CN107088570A - A kind of processing method of aluminium electroloysis waste refractory materials - Google Patents
A kind of processing method of aluminium electroloysis waste refractory materials Download PDFInfo
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- CN107088570A CN107088570A CN201710228178.5A CN201710228178A CN107088570A CN 107088570 A CN107088570 A CN 107088570A CN 201710228178 A CN201710228178 A CN 201710228178A CN 107088570 A CN107088570 A CN 107088570A
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- refractory materials
- processing method
- waste refractory
- filtrate
- aluminium electroloysis
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- 239000011819 refractory material Substances 0.000 title claims abstract description 79
- 239000002699 waste material Substances 0.000 title claims abstract description 73
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 72
- 239000004411 aluminium Substances 0.000 title claims abstract description 71
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 238000003672 processing method Methods 0.000 title claims abstract description 48
- 239000000706 filtrate Substances 0.000 claims abstract description 67
- 238000006243 chemical reaction Methods 0.000 claims abstract description 64
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims abstract description 54
- 238000000034 method Methods 0.000 claims abstract description 47
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims abstract description 40
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 37
- 239000011737 fluorine Substances 0.000 claims abstract description 37
- 239000002253 acid Substances 0.000 claims abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 32
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims abstract description 32
- 239000000843 powder Substances 0.000 claims abstract description 27
- 239000000463 material Substances 0.000 claims abstract description 26
- 238000001914 filtration Methods 0.000 claims abstract description 23
- 238000012545 processing Methods 0.000 claims abstract description 19
- 239000002002 slurry Substances 0.000 claims abstract description 16
- 239000011775 sodium fluoride Substances 0.000 claims abstract description 16
- 235000013024 sodium fluoride Nutrition 0.000 claims abstract description 16
- 238000002425 crystallisation Methods 0.000 claims abstract description 14
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000009491 slugging Methods 0.000 claims abstract description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 31
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 30
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 26
- 230000035484 reaction time Effects 0.000 claims description 20
- 239000000047 product Substances 0.000 claims description 15
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 13
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical group [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 12
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims description 12
- 230000008025 crystallization Effects 0.000 claims description 11
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 7
- 239000011575 calcium Substances 0.000 claims description 7
- 229910052791 calcium Inorganic materials 0.000 claims description 7
- 239000012445 acidic reagent Substances 0.000 claims description 6
- 239000000292 calcium oxide Substances 0.000 claims description 6
- 235000012255 calcium oxide Nutrition 0.000 claims description 6
- 239000003153 chemical reaction reagent Substances 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- ZKQDCIXGCQPQNV-UHFFFAOYSA-N Calcium hypochlorite Chemical compound [Ca+2].Cl[O-].Cl[O-] ZKQDCIXGCQPQNV-UHFFFAOYSA-N 0.000 claims description 5
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 5
- 239000007844 bleaching agent Substances 0.000 claims description 5
- 238000001704 evaporation Methods 0.000 claims description 5
- 230000008020 evaporation Effects 0.000 claims description 5
- 239000012065 filter cake Substances 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000004571 lime Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 238000006386 neutralization reaction Methods 0.000 claims description 5
- 239000012286 potassium permanganate Substances 0.000 claims description 5
- -1 calcirm-fluoride Chemical class 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 claims description 3
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 claims description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 3
- 239000001110 calcium chloride Substances 0.000 claims description 3
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 claims description 3
- 229910001635 magnesium fluoride Inorganic materials 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 238000004458 analytical method Methods 0.000 claims 1
- 238000004064 recycling Methods 0.000 abstract description 20
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 abstract description 3
- 150000002500 ions Chemical class 0.000 description 18
- 238000003756 stirring Methods 0.000 description 14
- 239000002893 slag Substances 0.000 description 12
- 230000002940 repellent Effects 0.000 description 10
- 239000005871 repellent Substances 0.000 description 10
- 229960002050 hydrofluoric acid Drugs 0.000 description 8
- 238000003801 milling Methods 0.000 description 6
- 238000002203 pretreatment Methods 0.000 description 6
- 238000011017 operating method Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 4
- 230000001698 pyrogenic effect Effects 0.000 description 3
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000003682 fluorination reaction Methods 0.000 description 2
- 239000002920 hazardous waste Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- OQVYMXCRDHDTTH-UHFFFAOYSA-N 4-(diethoxyphosphorylmethyl)-2-[4-(diethoxyphosphorylmethyl)pyridin-2-yl]pyridine Chemical compound CCOP(=O)(OCC)CC1=CC=NC(C=2N=CC=C(CP(=O)(OCC)OCC)C=2)=C1 OQVYMXCRDHDTTH-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 210000000476 body water Anatomy 0.000 description 1
- 150000001669 calcium Chemical class 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 150000002680 magnesium Chemical class 0.000 description 1
- 238000003913 materials processing Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000001473 noxious effect 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
- 238000001556 precipitation Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000003643 water by type 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
- B09B3/80—Destroying solid waste or transforming solid waste into something useful or harmless involving an extraction step
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B5/00—Operations not covered by a single other subclass or by a single other group in this subclass
Landscapes
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Processing Of Solid Wastes (AREA)
- Removal Of Specific Substances (AREA)
Abstract
A kind of processing method of aluminium electroloysis waste refractory materials, more particularly to aluminium cell waste refractory materials be innoxious and processing method of recycling.It is characterized in that the step of its processing procedure includes successively：(1) aluminium electroloysis waste refractory materials are crushed, be milled, levigate powder is stirred with water, mixed；(2) add except cyanogen agent carries out cyanogen reaction；(3) regulation slurry pH value is after 68, filtering；(4) defluorinating agent is added in filter residue to be handled, filtrate is handled using the difficult volatile acid of addition, fluorine fixing material or evaporative crystallisation process.The processing method of the present invention, fluoride solvable in waste refractory materials and cyanide can not only be carried out thoroughly innoxious, and recycling can be carried out to the solvable sodium fluoride of major part in waste refractory materials, because the indissoluble fluoride contained inside harmless slugging is considerably less, it can be made paving the way, the field such as brickmaking and refractory material is more widely used.
Description
Technical field
A kind of processing method of aluminium electroloysis waste refractory materials, be related to a kind of processing of aluminium electrolytic industry solid hazardous waste and
Resource recycling, particularly aluminium cell waste refractory materials be innoxious and processing method of recycling.
Background technology
In recent years, with the raising of China's aluminium yield, the outer discharge capacity of waste refractory materials is also increasing year by year, with production 7-8
The groove in year is calculated, and is often produced 1 ton of aluminium and is about discharged 15-25kg waste refractory materials, wherein：Useless negative electrode accounts for 55%, and the resistance to material that gives up is accounted for
45%.Waste refractory materials are inevitable solid hazardous wastes in aluminum electrolysis, wherein main noxious material is can
Molten fluoride and solvable cyanide, they are very harmful including soil, waters and air to environment, therefore to the nothing of waste refractory materials
Evilization processing is urgently to be resolved hurrily, very urgent.
At present, the domestic processing mode to waste refractory materials has following several：Pyrogenic process, wet method, store up, fill and send dangerous waste
Center, with attention of the country to environmental protection in recent years, overwhelming majority aluminium electroloysis enterprises were by the mode such as temporarily having stored up, having filled in the past
The requirement of environmental protection can not be met, send hazardous waste center then due to costly, seldom producer can select；Pyrogenic process and wet method can be to useless
Refractory material progress is thoroughly innoxious, but pyrogenic process is not industrialized so far, and output investment ratio is larger.This method
What is selected is wet-treating.
Number of patent application is CN20150924933.4 patent《Aluminium electroloysis based on chemical precipitation and redox reaction
Groove waste refractory materials processing method》For wet-treating, this method first passes through sodium hypochlorite except after cyanogen, filtering, with limewash to filter
Slag carries out fluorine removal, then by secondary filter, filter residue and filtrate are comprehensively utilized.This method can be entered to the filter residue after filtering
Row processing and utilization, but there is no clear and definite processing method to the fluoride in filtrate, experiment is found, after filtering, the fluorine in filtrate
Compound content is much more many than in filter residue.
Number of patent application is CN201310210403.4 patent《A kind of program control, manual electrolytic aluminium overhaul slag harmlessness life
Production. art》For wet-treating.In the patent, by successively adding water, powder into a reaction warehouse except cyanogen agent, defluorinating agent+salt
The method of acid, harmless treatment is carried out to aluminium electroloysis slag from delining, after reaction terminates, slurry is got into buffer pool, by buffer pool stream
Go out to carry out separation of solid and liquid.The patent contains industrial process and the engineering design of whole harmless treatment, while containing program control
With the explanation in terms of manual control.But, the patent is not recycled reasonably to the soluble fluoride in slag from delining, generation
Calcirm-fluoride mixed with slag from delining, it is impossible to separate.
Number of patent application is CN201610224385.9 patent《A kind of aluminium cell slag from delining innocuity disposal system and
Processing method》For wet-treating.It is innoxious to waste refractory materials progress using three reaction members in the patent, respectively soak
Export, the first reaction warehouse and the second reaction warehouse.During processing, powder and water are leaching storehouse progress Leach reaction, except cyanogen and fluorine removal are anti-
It should be carried out respectively in two reaction warehouses.Reacted slurry carries out separation of solid and liquid by the outflow of the second reaction warehouse or sells slurry
Material.The patent includes technical process and the engineering design of whole harmless treatment, and narration is comprehensive, and continuous production can be achieved.But
The processing method is reasonably recycled also without to the soluble fluoride in slag from delining, the indissoluble fluoride of generation with
Slag from delining is mixed, it is impossible to separated.
The content of the invention
There is provided a kind of harmless treatment and recycling aiming at the deficiency that above-mentioned prior art is present for the purpose of the present invention
The processing method of the good aluminium electroloysis waste refractory materials of utilizing status.
The purpose of the present invention is achieved through the following technical solutions.
A kind of processing method of aluminium electroloysis waste refractory materials, it is characterised in that include successively the step of its processing procedure：
(1) aluminium electroloysis waste refractory materials are crushed, be milled, levigate powder is stirred with water, mixed；
(2) add except cyanogen agent carries out cyanogen reaction；
(3) regulation slurry pH value is after 6-8, filtering；
(4) defluorinating agent is added in filter residue to be handled, filtrate is tied using the difficult volatile acid of addition, fluorine fixing material or evaporation
Crystal method is handled.
The processing method of a kind of aluminium electroloysis waste refractory materials of the present invention, it is characterised in that described step (1) is levigate
When powder is stirred with water, mixed, the mass ratio of powder and water is 3:10-10:10.
The processing method of a kind of aluminium electroloysis waste refractory materials of the present invention, it is characterised in that what described step (2) was added
Except cyanogen agent is the reagent with oxidisability, it by cyanide oxidation is N that addition, which is,2And CO2It is required except the 4.0-15 of cyanogen agent theoretical value
Times, except the cyanogen reaction time is 15-60min.
The processing method of a kind of aluminium electroloysis waste refractory materials of the present invention, it is characterised in that what described step (2) was added
Except cyanogen agent is bleaching powder, potassium permanganate.
A kind of processing method of aluminium electroloysis waste refractory materials of the present invention, it is characterised in that described step (3) regulation slurry
During liquid pH value, neutralization reaction, including phosphoric acid, sulfuric acid or mixed acid are carried out using acid reagent.
A kind of processing method of aluminium electroloysis waste refractory materials of the present invention, it is characterised in that described step (3) regulation slurry
The acid reagent that liquid pH value is added, calculates by 15% sulfuric acid of concentration, is every kilogram of powder 0.01-0.10L, during neutralization reaction
Between be 15-60min.
A kind of processing method of aluminium electroloysis waste refractory materials of the present invention, it is characterised in that filtrate in described step (4)
It is that difficult volatile acid is added into filtrate, addition is that sodium fluoride is converted into fluorine using the difficult volatile acid processing procedure of addition
1.1-2.0 times of theoretical value needed for changing hydrogen, reaction temperature is 75-85 DEG C, and the reaction time is 90-180min.
A kind of processing method of aluminium electroloysis waste refractory materials of the present invention, it is characterised in that filtrate in described step (4)
Using the difficult volatile acid processing procedure of addition, after the hydrogen fluoride gas water evaporated in course of reaction absorbs, hydrogen is converted into
Fluoric acid product is sold, and the content of hydrogen fluoride is more than 40% in hydrofluoric acid.
A kind of processing method of aluminium electroloysis waste refractory materials of the present invention, it is characterised in that filtrate in described step (4)
Using the difficult volatile acid processing procedure of addition, a part of liquid of acid solution is neutralized in neutrality as neutralizer, another part with landing alkali
Afterwards, recycle.
A kind of processing method of aluminium electroloysis waste refractory materials of the present invention, it is characterised in that filtrate in described step (4)
Using the difficult volatile acid processing procedure of addition, its difficult volatile acid is concentrated phosphoric acid, the concentrated sulfuric acid.
A kind of processing method of aluminium electroloysis waste refractory materials of the present invention, it is characterised in that filtrate in described step (4)
When being handled using fluorine fixing material, it adds fluorine fixing material to be calcium, magnesium, the soluble-salt of aluminium, and addition is to convert soluble fluoride
1.2-2.0 times of fluorine fixing material theoretical value for needed for corresponding difficulty soluble salt is calcirm-fluoride, magnesium fluoride, aluminum fluoride, the reaction time is 30-
60min, filtering, is dried to filter cake, obtains indissoluble fluoride product, filtrate cycle is used.
A kind of processing method of aluminium electroloysis waste refractory materials of the present invention, it is characterised in that filtrate in described step (4)
When being handled using fluorine fixing material, it adds fluorine fixing material to be calcium chloride, magnesium chloride, aluminum sulfate.
A kind of processing method of aluminium electroloysis waste refractory materials of the present invention, it is characterised in that filtrate in described step (4)
It is that filtrate is heated with steam when being handled using evaporative crystallisation process, separates out solvable sodium fluoride crystallization, heating temperature
Spend for 110-125 DEG C, reclaim sodium fluoride crystallization, obtain the sale of sodium fluoride product, the hydrogen fluoride gas that evaporation process is evaporated
Absorbed with alumina powder, form fluorinated alumina, the steam of generation is used to give filtrate heating, and after heat exchange, condensation forms water,
Recycle.
The processing method of a kind of aluminium electroloysis waste refractory materials of the present invention, it is characterised in that in filter in described step (4)
When addition defluorinating agent is handled in slag, the defluorinating agent used in processing filter residue is the reagent containing calcium, and addition is by soluble fluorine
1.5-3.0 times of theoretical value needed for compound is precipitated as corresponding insoluble fluoride, the reaction time is 30-60min.
The processing method of a kind of aluminium electroloysis waste refractory materials of the present invention, it is characterised in that in filter in described step (4)
It is quick lime, white lime that defluorinating agent is added in slag.
The processing method of a kind of aluminium electroloysis waste refractory materials of the present invention, it is characterised in that in filter in described step (4)
The filter residue after defluorinating agent is handled is added in slag and adds neutralizer, addition is theoretical for needed for added defluorinating agent is neutralized completely
0.9-1.1 times of value, the fluorine removal reaction time be 30-45min, reaction terminate after, filtering, harmless slugging be used for pave the way, brickmaking, life
Refractory material etc. is produced, filtrate cycle is used.
The processing method of a kind of aluminium electroloysis waste refractory materials of the present invention, it is characterised in that in filter in described step (4)
The neutralizer that the filter residue addition after defluorinating agent is handled is added in slag is phosphoric acid, sulfuric acid or its mixed acid.
A kind of processing method of aluminium electroloysis waste refractory materials of the present invention, can not only be to fluorine solvable in waste refractory materials
Compound and cyanide progress are thoroughly innoxious, and can carry out resource to the solvable sodium fluoride of major part in waste refractory materials
Change and utilize, rather than be completely converted into indissoluble precipitation, mixed with waste refractory materials, it is impossible to separate.The present invention is not only
The soluble fluoride in waste refractory materials can be made full use of, corresponding product is produced and carries out extra earning, for harmless slugging, by
The indissoluble fluoride contained in the inside is considerably less, it can be made paving the way, the field such as brickmaking and refractory material is obtained widely
Using.
Brief description of the drawings
Fig. 1 is that aluminium electroloysis waste refractory materials are innoxious and flow chart of method of recycling.
Specific implementation method
A kind of processing method of aluminium electroloysis waste refractory materials, its step includes：
A, pre-treatment：By aluminium electroloysis waste refractory materials by broken, milling after, added water into reaction warehouse, vertical stirring, side
The mass ratio that stirring side adds added powder and water in levigate powder, reaction warehouse into reaction warehouse is 3:10-10:10, online
Determine cryanide ion, the concentration and pH value of fluorine ion in solution.
B, except cyanogen：Added into reaction warehouse and remove cyanogen agent, it is added except cyanogen agent is the reagent with oxidisability, such as bleaching powder, height
Potassium manganate etc., it by cyanide oxidation is N that addition, which is,2And CO2Hung down in required 4.0-15 times except cyanogen agent theoretical value, course of reaction
Straight stirring, except the cyanogen reaction time is 15-60min, is down to after 0.5mg/L by cryanide ion content in on-line checking solution, is added
Neutralizer, slurries pH is between 6-8 for regulation, and neutralizer used is acid reagent, such as phosphoric acid, sulfuric acid or mixed acid, addition
Calculated by 15% sulfuric acid of concentration, be every kilogram of powder 0.01-0.10L, the neutralization reaction time is 15-60min, and reaction terminates
Afterwards, filter.
C, the content of fluoride ion determined in the fluorinion concentration in gained filtrate after filtering, calculating filter residue.
D, innoxious and recycling：To the fluoride in filtrate by adding difficult volatile acid, fluorine fixing material and evaporative crystallization
Three kinds of methods carry out recycling, and thoroughly harmless treatment is carried out by adding the method for defluorinating agent to filter residue.
A kind of processing method of aluminium electroloysis waste refractory materials of the present invention, have to the recycling of fluoride in filtrate with
Lower three kinds of methods：
A, the difficult volatile acid of addition：Difficult volatile acid such as concentrated phosphoric acid, the concentrated sulfuric acid etc. are added into filtrate, addition is by fluorine
Change needed for sodium is converted into hydrogen fluoride 1.1-2.0 times of theoretical value, reaction temperature is 75-85 DEG C, by can in on-line checking solution
Molten content of fluoride ion is down to after 10mg/L, terminates reaction, and the reaction time is the fluorine evaporated in 90-180min, course of reaction
After change hydrogen water absorbs, the content for being converted into hydrogen fluoride in the sale of hydrofluoric acid product, hydrofluoric acid is more than 40%, remaining acid solution
A part of liquid is neutralized in after neutrality with landing alkali, recycled as neutralizer, another part.
B, addition fluorine fixing material：Fluorine fixing material is added into filtrate, added fluorine fixing material is calcium, magnesium, such as soluble-salt of aluminium, chlorination
Calcium, magnesium chloride, aluminum sulfate etc., addition are that soluble fluoride is converted into corresponding difficulty soluble salt i.e. calcirm-fluoride, magnesium fluoride, aluminum fluoride
1.2-2.0 times of required fluorine fixing material theoretical value, is down to after 10mg/L by solvable content of fluoride ion in on-line checking solution, is terminated
Reaction, the reaction time is 30-60min, filtering, and filter cake is dried, indissoluble fluoride product is obtained, filtrate cycle is used.
C, evaporative crystallization：Filtrate is heated with steam, separates out solvable sodium fluoride crystallization, heating-up temperature is 110-
125 DEG C, sodium fluoride crystallization is reclaimed, the sale of sodium fluoride product, the hydrogen fluoride gas aluminum oxide that evaporation process is evaporated is obtained
Powder absorbs, and forms fluorinated alumina, and the steam of generation is used to give filtrate heating, and after heat exchange, condensation forms water, and circulation makes
With.
A kind of aluminium electroloysis waste refractory materials of the present invention are innoxious and method of recycling, the fluorine removal used in processing filter residue
Agent be the reagent containing calcium, such as quick lime, white lime, addition be by soluble fluoride be precipitated as accordingly insoluble fluoride institute
1.5-3.0 times of theoretical value is needed, the reaction time is 30-60min, neutralizer used is acid reagent, such as phosphoric acid, sulfuric acid or mixing
Acid etc., addition is 0.9-1.1 times of theoretical value for needed for added defluorinating agent is neutralized completely, and the fluorine removal reaction time is 30-
45min, after reaction terminates, filtering, harmless slugging is used to paving the way, brickmaking, production refractory material etc., filtrate cycle is used.
Embodiment 1
Aluminium electroloysis waste refractory materials are innoxious and operating procedure of recycling treatment is：
(1) pre-treatment：By aluminium electroloysis waste refractory materials by broken, milling after, 10 tons of water are added into reaction warehouse, vertically
Stirring, while stirring adds 3 tons of powders in reaction warehouse, and material water quality ratio is 3:10, in on-line determination solution cryanide ion, fluorine from
The concentration and pH value of son, wherein cryanide ion content are 36mg/L, and content of fluoride ion is 6978mg/L, pH=12.
(2) cyanogen is removed：The bleaching powder of 5 times of theoretical value, i.e. 41.25Kg are added into reaction warehouse.Reaction time is 60min, is led to
Cross on-line checking cryanide ion content to be down to after 0.5mg/L, add the mixed acid that 300L concentration is 10%, the pH for making slurries is 7, mistake
Filter.
(3) content of fluoride ion determined in filtrate is and pH value, and calculates the Oil repellent in filter residue.Fluorine ion is dense in filtrate
Spend for 6901mg/L, pH=7, volume is 9.4m3, moisture is 20% in filter residue, and wherein Oil repellent is 4.14Kg.
(4) recycling filtrate：Filtrate is added in another reaction warehouse, 1.8 times of theoretical value is added into reaction warehouse
The concentrated sulfuric acid, i.e. 170.71L, 80 DEG C, reaction 90min after, terminate reaction, to the hydrogen fluoride gas evaporated in course of reaction
After being absorbed with water, the content for being converted into hydrogen fluoride in the sale of hydrofluoric acid product, hydrofluoric acid is more than 40%, and volume is 189.0L, remains
A spent acid liquid part is as neutralizer, and another part uses industry landing alkali to neutralize in after neutrality, recycles.
(5) harmless treatment filter residue：Filter residue is transferred in filter residue process tank, 9.4 tons of water and reason are added into process tank
By the quick lime that 1.6 times of purity of value are 95%, i.e. 10.28Kg is reacted after 30min, adds the sulfuric acid 92.85L that concentration is 10%,
React after 30min, filtering, filter residue be used for brickmaking, pave the way, the industry such as fire resisting, filtrate cycle uses.
Embodiment 2
Aluminium electroloysis waste refractory materials are innoxious and operating procedure of recycling treatment is：
(1) pre-treatment：By aluminium electroloysis waste refractory materials by broken, milling after, 10 tons of water are added into reaction warehouse, vertically
Stirring, while stirring adds 6 tons of powders in reaction warehouse, and material water quality ratio is 6:10, in on-line determination powder cryanide ion, fluorine from
The concentration and pH value of son, wherein cryanide ion content are 48mg/L, and content of fluoride ion is 20497mg/L, pH=13.
(2) cyanogen is removed：The bleaching powder of 15 times of theoretical value, i.e. 165Kg are added into reaction warehouse.Reaction time is 30min, is passed through
On-line checking cryanide ion content is down to after 0.5mg/L, adds the sulfuric acid that 65L concentration is 23%, and the pH for making slurries is 7, filtering.
(3) content of fluoride ion determined in filtrate is and pH value, and calculates the Oil repellent in filter residue.Fluorine ion is dense in filtrate
Spend for 20402mg/L, pH=7, volume is 8.8m3, moisture is 20% in filter residue, and wherein Oil repellent is 24.48Kg.
(4) recycling filtrate：Filtrate is added in another reaction warehouse, 1.2 times of theoretical value is added into reaction warehouse
Concentrated phosphoric acid, i.e. 251.37L, 85 DEG C, reaction 120min after, terminate reaction, to the fluorination hydrogen evaporated in course of reaction
After body water absorbs, the content for being converted into hydrogen fluoride in the sale of hydrofluoric acid product, hydrofluoric acid is more than 40%, and volume is 421.1L,
A remaining acid solution part is as neutralizer, and another part uses industry landing alkali to neutralize in after neutrality, recycles.
(5) harmless treatment filter residue：Filter residue is transferred in filter residue process tank, 8.8 tons of water and reason are added into process tank
After the quick lime for being 95% by 2.2 times of purity of value, i.e. 83.54Kg, reaction 45min, the phosphoric acid that concentration is 20% is added
After 274.82L, reaction 40min, filtering, filter residue be used for brickmaking, pave the way, the industry such as fire resisting, filtrate cycle uses.
Embodiment 3
Aluminium electroloysis waste refractory materials are innoxious and operating procedure of recycling treatment is：
(1) pre-treatment：By aluminium electroloysis waste refractory materials by broken, milling after, 10 tons of water are added into reaction warehouse, vertically
Stirring, while stirring adds 5 tons of powders in reaction warehouse, and material water quality ratio is 5:10, in on-line determination powder cryanide ion, fluorine from
The concentration and pH value of son, wherein cryanide ion content are 25mg/L, and content of fluoride ion is 21012mg/L, pH=12.
(2) cyanogen is removed：The potassium permanganate of 8.0 times of theoretical value, i.e. 12.15Kg are added into reaction warehouse.Reaction time is
25min, is down to after 0.5mg/L by on-line checking cryanide ion content, is added the phosphoric acid that 400L concentration is 8%, is made the pH of slurries
For 7, filtering.
(3) content of fluoride ion determined in filtrate is and pH value, and calculates the Oil repellent in filter residue.Fluorine ion is dense in filtrate
Spend for 21010mg/L, pH=7, volume is 9.0m3, moisture is 20% in filter residue, and remaining Oil repellent is 21.01Kg.
(4) recycling filtrate：Filtrate is added in reaction warehouse, the purity of 1.3 times of theoretical value is added into reaction warehouse
It is 755.8Kg for 95% calcium chloride, filter cake is dried in filtering, obtains being fluorinated calcium product 388Kg, filtrate cycle is used.
(5) harmless treatment filter residue：Filter residue is transferred in filter residue process tank, 8 tons of water and theory are added into process tank
After the quick lime of purity 95% that 2.8 times of value, i.e. 91.26Kg, reaction 50min, the sulfuric acid 435.2L that concentration is 18%, reaction are added
After 35min, filtering, filter residue be used for brickmaking, pave the way, the industry such as fire resisting, filtrate cycle uses.
Embodiment 4
Aluminium electroloysis waste refractory materials are innoxious and operating procedure of recycling treatment is：
(1) pre-treatment：By aluminium electroloysis waste refractory materials by broken, milling after, 10 tons of water are added into reaction warehouse, vertically
Stirring, while stirring adds 8 tons of powders in reaction warehouse, and material water quality ratio is 8:10, in on-line determination powder cryanide ion, fluorine from
The concentration and pH value of son, wherein cryanide ion content are 13mg/L, and content of fluoride ion is 24570mg/L, pH=12.
(2) cyanogen is removed：The potassium permanganate of 6.0 times of theoretical value, i.e. 4.738Kg are added into reaction warehouse.Reaction time is
35min, is down to after 0.5mg/L by on-line checking cryanide ion content, is added the phosphoric acid that 200L concentration is 13%, is made the pH of slurries
For 7, filtering.
(3) content of fluoride ion determined in filtrate is and pH value, and calculates the Oil repellent in filter residue.Fluorine ion is dense in filtrate
Spend for 24570mg/L, pH=7, volume is 8.4m3, moisture is 20% in filter residue, and remaining Oil repellent is 39.312Kg.
(4) recycling filtrate：Filtrate is added in reaction warehouse, the purity of 1.8 times of theoretical value is added into reaction warehouse
It is 969.58Kg for 96% magnesium chloride, filter cake is dried in filtering, obtains being fluorinated magnesium products 338Kg, filtrate cycle is used.
(5) harmless treatment filter residue：Filter residue is transferred in filter residue process tank, 8 tons of water and theory are added into process tank
After the white lime of 2.2 times of purity 95% of value, i.e. 177.28Kg, reaction 60min, the sulfuric acid 404.06L that concentration is 30% is added, instead
Answer after 45min, filter, filter residue be used for brickmaking, pave the way, the industry such as fire resisting, filtrate cycle uses.
Embodiment 5
Aluminium electroloysis waste refractory materials are innoxious and operating procedure of recycling treatment is：
(1) pre-treatment：By aluminium electroloysis waste refractory materials by broken, milling after, 10 tons of water are added into reaction warehouse, vertically
Stirring, while stirring adds 10 tons of powders in reaction warehouse, and material water quality ratio is 10:10, cryanide ion, fluorine in on-line determination powder
The concentration and pH value of ion, wherein cryanide ion content are 260mg/L, and content of fluoride ion is 37020mg/L, pH=10.
(2) cyanogen is removed：Add in reaction warehouse, then add the potassium permanganate of 5.0 times of theoretical value, i.e. 79Kg.Vertical stirring, instead
It is 15min between seasonable, is down to by on-line checking cryanide ion content after 0.5mg/L, adds the mixed acid that 500L concentration is 15%,
The pH for making slurries is 7, filtering.
(3) content of fluoride ion determined in filtrate is and pH value, and calculates the Oil repellent in filter residue.Fluorine ion is dense in filtrate
Spend for 37020mg/L, pH=7, volume is 8.0m3, moisture is 20% in filter residue, and remaining Oil repellent is 74.04Kg.
(4) recycling filtrate：Filtrate is added in evaporator, solution is heated with steam, makes sodium fluoride knot
Partial crystallization goes out, and reclaims sodium fluoride crystallization, and the quality for obtaining sodium fluoride product is 654Kg.The fluorination hydrogen that evaporation process is evaporated
Body is absorbed with alumina powder, forms fluorinated alumina, and the steam of generation is used to give filtrate heating, after heat exchange, condense shape
Cheng Shui, is recycled.
(5) harmless treatment filter residue：Filter residue is transferred in filter residue process tank, 8 tons of water and theory are added into process tank
1.5 times of purity of value are 95% white lime, i.e. 227.66Kg is reacted after 45min, adds the mixed acid that concentration is 15%
After 641.9L, reaction 30min, filtering, filter residue be used for brickmaking, pave the way, the industry such as fire resisting, filtrate cycle uses.
Claims (17)
1. a kind of processing method of aluminium electroloysis waste refractory materials, it is characterised in that include successively the step of its processing procedure：
(1) aluminium electroloysis waste refractory materials are crushed, be milled, levigate powder is stirred with water, mixed；
(2) add except cyanogen agent carries out cyanogen reaction；
(3) regulation slurry pH value is after 6-8, filtering；
(4) add defluorinating agent in filter residue to be handled, by filtrate using the difficult volatile acid of addition, fluorine fixing material or evaporative crystallization side
Method is handled.
2. a kind of processing method of aluminium electroloysis waste refractory materials according to claim 1, it is characterised in that described step
(1) when levigate powder is stirred with water, mixed, the mass ratio of powder and water is 3:10-10:10.
3. a kind of processing method of aluminium electroloysis waste refractory materials according to claim 1, it is characterised in that described step
(2) add except cyanogen agent is the reagent with oxidisability, it by cyanide oxidation is N that addition, which is,2And CO2It is required to remove cyanogen agent theory
4.0-15 times of value, except the cyanogen reaction time is 15-60min.
4. a kind of processing method of aluminium electroloysis waste refractory materials according to claim 1, it is characterised in that described step
(2) the cyanogen agent that removes added is bleaching powder, potassium permanganate.
5. a kind of processing method of aluminium electroloysis waste refractory materials according to claim 1, it is characterised in that described step
(3) when adjusting slurry pH value, neutralization reaction, including phosphoric acid, sulfuric acid or mixed acid are carried out using acid reagent.
6. a kind of processing method of aluminium electroloysis waste refractory materials according to claim 1, it is characterised in that described step
(3) acid reagent that regulation slurry pH value is added, calculates by 15% sulfuric acid of concentration, is every kilogram of powder 0.01-0.10L,
The neutralization reaction time is 15-60min.
7. a kind of processing method of aluminium electroloysis waste refractory materials according to claim 1, it is characterised in that described step
(4) filtrate, using the difficult volatile acid processing procedure of addition, is that difficult volatile acid is added into filtrate, addition is by sodium fluoride in
1.1-2.0 times of theoretical value needed for being converted into hydrogen fluoride, reaction temperature is 75-85 DEG C, and the reaction time is 90-180min.
8. a kind of processing method of aluminium electroloysis waste refractory materials according to claim 1, it is characterised in that described step
(4) after the hydrogen fluoride gas water that filtrate is evaporated using adding in difficult volatile acid processing procedure, course of reaction in absorbs,
The content for being converted into hydrogen fluoride in the sale of hydrofluoric acid product, hydrofluoric acid is more than 40%.
9. a kind of processing method of aluminium electroloysis waste refractory materials according to claim 1, it is characterised in that described step
(4) filtrate is using the difficult volatile acid processing procedure of addition in, and a part of liquid of acid solution is as neutralizer, and another part is with landing alkali
After in neutrality, recycle.
10. a kind of processing method of aluminium electroloysis waste refractory materials according to claim 1, it is characterised in that described step
(4) filtrate is using the difficult volatile acid processing procedure of addition in, and its difficult volatile acid is concentrated phosphoric acid, the concentrated sulfuric acid.
11. a kind of processing method of aluminium electroloysis waste refractory materials according to claim 1, it is characterised in that described step
(4) when filtrate is handled using fluorine fixing material in, it adds fluorine fixing material to be calcium, magnesium, the soluble-salt of aluminium, and addition is by soluble fluorine
1.2-2.0 times of fluorine fixing material theoretical value needed for compound is converted into corresponding difficulty soluble salt i.e. calcirm-fluoride, magnesium fluoride, aluminum fluoride, during reaction
Between be 30-60min, filtering, filter cake is dried, indissoluble fluoride product is obtained, filtrate cycle is used.
12. a kind of processing method of aluminium electroloysis waste refractory materials according to claim 1, it is characterised in that described step
(4) when filtrate is handled using fluorine fixing material in, it adds fluorine fixing material to be calcium chloride, magnesium chloride, aluminum sulfate.
13. a kind of processing method of aluminium electroloysis waste refractory materials according to claim 1, it is characterised in that described step
(4) it is that filtrate is heated with steam when filtrate is handled using evaporative crystallisation process in, makes solvable sodium fluoride crystallization analysis
Go out, heating-up temperature is 110-125 DEG C, reclaim sodium fluoride crystallization, obtain the sale of sodium fluoride product, the fluorine that evaporation process is evaporated
Change hydrogen to be absorbed with alumina powder, form fluorinated alumina, the steam of generation is used to give filtrate heating, cold after heat exchange
It is solidifying to form water, recycle.
14. a kind of processing method of aluminium electroloysis waste refractory materials according to claim 1, it is characterised in that described step
(4) when addition defluorinating agent is handled in filter residue in, the defluorinating agent used in processing filter residue is the reagent containing calcium, and addition is
1.5-3.0 times of theoretical value needed for soluble fluoride is precipitated as into corresponding insoluble fluoride, the reaction time is 30-60min.
15. a kind of processing method of aluminium electroloysis waste refractory materials according to claim 1, it is characterised in that described step
(4) it is quick lime, white lime to add defluorinating agent in filter residue in.
16. a kind of processing method of aluminium electroloysis waste refractory materials according to claim 1, it is characterised in that described step
(4) in filter residue add defluorinating agent handled after filter residue add neutralizer, addition be by added defluorinating agent it is complete in
With 0.9-1.1 times of required theoretical value, the fluorine removal reaction time be 30-45min, reaction terminate after, filtering, harmless slugging be used for spread
Road, brickmaking, production refractory material etc., filtrate cycle is used.
17. a kind of processing method of aluminium electroloysis waste refractory materials according to claim 1, it is characterised in that described step
(4) neutralizer for adding the filter residue addition after defluorinating agent is handled in filter residue is phosphoric acid, sulfuric acid or mixed acid.
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Application publication date: 20170825 |