CN114560483A - Method for comprehensively recycling aluminum ash - Google Patents
Method for comprehensively recycling aluminum ash Download PDFInfo
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- CN114560483A CN114560483A CN202210194904.7A CN202210194904A CN114560483A CN 114560483 A CN114560483 A CN 114560483A CN 202210194904 A CN202210194904 A CN 202210194904A CN 114560483 A CN114560483 A CN 114560483A
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- aluminum ash
- aluminum
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- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 93
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 93
- 238000000034 method Methods 0.000 title claims abstract description 38
- 238000004064 recycling Methods 0.000 title claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 41
- 238000005406 washing Methods 0.000 claims abstract description 27
- 239000000463 material Substances 0.000 claims abstract description 25
- 239000002994 raw material Substances 0.000 claims abstract description 20
- 239000003513 alkali Substances 0.000 claims abstract description 17
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 17
- 238000002386 leaching Methods 0.000 claims abstract description 17
- 239000007788 liquid Substances 0.000 claims abstract description 16
- 239000002893 slag Substances 0.000 claims abstract description 16
- 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 claims abstract description 15
- 239000011734 sodium Substances 0.000 claims abstract description 15
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 15
- 238000004364 calculation method Methods 0.000 claims abstract description 14
- 230000002308 calcification Effects 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 10
- 230000004927 fusion Effects 0.000 claims abstract description 8
- 239000011737 fluorine Substances 0.000 claims abstract description 7
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 7
- 238000002791 soaking Methods 0.000 claims abstract description 7
- 239000004568 cement Substances 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 238000011033 desalting Methods 0.000 claims abstract description 3
- 238000000926 separation method Methods 0.000 claims abstract description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims abstract 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 12
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 12
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims description 9
- 229910001634 calcium fluoride Inorganic materials 0.000 claims description 9
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical group [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 9
- 239000000292 calcium oxide Substances 0.000 claims description 9
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- 239000001103 potassium chloride Substances 0.000 claims description 6
- 235000011164 potassium chloride Nutrition 0.000 claims description 6
- 239000011780 sodium chloride Substances 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 4
- 239000012528 membrane Substances 0.000 claims description 4
- 238000010521 absorption reaction Methods 0.000 claims description 2
- 238000004458 analytical method Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 8
- 239000003344 environmental pollutant Substances 0.000 abstract description 6
- 231100000719 pollutant Toxicity 0.000 abstract description 6
- 239000002920 hazardous waste Substances 0.000 abstract description 5
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- 238000000921 elemental analysis Methods 0.000 abstract 1
- 238000002441 X-ray diffraction Methods 0.000 description 12
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 10
- 239000011575 calcium Substances 0.000 description 10
- 229910052791 calcium Inorganic materials 0.000 description 10
- 239000007789 gas Substances 0.000 description 9
- 150000003839 salts Chemical class 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000001704 evaporation Methods 0.000 description 8
- 230000008020 evaporation Effects 0.000 description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- -1 aluminum compound Chemical class 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000010612 desalination reaction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 150000002222 fluorine compounds Chemical class 0.000 description 2
- 239000010797 grey water Substances 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000010587 phase diagram Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 101001018064 Homo sapiens Lysosomal-trafficking regulator Proteins 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 102100033472 Lysosomal-trafficking regulator Human genes 0.000 description 1
- 235000010703 Modiola caroliniana Nutrition 0.000 description 1
- 244000038561 Modiola caroliniana Species 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001698 pyrogenic effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
- C01F7/04—Preparation of alkali metal aluminates; Aluminium oxide or hydroxide therefrom
- C01F7/06—Preparation of alkali metal aluminates; Aluminium oxide or hydroxide therefrom by treating aluminous minerals or waste-like raw materials with alkali hydroxide, e.g. leaching of bauxite according to the Bayer process
- C01F7/0693—Preparation of alkali metal aluminates; Aluminium oxide or hydroxide therefrom by treating aluminous minerals or waste-like raw materials with alkali hydroxide, e.g. leaching of bauxite according to the Bayer process from waste-like raw materials, e.g. fly ash or Bayer calcination dust
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/24—Sulfates of ammonium
- C01C1/242—Preparation from ammonia and sulfuric acid or sulfur trioxide
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D3/00—Halides of sodium, potassium or alkali metals in general
- C01D3/04—Chlorides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D3/00—Halides of sodium, potassium or alkali metals in general
- C01D3/14—Purification
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
- C01F7/04—Preparation of alkali metal aluminates; Aluminium oxide or hydroxide therefrom
- C01F7/06—Preparation of alkali metal aluminates; Aluminium oxide or hydroxide therefrom by treating aluminous minerals or waste-like raw materials with alkali hydroxide, e.g. leaching of bauxite according to the Bayer process
- C01F7/0613—Pretreatment of the minerals, e.g. grinding
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B7/00—Hydraulic cements
- C04B7/24—Cements from oil shales, residues or waste other than slag
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B21/00—Obtaining aluminium
- C22B21/0015—Obtaining aluminium by wet processes
- C22B21/0023—Obtaining aluminium by wet processes from waste materials
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B21/00—Obtaining aluminium
- C22B21/0038—Obtaining aluminium by other processes
- C22B21/0069—Obtaining aluminium by other processes from scrap, skimmings or any secondary source aluminium, e.g. recovery of alloy constituents
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/001—Dry processes
- C22B7/002—Dry processes by treating with halogens, sulfur or compounds thereof; by carburising, by treating with hydrogen (hydriding)
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/04—Working-up slag
-
- 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
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding
Abstract
The invention discloses a method for comprehensively recycling aluminum ash, which comprises the following steps: washing and desalting the aluminum ash to obtain washed aluminum ash and washing liquid; drying the washed aluminum ash, and performing elemental analysis; then carrying out thermodynamic calculation of calcification alkali fusion according to the contents of aluminum and fluorine, then adding an alkali fusing agent and a calcification agent into the aluminum ash according to the result of the thermodynamic calculation, and uniformly mixing to obtain a roasting raw material; roasting the roasting raw material to obtain a roasted material; soaking the roasted material in water, and then carrying out solid-liquid separation to obtain a water leaching solution and water leaching residues; concentrating and crystallizing the water leaching solution to obtain sodium metaaluminate; and drying the water leaching slag, and then using the water leaching slag in the cement industry. The method of the invention treats the harmful substances in the aluminum ash and recycles the valuable elements in the aluminum ash, and no pollutant is discharged, and simultaneously the valuable metal resources in the aluminum ash are utilized to the maximum extent, thereby realizing the recycling of the aluminum metal resources and the harmless disposal of hazardous wastes.
Description
Technical Field
The invention belongs to the technical field of solid hazardous waste treatment, and particularly relates to a method for comprehensively recycling aluminum ash.
Background
In the process of producing aluminum, the aluminum processing industry (electrolytic aluminum, aluminum casting, waste aluminum regeneration and the like) can generate waste materials containing high-content aluminum elements, wherein the content of the aluminum elements is often several times of that of ore resources, and the waste materials have great resource property, meanwhile, aluminum ash is also the forty-eight harmful waste in national hazardous waste records, and heavy metals (the content of the heavy metals is less, and mainly fluoride and soluble salts) cause great harm to human health and environment.
Because the aluminum ash has complex components, difficult disposal and higher economic cost, the aluminum ash is only subjected to simple stockpiling or landfill treatment before. However, since it contains substances harmful to the natural environment and human health, it must be treated, and at present, the treatment methods of aluminum ash are divided into two categories, namely disposal methods and recycling treatment.
Aiming at the treatment method of the aluminum ash, although the harmless treatment method is simple, the utilization value of valuable elements in the aluminum ash is ignored, the resource treatment mode has complex process flow, great treatment difficulty and higher economic cost, so that the aluminum ash is still in the situation that a large amount of aluminum ash is stockpiled and cannot be recycled at present. Although the aluminum ash harmless treatment technology is relatively mature, the current harmless treatment method can cause that a large amount of valuable aluminum elements cannot be continuously recycled. At present, the research of a method for efficiently recycling valuable resources of aluminum ash to the maximum extent while harmlessly treating the aluminum ash is newly reported, so that the research of a simple and effective solid waste recycling method is necessary.
Disclosure of Invention
The invention aims to provide a method for comprehensively recycling aluminum ash, which has the advantages of simple process, environmental friendliness, no pollutant discharge and high-efficiency resource recycling.
The method for comprehensively recycling the aluminum ash comprises the following steps:
1) washing and desalting the aluminum ash to obtain washed aluminum ash and washing liquid;
2) drying the washed aluminum ash in the step 1), and performing element analysis; then carrying out thermodynamic calculation of calcification alkali fusion according to the contents of aluminum and fluorine, then adding an alkali fusing agent and a calcification agent into the aluminum ash according to the result of the thermodynamic calculation, and uniformly mixing to obtain a roasting raw material;
3) roasting the roasting raw material in the step 2) in a muffle furnace to obtain a roasted material after roasting is finished;
4) soaking the roasted material in the step 3) in water, and after the soaking is finished, carrying out solid-liquid separation to obtain a water leaching solution and water leaching slag;
5) concentrating and crystallizing the water extract obtained in the step 4) to obtain sodium metaaluminate; and drying the water leaching slag, and then using the water leaching slag in the cement industry.
And in the step 1), the obtained water washing liquid is further treated by an ion permeable membrane, and sodium chloride and potassium chloride are recovered.
In the step 1), gas can be generated in the washing process, the generated gas is collected and absorbed by dilute sulfuric acid, and the residual gas after absorption can supply energy for the roasting process. In the washing process, a small amount of metal aluminum in the material reacts with water to generate hydrogen, aluminum nitride is hydrolyzed to generate ammonia gas, the aqueous solution becomes alkaline, and the ammonia gas overflows.
In the step 1), washing is carried out according to a liquid-solid ratio of (7-9) mL/1g, and the washing time is 5-7 h.
In the step 2), the alkali fusing agent is sodium hydroxide, and the calcification agent is calcium oxide; according to thermodynamic calculation, the adding amount of sodium hydroxide is added according to the molar ratio of aluminum to sodium of 1: 0.6-1.4, and the adding amount of calcium oxide is added according to the molar ratio of calcium fluoride of 1: 2.0-7.0.
In the step 3), the roasting temperature is 600-1000 ℃, and the roasting time is 0.5-2.5 h.
In the step 4), the liquid-solid ratio of water leaching is (5-7) to 1, and the leaching time is 20-40 min.
The principle of the invention is as follows: the invention takes the aluminum ash as the main roasting raw material, calcium oxide and sodium hydroxide are added as external raw materials, fluorine in the aluminum ash and a calcium source are combined and solidified to generate stable calcium fluoride and calcium fluoroaluminate under the high temperature condition, simultaneously, an aluminum compound in the aluminum ash reacts with the sodium hydroxide to generate sodium metaaluminate, after water immersion, aluminum elements enter an aqueous solution in the form of the sodium metaaluminate, and the calcium fluoride and the calcium fluoroaluminate are stably remained in residues, thereby achieving the aim of harmlessly and efficiently recycling the aluminum elements.
The invention has the beneficial effects that: firstly, processing raw materials, knowing the basic physical and chemical properties of the raw materials, then carrying out thermodynamic calculation on known substances in the materials, mixing a calcification agent and an alkali flux with aluminum ash according to a calculation result, and carrying out roasting reaction, so that harmful fluorine elements in the aluminum ash can be solidified and recovered to utilize fluorine, and meanwhile, high-content aluminum resources are recovered in the form of sodium metaaluminate; the method treats the harmful substances in the aluminum ash and simultaneously recycles the valuable elements in the aluminum ash, discharges no pollutants, simultaneously utilizes the valuable metal resources in the aluminum ash to the maximum extent, realizes the recycling of the aluminum metal resources and the harmless disposal of hazardous wastes, and further has the advantages of simple process, no pollutant discharge in the whole process flow and environmental friendliness.
Drawings
FIG. 1 is a process flow diagram of the present invention;
FIG. 2 is an XRD analysis of the aluminum grey water wash of example 1 after evaporative crystallization;
FIG. 3 is an XRD analysis chart of an aluminum ash calcified alkali fused material in example 1;
FIG. 4 is an XRD analysis of the grey water aluminum dross in example 1;
FIG. 5 is an XRD analysis pattern of the water immersion liquid after evaporation and crystallization in example 1.
Detailed Description
The following description is only exemplary of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily made by those skilled in the art within the technical scope of the present invention are within the scope of the present invention and the disclosure.
Example 1
A harmless and efficient recycling treatment method for aluminum ash comprises the following steps according to the flow shown in figure 1:
(1) 30g of aluminum ash raw material is taken and washed for 6h for desalination pretreatment according to the liquid-solid ratio of 8mL:1g, bubbles can be generated during washing (in view of the fact that only a small amount of treatment is performed in the embodiment, gas is not recovered, and the generated gas needs to be collected during large-scale treatment), after washing, filtration and drying are performed on the washed water, evaporation concentration crystallization is performed on the washed water, and the XRD phase chromatogram after evaporation concentration of the washed water is shown in FIG. 2, which is known from FIG. 2: the main components of the water-soluble salt are soluble salts, mainly sodium chloride and potassium chloride (because the amount of the washing water in the embodiment is less, if the water-soluble salt is treated in a large scale, the water-soluble salt can be further purified through an ion permeable membrane, and the sodium chloride and the potassium chloride are recovered); and drying the washing slag to obtain the washed aluminum ash.
(2) And (3) analyzing the element content of the washed aluminum ash, wherein the aluminum ash as the raw material contains 33.52% of Al, 11% of F and a small amount of oxides of calcium, silicon, iron, magnesium and the like.
(3) And (3) carrying out thermodynamic calculation on the reaction process in the step (2), and mainly calculating the reaction thermodynamics of the aluminum compound and the fluorine compound after the calcium agent and the alkali fusing agent are added.
(4) Taking 20.0g of the aluminum ash washed by the water in the step (1), adding calcium hydroxide and calcium oxide into the aluminum ash to prepare a calcified alkali fusion mixed material; the adding amount of the sodium hydroxide is the ratio of the aluminum to the sodium in a molar ratio of 1:0.6, and the adding amount of the calcium oxide is the ratio of the calcium fluoride in a molar ratio of 1: 6.0.
(5) Adding the calcified alkali-fused mixed material obtained in the step (4) into a 100mL ceramic crucible, sending the mixture into a muffle furnace, adjusting the temperature to 1000 ℃, reacting for 2.0h to obtain a calcified alkali-fused material, and performing XRD (X-ray diffraction) test on the obtained calcified alkali-fused material, wherein the main components of the calcified alkali-fused material are sodium metaaluminate, calcium fluoride and calcium fluoroaluminate, and the result is shown in figure 3.
(6) And (3) soaking the calcified alkali fusion material obtained in the step (5) in water for 40min according to the liquid-solid ratio of 6mL:1g, filtering to obtain water-soaked slag and water-soaked liquid, and evaporating and crystallizing the water-soaked liquid to obtain a sodium metaaluminate product, wherein the water-soaked slag can be used as a cement production raw material. The XRD phase diagram of the water-immersed slag is shown in figure 4, and the main components of the water-immersed slag are calcium fluoride and calcium fluoroaluminate which can be used as raw materials in the cement preparation process. The XRD phase diagram of the water extract evaporation concentrated crystal is shown in figure 5, and the main component of the water extract evaporation concentrated crystal is sodium metaaluminate.
Example 2
A harmless and efficient recycling treatment method for aluminum ash comprises the following steps according to the flow shown in figure 1:
(2) 500g of aluminum ash raw material is taken to be washed with water for 6h for desalination pretreatment according to the liquid-solid ratio of 8mL to 1g, bubbles can be seen to be generated during washing, gas is collected at the same time, the aluminum ash raw material sequentially passes through a test tube with wet red test paper and a test tube with heated black copper oxide powder, the wet red test paper turns blue, the black copper oxide powder gradually turns to mauve along with the continuous introduction of the gas, and the fact that ammonia gas and hydrogen gas are generated in the washing process is proved (because the gas generation amount is less, the gas is not recovered). After the water washing is finished, filtering and drying, taking a small amount of water washing liquid to evaporate, concentrate and crystallize the water washing liquid, wherein the XRD phase atlas of the water washing liquid after evaporation and concentration is shown in figure 2, and can be known from figure 2: the main components of the water-soluble salt are soluble salts, mainly sodium chloride and potassium chloride (because the amount of the washing water in the embodiment is less, if the water-soluble salt is treated in a large scale, the water-soluble salt can be further purified through an ion permeable membrane, and the sodium chloride and the potassium chloride are recovered); and drying the washing slag to obtain the washed aluminum ash.
(2) And (3) analyzing the element content of the washed aluminum ash, wherein the aluminum ash as the raw material contains 34.45% of Al, 10.7% of F and a small amount of oxides of calcium, silicon, iron, magnesium and the like.
(3) And (3) carrying out thermodynamic calculation on the reaction process in the step (2), and mainly calculating the reaction thermodynamics of the aluminum compound and the fluorine compound after the calcium agent and the alkali fusing agent are added.
(4) Taking 20.0g of the aluminum ash washed by the water in the step (1), adding calcium hydroxide and calcium oxide into the aluminum ash to prepare a calcified alkali fusion mixed material; the adding amount of the sodium hydroxide is 1:1.0 of the molar ratio of the aluminum to the sodium and the adding amount of the calcium oxide is 1:5.0 of the molar ratio of the calcium fluoride.
(5) Adding the calcified alkali-fused mixed material obtained in the step (4) into a 100mL ceramic crucible, sending the mixture into a muffle furnace, adjusting the temperature to 800 ℃, reacting for 2.5 hours to obtain a calcified alkali-fused material, and performing XRD (X-ray diffraction) test on the obtained calcified alkali-fused material, wherein the main components of the calcified alkali-fused material are sodium metaaluminate, calcium fluoride and calcium fluoroaluminate, and the result is shown in figure 3.
(6) And (3) soaking the calcified alkali fusion material obtained in the step (5) in water for 30min according to the liquid-solid ratio of 7mL:1g, and filtering to obtain water-soaked slag and water-soaked liquid, evaporating and crystallizing the water-soaked liquid to obtain a sodium metaaluminate product, wherein the water-soaked slag can be used as a cement production raw material.
The method comprises the steps of mixing a calcification agent and an alkali fusion agent with aluminum ash according to a certain proportion for reaction, wherein the technical key point is pyrogenic treatment, so that valuable elements in the aluminum ash can be recycled while harmful substances in the aluminum ash are treated, no pollutant is discharged, valuable metal resources in the aluminum ash are utilized to the maximum extent, the recovery of the aluminum metal resources and the harmless treatment of hazardous wastes are realized, and the treatment method is simple in process and environment-friendly.
In conclusion, the method firstly needs to process the raw materials, knows the basic physical and chemical properties of the raw materials, then carries out thermodynamic calculation on the known substances in the materials, carries out reaction material proportioning on the materials according to the calculation result, takes the ceramic crucible as a container, and sends the materials into the muffle furnace for high-temperature reaction, so that harmful fluorine elements in the aluminum ash can be solidified and recycled, meanwhile, high-content aluminum resources can be recycled, and meanwhile, the whole process flow has no pollutant emission and is environment-friendly.
Claims (7)
1. A method for comprehensively recycling aluminum ash comprises the following steps:
1) washing and desalting the aluminum ash to obtain washed aluminum ash and washing liquid;
2) drying the washed aluminum ash in the step 1), and performing element analysis; then carrying out thermodynamic calculation of calcification alkali fusion according to the contents of aluminum and fluorine, then adding an alkali fusing agent and a calcification agent into the aluminum ash according to the result of the thermodynamic calculation, and uniformly mixing to obtain a roasting raw material;
3) roasting the roasting raw material in the step 2) in a muffle furnace to obtain a roasted material after roasting is finished;
4) soaking the roasted material in the step 3) in water, and after the soaking is finished, carrying out solid-liquid separation to obtain a water leaching solution and water leaching slag;
5) concentrating and crystallizing the water extract obtained in the step 4) to obtain sodium metaaluminate; and drying the water leaching slag, and then using the water leaching slag in the cement industry.
2. The method for comprehensively recycling aluminum ash as claimed in claim 1, wherein the water washing liquid obtained in step 1) is further treated by an ion permeable membrane to recover sodium chloride and potassium chloride.
3. The method for comprehensively recycling the aluminum ash according to claim 1, wherein in the step 1), gas is generated in the washing process, the generated gas is collected and absorbed by dilute sulfuric acid, and the residual gas after absorption can supply energy for the roasting process.
4. The method for comprehensively recycling the aluminum ash as claimed in claim 1, wherein in the step 1), the washing is carried out according to a liquid-solid ratio of (7-9) mL/1g, and the washing time is 5-7 h.
5. The method for comprehensively recycling aluminum ash according to claim 1, wherein in the step 2), the alkali fusing agent is sodium hydroxide, and the calcification agent is calcium oxide; according to thermodynamic calculation, the adding amount of sodium hydroxide is added according to the molar ratio of aluminum to sodium of 1: 0.6-1.4, and the adding amount of calcium oxide is added according to the molar ratio of calcium fluoride of 1: 2.0-7.0.
6. The method for comprehensively recycling the aluminum ash according to claim 1, wherein in the step 3), the roasting temperature is 600-1000 ℃ and the roasting time is 0.5-2.5 h.
7. The method for comprehensively recycling the aluminum ash according to claim 1, wherein in the step 4), the liquid-solid ratio of water leaching is 5-7 mL:1g, and the leaching time is 20-40 min.
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