CN112718805A - Electrolytic aluminum overhaul slag comprehensive treatment device and treatment method - Google Patents
Electrolytic aluminum overhaul slag comprehensive treatment device and treatment method Download PDFInfo
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- CN112718805A CN112718805A CN202011574616.1A CN202011574616A CN112718805A CN 112718805 A CN112718805 A CN 112718805A CN 202011574616 A CN202011574616 A CN 202011574616A CN 112718805 A CN112718805 A CN 112718805A
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- anode
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE
- B09B5/00—Operations not covered by a single other subclass or by a single other group in this subclass
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/24—Halogens or compounds thereof
- C25B1/245—Fluorine; Compounds thereof
Abstract
The invention discloses an electrolytic aluminum overhaul slag comprehensive treatment device and a treatment method, wherein the device is a diaphragm electrolysis device and comprises a plurality of groups of unit tanks, each unit tank is formed by spacing an anode and a cathode, an anion membrane is arranged in the unit tank at a position close to the anode, a cation membrane is arranged at a position close to the cathode, partition plates with chambers are respectively arranged among the anode, the anion membrane, the cation membrane and the cathode, and the unit tank is divided into an anode chamber, a solution chamber and a cathode chamber from the anode to the cathode; the multiple groups of the unit tanks are connected in series and among the tanks are connected in parallel, or the multiple groups of the unit tanks are connected in parallel and among the tanks are connected in series. The method comprises the following steps: sorting, crushing, wet grinding and water soaking, filtering and diaphragm electrolysis. The scheme can effectively classify and treat the overhaul slag and dispose the overhaul slag harmlessly. By adopting a diaphragm electrolysis method, the electrochemical cyanogen breaking is carried out while sodium fluoride is enriched, so that the aluminum slag, the carbon block, the refractory material and the sodium fluoride are respectively recycled.
Description
Technical Field
The invention belongs to the technical field of harmless treatment of hazardous wastes, and particularly relates to a comprehensive treatment device and a treatment method for electrolytic aluminum overhaul residues.
Background
China is a large country for producing primary aluminum, an electrolytic cell needs to be periodically overhauled in the production of electrolytic aluminum, an inner lining of the electrolytic cell needs to be replaced every 5-6 years, overhaul residues are a general name of waste cell linings removed in the overhaul of the electrolytic cell, and the overhaul residues contain carbonaceous materials, refractory heat-insulating materials and fluoride which respectively account for about 30 percent of the total weight of the electrolytic cell, and in addition, cyanide salts of about 0.2 percent are also contained. In 2018, the newly generated overhaul residues of the electrolytic aluminum enterprises in China exceed 100 million tons, and the overhaul residues stacked in the open air or buried in a fixed slag yard are more huge. The waste residues (i.e. overhaul residues) generated by the maintenance and abandonment of the electrolytic cell in the electrolytic aluminum production process are clearly defined as hazardous wastes in the national hazardous waste records revised 3, 30.2016, the category of the wastes is HW48, the codes of the wastes are 321-. Therefore, the overhaul slag is in urgent need of harmless disposal and comprehensive utilization.
Patent CN 109332352A discloses a method for solidifying soluble fluorine in electrolytic aluminum overhaul residues, which utilizes calcium hydroxide, calcium oxide, carbide slag and desulphurization slag to solidify the soluble fluorine in the residues, so as to treat wastes with processes of wastes against one another, but does not solve the problem of cyanogen pollution.
Patent CN 111517349 a discloses a method for recovering aluminum fluoride from overhaul residues of aluminum electrolysis cells, wherein the overhaul residues are leached in acid to obtain a soluble fluoride solution, and aluminum hydroxide is converted and precipitated into crude aluminum fluoride, so as to recover fluorine in the overhaul residues, and the problem of cyanogen pollution is not mentioned.
Patent CN 111495923A discloses a method for treating electrolytic aluminum overhaul waste residue, wherein calcium hypochlorite is used for breaking cyanogen, calcium chloride is used for fixing fluorine and is subjected to harmless treatment and then is buried, fluorine resources and carbon electrode materials cannot be effectively utilized, and chloride ions are introduced during harmless treatment to generate a large amount of waste salt, so that the treated solid waste cannot be recycled due to high chlorine content.
Patent CN 107313075A discloses a useless refractory material heap leaching processing method of building stove of aluminum cell, carries out sodium hydroxide solution heap leaching with broken refractory material to hydrogen peroxide breaks the cyanogen back, with the mixture of carbon dioxide neutralization production sodium bicarbonate, sodium carbonate and sodium fluoride, realizes useless refractory material innoxious, and its product can't direct utilization, and hydrogen peroxide belongs to dangerous chemicals, and hydrogen peroxide liquid transportation may have certain safety risk.
In summary, at present, the treatment of the electrolytic aluminum overhaul residues in China generally adopts a harmless disposal mode, the comprehensive utilization level is low, and the waste of resources is caused. Particularly, at present, governments at all levels pay attention to the action plan of non-waste city construction and waste clearing, how to effectively realize the harmlessness of electrolytic aluminum overhaul residues and how to carry out resource utilization with high added value becomes a hotspot and difficulty of research in the scientific and technological field and the industrial field.
Disclosure of Invention
The purpose of the invention is: the comprehensive treatment device and the comprehensive treatment method for the overhaul residues of the electrolytic aluminum are provided, under the condition that no new impurities are introduced, the harmless treatment of the overhaul residues is solved, the comprehensive utilization of resources is realized to the maximum extent, carbon block materials, sodium fluoride and harmless residues can be obtained, and the comprehensive treatment device and the comprehensive treatment method belong to a green process.
The invention is realized by the following technical scheme: the utility model provides an electrolytic aluminum overhaul sediment integrated processing device which characterized in that: the device is a diaphragm electrolysis device and comprises a plurality of groups of unit cells, wherein each unit cell is formed by spacing an anode and a cathode, an anion membrane is arranged in the unit cell close to the anode, a cation membrane is arranged in the unit cell close to the cathode, partition plates with chambers are respectively arranged among the anode, the anion membrane, the cation membrane and the cathode, and the unit cell is divided into an anode chamber, a solution chamber and a cathode chamber from the anode to the cathode;
the multiple groups of the unit tanks are connected in series and among the tanks are connected in parallel, or the multiple groups of the unit tanks are connected in parallel and among the tanks are connected in series.
Further: the anode adopts an inert electrode to anolyte; the partition board is made of insulating materials and used as a framework for isolating the electrode and the ionic membrane.
The comprehensive treatment method of the electrolytic aluminum overhaul slag is carried out by adopting the device, and is characterized in that: the method comprises the following steps: sorting, crushing, wet grinding and water leaching, filtering and diaphragm electrolysis:
in the sorting and crushing step, the overhaul slag is separated into aluminum slag, carbon blocks and refractory materials through manual sorting and crushed;
the wet milling and water leaching step is to add water into the crushed overhaul residues and grind the crushed overhaul residues to 80 to 200 meshes to form ore pulp, wherein the solid-liquid ratio is 1:2 to 10, and the crushed overhaul residues are soaked in water to prolong the solid-liquid contact time to 10 to 60 minutes;
filtering ore pulp and injecting the ore pulp into a solution chamber, wherein a cathode chamber and an anode chamber are both sodium hydroxide solution, and F is contained in filtrate after electrodes are electrified-、CN-The anode chamber is enriched and cyanogen is broken to produce sodium fluoride and Na+Sodium hydroxide is produced in the cathode chamber.
Further: and in the wet-milling and water-leaching step, water is added into the crushed overhaul slag to grind the crushed overhaul slag into ore pulp of 150 meshes and 200 meshes, the solid-liquid ratio is 1:3-5, and the water is leached to prolong the solid-liquid contact time to 20-40 minutes.
The invention has the advantages that: the method can effectively carry out classification treatment and harmless treatment on the overhaul residues. By adopting a diaphragm electrolysis method, the electrochemical cyanogen breaking is carried out while sodium fluoride is enriched, so that the aluminum slag, the carbon block, the refractory material and the sodium fluoride are respectively recycled.
Drawings
FIG. 1 is a schematic diagram of a parallel structure in a diaphragm electrolytic cell according to the present invention;
FIG. 2 is a schematic view of a series structure in a diaphragm electrolytic cell according to the present invention;
FIG. 3 is a schematic diagram of the structure of a unit cell in the diaphragm electrolytic cell of the present invention;
the sequence numbers in the figures illustrate:
1 is an electrode, 2 is an anion membrane, 3 is a cation membrane, 4 is an anode chamber, 5 is a cathode chamber, 6 is a solution chamber, 7 is an anode, 8 is a cathode, and 9 is a separator.
Detailed Description
As shown in figures 1-3, the comprehensive treatment device for the overhaul slag of the electrolytic aluminum is a diaphragm electrolysis device and comprises a plurality of groups of unit tanks, wherein a plurality of groups of the unit tanks are connected in series and in parallel, or a plurality of groups of the unit tanks are connected in parallel and in series. The unit tank is formed by an anode 7 and a cathode 8 at intervals, an anion membrane 2 is arranged in the unit tank close to the anode, a cation membrane 3 is arranged in the unit tank close to the cathode, partition plates 9 are respectively arranged between the anode, the anion membrane, the cation membrane and the cathode, a cavity is formed between the partition plates and two adjacent structures, each polar plate, each ion membrane and each partition plate divide the unit tank from the anode to the cathode into an anode chamber 4, a solution chamber 6 and a cathode chamber 5, and a liquid inlet and a liquid outlet are formed in each partition plate. The anode chamber 4, the solution chamber 6 and the cathode chamber 5 are all positioned in the cavity of the clapboard 9. Under the action of direct current, anions in the solution chamber 6 penetrate through the anion membrane 2 and enter the anode chamber 4, and easily-oxidizable ions are oxidized due to accumulation in anolyte; cations in the solution chamber 6 penetrate through the cation membrane 3 to enter the cathode chamber 5, and easily reducible ions are reduced by accumulating in the catholyte.
Preferably: the anode adopts an electrode inert to anolyte, the middle electrode is common to the unit tanks on two sides when the electrolysis unit tanks are connected in series, one side is a cathode, and the other side is an anode.
Preferably: the partition board is made of insulating materials and used as a framework (or a frame) for isolating the electrode and the ionic membrane, and the electric conducting liquid is introduced into the partition board, and the partition board, the electrode and the ionic membrane form an anode chamber, a solution chamber and a cathode chamber together.
Preferably: and the anolyte solution, the solution and the catholyte solution in the anode chamber, the solution chamber and the cathode chamber are respectively and independently circulated.
The invention also discloses a comprehensive treatment method of the electrolytic aluminum overhaul slag, which is carried out by adopting the device and comprises the following steps: sorting, crushing, wet grinding and water leaching, filtering and diaphragm electrolysis:
in the sorting and crushing step, the overhaul slag is separated into aluminum slag, carbon blocks and refractory materials through manual sorting and crushed;
the wet milling and water leaching step is to add water into the crushed overhaul residues and grind the crushed overhaul residues to 80 to 200 meshes to form ore pulp, wherein the solid-liquid ratio is 1:2 to 10, and the crushed overhaul residues are soaked in water to prolong the solid-liquid contact time to 10 to 60 minutes;
filtering ore pulp and injecting the ore pulp into a solution chamber, wherein a cathode chamber and an anode chamber are both sodium hydroxide solution, and F is contained in filtrate after electrodes are electrified-、CN-Enriching and breaking cyanogen in anode chamber to produce sodium fluoride，Na+Sodium hydroxide is produced in the cathode chamber.
Preferably: and in the wet-milling and water-leaching step, water is added into the crushed overhaul slag to grind the crushed overhaul slag into ore pulp of 150 meshes and 200 meshes, the solid-liquid ratio is 1:3-5, and the water is leached to prolong the solid-liquid contact time to 20-40 minutes.
The invention is further described below by means of specific examples.
Example 1: collecting 100g of-120 mesh waste refractory (electrolytic aluminum overhaul residue), adding 500ml of water, mechanically stirring at room temperature for 30 min, filtering, and collecting filtrate (using F as fluoride)-Calculated) 2674mg/l, cyanide (calculated as CN)-Calculated) 12.5 mg/l, water immersion constant-pressure diaphragm electrolysis, the electrolytic bath is divided into 6 areas by a graphite plate, an anion membrane, a cation membrane and a graphite plate which are sequentially arranged at intervals of 1cm, the volume of each area is about 120ml, three graphite electrodes are connected in series, the voltage is 8.5V, anolyte 10 percent NaOH, catholyte 2 percent NaOH, the water immersion, the anolyte and the catholyte are not circulated, and the anolyte F is electrolyzed after 1 hour-2632mg/l，CN-Less than 1mg/l, water extract F-35mg/l，CN-Less than 1mg/l, from which water leach F-Most of the carbon is transferred to anolyte to enrich CN-Transferring the solution to anolyte for oxidative decomposition.
Example 2: crushing the sorted carbon blocks, sieving with a 120-mesh sieve, taking 100g of the crushed carbon blocks, adding 450ml of water, mechanically stirring at normal temperature for 40 minutes, and filtering to obtain water extract fluoride (F)-Calculated) 3249mg/l, cyanide (calculated as CN)-Meter) 16.2 mg/l, water immersion constant voltage diaphragm electrolysis under the same electrolysis conditions as example 1 for 1 hour, and anode solution F-3186mg/l，CN-Less than 1mg/l, water extract F-58mg/l，CN-Less than 1mg/l, from which water leach F-Most of the carbon is transferred to anolyte to enrich CN-Transferring the solution to anolyte for oxidative decomposition.
Example 3: taking 100g of-120 mesh waste refractory material each time, adding 500ml of recycled water after diaphragm electrolysis, mechanically stirring at normal temperature for 30 minutes, filtering, subjecting the water extract to diaphragm electrolysis (electrolysis conditions are the same as example 1), returning to water extract for recycling, replacing the water extract during diaphragm electrolysis, continuously using the anode solution and the cathode solution, and recycling the anode solution and the cathode solution for 4 timesLiquid F-10.23g/l，CN-Less than 1mg/l, water extract F-84mg/l，CN-Less than 1mg/l, breaking cyanogen in the anode chamber and F in the anolyte-The enriched product is obtained, and the energy consumption of the NaF concentration and crystallization is greatly reduced.
Claims (4)
1. The utility model provides an electrolytic aluminum overhaul sediment integrated processing device which characterized in that: the device is a diaphragm electrolysis device and comprises a plurality of groups of unit cells, wherein each unit cell is formed by spacing an anode and a cathode, an anion membrane is arranged in the unit cell close to the anode, a cation membrane is arranged in the unit cell close to the cathode, partition plates with chambers are respectively arranged among the anode, the anion membrane, the cation membrane and the cathode, and the unit cell is divided into an anode chamber, a solution chamber and a cathode chamber from the anode to the cathode;
the multiple groups of the unit tanks are connected in series and among the tanks are connected in parallel, or the multiple groups of the unit tanks are connected in parallel and among the tanks are connected in series.
2. The apparatus of claim 1, wherein: the anode adopts an inert electrode to anolyte; the partition board is made of insulating materials and used as a framework for isolating the electrode and the ionic membrane.
3. An electrolytic aluminum overhaul slag comprehensive treatment method which is carried out by adopting the device as claimed in claim 1 or 2, and is characterized in that: the method comprises the following steps: sorting, crushing, wet grinding and water leaching, filtering and diaphragm electrolysis:
in the sorting and crushing step, the overhaul slag is separated into aluminum slag, carbon blocks and refractory materials through manual sorting and crushed;
the wet milling and water leaching step is to add water into the crushed overhaul residues and grind the crushed overhaul residues to 80 to 200 meshes to form ore pulp, wherein the solid-liquid ratio is 1:2 to 10, and the crushed overhaul residues are soaked in water to prolong the solid-liquid contact time to 10 to 60 minutes;
filtering ore pulp and injecting the ore pulp into a solution chamber, wherein a cathode chamber and an anode chamber are both sodium hydroxide solution, and F is contained in filtrate after electrodes are electrified-、CN-The anode chamber is enriched and cyanogen is broken to produce sodium fluoride and Na+Rich product in cathode chamberAnd (6) discharging sodium hydroxide.
4. The method of claim 3, wherein: and in the wet-milling and water-leaching step, water is added into the crushed overhaul slag to grind the crushed overhaul slag into ore pulp of 150 meshes and 200 meshes, the solid-liquid ratio is 1:3-5, and the water is leached to prolong the solid-liquid contact time to 20-40 minutes.
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| CN202011574616.1A CN112718805A (en) | 2020-12-28 | 2020-12-28 | Electrolytic aluminum overhaul slag comprehensive treatment device and treatment method |
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| CN202011574616.1A CN112718805A (en) | 2020-12-28 | 2020-12-28 | Electrolytic aluminum overhaul slag comprehensive treatment device and treatment method |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115744870A (en) * | 2022-11-23 | 2023-03-07 | 浙江天象环境服务有限公司 | Electrolytic aluminum waste carbon electrode wet resource utilization system and method |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115744870A (en) * | 2022-11-23 | 2023-03-07 | 浙江天象环境服务有限公司 | Electrolytic aluminum waste carbon electrode wet resource utilization system and method |
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