CN112442598A - Recycling treatment method of aluminum ash - Google Patents
Recycling treatment method of aluminum ash Download PDFInfo
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- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/04—Working-up slag
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- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0065—Leaching or slurrying
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- C22B15/00—Obtaining copper
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- C22B15/0089—Treating solutions by chemical methods
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- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B21/00—Obtaining aluminium
- C22B21/0007—Preliminary treatment of ores or scrap or any other metal source
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- 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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- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/20—Obtaining alkaline earth metals or magnesium
- C22B26/22—Obtaining magnesium
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- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
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- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/30—Obtaining chromium, molybdenum or tungsten
- C22B34/32—Obtaining chromium
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- C22B47/00—Obtaining manganese
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- 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
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Abstract
The invention relates to a resource treatment method of aluminum ash, belonging to the technical field of resource utilization of hazardous waste in aluminum industry. The resource treatment method of the aluminum ash comprises the following steps: 1) mixing aluminum ash and water for hydrolysis reaction, and carrying out solid-liquid separation after the reaction is finished to obtain a solid material A; 2) mixing the solid material A with acid for leaching reaction, leaching soluble components, and carrying out solid-liquid separation to obtain liquid B; 3) and respectively precipitating and recovering two or more metal elements of copper element, iron element, aluminum element, chromium element, manganese element and magnesium element from the liquid B according to the sequence of copper, iron, aluminum, chromium, manganese and magnesium. The resource treatment method of the aluminum ash solves the problems of environmental pollution and land waste caused by stacking of the aluminum ash, realizes the recycling of more valuable metal elements, and is beneficial to realizing the maximum recycling of valuable components in the aluminum ash.
Description
Technical Field
The invention relates to a resource treatment method of aluminum ash, belonging to the technical field of resource utilization of hazardous waste in aluminum industry.
Background
The aluminum ash is also called aluminum ash, and refers to solid waste discharged in the processes of aluminum electrolysis, aluminum processing and secondary aluminum melting, such as waste slag generated by maintenance and waste of an electrolytic cell in the production process of electrolytic aluminum, primary smelting slag generated in the aluminum pyrometallurgy process, salt slag and scum generated in the electrolytic aluminum process, inflammable skimming generated in the aluminum pyrometallurgy process and the like. The aluminum ash comprises the following main components: al, Al2O3、MgO、SiO2、AlN、Al4C3、Fe2O3、MnO、TiO2、CuO、V2O5、Cr2O3、SeO2NaCl, KCl and MgCl2(ii) a Chromium belongs to a heavy metal which is strictly limited and harmful to the environment, and manganese, copper, vanadium and selenium belong to heavy metals harmful to the environment. In 2017, the yield of electrolytic aluminum in China is 3227 ten thousand tons, the yield of aluminum processing is 5832 ten thousand tons, and the yield of recycled aluminum is 690 ten thousand tons. According to the estimation, the generalized aluminum ash output quantity in China is about 200 million tons each year. If the discharged aluminum ash is counted, the amount of the aluminum ash in China exceeds 1000 ten thousand tons. Along with the annual increase of electrolytic aluminum, aluminum processing and waste aluminum recovery yield in China, a larger amount of aluminum ash is generated every year, if the aluminum ash is not subjected to resource treatment, comprehensive utilization and waste change are realized, resources are wasted, a large amount of land is occupied, and the environment is seriously polluted.
Resource treatment refers to a method for recovering and utilizing substances and energy from solid waste by management or technological measures to create economic value. With increasingly strict environment situation, resource treatment methods of hazardous waste aluminum ash in some aluminum industries are successively developed in large aluminum enterprises, research institutions and colleges, for example, a method for harmlessly utilizing secondary aluminum ash is disclosed in Chinese patent application with application publication number CN109052445A, and the method comprises the following steps: adding secondary aluminum ash obtained by crushing and screening the primary aluminum ash and water into a reaction kettle according to the liquid-solid ratio of 1:5, and heating, stirring and leaching for 6 hours at the temperature of 100 ℃; and (3) carrying out solid-liquid separation after water leaching to obtain primary filtrate and primary filter residue, recovering salt from the primary filtrate by evaporation, using water vapor for heating and supplementing water in the water leaching process, allowing ammonia gas generated in the water leaching process to escape, recovering the ammonia gas, and absorbing the ammonia gas with water to prepare ammonia water. Conveying the primary filter residue into an acid leaching reaction kettle, heating and stirring the primary filter residue and hydrochloric acid with the concentration of 20 wt% in a liquid-solid ratio of 5:2 in the reaction kettle for leaching, wherein the leaching temperature is 80 ℃, the leaching time is 1h, filtering is carried out after the leaching is finished to obtain secondary filtrate and secondary filter residue, and the secondary filter residue can be used for making bricks and the like after being dried in the air; and (3) when the secondary filtrate is recycled, adjusting the pH value by using calcium hydroxide, keeping the pH value of the solution between 2.5 and 2.8, and then heating and curing to prepare the liquid polyaluminium chloride. Also, for example, chinese patent application publication No. CN106830025A discloses a method for recycling aluminum ash, comprising the steps of: s1: separating metal aluminum from aluminum ash to obtain aluminum ash powder; s2: and (3) deamination treatment: mixing aluminum ash powder and water in a mixing tank according to a mass ratio of 1: 1-1: 4, mixing the slurry for 5-15 h, keeping the temperature at 78-82 ℃, generating ammonia gas in the slurry mixing process, absorbing the ammonia gas with strong acid through an absorption tower to prepare ammonium salt, and conveying the slurry mixed slurry to a pressurized reaction kettle through a pump; s3: preparing alumina: and (3) pickling the ore pulp, standing for 3-5 h, filtering out insoluble impurities, adding equimolar sodium hydroxide, standing for a period of time to enable the impurities to react fully, generating a precipitate, filtering, and calcining the precipitate to form the aluminum oxide powder. In the two treatment methods, only aluminum element is recycled from the acid leaching liquid in the process of recycling the aluminum ash, but both have the problem of low recycling treatment degree.
Disclosure of Invention
The invention aims to provide a recycling treatment method of aluminum ash with higher recycling treatment degree.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the resource treatment of the aluminum ash comprises the following steps:
1) mixing aluminum ash and water for hydrolysis reaction, and carrying out solid-liquid separation after the reaction is finished to obtain a solid material A;
2) mixing the solid material A with acid for leaching reaction, leaching soluble components, and carrying out solid-liquid separation to obtain liquid B;
3) and respectively precipitating and recovering two or more metal elements of copper element, iron element, aluminum element, chromium element, manganese element and magnesium element from the liquid B according to the sequence of copper, iron, aluminum, chromium, manganese and magnesium.
In the step 1), aluminum nitride and aluminum carbide in the aluminum ash are hydrolyzed to generate aluminum hydroxide precipitate in the hydrolysis reaction process, and NH is released3、CH4A gas; meanwhile, cosolvents NaCl, KCl and MgCl are added during aluminum melting in aluminum ash2Dissolving into a liquid phase; the chemical reaction involved in the step 1) is as follows:
AlN+3H2O＝Al(OH)3↓+NH3↑；
Al4C3+12H2O＝4Al(OH)3↓+3CH4↑。
in the step 2), acid leaching is carried out on soluble components in the solid material A, and the chemical reaction involved in the leaching reaction is mainly as follows:
2Al+6H+＝2Al3++3H2↑+Q；
Al2O3+6H+＝2Al3++3H2O；
MgO+2H+＝Mg2++2H2O；
Fe2O3+6H+＝2Fe3++3H2O；
MnO+2H+＝Mn2++2H2O；
CuO+2H+＝Cu2++2H2O；
Cr2O3+6H+＝2Cr3++3H2O。
the resource treatment method of the aluminum ash solves the problems of environmental pollution and large amount of land waste of storage sites caused by stacking of the aluminum ash, and two or more than two metal elements are precipitated and recovered from the acid leaching solution after hydrolysis and acid leaching, so that the recycling of various valuable metals is realized, and the method is favorable for realizing the maximum recovery of valuable components in the aluminum ash. The method for recycling the aluminum ash is suitable for recycling the aluminum ash such as the primary aluminum ash and the secondary aluminum ash, and good economic benefit, environmental benefit and social benefit can be generated after the method is popularized.
In order to further reduce the cost of the aluminum ash resource treatment, improve the economic benefit and effectively solve the problem of byproduct hydrochloric acid, preferably, in the step 2), the acid adopted in the leaching reaction is the byproduct hydrochloric acid.
Preferably, the method for recovering copper element by precipitation comprises the following steps: and adding a precipitator soluble sulfide into the liquid B until the pH value of the system is 0.5-1.0, reacting and precipitating copper, and then carrying out solid-liquid separation. Further preferably, the method for recovering copper element by precipitation further comprises the following steps: before solid-liquid separation, adding a flocculating agent into the liquid B, and then carrying out heat preservation treatment on a system added with a precipitator soluble sulfide and the flocculating agent at 80-102 ℃. The added flocculating agent is kept warm to age the precipitate, so that the filtering is convenient and the recovery of the valuable heavy metals of the copper is realized; the chemical reaction involved comprises: cu2++S2-＝CuS↓。
Preferably, the method for precipitating iron element from the liquid B comprises the following steps: the method for recovering iron element by precipitation comprises the following steps: and adjusting the pH value of the liquid B or the liquid obtained after the copper element is recovered through precipitation to be 2.0-3.0, then adding a precipitator soluble phosphate to react to generate an iron phosphate precipitate, and performing solid-liquid separation. The chemical reaction involved comprises: fe3++PO4 3-＝FePO4↓. The method for precipitating and recovering the iron element not only can reduce the difficulty of separating ferric phosphate precipitate from solid and liquid, but also can reduce the iron in the subsequent precipitationCompound impurity components.
Preferably, at least iron and aluminum are precipitated and recovered from the liquid B. By precipitating the iron element from the liquid B, the recovery of the iron element can be realized, and the aluminum-containing compound solid with higher purity obtained by solid-liquid separation after aluminum precipitation is facilitated, so that the difficulty in recovering the high-purity aluminum compound is reduced.
Preferably, at least the copper element, the iron element and the aluminum element are precipitated and recovered from the liquid B. Before the iron element is recovered by precipitation, the copper element is precipitated, so that the recovery of the copper element can be realized, the liquid obtained after the aluminum is recovered by precipitation is convenient to process, and the processing technology is simplified while the purity of a compound in subsequent precipitation can be improved.
Preferably, at least the elements copper, iron, aluminum and chromium are recovered by precipitation from the liquid B. The chromium element is precipitated from the liquid B, so that the chromium is convenient to recover, and the harm of discharged liquid to the environment after the aluminum ash is subjected to resource treatment can be reduced.
In order to achieve the recovery of valuable metals manganese, it is preferable to precipitate and recover at least copper, iron, aluminum, chromium and manganese elements from the liquid B.
In order to achieve maximum recovery of valuable metals in the liquid B, it is preferable to precipitate and recover copper, iron, aluminum, chromium, manganese, and magnesium from the liquid B.
Preferably, at least the aluminum element and the magnesium element are precipitated and recovered from the liquid B. According to the chemical composition of the aluminum ash, the concentrations of aluminum ions and magnesium ions in the liquid B after acid leaching are the highest, and the economic benefit of resource utilization of the aluminum ash can be improved by recovering the aluminum element and the magnesium element through precipitation.
In order to achieve harmless discharge of liquid in the method for recycling aluminum ash, preferably, the method for recycling aluminum ash further comprises the following steps: recovering solute salt from the liquid after recovering magnesium element from the precipitate.
Preferably, in the step 3), the precipitant added in the precipitation recovery process is a sodium-containing precipitant. By controlling the added precipitator, solute salt with single main component can be obtained, and the economic benefit of the resource treatment of the aluminum ash is improved.
Detailed Description
The invention provides a resource treatment method of aluminum ash, which comprises the following steps:
1) mixing aluminum ash and water for hydrolysis reaction, and carrying out solid-liquid separation after the reaction is finished to obtain a solid material A;
2) mixing the solid material A with acid for leaching reaction, leaching soluble components, and carrying out solid-liquid separation to obtain liquid B;
3) and respectively precipitating and recovering two or more metal elements of copper element, iron element, aluminum element, chromium element, manganese element and magnesium element from the liquid B according to the sequence of copper, iron, aluminum, chromium, manganese and magnesium.
In a specific embodiment of the invention, in the step 1), the temperature of the hydrolysis reaction is 85-100 ℃ and the time is 3-5 hours. The water mixed with the aluminum ash in the step 1) should be sufficient so that AlN and Al in the aluminum ash can be contained4C3And (3) fully hydrolyzing, wherein the mass ratio of water to aluminum ash can be 1.5-3: 1. The temperature of the hydrolysis reaction is preferably 90-96 ℃.
In a specific embodiment of the invention, in order to further improve the utilization value of the aluminum ash, in step 1), in the hydrolysis reaction process, gas generated by the hydrolysis reaction is absorbed by acid, and then absorption liquid absorbed by the acid is subjected to evaporation crystallization and filtration, and the obtained filter cake is dried to obtain the product ammonium salt. The specific type of ammonium salt is related to the acid used for absorption, for example, when hydrochloric acid is used for absorption, the ammonium salt obtained is ammonium chloride. The acid used for absorption is preferably by-produced hydrochloric acid. Other generated by the hydrolysis reaction are absorbed and the absorbed tail gas is collected at the same time. The tail gas is methane gas which can be used as fuel after being purified.
In a specific embodiment of the invention, the solid material A and the liquid A obtained by solid-liquid separation in the step 1); the step 1) also comprises the following steps: and (3) evaporating and crystallizing the liquid A obtained by solid-liquid separation, then filtering, and drying a filter cake to obtain the mixed hydrochloride. Mixing ofThe compound hydrochloride comprises NaCl, KCl and MgCl2Can be used as an auxiliary agent to return to an aluminum smelting section for use.
In an embodiment of the present invention, in order to improve the efficiency and safety of the treatment, the method of mixing the solid material a with acid to perform the leaching reaction in step 2) comprises the following steps: and adding acid into the solid material A to an excessive amount, and then heating to 85-95 ℃ to react for 3-4 h. Preferably, the solid material A is added with acid until no gas is generated or no gas is obviously generated, and then the acid is continuously added until the solid material A is in excess. The acid is added till no gas is generated, and then the acid is added till the acid is excessive, so that the acid leaching process is easier to control, and the acid leaching time is shortened by heating. Since the iron oxide in the solid material a reacts slowly with the acid, the leaching time can be shortened by heating. The acid used in step 2) is preferably hydrochloric acid. In addition to hydrochloric acid, the acid used in step 2) may also be sulfuric acid or nitric acid. Further, the acid adopted in the step 2) is byproduct hydrochloric acid. In order to ensure that the leachable component of solid material a is completely leached into the liquid phase by reaction of the acid with solid material a, the acid is used in excess, e.g., 5% or more excess. In a specific embodiment of the present invention, in step 2), an excess of acid is added until the pH value is-2.5 to-2.0 as measured using a pH meter (manufactured by Shanghai apparatus and electronic sciences instruments, Ltd.) of the type pHS-3G. In the step 2), solid-liquid separation is carried out to obtain a solid material B and a liquid B; the main components of the solid material B are vanadium pentoxide, titanium dioxide, selenium dioxide, calcium fluoride and silicon dioxide. The solid material B can be further treated to recover heavy metals after being recovered.
In the specific embodiment of the present invention, in step 3), two or more metal elements of copper, iron, aluminum, chromium, manganese, and magnesium are respectively precipitated and recovered from the liquid B according to the sequence of copper, iron, aluminum, chromium, manganese, and magnesium, corresponding precipitating agents can be added by using the prior art, reaction conditions are controlled, precipitation of corresponding metal elements is realized, and then recovery of each metal element is realized by solid-liquid separation (such as filtration or centrifugation).
In a specific embodiment of the invention, the method for recovering copper element by precipitation comprises the following steps: and adding a precipitator soluble sulfide into the liquid B until the pH value of the system is 0.5-1.0, reacting and precipitating copper, and then carrying out solid-liquid separation. The soluble sulfide can be directly added into the liquid B in a solid form, or can be dissolved in water to prepare a sulfide solution, and then the sulfide solution is added into the liquid B. The mass fraction of soluble sulfides in the sulfide solution is 15-25%. The soluble sulfide is preferably sodium sulfide. The soluble sulfide can also be other soluble sulfides commonly used in the art, such as potassium sulfide or organic sulfides, and the like.
In a specific embodiment of the present invention, the method for recovering copper element by precipitation further comprises the following steps: before solid-liquid separation, adding a flocculating agent into the liquid B, and then carrying out heat preservation treatment on a system added with a precipitator soluble sulfide and the flocculating agent at 80-102 ℃. Further, the order of addition of the precipitant soluble sulfide and flocculant to the liquor B is: and adding a flocculant after the precipitant soluble sulfide is added into the liquid B. Further, the temperature of the system added with the precipitator soluble sulfide and the flocculating agent for heat preservation treatment is 85-95 ℃. The time of the heat preservation treatment is preferably 0.2-1 h. The flocculating agent is one or two of polymeric ferric sulfate and an organic flocculating agent. The addition amount of the flocculant is controlled according to the prior art. If polyferric sulfate is used as the flocculating agent, the adding mass of the flocculating agent can be 2-3 per mill of the mass of the liquid B.
In a specific embodiment of the invention, the method for recovering iron element by precipitation comprises the following steps: and adjusting the pH value of the liquid B or the liquid obtained by solid-liquid separation after recovering the copper element through precipitation to be 2.0-3.0, then adding a precipitator soluble phosphate to react to generate an iron phosphate precipitate, and carrying out solid-liquid separation. The soluble phosphate is preferably added until no more precipitate is formed. And in the process of adding soluble phosphate to react to generate iron phosphate precipitate, controlling the temperature of the system to be 80-90 ℃. The heating in the reaction iron precipitation process can increase the particle size of the precipitated particles, so that the precipitates are easier to separate by filtration, and the treatment time is shortened. The soluble phosphate can be directly added into the system in a solid form, or can be dissolved in water to prepare a phosphate solution, and then the phosphate solution is added into the system. The mass fraction of soluble phosphate in the phosphate solution is 20-30%. The soluble phosphate is preferably sodium phosphate. After the reaction for generating the ferric phosphate precipitate is finished, the system can be aged and then subjected to solid-liquid separation. The aging treatment can further increase the particle size of the precipitate, thereby facilitating the solid-liquid separation. The temperature for aging treatment after iron precipitation is preferably 80-90 ℃. The time for aging treatment after iron precipitation is preferably 0.2-1 h.
In a specific embodiment of the present invention, the method for recovering aluminum element by precipitation comprises the following steps: adjusting the pH value of the liquid obtained by solid-liquid separation after precipitating the iron element to 3.5-4.5, reacting and precipitating aluminum, and then carrying out solid-liquid separation. The chemical reaction involved comprises: al (Al)3++3OH-＝Al(OH)3↓. The temperature of the system is controlled to be 55-90 ℃, preferably 80-90 ℃ and further preferably 85-88 ℃ in the process of depositing aluminum in the reaction. By keeping the system at a higher temperature in the aluminum precipitation process, the particle size of the generated precipitation particles can be increased, and the separation is convenient. In the specific implementation mode of the invention, the system after aluminum precipitation can be aged and then subjected to solid-liquid separation. The temperature for aging the system after aluminum precipitation is 55-90 ℃, preferably 80-90 ℃, and more preferably 85-88 ℃. The aging time of the system after aluminum precipitation is preferably 0.2-3 h. The main component of the aluminum-containing compound solid obtained by adjusting the pH is aluminum hydroxide. In a specific embodiment of the present invention, the method for recovering aluminum by precipitation further comprises the following steps: dissolving the obtained aluminum-containing compound solid with hydrochloric acid, evaporating, cooling, crystallizing, and filtering to obtain crystalline aluminum chloride; the filtered filtrate is returned to be mixed with the solution obtained by dissolving the aluminum-containing compound by hydrochloric acid. The acid used to dissolve the aluminum-containing compound solid is preferably by-produced hydrochloric acid.
In a specific embodiment of the invention, the method for recovering chromium by precipitation comprises the following steps: adjusting the pH value of the liquid obtained by solid-liquid separation after recovering the aluminum element through precipitation to 5.0-7.0, reacting and precipitating chromium, and then carrying out solid-liquid separation. The chemical reaction involved in the reactive chromium deposition is as follows: cr (chromium) component3++3OH-＝Cr(OH)3↓. For enlarging the settled particlesThe particle size is convenient for solid-liquid separation, and the temperature of the system is controlled to be 55-90 ℃, preferably 80-90 ℃ and further preferably 85-88 ℃ in the process of chromium precipitation by reaction. The main component of the chromium-containing compound solid obtained by adjusting the pH value is chromium hydroxide, in the specific embodiment of the invention, after the chromium is precipitated and recovered, the pH value of the liquid obtained by solid-liquid separation is 5.0-7.0, and after the chromium is precipitated by reaction, the solid obtained by solid-liquid separation after the chromium precipitation can be dried and crushed, so that the chromium hydroxide product is prepared. In the specific implementation mode of the invention, the system after chromium precipitation can be aged and then subjected to solid-liquid separation. The time of the aging treatment of the system after chromium precipitation is preferably 0.2-2 h. The temperature of the aging treatment of the system after chromium precipitation is 55-90 ℃, preferably 80-90 ℃, and more preferably 85-88 ℃.
In a specific embodiment of the invention, the method for recovering manganese by precipitation comprises the following steps: and adjusting the pH value of the liquid obtained by solid-liquid separation after the chromium element is recovered through precipitation to 8.5-9.5, reacting and precipitating manganese, and then carrying out solid-liquid separation. The chemical reaction involved in manganese deposition comprises the following steps: mn2++2OH-＝Mn(OH)2↓. In order to increase the particle size of the precipitated particles and facilitate solid-liquid separation, the temperature of the system is controlled to be 55-85 ℃, preferably 70-85 ℃ and further preferably 75-80 ℃ in the process of manganese precipitation reaction. In the specific embodiment of the invention, after the chromium element is recovered by precipitation, the pH of the liquid obtained by solid-liquid separation is 8.5-9.5, and manganese is precipitated by reaction, the solid obtained by solid-liquid separation after manganese precipitation can be dried and crushed to prepare the manganese hydroxide product. In the specific implementation mode of the invention, the system after manganese precipitation can be aged and then subjected to solid-liquid separation. The temperature for aging the system after manganese precipitation is 55-85 ℃, preferably 70-85 ℃, and more preferably 75-80 ℃. The time for aging the system after manganese precipitation is preferably 0.2-2 h.
The pH regulator adopted in the aluminum precipitation, chromium precipitation and manganese precipitation through pH adjustment can be independently selected from caustic soda solution with the mass fraction of 10-30%.
In the embodiment of the invention, the method for recovering magnesium by precipitation comprises the following stepsThe method comprises the following steps: adding alkaline substances into the liquid obtained by solid-liquid separation after the manganese element is recovered by precipitation until no precipitate is generated, and then carrying out solid-liquid separation. In order to increase the particle size of the precipitated particles and facilitate solid-liquid separation, the temperature of the system is controlled to be 55-85 ℃, preferably 70-85 ℃, and further preferably 75-80 ℃ in the process of adding the alkaline substance solution. The alkaline substance is sodium hydroxide and/or sodium carbonate. The magnesium-containing compound solid can be magnesium hydroxide or basic magnesium carbonate according to different alkaline substances added. The alkaline substance is alkali carbonate, and the main component of the solid material obtained by recovery is basic magnesium carbonate; the chemical reaction involved is: 4Mg2++4CO3 2-+5H2O＝3MgCO3·Mg(OH)2·3H2O↓+CO2×) @. The alkali metal carbonate may be added in the form of a solid, or may be dissolved in water to prepare an alkali metal carbonate solution and then added. The mass fraction of the alkali carbonate in the alkali carbonate solution is 20-40%. In the embodiment of the present invention, before the solid-liquid separation after the alkaline substance is added until the precipitate is no longer generated, the system in which the precipitate is no longer generated may be aged and then subjected to the solid-liquid separation. The temperature of the aging treatment of the system which does not generate precipitates is preferably 55-85 ℃. The time for aging the system which does not generate precipitates is preferably 0.2-1.5 h. In the specific embodiment of the invention, alkaline substances can be added into the liquid obtained by solid-liquid separation after the manganese element is recovered by precipitation until the precipitate is not generated any more, and the solid obtained by solid-liquid separation after the precipitate is not generated any more can be dried and crushed to prepare the magnesium compound product. The purity of the magnesium compound in the obtained magnesium compound product is different according to the system of adding the alkaline substance. And adding alkaline substances into the liquid obtained by solid-liquid separation after the manganese element is recovered by precipitation to obtain the magnesium compound product with the highest purity.
In a specific embodiment of the present invention, the method for recycling aluminum ash further comprises the following steps: recovering solute salt from the liquid obtained by solid-liquid separation after recovering magnesium element from the precipitate. The recovery of solute salts may be carried out by a process comprising the steps of: evaporating and crystallizing the liquid obtained by solid-liquid separation after recovering the magnesium element from the precipitate, then filtering, and drying the solid obtained by filtering. The industrial salt is recovered from the liquid obtained by solid-liquid separation after the magnesium element is recovered from the precipitate, so that the influence on the environment generated in the resource treatment process of the aluminum ash can be reduced to the maximum extent, and the production cost can be reduced by further utilizing the industrial salt.
In a specific embodiment of the invention, the metal elements are recovered by precipitation from the liquid B by adding a precipitating agent; the precipitant is sodium-containing precipitant. As mentioned above, when the copper element is recovered by precipitation, sodium sulfide is used as a precipitating agent, and sodium sulfide is added into the system until the pH value of the system is 0.5-1.0 to precipitate copper; when the iron element is recovered by precipitation, sodium hydroxide and sodium phosphate are adopted as a precipitator, sodium hydroxide is added to adjust the pH of the system to 2.0-3.0, and then sodium phosphate is added; when aluminum element is recovered by precipitation, adding sodium hydroxide as a precipitating agent into a system, and adding sodium hydroxide into the system until the pH value of the system is 3.5-4.5 to precipitate aluminum; when chromium is recovered by precipitation, sodium hydroxide is used as a precipitating agent, and sodium hydroxide is added into the system until the pH value of the system is 5.0-7.0 for precipitating chromium; when manganese is recovered by precipitation, adding sodium hydroxide as a precipitating agent into a system, and adding sodium hydroxide into the system until the pH value of the system is 8.5-9.5 to precipitate manganese; when the magnesium element is recovered by precipitation, sodium hydroxide or sodium carbonate is used as a precipitating agent, and sodium hydroxide or sodium carbonate is added into the system until the precipitation is not generated. By controlling the precipitant adopted in the precipitation of each metal ion in the step 3), the industrial salt with a single main component can be obtained, and the additional value of the product in the aluminum ash recycling treatment process is improved.
The byproduct hydrochloric acid is a byproduct of many chemical enterprises in the production process of chemical products, the national yield is high, nearly 10 million tons of byproduct hydrochloric acid are generated every year only by unsealing, and the traditional acid-base neutralization treatment method has low economic benefit. Since the hydrochloric acid is in liquid state, is a volatile inorganic strong acid and is a chemical which is easy to prepare poison, only a company with related quality can process the hydrochloric acid. The byproduct hydrochloric acid is delivered to qualified companies for treatment, so that high treatment cost and transportation cost possibly need to be paid, and the production cost of enterprises is greatly increased. According to the resource treatment method for the aluminum ash, provided by the invention, ammonia gas is absorbed by using the byproduct hydrochloric acid during deamination treatment, the solid material A is leached by using the byproduct hydrochloric acid, and the aluminum-containing compound solid generated by aluminum precipitation is dissolved by using the byproduct hydrochloric acid, so that a large amount of byproduct hydrochloric acid can be consumed, the combined resource treatment of the aluminum ash and the byproduct hydrochloric acid can be realized, and the economic benefit is obvious.
In an embodiment of the present invention, the by-product hydrochloric acid is preferably at least 15% by mass, and may be, for example, 20% by mass.
The technical solution of the present invention will be further described with reference to the following embodiments.
In each example, pH was measured using a pH meter manufactured by Shanghai apparatus, electronic science instruments, Inc. and having a pH value of pHS-3G. The aluminum ash for resource treatment in each example is from a certain enterprise of inner Mongolia, and the main components of the aluminum ash are shown in Table 1 (the percentages are mass percentages); the hydrochloric acid adopted in each embodiment is a byproduct hydrochloric acid in the production process of chemical products.
TABLE 1 Main Components and contents of aluminum ash produced by certain enterprises of inner Mongolia
Example 1
The resource treatment method of the aluminum ash comprises the following steps:
1) to a 500mL four-necked flask with mechanical stirring, thermometer, reflux condenser and dropping funnel was added 200mL of water. The conduit at the upper opening of the reflux condenser is connected with a gas absorption device, and the absorbent is byproduct hydrochloric acid with the mass fraction of 20%.
The stirring was turned on and 100g of aluminum ash was slowly added in portions to the four-necked flask at normal temperature. After the addition is finished, starting heating, raising the temperature to 90 ℃, and then preserving the heat for 3 hours; and filtering after heat preservation is finished to obtain a filter cake I and a filtrate I.
Wherein, the filter cake I enters the step 2) for continuous treatment; evaporating and crystallizing the filtrate I, then filtering to obtain a filter cake a and a filtrate a, and drying the filter cake a obtained by filtering to obtain a mixed hydrochloride (namely a mixture of sodium chloride, potassium chloride and magnesium chloride), wherein the mixed hydrochloride can be used for returning to an aluminum melting working section for use; the filtrate a can be returned to be mixed with the filtrate I for evaporation and crystallization;
evaporating and crystallizing the absorption liquid, then filtering, and drying crystals obtained by filtering to obtain a product, namely ammonium chloride, weighing 15.1g and having the purity of 98%; the tail gas discharged by the collecting and absorbing device is additionally treated, for example, the tail gas can be pressurized to be prepared into liquefied gas to be used as fuel.
2) Adding 100mL of water into a 500mL four-neck flask with a mechanical stirrer, a thermometer, a reflux condenser and a dropping funnel, starting stirring, gradually adding the filter cake I obtained by filtering in the step 1), starting a cock of the dropping funnel after the addition and the uniform stirring, dropwise adding by-product hydrochloric acid with the mass fraction of 20%, and connecting a gas collecting device to the upper port of the reflux condenser to collect hydrogen generated by the reaction.
Dropwise adding by-product hydrochloric acid with the mass fraction of 20% until no gas is generated obviously, and adding excessive by-product hydrochloric acid with the mass fraction of 20% to adjust the pH value to-2.5; then starting heating, heating to 90 ℃, then preserving heat for reaction for 3.5h, and slightly cooling and filtering to obtain filtrate II and filter cake II; the collected hydrogen is further processed.
The filter cake II comprises the main components of vanadium pentoxide, titanium dioxide, selenium dioxide, calcium fluoride and silicon dioxide, and can be further treated to recover heavy metals; and (5) continuing the treatment of the filtrate II in the step 3).
3) Into a 500mL four-necked flask equipped with a mechanical stirrer, a thermometer, a reflux condenser and a dropping funnel was added the filtrate II obtained by filtration in step 2). Stirring and heating are started, a sodium sulfide solution with the mass fraction of 20% is dripped at the same time until the pH value of the system is 0.5, a flocculating agent polymeric ferric sulfate with the mass of 3 per mill of the filtrate II is added, then the temperature is kept at 90 ℃ for 0.5h, and the filtrate III and the filter cake III are obtained after slight cold filtration. The filter cake III can be further treated to recover heavy metals; the filtrate III enters the step 4) for continuous treatment;
4) into a 500mL four-necked flask equipped with a mechanical stirrer, a thermometer, a reflux condenser and a dropping funnel was added the filtrate III obtained by filtration in step 3). Stirring, dropwise adding 20% sodium hydroxide solution at normal temperature to neutralize until pH value is 3.0, heating to 85 deg.C, adding 25% sodium phosphate solution to precipitate iron, maintaining the temperature for 0.5h, and slightly cooling and filtering to obtain filtrate IV and filter cake IV. Drying and crushing the filter cake IV to obtain 1.92g of product iron phosphate with the purity of 96%; the filtrate IV enters the step 5) for continuous treatment;
5) to a 500mL four-necked flask with mechanical stirring, thermometer, reflux condenser and dropping funnel was added filtrate IV. Starting stirring and heating, heating to 85 ℃, adding 20% by mass of caustic soda solution, adjusting the pH value to 3.5, precipitating aluminum, keeping the temperature at 85 ℃ for 0.5h, and filtering slightly in a cold state to obtain filtrate V and a filter cake V;
adding the filter cake V into a flask, adding by-product hydrochloric acid with the mass fraction of 20% to dissolve completely to obtain an aluminum chloride solution, evaporating, cooling, crystallizing, and filtering to obtain a filtrate b and a filter cake b; the obtained filter cake b, namely the product of crystalline aluminum chloride, weighs 382g and has the purity of 98 percent; returning the filtrate b to be mixed with the aluminum chloride solution; the filtrate V enters the step 6) for continuous treatment;
6) to a 500mL four-necked flask with mechanical stirring, thermometer, reflux condenser and dropping funnel was added filtrate V. Stirring and heating are started, the temperature is increased to 63 ℃, 20 mass percent of caustic soda solution is added to adjust the pH value to 5.0 for chromium precipitation, then the temperature is kept at 63 ℃ for 0.5h, and then filtering is carried out, so as to obtain filtrate VI and filter cake VI. Wherein, the filter cake VI is dried and crushed to obtain the product chromium hydroxide; the filtrate VI enters the step 7) for continuous treatment;
7) to a 500mL four-necked flask with mechanical stirring, thermometer, reflux condenser and dropping funnel was added filtrate VI. Stirring and heating are started, after the temperature is raised to 63 ℃, 20% of caustic soda solution in mass fraction is added to adjust the pH value to 9.0 for manganese precipitation, then the temperature is kept at 63 ℃ for 0.5h, and then filtration is carried out to obtain filtrate VII and filter cake VII. Wherein, the filter cake VII is dried and crushed to obtain a product manganese hydroxide; the filtrate VII enters the step 8) for continuous treatment;
8) to a 500mL four-necked flask equipped with mechanical stirring, a thermometer, a reflux condenser and a dropping funnel was added the filtrate VII. Stirring and heating are started, after the temperature is raised to 75 ℃, a soda ash solution with the mass fraction of 30% is added for magnesium precipitation until no precipitate is generated, then the temperature is kept for 0.5h at 75 ℃, and the filtrate VIII and the filter cake VIII are obtained after slight cold filtration. Wherein, the filter cake VIII is dried and crushed to obtain 28g of basic magnesium carbonate with the purity of 98 percent; the filtrate VIII is evaporated, crystallized and then filtered to obtain a byproduct of 228g of sodium chloride with the purity of 98 percent.
The resource treatment of the aluminum ash of the embodiment 1 is carried out by preliminary economic analysis, the raw materials are added by the mass fraction of 20 percent of by-product hydrochloric acid, 99 percent of caustic soda and 96 percent of soda ash, the product is only calculated by 98 percent of ammonium chloride, 98 percent of crystalline aluminum chloride, 98 percent of sodium chloride and 98 percent of basic magnesium carbonate, and the profit is more than 5100 yuan per 1t of aluminum ash treated. From the above economic analysis, the method for the combined recycling treatment of aluminum ash and by-product hydrochloric acid of the embodiment 1 of the present invention has low investment and high yield, and shows that the method for the combined recycling treatment of aluminum ash and by-product hydrochloric acid of the present invention has good economic benefits and is suitable for popularization and application.
Example 2
The method for recycling aluminum ash of the present embodiment is different from embodiment 1 in that: step 3) of example 1 was omitted) and filtrate III of step 4) of example 1 was replaced with filtrate II of step 2) of example 1.
The purity of the obtained ferric phosphate product is 96 percent, and the crystalline aluminum chloride product is light yellow and has a molecular formula of AlCl3·6H2O) purity was 95%.
Example 3
The method for recycling aluminum ash of the present embodiment is different from the method for recycling aluminum ash of embodiment 1 in that:
in the step 1), after stirring, heating water to 96 ℃, then adding 100g of aluminum ash in batches, preserving heat for 3 hours after adding, and filtering after preserving heat;
in the step 2), after no obvious gas is generated, adding 20% by-product hydrochloric acid by mass to adjust the pH value to-2.0, starting heating, raising the temperature to 90 ℃, carrying out heat preservation reaction for 3.5h, and slightly cooling and filtering;
in the step 3), stirring and heating are started, a sodium sulfide solution with the mass fraction of 20% is dropwise added until the pH value of the solution is 0.5, a flocculating agent polymeric ferric sulfate with the mass of 2 per mill of the filtrate II is added, then the temperature is kept at 80 ℃ for 0.5h, and the solution is slightly cooled and filtered;
in the step 4), after stirring, dropwise adding a caustic soda solution with the mass fraction of 20% at normal temperature to neutralize until the pH value is 3.0, then heating to 85 ℃, adding a sodium phosphate solution with the mass fraction of 25% to precipitate iron until no precipitate is generated, preserving heat for 0.5h, and then slightly cooling and filtering;
in the step 5), stirring and heating are started, the temperature is raised to 85 ℃, then 20% of caustic soda solution is added to adjust the pH value to 3.5 for aluminum precipitation, then the temperature is kept at 85 ℃ for 0.2h, and then the mixture is cooled slightly and filtered;
in the step 6), stirring and heating are started, the temperature is raised to 63 ℃, 20 mass percent of caustic soda solution is added to adjust the pH value to 5.0 for chromium precipitation, then the temperature is kept at 63 ℃ for 0.2h, and then the filtration is carried out;
in the step 7), stirring and heating are started, the temperature is raised to 63 ℃, then 20% of caustic soda solution is added to adjust the pH value to 9.0 for manganese precipitation, then the temperature is kept at 63 ℃ for 0.2h, and then filtration is carried out;
in the step 8), stirring and heating are started, the temperature is increased to 75 ℃, then 30% of soda ash solution is added to precipitate magnesium until no precipitate is generated, then the temperature is kept for 1 hour, and the mixture is filtered slightly cold.
Example 4
The method for recycling aluminum ash of the present embodiment is different from the method for recycling aluminum ash of embodiment 1 in that:
in the step 1), after starting heating, heating to 85 ℃, preserving heat for 5 hours, and filtering after finishing preserving heat;
in the step 2), after no obvious gas is generated, adding 20% by-product hydrochloric acid by mass to adjust the pH to-2.5, starting heating, raising the temperature to 85 ℃, carrying out heat preservation reaction for 4 hours, and slightly cooling and filtering;
in the step 3), stirring and heating are started, a sodium sulfide solution with the mass fraction of 25% is dropwise added until the pH value of the solution is 0.8, then a flocculating agent polymeric ferric sulfate is added, and then the solution is subjected to heat preservation at 85 ℃ for 1 hour and is slightly cooled and filtered;
in the step 4), after stirring, dropwise adding 15% by mass of caustic soda solution at normal temperature to neutralize until the pH value is 2.5, then heating to 80 ℃, adding 25% by mass of sodium phosphate solution to precipitate iron until no precipitate is generated, preserving heat for 1h, and then slightly cooling and filtering;
in the step 5), stirring and heating are started, the temperature is raised to 90 ℃, then a caustic soda solution with the mass fraction of 30% is added to adjust the pH value to 4.0 for aluminum precipitation, then the temperature is kept at 90 ℃ for 2 hours, and then the mixture is cooled slightly and filtered;
in the step 6), stirring and heating are started, the temperature is raised to 90 ℃, a caustic soda solution with the mass fraction of 30% is added to adjust the pH value to 7.0 for chromium precipitation, then the temperature is kept at 90 ℃ for 1.5h, and then the filtration is carried out;
in the step 7), stirring and heating are started, the temperature is raised to 85 ℃, then 15% of caustic soda solution is added to adjust the pH value to 9.5 for manganese precipitation, then the temperature is kept at 85 ℃ for 1.5h, and then filtration is carried out;
in the step 8), stirring and heating are started, the temperature is increased to 85 ℃, then 20% of soda ash solution is added to precipitate magnesium until no precipitate is generated, then the temperature is kept for 0.2h, and the mixture is filtered slightly cold.
Example 5
The method for recycling aluminum ash of the present embodiment is different from the method for recycling aluminum ash of embodiment 1 in that:
in the step 1), after starting heating, heating to 100 ℃, preserving heat for 3 hours, and filtering after finishing preserving heat;
in the step 2), after starting heating, heating to 85 ℃, then preserving heat for reaction for 4 hours, and filtering slightly cold;
in the step 3), after starting stirring, dropwise adding a sodium sulfide solution with the mass fraction of 15% until the pH value of the solution is 0.8, then adding a flocculating agent polymeric ferric sulfate, then starting heating to 100 ℃, keeping the temperature for 1h, and slightly cooling and filtering;
in the step 4), after stirring, dropwise adding a caustic soda solution with the mass fraction of 30% at normal temperature to neutralize until the pH value is 2.5, then heating to 85 ℃, adding a sodium phosphate solution with the mass fraction of 25% to precipitate iron until no precipitate is generated, preserving heat for 1h, and then slightly cooling and filtering;
in the step 5), stirring and heating are started, the temperature is raised to 85 ℃, then 15% of caustic soda solution is added to adjust the pH value to 4.0 for aluminum precipitation, then the temperature is kept at 85 ℃ for 3 hours, and then the mixture is cooled slightly and filtered;
in the step 6), stirring and heating are started, the temperature is raised to 80 ℃, 15% of caustic soda solution in mass fraction is added to adjust the pH value to 7.0 for chromium precipitation, then the temperature is kept for 2 hours at 80 ℃, and then the filtration is carried out;
in the step 7), stirring and heating are started, the temperature is raised to 75 ℃, then caustic soda solution with the mass fraction of 30% is added to adjust the pH value to 9.5 for manganese precipitation, then the temperature is kept for 2 hours at 75 ℃ after the manganese precipitation, and then the filtration is carried out;
in the step 8), stirring and heating are started, the temperature is increased to 75 ℃, then soda ash solution with the mass fraction of 40% is added to precipitate magnesium until no precipitate is generated, then the temperature is kept for 1.5h, and the mixture is filtered slightly cold.
In another embodiment of the resource treatment of aluminum ash of the present invention, the 20% by-product hydrochloric acid used in embodiments 1 to 5 may be replaced with a by-product hydrochloric acid or industrial sulfuric acid of another concentration.
From the embodiments 1 to 5, the resource treatment method of the aluminum ash provided by the invention takes the byproduct hydrochloric acid as an acid source, can realize combined resource treatment and comprehensive recycling of the aluminum ash and the byproduct hydrochloric acid, changes waste into valuable, and saves resources; the byproduct hydrochloric acid is used as a leaching agent, so that valuable components in the aluminum ash are recovered to the maximum extent, and the obtained recovered product has high added value; the environmental pollution and the waste of a large amount of storage yard land caused by the existing aluminum ash storage are solved; the consumption of by-product hydrochloric acid is large; the method has the advantages of simple process flow, less equipment investment, mild reaction conditions and easy operation; sufficient raw material supply, low price, low production cost and strong market competitive advantage. The resource treatment method of the aluminum ash can produce good economic benefit, environmental benefit and social benefit after being implemented and popularized.
Claims (13)
1. A resource treatment method of aluminum ash is characterized in that: the method comprises the following steps:
1) mixing aluminum ash and water for hydrolysis reaction, and carrying out solid-liquid separation after the reaction is finished to obtain a solid material A;
2) mixing the solid material A with acid for leaching reaction, leaching soluble components, and carrying out solid-liquid separation to obtain liquid B;
3) and respectively precipitating and recovering two or more metal elements of copper element, iron element, aluminum element, chromium element, manganese element and magnesium element from the liquid B according to the sequence of copper, iron, aluminum, chromium, manganese and magnesium.
2. The method for recycling aluminum ash according to claim 1, wherein: in the step 2), the acid adopted in the leaching reaction is byproduct hydrochloric acid.
3. The method for recycling aluminum ash according to claim 1, wherein: the method for recovering copper element by precipitation comprises the following steps: and adding a precipitator soluble sulfide into the liquid B until the pH value of the system is 0.5-1.0, reacting and precipitating copper, and then carrying out solid-liquid separation.
4. The method for recycling aluminum ash according to claim 2, wherein: the method for recovering copper element by precipitation further comprises the following steps: before solid-liquid separation, adding a flocculating agent into the liquid B, and then carrying out heat preservation treatment on a system added with a precipitator soluble sulfide and the flocculating agent at 80-102 ℃.
5. The method for recycling aluminum ash according to claim 1, wherein: the method for recovering iron element by precipitation comprises the following steps: and adjusting the pH value of the liquid B or the liquid obtained after the copper element is recovered through precipitation to be 2.0-3.0, then adding a precipitator soluble phosphate to react to generate an iron phosphate precipitate, and performing solid-liquid separation.
6. The method for recycling aluminum ash according to claim 1, wherein: and precipitating and recovering at least iron element and aluminum element from the liquid B.
7. The method for recycling aluminum ash according to claim 1, wherein: and precipitating and recovering at least copper element, iron element and aluminum element from the liquid B.
8. The method for recycling aluminum ash according to claim 1, wherein: and precipitating and recovering at least copper element, iron element, aluminum element and chromium element from the liquid B.
9. The method for recycling aluminum ash according to claim 1, wherein: and precipitating and recovering at least copper element, iron element, aluminum element, chromium element and manganese element from the liquid B.
10. The method for recycling aluminum ash according to claim 1, wherein: and precipitating and recovering copper, iron, aluminum, chromium, manganese and magnesium from the liquid B.
11. The method for recycling aluminum ash according to claim 1, wherein: and precipitating and recovering at least aluminum element and magnesium element from the liquid B.
12. The method for recycling aluminum ash according to claim 10 or 11, wherein: further comprising the steps of: recovering solute salt from the liquid after recovering magnesium element from the precipitate.
13. The method for recycling aluminum ash according to claim 12, wherein: in the step 3), the precipitant added in the precipitation recovery process adopts a sodium-containing precipitant.
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| CN115959672A (en) * | 2023-01-06 | 2023-04-14 | 上饶鑫远达环保科技有限公司 | Harmless treatment method for aluminum ash |
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