CN112279283A - Method for comprehensively utilizing secondary aluminum ash - Google Patents
Method for comprehensively utilizing secondary aluminum ash Download PDFInfo
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- CN112279283A CN112279283A CN202011184078.5A CN202011184078A CN112279283A CN 112279283 A CN112279283 A CN 112279283A CN 202011184078 A CN202011184078 A CN 202011184078A CN 112279283 A CN112279283 A CN 112279283A
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 95
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 95
- 238000000034 method Methods 0.000 title claims abstract description 23
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910001388 sodium aluminate Inorganic materials 0.000 claims abstract description 20
- 239000013078 crystal Substances 0.000 claims abstract description 15
- 239000000654 additive Substances 0.000 claims abstract description 13
- 230000000996 additive effect Effects 0.000 claims abstract description 13
- 239000007788 liquid Substances 0.000 claims abstract description 12
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims abstract description 11
- 239000000292 calcium oxide Substances 0.000 claims abstract description 11
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 11
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000706 filtrate Substances 0.000 claims abstract description 7
- 238000000227 grinding Methods 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 238000000926 separation method Methods 0.000 claims abstract description 7
- 238000005245 sintering Methods 0.000 claims abstract description 7
- 239000003513 alkali Substances 0.000 claims abstract description 5
- 238000001816 cooling Methods 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims abstract 8
- 239000012045 crude solution Substances 0.000 claims abstract 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 44
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 26
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 17
- 239000007800 oxidant agent Substances 0.000 claims description 14
- 230000001590 oxidative effect Effects 0.000 claims description 14
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 13
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- 238000001354 calcination Methods 0.000 claims description 8
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 claims description 8
- 238000004090 dissolution Methods 0.000 claims description 8
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical group [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 5
- 239000004343 Calcium peroxide Substances 0.000 claims description 4
- LHJQIRIGXXHNLA-UHFFFAOYSA-N calcium peroxide Chemical compound [Ca+2].[O-][O-] LHJQIRIGXXHNLA-UHFFFAOYSA-N 0.000 claims description 4
- 235000019402 calcium peroxide Nutrition 0.000 claims description 4
- VTIIJXUACCWYHX-UHFFFAOYSA-L disodium;carboxylatooxy carbonate Chemical compound [Na+].[Na+].[O-]C(=O)OOC([O-])=O VTIIJXUACCWYHX-UHFFFAOYSA-L 0.000 claims description 4
- 239000004317 sodium nitrate Substances 0.000 claims description 4
- 235000010344 sodium nitrate Nutrition 0.000 claims description 4
- 229940045872 sodium percarbonate Drugs 0.000 claims description 4
- PFUVRDFDKPNGAV-UHFFFAOYSA-N sodium peroxide Chemical compound [Na+].[Na+].[O-][O-] PFUVRDFDKPNGAV-UHFFFAOYSA-N 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims 1
- 238000000354 decomposition reaction Methods 0.000 abstract description 14
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 9
- 239000000047 product Substances 0.000 abstract description 8
- 238000004064 recycling Methods 0.000 abstract description 7
- 150000004767 nitrides Chemical class 0.000 abstract 2
- 238000003837 high-temperature calcination Methods 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 229910052731 fluorine Inorganic materials 0.000 description 5
- 239000011737 fluorine Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000001035 drying Methods 0.000 description 4
- 125000001153 fluoro group Chemical group F* 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 241000565357 Fraxinus nigra Species 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 2
- 229910001634 calcium fluoride Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000002440 industrial waste Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 241001536352 Fraxinus americana Species 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000007777 multifunctional material Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
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
-
- 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
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/20—Halides
- C01F11/22—Fluorides
-
- 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
- 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
- C01F7/062—Digestion
-
- 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
- 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
- C01F7/08—Preparation of alkali metal aluminates; Aluminium oxide or hydroxide therefrom by treating aluminous minerals with sodium carbonate, e.g. sinter processes
-
- 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
- C01F7/14—Aluminium oxide or hydroxide from alkali metal aluminates
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Nutrition Science (AREA)
- Processing Of Solid Wastes (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention discloses a method for comprehensively utilizing secondary aluminum ash, which comprises the steps of crushing and grinding the secondary aluminum ash, uniformly mixing the crushed and ground aluminum ash with an additive, roasting, and recovering sintering gas; taking out the roasted clinker, cooling to room temperature, dissolving out with dilute alkali liquor or water, performing solid-liquid separation, wherein the filtrate is a sodium aluminate crude solution, adding the sodium aluminate solution after calcium oxide deep desiliconization, performing seed crystal decomposition and high-temperature calcination to obtain alumina, and returning insoluble filter residue to an electrolytic cell for use; the method not only effectively separates the alumina, the nitride and the fluoride in the aluminum ash, but also obtains the alumina product, realizes the recycling of the nitride and the fluoride, and opens up a new way for the comprehensive utilization of the secondary aluminum ash.
Description
Technical Field
The invention relates to the technical field of resource utilization of aluminum industrial wastes, in particular to a novel method for comprehensively utilizing secondary aluminum ash.
Background
The production of aluminium and secondary aluminium is cyclic and produces large quantities of waste slag, with annual production of aluminium ash of more than 250 million tons. The aluminum ash can be divided into primary aluminum ash and secondary aluminum ash, wherein the primary aluminum ash has higher aluminum content and is silver gray, also called white ash; the secondary aluminum ash contains lower aluminum and is black, also called black ash. The recycling of the secondary aluminum ash is the key point of the comprehensive utilization of the aluminum industrial waste, and the recycling of the aluminum ash at present can be mainly divided into the recycling of metal aluminum and aluminum oxide in the aluminum ash, the recycling of salt in the aluminum ash and the production of other multifunctional materials. The research on a new method for treating the aluminum ash can recover the valuable components in the aluminum ash to the maximum extent, reduce the stockpiling of the aluminum ash and avoid secondary pollution, and has very important significance for the whole aluminum industry. Although much research is carried out on aluminum ash, no mature method is available for recycling aluminum slag at present, most of black ash at the tail end of the aluminum industry is mainly stockpiled, land resources are occupied, and harmful substances in the black ash can enter the environment through diffusion, so that the human health is harmed, and the ecological environment is damaged. Aluminum ash is listed in the national records of hazardous waste as aluminum smelting waste. Therefore, the recovery of valuable components in the aluminum ash, the improvement of the recovery rate of aluminum in the aluminum ash and the realization of the resource and harmless utilization of the aluminum ash are the necessary ways for realizing sustainable development.
Although some methods in the prior art obtain alumina products with higher purity, fluoride and the like are not removed, and the residual waste residue after extracting alumina cannot achieve the effect of harmless treatment. Better methods are yet to be developed for the secondary aluminous ash treatment.
Disclosure of Invention
The invention aims to provide a novel method for comprehensively utilizing secondary aluminum ash, which aims at solving the problem of pollution caused by ammonia gas due to incomplete denitrification of aluminum ash by aiming at aluminum nitride in the aluminum ash and a large amount of fluoride in electrolytic refining, realizes removal of harmful elements in the aluminum ash and achieves the purposes of harmless treatment and resource utilization.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for comprehensively utilizing secondary aluminum ash comprises the following specific steps:
(1) crushing and grinding the secondary aluminum ash by using a crusher;
(2) uniformly mixing the aluminum ash crushed and ground in the step (1) with an additive, roasting, and recovering sintering gas;
(3) and (3) taking out the roasted clinker obtained in the step (2), cooling to room temperature, dissolving out with dilute alkali liquor or water, carrying out solid-liquid separation, taking the filtrate as a crude sodium aluminate solution, adding the sodium aluminate solution subjected to calcium oxide deep desiliconization, decomposing with seed crystals to obtain aluminum hydroxide, calcining at high temperature to obtain aluminum oxide, and returning insoluble filter residues to an electrolytic bath as fluorine-containing residues.
The granularity of the aluminum ash ground in the step (1) is 75-380 μm.
The additive in the step (2) is a mixture of sodium carbonate, an oxidant and calcium carbonate; the oxidant is sodium nitrate, sodium percarbonate, sodium peroxide or calcium peroxide, the addition amount of the sodium carbonate is 1.4-3 times of the amount of the aluminum oxide substance in the aluminum ash, and the addition amount of the oxidant is 1.2-2.4 times of the amount of the aluminum nitride substance in the aluminum ash; the calcium carbonate is added in an amount of 2.6 to 4.6 times the total amount of fluoride and silica in the aluminum ash.
The roasting temperature in the step (2) is 800-.
The dilute alkali solution in the step (3) is a sodium carbonate solution or a sodium hydroxide solution, wherein the concentration of the sodium carbonate solution is 2g/L-10g/L, and the concentration of the sodium hydroxide solution is 10g/L-30 g/L.
The dissolution temperature in the step (3) is 50-90 ℃, and the dissolution time is 0.5-3 hours.
The liquid-solid ratio mL/g in the dissolution in the step (3) is 2-10: 1.
The invention has the beneficial effects that:
the method utilizes the aluminum ash in the aluminum industry, takes the secondary aluminum ash as the main raw material, and converts aluminum nitride into aluminum oxide by adding a reaction agent into the aluminum ash and roasting at high temperature, so that on one hand, the recovery of the aluminum oxide can be improved, and in addition, nitrogen released by reaction can not cause environmental pollution and can be recycled; on the other hand, the added material containing calcium carbonate can react with fluoride in the secondary aluminum ash to generate calcium fluoride, and the calcium fluoride is used as a raw material for returning to an electrolytic cell and can also be used for producing building materials, thereby achieving the effect of recycling. The sodium aluminate solution obtained by dissolving out the roasted clinker is subjected to deep desiliconization and decomposition to obtain an aluminum hydroxide product, the aluminum hydroxide is calcined at high temperature to obtain an aluminum oxide product, the recovery rate of the aluminum oxide in the aluminum ash is improved, no secondary pollution is caused, the aim of harmlessly treating the secondary aluminum ash is fulfilled, and the reaction agent is low in price and can be used for industrial application and trial.
Detailed Description
The present invention is further illustrated by the following examples, wherein the details are not set forth in any detail as part of the common general knowledge or the technical skill in the art. The secondary aluminum ash composition (analyzed by XRF) used in the examples is shown in table 1:
TABLE 1 Mass% of main oxides in Secondary aluminum Ash/. omega.%
Example 1
A method for comprehensively utilizing secondary aluminum ash comprises the following specific steps:
(1) crushing and grinding the secondary aluminum ash to 75-380 μm by a crusher;
(2) uniformly mixing the aluminum ash crushed and ground in the step (1) with an additive, and then roasting at 800 ℃ for 4 hours, wherein the sintering gas is nitrogen and is recovered; wherein the additive is a mixture of sodium carbonate, sodium nitrate as an oxidant and calcium carbonate; the molar ratio of sodium carbonate to aluminum oxide in the aluminum ash is 1.4, the molar ratio of sodium nitrate as an oxidant to aluminum nitride in the aluminum ash is 1.2, and the total molar ratio of fluoride and silicon dioxide in the calcium carbonate and the aluminum ash is 2.6;
(3) dissolving the roasted clinker out by using a sodium carbonate solution, wherein the concentration of sodium carbonate is 2g/L, the liquid-solid ratio mL is 2:1, the dissolving-out temperature is 50 ℃, the dissolving-out time is 3 hours, and carrying out solid-liquid separation to obtain a filtrate, namely a crude sodium aluminate solution; the dissolution rate of the alumina is 87.6 percent, the insoluble filter residue is fluorine-containing residue which is returned to the electrolytic cell for use, and CaF in the insoluble residue2The content of (A) is 89%;
(4) adding calcium oxide into the sodium aluminate crude liquid for desiliconization, wherein the desiliconization temperature is 80 ℃, the stirring speed is 300r/min, the reaction time is 60min, and the added CaO and SiO in the solution2In a molar ratio of 10: 1; adding HCl with the mass fraction of 36% to adjust alphak=1.7, adding seed crystal aluminum hydroxide into sodium aluminate solution for decomposition, wherein the seed crystal coefficient is 1, the rotation speed is 200r/min, and the decomposition time is 60 h;
(5) drying the aluminum hydroxide after the seed crystal decomposition at 80 ℃ for 12h, and then calcining at 1200 ℃ for 1h to obtain the product aluminum oxide.
Example 2
A method for comprehensively utilizing secondary aluminum ash comprises the following specific steps:
(1) crushing and grinding the secondary aluminum ash to 75-380 μm by a crusher;
(2) uniformly mixing the aluminum ash crushed and ground in the step (1) with an additive, and then roasting at 800 ℃ for 2h, wherein the sintering gas is nitrogen and is recovered; wherein the additive is a mixture of sodium carbonate, an oxidant sodium peroxide and calcium carbonate; the molar ratio of sodium carbonate to aluminum oxide in the aluminum ash is 1.8, the molar ratio of sodium peroxide as an oxidant to aluminum nitride in the aluminum ash is 1.7, and the total molar ratio of fluoride and silicon dioxide in the calcium carbonate and the aluminum ash is 3;
(3) dissolving the roasted clinker out by using a sodium carbonate solution, wherein the concentration of sodium carbonate is 10g/L, the liquid-solid ratio mL is 5:1, the dissolving-out temperature is 65 ℃, the dissolving-out time is 1.5h, and carrying out solid-liquid separation to obtain a filtrate, namely a crude sodium aluminate solution; the dissolution rate of the alumina is 89.2 percent, the insoluble filter residue is fluorine-containing residue which is returned to the electrolytic cell for use, and CaF in the insoluble residue2The content of (A) is 91%;
(4) adding calcium oxide into the sodium aluminate crude liquid for desiliconization, wherein the desiliconization temperature is 80 ℃, the stirring speed is 300r/min, the reaction time is 60min, and the added CaO and SiO in the solution2In a molar ratio of 10: 1; adding HCl with the mass fraction of 36% to adjust alphak=1.7, adding seed crystal aluminum hydroxide into sodium aluminate solution for decomposition, wherein the seed crystal coefficient is 1, the rotation speed is 200r/min, and the decomposition time is 60 h;
(5) drying the aluminum hydroxide after the seed crystal decomposition at 80 ℃ for 12h, and then calcining at 1200 ℃ for 1h to obtain the product aluminum oxide.
Example 3
A method for comprehensively utilizing secondary aluminum ash comprises the following specific steps:
(1) crushing and grinding the secondary aluminum ash to 75-380 microns by using a crusher;
(2) uniformly mixing the aluminum ash crushed and ground in the step (1) with an additive, and then roasting at 1000 ℃ for 4 hours, wherein the sintering gas is nitrogen and is recovered; wherein the additive is a mixture of sodium carbonate, sodium percarbonate serving as an oxidant and calcium carbonate; the molar ratio of sodium carbonate to aluminum oxide in the aluminum ash is 2.2, the molar ratio of the oxidant sodium percarbonate to aluminum nitride in the aluminum ash is 2, and the total molar ratio of the calcium carbonate to fluoride and silicon dioxide in the aluminum ash is 3.6;
(3) dissolving the roasted clinker out by using a sodium carbonate solution, wherein the concentration of sodium carbonate is 5g/L, the liquid-solid ratio mL is 8:1, the dissolving-out temperature is 80 ℃, the dissolving-out time is 2 hours, and carrying out solid-liquid separation to obtain a filtrate, namely a crude sodium aluminate solution; the leaching rate of the alumina is 92.1 percent, the insoluble filter residue is fluorine-containing residue which is returned to the electrolytic cell for use, and CaF in the insoluble residue2The content of (A) is 89.5%;
(4) adding calcium oxide into the sodium aluminate crude liquid for desiliconization, wherein the desiliconization temperature is 80 ℃, the stirring speed is 300r/min, the reaction time is 60min, and the added CaO and SiO in the solution2In a molar ratio of 10: 1; adding HCl with the mass fraction of 36% to adjust alphak=1.7, adding seed crystal aluminum hydroxide into sodium aluminate solution for decomposition, wherein the seed crystal coefficient is 1, the rotation speed is 200r/min, and the decomposition time is 60 h;
(5) drying the aluminum hydroxide after the seed crystal decomposition at 80 ℃ for 12h, and then calcining at 1200 ℃ for 1h to obtain the product aluminum oxide.
Example 4
A method for comprehensively utilizing secondary aluminum ash comprises the following specific steps:
(1) crushing and grinding the secondary aluminum ash to 75-380 μm by a crusher;
(2) uniformly mixing the aluminum ash crushed and ground in the step (1) with an additive, and then roasting at 1200 ℃ for 1h, wherein the sintering gas is nitrogen and is recovered; wherein the additive is a mixture of sodium carbonate, an oxidant of calcium peroxide and calcium carbonate; the molar ratio of sodium carbonate to aluminum oxide in the aluminum ash is 3, the molar ratio of the oxidant calcium peroxide to aluminum nitride in the aluminum ash is 2.4, and the total molar ratio of calcium carbonate to fluoride and silicon dioxide in the aluminum ash is 4.6;
(3) dissolving the roasted clinker out by using a sodium hydroxide solution, wherein the concentration of the sodium hydroxide solution is 10g/L, the liquid-solid ratio mL is 10:1, the dissolving-out temperature is 90 ℃, the dissolving-out time is 0.5h, and carrying out solid-liquid separation to obtain a filtrate, namely a crude sodium aluminate solution; the dissolution rate of the alumina is 90.6 percent, the insoluble filter residue is fluorine-containing residue which is returned to the electrolytic cell for use, and CaF in the insoluble residue2The content of (A) is 86%;
(4) adding calcium oxide into the sodium aluminate crude liquid for desiliconization, wherein the desiliconization temperature is 80 ℃, the stirring speed is 300r/min, the reaction time is 60min, and the added CaO and SiO in the solution2In a molar ratio of 10: 1; adding HCl with the mass fraction of 36% to adjust alphak=1.7, adding seed crystal aluminum hydroxide into sodium aluminate solution for decomposition, wherein the seed crystal coefficient is 1, the rotation speed is 200r/min, and the decomposition time is 60 h;
(5) drying the aluminum hydroxide after the seed crystal decomposition at 80 ℃ for 12h, and then calcining at 1200 ℃ for 1h to obtain the product aluminum oxide.
The concentration of the sodium hydroxide solution in example 4 was adjusted to 15g/L or 30g/L, etc., and any concentration of 10g/L to 30g/L, etc., an effect not much different from example 4 could be obtained.
Claims (7)
1. A method for comprehensively utilizing secondary aluminum ash is characterized by comprising the following specific steps:
(1) crushing and grinding the secondary aluminum ash;
(2) uniformly mixing the aluminum ash crushed and ground in the step (1) with an additive, roasting, and recovering sintering gas;
(3) and (3) cooling the roasted clinker obtained in the step (2) to room temperature, dissolving out the clinker by using dilute alkali liquor or water, carrying out solid-liquid separation, adding a sodium aluminate crude solution into the filtrate, adding the sodium aluminate solution subjected to calcium oxide deep desiliconization, decomposing the sodium aluminate solution by using crystal seeds to obtain aluminum hydroxide, calcining the aluminum hydroxide at high temperature to obtain aluminum oxide, and returning insoluble filter residues to an electrolytic bath for use.
2. The method for comprehensively utilizing the secondary aluminum ash as claimed in claim 1, wherein the aluminum ash ground in step (1) has a particle size of 75 μm to 380 μm.
3. The method for comprehensively utilizing the secondary aluminum ash as claimed in claim 1, wherein the additive in the step (2) is a mixture of sodium carbonate, an oxidant and calcium carbonate; the oxidant is sodium nitrate, sodium percarbonate, sodium peroxide or calcium peroxide, the addition amount of the sodium carbonate is 1.4-3 times of the amount of an aluminum oxide substance in the aluminum ash, and the addition amount of the oxidant is 1.2-2.4 times of the amount of an aluminum nitride substance in the aluminum ash; the calcium carbonate is added in an amount of 2.6 to 4.6 times the total amount of fluoride and silica in the aluminum ash.
4. The method for comprehensively utilizing the secondary aluminum ash as claimed in claim 1, wherein the calcination temperature in step (2) is 800-1200 ℃ and the calcination time is 1-4 h.
5. The method for comprehensively utilizing secondary aluminum ash as claimed in claim 1, wherein the dilute alkali solution in step (3) is sodium carbonate solution or sodium hydroxide solution, wherein the concentration of the sodium carbonate solution is 2g/L-10g/L, and the concentration of the sodium hydroxide solution is 10g/L-30 g/L.
6. The method for comprehensively utilizing the secondary aluminum ash as claimed in claim 1, wherein the dissolution temperature in the step (3) is 50-90 ℃ and the dissolution time is 0.5-3 hours.
7. The method for comprehensively utilizing the secondary aluminum ash as claimed in claim 1, wherein the ratio of dissolved liquid to solid (mL: g) in the step (3) is 2-10: 1.
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| CN112744850A (en) * | 2021-02-18 | 2021-05-04 | 中铝环保节能集团有限公司 | Method for comprehensively utilizing secondary aluminum ash resources |
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