CN112142353B - Method for efficiently and harmlessly treating aluminum ash - Google Patents
Method for efficiently and harmlessly treating aluminum ash Download PDFInfo
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- CN112142353B CN112142353B CN202011108725.4A CN202011108725A CN112142353B CN 112142353 B CN112142353 B CN 112142353B CN 202011108725 A CN202011108725 A CN 202011108725A CN 112142353 B CN112142353 B CN 112142353B
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- C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B18/04—Waste materials; Refuse
- C04B18/14—Waste materials; Refuse from metallurgical processes
- C04B18/149—Waste materials; Refuse from metallurgical processes other than silica fume or slag
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- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/02—Preparation, purification or separation of ammonia
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- C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
- C04B20/02—Treatment
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- C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
- C04B20/02—Treatment
- C04B20/023—Chemical treatment
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- C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
- C04B20/02—Treatment
- C04B20/026—Comminuting, e.g. by grinding or breaking; Defibrillating fibres other than asbestos
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- 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
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- 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
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- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Abstract
The invention belongs to the technical field of environment-friendly materials and non-ferrous metal smelting, and particularly relates to a method for treating aluminum ash in aluminum industrial production. The method mainly uses a wet chemical ball milling process to strengthen the reaction of aluminum ash, and adds a catalyst, an accelerant and the like to strengthen the hydrolysis reaction effect of the aluminum ash so as to achieve the purpose of removing nitrogen in the aluminum ash, and the aluminum ash is changed into a usable harmless powder material after harmless treatment. The method for treating the harmless aluminum ash provided by the invention adopts a wet method to treat the aluminum ash, avoids the dangers of flammability, explosiveness and the like of the aluminum ash, and improves the safety coefficient of operation; replacing mechanical stirring with a wet ball milling mode, and strengthening the hydrolysis effect of the aluminum ash by using the mechanical force of ball milling in the stirring process; the process flow is shortened, the aluminum ash can be further refined while the ball milling is carried out on aluminum, the reaction is more sufficient, the denitrification effect of the aluminum ash is improved, the reaction time is shortened, and the energy can be greatly saved in the industrial production.
Description
Technical Field
The invention belongs to the technical field of environment-friendly materials and non-ferrous metal smelting, and particularly relates to a method for treating aluminum ash in aluminum industrial production.
Background
The aluminum ash is a high-pollution waste generated in the industrial processes of producing raw aluminum, aluminum alloy and processing, recovering waste aluminum and the like. The waste is a necessary product formed by the reaction of aluminum and air at high temperature, and the yield is huge. The aluminum ash has complex components, which are slightly changed due to different production links, different raw materials of manufacturers and different operation conditions, but generally contains metallic aluminum, aluminum oxide, aluminum nitride, aluminum chloride and other components. At present, most of aluminum ash is stockpiled or buried after metal aluminum is separated from the aluminum ash. However, nitrogen oxides contained in the aluminum ash are unstable and are easy to react chemically, so that flammable and harmful irritant gases are formed, and air pollution is caused. In addition, some water-soluble salt pollutants exist in the aluminum ash, which can cause serious pollution to soil and underground water. In the aluminum electrolysis production, 30-50 kg of aluminum ash to be treated is correspondingly generated when about 1t of raw aluminum is produced; in the aluminum processing and recycling production, 30-40 kg of aluminum ash to be treated is generated per ton of aluminum. Through investigation, the aluminum yield of China in 2019 reaches 3500 ten thousand tons/year, the actual aluminum ash yield breaks through 200 ten thousand tons, and the aluminum ash yield is continuously increased at a speed of about 2%.
In recent years, a great deal of research on the treatment of aluminum ash by a plurality of experts and scholars is carried out, and the Kangtian and the like of the university of northeast make researches on the treatment and recycling of the aluminum ash, so that after metal aluminum in the aluminum ash is recovered, the remaining secondary aluminum ash is added into an electrolytic bath, and the recycling of the aluminum ash is realized; zhouyingming and the like of Kunming theory university make researches on harmless treatment and comprehensive utilization of aluminum ash by adding a liquid-solid ratio of more than 4: 1, washing with water, and then adding an additive to roast to achieve the aim of harmlessly decomposing the aluminum ash.
Patent CN201410499871.2 discloses a method for harmlessly treating and recycling aluminum ash, which comprises the steps of carrying out secondary treatment on the aluminum ash to recycle metal aluminum, leaching the metal aluminum to remove nitrides by water, roasting to remove fluorides, carrying out alkali fusion sintering, dissolving out sintered materials, and removing impurities from a sodium aluminate solution to obtain a sand-shaped aluminum oxide raw material. Patent CN201611099617.9 discloses a resource treatment method of aluminum ash, which comprises the steps of carrying out denitrification, fluorine and arsenic treatment on aluminum ash, then roasting, crushing clinker, and acid leaching to remove metal impurities, thus obtaining finished aluminum oxide. Patent 201611266169.7 discloses a method for harmlessly treating aluminum ash, which comprises ball-milling aluminum ash, adding water, stirring, leaching, removing nitride from the aluminum ash, removing iron, centrifuging, dehydrating, and drying to obtain harmlessly treated aluminum ash. Patent CN201710104633.0 discloses a method for recycling aluminum ash, which comprises the steps of firstly mixing aluminum ash into slurry, carrying out deamination treatment, then conveying the slurry into a reaction kettle, and carrying out solid-liquid separation, drying and calcining after the reaction is finished to obtain aluminum oxide. Patent CN201710678051.3 discloses a method for harmless comprehensive utilization of secondary aluminum ash, which adopts a wet process to remove nitrides and salts in the aluminum ash, and obtains a filter cake for preparing a calcium aluminate material after solid-liquid separation. Patent CN201710893673.8 discloses a pressure regulating-hydrothermal cyclone process reinforced aluminum ash denitrification method, which comprises five steps of ash/aluminum separation, feeding, denitrification, sedimentation, filtration, washing and drying, wherein cyclone is applied in a reactor to control the escape rate of ammonia gas, control the denitrification reaction rate of aluminum ash and improve the denitrification efficiency of aluminum ash. Patent CN201810731116 discloses a method for treating inert aluminum ash in an aluminum ash treatment process, which comprises the steps of sequentially burning a mixture of aluminum ash and raw slurry in a rotary kiln, cooling by a cooling machine, and finally dissolving out clinker in a ball mill. Patent CN201810862255 discloses a low-pollution secondary aluminum ash treatment method, which mainly comprises the steps of secondary aluminum ash washing desalination, liquid-solid separation filtrate defluorination, filtrate evaporation crystallization to recover compound salt, and liquid-solid separation filter cake roasting denitrification, wherein the treated aluminum ash meets the national harmless requirement. Patent CN201811279802.5 discloses a safe and harmless treatment method of aluminum ash, which mainly comprises three steps of primary deamination treatment, pulping, deamination and catalytic deamination, so that aluminum nitride in the aluminum ash is decomposed in stages to generate ammonia gas and is safely recovered, thereby achieving the purpose of harmless treatment of the aluminum ash.
Along with the annual increase of electrolytic aluminum yield, aluminum processing and waste aluminum recovery in China, a large amount of aluminum ash is generated, if the aluminum ash is not treated well, resources are wasted, and the environment is polluted, so that the method has important significance for harmless treatment and utilization of the aluminum ash.
Disclosure of Invention
In order to solve the problem of a large amount of aluminum ash wastes generated in the aluminum industrial production, the invention aims to provide a method for efficiently treating aluminum ash, which mainly uses a wet chemical method ball milling process to strengthen the aluminum ash reaction, and adds a catalyst, an accelerant and the like to strengthen the hydrolysis reaction effect of the aluminum ash so as to achieve the purpose of removing nitrogen in the aluminum ash, and the aluminum ash is changed into a usable harmless powder material after harmless treatment. In order to achieve the purpose, the invention adopts the following technical scheme.
A method for harmlessly treating aluminum ash comprises the following specific steps.
And 2, conveying the mixed slurry into a wet ball milling tank, adding water, a catalyst and an accelerant into the ball milling tank in advance, accelerating the reaction, and discharging and collecting ammonia gas generated by the reaction through a negative pressure exhaust port.
And 3, after the reaction is finished, separating out grinding balls, aluminum particles and slurry through screening and washing, returning the separated grinding balls to the ball milling tank for reuse, intensively recovering and drying the separated aluminum particles for remelting aluminum ingots, and removing iron carried in aluminum ash and iron generated by ball milling from the separated slurry through an iron remover.
And 4, removing iron in the aluminum ash and iron slurry generated by ball milling obtained in the step 3, washing, filtering and drying to finally obtain the harmless aluminum ash for the refractory material.
Further, the mass of water added into the size mixing tank in the step 1 is 0.5-2 times of the mass of the aluminum ash.
Further, the temperature of the water added in the step 1 is 25-100 ℃.
Further, the ammonia gas generated in the step 1 is discharged from an exhaust port, and then is absorbed by dilute sulfuric acid to be used for preparing ammonium sulfate.
Further, the grinding balls in the wet ball milling tank in the step 2 are one or more of zirconia balls, alumina balls and iron balls, and the adding amount of the grinding balls is 0.5-2 times of the mass of the aluminum ash.
Further, the adding amount of water in the step 2 is 0.5-1 time of the mass of the aluminum ash.
Furthermore, the rotating speed of the wet ball mill in the step 2 is 30 r/min-120 r/min.
Furthermore, in the step 2, the two ends of the wet ball mill are capped and sealed after being charged, an exhaust port is arranged on the cap, and generated ammonia gas is absorbed by dilute sulfuric acid after being exhausted from the exhaust port and is used for preparing ammonium sulfate.
Further, in the step 2, after the slurry is conveyed into the wet ball milling tank, the reaction temperature is up to 85-100 ℃ by oil bath heating or steam heating.
Further, the catalyst added in the step 2 is one or a mixture of more of sodium hydroxide, sodium carbonate, calcium oxide and aluminum hydroxide, and the adding amount of the catalyst is 0.01-0.05 times of the mass of the aluminum ash.
Further, the accelerator added in the step 2 is one or a mixture of more of hydrogen peroxide, ammonia water, hydrochloric acid, sodium carbonate and ethanol, and the addition amount of the accelerator is 0.01-0.05 times of the mass of the aluminum ash.
Further, the reaction time in the step 2 is 1-3 h.
Furthermore, the mesh number of the screen for screening in the step 3 is 80-150 meshes, and the mesh screen is made of nylon.
Furthermore, the water washing in the step 3 is to wash off the aluminum ash adhered to the surfaces of the grinding balls and the aluminum particles, and the addition amount of the washing water is 0.1-0.3 times of the mass of the aluminum ash.
And further, in the washing process in the step 4, new water is adopted for countercurrent washing for 1-5 times, the addition amount of the new water is 0.5-2 times of the mass of the aluminum ash, and the washing water is returned to the step 1 and the step 2 for recycling.
Further, the filtrate filtered in the step 4 is subjected to evaporation crystallization, the crystallized product is used for recovering chloride, and water vapor generated by evaporation is returned to the step 1 and the step 2 for recycling.
And further, repeatedly washing the filtered filter cake for 1-5 times in the step 4, and returning the washing water to the step 1 and the step 2 for recycling.
Further, in the step 4, one of paddle drying, spray drying, flash drying and the like is adopted for the filtered filter cake.
Compared with the prior art, the invention has the following beneficial effects.
(1) The method for treating the harmless aluminum ash provided by the invention adopts a wet method to treat the aluminum ash, avoids the dangers of flammability, explosiveness and the like of the aluminum ash, and improves the safety coefficient of operation; and (3) replacing mechanical stirring with a wet ball milling mode, and strengthening the reaction of the aluminum ash and water by using the mechanical force of ball milling in the stirring process.
(2) The method for treating the harmless aluminum ash provided by the invention treats the aluminum ash by adopting a wet ball milling mode, shortens the process flow, further refines the aluminum ash while performing ball milling aluminum separation, and simultaneously performs denitrification reaction and shortens the reaction time. Can greatly save energy in industrial production.
(3) The method for treating the harmless aluminum ash provided by the invention treats the aluminum ash by adopting a wet ball milling mode, and carries out aluminum separation and iron removal processes in a slurry state, so that the escape of dust can be effectively reduced, and the dust pollution is avoided.
(4) The aluminum ash treated by the harmless aluminum ash treatment method provided by the invention is further refined, and the median diameter in the particle size distribution of the aluminum ash can reach below 30 mu m, so that the method is more beneficial to the use of subsequent products.
(5) The raw materials used by the method for treating the harmless aluminum ash provided by the invention are the aluminum ash which is accumulated in large quantities and is not fully utilized at present, the method for treating the harmless aluminum ash recycles the aluminum ash, saves resources, changes waste into valuable, has a simple process, is an energy-saving and environment-friendly treatment method with low cost, and has important significance for utilization and harmless treatment of the aluminum ash.
Drawings
FIG. 1 is a flow chart of a method for efficiently and harmlessly treating aluminum ash according to the invention.
FIG. 2 shows the experimental results of the effect of reaction temperature on the hydrolysis effect of the ball mill.
FIG. 3 shows the experimental results of the influence of the liquid-solid ratio of the ball-milling reaction slurry on the ball-milling hydrolysis effect.
FIG. 4 shows the experimental results of the effect of the reaction time of ball milling on the hydrolysis effect of ball milling.
Detailed Description
The invention is further illustrated by the following specific examples and figures in the specification.
The process flow diagram of the method for efficiently and harmlessly treating the aluminum ash is shown in figure 1, and the specific steps are as follows.
And 2, conveying the mixed slurry into a wet ball milling tank, filling grinding balls into the ball milling tank in advance, adding water, adding a catalyst and an accelerant, accelerating the reaction, and discharging ammonia gas generated by the reaction through a negative pressure exhaust port for collection and treatment.
And 3, after the reaction is finished, separating out grinding balls, aluminum particles and slurry through screening and washing, returning the separated grinding balls to the ball milling tank for reuse, intensively recovering and drying the separated aluminum particles for remelting aluminum ingots, and removing iron carried in aluminum ash and iron generated by ball milling from the separated slurry through an iron remover.
And 4, removing iron in the aluminum ash and iron slurry generated by ball milling obtained in the step 3, washing, filtering and drying to finally obtain the harmless aluminum ash for the refractory material.
Further, the mass of water added into the size mixing tank in the step 1 is 0.5-2 times of the mass of the aluminum ash.
Further, the temperature of the water added in the step 1 is 25-100 ℃.
Further, the ammonia gas generated in the step 1 is discharged from an exhaust port, and then is absorbed by dilute sulfuric acid to be used for preparing ammonium sulfate.
Further, the grinding balls in the wet ball milling tank in the step 2 are one or more of zirconia balls, alumina balls and iron balls, and the adding amount of the grinding balls is 0.5-2 times of the mass of the aluminum ash.
Further, the adding amount of water in the step 2 is 0.5-1 time of the mass of the aluminum ash.
Furthermore, the rotating speed of the wet ball mill in the step 2 is 30 r/min-120 r/min.
Furthermore, in the step 2, the two ends of the wet ball mill are capped and sealed after being charged, an exhaust port is arranged on the cap, and generated ammonia gas is absorbed by dilute sulfuric acid after being exhausted from the exhaust port and is used for preparing ammonium sulfate.
Further, in the step 2, after the slurry is conveyed into the wet ball milling tank, the reaction temperature is up to 85-100 ℃ by oil bath heating or steam heating.
Further, the catalyst added in the step 2 is one or a mixture of more of sodium hydroxide, sodium carbonate, calcium oxide and aluminum hydroxide, and the adding amount of the catalyst is 0.01-0.05 times of the mass of the aluminum ash.
Further, the accelerator added in the step 2 is one or a mixture of more of hydrogen peroxide, ammonia water, hydrochloric acid, sodium carbonate and ethanol, and the addition amount of the accelerator is 0.01-0.05 times of the mass of the aluminum ash.
Further, the reaction time in the step 2 is 1-3 h.
Furthermore, the mesh number of the screen for screening in the step 3 is 80-150 meshes, and the mesh screen is made of nylon.
Furthermore, the water washing in the step 3 is to wash off the aluminum ash adhered to the surfaces of the grinding balls and the aluminum particles, and the addition amount of the washing water is 0.1-0.3 times of the mass of the aluminum ash.
And further, in the washing process in the step 4, new water is adopted for countercurrent washing for 1-5 times, the addition amount of the new water is 0.5-2 times of the mass of the aluminum ash, and the washing water is returned to the step 1 and the step 2 for recycling.
Further, the filtrate filtered in the step 4 is subjected to evaporation crystallization, the crystallized product is used for recovering chloride, and water vapor generated by evaporation is returned to the step 1 and the step 2 for recycling.
And further, repeatedly washing the filtered filter cake for 1-5 times in the step 4, and returning the washing water to the step 1 and the step 2 for recycling.
Further, in the step 4, one of paddle drying, spray drying, flash drying and the like is adopted for the filtered filter cake.
Example 1 method for harmlessly treating aluminum ash key process parameter investigation experiments.
The key conditions for influencing the harmless hydrolysis of the aluminum ash in the method for harmlessly treating the aluminum ash provided by the invention are as follows: ball milling reaction temperature, ball milling slurry liquid-solid ratio and ball milling reaction time. The invention selects the optimal parameter interval through a single-factor experiment, and the experiment selects the raw aluminum ash with the nitrogen content of 5.4 percent.
1. Influence of the reaction temperature on the hydrolysis effect of the ball mill.
The experiment confirms that the reaction time is 2h, and the liquid-solid ratio of the ball-milling reaction slurry is 1: 1, comparing the nitrogen content of the aluminum ash powder after ball milling hydrolysis at the reaction temperature of 65 ℃, 75 ℃, 85 ℃, 95 ℃ and 100 ℃, wherein the nitrogen content of the aluminum ash powder is in a decreasing trend along with the increase of the ball milling reaction temperature of the temperature; when the reaction temperature is more than or equal to 85 ℃, the nitrogen content of the aluminum ash powder is obviously reduced along with the increase and change trend of the temperature and is reduced to be stable, as shown in figure 2, so that the temperature of the method for harmlessly treating the aluminum ash provided by the invention is selected from 85-100 ℃.
2. Influence of the liquid-solid ratio of the ball milling reaction slurry on the ball milling hydrolysis effect.
The experiment confirms that the reaction temperature is 90 ℃, the reaction time is 2 hours, and the solid-to-liquid ratio of the ball-milling reaction slurry is compared with 0.6: 1. 1: 1. 1.5: 1. 2: 1. 2.5: 1. 3: under 1, the nitrogen content of the aluminum ash powder after ball milling and hydrolysis is found to be in a decreasing trend along with the increase of the liquid-solid ratio, but when the liquid-solid ratio is more than or equal to 2.5: 1, the nitrogen content of the aluminum ash powder does not change basically with the increase of the liquid-solid ratio along with the increase of the liquid-solid ratio, and the liquid-solid ratio is more than 2.5; 1, the ball milling refinement and aluminum separation effect are poor. As shown in FIG. 3, the method for harmlessly treating aluminum ash provided by the invention selects a liquid-solid ratio interval of 1: 1-2: 1, compared with the traditional harmless treatment process, the water consumption is obviously reduced.
3. The influence of the ball milling reaction time on the ball milling hydrolysis effect.
The experiment confirms that the reaction temperature is 90 ℃, the solid-to-solid ratio of the ball-milling reaction slurry is 1: 1, comparing the nitrogen content of the aluminum ash powder after ball milling reaction time of 0.5h, 1h, 2h, 3h, 4h and 5h, the nitrogen content of the aluminum ash powder is in a decreasing trend along with the increase of the ball milling reaction time, but when the reaction time is more than or equal to 3h, the nitrogen content of the aluminum ash powder is basically not changed along with the increase of the reaction time, as shown in fig. 4, therefore, the ball milling reaction time interval is selected to be 1-3 h, and compared with the traditional mechanical stirring innocent treatment process, the efficiency is obviously improved.
Therefore, the method for harmlessly treating the aluminum ash selects the optimal reaction parameter interval as the ball milling reaction temperature: ball milling slurry solid ratio at 85-100 ℃: 1: 1-2.5: 1. ball milling reaction time: 1-3 h.
Example 2.
Adding 1000kg of aluminum ash to be treated into a slurry mixing tank, adding 800kg of water with the temperature of 25 ℃, starting stirring, uniformly stirring at the speed of 60r/min for about 0.5h, discharging generated ammonia gas from an exhaust port, absorbing the ammonia gas by using dilute sulfuric acid, conveying slurry into a wet ball milling tank through a screw feeder, pre-filling 1000kg of grinding balls into the ball milling tank, adding 200kg of water with the temperature of 25 ℃ into the ball milling tank, adding 20kg of sodium carbonate serving as a catalyst and 20kg of concentrated ammonia water serving as an accelerator, starting the ball milling tank, operating at the speed of 60r/min, heating the slurry in the ball milling tank to enable the reaction temperature to reach 95 ℃, reacting for 1h, discharging gas generated by reaction from the exhaust port, absorbing the gas by using the dilute sulfuric acid, pouring the mixture of the slurry and the grinding balls into a sieving machine after the reaction is finished, sieving by using a 100-mesh sieve, and leaching 100kg of water plus sieve in total in the sieving process, washing off aluminum ash adhered to the surfaces of the grinding balls and the aluminum particles to obtain 1020kg of grinding balls and 160kg of aluminum particles on the sieve portion, 1900kg of aluminum ash slurry after treatment on the sieve portion (20 kg of water is adhered to the balls and 10kg of water is adhered to the aluminum particles, 270kg of water is taken away by evaporation), adding a flocculating agent into the slurry, transferring the slurry into a belt filter for filtration to obtain 1357kg of filter cake with the water content of 30% and 543kg of filtrate, conveying the filtrate into a crystallization tank for crystallization, conveying the filter cake into a dryer for drying, and finally obtaining the median diameter D50=21 μm, dry powder 955kg with nitrogen content 0.44%.
Example 3.
Adding 1000kg of aluminum ash to be treated into a slurry mixing tank, adding 1200kg of water with the temperature of 25 ℃, starting stirring, uniformly stirring at the speed of 45r/min for about 0.5h, discharging generated ammonia gas from an exhaust port, absorbing the ammonia gas by using dilute sulfuric acid, conveying the slurry into a wet ball milling tank through a screw feeder, pre-loading 1500kg of grinding balls into the ball milling tank, adding 400kg of preheated 75 ℃ water into the ball milling tank, adding a mixture of 10kg of sodium hydroxide and 15kg of calcium oxide as a catalyst, taking 15kg of concentrated ammonia water and 15kg of anhydrous ethanol as an accelerator, starting the ball milling tank, operating at the speed of 50r/min, heating the slurry in the ball milling tank to ensure that the reaction temperature reaches 90 ℃, reacting for 1.5h, discharging gas generated by the reaction from the exhaust port, absorbing the gas by using dilute sulfuric acid, pouring the mixture of the slurry and the grinding balls into a sieving machine after the reaction is finished, passing through a 100-mesh sieve, leaching oversize materials with 200kg of water in total in the screening process to wash away aluminum ash adhered to the surfaces of grinding balls and aluminum particles to obtain 1575kg of grinding balls and 170kg of aluminum particles on the oversize parts, treating 2360kg of aluminum ash slurry on the undersize parts (75 kg of water is adhered to the balls and 15kg of water is adhered to the aluminum particles, 400kg of water is removed by evaporation), adding a flocculating agent into the slurry, transferring the slurry into a plate and frame filter press for filtering to obtain 1075kg of filter cakes with the water content of 15% and 1235kg of filtrate, conveying the filtrate into a crystallization tank for crystallization, conveying the filter cakes into a dryer for drying, and finally obtaining a median diameter D50930kg of dry powder with a nitrogen content of 0.55% and a particle size of 19 μm.
Example 4.
Adding 1000kg of aluminum ash to be treated into a slurry mixing tank, adding 2000kg of water with the temperature of 25 ℃, starting stirring, uniformly stirring at the speed of 30r/min for about 0.5h, discharging generated ammonia gas from an exhaust port, absorbing the ammonia gas by using dilute sulfuric acid, conveying the slurry into a wet ball milling tank through a screw feeder, wherein 2000kg of grinding balls are pre-filled in the ball milling tank, adding 500kg of preheated water with the temperature of 80 ℃ into the ball milling tank, adding 10kg of sodium carbonate, 10kg of calcium oxide and 15kg of aluminum hydroxide as catalysts, adding 10kg of hydrogen peroxide, 10kg of concentrated hydrochloric acid and 15kg of absolute ethyl alcohol as promoters, starting the ball milling tank, operating at the speed of 40r/min, heating the slurry in the ball milling tank to enable the reaction temperature to reach 90 ℃, reacting for 2h, and reacting for 2hDischarging generated gas from an exhaust port, absorbing the gas by dilute sulfuric acid, pouring a mixture of slurry and grinding balls into a sieving machine after reaction is finished, sieving the mixture through a 120-mesh sieve, leaching oversize products by using 300kg of water in total in the sieving process, washing off aluminum ash attached to the surfaces of the grinding balls and the aluminum particles to obtain 2100kg of the grinding balls and 260kg of the aluminum particles on the oversize parts, treating the aluminum ash slurry 3075kg on the undersize parts (75 kg of water is attached to the balls and 30kg of water on the aluminum particles is removed by evaporation), adding a flocculating agent into the slurry, transferring the slurry into a plate-and-frame filter press for filtering to obtain 945kg of filter cake with the water content of 16% and 2130kg of filtrate, conveying the filtrate into a crystallizing tank for crystallization, conveying the filter cake into a drying machine for drying, and finally obtaining a medium-diameter D50830kg of dry powder with a nitrogen content of 0.42% and a particle size of 18 μm.
Comparative example.
Preparing 1000kg of aluminum ash to be treated into slurry according to a liquid-solid ratio of 6:1, heating, stirring and deaminating in a sealed deamination reaction device at the reaction temperature of 95 ℃ for 10h, absorbing ammonia water by using ammonia gas generated in the reaction, performing liquid-solid separation on the slurry after the reaction, and evaporating and crystallizing a liquid phase at 120 ℃ to obtain a mixture of chloride and fluoride; the separated denitrified aluminum ash is subjected to solid phase washing, dehydration and drying to finally obtain the final medium diameter D50Dry filter cake 1137kg with a nitrogen content of 0.8%, 180 μm.
Compared with the aluminum ash treatment method provided by the comparative example, the embodiment 2 shows that the reaction temperature of the harmless aluminum ash treatment method provided by the invention is lower than that of the comparative example, the denitrification reaction time of the aluminum ash is shorter than that of the comparative example, the nitrogen content of the prepared powder is low, the median diameter of the aluminum ash in the particle size distribution can reach below 30 mu m, and the like, and the method for treating the harmless aluminum ash provided by the invention replaces the traditional mechanical stirring by a wet ball milling mode, so that the denitrification effect of the aluminum ash is enhanced, the reaction temperature is reduced, the denitrification reaction time of the aluminum ash is shortened, the generation of wastewater is reduced, the energy consumption of evaporative crystallization is reduced, the effects of efficiently separating aluminum and refining materials are realized, the industrial process is greatly shortened, the method provides convenience for further use of the harmless aluminum ash, is suitable for industrial production, realizes recycling of the aluminum ash, is energy-saving and environment-friendly, has low cost, and has important significance for utilization and harmless treatment of the aluminum ash.
Claims (17)
1. A method for harmlessly treating aluminum ash is characterized by comprising the following steps:
step 1, adding untreated aluminum ash into a size mixing tank, adding water, wherein the temperature of the water is 25-100 ℃, starting stirring, mixing the size, generating a small amount of ammonia gas, and discharging and collecting the ammonia gas through a negative pressure exhaust port;
step 2, conveying the mixed slurry into a wet ball milling tank, filling grinding balls into the ball milling tank in advance, adding water, adding a catalyst and an accelerant, accelerating the reaction at the reaction temperature of 85-100 ℃, and discharging and collecting ammonia gas generated by the reaction through a negative pressure exhaust port;
step 3, after the reaction is finished, separating out grinding balls, aluminum particles and slurry through screening and washing, returning the separated grinding balls to the ball milling tank for reuse, intensively recovering and drying the separated aluminum particles for remelting aluminum ingots, and removing iron carried in aluminum ash and iron generated by ball milling from the separated slurry through an iron remover;
and 4, removing iron in the aluminum ash and iron slurry generated by ball milling obtained in the step 3, washing, filtering and drying to finally obtain the harmless aluminum ash for the refractory material.
2. The method for harmlessly treating the aluminum ash according to claim 1, wherein the mass of water added to the slurry mixing tank in the step 1 is 0.5 to 2 times of the mass of the aluminum ash.
3. The method for detoxifying aluminum ash as claimed in claim 1 wherein ammonia gas generated in step 1 is exhausted through an exhaust port and absorbed in dilute sulfuric acid to produce ammonium sulfate.
4. The method for harmlessly treating the aluminum ash as claimed in claim 1, wherein the grinding balls in the wet ball milling tank in the step 2 are one or more of zirconia balls, alumina balls and iron balls, and the addition amount of the grinding balls is 0.5-2 times of the mass of the aluminum ash.
5. The method for innocent treatment of aluminum ash as claimed in claim 1, wherein the amount of water added in step 2 is 0.5-1 times of the mass of the aluminum ash.
6. The method for harmlessly treating the aluminum ash according to claim 1, wherein the wet ball mill rotation speed in the step 2 is 30r/min to 120 r/min.
7. The method for detoxifying aluminum ash as claimed in claim 1 wherein step 2 the wet ball mill is capped and sealed after charging at both ends, the cap is vented, and the ammonia gas produced is removed from the vent and absorbed in dilute sulfuric acid for use in the preparation of ammonium sulfate.
8. The method for detoxifying aluminum ash as claimed in claim 1 wherein step 2 is performed by heating with an oil bath or steam after the slurry is fed into the wet ball mill.
9. The method for harmlessly treating the aluminum ash as claimed in claim 1, wherein the catalyst added in the step 2 is one or more of sodium hydroxide, sodium carbonate, calcium oxide and aluminum hydroxide, and the addition amount of the catalyst is 0.01 to 0.05 times of the mass of the aluminum ash.
10. The method for innocent treatment of aluminum ash as claimed in claim 1, wherein the accelerator added in step 2 is one or more of hydrogen peroxide, ammonia water, hydrochloric acid, sodium carbonate and ethanol, and the addition amount of the accelerator is 0.01-0.05 times of the mass of the aluminum ash.
11. The method for innocent treatment of aluminum ash as claimed in claim 1, wherein the reaction time in step 2 is 1-3 h.
12. The method of claim 1, wherein the sieve used in step 3 has a mesh size of 80-150 meshes, and the material of the sieve is nylon.
13. The method for innocent treatment of aluminum ash as claimed in claim 1, wherein the amount of the washing water added in the step 3 is 0.1-0.3 times of the mass of the aluminum ash.
14. The method for innocent treatment of aluminum ash as claimed in claim 1, wherein the washing process in step 4 is carried out by adopting fresh water for countercurrent washing for 1-5 times, the addition amount of the fresh water is 0.5-2 times of the mass of the aluminum ash, and the washing water is returned to step 1 and step 2 for recycling.
15. The method for harmlessly treating the aluminum ash as claimed in claim 1, wherein the filtrate filtered in the step 4 is subjected to evaporation crystallization, the crystallized product is used for recovering chloride, and water vapor generated by evaporation is returned to the steps 1 and 2 for recycling.
16. The method for harmlessly treating the aluminum ash according to claim 1, wherein the filtered filter cake is repeatedly washed for 1-5 times in the step 4, and the washing water is returned to the steps 1 and 2 for recycling.
17. The method for harmlessly treating the aluminum ash as claimed in claim 1, wherein in the step 4, one of paddle drying, spray drying and flash drying is adopted for the filtered filter cake.
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| CN113321229A (en) * | 2021-07-05 | 2021-08-31 | 江西省科学院应用物理研究所 | Process for producing corundum phase alumina by adopting secondary aluminum ash |
| CN113694590A (en) * | 2021-08-24 | 2021-11-26 | 云南玉溪玉昆钢铁集团有限公司 | Steelmaking waste residue sediment thick liquid processing system |
| CN114307032A (en) * | 2021-12-28 | 2022-04-12 | 中国科学院过程工程研究所 | Secondary aluminum ash denitrification device system and method |
| CN114671636A (en) * | 2022-05-07 | 2022-06-28 | 济南大学 | Method for harmless treatment of secondary aluminum ash by alkalescent water washing |
| CN115215292A (en) * | 2022-06-29 | 2022-10-21 | 广东至道先进土木工程材料技术研究有限公司 | Method for preparing hydrogen by using secondary aluminum ash |
| CN115193877A (en) * | 2022-07-22 | 2022-10-18 | 广东金亿合金制品有限公司 | Method for comprehensively utilizing aluminum ash resources |
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