CN106180118A - A kind of ultrasonic assistant pressurized acid leaching reclaims the method for charcoal in aluminum electrolysis waste cathode - Google Patents
A kind of ultrasonic assistant pressurized acid leaching reclaims the method for charcoal in aluminum electrolysis waste cathode Download PDFInfo
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- CN106180118A CN106180118A CN201610498578.3A CN201610498578A CN106180118A CN 106180118 A CN106180118 A CN 106180118A CN 201610498578 A CN201610498578 A CN 201610498578A CN 106180118 A CN106180118 A CN 106180118A
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- charcoal
- waste cathode
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- acid leaching
- aluminum electrolysis
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- 238000000034 method Methods 0.000 title claims abstract description 70
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 61
- 239000002699 waste material Substances 0.000 title claims abstract description 60
- 239000003610 charcoal Substances 0.000 title claims abstract description 48
- 239000002253 acid Substances 0.000 title claims abstract description 38
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 238000002386 leaching Methods 0.000 title claims abstract description 38
- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 31
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 63
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 63
- 239000000843 powder Substances 0.000 claims abstract description 52
- 239000000706 filtrate Substances 0.000 claims abstract description 18
- 238000002425 crystallisation Methods 0.000 claims abstract description 14
- 230000008025 crystallization Effects 0.000 claims abstract description 14
- 159000000013 aluminium salts Chemical class 0.000 claims abstract description 12
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims abstract description 12
- 159000000000 sodium salts Chemical class 0.000 claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 24
- 239000007787 solid Substances 0.000 claims description 19
- 239000002002 slurry Substances 0.000 claims description 16
- 239000012153 distilled water Substances 0.000 claims description 11
- 239000003513 alkali Substances 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 10
- 238000002604 ultrasonography Methods 0.000 claims description 9
- 238000001556 precipitation Methods 0.000 claims description 7
- 238000000605 extraction Methods 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 238000010521 absorption reaction Methods 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 239000011833 salt mixture Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 238000011084 recovery Methods 0.000 abstract description 13
- 238000005516 engineering process Methods 0.000 abstract description 4
- 239000002910 solid waste Substances 0.000 abstract description 4
- 239000004411 aluminium Substances 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 238000004140 cleaning Methods 0.000 abstract description 2
- 239000011812 mixed powder Substances 0.000 abstract 1
- 235000021110 pickles Nutrition 0.000 abstract 1
- 238000002156 mixing Methods 0.000 description 9
- 238000001704 evaporation Methods 0.000 description 8
- 230000008020 evaporation Effects 0.000 description 8
- 239000011734 sodium Substances 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- 239000007788 liquid Substances 0.000 description 6
- 238000005188 flotation Methods 0.000 description 5
- 239000002893 slag Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 239000002920 hazardous waste Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- 239000011449 brick Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 230000009970 fire resistant effect Effects 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 238000009288 screen filtration Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- -1 build Substances 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 229910001610 cryolite Inorganic materials 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 230000032696 parturition Effects 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
-
- 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
- C25C3/12—Anodes
- C25C3/125—Anodes based on carbon
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Processing Of Solid Wastes (AREA)
- Electrolytic Production Of Metals (AREA)
Abstract
The present invention relates to a kind of ultrasonic assistant pressurized acid leaching and reclaim the method for charcoal in aluminum electrolysis waste cathode, belong to aluminium electroloysis solid waste recovery technology field.The present invention carries out ultrasonic pretreatment after broken for aluminum electrolysis waste cathode carbon block, and pretreatment powder adds pressure leaching in pickle liquor, is filtrated to get charcoal and filtrate, and filtrate evaporative crystallization separates out sodium salt and aluminium salt mixed powder.The present invention achieves efficient, cleaning, the high-purity of valuable material in aluminum electrolysis waste cathode carbon block under ultrasonic pretreatment and pressurized acid leaching synergism and reclaims.Present invention process is simple, and operation is convenient, and reaction rate is fast, does not produce secondary pollution, is suitable to extensive process aluminum electrolytic waste and old cathode carbon block.The process time of the present invention whole recovery charcoal is 60min, and the response rate of charcoal is 95.74%, powdered carbon purity 97.42%.
Description
Technical field
The present invention relates to a kind of ultrasonic assistant pressurized acid leaching and reclaim the method for charcoal in aluminum electrolysis waste cathode, belong to aluminum electricity
Solve solid waste recovery technology field.
Background technology
Aluminum is the metallic element that in the earth's crust, content is most, is also that to have the important foundation of supporting role in national economy former
Material.Current aluminum production mainly uses Hall-Ai Lu electrolysis process, and in production process, new electrolysis bath is accomplished by after using 3～6 years
Stopping groove overhaul, the waste and old cathode carbon block of generation is topmost solid waste during aluminum electrolysis.Research shows, often electricity
Solve one ton of primary aluminum of production and can produce about 10kg waste cathode material.Within 2015, Chinese waste and old cathode discharge capacity surpasses 300,000 tons.
Solvable F in aluminum cell waste cathode—Dissolution rate be about 6000mg/L, CN—Dissolution rate be about 10mg/L～
40mg/L, in remote super " hazardous waste judging standard general rule " (2007) " discriminating of hazardous waste judging standard corrosivity "
(GB5085.1-2007) F and in " hazardous waste judging standard leaching characteristic identification " (GB5085.3-2007)—And CN—Leach mark
Standard, belongs to dangerous solid waste.Waste and old cathode is very big to ecological environment harm, is mainly manifested in: 1. contain higher level
Soluble fluoride and cyanide, can be with polluted surface water and subsoil water；2. toxic gas (NH is discharged3, HF, HCN etc.) pollute big
Gas, makes animal skeleton and plant tissue blackening downright bad, affects Agro-ecology balance.
Processing for aluminum cell waste cathode carbon block, expert scholar and production line personnel have carried out many-sided spy
Rope is studied, and achieves certain achievement.
Patent CN discloses 105327933A chemically based precipitation and the aluminium electrolytic tank of redox reaction
Processing method, waste lining is broken, levigate to granularity 1-10mm, add in oxidation reaction pond；1.2-by theoretical response value
2.0 times add liquor natrii hypochloritis, control weakly alkaline pH value 7.0-8.5, and dangerous element cyanide is sent out with liquor natrii hypochloritis
Giving birth to redox reaction and be removed, the response time is 0.5-1.0 hour；Residual by after anticorrosion screen filtration oxidation reaction
Slag, is placed in precipitation pond；The lime water that concentration is saturated concentration value 0.8-1.0 times is added in precipitation pond, soaks
Residue 1.0-1.5 hour, is allowed to combine fluoride reaction and generates the CaF of indissoluble2, by anticorrosion screen filtration after precipitation,
Gained filtrate can be as soda industry and the raw material of aluminum oxide industry；Final residue after filter, oneself is innoxious through achieving, and can make
Be back to repair the roads for raw material, build, cement, the industry such as fire-resistant.
Patent CN102978659A discloses the Deep method of comprehensive utilization of a kind of electrolytic cell overhaul slag, and it is special
Levy and be, electrolytic cell overhaul slag is sorted, respectively obtain electrolyte block, cathode bar, waste cathode carbon block, useless fire-resistant
Brick, useless insulating brick, useless heat-insulating shield, useless bundle are stuck with paste, and remaining mixing slag charge；The block of sorting is carried out water logging respectively, selects
Broken, water logging again after block, the block selected reclaims, remaining powder pulverizing, flotation, selects carbon dust therein, resistance to
Fire material powder, remaining powder makes metallurgical slag former.
Patent CN101480658A discloses a kind of method comprehensively utilizing aluminum electrolysis waste cathode carbon block, including following step
Rapid: (1) is broken by waste and old cathode carbon block, ore grinding processes；(2) after ore grinding, the concentration of regulation ore pulp and pH value；Then flotation is used
Equipment carries out flotation process, the electrolyte in separating waste, worn cathode carbon pieces and charcoal；(3) aluminum salt solution is used to leach flotation gained carbon
Electrolyte in product, improves the grade of carbon products further；(4) ore grinding waste water, flotation waste water and leachate are mixed, add
CaO and CaC12Precipitation reclaims the aluminum in mixed liquor and fluorine.
The recovery processing technique about aluminum electrolysis waste cathode carbon block being currently adapted for industrial applications is the most few, and
The drawback existed also constrains the further genralrlization of technique, and these drawbacks mainly include that complex process, equipment corrosion are serious, have valency
Material can not efficient recovery, processing cost is high, environmental protection pressure is big, energy consumption is high, efficiency is low.
Summary of the invention
For the deficiencies in the prior art, the present invention provides a kind of ultrasonic assistant pressurized acid leaching to reclaim aluminum electrolysis waste cathode
The method of middle charcoal.
The present invention a kind of ultrasonic assistant pressurized acid leaching reclaims the method for charcoal in aluminum electrolysis waste cathode, including following step
Rapid:
Step one
Aluminum cell waste cathode carbon block is crushed, obtains standby powder；
Step 2
Standby for step one gained powder and water are made into slurry and pass through ultrasonic pretreatment；
Step 3
Material after pretreatment described in step 2 is carried out acid solution leaching of pressurizeing, filters after leaching, obtain powdered carbon and filtrate；
Step 4
By step 3 gained filtrate evaporative crystallization, produce precipitation, filter isolated sodium salt, aluminium salt mixture and distillation
Water, distilled water reuse.
The present invention a kind of ultrasonic assistant pressurized acid leaching reclaims the method for charcoal in aluminum electrolysis waste cathode, in step one, institute
State standby powder particle size less than 0.074mm.
The present invention a kind of ultrasonic assistant pressurized acid leaching reclaims the method for charcoal in aluminum electrolysis waste cathode, in step 2, super
In sound wave preprocessing process, standby powder and water liquid-solid ratio are 1-3:1.
The present invention a kind of ultrasonic assistant pressurized acid leaching reclaims the method for charcoal in aluminum electrolysis waste cathode, in step 2, institute
State ultrasonic frequency and select 25-40KHz, prioritizing selection 40KHz, ultrasonic power 50-600W, preferred 150-300W, ultrasound wave
Process time 5-60min, preferred 10-30min.
The present invention a kind of ultrasonic assistant pressurized acid leaching reclaims the method for charcoal in aluminum electrolysis waste cathode, in step 3, acid
Dipped journey is carried out in autoclave；When carrying out pressurization acid solution leaching, control extraction temperature and be 100-300 DEG C；Control extraction time
For 30-180min, prioritizing selection 30-60min；Controlling liquid-solid mass ratio is 5-10:1；Control stir speed (S.S.) 200-800r/min.
The present invention a kind of ultrasonic assistant pressurized acid leaching reclaims the method for charcoal in aluminum electrolysis waste cathode, in step 3, institute
State acid solution solute selected from HCl, H2SO4、HNO3、H3PO4In at least one, prioritizing selection H2SO4.
The present invention a kind of ultrasonic assistant pressurized acid leaching reclaims the method for charcoal in aluminum electrolysis waste cathode, in step 3, institute
State H in acid solution+Concentration be 1-10mol/L, prioritizing selection 3-7mol/L.
The present invention a kind of ultrasonic assistant pressurized acid leaching reclaims the method for charcoal in aluminum electrolysis waste cathode, in step 3, institute
The gas stating the generation of acidleach process is processed by alkali liquor absorption.
The present invention a kind of ultrasonic assistant pressurized acid leaching reclaims the method for charcoal in aluminum electrolysis waste cathode, in step 4, institute
State evaporative crystallization temperature 60-90 DEG C, time 60-240min, preferred 180-240min.
The present invention a kind of ultrasonic assistant pressurized acid leaching reclaims the method for charcoal in aluminum cell waste cathode, whole technique
Cycle is 60min.
The present invention a kind of ultrasonic assistant pressurized acid leaching reclaims the method for charcoal, the response rate of carbon in aluminum cell waste cathode
Reach as high as 95.74%, powdered carbon purity 97.42%.
The method have the advantages that
1. the ultrasonic pretreatment of appropriate frequency increases charcoal and the separation of other materials, beneficially acidleach process in powder
Middle soluble substance dissolves with acid reaction, is effectively increased acidleach effect.
2. the application of pressure leaching technology, accelerates response speed, shortens the response time, improves the pure of product powdered carbon
Degree.
3. acidleach filtrate evaporative crystallization separates out sodium salt and aluminium salt, can enter aluminium electroloysis industry after cryolite proportioning.
In a word, the present invention under the synergism of each technique, especially ultrasonic pretreatment and the application of pressure leaching,
Achieve efficiently, cleaning reclaim the charcoal contained in aluminum electrolysis waste cathode carbon block.
Detailed description of the invention
It is described further below in conjunction with specific embodiment, but the present invention is not therefore subject to any restriction.
Embodiment 1
Taking domestic certain factory aluminum cell waste cathode carbon block 10g, recording essential element content is (wt%): C 65.46, Al
9.47、O 6.39、F 7.51、Na 6.28。
Step one
Being crushed by aluminum cell waste cathode carbon block, obtain standby powder, in standby powder, particle diameter is less than 200 mesh；
Step 2
By liquid-solid ratio 2:1, standby for step one gained powder and water are made into slurry, and slurry processes 15min in ultrasound wave,
Ultrasonic frequency 40KHz, power 200W；
Step 3
Ultrasonic pretreatment powder is added H by liquid-solid ratio 8:12SO4In the alkali liquor of concentration 2mol/L, acidleach process is at height
Pressure still is carried out under pressurized conditions, constant temperature 180 DEG C, mixing speed 600rpm, response time 45min, be filtrated to get powdered carbon and filter
Liquid, obtains the powdered carbon of 6.43g purity 97.42% after drying.
Step 4
Step 3 gained filtrate is evaporated crystallization, constant temperature 90 DEG C, evaporation time 180min, obtains sodium salt and aluminium salt is mixed
Closing powder body, distilled water recycles.
The technique of whole recovery charcoal (step 2, the three) time is 60min (calculating after broken), and the response rate of its charcoal is
95.74%, powdered carbon purity 97.42%.
Comparative example 1
Taking domestic certain factory aluminum cell waste cathode carbon block 10g, recording essential element content is (wt%): C 65.46, Al
9.47、O 6.39、F 7.51、Na 6.28。
Step one
Being crushed by aluminum cell waste cathode carbon block, obtain standby powder, in standby powder, particle diameter is less than 200 mesh；
Step 2
Standby for step one gained powder liquid-solid ratio 8:1 is added H2SO4In the alkali liquor of concentration 2mol/L, acidleach process is at height
Pressure still is carried out under pressurized conditions, constant temperature 180 DEG C, mixing speed 600rpm, response time 45min, be filtrated to get powdered carbon and filter
Liquid, obtains the powdered carbon of 7.11g purity 87.67% after drying.
Step 3
Step 2 gained filtrate is evaporated crystallization, constant temperature 90 DEG C, evaporation time 180min, obtains sodium salt and aluminium salt is mixed
Closing powder body, distilled water recycles.
Technique (step 2) time of whole recovery charcoal is 45min (calculating after broken), and the response rate of its charcoal is
95.24%, powdered carbon purity 87.67%.
Comparative example 2
Taking domestic certain factory aluminum cell waste cathode carbon block 10g, recording essential element content is (wt%): C 65.46, Al
9.47、O 6.39、F 7.51、Na 6.28。
Step one
Being crushed by aluminum cell waste cathode carbon block, obtain standby powder, in standby powder, particle diameter is less than 200 mesh；
Step 2
By liquid-solid ratio 2:1, standby for step one gained powder and water are made into slurry, and slurry processes 15min in ultrasound wave,
Ultrasonic frequency 40KHz, power 200W；
Step 3
Ultrasonic pretreatment powder is added H by liquid-solid ratio 8:12SO4In the alkali liquor of concentration 2mol/L, acidleach process is at water
Bath is carried out, constant temperature 100 DEG C, mixing speed 600rpm, response time 45min, be filtrated to get powdered carbon and filtrate, dried
Powdered carbon to 7.14g purity 87.43%.
Step 4
Step 3 gained filtrate is evaporated crystallization, constant temperature 90 DEG C, evaporation time 180min, obtains sodium salt and aluminium salt is mixed
Closing powder body, distilled water recycles.
The technique of whole recovery charcoal (step 2, the three) time is 60min (calculating after broken), and the response rate of its charcoal is
95.36%, powdered carbon purity 87.43%.
Embodiment 2
Taking domestic certain factory aluminum cell waste cathode carbon block 20g, recording essential element content is (wt%): C 65.46, Al
9.47、O 6.39、F 7.51、Na 6.28。
Step one
Being crushed by aluminum cell waste cathode carbon block, obtain standby powder, in standby powder, particle diameter is less than 200 mesh；
Step 2
By liquid-solid ratio 2:1, standby for step one gained powder and water are made into slurry, and slurry processes 20min in ultrasound wave,
Ultrasonic frequency 40KHz, power 200W；
Step 3
Ultrasonic pretreatment powder is added H by liquid-solid ratio 10:12SO4In the alkali liquor of concentration 3mol/L, acidleach process is at height
Pressure still is carried out under pressurized conditions, constant temperature 180 DEG C, mixing speed 800rpm, response time 90min, be filtrated to get powdered carbon and filter
Liquid, obtains the powdered carbon of 12.9g purity 97.07% after drying.
Step 4
Step 3 gained filtrate is evaporated crystallization, constant temperature 90 DEG C, evaporation time 120min, obtains sodium salt and aluminium salt is mixed
Closing powder body, distilled water recycles.
The technique of whole recovery charcoal (step 2, the three) time is 110min (calculating after broken), and the response rate of its charcoal is
95.67%, powdered carbon purity 97.07%.
Embodiment 3
Taking domestic certain factory aluminum cell waste cathode carbon block 30g, recording essential element content is (wt%): C 65.46, Al
9.47、O 6.39、F 7.51、Na 6.28。
Step one
Being crushed by aluminum cell waste cathode carbon block, obtain standby powder, in standby powder, particle diameter is less than 200 mesh；
Step 2
By liquid-solid ratio 1:1, standby for step one gained powder and water are made into slurry, and slurry processes 15min in ultrasound wave,
Ultrasonic frequency 25KHz, power 200W；
Step 3
Ultrasonic pretreatment powder is added H by liquid-solid ratio 5:12SO4In the alkali liquor of concentration 1mol/L, acidleach process is at height
Pressure still is carried out under pressurized conditions, constant temperature 100 DEG C, mixing speed 800rpm, response time 180min, be filtrated to get powdered carbon and filter
Liquid, obtains the powdered carbon of 19.27g purity 97.32% after drying.
Step 4
Step 3 gained filtrate is evaporated crystallization, constant temperature 90 DEG C, evaporation time 60min, obtains sodium salt and aluminium salt is mixed
Closing powder body, distilled water recycles.
The technique of whole recovery charcoal (step 2, the three) time is 195min (calculating after broken), and the response rate of its charcoal is
95.49%, powdered carbon purity 97.32%.
Embodiment 4
Taking domestic certain factory aluminum cell waste cathode carbon block 10g, recording essential element content is (wt%): C 68.31, Al
8.14、O 6.55、F 5.27、Na 6.75。
Step one
Being crushed by aluminum cell waste cathode carbon block, obtain standby powder, in standby powder, particle diameter is less than 200 mesh；
Step 2
By liquid-solid ratio 2:1, standby for step one gained powder and water are made into slurry, and slurry processes 60min in ultrasound wave,
Ultrasonic frequency 40KHz, power 80W；
Step 3
Ultrasonic pretreatment powder is added H by liquid-solid ratio 8:12SO4In the alkali liquor of concentration 0.5mol/L, acidleach process exists
Autoclave is carried out under pressurized conditions, constant temperature 300 DEG C, mixing speed 200rpm, response time 90min, be filtrated to get powdered carbon and
Filtrate, obtains the powdered carbon of 6.7g purity 97.21% after drying.
Step 4
Step 3 gained filtrate is evaporated crystallization, constant temperature 60 DEG C, evaporation time 240min, obtains sodium salt and aluminium salt is mixed
Closing powder body, distilled water recycles.
The technique of whole recovery charcoal (step 2, the three) time is 150min (calculating after broken), and the response rate of its charcoal is
95.39%, powdered carbon purity 97.21%.
Embodiment 5
Taking domestic certain factory aluminum cell waste cathode carbon block 20g, recording essential element content is (wt%): C 68.31, Al
8.14、O 6.55、F 5.27、Na 6.75。
Step one
Being crushed by aluminum cell waste cathode carbon block, obtain standby powder, in standby powder, particle diameter is less than 200 mesh；
Step 2
By liquid-solid ratio 3:1, standby for step one gained powder and water are made into slurry, and slurry processes 50min in ultrasound wave,
Ultrasonic frequency 25KHz, power 50W；
Step 3
Ultrasonic pretreatment powder is added H by liquid-solid ratio 7:12SO4In the alkali liquor of concentration 5mol/L, acidleach process is at height
Pressure still is carried out under pressurized conditions, constant temperature 300 DEG C, mixing speed 600rpm, response time 30min, be filtrated to get powdered carbon and filter
Liquid, obtains the powdered carbon of 13.42g purity 97.27% after drying.
Step 4
Step 3 gained filtrate is evaporated crystallization, constant temperature 80 DEG C, evaporation time 180min, obtains sodium salt and aluminium salt is mixed
Closing powder body, distilled water recycles.
The technique of whole recovery charcoal (step 2, the three) time is 80min (calculating after broken), and the response rate of its charcoal is
95.54%, powdered carbon purity 97.27%.
Embodiment 6
Taking domestic certain factory aluminum cell waste cathode carbon block 30g, recording essential element content is (wt%): C 68.31, Al
8.14、O 6.55、F 5.27、Na 6.75。
Step one
Being crushed by aluminum cell waste cathode carbon block, obtain standby powder, in standby powder, particle diameter is less than 200 mesh；
Step 2
By liquid-solid ratio 3:1, standby for step one gained powder and water are made into slurry, and slurry processes 5min in ultrasound wave, super
Frequency of sound wave 40KHz, power 600W；
Step 3
Ultrasonic pretreatment powder is added H by liquid-solid ratio 8:12SO4In the alkali liquor of concentration 3mol/L, acidleach process is at height
Pressure still is carried out under pressurized conditions, constant temperature 180 DEG C, mixing speed 600rpm, response time 90min, be filtrated to get powdered carbon and filter
Liquid, obtains the powdered carbon of 20.11g purity 97.33% after drying.
Step 4
Step 3 gained filtrate is evaporated crystallization, constant temperature 90 DEG C, evaporation time 150min, obtains sodium salt and aluminium salt is mixed
Closing powder body, distilled water recycles.
The technique of whole recovery charcoal (step 2, the three) time is 95min (calculating after broken), and the response rate of its charcoal is
95.5%, powdered carbon purity 97.33%.
Claims (10)
1. a ultrasonic assistant pressurized acid leaching reclaims the method for charcoal in aluminum electrolysis waste cathode, it is characterised in that include following
Step:
Step one
Aluminum cell waste cathode carbon block is crushed, obtains standby powder；
Step 2
Standby for step one gained powder and water are made into slurry and pass through ultrasonic pretreatment；
Step 3
Material after pretreatment described in step 2 is carried out acid solution leaching of pressurizeing, filters after leaching, obtain powdered carbon and filtrate；
Step 4
By step 3 gained filtrate evaporative crystallization, produce precipitation, filter isolated sodium salt, aluminium salt mixture and distilled water, steam
Distilled water reuse.
A kind of ultrasonic assistant pressurized acid leaching the most according to claim 1 reclaims the method for charcoal in aluminum electrolysis waste cathode；
It is characterized in that: in step one, described standby powder particle size is less than 0.074mm.
A kind of ultrasonic assistant pressurized acid leaching the most according to claim 2 reclaims the method for charcoal in aluminum electrolysis waste cathode；
It is characterized in that: in step 2, during ultrasonic pretreatment, standby powder and water liquid-solid ratio are 1-3:1.
A kind of ultrasonic assistant pressurized acid leaching the most according to claim 3 reclaims the method for charcoal in aluminum electrolysis waste cathode；
It is characterized in that: in step 2, described ultrasonic frequency selects 25KHz or 40KHz, and ultrasonic power 50-600W, at ultrasound wave
Reason time 5-60min.
A kind of ultrasonic assistant pressurized acid leaching the most according to claim 4 reclaims the method for charcoal in aluminum electrolysis waste cathode；
It is characterized in that: in step 3, acidleach process is carried out in autoclave；When carrying out pressurization acid solution leaching, controlling extraction temperature is
100-300℃；Control extraction time is 30-180min；Controlling liquid-solid mass ratio is 5-10:1；Control stir speed (S.S.) 200-
800r/min。
A kind of ultrasonic assistant pressurized acid leaching the most according to claim 5 reclaims the method for charcoal in aluminum electrolysis waste cathode；
It is characterized in that: in step 3, described acid solution solute is selected from HCl, H2SO4、HNO3、H3PO4In at least one.
A kind of ultrasonic assistant pressurized acid leaching the most according to claim 6 reclaims the method for charcoal in aluminum electrolysis waste cathode；
It is characterized in that: in step 3, H in described acid solution+Concentration be 1-10mol/L.
A kind of ultrasonic assistant pressurized acid leaching the most according to claim 7 reclaims the method for charcoal in aluminum electrolysis waste cathode；
It is characterized in that: in step 3, the gas that described acidleach process produces is processed by alkali liquor absorption.
A kind of ultrasonic assistant pressurized acid leaching the most according to claim 8 reclaims the method for charcoal in aluminum electrolysis waste cathode；
It is characterized in that: in step 4, described evaporative crystallization temperature 60-90 DEG C, time 60-240min.
A kind of ultrasonic assistant pressurized acid leaching the most according to claim 9 reclaims the side of charcoal in aluminum cell waste cathode
Method；It is characterized in that: carry out pressurized acid leaching 45min after 15min supersound process, the response rate of carbon is up to 95.74%, powdered carbon
Purity reaches 97.42%.
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| CN114749465A (en) * | 2022-05-02 | 2022-07-15 | 郑州大学 | Method for purifying aluminum electrolysis waste cathode carbon and preparing porous carbon adsorbent |
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| 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 |
| CN114749465A (en) * | 2022-05-02 | 2022-07-15 | 郑州大学 | Method for purifying aluminum electrolysis waste cathode carbon and preparing porous carbon adsorbent |
| CN116022835A (en) * | 2023-02-21 | 2023-04-28 | 贵州师范大学 | Recycling treatment method of aluminum electrolysis carbon-containing hazardous waste |
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