CN105821445A - Method for recycling carbon and electrolytes from waste cathode carbon block of aluminum electrolytic cell - Google Patents
Method for recycling carbon and electrolytes from waste cathode carbon block of aluminum electrolytic cell Download PDFInfo
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- CN105821445A CN105821445A CN201610362843.5A CN201610362843A CN105821445A CN 105821445 A CN105821445 A CN 105821445A CN 201610362843 A CN201610362843 A CN 201610362843A CN 105821445 A CN105821445 A CN 105821445A
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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 method for recycling carbon and electrolytes from a waste cathode carbon block of an aluminum electrolytic cell. The method comprises the following steps that 1, the cathode carbon block is crushed and grinded; 2, cathode carbon powder obtained from the cathode carbon block subjected to crushing and grinding in the step 1 is stirred and leached in alkali liquor and then filtered, so that a filter cake A1 and filtrate B1 are obtained; and a precipitating agent is added into the filtrate B1, so that a filter cake A2 and filtrate B2 are obtained after filtering is conducted; and 3, the filter cake A1, the filter cake A2, a flotation medium and flotation reagents are subjected to mixing and pulp conditioning, and thus the carbon and electrolytes are obtained through flotation and separation; the flotation reagents comprises the collecting agents, the foaming agents and the conditioning agents; the collecting agents are composed of the collecting agent C1 and the collecting agent C2 at the mass ratio of 0.65-0.75:0.25-0.35; the collecting agent C1 is selected from at least one of coal tar, heavy oil, kerosene and diesel oil; and the collecting agent C2 is selected from at least one of dodecylamine, sodium dodecyl benzene sulfonate, sodium oleate and sodium dodecyl sulfate. According to the method for recycling the carbon and the electrolytes from the waste cathode carbon block of the aluminum electrolytic cell, the carbon powder and the electrolytes are effectively separated and recycled from the waste cathode carbon block.
Description
Technical field
The invention belongs to carbon field of waste recycle, be specifically related to a kind of negative electrode from aluminum cell waste
Carbon block reclaims charcoal and the method for electrolyte.
Background technology
Metallic aluminium has become as the important foundation material of the national economic development.But produced at aluminum smelting technology
Cheng Zhong, owing to being corroded by electrolyte, often produces 1 ton of electrolytic aluminium, it will produce about 10kg's
Waste and old cathode carbon block, this becomes solid pollutant main in aluminium electroloysis industry.As calculated by this, 2015
Year, domestic electrolytic aluminium yield reached 31,410,000 tons, produced waste and old cathode carbon block more than 300,000 tons,
Its enormous amount is very important.
Aluminium electroloysis produce waste and old cathode carbon block in, be mainly composed of charcoal, cryolite, sodium fluoride,
Aluminium oxide, aluminium fluoride, and a small amount of aluminium carbide, sodium carbide and a small amount of cyanide.Current China
Process waste and old cathode carbon block and mainly use stacking or the method for security landfill.But waste and old cathode carbon block
Middle charcoal accounts for 50%～70% and high-graphitized, and remaining is the electrolyte based on cryolite, all
Being available resource, cryolite resource the most therein is seriously deficient, the separation to them
Recovery has preferable economic benefit.Therefore, the recycling of waste and old cathode carbon block has preferable sending out
Exhibition prospect.
At present, waste and old cathode carbon block separation and recovery charcoal and the method for electrolyte have floatation, roasting method,
Pyrohydrolytic method, acidization etc..Wherein, there is high energy in roasting method, pyrohydrolytic method, acidization etc.
Consumption, the problem of high acid and alkali consumption.To this end, patent 01138204.X, 201010140919.2,
201010140908.4,201410561966.2 propose to use floatations waste and old cathode carbon block to be carried out point
From recovery, powdered carbon and electrolyte are efficiently separated, after multistage flotation, powdered carbon in electrolyte
Content is only 5%～10%, can efficiently solve the problems referred to above.But, floatation process Chinese medicine is used
Amount is big, and flotation progression is many and flotation waste water needs to process.
Purify high-purity additionally, the Chinese patent literature of Publication No. CN101973545A discloses one
The method of graphite, graphite raw ore after the operation such as broken, ball milling, screening, use floatation equipment or
Gravitational separation equipment carries out ore dressing process to it, obtains graphite concentrate；Graphite concentrate is first in compressive reaction still
Carry out alkali leaching process, in ultrasound field or microwave field, then carry out normal pressure acidleach process；After process
Graphite powder leaches with Fluohydric acid. or the sodium fluoride Han villiaumite again, obtains the graphite products that purity is higher.
The method flotation efficiency is low, weak effect, and added amount of chemical is big.
Summary of the invention
Big in order to solve existing waste and old cathode carbon block floatation process Chinese medicine consumption, the skills such as flotation progression is many
Art problem, the invention provides a kind of recovery powdered carbon and electrolysis from the cathode carbon pieces of aluminum cell waste
The method of matter, to reach at less dosing, also ensures that good in the case of less flotation progression
The purity of powdered carbon and the purpose of the response rate.
A kind of recovery charcoal and method of electrolyte from the cathode carbon pieces of aluminum cell waste, its feature exists
In, comprise the following steps:
Step (1): cathode carbon pieces is broken, grinding；
Step (2): the negative electrode powdered carbon obtained after step (1) being processed stirs in alkali liquor, leaches, with
After be filtrated to get filter cake A1 and liquor B 1；
Step (3): filter cake A1 and floating agent are mixed and sizes mixing, flotation, separation, flotation froth
Product is charcoal, and flotation tailing is that electrolyte is (with CaF2For main body)；Described floating agent includes collecting
Agent, foaming agent and regulator；Wherein, described collecting agent is 0.65-0.75: 0.25-0.35 by mass ratio
Collecting agent C1 and collecting agent C2 composition；Collecting agent C1 is selected from coal tar, heavy oil, kerosene, bavin
At least one in oil, collecting agent C2 selected from lauryl amine, dodecylbenzene sodium sulfonate, enuatrol,
At least one in dodecyl sodium sulfate.
In the present invention, described alkaline leaching processes and described floating agent is worked in coordination with and improved flotation, separation
Efficiency and effect, improve the charcoal response rate of cathode carbon pieces and reclaim the purity of charcoal, reducing floatation process medicine
The usage amount of agent.Compared to existing flotation recovery method, dosing is few, easy and simple to handle；Processed
Cheng Wuxu consumes more heat transfer, and energy consumption is relatively low.
In step (1), cathode carbon pieces is broken, grinding to-200 mesh accounts for more than 80%.
The electrolyte among cathode carbon pieces crack and hole and raw material of wood-charcoal can be will be distributed over by physics is broken
Material dissociates.Under described grain diameter, alkali leaching (alkaline leaching) effect of step (2) can be improved, enter
And improve the flotation effect of step (3), reach to improve the response rate and the purpose of purity of charcoal.
As preferably, in step (1), first use jaw crusher that cathode carbon pieces is crushed to-30mm,
Being crushed to-2mm with fine crusher again, finally employing ball mill grinding is to granularity to 200 mesh, its
In-200 mesh account for more than 80%.
Further preferably, in step (1), cathode carbon pieces is broken, the granule of grinding to-200 mesh
Account for the 85-90% of total particle weight.
In step (2), negative electrode powdered carbon and alkali liquor are made into slurry according to solid-liquid mass ratio 1: 6～8, and in temperature
Spending 20～60 DEG C, leach under conditions of rotating speed 60～100r/min, extraction time is 30-60min.
Described alkali liquor is the aqueous solution of alkali compounds, and its concentration is 4～8mol/L.
As preferably, described alkali liquor is the aqueous solution of alkali metal hydroxide.
Further preferably, described alkali metal hydroxide is Lithium hydrate, sodium hydroxide, hydroxide
The aqueous solution of at least one in potassium.
In step (2), slurry preparation obtained is alkali leaching at described temperature and rotating speed.
The dominant response of leaching process is for example:
Na3AlF6+ 4NaOH=NaAl (OH)4+6NaF
Powdered carbon and the ratio of alkali liquor, temperature, mixing time, mixing speed interacts, and promotes alkali leaching
Efficiency, that improves above-mentioned reaction carries out degree.
As preferably, in step (2), alkali leaching temperature is 50～60 DEG C, and mixing speed is 80～100r/min,
The stirring alkali leaching time is 30-45min.
After alkali leaching process terminates, filtration treatment obtains filter cake A1 and liquor B 1；Liquor B 1 contains
There is the fluoride of recovery value；In order to improve the response rate of electrolyte in cathode carbon pieces, as preferably,
In step (2), also include: in liquor B 1, add precipitant, be filtrated to get filter cake A2 and filter
Liquid B2；Filter cake A2 and filter cake A1 merging carries out step (3).
Adding precipitant in liquor B 1 and carry out precipitation, described precipitant is that solubility product is more than
CaF2Calcium containing compound, be mainly used in the F-of precipitation filtrates B1, the reaction that precipitant participates in is:
Ca2++2F-=CaF2↓
As preferably, described precipitant is CaO, CaCl2、Ca(OH)2At least one, described
The consumption of precipitant be step (1) cathode carbon pieces in soluble fluoride material amount 1.05～1.1
Times.
After precipitation terminates, charcoal is reclaimed in filter cake A1 (or/and filter cake A2 merges) flotation.
In step (3), adopt and use water as flotation medium and carry out sizing mixing process, wherein, filter cake A1 and
The gross weight of filter cake A2 and the mass ratio of flotation medium are 1: 10～20.If liquor B 1 not being sunk
Shallow lake processes, i.e. during sizing mixing in step (3), and the weight of filter cake A1 and the quality of flotation medium
Ratio is 1: 10～20.
As preferably, the liquor B 2 that step (2) obtains is applied to the process of sizing mixing of step (3).
Liquor B 1 processes through precipitant, is stripped of more F-, improve the response rate of electrolyte.Obtain
Liquor B 2 can be applied to the process of sizing mixing of step (3) by direct circulation.Additionally, liquor B 2 also can be through
Cross prior art to concentrate, reclaim the calcium containing compound obtaining excess, concentrate the condensed water recycling collected
It is applied to the process such as size mixing of the Alkali liquid compounding of step (2), step (3).
Liquor B 2 is applied to the process of sizing mixing, and can realize the closed cycle in whole processing procedure, saves
Water consumption.Liquor B 2 is applied to step (3) front dilute with water as flotation medium, as preferably,
The volume of liquor B 2 is less than or equal to 0.8 times of thinned water volume.
As preferably, in step (3), during sizing mixing, the gross weight of filter cake A1 and filter cake A2 with
The mass ratio of flotation medium is 1: 10～15.Described flotation medium is the water dilution of water or liquor B 2
Liquid.
Flotation processes isolated upper strata (flotation froth layer) powdered carbon and with CaF2Lower floor for main body is (floating
Select mine tailing layer) electrolyte.Flotation medium after flotation processes can be many by filter operation removal doping
Excess material, directly returns floatation process, it is also possible to by existing technology evaporation and concentration, will collect
Condensed water return alkali leaching or floatation process.Product after the material of doping and concentration can be according to production
The practical situation of process, returns flotation flowsheet and utilizes.
In floatation process, described floating agent has considerable influence to the recovery of charcoal, and the present invention uses
Collecting agent be that described quality is than collecting agent C1 and the compositions of collecting agent C2.
By collecting agent C1 and collecting agent C2 combination, coordinated, make collecting agent and other medicine
Agent is uniformly dispersed in ore pulp, contributes to reducing dosing, enhances the efficiency of a flotation, enter
And decrease flotation progression.
As preferably, on the basis of cathode carbon pieces weight, described collector dosage is 100～600g/t.
Further preferably, in described collecting agent, collecting agent C1 is kerosene and the diesel oil of mass ratio 1-2: 1
Mixture；Collecting agent C2 be mass ratio be 1: 1-1.5 dodecylbenzene sodium sulfonate and enuatrol mixing
Thing.Under this preferred feed, on the basis of cathode carbon pieces weight, described collector dosage is
200～500g/t.
As preferably, described foaming agent is selected from No. two oil, Oleum Camphora, methyl isobutyl carbinol, mixes
Close at least one in fatty alcohol；On the basis of cathode carbon pieces weight, described frother dosages is
50～120g/t.
Further preferably, described foaming agent is No. two oil and the Oleum Camphora mixture of mass ratio 1.5-2: 1.
Under this preferred feed, on the basis of cathode carbon pieces weight, described frother dosages is 100～120g/t.
As preferably, described regulator is selected from triisopropanolamine (NTP), ethylenediaminetetraacetic acid
(EDTA), at least one in ethylene diamine tetra methylene phosphonic acid salt (HDTP), waterglass；With negative electrode
On the basis of carbon block weight, described regulator consumption is 100～300g/t.
Further preferably, described regulator is NTP and the HDTP mixture of mass ratio 1-1.5: 1.
Under this preferred feed, on the basis of cathode carbon pieces weight, described regulator consumption is 200～300g/t.
In the present invention, g/t be each component in floating agent add unit, all with cathode carbon pieces weight
On the basis of amount, being, cathode carbon pieces per ton adds the corresponding material of corresponding g weight.
In described floating agent, each component and to add proportion the most collaborative, improves flotation effect, joins
The alkali leaching closing step (2) processes, the collaborative charcoal improving charcoal and the response rate of electrolyte and recovery pure
Degree.
As preferably, the time that flotation processes is 5-10min.Under the described conditions, flotation is once
Can complete goal of the invention, and flotation time is shorter, relative to prior art, treatment effeciency is high, effect
Good.
The present invention has a following preferable effect:
1, the present invention uses floatation, for existing floatation, due to collecting agent C2
Addition, make collecting agent and other medicament be uniformly dispersed in ore pulp, thus effectively reduce medicine
(collector dosage reduces 100～400g/t to agent consumption, and frother dosages decreases 30～80g/t, regulation
The minimum amount of agent amount ratio current methods is the fewest), enhance the efficiency of a flotation, and then reduce
Flotation progression.
2, the present invention uses the method that alkali soaks, and insoluble fluorion is converted into soluble fluoride ion,
Calcium containing compound is used to be fixed by whole free fluoride ion, during reducing follow-up FLOTATION SEPARATION
The free fluoride ion impact on floatation process, and before making the material of FLOTATION SEPARATION relative to converting, electricity
Solve matter composition simpler, only need to separate powdered carbon and CaF2。
3, the floatation that the present invention uses need not follow-up waste water process, and its waste water produced is at stream
Just complete purification in journey, and the fluorion in leachate has been carried out effective recovery, simplify place
Science and engineering sequence.
4, the present invention has exceeded 90% to the response rate of electrolyte, and the fluoride in electrolyte changes into
For CaF2, after subsequent treatment, quality has reached the requirement of industrial application, can substitute for fluorite ore
Use, alleviate mineral resources pressure；The purity of powdered carbon has also reached 85%～90%, and the response rate is
90%～95%；Achieve the separation and recovery to waste and old cathode carbon block, improve economic benefit, and subtract
Light environmental protection pressure.
Detailed description of the invention
Following example are pressed aforesaid operations method and are implemented, and wherein cathode carbon pieces used is that same composition contains
Amount, phosphorus content is 55.42%, content of fluoride 30.65%.
Embodiment 1
Step (1): broken pulverizing:
Jaw crusher is first used to be crushed to by cathode carbon pieces 1kg aluminum electrolytic tank waste and old cathode carbon block
-30mm, then it is crushed to-2mm with fine crusher, finally use ball mill grinding to granularity to 200
Mesh, wherein-200 mesh account for 80%.
Step (2): the dipped filter of alkali:
Take the waste and old cathode carbon powder 1kg that step (1) grinding is good, add the sodium hydroxide solution of 4mol/L
In be made into slurry (solid-liquid mass ratio is 1: 6), under conditions of temperature 50 C, rotating speed 100r/min,
Stirred leaching tank leaches, filters after leaching 45min, obtain filter cake A1, liquor B 1；
The CaO being equivalent to soluble fluoride content (or amount of material) 105% is added, extremely in liquor B 1
Precipitation terminates, and is filtrated to get filter cake A2, liquor B 2.
Step (3): flotation: by the filter cake (filter cake A1 and filter cake A2) in step (2) according to solid-liquid quality
Than being to be added to the water at 1: 10, add the collecting agent being made up of 0.355g kerosene and 0.175g enuatrol,
Foaming agent: Oleum Camphora 0.12g, regulator: waterglass 0.2g；Flotation 10min, in isolated
Layer powdered carbon and with CaF2Lower floor's electrolyte for main body.By calculating, the electrolyte response rate is
91.53%, powdered carbon purity 86.79%, the response rate is 93.31%.
Comparative example 1
Comparing with embodiment 1, difference is, does not carry out the alkali leaching filtration step of step (2), by step
(1) fine powder of milled directly carries out the flotation process of step (3).After flotation terminates, isolated
Upper strata powdered carbon and with CaF2Lower floor's electrolyte for main body.By calculating, the electrolyte response rate is
84.62%, powdered carbon purity 78.92%, the response rate is 86.45%.
Comparative example 2
Comparing with embodiment 1, difference is, substitutes enuatrol with kerosene, and the collecting agent i.e. used is
Single kerosene composition, the weight that adds of kerosene is 0.530g.After flotation terminates, isolated upper strata charcoal
Powder and with CaF2Lower floor's electrolyte for main body.By calculating, the electrolyte response rate is 80.53%,
Powdered carbon purity 79.27%, the response rate is 83.86%.
Comparative example 3
Comparing with embodiment 1, difference is, substitutes kerosene with enuatrol, and the collecting agent i.e. used is
0.530g enuatrol.After flotation terminates, isolated upper strata powdered carbon and with CaF2Lower floor for main body
Electrolyte.By calculating, the electrolyte response rate is 75.62%, powdered carbon purity 74.42%, the response rate
It is 81.18%.
Comparative example 4
Comparing with embodiment 1, difference is, becoming of collecting agent does not changes, and consumption is not at invention model
In enclosing, the collecting agent i.e. used is made up of 0.3g kerosene and 0.3g enuatrol.After flotation terminates, point
From obtaining upper strata powdered carbon and with CaF2Lower floor's electrolyte for main body.By calculating, electrolyte reclaims
Rate is 85.04%, powdered carbon purity 82.79%, and the response rate is 86.58%.
Embodiment 2
Comparing with embodiment 1, difference is, replaces step (3) with flotation medium during preparation slurry
In water, the liquid after flotation medium liquor B 2 dilute with water 0.6 times.After flotation terminates, separate
Obtain upper strata powdered carbon and with CaF2Lower floor's electrolyte for main body.By calculating, the electrolyte response rate
Being 91.44%, powdered carbon purity 86.64%, the response rate is 93.21%.
Embodiment 3
Step (1): broken pulverizing:
Jaw crusher is first used to be crushed to by cathode carbon pieces 1kg aluminum electrolytic tank waste and old cathode carbon block
-30mm, then it is crushed to-2mm with fine crusher, finally use ball mill grinding to granularity to 200
Mesh, wherein-200 mesh account for 85%.
Step (2): the dipped filter of alkali:
Take the waste and old cathode powder 1kg that step (1) grinding is good, add the sodium hydroxide solution of 6mol/L
In be made into slurry (solid-liquid mass ratio is 1: 7), temperature 40 DEG C, under conditions of rotating speed 90r/min,
Stirred leaching tank leaches, filters after leaching 60min, obtain filter cake A1, liquor B 1；
The CaO being equivalent to soluble fluoride content (or amount of material) 107% is added in liquor B 1,
Terminate to precipitation, be filtrated to get filter cake A2, liquor B 2.
Step (3): flotation:
By the filter cake (filter cake A1 and filter cake A2) in step (2) according to solid-liquid mass ratio be 1: 15 add
In water, add by 0.15g kerosene, the diesel oil of 0.15g, 0.06g dodecylbenzene sodium sulfonate and 0.09g
Enuatrol composition collecting agent；No. bis-oil of foaming agent: 0.08g, 0.04g Oleum Camphora；Regulator:
0.15g triisopropanolamine (NTP) and 0.1gHDTP；Flotation 8min, isolated upper strata powdered carbon and with
CaF2Lower floor's electrolyte for main body.By calculating, the electrolyte response rate is 93.04%, and powdered carbon is pure
Degree 88.67%, the response rate is 94.35%.
Embodiment 4
Comparing with embodiment 3, difference is, collecting agent is by 0.2g kerosene, the diesel oil of 0.2g, 0.12g
The enuatrol composition of dodecyl sodium sulfate and 0.08g.After flotation terminates, isolated upper strata powdered carbon
With with CaF2Lower floor's electrolyte for main body.By calculating, the electrolyte response rate is 90.81%, charcoal
Powder purity 86.78%, the response rate is 92.53%.
Embodiment 5
Comparing with embodiment 4, difference is, collecting agent is by 0.2g heavy oil, the diesel oil of 0.2g, 0.08g
The enuatrol composition of dodecylbenzene sodium sulfonate and 0.12g.After flotation terminates, isolated upper strata charcoal
Powder and with CaF2Lower floor's electrolyte for main body.By calculating, the electrolyte response rate is 91.15%,
Powdered carbon purity 85.83%, the response rate is 91.88%.
Embodiment 6
Comparing with embodiment 3, difference is, foaming agent is by No. two oily 0.06g and Oleum Camphora 0.06g
Composition.After flotation terminates, isolated upper strata powdered carbon and with CaF2Lower floor's electrolyte for main body.
By calculating, the electrolyte response rate is 90.58%, powdered carbon purity 85.06%, and the response rate is 89.46%.
Embodiment 7
Step (1): broken pulverizing:
Jaw crusher is first used to be crushed to by cathode carbon pieces 1kg aluminum electrolytic tank waste and old cathode carbon block
-30mm, then it is crushed to-2mm with fine crusher, finally use ball mill grinding to granularity to 200
Mesh, wherein-200 mesh account for 90%.
Step (2): the dipped filter of alkali:
Take the waste and old cathode powdered carbon 1kg that step (1) grinding is good, add the sodium hydroxide solution of 8mol/L
In be made into slurry (solid-liquid mass ratio is 1: 8), at temperature 60 C, under conditions of rotating speed 80r/min,
Stirred leaching tank leaches, filters after leaching 30min, obtain filter cake A1, liquor B 1；
The CaO being equivalent to soluble fluoride content (or amount of material) 110% is added in liquor B 1,
Terminate to precipitation, be filtrated to get filter cake A2, liquor B 2.
Step (3): flotation:
By the filter cake (filter cake A1 and filter cake A2) in step (2) according to solid-liquid mass ratio be 1: 20 add
In water, add the collecting agent being made up of 0.35g coal tar and 0.15g dodecyl sodium sulfate, bubble
Agent mixed fatty alcohol 0.08g, regulator HDTP0.3g；Flotation 5min, isolated upper strata powdered carbon
With with CaF2Lower floor's electrolyte for main body.By calculating, the electrolyte response rate is 91.63%, charcoal
Powder purity 86.33%, the response rate is 93.57%.
Embodiment 8
Step (1): broken pulverizing:
Jaw crusher is first used to be crushed to by cathode carbon pieces 1kg aluminum electrolytic tank waste and old cathode carbon block
-30mm, then it is crushed to-2mm with fine crusher, finally use ball mill grinding to granularity to 200
Mesh, wherein-200 mesh account for 90%.
Step (2): the dipped filter of alkali:
Take the waste and old cathode carbon block 1kg that step (1) grinding is good, add in the potassium hydroxide solution of 8mol/L
Be made into slurry (solid-liquid mass ratio is 1: 8), at temperature 60 C, under conditions of rotating speed 80r/min,
Stirred leaching tank leaches, filters after leaching 30min, obtain filter cake A1, liquor B 1；
The CaO being equivalent to soluble fluoride content (or amount of material) 110% is added in liquor B 1,
Terminate to precipitation, be filtrated to get filter cake A2, liquor B 2.
(3) flotation:
It is to be added to the water the filtering residue in step (2) at 1: 10 according to solid-liquid mass ratio, adds by 0.4g bavin
Oil and the collecting agent of 0.175g dodecylbenzene sodium sulfonate composition, foaming agent: methyl isobutyl carbinol
0.1g, regulator: triisopropanolamine (NTP) 0.25g；Flotation 5min, isolated upper strata powdered carbon and
With CaF2Lower floor's electrolyte for main body.By calculating, the electrolyte response rate is 92.13%, powdered carbon
Purity 87.25%, the response rate is 93.07%.
The above, the only result of embodiment of the present invention.
Claims (10)
1. reclaiming charcoal and a method for electrolyte from the cathode carbon pieces of aluminum cell waste, it is special
Levy and be, comprise the following steps:
Step (1): cathode carbon pieces is broken, grinding；
Step (2): the negative electrode powdered carbon obtained after step (1) being processed stirs in alkali liquor, leaches, with
After be filtrated to get filter cake A1 and liquor B 1；
Step (3): filter cake A1 and floating agent are mixed and sizes mixing, flotation, separation, flotation froth
Product is charcoal, and flotation tailing is electrolyte；Described floating agent includes collecting agent, foaming agent and tune
Joint agent；Wherein, described collecting agent by the collecting agent C1 that mass ratio is 0.65-0.75: 0.25-0.35 and
Collecting agent C2 forms；Collecting agent C1 is selected from least in coal tar, heavy oil, kerosene, diesel oil
Kind, collecting agent C2 is selected from lauryl amine, dodecylbenzene sodium sulfonate, enuatrol, dodecyl sodium sulfonate
At least one in sodium.
2. according to the cathode carbon pieces from aluminum cell waste described in claims 1 reclaim charcoal and
The method of electrolyte, it is characterised in that in described collecting agent, collecting agent C1 is mass ratio 1-2: 1
Kerosene and diesel fuel mixtures；Collecting agent C2 be mass ratio be the dodecylbenzene sodium sulfonate of 1: 1-1.5
With enuatrol mixture.
3. according to the cathode carbon pieces from aluminum cell waste described in claims 2 reclaim charcoal and
The method of electrolyte, it is characterised in that in step (1), cathode carbon pieces is broken, grinding to-200
Mesh accounts for more than 80%.
4. according to the cathode carbon pieces from aluminum cell waste described in claims 1 reclaim charcoal and
The method of electrolyte, it is characterised in that in step (2), also include: it is heavy to add in liquor B 1
Shallow lake agent, is filtrated to get filter cake A2 and liquor B 2；Filter cake A2 and filter cake A1 merging carries out step (3).
5. according to the cathode carbon pieces from aluminum cell waste described in claims 4 reclaim charcoal and
The method of electrolyte, it is characterised in that described precipitant is CaO, CaCl2、Ca(OH)2Extremely
Few one, the consumption of described precipitant be step (1) cathode carbon pieces in soluble fluoride material
1.05～1.1 times of amount.
6. according to the cathode carbon pieces from aluminum cell waste described in claims any one of 1-5
Reclaim charcoal and the method for electrolyte, it is characterised in that described alkali liquor is the aqueous solution of alkali compounds,
Its concentration is 4～8mol/L.
7. according to the cathode carbon pieces from aluminum cell waste described in claims 6 reclaim charcoal and
The method of electrolyte, it is characterised in that in step (2), negative electrode powdered carbon and alkali liquor are according to solid-liquid mass ratio
1: 6～8 are made into slurry, and leach under conditions of temperature 20～60 DEG C, rotating speed 60～100r/min,
Extraction time is 30-60min.
8. according to the cathode carbon pieces from aluminum cell waste described in claims any one of 1-5
Reclaim charcoal and the method for electrolyte, it is characterised in that on the basis of cathode carbon pieces weight, described collecting
Agent consumption is 100～600g/t.
9. according to the cathode carbon pieces from aluminum cell waste described in claims 8 reclaim charcoal and
The method of electrolyte, it is characterised in that described foaming agent is different selected from No. two oil, Oleum Camphora, methyl
At least one in butyl carbinol, mixed fatty alcohol；On the basis of cathode carbon pieces weight, described foaming
Agent consumption is 50～120g/t.
10. according to the cathode carbon pieces from aluminum cell waste described in claims 9 reclaim charcoal and
The method of electrolyte, it is characterised in that described regulator selected from triisopropanolamine, ethylenediaminetetraacetic acid,
At least one in ethylene diamine tetra methylene phosphonic acid salt, waterglass；On the basis of cathode carbon pieces weight, institute
Stating regulator consumption is 100～300g/t.
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