CN107381534A - A kind of cleaning recoverying and utilizing method of aluminium cell carbonaceous waste material - Google Patents
A kind of cleaning recoverying and utilizing method of aluminium cell carbonaceous waste material Download PDFInfo
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- CN107381534A CN107381534A CN201710599982.4A CN201710599982A CN107381534A CN 107381534 A CN107381534 A CN 107381534A CN 201710599982 A CN201710599982 A CN 201710599982A CN 107381534 A CN107381534 A CN 107381534A
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
A kind of cleaning recoverying and utilizing method of aluminium cell carbonaceous waste material, comprises the following steps：（1）Aluminium cell carbonaceous waste material supercritical carbon dioxide fluid or the liquid carbon dioxide leaching of crushing is molten, obtain carbon dioxide charcoal slurry；（2）The temperature and/or pressure of adjustment charcoal slurry, and/or the mass concentration of adjustment charcoal slurry, then chromatography in gravity settling separation or centrifugation or flowing is stood, inanimate matter component and carbon pulp components are obtained respectively；（3）Inanimate matter component and carbon pulp components are subjected to decompression separation recovery carbon dioxide respectively, obtain inanimate matter raw material and carbon raw.The inventive method can effectively reclaim inanimate matter electrolyte and carbon materials in aluminium cell carbonaceous waste material, and can obtain high-quality electrolyte raw material and carbon raw；The inventive method technique is simple, non-secondary pollution, low energy consumption, low cost, suitable industrialized production.
Description
Technical field
The present invention relates to a kind of cleaning recoverying and utilizing method of aluminium cell carbonaceous waste material, and in particular to one kind overcritical two
Carbon oxide fluid or liquid carbon dioxide soak the cleaning recoverying and utilizing method of molten aluminium cell carbonaceous waste material.
Background technology
At present, the development of the electrolytic aluminium yield in China and the world is swift and violent.According to statistics, in by the end of December, 2016, China's electrolytic aluminium
Aluminium smelter enterprise be completed production capacity up to 4369.8 ten thousand tons, run production capacity up to 3673.9 ten thousand tons.With the increasing of electrolytic aluminium yield
Add, caused solid waste in electrolytic process, such as waste cathode carbon block, scrap anode carbon granule, useless refractory brick, useless insulating brick, useless guarantor
The yield of warm clinker also increases sharply, wherein only the caused negative electrode that gives up is up to 250,000 tons every year for China's aluminum electrolysis industry, in recent years still
The accumulative volume of cargo in storage for having more than 400 ten thousand tons fills without suitable area, and the waste cathode carbon block actual amount of whole world stockpiling is up to ten million
Ton.
Aluminium cell carbonaceous waste material includes caused waste cathode carbon block and scrap anode carbon granule during electrolytic aluminium etc., predominantly
Waste cathode carbon block.The main component of waste cathode of aluminum electrolytic cell carbon block is C, also contains Na3AlF6、CaF2、NaF、AlF3、α-Al2O3
Deng, wherein carbon content be 50~70%, electrolyte fluoride be 30~50%, cyanide is about 0.2%.Do not have in aluminium electrolysis process
Participate in the anode carbon granule of electrolyte in electrolysis and Electolyte-absorptive（Also known as anode breeze）Main component be with Na3AlF6Based on
Sodium aluminium fluoride, α-Al2O3And C, remaining is electrolyte fluoride, wherein, carbon content is 40~60%.
Electrolytic aluminium waste cathode carbon block belongs to the high artificial material of degree of graphitization, it is well known that electrolytic aluminium negative electrode is to forge
The anthracite of burning, metallurgical coke, graphite etc. are that aggregate, coal tar pitch etc. is made up of binding agent shaping and roasting, for charcoal containing aluminium cell
The block class or paste class carbon product of matter liner, are graphitization or graphite-like carbon materials, with hardness is big, coefficient of friction is small, no
Broken, extremely difficult combustion（Relative to fire coal）The characteristics of.The electrolysis temperature of modern large-scale aluminium electrolysis pre-baking tank 950~970 DEG C it
Between, the electrolyte such as 1 ton of aluminium consumption about 50kg ice crystals, aluminum fluoride, magnesium fluoride are often produced, due to heat effect, chemical action, machinery
Erosion effect, electro ultrafiltration, sodium and electrolyte infiltration etc. caused by fused salt reaction, chemical reaction, the negative electrode charcoal in aluminium cell
Block can be damaged after using certain time, needs to carry out large repairs after typically running 4~7 years, the mainly waste cathode carbon block that removes,
Waste refractory materials, useless insulation material etc., while a certain amount of anode carbon granule is also produced in electrolytic process.
For the treatment technology of the less scrap anode carbon granule of quantity, current research is concentrated mainly on is returned using floatation process
Charcoal and electrolyte are received, by scrap anode carbon granule grinding to certain particle size, adds water to add collecting agent after sizing mixing, makes charcoal abundant with electrolyte
Separation, so as to obtain using electrolyte as two kinds of products advocating peace based on charcoal.Electrolyte therein can back within aluminium electroloysis
In groove, powdered carbon can be used for the raw material that Soderberg Anode In Aluminium Electrolysis Cells make anode mix, but processing cost is high and secondary pollution is big.
For waste cathode of aluminum electrolytic cell carbon block, at present both at home and abroad the technical method of processing waste cathode carbon block up to tens of kinds it
It is more, it may be summarized to be wet method, high temperature hydro-thermal method, superhigh temperature partition method, burning partition method, fuel process and security landfill method etc..
（1）Wet method：For the main direction of studying of current internal lining of aluminium electrolytic bath, basic working procedure is grinding, water logging/alkali leaching/acid
Wash, flotation, separation, drying etc..The external representative use aquation method released for M.M.Williams handles waste cathode carbon
Block（Isolated thick carbon granule and fine grain electrolyte）, and Austrian Lun Sihuofen aluminium manufacturers and Li Sita aluminium manufacturers of U.S. alkali
The molten leaching electrolyte therein of liquid（Leachate is used for synthetic cryolite, and charcoal is used as the fuel of high temperature furnace collocation）.Chalco stock
Part Co., Ltd, Beijing Mine and Metallurgy General Inst, Central South University etc. have also carried out substantial amounts of research and practice, as Lu Huimin et al. is used
Floatation reclaims charcoal and electrolyte, and waste cathode carbon block is crushed, obtains the powder of certain particle size after classification, adds water to be added after sizing mixing
Collecting agent, to realize farthest separating for carbon and electrolyte, so as to obtain using electrolyte as advocate peace based on charcoal two kinds
Product.Electrolyte therein can be backed within aluminium cell, and graphited powdered carbon can return to negative electrode production system.But
It is that the toner value that method for wet separation obtains at present is not high, and resource utilization efficiency is low, and the processing power consumption such as grinding is high, place
It is high to manage cost, and serious secondary pollution be present.
（2）High temperature hydro-thermal method separation method：It is most representational to be used for J.E.Dentschman and J.S.Lobos etc.
More than 1200 DEG C of hot water Hydrolyze method processing waste cathode carbon block, make fluoride and the hydrogen fluoride of steam reaction generation concentration 25% molten
Liquid, then aluminum fluoride is produced with synthetic method, and collect the fluorine ion in solution with gypsum.But this method investment is big, high energy consumption,
Processing cost is high, and difficulty is administered in secondary pollution.
（3）Superhigh temperature separation method：External representative " AUMSET " technique for the exploitation of Alcoa companies, in powder
Adding the flux such as lime in broken waste lining carbon block, blended stock is heat-treated in AUS-MELT stoves at 1300 DEG C of temperature,
Lime etc. is reacted with the electrolyte in waste cathode carbon block, obtain calcirm-fluoride, sodium fluoride and aluminum fluoride, reclaim high-temperature flue gas
Middle HF gases generate aluminum fluoride, make fluorine obtain solidifying to re-use, final products are glassy state slag, and the charcoal of recovery is used again
In manufacture cathode material.The technique has carried out commercial Application, handles waste lining year up to 12000t, but invests big, processing energy consumption
Height, processing cost are too high.It is domestic also to have research more, as CN105642649A discloses a kind of high-temperature treatment of electrolytic aluminium waste cathode
Method, it is that electrolytic aluminium waste cathode carbon block is crushed to 3~15mm, then, is roasted in 2600~2800 DEG C of superhigh temperature vacuum electric furnaces
Burning processing, it be nitride to volatilize fluoride therein, decompose cyanide therein, and high-temperature flue gas is by the way of water smoke absorbs
Absorb again by the processing such as filtering drying, obtain can reuse fluoride, the negative electrode carbon materials after superhigh temperature roasting is through being cooled to
Reach 97% carbon materials for fixed carbon content.But this method is significantly present of following problem：First, electrolytic aluminium waste cathode carbon is broken
Toxic dust and toxic gas containing cyanide are produced in broken screening process；Second, it is actual to 2600~2800 DEG C for electrical heating
Power consumption is very high, maintain vacuum suction power consumption it is higher, the requirement of equipment and cost are also very high；Third, 2600~2800 DEG C volatilization
It is too high that fluoride gas using water smoke absorb requirement to equipment, because 1200 DEG C of water vapour can be so that calcirm-fluoride etc. to be fluorinated
Thing is converted into the hydrogen fluoride of the severe corrosive of severe toxicity；Fourth, serious secondary pollution is also easy to produce, and the carbon materials reclaimed
In still contain 3% or more fluoride, recycling can shorten overhaul life and uneconomical.CN106269787A discloses one kind
For disposing the high temperature continous way processing method of electrolytic aluminium waste cathode, teach one kind and be crushed to electrolytic aluminium waste cathode carbon block not
Particle more than 3mm, 3~100mm compound particles are made with kneadings such as pitches, then, compound particles are placed in superelevation
In warm vacuum electric furnace, in not less than 2000 DEG C（2300~2600 DEG C）Continous way calcination process in superhigh temperature vacuum electric furnace, is obtained high
Warm electro-forge flue gas and electrolytic aluminium waste cathode carbon granules, then high temperature electro-forge flue gas is subjected to second-time burning, completely burned volatile matter flue gas
In carbon dust, carbon powder and ice crystal, it is nitride to decompose cyanide therein, after cooling, dedusting, desulphurization denitration, obtains reuse
Fluoride and fixed carbon content reach 95% carbon materials.But this method is significantly present of following problem：First, electrolytic aluminium waste is cloudy
Toxic dust and toxic gas containing cyanide are produced during the carbon crushing and screening of pole；Second, electrical heating to 2000~2600 DEG C its
Actual power consumption is very high, maintains that the power consumption of vacuum suction is higher, and the requirement of equipment and cost are also very high；Third, after second-time burning
Gas cleaning investment is high, is also easy to produce serious secondary pollution；Fourth, still contain in the carbon of 2000~2600 DEG C of electric furnace calcination processing
Substantial amounts of fluoride, because more than 2497 DEG C of the boils up till of calcirm-fluoride, fluorine-containing carbon materials, which recycles, can shorten overhaul time
Limit and it is uneconomical.
（3）Burn separation method：It is to use professional incinerator and fluid bed furnace technique etc., because electrolytic aluminium waste cathode carbon is different
In fire coal, though calorific value is generally up to 4000~5500kcal/kg, activation energy needed for oxidation reaction is high, need to reach 1500 DEG C of height
It is warm could the efficient oxidation burning, therefore combustion method is present that separating process is cumbersome, the heat time needed for after-flame is long, energy consumption is big and difficult
The problem of effectively to reclaim wherein fluoride, and secondary pollution issue handling difficulty is also big.
（4）Fuel process：Because the main component of electrolytic aluminium waste cathode carbon block is charcoal, and the theoretical combustion heat of completely burned is typically up to
More than 4000kcal/kg, high reaches 5500kcal/kg equivalent to conventional anthracitic calorific value, so, domestic and international substantial amounts of skill
Art worker has carried out unremitting effort, and effect pole is not so good as people's will so far.The domestic method as fuel has China YouSe metal
The identification for the Shandong Aluminum Co., Ltd. factory " recycling of waste cathode of aluminum electrolytic cell carbon block " that Industry Corporation organized on November 16th, 1988
Achievement.Specific method is：" Shandong Aluminum Plant in alumina producing, using waste and old cathode carbon block it is levigate after as desulfurizing agent and substitute
Part anthracite is added in alumina rotary kiln, produces alumina sintering block.Contained fluoride salt changes into sinter leaching
Insoluble calcirm-fluoride enters red mud, and red mud replaces fluorescent mineralizer for manufacture of cement dispensing when preparing cement." still,
This method grinding energy is high, the discharge capacity increase of pernicious gas in flue gas.Further to solve the turning sludge into fuel profit of waste cathode carbon block
With problem, research institute of Shandong branch company of Chinese Aluminium Co., Ltd poplar meeting guest waits the cement producing line in Shandong Aluminum Plant enterprising
In-depth study practice is gone, with calorific value 21MJ/kg（5024kcal/kg）Waste cathode carbon block be applied to cement producing line work
Industry is tested, and is specifically first crushed waste cathode carbon block, by the maximum ratio dosage of clinker 5kg waste cathode carbon blocks per ton（Convert and be
About less than the 3% of coal consumption）, together grinding is incorporated in coal mill in grinding coal dust, and conclusion (of pressure testing) is clinker per ton by the useless the moon of 5kg
Pole carbon block is to clinker quality without visible influences（Application study light metal of the waste cathode carbon blocks such as Yang Huibin in manufacture of cement,
2nd phase in 2008, P59-64.）.Yang Huibin etc. is high using cement kiln internal reaction temperature, carbon block residence time on stream
The condition such as long, makes the harmful substance in waste cathode carbon block carry out decomposition displacement in hot environment, and it is ripe to be finally solidificated in cement
In material, while attempt to reducing the consumption of coal by the use of the carbon in waste cathode carbon block as fuel.But its still have safety problem,
Addition problem and the influence problem to production, after all, waste cathode carbon are not coal-fired, the extremely difficult combustions of charcoal in waste cathode carbon block.So
And the defects of real is not the problem of fluorine is exceeded in the erosion of refractory material caused by fluoride and flue gas, because calcium aluminum fluoride
The production of cement also ensure that refractory material safety and flue gas in fluorine it is not exceeded, normal cement kiln preheaters system visitor after all
There is the preheater for realizing that Pyatyi exchanges trapping with Alkaline high-strength powder in sight；Nor the problem of alkali content is high, because often
Ton clinker consumption coal normally only 0.15~0.18t, the electrolyte in a small amount of cathode carbon pieces is mainly aluminum fluoride, calcirm-fluoride, fluorine aluminium
Sour sodium, fluoaluminic acid magnesium, sodium fluoride only account on a small quantity, dosage hour it is limited with the total alkali content in cryolite and sodium fluoride, typically
Influence to cement later strength is limited.Therefore, Shandong Aluminum Plant so far still can not be using negative electrode charcoal normal use as alternative combustion
The true cause of coal is：First the mill efficiency of coal mill is influenceed, is second that the graphitic carbon of low activity seriously reduces the whole of coal dust
Body combustibility, the serious normal combustion efficiency that have impact on coal dust, it is impossible to which the timely and effective exothermic carbon of burning is fallen into
Clinker entrains into the strong reduction of generation in powder, have impact on kiln system operating mode, have impact on clinker quality.Obviously, prior art is not still
Can be using electrolytic aluminium waste cathode carbon block as effective alternative fuel.
（5）Security landfill method：Because high energy consumption, high cost and secondary pollution problems be present in existing processing method, because
This, the problem of environmental pollution of electrolytic aluminium waste cathode carbon block is never effectively solved, and causes most aluminium electrolytics
Cathode carbon pieces are still thrown aside, and use the security landfill method of high cost at present or mainly.And the current landfill generally used, stockpiling
Method handles electrolytic aluminium solid waste method, high risks can be caused to environment, even completely by the harmless of hazardous waste
Lasting contact scar will be produced by changing landfill, and cause ample resources waste.
In addition, electrolytic aluminium solid waste is due to containing substantial amounts of soluble fluoride and a small amount of cyanide（Predominantly
Cymag and the sodium ferricyanide）, belong to danger wastes, must be dealt carefully with.And under the conditions of prior art, electrolytic aluminium factory is universal
Landfill, the stacked arrangement of use handle these solid waste, and contained soluble fluoride and cyanide can pass through wind, day
The effect transfer that shine, drenches with rain is volatized into air, or be mixed into rivers with rainwater, permeate the ground contaminated soil and underground water, right
Animals and plants and human body produce very big infringement, destroy ecological environment, influence Agro-ecology balance, make crop production reduction, and it endangers will
It is long-term.Processing for cyanide in waste cathode carbon block, treatment technology mainly have weak acid dissolving+polysulfide to be converted into sulphur
For the method for cyanate and metal thiophosphate thing, manganese ion+ultraviolet catalytic oxidation method, ozone and sodium hypochlorite co-oxidation side
Method, high temperature chlorination processing method, high-temperature oxidation method, biochemical process processing cyanide technology.But at these existing cyanides
Reason technical method is cumbersome, cost is high, and secondary pollution be present.CN101811695A discloses a kind of from electrolytic aluminium waste cathode carbon block
The method of middle recovery graphite, it is that the process such as acidleach removes fluoride therein again using grinding, water logging, flotation, separates and recovers it
In carbon materials drying to obtain refined graphite powder.But this method process is numerous and diverse, secondary pollution is big, high energy consumption, the stone of recovery
Black fine powder impurity content is high.
To sum up, the outstanding problem as aluminum electrolysis industry general character, it is necessary to it is harmless to break through electrolytic aluminium solid waste as early as possible
Change industrialization technology problem.The characteristic of electrolytic aluminium solids waste material how is utilized to implement recycling, it is especially safe
, low energy consumption, inexpensive recycling be the technical method for being worth a researching and solving problem.
The content of the invention
The technical problems to be solved by the invention are to overcome drawbacks described above existing for prior art, there is provided a kind of technique letter
Single, non-secondary pollution, low energy consumption, low cost, the cleaning recycling side of the aluminium cell carbonaceous waste material of suitable industrialized production
Method.
The technical solution adopted for the present invention to solve the technical problems is as follows：A kind of cleaning of aluminium cell carbonaceous waste material is returned
Application way is received, is comprised the following steps：
（1）Carbon dioxide charcoal slurry processed：The aluminium cell carbonaceous waste material of crushing is placed in pressure leaching fluid bowl/tank, with overcritical two
In carbon oxide fluid or liquid carbon dioxide drain tank air and as solvent soak it is molten, obtain supercritical carbon dioxide fluid charcoal slurry or
Liquid carbon dioxide charcoal is starched；
（2）Size mixing separation：Set-up procedure（1）Gained supercritical carbon dioxide fluid charcoal is starched or the temperature of liquid carbon dioxide charcoal slurry
And/or pressure, and/or the mass concentration of adjustment supercritical carbon dioxide fluid charcoal slurry or liquid carbon dioxide charcoal slurry so that two
Carbonoxide is close to gas-liquid critical point or supercriticality, then stands chromatography point in gravity settling separation or centrifugation or flowing
From, respectively component and carbon pulp components based on inanimate matter；
（3）Separating-purifying：Respectively by step（2）Component and carbon pulp components based on gained inanimate matter are respectively placed in titanium dioxide
In carbon separation unit, decompression separation recovery carbon dioxide is carried out, obtains inanimate matter raw material and carbon raw.
Preferably, step（1）In, the aluminium cell carbonaceous waste material and supercritical carbon dioxide fluid or liquid titanium dioxide
The mass ratio of carbon is 1:0.15~9.0（More preferably 1:0.18~5.0）.With supercritical carbon dioxide fluid or liquid carbon dioxide
Molten aluminium cell carbonaceous waste material is soaked, to be efficiently swelled, dissolve dissociation inanimate matter and carbon and form charcoal slurry, is easy to industrialized economy
Scale processing.
Preferably, step（1）In, the molten temperature of the leaching is 0~60 DEG C（More preferably 10~40 DEG C）, soaking molten pressure is
3.5~50MPa（More preferably 5~10MPa）, it is 0.2~8.0h to soak the molten time（More preferably 0.3~3.0h）.Due to carbon material
Material and liquid carbon dioxide have certain " mixing " compatibility, by soak it is molten carbon is scattered in liquefied carbon dioxide,
Being formed has certain density liquid carbon dioxide charcoal slurry.
Preferably, step（1）In, the main component of the aluminium cell carbonaceous waste material is waste cathode carbon block and/or useless sun
Pole carbon granule, wherein, inanimate matter content 20~50%, carbon content 50~80%, wherein, in inanimate matter, cyanide content ＜ 2.0%, respectively
Gross mass percentage≤100% of composition.
Preferably, step（1）In, the aluminium cell carbonaceous waste material of the crushing is particle diameter≤5mm bulk goods or 80 μm
Tail over ＜ 25% powder-material.Pressure leaching fluid bowl/tank of the pressure leaching fluid bowl/tank preferably with agitating device, particularly, works as aluminium
When electrolytic cell carbonaceous waste material is bulk goods, fluid bowl/tank is soaked with the pressure for rolling over mixed/milling device, is more easy to the particulate matter of swelling
Material is dispersed into slurry.
Preferably, step（2）In, the temperature of adjustment supercritical carbon dioxide charcoal slurry or liquid carbon dioxide charcoal slurry to 30~
60℃（More preferably 31~45 DEG C）.
Preferably, step（2）In, the pressure of adjustment supercritical carbon dioxide charcoal slurry or liquid carbon dioxide charcoal slurry to 5~
15MPa（More preferably 6~10MPa）.
Preferably, step（2）In, adjust supercritical carbon dioxide charcoal slurry or liquid dioxy by adding liquid carbon dioxide
Change the mass concentration of carbon charcoal slurry to 5~60%（More preferably 20~50%）.It is described size mixing separation can directly pulping pressure soak fluid bowl/
Implement in tank, or be delivered in surge tank/tank and implemented with charcoal stock pump, or separator separation is sent into after sizing mixing.
Step（2）In, using supercritical carbon dioxide and inanimate matter " immiscible " but with carbon " mixing " the characteristics of, and
The difference of the density of inanimate matter density and carbon slurry, using standing gravity settling separation or centrifugation or in pipeline or groove
The method of chromatography in flowing, easily inanimate matter raw material and carbon raw are separated.
Preferably, step（3）In, decompression separation recovery carbon dioxide, the temperature of decompression separation is 30~50 DEG C, and pressure is
0.1013~5.5MPa.Inanimate matter or carbon are parsed after decompression separation and discharges carbon dioxide.The dioxy of decompression separation recovery
Changing carbon can utilize through cooling down, compressing and liquefying Posterior circle.
Preferably, by step（3）Gained inanimate matter raw material and carbon raw are respectively according to step（1）~（3）Reprocessing
>=1 time, molten separating-purifying is further soaked in realization.
Preferably, step（3）In, gained inanimate matter raw material and carbon raw can further separating-purifying, obtain high-quality
The raw material of recoverable or the product of export trade.The separating-purifying refers to remove in inanimate matter less using known mode of washing
The carbon of amount, and inanimate matter a small amount of in carbon, or each mineral in inanimate matter component are pressed into known physics, chemical method separation
Purify as different mineral.
Preferably, step（1）In, before supercritical carbon dioxide fluid or liquid carbon dioxide add, successively add oxygen
Agent and/or dispersant or its solution, and/or when adding supercritical carbon dioxide fluid or liquid carbon dioxide, carry oxygen secretly
Agent and/or dispersant or its solution.
Preferably, step（1）In, before being added in supercritical carbon dioxide fluid or liquid carbon dioxide, successively add
When oxidant and/or dispersant or its solution, the dosage of the oxidant or its solution is the 0.2~3.0% of carbonaceous waste material quality
（More preferably 0.5~2.0%）, after adding oxidant, stir evenly 0.3~1.5h of ageing（More preferably 0.5~1.0h）, the dispersant
Or 0.05~5% that the dosage of its solution is carbonaceous waste material quality（More preferably 0.5~3.0%）.
Preferably, step（1）In, when adding supercritical carbon dioxide fluid or liquid carbon dioxide, entrainment oxidation
When agent and/or dispersant or its solution, the dosage of oxidant or its solution is supercritical carbon dioxide fluid or liquid titanium dioxide
The dosage of the 0.1~2.0% of carbonaceous amount, dispersant or its solution is supercritical carbon dioxide fluid or liquid carbon dioxide quality
0.03~5%（More preferably 0.5~3.0%）.
Preferably, the oxidant be can efficient digestion cyanide hypertoxicity material, be chlorosulfonic acid oxidant, ferric acid
Salt oxidizing agent, bichromate oxidant, dichromic acid acid anhydride oxidant, thiosulfuric acid salt oxidizing agent, perchlorate oxidizing agents, hypochlorous acid
One or more in salt oxidizing agent, hydroxide oxidant or Chlorine Dioxide Oxidation agent etc.；The ferrate oxidation agent is
One or more in potassium ferrate, ferrate-lithium or Na2Fe04 etc., the bichromate oxidant are potassium bichromate, weight chromium
One or more in sour sodium or dichromic acid cobalt etc., the thiosulfuric acid salt oxidizing agent are sodium thiosulfate and/or thiosulfuric acid
Potassium etc., the perchlorate oxidizing agents are cobaltous perchlorate and/or lithium perchlorate etc., and the hypochlorite oxidant is sodium hypochlorite
And/or calcium hypochlorite etc., the hydroxide oxidant are one kind or several in cobalt hydroxide, iron hydroxide or potassium hydroxide etc.
Kind.After the oxidant adds, it can be achieved to remove the safety conversion of cyanide and/or oxidation Decomposition.
It is further preferred that the oxidant is ZC-XJ1 type oxidizing agent solutions（That is ferrate oxidation agent and time chlorine
Hydrochlorate oxidant is with mass ratio 1:1 saturated solution prepared）.Above-mentioned oxidant is purchased from Hunan Province little Yin Wujis environmental energy science and technology
Development corporation, Ltd..
Preferably, the dispersant is that adjustable carbon disperses in supercritical carbon dioxide or liquid carbon dioxide medium
Property and stability material, be one kind in carbonats compound, surfactant, aminated compounds or ether compound etc.
It is or several；The carbonats compound is in ethylene carbonate, propene carbonate, butylene or dimethyl carbonate etc.
One or more, the surfactant are one kind or several in sulfamic acid sodium, sodium alkyl sulfonate or sodium alkyl benzene sulfonate etc.
Kind, the aminated compounds is dimethylformamide and/or 1-METHYLPYRROLIDONE etc., and the ether compound is ethylene glycol
One or more in ether, NPE or dimethyl ether etc..The addition of the dispersant, it can strengthen super
The molten peptizaiton of the leaching of critical carbon dioxide or liquid carbon dioxide to carbon materials, and stable carbon slurry, it is inorganic to improve
The separative efficiency of matter and carbon.
It is further preferred that the dispersant is ZC-FS3 type liquid dispersants（That is carbonats compound and surface
Activating agent is with mass ratio 1:1 mixture）Or ZC-FS5 type liquid dispersants（I.e. carbonats compound and ether compound with
Mass ratio 2:1 mixture）.Above-mentioned dispersant is purchased from Hunan Province little Yin Wuji environmental energy Science and Technology Development Co., Ltd..
Preferably, the oxidant is potassium ferrate, cobaltous perchlorate, calcium hypochlorite in mass ratio 2:1:1 is mixed
Powdered oxidant；The dispersant is ethylene carbonate, 1-METHYLPYRROLIDONE, NPE, DPG two
Methyl ether in mass ratio 1:2:1:The liquid dispersant that 1 ratio is mixed.
The technical principle of the present invention：
The aluminium cell carbonaceous waste material that the inventive method is recycled is caused waste cathode carbon block during electrolytic aluminium and gives up
Anode carbon granule, its main component is for carbon materials and with Na3AlF6、CaF2、NaF、AlF3、α-Al2O3Deng the electricity for main component
Solve matter class inorganic matter（Wherein, containing the cyanide that a small amount of main component is Cymag and the sodium ferricyanide, content about 0.2%）, carbonaceous gives up
Carbonaceous material and other compositions in material is there is obvious interface, and these inorganic matters have the characteristics of density/specific gravity is larger
（Na3AlF6 2.75~3.00g/cm3、CaF2 3.18g/cm3、NaF 2.558g/cm3、AlF3 1.91g/cm3、Al2O3 3.9~
4.0g/cm3）, there is certain " mixing " compatibility using carbon materials and supercritical carbon dioxide or liquid carbon dioxide, will
Supercritical carbon dioxide or liquid carbon dioxide as a kind of solvent, meanwhile, using supercritical carbon dioxide density close to liquid
Body, viscosity is close to gas, and diffusion coefficient is 100 times of liquid, and the leaching solution cleavage ability to carbon materials is strong, can effectively soak
Molten and softening carbonaceous waste granules, and good fluidity, the characteristics of transporting resistance is low, make carbon materials be more readily dispersed in overcritical two
In carbonoxide or liquid carbon dioxide, being formed has certain density liquid carbon dioxide charcoal slurry, and it is overcritical to obtain carbonaceous waste material
Carbon dioxide or liquid carbon dioxide charcoal slurry；Using supercritical carbon dioxide or liquid carbon dioxide and inanimate matter " immiscible " but
With the characteristics of carbon " mixing " and inanimate matter density and carbon slurry density variation, using standing gravity settling separation or centrifugation
Separate or flow chromatographic is separated into inanimate matter component and carbon pulp components in pipeline/groove；
Beneficial effects of the present invention：
（1）The inventive method can effectively reclaim inanimate matter electrolyte and carbon materials in aluminium cell carbonaceous waste material, and can obtain
Obtain high-quality electrolyte raw material and carbon raw；Wherein, in gained one-level inanimate matter dry powder, inanimate matter content may be up to 94.7%；
In gained one-level carbon dry powder, carbon content may be up to 98.1%；In gained two level inanimate matter dry powder, inanimate matter content may be up to
99.4%；In gained two level carbon dry powder, carbon content may be up to 99.7%；
（2）The inventive method technique is simple, non-secondary pollution, low energy consumption, low cost, suitable industrialized production.
Embodiment
With reference to embodiment, the invention will be further described.
Raw material used in the embodiment of the present invention or chemical reagent, unless otherwise specified, obtained by routine business approach
.
Embodiment 1
Aluminium cell carbonaceous waste material used in the embodiment of the present invention is derived from the block carbonaceous waste material stored up in certain aluminium manufacturer storehouse, detection
Aggregate sample inanimate matter content 31.87%（Wherein, cyanide content 0.27%）, carbon content 68.13%；Precomminution tails over ＜ to 80 μm
3% powder.
（1）Carbon dioxide charcoal slurry processed：The 50kg aluminium cell carbonaceous waste materials crushed are placed in into the pressure with agitating device to soak
In molten tank, by the use of 75kg liquid carbon dioxide drain tanks in air and as solvent, at 18 DEG C, under 5.7MPa, soak molten 0.5h, obtain matter
Measure the liquid carbon dioxide charcoal slurry of concentration 40%；
（2）Size mixing separation：Set-up procedure（1）The temperature of the liquid carbon dioxide charcoal slurry of gained mass concentration 40% is to 31 DEG C, pressure
To 8MPa so that carbon dioxide is close to gas-liquid critical point, then stands gravity settling separation, obtains inanimate matter component and carbon slurry respectively
Expect component；
（3）Separating-purifying：Respectively by step（2）Gained inanimate matter component and carbon pulp components, it is respectively placed in carbon dioxide point
From in device, at 40 DEG C, normal pressure separation is decompressed to, reclaims carbon dioxide, one-level inanimate matter dry powder is obtained respectively and one-level carbon is done
Powder.
After testing：In one-level inanimate matter dry powder obtained by the present embodiment, inanimate matter content is 86.3%, and carbon content is 13.7 %；
In gained one-level carbon dry powder, carbon content is 97.4 %, and inanimate matter content is 2.6%.
By gained one-level inanimate matter dry powder and one-level carbon dry powder respectively according to step（1）~（3）Reprocessing is once.Its
Differ only in：Step（1）In, one-level inanimate matter dry powder and one-level carbon dry powder are respectively placed in the pressure with agitating device and soaked
In molten tank, by the use of liquid carbon dioxide drain tank in air and be used as solvent, one-level inanimate matter dry powder or one-level carbon dry powder and liquid
The mass ratio of state carbon dioxide is 1:5, at 18 DEG C, under 6.5MPa, molten 0.4h is soaked, obtains the liquid dioxy of mass concentration 16.7%
Change carbon pastes；Yu Tong；Finally, two level inanimate matter dry powder and two level carbon dry powder are separated to obtain respectively.
After testing：After repeated processing, in gained two level inanimate matter dry powder, inanimate matter content is 98.7%, and carbon content is
1.3%；In gained two level carbon dry powder, carbon content 98.6%, inanimate matter content is 1.4%.
By two level carbon dry powder by washing, dry, obtain the carbon raw of carbon content 99.9%.
Step（3）The carbon dioxide of decompression separation recovery utilizes through cooling, compressor compresses liquefaction Posterior circle.
Embodiment 2
Aluminium cell carbonaceous waste material used in the embodiment of the present invention is derived from the block carbonaceous waste material stored up in certain aluminium manufacturer storehouse, detection
Aggregate sample inanimate matter content 30.83%（Wherein, cyanide content 0.17%）, carbon content 69.17%；Precomminution tails over ＜ to 80 μm
12% powder；Oxidant used in the present embodiment is ZC-XJ1 type oxidizing agent solutions（That is ferrate oxidation agent and hypochlorous acid
Salt oxidizing agent is with mass ratio 1:1 saturated solution prepared）；Dispersant used in the present embodiment is ZC-FS3 type liquid dispersants
（That is carbonats compound and surfactant is with mass ratio 1:1 mixture）, it is purchased from Hunan Province little Yin Wuji environment energy
Source Science and Technology Development Co., Ltd..
（1）Carbon dioxide charcoal slurry processed：The 60kg aluminium cell carbonaceous waste materials crushed are placed in into the pressure with agitating device to soak
In molten tank, 0.9kgZC-XJ1 type oxidizing agent solutions are added, ageing 0.5h is stirred evenly, adds 1.2kgZC-FS3 type liquid disperseds
Agent, stir evenly, by the use of 40kg liquid carbon dioxide drain tanks in air and as solvent, at 22 DEG C, under 7.3MPa, soak molten 0.5h, obtain
The liquid carbon dioxide charcoal slurry of mass concentration 60%；
（2）Size mixing separation：By step（1）The liquid carbon dioxide charcoal slurry of gained mass concentration 60% is delivered to charcoal stock pump sizes mixing
In tank, it is 30% to add the mass concentration that liquid carbon dioxide to liquid carbon dioxide charcoal is starched, and adjusts temperature to 35 DEG C so that
Carbon dioxide is close to gas-liquid critical point, then charcoal slurry after being sized mixing with charcoal stock pump is delivered to the centrifugation of pulp separation device, respectively
Obtain inanimate matter component and carbon pulp components；
（3）Separating-purifying：Respectively by step（2）Gained inanimate matter component and carbon pulp components, it is respectively placed in carbon dioxide point
From in device, at 45 DEG C, 4.5MPa separation is decompressed to, reclaims carbon dioxide, obtains inanimate matter dry powder and carbon dry powder respectively.
After testing：In inanimate matter dry powder obtained by the present embodiment, inanimate matter content is 94.3%, carbon content 5.7%；Gained carbon
In plain dry powder, carbon content 98.1%, inanimate matter content is 1.9%.
Step（3）The carbon dioxide of decompression separation recovery utilizes through cooling, compressor compresses liquefaction Posterior circle.
Embodiment 3
Aluminium cell carbonaceous waste material used in the embodiment of the present invention is derived from the block carbonaceous waste material stored up in certain aluminium manufacturer storehouse, detection
Aggregate sample inanimate matter content 30.76%（Wherein, cyanide content 0.21%）, carbon content 69.17%；Using impact crusher, in advance
Crush as particle diameter ＜ 5mm particulate material；Oxidant used in the present embodiment is potassium ferrate, cobaltous perchlorate, calcium hypochlorite are pressed
Mass ratio 2:1:1 powdered oxidant being mixed；Dispersant used in the present embodiment is ZC-FS5 type liquid dispersants（I.e.
Carbonats compound is with ether compound with mass ratio 2:1 mixture）, it is purchased from Hunan Province little Yin Wujis environmental energy science and technology
Development corporation, Ltd..
（1）Carbon dioxide charcoal slurry processed：The 69kg aluminium cell carbonaceous waste materials crushed are placed in into the pressure with agitating device to soak
In molten tank, add 2kg powdered oxidants, stir evenly ageing 1.0h, then by the use of air in 30kg liquid carbon dioxide drain tanks and as
Solvent, 0.75kgZC-FS5 type liquid dispersants are entrained with the liquid carbon dioxide, at 22 DEG C, under 7.0MPa, molten 2h is soaked, obtains
The liquid carbon dioxide charcoal slurry of mass concentration 70%；
（2）Size mixing separation：By step（1）The liquid carbon dioxide charcoal slurry of gained mass concentration 70% is delivered to charcoal stock pump sizes mixing
In tank, adjustment temperature is to 45 DEG C so that carbon dioxide is close to gas-liquid critical point, then charcoal slurry after being sized mixing with charcoal stock pump is delivered to
Pulp separation device centrifuges, and obtains inanimate matter component and carbon pulp components respectively；
（3）Separating-purifying：Respectively by step（2）Gained inanimate matter component and carbon pulp components, it is respectively placed in carbon dioxide point
From in device, at 50 DEG C, 5.5MPa separation is decompressed to, reclaims carbon dioxide, obtains inanimate matter dry powder and carbon dry powder respectively.
After testing：In inanimate matter dry powder obtained by the present embodiment, inanimate matter content is 87.4%%, carbon content 12.6%；Gained
In carbon dry powder, carbon content 97.2%, inanimate matter content is 2.8%.
Step（3）The carbon dioxide of decompression separation recovery utilizes through cooling, compressor compresses liquefaction Posterior circle.
Embodiment 4
Aluminium cell carbonaceous waste material used in the embodiment of the present invention is derived from the block carbonaceous waste material stored up in certain aluminium manufacturer storehouse, detection
Aggregate sample inanimate matter content 31.87%（Wherein, cyanide content 0.3%）, carbon content 68.13%；Precomminution tails over ＜ 3% to 80 μm
Powder；Dispersant used in the present embodiment is ethylene carbonate, 1-METHYLPYRROLIDONE, NPE, two
Propylene Glycol Dimethyl Ether in mass ratio 1:2:1:The liquid dispersant that 1 ratio is mixed.
（1）Carbon dioxide charcoal slurry processed：The 20kg aluminium cell carbonaceous waste materials crushed are placed in into the pressure with agitating device to soak
In molten tank, by the use of 80kg liquid carbon dioxide drain tanks in air and as solvent, be entrained with 2.1kg liquid in the liquid carbon dioxide
State dispersant, at 30 DEG C, under 7.5MPa, molten 0.8h is soaked, obtain the liquid carbon dioxide charcoal slurry of mass concentration 20%；
（2）Size mixing separation：By step（1）The liquid carbon dioxide charcoal slurry of gained mass concentration 20% is delivered to charcoal stock pump sizes mixing
In tank, adjustment temperature is to 32 DEG C so that carbon dioxide is close to gas-liquid critical point, then charcoal slurry after being sized mixing with charcoal stock pump is delivered to
Pulp separation device centrifuges, and obtains inanimate matter component and carbon pulp components respectively；
（3）Separating-purifying：Respectively by step（2）Gained inanimate matter component and carbon pulp components, it is respectively placed in carbon dioxide point
From in device, at 35 DEG C, normal pressure is decompressed to, separates and recovers carbon dioxide, obtains inanimate matter dry powder and carbon dry powder respectively.
After testing：In inanimate matter dry powder obtained by the present embodiment, inanimate matter content is 94.7%, carbon content 5.3%；Gained carbon
In plain dry powder, carbon content 97.9%, inanimate matter content is 2.1%.
Step（3）The carbon dioxide of decompression separation recovery utilizes through cooling, compressor compresses liquefaction Posterior circle.
Embodiment 5
Aluminium cell carbonaceous waste material used in the embodiment of the present invention is derived from the block carbonaceous waste material stored up in certain aluminium manufacturer storehouse, detection
Aggregate sample inanimate matter content 34.76%（Wherein, cyanide content 0.32%）, carbon content 65.24%；Precomminution tails over ＜ to 80 μm
5% powder.
（1）Carbon dioxide charcoal slurry processed：The 35kg aluminium cell carbonaceous waste materials crushed are placed in into the pressure with agitating device to soak
In molten tank, by the use of 6.5kg liquid carbon dioxide drain tanks in air and as solvent, at 15 DEG C, under 5.8MPa, soak molten 1.0h, obtain
The liquid carbon dioxide charcoal slurry of mass concentration 84.3%；
（2）Size mixing separation：By step（1）The liquid carbon dioxide charcoal slurry of gained mass concentration 84.3% is delivered to tune with charcoal stock pump
Starch in tank, it is 40% to add the mass concentration that liquid carbon dioxide to liquid carbon dioxide charcoal is starched, and adjusts temperature to 32 DEG C, is made
Carbon dioxide close to gas-liquid critical point, then chromatography in flowing, respectively inanimate matter component and carbon pulp components；
（3）Separating-purifying：Respectively by step（2）Gained inanimate matter component and carbon pulp components, it is respectively placed in carbon dioxide point
From in device, at 40 DEG C, normal pressure separation is decompressed to, reclaims carbon dioxide, one-level inanimate matter dry powder is obtained respectively and one-level carbon is done
Powder.
After testing：In one-level inanimate matter dry powder obtained by the present embodiment, inanimate matter content is 86.9%, carbon content 13.1%；
In gained one-level carbon dry powder, carbon content is 97.5 %, and inanimate matter content is 2.5%.
By gained one-level inanimate matter dry powder and one-level carbon dry powder respectively according to step（1）~（3）Reprocessing 1 time.Its
Differ only in：Step（1）In, one-level inanimate matter dry powder and one-level carbon dry powder are respectively placed in the pressure with agitating device and soaked
In molten tank, by the use of liquid carbon dioxide drain tank in air and be used as solvent, one-level inanimate matter dry powder or one-level carbon dry powder and liquid
The mass ratio of state carbon dioxide is 1:4, at 18 DEG C, under 6.8MPa, molten 0.3h is soaked, obtains the liquid titanium dioxide of mass concentration 20%
Carbon pastes；Yu Tong；Finally, two level inanimate matter dry powder and two level carbon dry powder are separated to obtain respectively.
After testing：After repeated processing, in gained two level inanimate matter dry powder, inanimate matter content is 99.4%, and carbon content is
0.6 %；In gained two level carbon dry powder, carbon content 99.7%, inanimate matter content is 0.3%.
Step（3）The carbon dioxide of decompression separation recovery utilizes through cooling, compressor compresses liquefaction Posterior circle.
Claims (9)
1. a kind of cleaning recoverying and utilizing method of aluminium cell carbonaceous waste material, it is characterised in that comprise the following steps：
（1）Carbon dioxide charcoal slurry processed：The aluminium cell carbonaceous waste material of crushing is placed in pressure leaching fluid bowl/tank, with overcritical two
In carbon oxide fluid or liquid carbon dioxide drain tank air and as solvent soak it is molten, obtain supercritical carbon dioxide fluid charcoal slurry or
Liquid carbon dioxide charcoal is starched；
（2）Size mixing separation：Set-up procedure（1）Gained supercritical carbon dioxide fluid charcoal is starched or the temperature of liquid carbon dioxide charcoal slurry
And/or pressure, and/or the mass concentration of adjustment supercritical carbon dioxide fluid charcoal slurry or liquid carbon dioxide charcoal slurry so that two
Carbonoxide is close to gas-liquid critical point or supercriticality, then stands chromatography point in gravity settling separation or centrifugation or flowing
From, respectively component and carbon pulp components based on inanimate matter；
（3）Separating-purifying：Respectively by step（2）Component and carbon pulp components based on gained inanimate matter are respectively placed in titanium dioxide
In carbon separation unit, decompression separation recovery carbon dioxide is carried out, obtains inanimate matter raw material and carbon raw.
2. the cleaning recoverying and utilizing method of aluminium cell carbonaceous waste material according to claim 1, it is characterised in that：Step（1）
In, the aluminium cell carbonaceous waste material is 1 with the mass ratio of supercritical carbon dioxide fluid or liquid carbon dioxide:0.15~
9.0。
3. the cleaning recoverying and utilizing method of aluminium cell carbonaceous waste material according to claim 1 or claim 2, it is characterised in that：Step
（1）In, the molten temperature of the leaching is 0~60 DEG C, and it is 3.5~50MPa to soak molten pressure, and it is 0.2~8.0h to soak the molten time.
4. according to the cleaning recoverying and utilizing method of one of claims 1 to 3 aluminium cell carbonaceous waste material, it is characterised in that：
Step（1）In, the main component of the aluminium cell carbonaceous waste material is waste cathode carbon block and/or scrap anode carbon granule, wherein, it is inorganic
Matter content 20~50%, carbon content 50~80%, wherein, in inanimate matter, cyanide content ＜ 2.0%, the gross mass percentage of each composition
Number≤100%；The aluminium cell carbonaceous waste material of the crushing is particle diameter≤5mm bulk goods or 80 μm of powderies for tailing over ＜ 25%
Material.
5. according to the cleaning recoverying and utilizing method of one of Claims 1 to 4 aluminium cell carbonaceous waste material, it is characterised in that：
Step（2）In, the temperature of adjustment supercritical carbon dioxide charcoal slurry or liquid carbon dioxide charcoal slurry is to 30~60 DEG C；Adjust overcritical
Carbon dioxide charcoal is starched or the pressure of liquid carbon dioxide charcoal slurry is to 5~15MPa；It is overcritical by adding liquid carbon dioxide adjustment
Carbon dioxide charcoal is starched or the mass concentration of liquid carbon dioxide charcoal slurry is to 5~60%.
6. according to the cleaning recoverying and utilizing method of one of Claims 1 to 5 aluminium cell carbonaceous waste material, it is characterised in that：
Step（3）In, decompression separation recovery carbon dioxide, the temperature of decompression separation is 30~50 DEG C, and pressure is 0.1013~5.5MPa.
7. according to the cleaning recoverying and utilizing method of one of claim 1~6 aluminium cell carbonaceous waste material, it is characterised in that：
Step（1）In, before supercritical carbon dioxide fluid or liquid carbon dioxide add, successively add oxidant and/or dispersant
Or its solution, and/or when adding supercritical carbon dioxide fluid or liquid carbon dioxide, carry oxidant and/or dispersant secretly
Or its solution；Before being added in supercritical carbon dioxide fluid or liquid carbon dioxide, oxidant and/or dispersant are successively added
Or during its solution, the dosage of the oxidant or its solution is the 0.2~3.0% of carbonaceous waste material quality, after adding oxidant, is stirred
0.3~1.5h of even ageing, the dosage of the dispersant or its solution are the 0.05~5% of carbonaceous waste material quality；Face when surpassing in addition
When boundary's CO 2 fluid or liquid carbon dioxide, when carrying oxidant and/or dispersant or its solution secretly, oxidant or its solution
Dosage be the 0.1~2.0% of supercritical carbon dioxide fluid or liquid carbon dioxide quality, the dosage of dispersant or its solution
For the 0.03~5% of supercritical carbon dioxide fluid or liquid carbon dioxide quality.
8. according to the cleaning recoverying and utilizing method of one of claim 1~7 aluminium cell carbonaceous waste material, it is characterised in that：
The oxidant is chlorosulfonic acid oxidant, ferrate oxidation agent, bichromate oxidant, dichromic acid acid anhydride oxidant, thio sulphur
One in hydrochlorate oxidant, perchlorate oxidizing agents, hypochlorite oxidant, hydroxide oxidant or Chlorine Dioxide Oxidation agent
Kind is several；The ferrate oxidation agent is the one or more in potassium ferrate, ferrate-lithium or Na2Fe04, described heavy
Chromate oxidations agent be potassium bichromate, sodium dichromate or dichromic acid cobalt in one or more, the thiosulfuric acid salt oxidizing agent
For sodium thiosulfate and/or potassium thiosulfate, the perchlorate oxidizing agents are cobaltous perchlorate and/or lithium perchlorate, described time
Chlorate oxidizer is sodium hypochlorite and/or calcium hypochlorite, and the hydroxide oxidant is cobalt hydroxide, iron hydroxide or hydrogen
One or more in potassium oxide；The dispersant is carbonats compound, surfactant, aminated compounds or ethers
One or more in compound；The carbonats compound is ethylene carbonate, propene carbonate, butylene or carbonic acid
One or more in dimethyl ester, the surfactant are in sulfamic acid sodium, sodium alkyl sulfonate or sodium alkyl benzene sulfonate
One or more, the aminated compounds are dimethylformamide and/or 1-METHYLPYRROLIDONE, and the ether compound is second
One or more in glycol ethers, NPE or dimethyl ether.
9. according to the cleaning recoverying and utilizing method of one of claim 1~8 aluminium cell carbonaceous waste material, it is characterised in that：
The oxidant is potassium ferrate, cobaltous perchlorate, calcium hypochlorite in mass ratio 2:1:1 powdered oxidant being mixed；It is described
Dispersant is ethylene carbonate, 1-METHYLPYRROLIDONE, NPE, dimethyl ether in mass ratio 1:2:
1:The liquid dispersant that 1 ratio is mixed.
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| CN113426807A (en) * | 2021-06-29 | 2021-09-24 | 云南云铝润鑫铝业有限公司 | Method for combined treatment and comprehensive utilization of resources of dangerous waste residues generated in aluminum electrolysis |
| CN113426808A (en) * | 2021-06-29 | 2021-09-24 | 云南云铝润鑫铝业有限公司 | Method for recovering fluoride salt from aluminum electrolysis overhaul residues through pressurized alkaline leaching |
| CN115156238A (en) * | 2022-07-12 | 2022-10-11 | 华南理工大学 | Comprehensive recycling method for aluminum electrolysis waste cathode carbon blocks and application thereof |
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- 2017-07-21 CN CN201710599982.4A patent/CN107381534A/en active Pending
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113426807A (en) * | 2021-06-29 | 2021-09-24 | 云南云铝润鑫铝业有限公司 | Method for combined treatment and comprehensive utilization of resources of dangerous waste residues generated in aluminum electrolysis |
| CN113426808A (en) * | 2021-06-29 | 2021-09-24 | 云南云铝润鑫铝业有限公司 | Method for recovering fluoride salt from aluminum electrolysis overhaul residues through pressurized alkaline leaching |
| CN113426808B (en) * | 2021-06-29 | 2022-05-17 | 云南云铝润鑫铝业有限公司 | Method for recovering fluoride salt from aluminum electrolysis overhaul residues through pressurized alkaline leaching |
| CN113426807B (en) * | 2021-06-29 | 2022-05-17 | 云南云铝润鑫铝业有限公司 | Method for combined treatment and comprehensive utilization of resources of dangerous waste residues generated in aluminum electrolysis |
| CN115156238A (en) * | 2022-07-12 | 2022-10-11 | 华南理工大学 | Comprehensive recycling method for aluminum electrolysis waste cathode carbon blocks and application thereof |
| CN115156238B (en) * | 2022-07-12 | 2023-05-30 | 华南理工大学 | Comprehensive recycling method for aluminum electrolysis waste cathode carbon blocks and application thereof |
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Application publication date: 20171124 |