CN106180118B - A kind of method that charcoal in aluminum electrolysis waste cathode is recycled in the acidleach of ultrasonic wave auxiliary pressurized - Google Patents
A kind of method that charcoal in aluminum electrolysis waste cathode is recycled in the acidleach of ultrasonic wave auxiliary pressurized Download PDFInfo
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- CN106180118B CN106180118B CN201610498578.3A CN201610498578A CN106180118B CN 106180118 B CN106180118 B CN 106180118B CN 201610498578 A CN201610498578 A CN 201610498578A CN 106180118 B CN106180118 B CN 106180118B
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- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 58
- 239000002699 waste material Substances 0.000 title claims abstract description 57
- 239000003610 charcoal Substances 0.000 title claims abstract description 56
- 238000000034 method Methods 0.000 title claims abstract description 53
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 29
- 239000000843 powder Substances 0.000 claims abstract description 54
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 52
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 52
- 238000004064 recycling Methods 0.000 claims abstract description 32
- 239000000706 filtrate Substances 0.000 claims abstract description 20
- 238000002425 crystallisation Methods 0.000 claims abstract description 14
- 230000008025 crystallization Effects 0.000 claims abstract description 14
- 238000011084 recovery Methods 0.000 claims abstract description 14
- 239000002253 acid Substances 0.000 claims abstract description 13
- 159000000013 aluminium salts Chemical class 0.000 claims abstract description 12
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims abstract description 12
- 238000002386 leaching Methods 0.000 claims abstract description 12
- 159000000000 sodium salts Chemical class 0.000 claims abstract description 12
- 238000001914 filtration Methods 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 24
- 239000007787 solid Substances 0.000 claims description 17
- 239000002002 slurry Substances 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 8
- 238000000605 extraction Methods 0.000 claims description 4
- 239000012153 distilled water Substances 0.000 claims description 3
- 238000007781 pre-processing Methods 0.000 claims description 3
- 230000001376 precipitating effect Effects 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
- 239000002245 particle Substances 0.000 claims description 2
- 239000011833 salt mixture Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 239000011812 mixed powder Substances 0.000 abstract description 9
- 239000004411 aluminium Substances 0.000 abstract description 6
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 239000002910 solid waste Substances 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 3
- 238000004140 cleaning Methods 0.000 abstract description 2
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- 235000021110 pickles Nutrition 0.000 abstract 1
- 230000035484 reaction time Effects 0.000 description 10
- 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
- 238000005188 flotation Methods 0.000 description 5
- 239000002893 slag Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 239000002920 hazardous waste Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000126 substance 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
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000011449 brick Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000005611 electricity 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
- 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
- 239000010406 cathode material Substances 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000007599 discharging Methods 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
- 230000017074 necrotic cell death Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000007780 powder milling Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000036632 reaction speed Effects 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
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Processing Of Solid Wastes (AREA)
- Electrolytic Production Of Metals (AREA)
Abstract
The present invention relates to the methods of charcoal in a kind of ultrasonic wave auxiliary pressurized acidleach recycling aluminum electrolysis waste cathode, belong to aluminium electroloysis solid waste recovery technology field.The present invention carries out ultrasonic pretreatment after being crushed aluminum electrolysis waste cathode carbon block, pressure leaching in pickle liquor is added in pretreatment powder, and charcoal and filtrate is obtained by filtration, and sodium salt and aluminium salt mixed powder is precipitated in filtrate evaporative crystallization.The present invention realizes the efficient of valuable material in aluminum electrolysis waste cathode carbon block, cleaning, high-purity recycling under ultrasonic pretreatment and pressurized acid leaching synergistic effect.Present invention process is simple, operates conveniently, and reaction rate is fast, does not generate secondary pollution, is suitable for large scale processing aluminum electrolysis waste cathode carbon block.The process time that the present invention entirely recycles charcoal is 60min, and the rate of recovery of charcoal is 95.74%, charcoal powder purity 97.42%.
Description
Technical field
The present invention relates to the methods of charcoal in a kind of ultrasonic wave auxiliary pressurized acidleach recycling aluminum electrolysis waste cathode, belong to aluminium electricity
Solve solid waste recovery technology field.
Background technique
Aluminium is that the important foundation in the metallic element that content is most in the earth's crust and national economy with supporting role is former
Material.Current aluminum production mainly uses Hall-Ai Lu electrolysis process, and new electrolytic cell just needs after using 3~6 years in production process
Stop groove overhaul, the waste and old cathode carbon block of generation is most important solid waste during aluminum electrolysis.Studies have shown that every electricity
Solution one ton of primary aluminum of production can generate 10kg or so waste cathode material.Chinese waste and old cathode discharge amount surpasses 300,000 tons within 2015.
Solvable F in aluminum cell waste cathode—Dissolution rate be about 6000mg/L, CN—Dissolution rate be about 10mg/L~
40mg/L, in far super " hazardous waste judging standard general rule " (2007) " identification 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. containing higher level
Soluble fluoride and cyanide, can be with polluted surface water and underground water；2. discharging toxic gas (NH3, HF, HCN etc.) pollution is big
Gas makes animal skeleton and plant tissue blackening necrosis, influences Agro-ecology balance.
For aluminum cell waste cathode carbon block processing, expert scholar and production line personnel have carried out many-sided spy
Rope research, achieves certain achievement.
Patent CN discloses a kind of aluminium electrolytic tank based on chemical precipitation and redox reaction of 105327933A
Processing method is added in oxidation reaction pond by waste lining after broken, the levigate 1-10mm to granularity；By the 1.2- of theoretical response value
2.0 times of addition liquor natrii hypochloritis, control weakly alkaline pH value 7.0-8.5, and dangerous element cyanide and liquor natrii hypochloritis send out
It gives birth to redox reaction and is removed, the reaction time is 0.5-1.0 hours；By residual after anti-corrosion the screen to filtrate oxidation reaction
Slag is placed in precipitation reaction pond；The limewash that concentration is 0.8-1.0 times of saturated concentration value is added in precipitation reaction pond, is impregnated
Residue 1.0-1.5 hours, it is allowed to the CaF for combining fluoride reaction to generate indissoluble2, pass through anti-corrosion the screen to filtrate after precipitation reaction,
Gained filtrate can be used as the raw material of soda industry and aluminum oxide industry；Final residue after filter, oneself is innoxious through realizing, and can make
Be back to for raw material repair the roads, build, cement, the industries such as fire resisting.
Patent CN102978659A discloses a kind of Deep method of comprehensive utilization of electrolytic cell overhaul slag, special
Sign is, sorts to electrolytic cell overhaul slag, respectively obtains electrolyte block, cathode bar, waste cathode carbon block, useless fire resisting
Brick, useless insulating brick, abolish hot plate, useless bundle paste and remaining mixing slag charge；Water logging is carried out to the block of sorting respectively, is selected
It is crushed again after block, water logging, the block selected recycled, remaining powder milling, flotation, selects carbon dust therein, resistance to
Fiery material powder, remaining powder make metallurgical slag former.
Patent CN101480658A discloses a kind of method for comprehensively utilizing aluminum electrolysis waste cathode carbon block, including following step
It is rapid: (1) waste and old cathode carbon block is broken, ore grinding processing；(2) after ore grinding, the concentration and pH value of ore pulp are adjusted；Then flotation is used
Equipment carries out flotation processing, electrolyte and charcoal in separating waste, worn cathode carbon pieces；(3) carbon obtained by flotation is leached using aluminum salt solution
Electrolyte in product further increases the grade of carbon products；(4) ore grinding waste water, flotation waste water and leachate are mixed, is added
CaO and CaC12Aluminium and fluorine in precipitating recycling mixed liquor.
Be currently adapted for industrial applications about the recovery processing technique of aluminum electrolysis waste cathode carbon block and few, and
There are the drawbacks of also constrain the further genralrlization of technique, these drawbacks mainly include complex process, equipment seriously corroded, valuable
Substance cannot be recycled effectively, processing cost is high, environmental protection pressure is big, high energy consumption and efficiency is low etc..
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of ultrasonic wave auxiliary pressurized acidleach recycling aluminum electrolysis waste cathode
The method of middle charcoal.
The method of charcoal in a kind of ultrasonic wave auxiliary pressurized acidleach recycling aluminum electrolysis waste cathode of the present invention, including following steps
It is rapid:
Step 1
Aluminum cell waste cathode carbon block is crushed, spare powder is obtained；
Step 2
Spare powder and water obtained by step 1 are made into slurry and pass through ultrasonic pretreatment；
Step 3
Material carries out pressurization acid solution leaching after pre-processing described in step 2, filters after leaching, obtains powdered carbon and filtrate；
Step 4
By filtrate evaporative crystallization obtained by step 3, precipitating is generated, is separated by filtration to obtain sodium salt, aluminium salt mixture and distillation
Water, distilled water reuse.
The method of charcoal in a kind of present invention ultrasonic wave auxiliary pressurized acidleach recycling aluminum electrolysis waste cathode, in step 1, institute
Spare powder particle size is stated less than 0.074mm.
The method of charcoal in a kind of present invention ultrasonic wave auxiliary pressurized acidleach recycling aluminum electrolysis waste cathode in step 2, surpasses
Spare powder and water liquid-solid ratio are 1-3:1 in sound wave preprocessing process.
The method of charcoal in a kind of present invention ultrasonic wave auxiliary pressurized acidleach recycling aluminum electrolysis waste cathode, in step 2, institute
It states ultrasonic frequency selection 25-40KHz, preferentially select 40KHz, ultrasonic power 50-600W, preferably 150-300W, ultrasonic wave
Handle time 5-60min, preferably 10-30min.
The method of charcoal in a kind of present invention ultrasonic wave auxiliary pressurized acidleach recycling aluminum electrolysis waste cathode, in step 3, acid
Dipped journey carries out in autoclave；When carrying out pressurization acid solution leaching, control extraction temperature is 100-300 DEG C；Control extraction time
For 30-180min, 30-60min is preferentially selected；It is 5-10:1 that control liquid, which consolidates mass ratio,；Control stirring rate 200-800r/min.
The method of charcoal in a kind of present invention ultrasonic wave auxiliary pressurized acidleach recycling aluminum electrolysis waste cathode, in step 3, institute
It states acid solution solute and is selected from HCl, H2SO4、HNO3、H3PO4At least one of, preferentially select H2SO4.
The method of charcoal in a kind of present invention ultrasonic wave auxiliary pressurized acidleach recycling aluminum electrolysis waste cathode, in step 3, institute
State H in acid solution+Concentration be 1-10mol/L, preferentially select 3-7mol/L.
The method of charcoal in a kind of present invention ultrasonic wave auxiliary pressurized acidleach recycling aluminum electrolysis waste cathode, in step 3, institute
The gas for stating the generation of acidleach process is handled by lye absorption.
The method of charcoal in a kind of present invention ultrasonic wave auxiliary pressurized acidleach recycling aluminum electrolysis waste cathode, in step 4, institute
State 60-90 DEG C of evaporative crystallization temperature, time 60-240min, preferably 180-240min.
The method of charcoal in a kind of ultrasonic wave auxiliary pressurized acidleach recycling aluminum cell waste cathode of the present invention, entire technique
Period is 60min.
The method of charcoal, the rate of recovery of carbon in a kind of ultrasonic wave auxiliary pressurized acidleach recycling aluminum cell waste cathode of the present invention
95.74% is reached as high as, charcoal powder purity 97.42%.
The invention has the following advantages:
1. the ultrasonic pretreatment of appropriate frequency increases the separation of charcoal and other substances in powder, be conducive to acidleach process
Middle soluble substance reacts dissolution with acid, effectively increases acidleach effect.
2. the application of pressure leaching technology, accelerates reaction speed, the reaction time is shortened, improves the pure of product powdered carbon
Degree.
3. sodium salt and aluminium salt is precipitated in acidleach filtrate evaporative crystallization, enter aluminium electroloysis industry after can matching with ice crystal.
In short, the present invention is under the synergistic effect of each technique, the especially application of ultrasonic pretreatment and pressure leaching,
Realize charcoal that is efficient, containing in cleaning recycling aluminum electrolysis waste cathode carbon block.
Specific embodiment
It is described further combined with specific embodiments below, but the present invention is not therefore subject to any restriction.
Embodiment 1
The country certain factory aluminum cell waste cathode carbon block 10g is taken, measuring essential element content is (wt%): C 65.46, Al
9.47、O 6.39、F 7.51、Na 6.28。
Step 1
Aluminum cell waste cathode carbon block is crushed, obtains spare powder, partial size is less than 200 mesh in spare powder；
Step 2
Spare powder obtained by step 1 and water are made into slurry by liquid-solid ratio 2:1, slurry handles 15min in ultrasonic wave,
Ultrasonic frequency 40KHz, power 200W；
Step 3
H is added by liquid-solid ratio 8:1 in ultrasonic pretreatment powder2SO4In the lye of concentration 2mol/L, acidleach process is in height
It is carried out under pressurized conditions in pressure kettle, 180 DEG C of constant temperature, powdered carbon and filter is obtained by filtration in mixing speed 600rpm, reaction time 45min
Liquid obtains the powdered carbon of 6.43g purity 97.42% after dry.
Step 4
Filtrate obtained by step 3 is evaporated crystallization, 90 DEG C of constant temperature, evaporation time 180min, sodium salt is obtained and aluminium salt is mixed
Powder is closed, water circulation use is distilled.
Technique (Step 2: three) time of entire recycling charcoal is 60min (calculating after being crushed), and the rate of recovery of charcoal is
95.74%, charcoal powder purity 97.42%.
Comparative example 1
The country certain factory aluminum cell waste cathode carbon block 10g is taken, measuring essential element content is (wt%): C 65.46, Al
9.47、O 6.39、F 7.51、Na 6.28。
Step 1
Aluminum cell waste cathode carbon block is crushed, obtains spare powder, partial size is less than 200 mesh in spare powder；
Step 2
H is added in spare powder liquid-solid ratio 8:1 obtained by step 12SO4In the lye of concentration 2mol/L, acidleach process is in height
It is carried out under pressurized conditions in pressure kettle, 180 DEG C of constant temperature, powdered carbon and filter is obtained by filtration in mixing speed 600rpm, reaction time 45min
Liquid obtains the powdered carbon of 7.11g purity 87.67% after dry.
Step 3
Filtrate obtained by step 2 is evaporated crystallization, 90 DEG C of constant temperature, evaporation time 180min, sodium salt is obtained and aluminium salt is mixed
Powder is closed, water circulation use is distilled.
Technique (step 2) time of entire recycling charcoal is 45min (calculating after being crushed), and the rate of recovery of charcoal is
95.24%, charcoal powder purity 87.67%.
Comparative example 2
The country certain factory aluminum cell waste cathode carbon block 10g is taken, measuring essential element content is (wt%): C 65.46, Al
9.47、O 6.39、F 7.51、Na 6.28。
Step 1
Aluminum cell waste cathode carbon block is crushed, obtains spare powder, partial size is less than 200 mesh in spare powder；
Step 2
Spare powder obtained by step 1 and water are made into slurry by liquid-solid ratio 2:1, slurry handles 15min in ultrasonic wave,
Ultrasonic frequency 40KHz, power 200W；
Step 3
H is added by liquid-solid ratio 8:1 in ultrasonic pretreatment powder2SO4In the lye of concentration 2mol/L, acidleach process is in water
It is carried out in bath, 100 DEG C of constant temperature, mixing speed 600rpm, reaction time 45min, powdered carbon and filtrate is obtained by filtration, is obtained after dry
To the powdered carbon of 7.14g purity 87.43%.
Step 4
Filtrate obtained by step 3 is evaporated crystallization, 90 DEG C of constant temperature, evaporation time 180min, sodium salt is obtained and aluminium salt is mixed
Powder is closed, water circulation use is distilled.
Technique (Step 2: three) time of entire recycling charcoal is 60min (calculating after being crushed), and the rate of recovery of charcoal is
95.36%, charcoal powder purity 87.43%.
Embodiment 2
The country certain factory aluminum cell waste cathode carbon block 20g is taken, measuring essential element content is (wt%): C 65.46, Al
9.47、O 6.39、F 7.51、Na 6.28。
Step 1
Aluminum cell waste cathode carbon block is crushed, obtains spare powder, partial size is less than 200 mesh in spare powder；
Step 2
Spare powder obtained by step 1 and water are made into slurry by liquid-solid ratio 2:1, slurry handles 20min in ultrasonic wave,
Ultrasonic frequency 40KHz, power 200W；
Step 3
H is added by liquid-solid ratio 10:1 in ultrasonic pretreatment powder2SO4In the lye of concentration 3mol/L, acidleach process is in height
It is carried out under pressurized conditions in pressure kettle, 180 DEG C of constant temperature, powdered carbon and filter is obtained by filtration in mixing speed 800rpm, reaction time 90min
Liquid obtains the powdered carbon of 12.9g purity 97.07% after dry.
Step 4
Filtrate obtained by step 3 is evaporated crystallization, 90 DEG C of constant temperature, evaporation time 120min, sodium salt is obtained and aluminium salt is mixed
Powder is closed, water circulation use is distilled.
Technique (Step 2: three) time of entire recycling charcoal is 110min (calculating after being crushed), and the rate of recovery of charcoal is
95.67%, charcoal powder purity 97.07%.
Embodiment 3
The country certain factory aluminum cell waste cathode carbon block 30g is taken, measuring essential element content is (wt%): C 65.46, Al
9.47、O 6.39、F 7.51、Na 6.28。
Step 1
Aluminum cell waste cathode carbon block is crushed, obtains spare powder, partial size is less than 200 mesh in spare powder；
Step 2
Spare powder obtained by step 1 and water are made into slurry by liquid-solid ratio 1:1, slurry handles 15min in ultrasonic wave,
Ultrasonic frequency 25KHz, power 200W；
Step 3
H is added by liquid-solid ratio 5:1 in ultrasonic pretreatment powder2SO4In the lye of concentration 1mol/L, acidleach process is in height
It is carried out under pressurized conditions in pressure kettle, 100 DEG C of constant temperature, powdered carbon and filter is obtained by filtration in mixing speed 800rpm, reaction time 180min
Liquid obtains the powdered carbon of 19.27g purity 97.32% after dry.
Step 4
Filtrate obtained by step 3 is evaporated crystallization, 90 DEG C of constant temperature, evaporation time 60min, sodium salt is obtained and aluminium salt is mixed
Powder is closed, water circulation use is distilled.
Technique (Step 2: three) time of entire recycling charcoal is 195min (calculating after being crushed), and the rate of recovery of charcoal is
95.49%, charcoal powder purity 97.32%.
Embodiment 4
The country certain factory aluminum cell waste cathode carbon block 10g is taken, measuring essential element content is (wt%): C 68.31, Al
8.14、O 6.55、F 5.27、Na 6.75。
Step 1
Aluminum cell waste cathode carbon block is crushed, obtains spare powder, partial size is less than 200 mesh in spare powder；
Step 2
Spare powder obtained by step 1 and water are made into slurry by liquid-solid ratio 2:1, slurry handles 60min in ultrasonic wave,
Ultrasonic frequency 40KHz, power 80W；
Step 3
H is added by liquid-solid ratio 8:1 in ultrasonic pretreatment powder2SO4In the lye of concentration 0.5mol/L, acidleach process exists
Carried out under pressurized conditions in autoclave, 300 DEG C of constant temperature, mixing speed 200rpm, reaction time 90min, be obtained by filtration powdered carbon and
Filtrate obtains the powdered carbon of 6.7g purity 97.21% after dry.
Step 4
Filtrate obtained by step 3 is evaporated crystallization, 60 DEG C of constant temperature, evaporation time 240min, sodium salt is obtained and aluminium salt is mixed
Powder is closed, water circulation use is distilled.
Technique (Step 2: three) time of entire recycling charcoal is 150min (calculating after being crushed), and the rate of recovery of charcoal is
95.39%, charcoal powder purity 97.21%.
Embodiment 5
The country certain factory aluminum cell waste cathode carbon block 20g is taken, measuring essential element content is (wt%): C 68.31, Al
8.14、O 6.55、F 5.27、Na 6.75。
Step 1
Aluminum cell waste cathode carbon block is crushed, obtains spare powder, partial size is less than 200 mesh in spare powder；
Step 2
Spare powder obtained by step 1 and water are made into slurry by liquid-solid ratio 3:1, slurry handles 50min in ultrasonic wave,
Ultrasonic frequency 25KHz, power 50W；
Step 3
H is added by liquid-solid ratio 7:1 in ultrasonic pretreatment powder2SO4In the lye of concentration 5mol/L, acidleach process is in height
It is carried out under pressurized conditions in pressure kettle, 300 DEG C of constant temperature, powdered carbon and filter is obtained by filtration in mixing speed 600rpm, reaction time 30min
Liquid obtains the powdered carbon of 13.42g purity 97.27% after dry.
Step 4
Filtrate obtained by step 3 is evaporated crystallization, 80 DEG C of constant temperature, evaporation time 180min, sodium salt is obtained and aluminium salt is mixed
Powder is closed, water circulation use is distilled.
Technique (Step 2: three) time of entire recycling charcoal is 80min (calculating after being crushed), and the rate of recovery of charcoal is
95.54%, charcoal powder purity 97.27%.
Embodiment 6
The country certain factory aluminum cell waste cathode carbon block 30g is taken, measuring essential element content is (wt%): C 68.31, Al
8.14、O 6.55、F 5.27、Na 6.75。
Step 1
Aluminum cell waste cathode carbon block is crushed, obtains spare powder, partial size is less than 200 mesh in spare powder；
Step 2
Spare powder obtained by step 1 and water are made into slurry by liquid-solid ratio 3:1, slurry handles 5min in ultrasonic wave, surpasses
Frequency of sound wave 40KHz, power 600W；
Step 3
H is added by liquid-solid ratio 8:1 in ultrasonic pretreatment powder2SO4In the lye of concentration 3mol/L, acidleach process is in height
It is carried out under pressurized conditions in pressure kettle, 180 DEG C of constant temperature, powdered carbon and filter is obtained by filtration in mixing speed 600rpm, reaction time 90min
Liquid obtains the powdered carbon of 20.11g purity 97.33% after dry.
Step 4
Filtrate obtained by step 3 is evaporated crystallization, 90 DEG C of constant temperature, evaporation time 150min, sodium salt is obtained and aluminium salt is mixed
Powder is closed, water circulation use is distilled.
Technique (Step 2: three) time of entire recycling charcoal is 95min (calculating after being crushed), and the rate of recovery of charcoal is
95.5%, charcoal powder purity 97.33%.
Claims (7)
1. a kind of method of charcoal in ultrasonic wave auxiliary pressurized acidleach recycling aluminum electrolysis waste cathode, which is characterized in that including following
Step:
Step 1
Aluminum cell waste cathode carbon block is crushed, spare powder is obtained；
Step 2
Spare powder and water obtained by step 1 are made into slurry and pass through ultrasonic pretreatment；Spare powder during ultrasonic pretreatment
Material is 1-3:1 with water liquid-solid ratio；The ultrasonic frequency selects 25KHz or 40KHz, ultrasonic power 50-600W, at ultrasonic wave
Manage time 5-60min；
Step 3
Material carries out pressurization acid solution leaching after pre-processing described in step 2, filters after leaching, obtains powdered carbon and filtrate；Acidleach
Journey carries out in autoclave；When carrying out pressurization acid solution leaching, control extraction temperature is 100-300 DEG C；Control extraction time is 30-
180min；It is 5-10:1 that control liquid, which consolidates mass ratio,；Control stirring rate 200-800r/min；
Step 4
By filtrate evaporative crystallization obtained by step 3, precipitating is generated, is separated by filtration to obtain sodium salt, aluminium salt mixture and distilled water, steamed
Distilled water reuse.
2. the method for charcoal in a kind of ultrasonic wave auxiliary pressurized acidleach recycling aluminum electrolysis waste cathode according to claim 1；
It is characterized by: the spare powder particle size is less than 0.074mm in step 1.
3. the method for charcoal in a kind of ultrasonic wave auxiliary pressurized acidleach recycling aluminum electrolysis waste cathode according to claim 1；
It is characterized by: acid solution solute is selected from HCl, H in step 32SO4、HNO3、H3PO4At least one of.
4. the method for charcoal in a kind of ultrasonic wave auxiliary pressurized acidleach recycling aluminum electrolysis waste cathode according to claim 1；
It is characterized by: in step 3, H in acid solution+Concentration be 1-10mol/L.
5. the method for charcoal in a kind of ultrasonic wave auxiliary pressurized acidleach recycling aluminum electrolysis waste cathode according to claim 1；
It is characterized by: pressurization acid solution leaches the gas generated and is handled by lye absorption in step 3.
6. the method for charcoal in a kind of ultrasonic wave auxiliary pressurized acidleach recycling aluminum electrolysis waste cathode according to claim 1；
It is characterized by: in step 4, described 60-90 DEG C of evaporative crystallization temperature, time 60-240min.
7. the method for charcoal in a kind of ultrasonic wave auxiliary pressurized acidleach recycling aluminum electrolysis waste cathode according to claim 1；
It is characterized by: carrying out pressurized acid leaching 45min after 15min is ultrasonically treated, the rate of recovery of carbon is up to 95.74%, charcoal powder purity
Up to 97.42%.
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| CN107857263A (en) * | 2017-11-28 | 2018-03-30 | 国家电投集团远达环保催化剂有限公司 | A kind of ultrasonic wave alkali leaching and the method for pressurized acid leaching Combined Treatment electrolytic aluminium waste cathode carbon block |
| WO2021143887A1 (en) * | 2020-01-19 | 2021-07-22 | 中南大学 | Method for recycling waste cathode carbon blocks of aluminum electrolysis |
| CN112322076B (en) * | 2020-11-04 | 2021-10-01 | 中南大学 | Method for preparing carbon black |
| 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 |
| CN114749465B (en) * | 2022-05-02 | 2023-07-11 | 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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| CN101386017B (en) * | 2008-10-17 | 2010-06-16 | 东北大学 | Method for treating aluminum electrolysis waste cathode carbon block using acid and alkali combination method |
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