sulfate.The present invention realizes efficiently separates recovery powdered carbon and electrolyte from waste and old cathode carbon block.
Description
Technical field
The invention belongs to carbon field of waste recycle, and in particular to be reclaimed in a kind of cathode carbon pieces from aluminum cell waste
The method of charcoal and electrolyte.
Background technology
Metallic aluminium has become the important foundation material of the national economic development.But in aluminum smelting technology production process, due to
Corroded by electrolyte, often produce 1 ton of electrolytic aluminium, it will produce about 10kg waste and old cathode carbon block, this turns into aluminium electroloysis row
Main solid pollutant in industry.As reached 31,410,000 tons by this calculating, domestic electrolytic aluminium yield in 2015, produce waste and old
More than 300,000 tons of cathode carbon pieces, its enormous amount is very important.
In waste and old cathode carbon block caused by aluminium electroloysis, main component is charcoal, ice crystal, sodium fluoride, aluminum oxide, fluorination
Aluminium, and a small amount of aluminium carbide, sodium carbide and a small amount of cyanide.Current China's processing waste and old cathode carbon block is mainly using stacking
Or the method for security landfill.But charcoal accounts for 50%~70% and high-graphitized in waste and old cathode carbon block, remaining is with ice
Spar is the electrolyte of main body, is available resource, and ice crystal resource especially therein is seriously deficient, to them
Separation and recovery there is preferable economic benefit.Therefore, the recycling of waste and old cathode carbon block has preferable development prospect.
At present, waste and old cathode carbon block separation and recovery charcoal and electrolyte method have floatation, roasting method, pyrohydrolytic method,
Acidization etc..Wherein, there is the problem of high energy consumption, high acid and alkali consumption in roasting method, pyrohydrolytic method, acidization etc..Therefore, patent
01138204.X, 201010140919.2,201010140908.4,201410561966.2 are proposed using floatation to waste and old the moon
Pole carbon block is separated and recovered, and powdered carbon and electrolyte are efficiently separated, after multistage flotation, powdered carbon content in electrolyte
Only 5%~10%, above mentioned problem can be efficiently solved.But floatation process Chinese medicine dosage is big, flotation series is more and floating
Waste water is selected to need to handle.
In addition, Publication No. CN101973545A Chinese patent literature discloses a kind of method of purifying high-purity graphite,
Graphite raw ore carries out ore dressing processing to it using floatation equipment or gravitational separation equipment, obtained after the processes such as broken, ball milling, screening
To graphite concentrate；Graphite concentrate first carries out alkali leaching processing in compressive reaction kettle, is then carried out in ultrasound field or microwave field
Normal pressure acidleach is handled；Graphite powder after processing is leached with hydrofluoric acid or fluorine-containing salts sodium fluoride again, obtains the higher stone of purity
Graphite product.This method flotation efficiency is low, and effect is poor, and added amount of chemical is big.
The content of the invention
It is big in order to solve existing waste and old cathode carbon block floatation process Chinese medicine dosage, the technical problems such as flotation series is more, this
Invention provides a kind of method that powdered carbon and electrolyte are reclaimed in cathode carbon pieces from aluminum cell waste, to reach in less medicine
Agent dosage, the purity of good powdered carbon and the purpose of the rate of recovery are also ensured in the case of less flotation series.
A kind of method that charcoal and electrolyte are reclaimed in cathode carbon pieces from aluminum cell waste, it is characterised in that including with
Lower step：
Step (1)：Cathode carbon pieces are crushed, grinding；
Step (2)：The negative electrode powdered carbon obtained after step (1) processing is stirred in alkali lye, leached, is then filtrated to get filter
Cake A1 and liquor B 1；
Step (3)：Filter cake A1 and floating agent are mixed and sized mixing, flotation, separation, flotation froth product is charcoal, flotation tail
Ore deposit is electrolyte (with CaF2For main body)；Described floating agent includes collecting agent, foaming agent and conditioning agent；Wherein, it is described
Collecting agent is made up of the collecting agent C1 and collecting agent C2 that mass ratio is 0.65-0.75: 0.25-0.35；Collecting agent C1 is selected from coal tar
At least one of oil, heavy oil, kerosene, diesel oil, collecting agent C2 are selected from lauryl amine, neopelex, enuatrol, 12
At least one of sodium alkyl sulfonate.
In the present invention, the alkaline leaching processing and floating agent collaboration improve flotation, the efficiency and effect of separation,
The charcoal rate of recovery of cathode carbon pieces and the purity of recovery charcoal are improved, reduces the usage amount of floatation process medicament.Compared to existing flotation
Recovery method, dosing is few, easy to operate；Processing procedure need not consume more heat transfer, and energy consumption is relatively low.
In step (1), cathode carbon pieces are crushed, grinding to -200 mesh accounts for more than 80%.
Dissociated by the broken electrolyte that can be will be distributed among cathode carbon pieces crack and hole of physics and Carbon Materials.Institute
State under grain diameter, alkali leaching (alkaline leaching) effect of step (2) can be improved, and then improve the flotation effect of step (3), reach
Improve the rate of recovery of charcoal and the purpose of purity.
Preferably, in step (1), cathode carbon pieces are first crushed to by -30mm using jaw crusher, then will with fine crusher
It is crushed to -2mm, finally using ball mill grinding to granularity to 200 mesh, wherein -200 mesh account for more than 80%.
Further preferably, in step (1), cathode carbon pieces are crushed, the particle of grinding to -200 mesh accounts for total particle weight
85-90%.
In step (2), negative electrode powdered carbon is made into slurry with alkali lye according to solid-liquid mass ratio 1: 6~8, and in temperature 20~60
DEG C, leached under conditions of 60~100r/min of rotating speed, extraction time 30-60min.
Described alkali lye is the aqueous solution of alkali compounds, and its concentration is 4~8mol/L.
Preferably, described alkali lye is the aqueous solution of alkali metal hydroxide.
Further preferably, described alkali metal hydroxide is at least one in lithium hydroxide, sodium hydroxide, potassium hydroxide
The aqueous solution of kind.
In step (2), obtained slurry alkali at the temperature and rotating speed will be prepared and soaked.
The key reaction of leaching process is, for example,：
Na3AlF6+ 4NaOH=NaAl (OH)4+6NaF
The ratio of powdered carbon and alkali lye, temperature, mixing time, mixing speed interaction, promote alkali leaching efficiency, improve above-mentioned
The carry out degree of reaction.
Preferably, in step (2), alkali leaching temperature is 50~60 DEG C, and mixing speed is 80~100r/min, stirring alkali leaching
Time is 30-45min.
After alkali leaching processing terminates, filtration treatment obtains filter cake A1 and liquor B 1；Contain in liquor B 1 with recovery value
Fluoride；In order to improve the rate of recovery of electrolyte in cathode carbon pieces, preferably, in step (2), in addition to：Into liquor B 1
Precipitating reagent is added, is filtrated to get filter cake A2 and liquor B 2；Filter cake A2 and filter cake A1, which merges, carries out step (3).
Precipitating reagent is added into liquor B 1 and carries out precipitation reaction, the precipitating reagent is that solubility product is more than CaF2Calcic chemical combination
Thing, is mainly used in precipitation filtrates B1 F-, and the reaction that precipitating reagent participates in is：
Ca2++2F-=CaF2↓
Preferably, described precipitating reagent is CaO, CaCl2、Ca(OH)2At least one, the dosage of the precipitating reagent is
1.05~1.1 times of the amount of soluble fluoride material in the cathode carbon pieces of step (1).
After precipitation reaction terminates, charcoal is reclaimed into filter cake A1 (or/and filter cake A2 merges) flotation.
In step (3), process of sizing mixing is carried out as flotation medium using water, wherein, filter cake A1 and filter cake A2 gross weight
The mass ratio of amount and flotation medium is 1: 10~20.If precipitation process, i.e. process of sizing mixing in step (3) are not carried out to liquor B 1
In, filter cake A1 weight and the mass ratio of flotation medium are 1: 10~20.
Preferably, the liquor B 2 that step (2) is obtained is applied to the process of sizing mixing of step (3).Liquor B 1 is through precipitating reagent
Processing, is stripped of more F-, improve the rate of recovery of electrolyte.Obtained liquor B 2 can direct circulation be applied to step (3)
Size mixing process.In addition, liquor B 2 may also pass through prior art concentration, recovery obtains excessive calcium containing compound, concentrates collection
Condensed water recycling is applied to the Alkali liquid compounding of step (2), the process such as size mixing of step (3).
Liquor B 2 is applied to the process of sizing mixing, and the closed cycle in whole processing procedure can be achieved, saved water consumption.Filtrate
B2 is diluted with water before being applied to step (3) as flotation medium, preferably, the volume of liquor B 2 is less than or equal to thinned water
0.8 times of volume.
Preferably, in step (3), during sizing mixing, the quality of filter cake A1 and filter cake A2 gross weight and flotation medium
Than for 1: 10~15.Described flotation medium is water or the water diluent of liquor B 2.
Flotation handles isolated upper strata (flotation froth layer) powdered carbon and with CaF2For lower floor's (flotation tailing layer) of main body
Electrolyte.Flotation medium after flotation processing can remove the unnecessary material of doping by filter operation, directly return to floatation process,
It can also be concentrated by evaporation by existing technology, the condensed water being collected into is returned into alkali leaching or floatation process.The material of doping and
Product after concentration can return to flotation flowsheet and utilized according to the actual conditions of production process.
In floatation process, recovery of the described floating agent to charcoal has a considerable influence, the collecting agent that the present invention uses for
The quality is than collecting agent C1 and collecting agent C2 composition.
By collecting agent C1 and collecting agent C2 combinations, coordinated, collecting agent and other medicaments is set to disperse in ore pulp
Uniformly, contribute to reduce dosing, enhance the efficiency of a flotation, and then reduce flotation series.
Preferably, on the basis of cathode carbon pieces weight, the collector dosage is 100~600g/t.
Further preferably, in the collecting agent, collecting agent C1 is the kerosene and diesel fuel mixtures of mass ratio 1-2: 1；Collecting
Agent C2 is the neopelex that mass ratio is 1: 1-1.5 and enuatrol mixture.Under the preferred feed, with negative electrode charcoal
On the basis of block weight, the collector dosage is 200~500g/t.
Preferably, described foaming agent is in No. two oil, camphorated oil, methyl isobutyl carbinol, mixed fatty alcohols
It is at least one；On the basis of cathode carbon pieces weight, the frother dosages are 50~120g/t.
Further preferably, the foaming agent is No. two oil and camphor oil mixture of mass ratio 1.5-2: 1.In the preferred thing
Under material, on the basis of cathode carbon pieces weight, the frother dosages are 100~120g/t.
Preferably, the conditioning agent is selected from triisopropanolamine (NTP), ethylenediamine tetra-acetic acid (EDTA), ethylenediamine tetramethyl
Pitch at least one of phosphonate (HDTP), waterglass；On the basis of cathode carbon pieces weight, the conditioning agent dosage be 100~
300g/t。
Further preferably, the conditioning agent is NTP the and HDTP mixtures of mass ratio 1-1.5: 1.Under the preferred feed,
On the basis of cathode carbon pieces weight, the conditioning agent dosage is 200~300g/t.
In the present invention, g/t adds unit for each component in floating agent, on the basis of cathode carbon pieces weight, i.e.,
For cathode carbon pieces per ton add the corresponding material of corresponding g weight.
In described floating agent, each component and add proportion and mutually cooperate with, improve flotation effect, matching step (2)
Alkali leaching is handled, and collaboration improves the rate of recovery of charcoal and electrolyte and the purity of the charcoal of recovery.
Preferably, the time of flotation processing is 5-10min.Under the described conditions, flotation can once complete invention mesh
, and flotation time is shorter, relative to prior art, treatment effeciency is high, and effect is good.
The present invention has following preferable effect：
1st, the present invention uses floatation, for existing floatation, due to collecting agent C2 addition, make collecting agent
And other medicaments are uniformly dispersed in ore pulp, thus effectively reduce dosing (collector dosage reduce 100~
400g/t, frother dosages reduce 30~80g/t, and the minimum amount of conditioning agent amount ratio current methods is also few), enhance one
The efficiency of secondary flotation, and then reduce flotation series.
2nd, insoluble fluorine ion is converted into soluble fluoride ion, is used calcic chemical combination by the present invention using the method for alkali leaching
The free fluoride ion of whole is fixed thing, reduces during follow-up FLOTATION SEPARATION free fluoride ion to the shadow of floatation process
Ring, and before making the material of FLOTATION SEPARATION relative to conversion, electrolyte ingredient is simpler, only need to separate powdered carbon and CaF2。
3rd, the floatation that the present invention uses does not need follow-up wastewater treatment, and its caused waste water just completes in flow
Purification, and the fluorine ion in leachate has been subjected to effective recovery, simplify treatment process.
4th, the present invention has exceeded 90% to the rate of recovery of electrolyte, and the fluoride in electrolyte transforms into CaF2, after
After continuous processing, quality has reached the requirement of industrial application, can replace the use of fluorite ore, alleviate mineral resources pressure；Charcoal
The purity of powder has also reached 85%~90%, and the rate of recovery is 90%~95%；The separation and recovery to waste and old cathode carbon block is realized,
Economic benefit is improved, and alleviates environmental protection pressure.
Embodiment
Following examples are implemented by aforesaid operations method, wherein cathode carbon pieces used are same component content, phosphorus content is
55.42%, content of fluoride 30.65%.
Embodiment 1
Step (1)：Broken milling：
Cathode carbon pieces are first crushed to -30mm by 1kg aluminum electrolytic tanks waste and old cathode carbon block using jaw crusher, then with carefully
Broken machine is crushed to -2mm, finally using ball mill grinding to granularity to 200 mesh, wherein -200 mesh account for 80%.
Step (2)：The dipped filter of alkali：
The good waste and old cathode carbon powder 1kg of step (1) grinding is taken, adds in 4mol/L sodium hydroxide solution and is made into slurry
(solid-liquid mass ratio 1: 6), under conditions of temperature 50 C, rotating speed 100r/min, leached, stirred in stirred leaching tank
Filtered after leaching 45min, obtain filter cake A1, liquor B 1；Added into liquor B 1 equivalent to soluble fluoride content (or material
Amount) 105% CaO, terminate to precipitation, be filtrated to get filter cake A2, liquor B 2.
Step (3)：Flotation：Filter cake (filter cake A1 and filter cake A2) in step (2) is added according to solid-liquid mass ratio for 1: 10
Enter in water, add the collecting agent being made up of 0.355g kerosene and 0.175g enuatrols, foaming agent：Camphorated oil 0.12g, conditioning agent：
Waterglass 0.2g；Flotation 10min, isolated upper strata powdered carbon and with CaF2For lower floor's electrolyte of main body.By calculating, electrolysis
The matter rate of recovery is 91.53%, powdered carbon purity 86.79%, the rate of recovery 93.31%.
Comparative example 1
Compared with embodiment 1, difference is, filtration step is soaked without the alkali of step (2), by the thin of step (1) milled
Powder directly carries out the flotation processing of step (3).After flotation terminates, isolated upper strata powdered carbon and with CaF2For lower floor's electricity of main body
Xie Zhi.By calculating, the electrolyte rate of recovery is 84.62%, powdered carbon purity 78.92%, the rate of recovery 86.45%.
Comparative example 2
Compared with embodiment 1, difference is, with kerosene substitute enuatrol, that is, the collecting agent used for single kerosene composition,
The weight that adds of kerosene is 0.530g.After flotation terminates, isolated upper strata powdered carbon and with CaF2For lower floor's electrolyte of main body.
By calculating, the electrolyte rate of recovery is 80.53%, powdered carbon purity 79.27%, the rate of recovery 83.86%.
Comparative example 3
Compared with embodiment 1, difference is, substitutes kerosene with enuatrol, that is, the collecting agent used is 0.530g enuatrol.
After flotation terminates, isolated upper strata powdered carbon and with CaF2For lower floor's electrolyte of main body.By calculating, the electrolyte rate of recovery is
75.62%, powdered carbon purity 74.42%, the rate of recovery 81.18%.
Comparative example 4
Compared with embodiment 1, difference is, turning into for collecting agent does not change, dosage uses not in invention scope
Collecting agent is made up of 0.3g kerosene and 0.3g enuatrols.After flotation terminates, isolated upper strata powdered carbon and with CaF2For main body
Lower floor's electrolyte.By calculating, the electrolyte rate of recovery is 85.04%, powdered carbon purity 82.79%, the rate of recovery 86.58%.
Embodiment 2
Compared with embodiment 1, difference is, replaces the water in step (3), flotation during preparation slurry with flotation medium
The liquid after 0.6 times is diluted with water in medium liquor B 2.After flotation terminates, isolated upper strata powdered carbon and with CaF2For under main body
Layer electrolyte.By calculating, the electrolyte rate of recovery is 91.44%, powdered carbon purity 86.64%, the rate of recovery 93.21%.
Embodiment 3
Step (1)：Broken milling：
Cathode carbon pieces are first crushed to -30mm by 1kg aluminum electrolytic tanks waste and old cathode carbon block using jaw crusher, then with carefully
Broken machine is crushed to -2mm, finally using ball mill grinding to granularity to 200 mesh, wherein -200 mesh account for 85%.
Step (2)：The dipped filter of alkali：
The good waste and old cathode powder 1kg of step (1) grinding is taken, adds in 6mol/L sodium hydroxide solution and is made into slurry
(solid-liquid mass ratio 1: 7), under conditions of 40 DEG C of temperature, rotating speed 90r/min, leached, stirred in stirred leaching tank
Filtered after leaching 60min, obtain filter cake A1, liquor B 1；Added into liquor B 1 equivalent to soluble fluoride content (or material
Amount) 107% CaO, terminate to precipitation, be filtrated to get filter cake A2, liquor B 2.
Step (3)：Flotation：
According to solid-liquid mass ratio be to be added to the water at 1: 15 by the filter cake (filter cake A1 and filter cake A2) in step (2), add by
0.15g kerosene, 0.15g diesel oil, 0.06g neopelexes and 0.09g enuatrol composition collecting agent；Foaming
Agent：No. bis- oil of 0.08g, 0.04g camphorated oils；Conditioning agent：0.15g triisopropanolamines (NTP) and 0.1gHDTP；Flotation 8min, point
From obtaining upper strata powdered carbon and with CaF2For lower floor's electrolyte of main body.By calculating, the electrolyte rate of recovery is 93.04%, powdered carbon
Purity 88.67%, the rate of recovery 94.35%.
Embodiment 4
Compared with embodiment 3, difference is, collecting agent is by 0.2g kerosene, 0.2g diesel oil, 0.12g dodecyl sodium sulfonates
Sodium and 0.08g enuatrol form.After flotation terminates, isolated upper strata powdered carbon and with CaF2For lower floor's electrolyte of main body.
By calculating, the electrolyte rate of recovery is 90.81%, powdered carbon purity 86.78%, the rate of recovery 92.53%.
Embodiment 5
Compared with embodiment 4, difference is, collecting agent is by 0.2g heavy oil, 0.2g diesel oil, 0.08g detergent alkylate sulphurs
The enuatrol composition of sour sodium and 0.12g.After flotation terminates, isolated upper strata powdered carbon and with CaF2It is electrolysed for the lower floor of main body
Matter.By calculating, the electrolyte rate of recovery is 91.15%, powdered carbon purity 85.83%, the rate of recovery 91.88%.
Embodiment 6
Compared with embodiment 3, difference is, foaming agent is made up of No. two oily 0.06g and camphorated oil 0.06g.Flotation terminates
Afterwards, isolated upper strata powdered carbon and with CaF2For lower floor's electrolyte of main body.By calculating, the electrolyte rate of recovery is 90.58%,
Powdered carbon purity 85.06%, the rate of recovery 89.46%.
Embodiment 7
Step (1)：Broken milling：
Cathode carbon pieces are first crushed to -30mm by 1kg aluminum electrolytic tanks waste and old cathode carbon block using jaw crusher, then with carefully
Broken machine is crushed to -2mm, finally using ball mill grinding to granularity to 200 mesh, wherein -200 mesh account for 90%.
Step (2)：The dipped filter of alkali：
The good waste and old cathode powdered carbon 1kg of step (1) grinding is taken, adds in 8mol/L sodium hydroxide solution and is made into slurry
(solid-liquid mass ratio 1: 8), in temperature 60 C, under conditions of rotating speed 80r/min, leached, stirred in stirred leaching tank
Filtered after leaching 30min, obtain filter cake A1, liquor B 1；Added into liquor B 1 equivalent to soluble fluoride content (or material
Amount) 110% CaO, terminate to precipitation, be filtrated to get filter cake A2, liquor B 2.
Step (3)：Flotation：
According to solid-liquid mass ratio be to be added to the water at 1: 20 by the filter cake (filter cake A1 and filter cake A2) in step (2), add by
The collecting agent of 0.35g coal tar and 0.15g dodecyl sodium sulfates composition, foaming agent mixed fatty alcohol 0.08g, conditioning agent
HDTP0.3g；Flotation 5min, isolated upper strata powdered carbon and with CaF2For lower floor's electrolyte of main body.By calculating, electrolyte
The rate of recovery is 91.63%, powdered carbon purity 86.33%, the rate of recovery 93.57%.
Embodiment 8
Step (1)：Broken milling：
Cathode carbon pieces are first crushed to -30mm by 1kg aluminum electrolytic tanks waste and old cathode carbon block using jaw crusher, then with carefully
Broken machine is crushed to -2mm, finally using ball mill grinding to granularity to 200 mesh, wherein -200 mesh account for 90%.
Step (2)：The dipped filter of alkali：
The good waste and old cathode carbon block 1kg of step (1) grinding is taken, adds in 8mol/L potassium hydroxide solution and is made into slurry
(solid-liquid mass ratio 1: 8), in temperature 60 C, under conditions of rotating speed 80r/min, leached, stirred in stirred leaching tank
Filtered after leaching 30min, obtain filter cake A1, liquor B 1；Added into liquor B 1 equivalent to soluble fluoride content (or material
Amount) 110% CaO, terminate to precipitation, be filtrated to get filter cake A2, liquor B 2.
(3) flotation：
Filter residue in step (2) is added to the water according to solid-liquid mass ratio for 1: 10, added by 0.4g diesel oil and 0.175g
The collecting agent of neopelex composition, foaming agent：Methyl isobutyl carbinol 0.1g, conditioning agent：Triisopropanolamine (NTP)
0.25g；Flotation 5min, isolated upper strata powdered carbon and with CaF2For lower floor's electrolyte of main body.By calculating, electrolyte recovery
Rate is 92.13%, powdered carbon purity 87.25%, the rate of recovery 93.07%.
It is described above, the only result of embodiment of the present invention.
Claims (9)
1. the method for charcoal and electrolyte is reclaimed in a kind of cathode carbon pieces from aluminum cell waste, it is characterised in that including following
Step：
Step (1)：Cathode carbon pieces are crushed, grinding；
Step (2)：The negative electrode powdered carbon obtained after step (1) processing is stirred in alkali lye, leached, is then filtrated to get filter cake A1
With liquor B 1；
Precipitating reagent is added into liquor B 1, is filtrated to get filter cake A2 and liquor B 2；
Step (3)：Filter cake A1, filter cake A2 and floating agent are mixed and sized mixing, flotation, separation, flotation froth product is charcoal, flotation
Mine tailing is electrolyte；Described floating agent includes collecting agent, foaming agent and conditioning agent；Wherein, described collecting agent is by quality
Than collecting agent C1 and collecting agent the C2 composition for 0.65-0.75: 0.25-0.35；Collecting agent C1 be selected from coal tar, heavy oil, kerosene,
At least one of diesel oil, collecting agent C2 is in lauryl amine, neopelex, enuatrol, dodecyl sodium sulfate
At least one.
2. reclaiming the method for charcoal and electrolyte in the cathode carbon pieces according to claim 1 from aluminum cell waste, it is special
Sign is, in the collecting agent, collecting agent C1 is the kerosene and diesel fuel mixtures of mass ratio 1-2: 1；Collecting agent C2 is mass ratio
Neopelex and enuatrol mixture for 1: 1-1.5.
3. reclaiming the method for charcoal and electrolyte in the cathode carbon pieces according to claim 2 from aluminum cell waste, it is special
Sign is, in step (1), cathode carbon pieces is crushed, grinding to -200 mesh accounts for more than 80%.
4. reclaiming the method for charcoal and electrolyte in the cathode carbon pieces according to claim 1 from aluminum cell waste, it is special
Sign is that described precipitating reagent is CaO, CaCl2、Ca(OH)2At least one, the dosage of the precipitating reagent is the moon of step (1)
1.05~1.1 times of the amount of soluble fluoride material in the carbon block of pole.
5. the side of charcoal and electrolyte is reclaimed in the cathode carbon pieces from aluminum cell waste according to claim any one of 1-4
Method, it is characterised in that described alkali lye is the aqueous solution of alkali compounds, and its concentration is 4~8mol/L.
6. reclaiming the method for charcoal and electrolyte in the cathode carbon pieces according to claim 5 from aluminum cell waste, it is special
Sign is, in step (2), negative electrode powdered carbon and alkali lye are made into slurry according to solid-liquid mass ratio 1: 6~8, and 20~60 DEG C of temperature,
Leached under conditions of 60~100r/min of rotating speed, extraction time 30-60min.
7. the side of charcoal and electrolyte is reclaimed in the cathode carbon pieces from aluminum cell waste according to claim any one of 1-4
Method, it is characterised in that on the basis of cathode carbon pieces weight, the collector dosage is 100~600g/t.
8. reclaiming the method for charcoal and electrolyte in the cathode carbon pieces according to claim 7 from aluminum cell waste, it is special
Sign is that described foaming agent is selected from least one of No. two oil, camphorated oil, methyl isobutyl carbinol, mixed fatty alcohols；With
On the basis of cathode carbon pieces weight, the frother dosages are 50~120g/t.
9. reclaiming the method for charcoal and electrolyte in the cathode carbon pieces according to claim 8 from aluminum cell waste, it is special
Sign is, the conditioning agent in triisopropanolamine, ethylenediamine tetra-acetic acid, ethylene diamine tetra methylene phosphonic acid salt, waterglass extremely
Few one kind；On the basis of cathode carbon pieces weight, the conditioning agent dosage is 100~300g/t.
Priority Applications (1)
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| CN109127655B (en) * | 2018-08-01 | 2021-05-07 | 湘潭大学 | Method and system for converting sodium-containing and fluorine-containing compounds in aluminum electrolysis waste carbon slag |
| CN109127656B (en) * | 2018-08-01 | 2021-04-02 | 湘潭大学 | Mechanochemical conversion and recovery method of sodium-containing and fluorine-containing compounds in aluminum electrolysis hazardous waste residues |
| CN109108050B (en) * | 2018-08-01 | 2021-05-07 | 湘潭大学 | Method and system for converting sodium-containing and fluorine-containing compounds in aluminum electrolysis overhaul residues |
| CN109047285B (en) * | 2018-08-01 | 2021-05-07 | 湘潭大学 | Method and system for converting sodium-containing and fluorine-containing compounds in waste cathode carbon blocks of aluminum electrolytic cell |
| CN109108049B (en) * | 2018-08-01 | 2021-06-18 | 湘潭大学 | Method and system for converting sodium-containing and fluorine-containing compounds in aluminum electrolysis hazardous waste residues |
| CN108787718B (en) * | 2018-08-01 | 2021-05-07 | 湘潭大学 | Mechanochemical conversion and recovery method for sodium-containing and fluorine-containing compounds in aluminum electrolysis waste carbon slag |
| CN109133028A (en) * | 2018-08-14 | 2019-01-04 | 北京清新环境技术股份有限公司 | A method of electrolytic cell waste cathode carbon block recycling is disposed with alkaline process |
| CN109701989B (en) * | 2018-12-24 | 2021-05-28 | 东北大学 | Method for treating aluminum electrolysis waste cathode carbon blocks by using NaOH sub-molten salt |
| CN111943190B (en) * | 2019-05-14 | 2021-11-05 | 郑州轻工业学院 | Method for recovering graphite from electrolytic aluminum waste cathode carbon block |
| CN111943189B (en) * | 2019-05-14 | 2021-11-16 | 郑州轻工业学院 | Method for purifying graphite from waste cathode carbon block |
| CN110408959B (en) * | 2019-07-25 | 2021-03-26 | 中南大学 | Method for recovering carbon and electrolyte from aluminum electrolysis waste cathode carbon blocks |
| CN113502396A (en) * | 2021-05-31 | 2021-10-15 | 广东邦普循环科技有限公司 | Method for safely leaching waste battery and application |
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| EP1257501B1 (en) * | 2000-02-25 | 2008-07-30 | Hydro-Québec | Surface purification of natural graphite and effect of impurities on grinding and particle size distribution |
| CA2367544A1 (en) * | 2002-01-08 | 2003-07-08 | Boleslaw Ignasiak | Method for spent potliner processing, separating and recycling the products therefrom |
| CN101480658B (en) * | 2008-12-26 | 2011-06-22 | 东北大学 | Method for electrolyzing waste and old cathode carbon block by comprehensive utilization of aluminum |
| CN101829670B (en) * | 2010-04-02 | 2012-07-11 | 北京矿冶研究总院 | Method for recovering carbon from electrolytic aluminum waste cathode carbon block |
| CN101811695B (en) * | 2010-04-02 | 2012-07-11 | 北京矿冶研究总院 | Method for recovering graphite from electrolytic aluminum waste cathode carbon block |
| CN102146570A (en) * | 2011-02-26 | 2011-08-10 | 王建军 | Method for producing aluminum anode by using waste cathode carbon block of aluminum cell |
| CN102389891A (en) * | 2011-09-30 | 2012-03-28 | 巨锋 | Electrolytic aluminum anode waste separating and recovering method |
| CN104438280A (en) * | 2014-10-21 | 2015-03-25 | 北京森泉伟业科技有限公司 | Method for sorting waste aluminum electrolytic cathodes |
| CN204685645U (en) * | 2015-05-22 | 2015-10-07 | 沈阳银海机械设备制造有限公司 | The treating apparatus of waste cathode carbon block |
| CN204685646U (en) * | 2015-05-22 | 2015-10-07 | 沈阳银海机械设备制造有限公司 | The treating apparatus of aluminium electroloysis waste lining |
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