CN116022835A - Recycling treatment method of aluminum electrolysis carbon-containing hazardous waste - Google Patents
Recycling treatment method of aluminum electrolysis carbon-containing hazardous waste Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 88
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 79
- 238000000034 method Methods 0.000 title claims abstract description 64
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 61
- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 59
- 239000002920 hazardous waste Substances 0.000 title claims abstract description 50
- 238000004064 recycling Methods 0.000 title claims abstract description 36
- 238000002386 leaching Methods 0.000 claims abstract description 114
- 239000002699 waste material Substances 0.000 claims abstract description 97
- 230000004913 activation Effects 0.000 claims abstract description 45
- 238000000498 ball milling Methods 0.000 claims abstract description 32
- 238000000926 separation method Methods 0.000 claims abstract description 31
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 30
- 238000004137 mechanical activation Methods 0.000 claims abstract description 30
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 26
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 230000008569 process Effects 0.000 claims abstract description 12
- 239000007788 liquid Substances 0.000 claims description 113
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 76
- 239000007787 solid Substances 0.000 claims description 61
- 239000002253 acid Substances 0.000 claims description 44
- 239000000463 material Substances 0.000 claims description 25
- 239000002994 raw material Substances 0.000 claims description 25
- 238000007654 immersion Methods 0.000 claims description 21
- -1 aluminum hydroxyfluoride Chemical compound 0.000 claims description 13
- 239000000047 product Substances 0.000 claims description 12
- 230000002378 acidificating effect Effects 0.000 claims description 11
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 9
- 229910017604 nitric acid Inorganic materials 0.000 claims description 9
- 238000012216 screening Methods 0.000 claims description 9
- 239000002244 precipitate Substances 0.000 claims description 8
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 6
- 238000007255 decyanation reaction Methods 0.000 claims description 6
- 230000001590 oxidative effect Effects 0.000 claims description 6
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 5
- 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 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 238000002425 crystallisation Methods 0.000 claims description 4
- 230000008025 crystallization Effects 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 239000001569 carbon dioxide Substances 0.000 claims description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 3
- 239000003153 chemical reaction reagent Substances 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 2
- 238000003672 processing method Methods 0.000 claims 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract description 20
- 239000011737 fluorine Substances 0.000 abstract description 20
- 229910052731 fluorine Inorganic materials 0.000 abstract description 20
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 abstract description 12
- 239000012535 impurity Substances 0.000 abstract description 5
- XWROUVVQGRRRMF-UHFFFAOYSA-N F.O[N+]([O-])=O Chemical compound F.O[N+]([O-])=O XWROUVVQGRRRMF-UHFFFAOYSA-N 0.000 abstract description 4
- 231100000419 toxicity Toxicity 0.000 abstract description 4
- 230000001988 toxicity Effects 0.000 abstract description 4
- 238000001994 activation Methods 0.000 description 40
- 238000011084 recovery Methods 0.000 description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 230000001376 precipitating effect Effects 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 239000012190 activator Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910017053 inorganic salt Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 239000003440 toxic substance Substances 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- 229910001021 Ferroalloy Inorganic materials 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 150000004673 fluoride salts Chemical class 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000001698 pyrogenic effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000007725 thermal activation Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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Abstract
The invention belongs to the technical field of treatment of dangerous waste in aluminum electrolysis, in particular to a recycling treatment method of dangerous waste in carbon-containing in aluminum electrolysis, which adopts high-temperature mechanical activation to assist in recycling carbon materials and fluorine-containing components in the dangerous waste in carbon-containing in aluminum electrolysis, and utilizes a high-temperature ball milling device to construct a pressure activation leaching system, on one hand, the separation efficiency of the carbon materials and the fluorine-containing components can be improved through the cooperation of mechanical activation and high-pressure environment to strengthen the wet leaching process; on the other hand, compared with the traditional mechanical activation-pressure leaching method, the method has the advantages that the method is completed in different equipment links, so that the process flow is effectively shortened, the equipment investment and the occupied space are saved, and the treatment efficiency is remarkably improved; the leaching toxicity of the carbon-containing hazardous waste in aluminum electrolysis is fully utilized, a hydrofluoric acid-nitric acid/sulfuric acid/hydrochloric acid mixed leaching system is established, the impurity removing capability of the reaction system is further improved, the fixed carbon content of the recovered carbon material is more than or equal to 98.5%, and the leaching rate of fluoride is more than or equal to 99.0%.
Description
Technical Field
The invention relates to the technical field of treatment of aluminum electrolysis hazardous waste, in particular to a recycling treatment method of aluminum electrolysis carbon-containing hazardous waste.
Background
The national hazardous waste directory lists the carbon residue (321-025-48) produced in the electrolytic aluminum production process and the waste cathode carbon block (321-023-48) produced by cathode lining maintenance and replacement as toxic hazardous waste. However, as the electrolytic aluminum industry in China lacks a technical support system suitable for large-scale popularization, more than 50% of aluminum electrolysis carbon-containing dangerous wastes are deposited or buried indefinitely, and serious pollution risks are caused to the ecological environment, so that a large amount of valuable resources such as carbon materials, fluorine-containing components and the like are in an idle state. At present, the recycling treatment method of the carbon-containing hazardous waste in aluminum electrolysis can be mainly divided into the following three types:
(1) And (3) recycling: the method utilizes the strong reducibility and high energy density of the carbon material in the carbon-containing hazardous waste of aluminum electrolysis and the fluxing agent characteristic of fluoride, and directly applies the carbon-containing hazardous waste to industries such as alumina production, iron and steel production (blast furnace ironmaking, secondary refining and ferroalloy smelting), cement production, glass production and the like, can realize harmless treatment of cyanide/fluorine toxic substances while reducing the cost of raw materials for production, and has the defects that the comprehensive utilization of graphite carbon and fluoride salt cannot be considered, the unbalanced utilization of valuable resources is caused, and large-scale popularization and application are difficult to realize.
(2) And (3) performing pyrogenic treatment: the method utilizes the remarkable difference of complex inorganic salt systems in saturated vapor pressure or boiling point in the carbon-containing hazardous waste of aluminum electrolysis, and promotes the electrolyte and other non-carbon components to be deintercalated in a gaseous form and collected by condensation through treatment methods such as high-temperature roasting, ultrahigh-temperature graphitization, vacuum distillation, microwave-high-temperature roasting and the like, and has simple process flow, high treatment efficiency and large treatment capacity per unit time. The method has the defects that huge energy consumption and carbon emission can be generated, part of high-temperature treatment equipment has extremely high investment cost, and fluorine-containing flue gas has serious corrosiveness and environmental pollution risks.
(3) Wet treatment: construction of H by utilizing chemical reaction characteristic difference of complex inorganic salt system in aluminum electrolysis carbon-containing hazardous waste 2 O→NaOH→H + 、NaOH→H + Water → H + -Al 3+ /Fe 3+ The multi-stage wet leaching system regulates and controls the complex ore phase, can simultaneously realize the recovery of graphite carbon and fluoride, and has higher purity of recovered products. Its disadvantages are complex technological process and secondary pollution easily caused by wet treatment of waste liquid.
Disclosure of Invention
In order to solve the problems in the prior art, the main purpose of the invention is to provide a recycling treatment method for aluminum electrolysis carbon-containing hazardous waste, which can realize safe dissociation of toxic substances and simultaneously efficiently recycle valuable components (carbon materials and fluorine-containing components) in the aluminum electrolysis carbon-containing hazardous waste, and has the characteristics of simple process, high treatment efficiency and high resource utilization rate.
In order to solve the technical problems, according to one aspect of the present invention, the following technical solutions are provided:
a recycling treatment method of aluminum electrolysis carbon-containing hazardous waste comprises the following steps:
s1, carrying out multistage crushing and screening treatment on aluminum electrolysis carbon-containing hazardous waste to prepare a raw material for standby;
s2, adding the raw materials to be used into high-temperature ball milling equipment for high-temperature mechanical activation to obtain an activated material, wherein the ball milling speed is 50-350 r/min, the activation time is 0.1-2.0 h, and the activation temperature is 100-250 ℃;
s3, after the high-temperature mechanical activation is finished, adding a liquid reaction reagent into high-temperature ball milling equipment to perform pressure activation leaching; the activation rotating speed is 100-300 r/min, the leaching time is 0.1-4.0 h, the leaching temperature is 120-240 ℃, and after the leaching is finished, liquid-solid separation and ball material separation are sequentially carried out to obtain acid waste liquid and solid residues;
s4, carrying out water leaching treatment on the solid residues to obtain a recovered carbon material and water leaching waste liquid; the water immersion temperature is 30-80 ℃, the water immersion time is 0.1-1.0 h, and the liquid-solid ratio of water to solid residues is 5-25 mL/g.
As a preferable scheme of the recycling treatment method of the aluminum electrolysis carbon-containing hazardous waste, the invention comprises the following steps: the step S4 further includes:
s5, adding the solid aluminum salt into the acid waste liquid generated in the step S3, separating out precipitate, and carrying out solid-liquid separation to obtain the aluminum hydroxyfluoride product.
As a preferable scheme of the recycling treatment method of the aluminum electrolysis carbon-containing hazardous waste, the invention comprises the following steps: in the step S1, the grain size of the raw materials to be used is less than or equal to 0.15mm.
As a preferable scheme of the recycling treatment method of the aluminum electrolysis carbon-containing hazardous waste, the invention comprises the following steps: in the step S1, the aluminum electrolysis carbon-containing dangerous waste is carbon residue or waste cathode carbon blocks.
As a preferable scheme of the recycling treatment method of the aluminum electrolysis carbon-containing hazardous waste, the invention comprises the following steps: in the step S2, the top of the high-temperature mechanical activation device is provided with an air inlet/outlet valve and a polytetrafluoroethylene lining.
As a preferable scheme of the recycling treatment method of the aluminum electrolysis carbon-containing hazardous waste, the invention comprises the following steps: in the step S2, if the raw material to be used is the waste cathode carbon block, oxidizing gas is introduced to carry out decyanation treatment.
As a preferable scheme of the recycling treatment method of the aluminum electrolysis carbon-containing hazardous waste, the invention comprises the following steps: in the step S2, the oxidizing gas is air, oxygen-enriched gas or carbon dioxide.
As a preferable scheme of the recycling treatment method of the aluminum electrolysis carbon-containing hazardous waste, the invention comprises the following steps: in the step S3, the liquid reaction agent is one or more of nitric acid, sulfuric acid and hydrochloric acid.
As a preferable scheme of the recycling treatment method of the aluminum electrolysis carbon-containing hazardous waste, the invention comprises the following steps: in the step S3, the concentration of the liquid reaction agent is 2-12 mol/L, and the liquid-solid ratio of the liquid reaction agent to the activated material is 5-30 mL/g.
As a preferable scheme of the recycling treatment method of the aluminum electrolysis carbon-containing hazardous waste, the invention comprises the following steps: in the step S4, the water leaching waste liquid comprises strong acid water leaching waste liquid and weak acid water leaching waste liquid, wherein the pH value of the strong acid water leaching waste liquid is less than or equal to 2, the strong acid water leaching waste liquid and the acid waste liquid in the step S3 are mixed to obtain combined waste liquid, the pH value of the weak acid water leaching waste liquid is more than 2, and the combined waste liquid is returned to water leaching treatment.
As a preferable scheme of the recycling treatment method of the aluminum electrolysis carbon-containing hazardous waste, the invention comprises the following steps: in the step S5, solid aluminum salt is added into the combined waste liquid, the pH value is adjusted to 3.5-6.5, the crystallization temperature is 40-90 ℃, and precipitation is carried out.
As a preferable scheme of the recycling treatment method of the aluminum electrolysis carbon-containing hazardous waste, the invention comprises the following steps: in the step S5, the solid aluminum salt is one or more of aluminum nitrate, aluminum sulfate or aluminum chloride.
The beneficial effects of the invention are as follows:
the invention provides a recycling treatment method of aluminum electrolysis carbon-containing hazardous waste, which adopts high-temperature mechanical activation to assist in recycling carbon materials and fluorine-containing components in the aluminum electrolysis carbon-containing hazardous waste, and utilizes a high-temperature ball milling device to construct a pressurized activation leaching system, on one hand, the separation efficiency of the carbon materials and the fluorine-containing components can be improved through the mechanical activation and high-pressure environment collaborative strengthening wet leaching process; on the other hand, compared with the traditional mechanical activation-pressure leaching method, the method has the advantages that the method is completed in different equipment links, so that the process flow is effectively shortened, the equipment investment and the occupied space are saved, and the treatment efficiency is remarkably improved; the leaching toxicity of the carbon-containing hazardous waste in aluminum electrolysis is fully utilized, a hydrofluoric acid-nitric acid/sulfuric acid/hydrochloric acid mixed leaching system is established, the impurity removing capability of the reaction system is further improved, the fixed carbon content of the recovered carbon material is more than or equal to 98.5%, and the leaching rate of fluoride is more than or equal to 99.0%.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings may be obtained according to the structures shown in these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic flow chart of a recycling treatment method of the carbon-containing hazardous waste in aluminum electrolysis.
The achievement of the objects, functional features and advantages of the present invention will be further described with reference to the accompanying drawings, in conjunction with the embodiments.
Detailed Description
The following description will be made clearly and fully with reference to the technical solutions in the embodiments, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides a recycling treatment method of aluminum electrolysis carbon-containing hazardous waste, which adopts high-temperature mechanical activation to assist in recycling carbon materials and fluorine-containing components in the aluminum electrolysis carbon-containing hazardous waste:
(1) The high-temperature mechanical activation can not only improve the reactivity of the components contained in the carbon-containing hazardous waste of aluminum electrolysis, but also promote the decomposition of part of simple compounds, has the dual functions of mechanical activation and thermal activation, and is beneficial to the removal of non-carbon impurities in the activation leaching link.
(2) The pressurization activation leaching system is innovatively constructed by utilizing a high-temperature ball milling device, on one hand, the separation efficiency of the carbon material and the fluorine-containing component can be improved by the mechanical activation and high-pressure environment synergistic reinforcement wet leaching process; on the other hand, compared with the traditional mechanical activation-pressure leaching method, the method has the advantages that the method is completed in different equipment links, the process flow is effectively shortened, the equipment investment and the occupied space are saved, and the treatment efficiency is remarkably improved.
(3) The leaching toxicity of the carbon-containing hazardous waste in aluminum electrolysis is fully utilized, a hydrofluoric acid-nitric acid/sulfuric acid/hydrochloric acid mixed leaching system is established, the impurity removing capability of the reaction system is further improved, the fixed carbon content of the recovered carbon material is more than or equal to 98.5%, and the leaching rate of fluoride is more than or equal to 99.0%.
(4) Through aluminum salt addition, pH value and temperature regulation, aluminum hydroxyfluoride products can be extracted from the acidic waste liquid, secondary pollution is avoided, and recycling recovery of non-carbon valuable components of the carbon-containing hazardous waste of aluminum electrolysis is realized, wherein the recovery rate of fluorine is more than or equal to 98.0%.
According to one aspect of the invention, the invention provides the following technical scheme:
as shown in fig. 1, the recycling treatment method of the carbon-containing hazardous waste in aluminum electrolysis comprises the following steps:
s1, carrying out multistage crushing and screening treatment on aluminum electrolysis carbon-containing hazardous waste to prepare a raw material for standby;
s2, adding the raw materials to be used into high-temperature ball milling equipment for high-temperature mechanical activation to obtain an activated material, wherein the ball milling speed is 50-350 r/min, the activation time is 0.1-2.0 h, and the activation temperature is 100-250 ℃; specifically, the ball milling rotation speed can be, for example, but not limited to, any one of 50r/min, 100r/min, 150r/min, 200r/min, 250r/min, 300r/min, 350r/min or a range between any two of the above; the activation time may be, for example, but is not limited to, any one or a range between any two of 0.1h, 0.5h, 1.0h, 1.5h, 2.0 h; the activation temperature may be, for example, but is not limited to, any one or a range between any two of 100 ℃, 150 ℃, 200 ℃, 250 ℃;
s3, after the high-temperature mechanical activation is finished, adding a liquid reaction reagent into high-temperature ball milling equipment to perform pressure activation leaching; the activation rotating speed is 100-300 r/min, the leaching time is 0.1-4.0 h, the leaching temperature is 120-240 ℃, and after the leaching is finished, liquid-solid separation and ball material separation are sequentially carried out to obtain acid waste liquid and solid residues; specifically, the activation rotation speed may be, for example, but not limited to, any one of 100r/min, 150r/min, 200r/min, 250r/min, 300r/min or a range between any two thereof; the leaching time may be, for example, but is not limited to, any one or a range between any two of 0.1h, 0.5h, 1.0h, 1.5h, 2.0h, 2.5h, 3.0h, 3.5h, 4.0 h;
s4, carrying out water leaching treatment on the solid residues to obtain a recovered carbon material and water leaching waste liquid; the water immersion temperature is 30-80 ℃, the water immersion time is 0.1-1.0 h, and the liquid-solid ratio of water to solid residues is 5-25 mL/g. In particular, the water immersion temperature may be, for example, but not limited to, any one or a range between any two of 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃; the water immersion time may be, for example, but is not limited to, any one or a range between any two of 0.1h, 0.2h, 0.3h, 0.4h, 0.5h, 0.6h, 0.7h, 0.8h, 0.9h, 1.0 h; the liquid to solid ratio of water to solid residue may be, for example, but is not limited to, in the range of between any one or any two of 5mL/g, 10mL/g, 15mL/g, 20mL/g, 25 mL/g;
preferably, the step S4 further includes:
s5, adding solid aluminum salt into the acidic waste liquid generated in the step S3 or the combined waste liquid obtained by mixing the strong acid water leaching waste liquid generated in the step S4 with the acidic waste liquid generated in the step S3, separating out precipitate, and carrying out solid-liquid separation to obtain the aluminum hydroxyfluoride product.
Preferably, in the step S1, the particle size of the raw material to be used is less than or equal to 0.15mm. The aluminum electrolysis carbon-containing dangerous waste is carbon residue or waste cathode carbon blocks.
Preferably, in the step S2, the top of the high-temperature mechanical activation device is provided with an air inlet/outlet valve and a polytetrafluoroethylene lining.
Preferably, in the step S2, if the raw material to be used is a spent cathode carbon block, an oxidizing gas is introduced to perform decyanation treatment. The oxidizing gas is air, oxygen-enriched gas or carbon dioxide.
Preferably, in the step S3, the liquid reaction agent is one or more of nitric acid, sulfuric acid and hydrochloric acid. The concentration of the liquid reaction agent is 2-12 mol/L, and the liquid-solid ratio of the liquid reaction agent to the activated material is 5-30 mL/g. Specifically, the concentration of the liquid reactant may be, for example, but not limited to, any one or any range between two of 2mol/L, 3mol/L, 4mol/L, 5mol/L, 6mol/L, 7mol/L, 8mol/L, 9mol/L, 10mol/L, 11mol/L, 12 mol/L; the liquid-to-solid ratio of the liquid reaction agent to the activation material may be, for example, but not limited to, any one or between any two of 5mL/g, 10mL/g, 15mL/g, 20mL/g, 25mL/g, 30 mL/g;
preferably, in the step S4, the solid residue needs to be immersed for 3-4 times, the pH value of the 1 st immersed waste liquid is very small, and the pH value of the immersed waste liquid increases gradually with the immersion times, so the immersed waste liquid comprises a strong acid immersed waste liquid and a weak acid immersed waste liquid, wherein the pH value of the strong acid immersed waste liquid is less than or equal to 2, the strong acid immersed waste liquid is mixed with the acid waste liquid in the step S3 to obtain a combined waste liquid, the pH value of the weak acid immersed waste liquid is more than 2, and the combined waste liquid is returned to the immersed treatment.
Preferably, in the step S5, solid aluminum salt is added into the acidic waste liquid generated in the step S3 or the combined waste liquid obtained by mixing the acidic water leaching waste liquid generated in the step S4 and the acidic waste liquid generated in the step S3, the pH value is adjusted to 3.5-6.5, the crystallization temperature is 40-90 ℃, and precipitation is performed. The solid aluminum salt is one or more of aluminum nitrate, aluminum sulfate or aluminum chloride. Specifically, the pH may be, for example, but not limited to, any one or a range between any two of 3.5, 4.0, 4.5, 5.0, 5.5, 6.0, 6.5; the crystallization temperature may be, for example, but not limited to, any one or a range between any two of 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃.
The technical scheme of the invention is further described below by combining specific embodiments.
Example 1
A recycling treatment method of aluminum electrolysis carbon-containing hazardous waste comprises the following steps:
s1, carrying out multistage crushing and screening treatment on aluminum electrolysis waste cathode carbon blocks to prepare a raw material with the grain diameter less than or equal to 0.15mm for later use;
s2, adding the raw materials to be used into high-temperature ball milling equipment for high-temperature mechanical activation to obtain an activated material, wherein the ball milling rotating speed is 250r/min, the activation time is 0.5h, the activation temperature is 240 ℃, and air is introduced for decyanation treatment;
s3, after the high-temperature mechanical activation is finished, adding sulfuric acid solution into high-temperature ball milling equipment for pressurized activation leaching; closing the air inlet valve and the air outlet valve, wherein the activation rotating speed is 300r/min, the leaching time is 1.0h, the leaching temperature is 220 ℃, the concentration of sulfuric acid solution is 6mol/L, and the solid-liquid ratio of sulfuric acid solution to activator is 20mL/g; after leaching is finished, sequentially carrying out liquid-solid separation and ball material separation to obtain acid waste liquid and solid residues;
s4, carrying out water leaching treatment on the solid residues to obtain a recovered carbon material and water leaching waste liquid; the water immersion temperature is 60 ℃, the water immersion time is 0.5h, and the liquid-solid ratio of water to solid residues is 20mL/g; the fixed carbon content of the recovered carbon material is 99.24%, and the leaching rate of fluoride is 99.58%; the strong acid water leaching waste liquid and the acid waste liquid are mixed to obtain a combined waste liquid, and the weak acid water leaching waste liquid is returned to water leaching treatment.
S5, adding aluminum sulfate into the combined waste liquid, adjusting the pH value to 5.5, crystallizing at 80 ℃, precipitating precipitate, and carrying out solid-liquid separation to obtain an aluminum hydroxyfluoride product, wherein the recovery rate of fluorine is 98.82%.
Example 2
A recycling treatment method of aluminum electrolysis carbon-containing hazardous waste comprises the following steps:
s1, carrying out multistage crushing and screening treatment on aluminum electrolysis waste cathode carbon blocks to prepare a raw material with the grain diameter less than or equal to 0.15mm for later use;
s2, adding the raw materials to be used into high-temperature ball milling equipment for high-temperature mechanical activation to obtain an activated material, wherein the ball milling rotating speed is 200r/min, the activation time is 1.0h, the activation temperature is 220 ℃, and oxygen enrichment is introduced for decyanation treatment;
s3, adding hydrochloric acid solution into high-temperature ball milling equipment for pressurized activation leaching after the high-temperature mechanical activation is finished; closing an air inlet valve and an air outlet valve, wherein the activation rotating speed is 250r/min, the leaching time is 1.5h, the leaching temperature is 200 ℃, the concentration of hydrochloric acid solution is 10mol/L, the solid-liquid ratio of the hydrochloric acid solution to the activator is 25mL/g, and after the leaching is finished, sequentially carrying out liquid-solid separation and ball material separation to obtain acid waste liquid and solid residues;
s4, carrying out water leaching treatment on the solid residues to obtain a recovered carbon material and water leaching waste liquid; the water immersion temperature is 70 ℃, the water immersion time is 1.0h, and the liquid-solid ratio of water to solid residues is 20mL/g; the fixed carbon content of the recovered carbon material is 99.13 percent, and the leaching rate of fluoride is 99.39 percent; the strong acid water leaching waste liquid and the acid waste liquid are mixed to obtain a combined waste liquid, and the weak acid water leaching waste liquid is returned to water leaching treatment.
S5, adding aluminum chloride into the combined waste liquid, adjusting the pH value to be 5.75, crystallizing at 60 ℃, precipitating precipitate, and carrying out solid-liquid separation to obtain an aluminum hydroxyfluoride product, wherein the recovery rate of fluorine is 98.59%.
Example 3
A recycling treatment method of aluminum electrolysis carbon-containing hazardous waste comprises the following steps:
s1, carrying out multistage crushing and screening treatment on aluminum electrolysis waste cathode carbon blocks to prepare a raw material with the grain diameter less than or equal to 0.15mm for later use;
s2, adding the raw materials to be used into high-temperature ball milling equipment for high-temperature mechanical activation to obtain an activated material, wherein the ball milling rotating speed is 150r/min, the activation time is 0.5h, the activation temperature is 240 ℃, and air is introduced for decyanation treatment;
s3, adding a nitric acid solution into the high-temperature ball milling equipment to perform pressurized activation leaching after the high-temperature mechanical activation is finished; closing an air inlet valve and an air outlet valve, wherein the activation rotating speed is 200r/min, the leaching time is 1.0h, the leaching temperature is 180 ℃, the concentration of nitric acid solution is 8mol/L, the solid-liquid ratio of nitric acid solution to activated material is 15mL/g, and after leaching is finished, sequentially carrying out liquid-solid separation and ball material separation to obtain acidic waste liquid and solid residues;
s4, carrying out water leaching treatment on the solid residues to obtain a recovered carbon material and water leaching waste liquid; the water immersion temperature is 50 ℃, the water immersion time is 0.5h, and the liquid-solid ratio of water to solid residues is 20mL/g; the fixed carbon content of the recovered carbon material is 98.65 percent, and the leaching rate of fluoride is 99.08 percent; the strong acid water leaching waste liquid and the acid waste liquid are mixed to obtain a combined waste liquid, and the weak acid water leaching waste liquid is returned to water leaching treatment.
S5, adding aluminum nitrate into the combined waste liquid, adjusting the pH value to 6.0, crystallizing at 80 ℃, precipitating precipitate, and carrying out solid-liquid separation to obtain an aluminum hydroxyfluoride product, wherein the recovery rate of fluorine is 98.26%.
Example 4
A recycling treatment method of aluminum electrolysis carbon-containing hazardous waste comprises the following steps:
s1, carrying out multistage crushing and screening treatment on aluminum electrolysis carbon residues to prepare a raw material with the grain diameter less than or equal to 0.15mm for later use;
s2, adding the raw materials to be used into high-temperature ball milling equipment for high-temperature mechanical activation to obtain an activated material, wherein the ball milling speed is 250r/min, the activation time is 1.5h, and the activation temperature is 200 ℃;
s3, adding hydrochloric acid solution into high-temperature ball milling equipment for pressurized activation leaching after the high-temperature mechanical activation is finished; closing an air inlet valve and an air outlet valve, wherein the activation rotating speed is 250r/min, the leaching time is 1.0h, the leaching temperature is 220 ℃, the concentration of hydrochloric acid solution is 8mol/L, the solid-liquid ratio of the hydrochloric acid solution to the activator is 30mL/g, and after the leaching is finished, sequentially carrying out liquid-solid separation and ball material separation to obtain acid waste liquid and solid residues;
s4, carrying out water leaching treatment on the solid residues to obtain a recovered carbon material and water leaching waste liquid; the water immersion temperature is 60 ℃, the water immersion time is 1.0h, and the liquid-solid ratio of water to solid residues is 20mL/g; the fixed carbon content of the recovered carbon material is 98.88 percent, and the leaching rate of fluoride is 99.35 percent; the strong acid water leaching waste liquid and the acid waste liquid are mixed to obtain a combined waste liquid, and the weak acid water leaching waste liquid is returned to water leaching treatment.
S5, adding aluminum chloride into the combined waste liquid, adjusting the pH value to 5.25, crystallizing at 80 ℃, precipitating, and carrying out solid-liquid separation to obtain an aluminum hydroxyfluoride product, wherein the recovery rate of fluorine is 98.52%.
Example 5
A recycling treatment method of aluminum electrolysis carbon-containing hazardous waste comprises the following steps:
s1, carrying out multistage crushing and screening treatment on aluminum electrolysis carbon residues to prepare a raw material with the grain diameter less than or equal to 0.15mm for later use;
s2, adding the raw materials to be used into high-temperature ball milling equipment for high-temperature mechanical activation to obtain an activated material, wherein the ball milling speed is 300r/min, the activation time is 1.0h, and the activation temperature is 240 ℃;
s3, after the high-temperature mechanical activation is finished, adding sulfuric acid solution into high-temperature ball milling equipment for pressurized activation leaching; closing an air inlet valve and an air outlet valve, wherein the activation rotating speed is 300r/min, the leaching time is 2.0h, the leaching temperature is 220 ℃, the concentration of sulfuric acid solution is 6mol/L, the solid-liquid ratio of sulfuric acid solution to activated material is 25mL/g, and after leaching is finished, sequentially carrying out liquid-solid separation and ball material separation to obtain acidic waste liquid and solid residues;
s4, carrying out water leaching treatment on the solid residues to obtain a recovered carbon material and water leaching waste liquid; the water immersion temperature is 60 ℃, the water immersion time is 0.5h, and the liquid-solid ratio of water to solid residues is 20mL/g; the fixed carbon content of the recovered carbon material is 99.05%, and the leaching rate of fluoride is 99.47%; the strong acid water leaching waste liquid and the acid waste liquid are mixed to obtain a combined waste liquid, and the weak acid water leaching waste liquid is returned to water leaching treatment.
S5, adding aluminum sulfate into the combined waste liquid, adjusting the pH value to 5.5, crystallizing at 90 ℃, precipitating precipitate, and carrying out solid-liquid separation to obtain an aluminum hydroxyfluoride product, wherein the recovery rate of fluorine is 98.77%.
Example 6
A recycling treatment method of aluminum electrolysis carbon-containing hazardous waste comprises the following steps:
s1, carrying out multistage crushing and screening treatment on aluminum electrolysis carbon residues to prepare a raw material with the grain diameter less than or equal to 0.15mm for later use;
s2, adding the raw materials to be used into high-temperature ball milling equipment for high-temperature mechanical activation to obtain an activated material, wherein the ball milling speed is 200r/min, the activation time is 2.0h, and the activation temperature is 240 ℃;
s3, adding a nitric acid solution into the high-temperature ball milling equipment to perform pressurized activation leaching after the high-temperature mechanical activation is finished; closing an air inlet valve and an air outlet valve, wherein the activation rotating speed is 200r/min, the leaching time is 1.0h, the leaching temperature is 180 ℃, the concentration of nitric acid solution is 6mol/L, the solid-liquid ratio of nitric acid solution to activated material is 20mL/g, and after leaching is finished, sequentially carrying out liquid-solid separation and ball material separation to obtain acidic waste liquid and solid residues;
s4, carrying out water leaching treatment on the solid residues to obtain a recovered carbon material and water leaching waste liquid; the water immersion temperature is 60 ℃, the water immersion time is 1.0h, and the liquid-solid ratio of water to solid residues is 20mL/g; the fixed carbon content of the recovered carbon material is 98.59 percent, and the leaching rate of fluoride is 99.07 percent; the strong acid water leaching waste liquid and the acid waste liquid are mixed to obtain a combined waste liquid, and the weak acid water leaching waste liquid is returned to water leaching treatment.
S5, adding aluminum nitrate into the combined waste liquid, adjusting the pH value to 5.0, crystallizing at 60 ℃, precipitating precipitate, and carrying out solid-liquid separation to obtain an aluminum hydroxyfluoride product, wherein the recovery rate of fluorine is 98.34%.
According to the invention, the high-temperature mechanical activation is adopted to assist in recycling the carbon material and fluorine-containing components in the carbon-containing hazardous waste of aluminum electrolysis, and a high-temperature ball milling device is utilized to construct a pressurized activation leaching system, so that on one hand, the separation efficiency of the carbon material and the fluorine-containing components can be improved through the mechanical activation and high-pressure environment synergistic reinforcement wet leaching process; on the other hand, compared with the traditional mechanical activation-pressure leaching method, the method has the advantages that the method is completed in different equipment links, so that the process flow is effectively shortened, the equipment investment and the occupied space are saved, and the treatment efficiency is remarkably improved; the leaching toxicity of the carbon-containing hazardous waste in aluminum electrolysis is fully utilized, a hydrofluoric acid-nitric acid/sulfuric acid/hydrochloric acid mixed leaching system is established, the impurity removal capability of the reaction system is further improved, the fixed carbon content of the recovered carbon material is more than or equal to 98.5%, and the leaching rate of fluoride is more than or equal to 99.0%; through aluminum salt addition, pH value and temperature regulation, aluminum hydroxyfluoride products can be extracted from the acidic waste liquid, secondary pollution is avoided, and recycling recovery of non-carbon valuable components of the carbon-containing hazardous waste of aluminum electrolysis is realized, wherein the recovery rate of fluorine is more than or equal to 98.0%.
The foregoing description is only of the preferred embodiments of the present invention and is not intended to limit the scope of the invention, and all equivalent structural changes made by the content of the present invention or direct/indirect application in other related technical fields are included in the scope of the present invention.
Claims (10)
1. The recycling treatment method of the carbon-containing hazardous waste in the aluminum electrolysis is characterized by comprising the following steps of:
s1, carrying out multistage crushing and screening treatment on aluminum electrolysis carbon-containing hazardous waste to prepare a raw material for standby;
s2, adding the raw materials to be used into high-temperature ball milling equipment for high-temperature mechanical activation to obtain an activated material, wherein the ball milling speed is 50-350 r/min, the activation time is 0.1-2.0 h, and the activation temperature is 100-250 ℃;
s3, after the high-temperature mechanical activation is finished, adding a liquid reaction reagent into high-temperature ball milling equipment to perform pressure activation leaching; the activation rotating speed is 100-300 r/min, the leaching time is 0.1-4.0 h, the leaching temperature is 120-240 ℃, and after the leaching is finished, liquid-solid separation and ball material separation are sequentially carried out to obtain acid waste liquid and solid residues;
s4, carrying out water leaching treatment on the solid residues to obtain a recovered carbon material and water leaching waste liquid; the water immersion temperature is 30-80 ℃, the water immersion time is 0.1-1.0 h, and the liquid-solid ratio of water to solid residues is 5-25 mL/g.
2. The processing method according to claim 1, wherein after the step S4, further comprises:
s5, adding the solid aluminum salt into the acid waste liquid generated in the step S3, separating out precipitate, and carrying out solid-liquid separation to obtain the aluminum hydroxyfluoride product.
3. The method according to claim 1 or 2, wherein in the step S1, the particle size of the raw material to be used is 0.15mm or less.
4. The method according to claim 1 or 2, wherein in the step S1, the hazardous waste containing carbon in the aluminum electrolysis is carbon residue or waste cathode carbon block.
5. The method according to claim 1 or 2, wherein in the step S2, if the raw material to be used is a spent cathode carbon block, an oxidizing gas is introduced to perform decyanation treatment.
6. The process according to claim 1 or 2, wherein in step S2, the oxidizing gas is air, oxygen-enriched gas or carbon dioxide.
7. The method according to claim 1 or 2, wherein in the step S3, the liquid reaction agent is one or more of nitric acid, sulfuric acid, and hydrochloric acid; the concentration of the liquid reaction agent is 2-12 mol/L, and the liquid-solid ratio of the liquid reaction agent to the activated material is 5-30 mL/g.
8. The method according to claim 1 or 2, wherein in the step S4, the aqueous effluent includes a strong acid aqueous effluent and a weak acid aqueous effluent, wherein the pH value of the strong acid aqueous effluent is less than or equal to 2, the strong acid aqueous effluent is mixed with the acidic effluent in the step S3 to obtain a combined effluent, the pH value of the weak acid aqueous effluent is greater than 2, and the combined effluent is returned to the aqueous effluent for treatment.
9. The method according to claim 2, wherein in the step S5, solid aluminum salt is added to the combined waste liquid, the pH is adjusted to 3.5-6.5, the crystallization temperature is 40-90 ℃, and precipitation is performed.
10. The method according to claim 2, wherein in the step S5, the solid aluminum salt is one or more of aluminum nitrate, aluminum sulfate and aluminum chloride.
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