CN115193894B - Clean recycling treatment system and method for aluminum ash - Google Patents
Clean recycling treatment system and method for aluminum ash Download PDFInfo
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- CN115193894B CN115193894B CN202210784501.8A CN202210784501A CN115193894B CN 115193894 B CN115193894 B CN 115193894B CN 202210784501 A CN202210784501 A CN 202210784501A CN 115193894 B CN115193894 B CN 115193894B
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 113
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 110
- 238000000034 method Methods 0.000 title claims abstract description 39
- 238000004064 recycling Methods 0.000 title claims abstract description 27
- 239000001257 hydrogen Substances 0.000 claims abstract description 36
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 36
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000007789 gas Substances 0.000 claims abstract description 20
- 239000000047 product Substances 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims description 43
- 239000002253 acid Substances 0.000 claims description 39
- 238000005406 washing Methods 0.000 claims description 39
- 239000007788 liquid Substances 0.000 claims description 33
- 238000004090 dissolution Methods 0.000 claims description 29
- 238000000498 ball milling Methods 0.000 claims description 25
- 238000001354 calcination Methods 0.000 claims description 25
- 239000000463 material Substances 0.000 claims description 25
- 238000003860 storage Methods 0.000 claims description 23
- 238000001035 drying Methods 0.000 claims description 17
- 238000000926 separation method Methods 0.000 claims description 17
- 238000010517 secondary reaction Methods 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 15
- 239000002893 slag Substances 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 11
- 238000012216 screening Methods 0.000 claims description 11
- 230000018044 dehydration Effects 0.000 claims description 10
- 238000006297 dehydration reaction Methods 0.000 claims description 10
- 239000003513 alkali Substances 0.000 claims description 9
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 9
- 239000012535 impurity Substances 0.000 claims description 9
- 238000000746 purification Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 8
- -1 hydrogen ions Chemical class 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 8
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 7
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 7
- 238000010521 absorption reaction Methods 0.000 claims description 7
- 238000002485 combustion reaction Methods 0.000 claims description 7
- 239000004571 lime Substances 0.000 claims description 7
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 7
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 claims description 6
- 239000000706 filtrate Substances 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 229910052749 magnesium Inorganic materials 0.000 claims description 5
- 239000011777 magnesium Substances 0.000 claims description 5
- 238000012545 processing Methods 0.000 claims description 5
- 238000005273 aeration Methods 0.000 claims description 4
- 239000012295 chemical reaction liquid Substances 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- 230000000087 stabilizing effect Effects 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 8
- 239000002699 waste material Substances 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 238000011084 recovery Methods 0.000 abstract description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052799 carbon Inorganic materials 0.000 abstract description 3
- 239000011737 fluorine Substances 0.000 abstract description 3
- 229910052731 fluorine Inorganic materials 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 abstract description 2
- 235000011130 ammonium sulphate Nutrition 0.000 abstract description 2
- 239000007795 chemical reaction product Substances 0.000 abstract description 2
- 238000004134 energy conservation Methods 0.000 abstract description 2
- 150000002431 hydrogen Chemical class 0.000 abstract description 2
- 239000002351 wastewater Substances 0.000 abstract description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 abstract 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000003723 Smelting Methods 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000002910 solid waste Substances 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- 239000002585 base Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000011978 dissolution method Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000002920 hazardous waste Substances 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000012629 purifying agent Substances 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- 238000011278 co-treatment Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- QPILZZVXGUNELN-UHFFFAOYSA-M sodium;4-amino-5-hydroxynaphthalene-2,7-disulfonate;hydron Chemical compound [Na+].OS(=O)(=O)C1=CC(O)=C2C(N)=CC(S([O-])(=O)=O)=CC2=C1 QPILZZVXGUNELN-UHFFFAOYSA-M 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/80—Destroying solid waste or transforming solid waste into something useful or harmless involving an extraction step
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/30—Destroying solid waste or transforming solid waste into something useful or harmless involving mechanical treatment
- B09B3/35—Shredding, crushing or cutting
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/40—Destroying solid waste or transforming solid waste into something useful or harmless involving thermal treatment, e.g. evaporation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/70—Chemical treatment, e.g. pH adjustment or oxidation
-
- 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
- C01F7/48—Halides, with or without other cations besides aluminium
- C01F7/56—Chlorides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B2101/00—Type of solid waste
- B09B2101/55—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
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Environmental & Geological Engineering (AREA)
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Thermal Sciences (AREA)
- Geology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention relates to a clean recycling treatment system and method for aluminum ash, and belongs to the technical field of energy conservation, emission reduction and recycling. The recovery system and the method utilize simple substance aluminum resources in aluminum ash, combine with the subsequent aluminum resource recovery process, generate clean energy hydrogen, and simultaneously, the hydrogen energy is used as raw materials for producing rear-end products, thereby greatly reducing the discharge amount of aluminum ash roasting carbon, realizing self-sufficiency of heat sources, removing nitrogen and fluorine before the aluminum polymer production stage, recovering tail gas ammonia gas to produce ammonium sulfate, finally preparing industrial products of aluminum polychloride with higher quality, avoiding the problems of waste tail gas, waste residue, waste water and the like in the process treatment process, and realizing clean recycling treatment in the true sense.
Description
Technical Field
The invention relates to a smelting aluminum ash recycling process, belongs to the technical field of energy conservation, emission reduction and recycling, and particularly relates to a clean recycling treatment system and method for aluminum ash.
Background
The aluminum ash is produced in all molten aluminum processes, and mainly includes: raw aluminum production (electrolytic aluminum), aluminum alloy production, waste aluminum recovery and regeneration and aluminum ash treatment process. Generally, the aluminum ash is classified into primary aluminum ash and secondary aluminum ash according to the content of aluminum metal in the aluminum ash. The aluminum slag scraped from the smelting furnace is called primary aluminum ash, appears gray white in appearance and is mainly a mixture composed of metal aluminum and aluminum oxide, and the aluminum content can reach 15% -70%, and is also called white aluminum ash; the secondary aluminum ash is waste after the primary aluminum ash extracts aluminum metal, and the main components of the secondary aluminum ash are aluminum oxide, aluminum nitride, aluminum metal, salts and other components, and the secondary aluminum ash is solidified into a block shape and is also called as salt cake.
After aluminum ash is defined as hazardous waste, conventional rough handling is not feasible. The utilization of the aluminum ash treatment process flow should fully consider the environmental risk in the utilization process, and accords with the relevant technical requirements of solid waste identification standard rule (GB 34330), solid waste recycling pollution control technical rule (HJ 1091), cement kiln co-treatment solid waste environmental protection technical specification (HJ 662) and the like. For the aluminum ash which is difficult to be utilized, harmless treatment is carried out in a landfill mode and the like, and the aluminum ash meets the related technical requirements of hazardous waste landfill pollution control standard (GB 18598) and the like.
One recycling mode of the aluminum ash is to prepare a water purifying agent, and the aluminum sulfate water purifying agent produced by a sulfuric acid dissolution method is the main application of the aluminum ash at present, and the production flow of aluminum sulfate is as follows: aluminum ash-reaction (adding sulfuric acid solution) -filtration-impurity removal-concentration-cooling crystallization-aluminum sulfate finished product. The prior art also provides a method for preparing liquid polyaluminium chloride by taking aluminum ash and hydrochloric acid as raw materials and adopting an acid dissolution method. However, pollutants still can be generated in the recycling process, and the technical purposes of low carbon, cleaning and recycling cannot be achieved.
Disclosure of Invention
In order to solve the technical problems, the invention discloses a clean recycling treatment system and method for aluminum ash. The system and the method not only recycle the waste, but also realize clean recycling treatment in the true sense.
In order to achieve the technical aim, the invention discloses a clean recycling treatment system for aluminum ash, which comprises a first ball milling device, a screening device, a secondary micro negative pressure water washing tank, a centrifugal solid-liquid separation system, an acid dissolution reaction kettle, a first filter press, a second ball milling device, a drying calcining kiln, a secondary reaction kettle and a second filter press which are connected in sequence;
the secondary micro negative pressure washing tank comprises a primary washing tank and a secondary washing tank which are connected in series, a liquid discharge end is arranged on the centrifugal solid-liquid separation system and connected with the primary washing tank, a solid outlet is also arranged on the centrifugal solid-liquid separation system and is respectively connected with the acid dissolution reaction kettle and the second ball milling device;
the liquid outlet on the first filter press is connected with the secondary reaction kettle, and the solid outlet on the first filter press is connected with the second ball milling device;
the exhaust port of the acid dissolution reaction kettle is sequentially connected with a primary alkali filtration deacidification tank and an active alumina dehydration tank, the active alumina dehydration tank is connected with a PSA hydrogen purification system through a pressure pump, the PSA hydrogen purification system is connected with a hydrogen storage tank, and the hydrogen storage tank is respectively connected with a combustion device arranged on the drying calcining kiln and a steam boiler arranged on the secondary reaction kettle;
an air inlet of the acid dissolution reaction kettle is connected with an inert gas storage tank.
Further, the exhaust port and the air inlet end of the acid dissolution reaction kettle are both provided with flow control valves, and a pressure pump is also arranged on a connecting pipeline of the exhaust port and the primary alkali filtration deacidification tank.
Further, the pressure in the acid dissolution reaction kettle is less than 0.05-0.1 MPa.
Further, a pressure reducing valve and a pressure stabilizing valve component are arranged on a pipeline connected with the combustion device and the steam boiler of the hydrogen storage tank.
Further, the exhaust end of the secondary washing tank is connected with a gas absorption tower for containing acid liquor.
The second purpose of the invention is to disclose a clean recycling treatment method of aluminum ash, which is carried out in a treatment system, wherein the treatment system comprises a first ball milling device, a screening device, a secondary micro negative pressure washing tank, a centrifugal solid-liquid separation system, an acid dissolution reaction kettle, a first filter press, a second ball milling device, a drying calcining kiln, a secondary reaction kettle and a second filter press which are connected in sequence; the exhaust port of the acid dissolution reaction kettle is sequentially connected with a primary alkali filtration deacidification tank and an active alumina dehydration tank, the active alumina dehydration tank is connected with a PSA hydrogen purification system through a pressure pump, the PSA hydrogen purification system is connected with a hydrogen storage tank, and the hydrogen storage tank is respectively connected with a combustion device arranged on the drying calcining kiln and a steam boiler arranged on the secondary reaction kettle;
the specific processing steps are as follows:
1) The aluminum ash is ball-milled by a first ball milling device and then is sent to a screening device for screening to obtain coarse materials and fine materials; wherein the grain diameter of the fine material is smaller than 100 meshes, and the coarse material is used as the secondary smelting of the metal aluminum.
2) Fine materials enter a secondary micro negative pressure washing tank, are washed by a primary washing tank, enter the secondary washing tank, are subjected to aeration treatment, and are transferred to a centrifugal solid-liquid separation system, and gas is discharged into a gas absorption tower connected with the secondary washing tank; wherein, the micro negative pressure is to maintain the micro negative pressure of the reaction system to prevent the generated ammonia from leaking out, the invention preferably carries out primary water washing for 30-60 min, and more preferably 30min; aeration treatment is carried out for 10-30 min, preferably 30min in the secondary water washing process;
3) The solid obtained by separating the mixed material in a centrifugal solid-liquid separation system is water-washed aluminum ash A, and filtrate is recycled to a first-stage water washing tank after being added with a defluorinating agent for precipitation; the fluorine removing agent is a common type;
4) Delivering part of the water-washed aluminum ash A into an acid dissolution reaction kettle, delivering tail gas generated by the reaction of the water-washed aluminum ash A and acid liquor into a hydrogen storage tank, treating reaction liquid by a first filter press to obtain acid dissolution slag B and solution A, and leaving the water-washed aluminum ash A for later use; wherein the mass ratio of the water-washed aluminum ash A to the acid liquor is 1 (3-7); controlling the pressure in the acid dissolution reaction kettle to be 0.05-0.1 MPa, and introducing inert gases such as nitrogen, helium and the like into the acid dissolution reaction kettle to discharge air in the kettle before reaction; the reaction liquid is subjected to filter pressing treatment by a first filter press for more than 1 hour at normal temperature;
5) Mixing the rest water-washed aluminum ash slag A with lime according to a ratio of 2:1 to obtain a mixture C1, mixing the acid-soluble slag B in the step 4) with lime according to a ratio of 3:2 to obtain a mixture C2, sending the mixture C2 into a second ball milling device, ball milling and crushing the mixture to obtain fine powder with a particle size not more than 180 meshes, sending the fine powder into a drying calcining kiln, controlling the temperature of the first-stage calcining kiln to be 720-750 ℃ and the reaction time to be 80-120 minutes, sending the fine powder into a second-stage calcining kiln, and cooling the second-stage calcining kiln to obtain an aluminum-based calcined material, wherein the temperature is 1100-1115 ℃ and the reaction time is 110-130 minutes; wherein 20-40% of the heat source of the drying calcining kiln is from a hydrogen storage tank; and the quality of the lime meets the requirements of HGT4205-2011 standards.
6) Transferring the solution A in the step 4) to a secondary reaction kettle, adding aluminum hydroxide, controlling the mass ratio to be solution A, namely aluminum hydroxide= (10-14): 1, heating to 85-95 ℃, reacting for 1-3 hours, then slowly adding the aluminum-based roasting material in the step 5), heating to 95-100 ℃, reacting for 80-100 minutes, and filtering by a second filter press after the reaction is finished to obtain filtrate which is a polyaluminium chloride liquid finished product.
In step 4), the concentration of hydrogen ions in the acid solution is not more than 3.0mol/L, the water-washed aluminum ash A is added at one time, the stirring speed is 60-80 r/min, and hydrochloric acid with the mass percentage concentration of about 10% is preferably adopted in the invention.
Further, in the step 4), the mass ratio of the water-washed aluminum ash slag A reacted with the acid liquor to the standby part is 3:2, and the metal aluminum content in the aluminum ash is adjusted when the metal aluminum content is changed.
Further, in step 5), the mass ratio between the mixture C1 and the mixture C2 is 3:1.
Further, in step 6), solution-a: aluminum hydroxide: the mass ratio of the aluminum base roasting material to the aluminum is (10-14) 1 (3-15).
Preferably, solution-a: aluminum hydroxide: the mass ratio of aluminum in the aluminum-based roasting material is 12:1:3.
Further, the aluminum ash contains 6-10% of simple substance aluminum, 28-35% of magnesium aluminate, 10-15% of aluminum nitride, 20-24% of aluminum oxide and the balance of indispensable impurities by mass percent.
Further, the primary alkali filtering deacidification tank is filled with sodium hydroxide and is used for absorbing acid gas.
Further, an activated alumina dehydration tank contains alumina balls, and the tank is used for drying and removing moisture in the gas. Therefore, the purity of the hydrogen recovered by the method is higher, the impurities are less, and the safety use standard is met.
Compared with the prior art, the technical scheme provided by the embodiment of the invention has the following advantages:
1. the system designed by the invention fully recycles all components in the aluminum ash, and realizes clean recycling treatment in a true sense.
2. The polyaluminum chloride liquid prepared by the recovery method has high product quality.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the invention and together with the description, serve to explain the principles of the invention.
In order to more clearly illustrate the embodiments of the invention or the technical solutions of the prior art, the drawings which are used in the description of the embodiments or the prior art will be briefly described, and it will be obvious to a person skilled in the art that other drawings can be obtained from these drawings without inventive effort.
FIG. 1 is a schematic diagram of a connection relationship of a processing system according to the present invention;
fig. 2 is a process flow diagram of a process performed using the system of fig. 1.
Wherein, each part numbers in the drawings are as follows:
the device comprises a first ball milling device 101, a screening device 102, a secondary micro negative pressure washing tank 103 (wherein a primary washing tank 103-1, a secondary washing tank 103-2 and a gas absorption tower 103-3), a centrifugal solid-liquid separation system 104 (wherein a liquid discharge end 104-1 and a solid outlet 104-2), an acid dissolution reaction kettle 105 (wherein an exhaust port 105-1, a pressure pump 105-2, a primary alkali filtration deacidification tank 105-3, an active alumina dehydration tank 105-4, a PSA hydrogen purification system 105-5, a hydrogen storage tank 105-6, an air inlet 105-7 and an inert gas storage tank 105-8), a first filter press 106, a second ball milling device 107, a drying calcining kiln 108 (wherein a primary calcining kiln 108-1 and a secondary calcining kiln 108-2), a secondary reaction kettle 109 and a second filter press 110.
Detailed Description
In order that the above objects, features and advantages of the invention will be more clearly understood, a further description of the invention will be made. It should be noted that, without conflict, the embodiments of the present invention and features in the embodiments may be combined with each other.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced otherwise than as described herein; it will be apparent that the embodiments in the specification are only some, but not all, embodiments of the invention.
Example 1
The embodiment discloses a clean recycling treatment system for aluminum ash, as shown in fig. 1, which comprises a first ball milling device 101, a screening device 102, a secondary micro negative pressure washing tank 103, a centrifugal solid-liquid separation system 104, an acid dissolution reaction kettle 105, a first filter press 106, a second ball milling device 107, a drying calcining kiln 108, a secondary reaction kettle 109 and a second filter press 110 which are sequentially connected;
the secondary micro negative pressure washing tank 103 comprises a primary washing tank 103-1 and a secondary washing tank 103-2 which are connected in series, a liquid discharge end 104-1 is arranged on the centrifugal solid-liquid separation system 104, the liquid discharge end 104-1 is connected with the primary washing tank 103-1, a solid outlet 104-2 is also arranged on the centrifugal solid-liquid separation system 104, and the solid outlet 104-2 is respectively connected with the acid dissolution reaction kettle 105 and the second ball milling device 107; the liquid outlet 106-1 of the first filter press 106 is connected with the secondary reaction kettle 109, and the solid outlet 106-2 of the first filter press 106 is connected with the second ball milling device 107.
Meanwhile, the exhaust port 105-1 of the acid dissolution reaction kettle 105 is sequentially connected with a first-stage alkali filtration deacidification tank 105-3 and an active alumina dehydration tank 105-4, a pressure pump 105-2 is further arranged on a connecting pipeline for connecting the exhaust port 105-1 with the first-stage alkali filtration deacidification tank 105-3, the active alumina dehydration tank 105-4 is also connected with a PSA hydrogen purification system 105-5 through the pressure pump, the PSA hydrogen purification system 105-5 is connected with a hydrogen storage tank 105-6, and the hydrogen storage tank 105-6 is respectively connected with a combustion device arranged on a drying calcining kiln 108 and a steam boiler arranged on the second-stage reaction kettle 109; the pipeline that the hydrogen storage tank 105-6 is connected with the combustion device and the steam boiler is provided with a pressure reducing valve and a pressure stabilizing valve component, so that the heat of the drying and calcining kiln 108 and 20-40% of the heat of the secondary reaction kettle 109 are all from hydrogen generated by the reaction in the acid dissolution reaction kettle 105 on the basis of safe production. And the gas inlet 105-7 of the acid dissolution reaction kettle 105 is connected with an inert gas storage tank 105-8. The invention designs that the pressure in the acid dissolution reaction kettle is controlled to be less than 0.05-0.1 Mpa. The acid-soluble reaction kettle is made of acid-base resistant and high-pressure and high-temperature resistant materials, such as polytetrafluoroethylene.
In addition, the exhaust end of the secondary washing tank 103-2 is connected with a gas absorption tower 103-3 for containing acid liquor.
Example 2
The embodiment discloses a method for carrying out clean recycling treatment on aluminum ash by adopting the system disclosed in the embodiment 1 and the attached figure 1 in the specification, wherein the specific process flow is shown in the attached figure 2 in the specification; it comprises the following steps:
1) The aluminum ash is ball-milled by a first ball milling device and then is sent to a screening device for screening to obtain coarse materials and fine materials; wherein the grain size of the fine materials is smaller than 100 meshes, and the aluminum ash contains 6 mass percent of simple substance aluminum, 28 mass percent of magnesium aluminate, 10 mass percent of aluminum nitride, 20 mass percent of aluminum oxide and the balance of indispensable impurities.
2) Fine materials enter a secondary micro negative pressure washing tank, are washed for 30min by a primary washing tank, enter the secondary washing tank, are subjected to aeration treatment for 30min, and are transferred to a centrifugal solid-liquid separation system, and gas is discharged into a gas absorption tower connected with the secondary washing tank;
3) The solid obtained by separating the mixed material in a centrifugal solid-liquid separation system is water-washed aluminum ash A, and filtrate is recycled to a first-stage water washing tank after being added with a defluorinating agent for precipitation;
4) Sending part of water-washed aluminum ash slag A into an acid dissolution reaction kettle, sending tail gas generated by reaction of the water-washed aluminum ash slag A and hydrochloric acid solution with the hydrogen ion concentration of 3.0mol/L into a hydrogen storage tank, processing reaction solution by a first filter press to obtain acid dissolution slag B and solution A, and leaving water-washed aluminum ash slag A for later use; wherein, the adding ratio of the water-washed aluminum ash A to the acid liquor is 1:5; controlling the pressure in the acid dissolution reaction kettle to be less than 0.05Mpa. Before the reaction, introducing inert gases such as nitrogen, helium and the like into the acid dissolution reaction kettle to discharge air in the kettle; the reaction liquid is subjected to filter pressing treatment by a first filter press for more than 1 hour at normal temperature;
5) Mixing the rest water-washed aluminum ash slag A with lime according to a ratio of 2:1 to obtain a mixture C1, mixing the acid-soluble slag B in the step 4) with the lime according to a ratio of 3:2 to obtain a mixture C2, sending the mixture C2 into a second ball milling device, ball milling and crushing the mixture to obtain fine powder with particle size not more than 180 meshes, sending the fine powder into a drying calcining kiln, controlling the temperature of the first calcining kiln to be 720 ℃, controlling the reaction time to be 90 minutes, sending the fine powder into a second calcining kiln, controlling the temperature to be 1100 ℃, controlling the reaction time to be 110 minutes, and cooling the fine powder to obtain an aluminum-based roasting material; wherein 20-40% of the heat source of the drying calcining kiln is from a hydrogen storage tank;
6) Transferring the solution A obtained in the step 4) to a secondary reaction kettle, adding aluminum hydroxide, heating to 90 ℃, reacting for 1-3 hours, controlling the casting speed to be 100kg/min, adding the aluminum-based roasting material obtained in the step 5), and adding the solution A: aluminum hydroxide: the mass ratio of aluminum in the aluminum-based roasting material is 12:1:3, the temperature is raised to 95 ℃, the reaction is carried out for 80 minutes, and after the reaction is finished, the filtrate obtained by filtering through a second filter press is the polyaluminum chloride liquid finished product.
Example 3
This example differs from example 2 above in that the aluminum ash contains 10% by mass of elemental aluminum, 35% by mass of magnesium aluminate, 15% by mass of aluminum nitride, 24% by mass of aluminum oxide, and the balance being indispensable impurities.
Example 4
This example differs from example 2 above in that the aluminum ash contains 8% by mass of elemental aluminum, 30% by mass of magnesium aluminate, 12% by mass of aluminum nitride, 22% by mass of aluminum oxide, and the balance being indispensable impurities.
Example 5
This example differs from example 2 above in that in step 5) the temperature of the primary calciner is controlled to 750 ℃, the reaction time is 90 minutes, and the primary calciner is fed to the secondary calciner at 1115 ℃ and the reaction time is 90 minutes.
Example 6
This example differs from example 2 above in that in step 6), solution a: aluminum hydroxide: aluminum-based firing stock aluminum=14:1:3.
The quality of the polyaluminum chloride liquid finished products prepared in the above examples 2 to 6 are shown in Table 1:
table 1 list of quality of final polyaluminum chloride liquid products prepared in examples 2 to 6
In addition, in the liquid polyaluminum chloride prepared by the embodiment, the impurity ions such as hexavalent chromium are less than or equal to 0.0005wt percent, lead ions are less than or equal to 0.001wt percent, and other impurity ions also accord with the national standard.
In summary, the recovery system and the method designed by the invention utilize simple substance aluminum resources in aluminum ash, combine with the subsequent aluminum resource recovery process, generate clean energy hydrogen, and simultaneously, the hydrogen energy is used as raw materials for producing rear-end products, thereby greatly reducing the roasting carbon emission of the aluminum ash, realizing the self-sufficient heat source energy, removing nitrogen and fluorine before the aluminum polymerization production stage, recovering tail gas ammonia gas to produce ammonium sulfate, preparing industrial products of aluminum polychloride with higher quality, avoiding the problems of waste tail gas, waste slag, waste water and the like in the process treatment process, and realizing clean recycling treatment in the true sense.
It should be noted that, in this document, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising one … …" does not exclude the presence of other like elements in a process, method, article, or apparatus that comprises the element.
The foregoing is only a specific embodiment of the invention to enable those skilled in the art to understand or practice the invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown and described herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (7)
1. The clean recycling treatment method for the aluminum ash is characterized by being carried out in a treatment system, wherein the treatment system comprises a first ball milling device, a screening device, a secondary micro negative pressure water washing tank, a centrifugal solid-liquid separation system, an acid dissolution reaction kettle, a first filter press, a second ball milling device, a drying calcining kiln, a secondary reaction kettle and a second filter press which are connected in sequence;
the secondary micro negative pressure washing tank comprises a primary washing tank and a secondary washing tank which are connected in series, the exhaust end of the secondary washing tank is connected with a gas absorption tower for containing acid liquor, the centrifugal solid-liquid separation system is provided with a liquid discharge end, the liquid discharge end is connected with the primary washing tank, the centrifugal solid-liquid separation system is also provided with a solid outlet, and the solid outlet is respectively connected with the acid dissolution reaction kettle and the second ball milling device;
the liquid outlet on the first filter press is connected with the secondary reaction kettle, and the solid outlet on the first filter press is connected with the second ball milling device;
the exhaust port of the acid dissolution reaction kettle is sequentially connected with a primary alkali filtration deacidification tank and an active alumina dehydration tank, the active alumina dehydration tank is connected with a PSA hydrogen purification system through a pressure pump, the PSA hydrogen purification system is connected with a hydrogen storage tank, and the hydrogen storage tank is respectively connected with a combustion device arranged on the drying calcining kiln and a steam boiler arranged on the secondary reaction kettle;
an air inlet of the acid dissolution reaction kettle is connected with an inert gas storage tank;
the specific processing steps are as follows:
1) The aluminum ash is ball-milled by a first ball milling device and then is sent to a screening device for screening to obtain coarse materials and fine materials;
2) Fine materials enter a secondary micro negative pressure washing tank, are washed by a primary washing tank, enter the secondary washing tank, are subjected to aeration treatment, and are transferred to a centrifugal solid-liquid separation system, and gas is discharged into a gas absorption tower connected with the secondary washing tank;
3) The solid obtained by separating the mixed material in a centrifugal solid-liquid separation system is water-washed aluminum ash A, and filtrate is recycled to a first-stage water washing tank after being added with a defluorinating agent for precipitation;
4) Sending part of water-washed aluminum ash A into an acid-soluble reaction kettle, sending tail gas generated by reaction of the water-washed aluminum ash A with hydrochloric acid into a hydrogen storage tank, and processing reaction liquid by a first filter press to obtain acid-soluble slag B and solution A, wherein the rest water-washed aluminum ash A is ready for use; wherein the mass ratio of the water-washed aluminum ash A to the hydrochloric acid is 1 (3-7), and the mass ratio of the water-washed aluminum ash A reacted with the hydrochloric acid to the standby part is 3:2;
5) Mixing the rest water-washed aluminum ash slag A with lime according to a ratio of 2:1 to obtain a mixture C1, mixing the acid-soluble slag B in the step 4) with lime according to a ratio of 3:2 to obtain a mixture C2, sending the mixture C2 into a second ball milling device, ball milling and crushing the mixture to obtain fine powder, sending the fine powder into a drying calcining kiln, controlling the temperature of the first-stage calcining kiln to be 720-750 ℃, the reaction time to be 80-120 minutes, sending the fine powder into a second-stage calcining kiln, and cooling the fine powder to obtain an aluminum-based calcined material, wherein the temperature is 1100-1115 ℃, and the reaction time to be 110-130 minutes; wherein 20-40% of the heat source of the drying calcining kiln is from a hydrogen storage tank;
6) Transferring the solution A in the step 4) to a secondary reaction kettle, adding aluminum hydroxide, controlling the mass ratio to be solution A, namely aluminum hydroxide= (10-14): 1, heating to 85-95 ℃, reacting for 1-3 hours, then slowly adding the aluminum-based roasting material in the step 5), heating to 95-100 ℃, reacting for 80-100 minutes, and filtering by a second filter press after the reaction is finished to obtain filtrate which is a polyaluminium chloride liquid finished product.
2. The method for cleaning and recycling aluminum ash according to claim 1, wherein in the step 4), the concentration of hydrogen ions in the hydrochloric acid is not more than 3.0mol/L, the water-washed aluminum ash A is added at one time, and the stirring speed is 60-80 revolutions/min.
3. The method for clean recycling of aluminum ash according to claim 1 or 2, wherein in the step 6), the secondary reaction kettle is heated by steam, and 20-40% of the heat source is from a hydrogen storage tank.
4. The method for clean recycling treatment of aluminum ash according to claim 1 or 2, wherein the aluminum ash contains 6 to 10 mass% of elemental aluminum, 28 to 35 mass% of magnesium aluminate, 10 to 15 mass% of aluminum nitride, 20 to 24 mass% of aluminum oxide, and the balance of indispensable impurities.
5. The method for cleaning and recycling aluminum ash according to claim 1, wherein the exhaust port and the air inlet end of the acid dissolution reaction kettle are respectively provided with a flow control valve, and a pressure pump is also arranged on a connecting pipeline of the exhaust port and the primary alkali filtration deacidification tank.
6. The method for clean recycling of aluminum ash according to claim 1, wherein the pressure in the acid dissolution reaction kettle is less than 0.1MPa.
7. The method for clean recycling of aluminum ash according to claim 1, wherein a pressure reducing valve and a pressure stabilizing valve assembly are arranged on a pipeline connected with the combustion device and the steam boiler of the hydrogen storage tank.
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