CN110820028B - Treatment method for recycling waste acid of aluminum profile anodic oxidation tank - Google Patents
Treatment method for recycling waste acid of aluminum profile anodic oxidation tank Download PDFInfo
- Publication number
- CN110820028B CN110820028B CN201810901764.6A CN201810901764A CN110820028B CN 110820028 B CN110820028 B CN 110820028B CN 201810901764 A CN201810901764 A CN 201810901764A CN 110820028 B CN110820028 B CN 110820028B
- Authority
- CN
- China
- Prior art keywords
- aluminum
- acid
- anodic oxidation
- oxidation tank
- aluminum profile
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/06—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used
- C25D11/08—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used containing inorganic acids
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/06—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used
- C25D11/10—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used containing organic acids
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D21/00—Processes for servicing or operating cells for electrolytic coating
- C25D21/06—Filtering particles other than ions
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D21/00—Processes for servicing or operating cells for electrolytic coating
- C25D21/16—Regeneration of process solutions
- C25D21/18—Regeneration of process solutions of electrolytes
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a treatment method for recycling waste acid of an aluminum profile anodic oxidation tank, which comprises the following steps: the method comprises the following steps of: taking waste acid of an aluminum profile anodic oxidation tank into a strong acid resistant reaction kettle, starting cooling water for refluxing, continuously stirring, adding a chemical agent, heating the mixture to a reaction temperature, maintaining the reaction temperature, and continuously heating and stirring; preparing seed crystals: taking solid aluminum salt which is formed by chemical mixture acid radicals and aluminum ions and is difficult to be dissolved in water and dilute sulfuric acid, and crushing and sieving the solid aluminum salt by using a stainless steel crusher; inducing seed crystal: aluminum salt in the seed crystal induction reaction liquid is utilized to form aluminum salt precipitate; fourthly, natural settlement: the temperature of the reaction solution precipitated by the aluminum salt is controlled by the stirring speed, the stirring is continued, and the supernatant fluid of the precipitation is taken. Fifthly, membrane separation: precisely filtering the obtained settled supernatant by using microporous membrane equipment to obtain dealuminizing acid liquor of an aluminum profile anodic oxidation tank; sixthly, adjusting components. Low cost, no pollution, full removal of aluminum ions, recyclable acid, high utilization rate of raw materials, simple and convenient process and mechanization.
Description
Technical Field
The invention belongs to the technical field of aluminum profile processing, and particularly relates to a treatment method for recycling waste acid of an aluminum profile anodic oxidation tank. The method is suitable for the treatment of the aluminum profile anodic oxidation tank waste acid with any formula in the aluminum profile processing industry in a recycling manner, and the treatment of the aluminum profile electrolytic polishing tank waste acid in the aluminum profile processing industry in a recycling manner, and comprises the treatment of waste acid generated by a sulfuric acid anodic oxidation process, a chromic acid anodic oxidation process, an oxalic acid anodic oxidation process and a phosphoric acid anodic oxidation process, and the treatment of aluminum-containing waste acid in the aluminum profile processing industry in a recycling manner.
Background
Anodic oxidation is an electrolytic oxidation in which the surface of an aluminum profile generally forms an oxide film whose constituent is aluminum oxide. This film has some functionality, among others, protective, decorative. Oxide films fall into two broad categories: a barrier type oxide film which is a thin dense nonporous oxide film against the metal surface and whose thickness is generally not more than 0.1um depending on the applied voltage, and a porous type oxide film. The porous oxide film is composed of two oxide films, a barrier layer whose thickness is dependent on the applied voltage and a porous layer whose thickness depends on the amount of electricity passing. The characteristics of the anodic oxide film were as follows: a. the oxide film structure is a porous honeycomb knot, the porosity of the film enables the film to have good adsorption capacity, the film can be used as a bottom layer of a coating layer and can also be dyed, and the decorative effect of metal is improved. b. The hardness of the oxide film is high, the hardness of the anodic oxide film is high, and the hardness is about 196-490 HV, because the high hardness determines that the wear resistance of the oxide film is very good. c. The corrosion resistance of the oxide film is stable in air and soil, the bonding force with a matrix is strong, and the aluminum oxide film can be subjected to dyeing hole sealing or spraying treatment after oxidation in general, so that the corrosion resistance of the aluminum oxide film is further enhanced. d. The oxide film has strong binding force and strong binding force with the base metal, so that the oxide film is difficult to separate by a mechanical method, even if the film layer bends along with the metal, the film layer still keeps good binding with the base metal, but the oxide film has small plasticity and large brittleness, and when the film layer is subjected to larger impact load and bending deformation, cracks can be generated, so the oxide film is difficult to use under the mechanical action and can be used as a bottom layer of a paint layer. e. The insulation of the oxide film, the impedance of the anodic oxide film of aluminum is high, the thermal conductivity is low, the thermal stability can reach 1500 degrees, the thermal conductivity is 0.419W/(m.K) to 1.26W/(m.K), and the aluminum anode oxide film can be used as a dielectric layer of an electrolytic capacitor or an insulating layer of an electric product.
Common processes for anodizing aluminum profiles include a sulfuric acid anodizing process, a chromic acid anodizing process, an oxalic acid anodizing process, and a phosphoric acid anodizing process. The most common is the sulfuric acid anodizing process. The most common aluminum profile sulfuric acid anodic oxidation process is as follows: 1. anodic oxidation acid solution: acid liquor consisting of 16-18 percent (mass fraction) of sulfuric acid, 3-5 percent (mass fraction) of LY-920 wide-temperature oxidant special for aluminum profile anodic oxidation and pure water; 2. the oxidation temperature is 15-25 ℃ (preferably 18-22 ℃); 3. the voltage is 12-20V, and the current density is 1-1. A/dm 2; 4. the oxidation time is 10-25 min.
The surface oxide film with protectiveness, decorativeness and brightness is generated along with the corrosion of the aluminum section in the anodic oxidation tank by the acid liquor, aluminum ions can be formed on the aluminum on the surface part of the aluminum section and dissolved in the acid liquor, and meanwhile, the concentration of the acid liquor can be reduced due to the corrosion of the acid liquor and the aluminum section. When the concentration of aluminum ions in the acid liquor of the anodic oxidation tank rises to a certain value and the concentration of the acid liquor is reduced to a certain value, the anodic oxidation effect is seriously reduced because the high-concentration aluminum ions can generate strong heating action and the concentration of the acid liquor is reduced, at the moment, the acid liquor of the anodic oxidation tank needs to be replaced by the freshly prepared acid liquor, and the waste acid of the anodic oxidation tank is generated. A medium-sized aluminum profile processing company produces about 20-35 tons of waste acid of the anodic oxidation tank per day. Because the acid liquor formula and the process of the anodic oxidation tank of each company are different, the composition of the waste acid of the anodic oxidation tank is also different, but the basic composition of the waste acid of the anodic oxidation tank is as follows: 10-30 percent of sulfuric acid (mass fraction), 1.0-3 percent of aluminum ions (mass fraction), 69-89 percent of water (mass fraction) and a small amount of other metal ions.
The waste acid in the aluminum profile anodic oxidation tank has high acidity, strong acidity, high concentration and toxic metal ions, so the treatment cost is extremely high, the treatment difficulty is extremely high, and the produced solid waste has extremely high pollution to the environment. An effective method for treating and utilizing waste acid of an aluminum profile anodic oxidation tank is lacked at present. Therefore, the research on the treatment technology of the waste acid in the aluminum profile anodic oxidation tank has important and practical social, economic and environmental protection significance for the aspects of clean production, environmental pollution reduction, economic benefit increase and the like in the aluminum profile industry.
Disclosure of Invention
Aiming at the defects of high treatment difficulty, high cost, serious waste pollution and the prior art of the waste acid of the aluminum profile anodic oxidation tank at present, the invention aims to provide a treatment method for recycling the waste acid of the aluminum profile anodic oxidation tank, which has the advantages of low cost, no pollution, sufficient removal of aluminum ions, recyclable acid, high raw material utilization rate, simple and convenient process and mechanization.
In order to achieve the purpose, the invention adopts the following technical measures:
the technical concept of the invention is as follows: by utilizing the property that aluminum ions in the waste acid of the aluminum profile anodic oxidation tank can react with a chemical mixture to generate aluminum salt which is insoluble in water and dilute acid, supernatant obtained by heating reaction, seed crystal induction and natural sedimentation of the waste acid of the aluminum profile anodic oxidation tank is subjected to membrane separation filtration and component adjustment to obtain recyclable acid liquor of the aluminum profile anodic oxidation tank.
A treatment method for recycling waste acid from an aluminum profile anodic oxidation tank is characterized by comprising the following steps:
1.a treatment method for recycling waste acid of an aluminum profile anodic oxidation tank comprises the following steps:
the method comprises the following steps of: taking waste acid of an aluminum profile anodic oxidation tank to a strong acid resistant reaction kettle or other containers, starting cooling water to reflux, adding a chemical mixture with the mass of 0.3-25% of that of the waste acid under the condition of continuous stirring, heating the mixture to the dissociation reaction temperature of the chemical mixture and maintaining the dissociation reaction temperature of the chemical mixture, and continuously heating, stirring and reacting for 1.0-15 hours to enable the chemical mixture to react with aluminum ions to generate corresponding aluminum salts, thereby obtaining reaction liquid for later use.
The waste acid of the aluminum profile anodic oxidation tank is the acid liquor which is remained after the aluminum profile is anodized in the oxidation tank by using the mixed acid liquor for anodic oxidation of the aluminum profile, has high aluminum ion content, can not be reused and needs to be discarded, and comprises the following components: 10-30% of sulfuric acid, 0.8-3.0% of aluminum ions, 0.1-5% of LY-920 wide-temperature oxidant special for anodic oxidation of aluminum profiles and 68-86% of water; the chemical mixture is one of analytically pure or chemically pure dodecyl benzene sulfonic acid, phytic acid, oxalic acid, phosphoric acid, silicic acid, polysilicic acid, fluosilicic acid and hydrofluoric acid, or a mixture of two to eight of the analytically pure or chemically pure dodecyl benzene sulfonic acid, phytic acid, oxalic acid, phosphoric acid, silicic acid, polysilicic acid, fluosilicic acid and hydrofluoric acid in any proportion; the dissociation reaction temperature of the chemical-mixture agent is the temperature capable of promoting the generation of corresponding aluminum salt, and the range of the dissociation reaction temperature is 15-120 ℃.
Preferably, the waste acid from the aluminum profile anodic oxidation tank is the acid liquor which is left after the aluminum profile is anodized in the oxidation tank by using the mixed acid liquor for aluminum profile anodic oxidation, has high aluminum ion content, cannot be reused and needs to be discarded, and mainly comprises the following components: 13-25% of sulfuric acid (mass fraction), 1.2-2.5% of aluminum ions (mass fraction), 0.5-3% of LY-920 wide-temperature oxidant special for aluminum profile anodic oxidation and 70-85.3% of water (mass fraction); the chemical mixture is one of analytically pure dodecyl benzene sulfonic acid, phytic acid, phosphoric acid, silicic acid, polysilicic acid, fluosilicic acid and hydrofluoric acid, or a mixture of two of the dodecyl benzene sulfonic acid, the phytic acid, the phosphoric acid, the silicic acid, the polysilicic acid, the fluosilicic acid and the hydrofluoric acid in any proportion, or a mixture of three of the dodecyl benzene sulfonic acid, the phytic acid, the phosphoric acid, the silicic acid, the polysilicic acid and the hydrofluoric acid in any proportion; the dissociation reaction temperature of the chemical-mixture agent is the temperature capable of promoting the generation of corresponding aluminum salt, and the range of the dissociation reaction temperature is 30-110 ℃.
Preparing seed crystals: taking solid aluminum salt which is formed by corresponding chemical mixture acid radicals and aluminum ions and is difficult to dissolve in water and dilute sulfuric acid, crushing the solid aluminum salt by a stainless steel crusher, and sieving the crushed material by a standard sieve to obtain aluminum salt seed crystal.
The solid aluminum salt is any one of analytically pure or chemically pure aluminum dodecylbenzene sulfonate, aluminum phytate, aluminum oxalate, aluminum phosphate, aluminum silicate, aluminum polysilicate, aluminum fluosilicate and aluminum hydrofluoride, or a mixture of two to eight of the aluminum dodecylbenzene sulfonate, the aluminum phytate, the aluminum oxalate, the aluminum phosphate, the aluminum silicate, the aluminum polysilicate, the aluminum fluosilicate and the aluminum hydrofluoride in any proportion; the screening is 40-600 meshes.
Preferably, the solid aluminum salt is one of analytically pure aluminum dodecylbenzene sulfonate, aluminum phytate, aluminum phosphate, aluminum silicate, aluminum polysilicate, aluminum fluosilicate and aluminum hydrofluoride, or a mixture of two to eight of the analytically pure aluminum dodecylbenzene sulfonate, aluminum phytate, aluminum phosphate, aluminum silicate, aluminum polysilicate, aluminum fluosilicate and aluminum hydrofluoride in any proportion; the standard sieve is sieved by a standard sieve of 80-400 meshes.
Inducing seed crystal: the method comprises the steps of reducing the temperature of the reaction liquid obtained in the step to 0-45 ℃ and maintaining the temperature at 0-45 ℃, adding seed crystals which are obtained in the step two and have a mass component capable of playing an inducing role into the reaction liquid under the condition of continuous stirring, and continuously stirring for 1.0-25 hours to enable aluminum salts in the seed crystal induction reaction liquid to form aluminum salt precipitates, so as to obtain the reaction liquid with the aluminum salt precipitates.
The mass fraction capable of playing an inducing role is the mass fraction capable of playing an inducing role in crystallization generation, and the range of the mass fraction is 0.05-5%.
Preferably, the mass fraction capable of inducing is a mass fraction capable of inducing crystal formation, and the range of the mass fraction is 0.05-5%.
Preferably, the appropriate mass fraction is a mass fraction capable of inducing crystal formation, and the range of the mass fraction is 0.1-2%.
Fourthly, natural settlement: maintaining the temperature of the reaction liquid precipitated by the aluminum salt precipitate obtained in the step three to be 0-40 ℃, controlling the sedimentation stirring speed, continuing stirring for 5-45 hours, stopping stirring, naturally settling the precipitate for 3-15 hours, and taking the supernatant for later use.
The sedimentation stirring speed is the stirring speed at which the aluminum salt can be settled, and the range of the sedimentation stirring speed is 1-50 rpm.
Preferably, the sedimentation stirring speed is a stirring speed at which the aluminum salt can be sedimented, and the range of the sedimentation stirring speed is 5-40 rpm.
Fifthly, membrane separation: and d, precisely filtering the settled supernatant obtained in the step four by using microporous membrane equipment to obtain the dealuminizing acid solution of the aluminum profile anodic oxidation tank for later use.
The membrane material of the microporous membrane equipment is silicon carbide, the membrane component is a honeycomb briquette type inner tubular membrane, and the sizes of membrane pores are 1, 0.5, 0.1 and 0.04 mu m.
Preferably, the membrane material of the microporous membrane equipment is silicon carbide, the membrane component is in the form of a honeycomb briquette type inner tubular membrane, and the membrane pore size is 0.1 and 0.04 mu m.
Sixthly, component adjustment: analyzing and determining the mass percent of sulfuric acid of the dealuminizing acid solution for the aluminum profile anodic oxidation tank obtained in the step fifthly, adding concentrated sulfuric acid and a LY-920 wide-temperature oxidizing agent special for aluminum profile anodic oxidation according to the mass percent of sulfuric acid of the aluminum profile anodic oxidation tank acid solution for the aluminum profile anodic oxidation process, and uniformly stirring to obtain the recyclable anodic oxidation tank acid solution for anodic oxidation of the next batch of aluminum profiles.
The concentrated sulfuric acid is sulfuric acid with 98% of mass fraction and is analytically pure or chemically pure.
Preferably, the concentrated sulfuric acid is sulfuric acid with 98% mass fraction of analytical purity or chemical purity.
Through the technical measures of the six steps, the most important step is heating reaction, step three, seed crystal induction and step membrane separation, the heating reaction mainly through controlling the temperature solves the technical problems and difficulties that the insoluble aluminum salt is generated by acid dissociation of the insoluble aluminum salt generated by the seed crystal of the insoluble aluminum salt, the solid phase precipitation of the insoluble aluminum salt is solved by utilizing the seed crystal of the insoluble aluminum salt to induce the crystallization of the insoluble aluminum salt, and the filtration of insoluble impurities in the aluminum profile chemical polishing tank dealuminizing waste acid with high acid concentration and strong acidity is solved by filtering the silicon carbide film with strong corrosion resistance. The technical effects of salifying removal of aluminum ions which hinder recycling in the waste acid liquor of the aluminum profile anodic oxidation tank, complete separation of insoluble aluminum salt with tiny particles and insoluble impurities in the dealuminizing acid liquor of the aluminum profile anodic oxidation tank and recycling of the dealuminizing waste acid of the aluminum profile anodic oxidation tank through component adjustment are mainly achieved. Because acid liquor waste acid in the aluminum profile anodic oxidation tank is directly used as waste to be discharged after being neutralized by alkali at present, and almost no technical scheme exists, compared with the prior art, the method has the advantages of innovation, resource utilization, environmental protection and the like.
Through the technical treatment of the invention, the retention rate of sulfuric acid in the waste acid of the aluminum profile anodic oxidation tank is 100 percent; the total acid amount is increased; the removal rate of aluminum ions is more than or equal to 85 percent; the removal rate of insoluble impurities is 100%; the appearance is colorless, clear and transparent. The aluminum section anodic oxidation tank dealumination acid solution obtained after the components of the aluminum section anodic oxidation tank dealumination acid solution are adjusted can be completely used for anodic oxidation of aluminum sections of the next batch.
Compared with the prior art, the method has the advantages and beneficial effects that:
low cost, no pollution, sufficient removal of aluminum ions, recyclable acid, high utilization rate of raw materials, simple and convenient process, capability of mechanical treatment and suitability for large-scale and small-scale production.
Aiming at the defects of high treatment difficulty, serious waste pollution and the prior art of the waste acid of the aluminum profile anodic oxidation tank at present, the invention aims to provide the treatment method for recycling the waste acid of the aluminum profile anodic oxidation tank, which has the advantages of low cost, no pollution, recyclable acid, high raw material utilization rate, simple and convenient process and mechanization.
The aluminum profile anodic oxidation tank waste acid which is treated by the method is colorless and clear uniform liquid, aluminum ions which affect the anodic oxidation effect are removed, sulfuric acid is reserved, the recycling effect is the same as that of a freshly prepared anodic oxidation acid liquid, and the environmental pollution, high treatment cost and waste of useful resources of the waste acid are avoided.
Drawings
FIG. 1 is a process flow diagram of a treatment method for recycling waste acid from an aluminum profile anodic oxidation tank.
Detailed Description
The present invention will be described in further detail with reference to the following detailed description and the accompanying drawings.
Example 1:
a treatment method for recycling waste acid of an aluminum profile anodic oxidation tank comprises the following steps:
the method comprises the following steps of: taking 500 grams of waste acid of an aluminum profile anodic oxidation tank, the waste acid mainly comprising 19 mass percent of sulfuric acid, 1.8 mass percent of aluminum ions, 1.7 mass percent of LY-920 wide-temperature oxidant special for aluminum profile anodic oxidation and 77.5 mass percent of water, adding 1.5 mass percent of dodecylbenzene sulfonic acid under the stirring condition with the stirring speed of 100rpm, starting cold water reflux, heating the mixture to 85 ℃ and maintaining the temperature at 85 ℃, and continuing heating, stirring and reacting for 8 hours to enable the dodecylbenzene sulfonic acid and the aluminum ions to react to generate corresponding aluminum dodecylbenzene sulfonate, thereby obtaining reaction liquid for later use.
Preparing seed crystals: taking solid analytically pure aluminum dodecylbenzene sulfonate, crushing the solid analytically pure aluminum dodecylbenzene sulfonate by a stainless steel crusher, and sieving the crushed material by a 200-mesh standard sieve to obtain the aluminum dodecylbenzene sulfonate seed crystal.
Inducing seed crystal: and (2) reducing the temperature of the reaction liquid obtained in the step (c) to 25 ℃ and maintaining the temperature at 25 ℃, adding aluminum dodecyl benzene sulfonate seed crystals with the mass fraction of 0.5% into the reaction liquid under the stirring condition that the stirring speed is 200rpm, and continuously stirring for 15 hours to enable aluminum salts in the seed crystal induction reaction liquid to fully form aluminum dodecyl benzene sulfonate precipitates, thereby obtaining the reaction liquid with the aluminum salt precipitates.
Fourthly, natural settlement: maintaining the temperature of the reaction liquid precipitated by the aluminum salt precipitate obtained in the step three at 25 ℃, continuing stirring for 25 hours under the stirring condition that the stirring speed is 20rpm, stopping stirring, naturally settling the precipitate for 10 hours, and taking the settled supernatant for later use.
Fifthly, membrane separation: and (3) precisely filtering the settled supernatant obtained in the step four by using microporous membrane equipment of which the membrane material is silicon carbide, the membrane pores are 0.04 mu m and the membrane component is a honeycomb briquette type inner tubular membrane to obtain 493 g of the dealuminizing acid solution of the aluminum profile anodic oxidation tank with the aluminum ion content of less than or equal to 0.20 percent (mass fraction) and the sulfuric acid content of 18 percent (mass fraction).
Sixthly, component adjustment: according to the requirement of the mass percentage content of sulfuric acid of the aluminum profile anodic oxidation tank acid liquid required by the aluminum profile anodic oxidation process, adding analytically pure concentrated sulfuric acid and the LY-920 wide-temperature oxidizing agent special for aluminum profile anodic oxidation, and uniformly stirring to obtain the recyclable anodic oxidation tank acid liquid for anodic oxidation of the next batch of aluminum profiles.
According to the determination, after the aluminum profile anodic oxidation waste acid is treated by the method, the retention rate of sulfuric acid is 100%, the removal rate of aluminum ions is more than or equal to 85%, the removal rate of insoluble impurities is 100%, and the appearance is clear and transparent. The aluminum section anodic oxidation tank dealumination acid solution obtained after the components of the aluminum section anodic oxidation tank dealumination acid solution are adjusted can be completely used for anodic oxidation of aluminum sections of the next batch.
Example 2:
a treatment method for recycling waste acid of an aluminum profile anodic oxidation tank comprises the following steps:
the method comprises the following steps of: taking 650 grams of waste acid of an aluminum profile anodic oxidation tank, wherein the waste acid mainly comprises 16 mass percent of sulfuric acid, 2.1 mass percent of aluminum ions, 1.3 mass percent of LY-920 wide-temperature oxidant special for aluminum profile anodic oxidation and 80.6 mass percent of water, adding 2.5 mass percent of phytic acid into the aluminum profile anodic oxidation tank under the stirring condition of the stirring speed of 130rpm, starting cold water to reflux, heating the mixture to 90 ℃ and maintaining the temperature at 90 ℃, continuously heating and stirring for reaction for 9 hours, and reacting the phytic acid with the aluminum ions to generate corresponding aluminum phytate to obtain a reaction solution for later use.
Preparing seed crystals: taking solid analytically pure aluminum phytate, crushing the solid analytically pure aluminum phytate by using a stainless steel crusher, and sieving the crushed material by using a 160-mesh standard sieve to obtain aluminum phytate seed crystals.
Inducing seed crystal: reducing the temperature of the reaction liquid obtained in the step to 30 ℃, maintaining the temperature at 30 ℃, adding phytic acid aluminum seed crystals with the mass fraction of 0.3% into the reaction liquid under the stirring condition that the stirring speed is 200rpm, and continuously stirring for 15 hours to enable aluminum salts in the seed crystal induction reaction liquid to fully form phytic acid aluminum precipitates, thereby obtaining the reaction liquid with the aluminum salt precipitates.
Fourthly, natural settlement: maintaining the temperature of the reaction liquid precipitated by the aluminum salt precipitate obtained in the step three to be 30 ℃, continuing stirring for 20 hours under the stirring condition that the stirring speed is 15rpm, stopping stirring, naturally settling the precipitate for 13 hours, and taking the settled supernatant for later use.
Fifthly, membrane separation: and (3) precisely filtering the settled supernatant obtained in the step four by using microporous membrane equipment of which the membrane material is silicon carbide, the membrane pores are 0.1 mu m and the membrane component is a honeycomb briquette type inner tubular membrane to obtain 639 g of dealuminizing acid liquid of the aluminum profile anodic oxidation tank, wherein the aluminum ion content of the dealuminizing acid liquid is less than or equal to 0.20 percent (mass fraction) and the sulfuric acid content of the dealuminizing acid liquid is 14.9 percent (mass fraction).
Sixthly, component adjustment: according to the requirement of the mass percentage content of sulfuric acid of the aluminum profile anodic oxidation tank acid liquid required by the aluminum profile anodic oxidation process, adding analytically pure concentrated sulfuric acid and the LY-920 wide-temperature oxidizing agent special for aluminum profile anodic oxidation, and uniformly stirring to obtain the recyclable anodic oxidation tank acid liquid for anodic oxidation of the next batch of aluminum profiles.
According to the determination, after the aluminum profile anodic oxidation waste acid is treated by the method, the retention rate of sulfuric acid is 100%, the removal rate of aluminum ions is more than or equal to 85%, the removal rate of insoluble impurities is 100%, and the appearance is clear and transparent. The aluminum section anodic oxidation tank dealumination acid solution obtained after the components of the aluminum section anodic oxidation tank dealumination acid solution are adjusted can be completely used for anodic oxidation of aluminum sections of the next batch.
Example 3:
a treatment method for recycling waste acid of an aluminum profile anodic oxidation tank comprises the following steps:
the method comprises the following steps of: taking 832 grams of aluminum profile anodic oxidation tank which mainly comprises 20.5 percent (mass fraction) of sulfuric acid, 2.4 percent (mass fraction) of aluminum ions, 0.7 percent (mass fraction) of LY-920 wide-temperature oxidant special for aluminum profile anodic oxidation and 76.4 percent (mass fraction) of water, adding oxalic acid with the mass fraction of 3.0 percent under the stirring condition of the stirring speed of 150rpm, starting cold water to reflux, heating the mixture to 80 ℃ and maintaining the temperature at 80 ℃, continuously heating and stirring for reaction for 12 hours, and enabling the oxalic acid in the waste acid to react with the aluminum ions to generate corresponding aluminum oxalate to obtain reaction liquid for later use.
Preparing seed crystals: taking solid analytically pure aluminum oxalate, crushing the solid analytically pure aluminum oxalate by using a stainless steel crusher, and sieving the crushed material by using a 300-mesh standard sieve to obtain the aluminum oxalate seed crystal.
Inducing seed crystal: reducing the temperature of the reaction liquid obtained in the step to 15 ℃, maintaining the temperature at 15 ℃, adding aluminum oxalate seed crystals with the mass fraction of 0.25% into the reaction liquid under the stirring condition that the stirring speed is 160rpm, and continuing stirring for 20 hours to enable aluminum salts in the seed crystal induced reaction liquid to fully form aluminum oxalate precipitates, thereby obtaining the reaction liquid with aluminum salt precipitates.
Fourthly, natural settlement: maintaining the temperature of the reaction liquid precipitated by the aluminum salt precipitate obtained in the step three to be 15 ℃, continuing stirring for 20 hours under the stirring condition that the stirring speed is 25rpm, stopping stirring, naturally settling the precipitate for 8 hours, and taking the settled supernatant for later use.
Fifthly, membrane separation: and (3) precisely filtering the settled supernatant obtained in the step four by using microporous membrane equipment of which the membrane material is silicon carbide, the membrane pores are 0.04 mu m and the membrane component is a honeycomb briquette type inner tubular membrane to obtain 812 g of dealuminizing acid solution of an aluminum profile anodic oxidation tank, wherein the aluminum ion content is less than or equal to 0.25 percent (mass fraction) and the sulfuric acid content is 19.2 percent (mass fraction).
Sixthly, component adjustment: according to the requirement of the mass percentage content of sulfuric acid of the aluminum profile anodic oxidation tank acid liquid required by the aluminum profile anodic oxidation process, adding analytically pure concentrated sulfuric acid and the LY-920 wide-temperature oxidizing agent special for aluminum profile anodic oxidation, and uniformly stirring to obtain the recyclable anodic oxidation tank acid liquid for anodic oxidation of the next batch of aluminum profiles.
According to the determination, after the aluminum profile anodic oxidation waste acid is treated by the method, the retention rate of sulfuric acid is 100%, the removal rate of aluminum ions is more than or equal to 85%, the removal rate of insoluble impurities is 100%, and the appearance is clear and transparent. The aluminum section anodic oxidation tank dealumination acid solution obtained after the components of the aluminum section anodic oxidation tank dealumination acid solution are adjusted can be completely used for anodic oxidation of aluminum sections of the next batch.
Example 4:
a treatment method for recycling waste acid of an aluminum profile anodic oxidation tank comprises the following steps:
the method comprises the following steps of: taking 500 grams of waste acid of an aluminum profile anodic oxidation tank, the waste acid mainly comprising 19 mass percent of sulfuric acid, 1.8 mass percent of aluminum ions, 1.7 mass percent of LY-920 wide-temperature oxidant special for aluminum profile anodic oxidation and 77.5 mass percent of water, adding 9.5 mass percent of phosphoric acid (85 mass percent of phosphoric acid) under the stirring condition of the stirring speed of 100rpm, starting cold water to reflux, heating the mixture to 85 ℃, maintaining the temperature at 85 ℃, continuing heating, stirring and reacting for 8 hours to enable the phosphoric acid and the aluminum ions to react to generate corresponding aluminum phosphate, and obtaining reaction liquid for later use.
Preparing seed crystals: taking solid analytically pure aluminum phosphate, crushing the solid analytically pure aluminum phosphate by using a stainless steel crusher, and sieving the crushed material by using a 200-mesh standard sieve to obtain aluminum phosphate seed crystals.
Inducing seed crystal: reducing the temperature of the reaction liquid obtained in the step to 25 ℃, maintaining the temperature at 25 ℃, adding aluminum phosphate seed crystals with the mass fraction of 0.5% into the reaction liquid under the stirring condition that the stirring speed is 200rpm, and continuing stirring for 15 hours to enable aluminum salts in the seed crystal induction reaction liquid to fully form aluminum phosphate precipitates, thereby obtaining the reaction liquid with the aluminum salt precipitates separated out.
Fourthly, natural settlement: maintaining the temperature of the reaction liquid precipitated by the aluminum salt precipitate obtained in the step three at 25 ℃, continuing stirring for 25 hours under the stirring condition that the stirring speed is 20rpm, stopping stirring, naturally settling the precipitate for 10 hours, and taking the settled supernatant for later use.
Fifthly, membrane separation: and (3) precisely filtering the settled supernatant obtained in the step four by using microporous membrane equipment of which the membrane material is silicon carbide, the membrane pores are 0.04 mu m and the membrane component is a honeycomb briquette type inner tubular membrane to obtain 493 g of the dealuminizing acid solution of the aluminum profile anodic oxidation tank with the aluminum ion content of less than or equal to 0.25 percent (mass fraction) and the sulfuric acid content of 18 percent (mass fraction).
Sixthly, component adjustment: according to the requirement of the mass percentage content of sulfuric acid of the aluminum profile anodic oxidation tank acid liquid required by the aluminum profile anodic oxidation process, adding analytically pure concentrated sulfuric acid and the LY-920 wide-temperature oxidizing agent special for aluminum profile anodic oxidation, and uniformly stirring to obtain the recyclable anodic oxidation tank acid liquid for anodic oxidation of the next batch of aluminum profiles.
According to the determination, after the aluminum profile anodic oxidation waste acid is treated by the method, the retention rate of sulfuric acid is 100%, the removal rate of aluminum ions is more than or equal to 85%, the removal rate of insoluble impurities is 100%, and the appearance is clear and transparent. The aluminum section anodic oxidation tank dealumination acid solution obtained after the components of the aluminum section anodic oxidation tank dealumination acid solution are adjusted can be completely used for anodic oxidation of aluminum sections of the next batch.
Example 5:
a treatment method for recycling waste acid of an aluminum profile anodic oxidation tank comprises the following steps:
the method comprises the following steps of: taking 500 grams of waste acid of an aluminum profile anodic oxidation tank, the waste acid mainly comprising 19 mass percent of sulfuric acid, 1.8 mass percent of aluminum ions, 1.7 mass percent of LY-920 wide-temperature oxidant special for aluminum profile anodic oxidation and 77.5 mass percent of water, adding silicic acid with the mass percent of 6.5 percent of the waste acid into a ground triangular flask under the stirring condition of the stirring speed of 100rpm, starting cold water to reflux, heating the mixture to 85 ℃ and maintaining the temperature at 85 ℃, and continuously heating, stirring and reacting for 8 hours to enable the silicic acid in the waste acid to react with the aluminum ions to generate corresponding aluminum silicate to obtain reaction liquid for later use.
Preparing seed crystals: taking solid analytically pure aluminum silicate, crushing the solid analytically pure aluminum silicate by using a stainless steel crusher, and sieving the crushed material by using a 200-mesh standard sieve to obtain aluminum silicate seed crystals.
Inducing seed crystal: reducing the temperature of the reaction liquid obtained in the step to 25 ℃, maintaining the temperature at 25 ℃, adding aluminum silicate seed crystals with the mass fraction of 0.5% into the reaction liquid under the stirring condition that the stirring speed is 200rpm, and continuously stirring for 15 hours to enable aluminum salts in the seed crystal induction reaction liquid to fully form aluminum silicate precipitates, thereby obtaining the reaction liquid with the aluminum salt precipitates separated out.
Fourthly, natural settlement: maintaining the temperature of the reaction liquid precipitated by the aluminum salt precipitate obtained in the step three at 25 ℃, continuing stirring for 25 hours under the stirring condition that the stirring speed is 20rpm, stopping stirring, naturally settling the precipitate for 10 hours, and taking the settled supernatant for later use.
Fifthly, membrane separation: and (3) precisely filtering the settled supernatant obtained in the step four by using microporous membrane equipment of which the membrane material is silicon carbide, the membrane pores are 0.04 mu m and the membrane component is a honeycomb briquette type inner tubular membrane to obtain 493 g of the dealuminizing acid solution of the aluminum profile anodic oxidation tank with the aluminum ion content of less than or equal to 0.25 percent (mass fraction) and the sulfuric acid content of 18 percent (mass fraction).
Sixthly, component adjustment: according to the requirement of the mass percentage content of sulfuric acid of the aluminum profile anodic oxidation tank acid liquid required by the aluminum profile anodic oxidation process, adding analytically pure concentrated sulfuric acid and the LY-920 wide-temperature oxidizing agent special for aluminum profile anodic oxidation, and uniformly stirring to obtain the recyclable anodic oxidation tank acid liquid for anodic oxidation of the next batch of aluminum profiles.
According to the determination, after the aluminum profile anodic oxidation waste acid is treated by the method, the retention rate of sulfuric acid is 100%, the removal rate of aluminum ions is more than or equal to 85%, the removal rate of insoluble impurities is 100%, and the appearance is clear and transparent. The aluminum section anodic oxidation tank dealumination acid solution obtained after the components of the aluminum section anodic oxidation tank dealumination acid solution are adjusted can be completely used for anodic oxidation of aluminum sections of the next batch.
Example 6:
a treatment method for recycling waste acid of an aluminum profile anodic oxidation tank comprises the following steps:
the method comprises the following steps of: taking 500 grams of waste acid of an aluminum profile anodic oxidation tank, the waste acid mainly comprising 19 mass percent of sulfuric acid, 1.8 mass percent of aluminum ions, 1.7 mass percent of LY-920 wide-temperature oxidant special for aluminum profile anodic oxidation and 77.5 mass percent of water, adding 8.5 mass percent of polysilicic acid under the stirring condition with the stirring speed of 100rpm, starting cold water to reflux, heating the mixture to 85 ℃ and maintaining the temperature at 85 ℃, and continuing heating, stirring and reacting for 8 hours to enable the polysilicic acid and the aluminum ions to react to generate corresponding aluminum polysilicate, thereby obtaining a reaction solution for later use.
Preparing seed crystals: taking solid analytically pure polyaluminium silicate, crushing the solid analytically pure polyaluminium silicate by using a stainless steel crusher, and sieving the crushed material by using a 200-mesh standard sieve to obtain the polyaluminium silicate seed crystal.
Inducing seed crystal: reducing the temperature of the reaction liquid obtained in the step to 25 ℃ and maintaining the temperature at 25 ℃, adding polysilicate aluminum seed crystals with the mass fraction of 0.5% into the reaction liquid under the stirring condition that the stirring speed is 200rpm, and continuing stirring for 15 hours to enable aluminum salts in the seed crystal induction reaction liquid to fully form polysilicate aluminum precipitates, thereby obtaining the reaction liquid with the aluminum salt precipitates.
Fourthly, natural settlement: maintaining the temperature of the reaction liquid precipitated by the aluminum salt precipitate obtained in the step three at 25 ℃, continuing stirring for 25 hours under the stirring condition that the stirring speed is 20rpm, stopping stirring, naturally settling the precipitate for 10 hours, and taking the settled supernatant for later use.
Fifthly, membrane separation: and (3) precisely filtering the settled supernatant obtained in the step four by using microporous membrane equipment of which the membrane material is silicon carbide, the membrane pores are 0.04 mu m and the membrane component is a honeycomb briquette type inner tubular membrane to obtain 493 g of the dealuminizing acid solution of the aluminum profile anodic oxidation tank with the aluminum ion content of less than or equal to 0.25 percent (mass fraction) and the sulfuric acid content of 18 percent (mass fraction).
Sixthly, component adjustment: according to the requirement of the mass percentage of sulfuric acid of the aluminum profile anodic oxidation tank acid liquid required by the aluminum profile anodic oxidation process, adding the analytically pure concentrated sulfuric acid and the LY-920 wide-temperature oxidizing agent special for aluminum profile anodic oxidation, and uniformly stirring to obtain the recyclable anodic oxidation tank acid liquid for anodic oxidation of the next batch of aluminum profiles.
According to the determination, after the aluminum profile anodic oxidation waste acid is treated by the method, the retention rate of sulfuric acid is 100%, the removal rate of aluminum ions is more than or equal to 85%, the removal rate of insoluble impurities is 100%, and the appearance is clear and transparent. The aluminum section anodic oxidation tank dealumination acid solution obtained after the components of the aluminum section anodic oxidation tank dealumination acid solution are adjusted can be completely used for anodic oxidation of aluminum sections of the next batch.
Example 7:
a treatment method for recycling waste acid of an aluminum profile anodic oxidation tank comprises the following steps:
the method comprises the following steps of: taking 500 grams of aluminum profile anodic oxidation tank waste acid with the main components of 19 percent (mass fraction) of sulfuric acid, 1.8 percent (mass fraction) of aluminum ions, 1.7 percent (mass fraction) of LY-920 wide-temperature oxidant special for aluminum profile anodic oxidation and 77.5 percent (mass fraction) of moisture in a ground triangular flask, adding 15.5 percent (mass fraction) of fluosilicic acid (aqueous solution with the mass fraction of fluosilicic acid being 30 percent) under the stirring condition with the stirring speed of 100rpm, starting cold water to reflux, heating the mixture to 85 ℃, maintaining the temperature at 85 ℃, continuously heating, stirring and reacting for 8 hours to enable the fluosilicic acid in the mixture to react with the aluminum ions to generate corresponding aluminum fluosilicate, and obtaining reaction liquid for later use.
Preparing seed crystals: taking solid analytically pure aluminum fluosilicate, crushing the solid analytically pure aluminum fluosilicate by using a stainless steel crusher, and sieving the crushed material by using a 200-mesh standard sieve to obtain the aluminum fluosilicate seed crystal.
Inducing seed crystal: reducing the temperature of the reaction liquid obtained in the step to 25 ℃, maintaining the temperature at 25 ℃, adding aluminum fluosilicate seed crystals with the mass fraction of 0.5% into the reaction liquid under the stirring condition that the stirring speed is 200rpm, and continuing stirring for 15 hours to enable aluminum salts in the seed crystal induction reaction liquid to fully form aluminum fluosilicate precipitates, thereby obtaining the reaction liquid in which the aluminum salt precipitates are separated out.
Fourthly, natural settlement: maintaining the temperature of the reaction liquid precipitated by the aluminum salt precipitate obtained in the step three at 25 ℃, continuing stirring for 25 hours under the stirring condition that the stirring speed is 20rpm, stopping stirring, naturally settling the precipitate for 10 hours, and taking the settled supernatant for later use.
Fifthly, membrane separation: and (3) precisely filtering the settled supernatant obtained in the step four by using microporous membrane equipment of which the membrane material is silicon carbide, the membrane pores are 0.04 mu m and the membrane component is a honeycomb briquette type inner tubular membrane to obtain 561 g of dealuminizing acid liquid in the aluminum profile anodic oxidation tank, wherein the aluminum ion content is less than or equal to 0.25 percent (mass fraction) and the sulfuric acid content is 14.1 percent (mass fraction).
Sixthly, component adjustment: according to the requirement of the mass percentage content of sulfuric acid of the aluminum profile anodic oxidation tank acid liquid required by the aluminum profile anodic oxidation process, adding analytically pure concentrated sulfuric acid and the LY-920 wide-temperature oxidizing agent special for aluminum profile anodic oxidation, and uniformly stirring to obtain the recyclable anodic oxidation tank acid liquid for anodic oxidation of the next batch of aluminum profiles.
According to the determination, after the aluminum profile anodic oxidation waste acid is treated by the method, the retention rate of sulfuric acid is 100%, the removal rate of aluminum ions is more than or equal to 85%, the removal rate of insoluble impurities is 100%, and the appearance is clear and transparent. The aluminum section anodic oxidation tank dealumination acid solution obtained after the components of the aluminum section anodic oxidation tank dealumination acid solution are adjusted can be completely used for anodic oxidation of aluminum sections of the next batch.
Example 8:
a treatment method for recycling waste acid of an aluminum profile anodic oxidation tank comprises the following steps:
the method comprises the following steps of: taking 500 grams of aluminum profile anodic oxidation tank waste acid with the main components of 19 mass percent of sulfuric acid, 1.8 mass percent of aluminum ions, 1.7 mass percent of LY-920 wide-temperature oxidizing agent special for aluminum profile anodic oxidation and 77.5 mass percent of moisture in a ground triangular flask, adding hydrofluoric acid (aqueous solution with the mass percent concentration of the hydrofluoric acid of 40%) with the mass percent of 2.5% under the stirring condition with the stirring speed of 100rpm, starting cold water to reflux, heating the mixture to 85 ℃, maintaining the temperature at 85 ℃, continuing to heat, stir and react for 8 hours to enable the hydrofluoric acid and the aluminum ions in the mixture to react to generate corresponding aluminum fluoride, and obtaining reaction liquid for later use.
Preparing seed crystals: taking solid analytically pure aluminum fluoride, crushing the solid analytically pure aluminum fluoride by using a stainless steel crusher, and sieving the crushed material by using a 200-mesh standard sieve to obtain aluminum fluoride crystal seeds.
Inducing seed crystal: and (3) reducing the temperature of the reaction liquid obtained in the step (c) to 25 ℃ and maintaining the temperature at 25 ℃, adding 0.5 mass percent of aluminum fluoate seed crystals into the reaction liquid under the stirring condition that the stirring speed is 200rpm, and continuing stirring for 15 hours to enable aluminum salts in the seed crystal induction reaction liquid to fully form aluminum fluoate precipitates, thereby obtaining the reaction liquid with aluminum salt precipitates.
Fourthly, natural settlement: maintaining the temperature of the reaction liquid precipitated by the aluminum salt precipitate obtained in the step three at 25 ℃, continuing stirring for 25 hours under the stirring condition that the stirring speed is 20rpm, stopping stirring, naturally settling the precipitate for 10 hours, and taking the settled supernatant for later use.
Fifthly, membrane separation: and (3) precisely filtering the settled supernatant obtained in the step four by using microporous membrane equipment of which the membrane material is silicon carbide, the membrane pores are 0.04 mu m and the membrane component is a honeycomb briquette type inner tubular membrane to obtain 503 g of dealuminizing acid solution of the aluminum profile anodic oxidation tank, wherein the aluminum ion content is less than or equal to 0.25 percent (mass fraction) and the sulfuric acid content is 16.8 percent (mass fraction).
Sixthly, component adjustment: according to the requirement of the mass percentage content of sulfuric acid of the aluminum profile anodic oxidation tank acid liquid required by the aluminum profile anodic oxidation process, adding analytically pure concentrated sulfuric acid and the LY-920 wide-temperature oxidizing agent special for aluminum profile anodic oxidation, and uniformly stirring to obtain the recyclable anodic oxidation tank acid liquid for anodic oxidation of the next batch of aluminum profiles.
According to the determination, after the aluminum profile anodic oxidation waste acid is treated by the method, the retention rate of sulfuric acid is 100%, the removal rate of aluminum ions is more than or equal to 85%, the removal rate of insoluble impurities is 100%, and the appearance is clear and transparent. The aluminum section anodic oxidation tank dealumination acid solution obtained after the components of the aluminum section anodic oxidation tank dealumination acid solution are adjusted can be completely used for anodic oxidation of aluminum sections of the next batch.
Example 9:
a treatment method for recycling waste acid of an aluminum profile anodic oxidation tank comprises the following steps:
the method comprises the following steps of: an aluminum profile anodic oxidation tank 1760 g mainly comprising 16.5 mass percent of sulfuric acid, 2.0 mass percent of aluminum ions, 0.9 mass percent of LY-920 wide-temperature oxidant special for aluminum profile anodic oxidation and 80.6 mass percent of water is taken to be arranged in a ground-mouth triangular flask, under the stirring condition with the stirring speed of 100rpm, dodecylbenzene sulfonic acid with the mass percent of 0.5 percent and waste acid (aqueous solution with the mass percent of fluosilicic acid of 30 percent) with the mass percent of 7.5 percent are added, cold water reflux is started, the mixture is heated to 89 ℃ and maintained at 89 ℃, the mixture is continuously heated and stirred for reaction for 12 hours, and the dodecylbenzene sulfonic acid and the fluosilicic acid in the mixture react with the aluminum ions to generate corresponding dodecylbenzene sulfonic acid aluminum and aluminum fluosilicic acid, so that reaction liquid is obtained for later use.
Preparing seed crystals: mixing solid analytically pure aluminum dodecylbenzene sulfonate and aluminum fluosilicate according to the mass ratio of 1:3, crushing by a stainless steel crusher, and sieving the crushed material by a 300-mesh standard sieve to obtain the mixed seed crystal of the aluminum dodecylbenzene sulfonate and the aluminum fluosilicate.
Inducing seed crystal: reducing the temperature of the reaction liquid obtained in the step to 25 ℃, maintaining the temperature at 15 ℃, adding 0.3 mass percent of mixed seed crystal into the reaction liquid under the stirring condition that the stirring speed is 200rpm, and continuing stirring for 18 hours to ensure that aluminum salt in the seed crystal induction reaction liquid fully forms aluminum dodecyl benzene sulfonate and aluminum fluosilicate precipitates, thereby obtaining the reaction liquid with aluminum salt precipitates.
Fourthly, natural settlement: maintaining the temperature of the reaction liquid precipitated by the aluminum salt precipitate obtained in the step three to be 15 ℃, continuing stirring for 25 hours under the stirring condition that the stirring speed is 20rpm, stopping stirring, naturally settling the precipitate for 10 hours, and taking the settled supernatant for later use.
Fifthly, membrane separation: and (3) precisely filtering the settled supernatant obtained in the step four by using microporous membrane equipment of which the membrane material is silicon carbide, the membrane pores are 0.04 mu m and the membrane component is a honeycomb briquette type inner tubular membrane to obtain 1859 g of dealuminizing acid liquid in the aluminum profile anodic oxidation tank, wherein the content of aluminum ions is less than or equal to 0.25 percent (mass fraction) and the content of sulfuric acid is 14.1 percent (mass fraction).
Sixthly, component adjustment: according to the requirement of the mass percentage content of sulfuric acid of the aluminum profile anodic oxidation tank acid liquid required by the aluminum profile anodic oxidation process, adding analytically pure concentrated sulfuric acid and the LY-920 wide-temperature oxidizing agent special for aluminum profile anodic oxidation, and uniformly stirring to obtain the recyclable anodic oxidation tank acid liquid for anodic oxidation of the next batch of aluminum profiles.
According to the determination, after the aluminum profile anodic oxidation waste acid is treated by the method, the retention rate of sulfuric acid is 100%, the removal rate of aluminum ions is more than or equal to 85%, the removal rate of insoluble impurities is 100%, and the appearance is clear and transparent. The aluminum section anodic oxidation tank dealumination acid solution obtained after the components of the aluminum section anodic oxidation tank dealumination acid solution are adjusted can be completely used for anodic oxidation of aluminum sections of the next batch.
Example 10:
a treatment method for recycling waste acid of an aluminum profile anodic oxidation tank comprises the following steps:
the method comprises the following steps of: an aluminum profile anodic oxidation tank 5280 which mainly comprises 17.2 mass percent of sulfuric acid, 2.2 mass percent of aluminum ions, 1.1 mass percent of LY-920 wide-temperature oxidant special for aluminum profile anodic oxidation and 79.5 mass percent of water is taken and placed in a ground-mouth triangular flask, 5.5 mass percent of phosphoric acid and 3.5 mass percent of fluosilicic acid (aqueous solution with the mass percent of fluosilicic acid) are added under the stirring condition with the stirring speed of 100rpm, cold water reflux is started, the mixture is heated to 95 ℃ and maintained at 95 ℃, the mixture is continuously heated and stirred for reaction for 11 hours, the phosphoric acid and the fluosilicic acid in the mixture react with the aluminum ions to generate corresponding aluminum phosphate and aluminum fluosilicate, and reaction liquid is obtained for later use.
Preparing seed crystals: mixing solid analytically pure aluminum phosphate and aluminum fluosilicate according to the mass ratio of 2:1, crushing by using a stainless steel crusher, and sieving the crushed materials by using a 300-mesh standard sieve to obtain the mixed aluminum seed crystal consisting of the aluminum phosphate and the aluminum fluosilicate.
Inducing seed crystal: and (3) reducing the temperature of the reaction liquid obtained in the step (C) to 10 ℃, maintaining the temperature at 10 ℃, adding mixed seed crystals with the mass fraction of 0.3% into the reaction liquid under the stirring condition that the stirring speed is 220rpm, and continuing stirring for 16 hours to enable aluminum salts in the seed crystal induced reaction liquid to fully form aluminum phosphate and aluminum fluosilicate precipitates, thereby obtaining the reaction liquid with aluminum salt precipitates.
Fourthly, natural settlement: maintaining the temperature of the reaction liquid precipitated by the aluminum salt precipitate obtained in the step three to be 10 ℃, continuing stirring for 22 hours under the stirring condition that the stirring speed is 25rpm, stopping stirring, naturally settling the precipitate for 12 hours, and taking the settled supernatant for later use.
Fifthly, membrane separation: and (3) precisely filtering the settled supernatant obtained in the step four by using microporous membrane equipment of which the membrane material is silicon carbide, the membrane pores are 0.04 mu m and the membrane component is a honeycomb briquette type inner tubular membrane to obtain 5410 g of dealuminizing acid liquid of the aluminum profile anodic oxidation tank, wherein the aluminum ion content is less than or equal to 0.25 percent (mass fraction) and the sulfuric acid content is 15.3 percent (mass fraction).
Sixthly, component adjustment: according to the requirement of the mass percentage content of sulfuric acid of the aluminum profile anodic oxidation tank acid liquid required by the aluminum profile anodic oxidation process, adding analytically pure concentrated sulfuric acid and the LY-920 wide-temperature oxidizing agent special for aluminum profile anodic oxidation, and uniformly stirring to obtain the recyclable anodic oxidation tank acid liquid for anodic oxidation of the next batch of aluminum profiles.
According to the determination, after the aluminum profile anodic oxidation waste acid is treated by the method, the retention rate of sulfuric acid is 100%, the removal rate of aluminum ions is more than or equal to 85%, the removal rate of insoluble impurities is 100%, and the appearance is clear and transparent. The aluminum section anodic oxidation tank dealumination acid solution obtained after the components of the aluminum section anodic oxidation tank dealumination acid solution are adjusted can be completely used for anodic oxidation of aluminum sections of the next batch.
The specific embodiments described in this specification are merely illustrative of the spirit of the invention. Various modifications or additions may be made to the described embodiments or alternatives may be employed by those skilled in the art without departing from the spirit or ambit of the invention as defined in the appended claims.
Claims (7)
1.A treatment method for recycling waste acid of an aluminum profile anodic oxidation tank comprises the following steps:
the method comprises the following steps of: taking waste acid of an aluminum profile anodic oxidation tank to a strong acid resistant reaction kettle or other containers, starting cooling water to reflux, adding a chemical mixture with the mass of 0.3-25% of that of the waste acid under the condition of continuous stirring, heating the mixture to the dissociation reaction temperature of the chemical mixture and maintaining the dissociation reaction temperature of the chemical mixture, and continuously heating, stirring and reacting for 1.0-15 hours to enable the chemical mixture to react with aluminum ions to generate corresponding aluminum salts, thereby obtaining reaction liquid for later use;
preparing seed crystals: taking solid aluminum salt which is formed by corresponding chemical mixture acid radicals and aluminum ions and is insoluble in water and dilute sulfuric acid, crushing the solid aluminum salt by a stainless steel crusher, and sieving the crushed product by a standard sieve to obtain aluminum salt seed crystals, wherein the chemical mixture is one of analytically pure or chemically pure dodecyl benzene sulfonic acid, phytic acid, oxalic acid, phosphoric acid, silicic acid, polysilicic acid, fluosilicic acid and hydrofluoric acid, or a mixture of two to eight of the analytically pure or chemically pure dodecyl benzene sulfonic acid, phytic acid, oxalic acid, phosphoric acid, silicic acid, polysilicic acid and hydrofluoric acid in any proportion;
inducing seed crystal: lowering the temperature of the reaction liquid obtained in the step to 0-45 ℃, maintaining the temperature at 0-45 ℃, adding seed crystals which are obtained in the step two and have an inducing effect into the reaction liquid under the condition of continuous stirring, and continuously stirring for 1.0-25 hours to enable aluminum salts in the seed crystal inducing reaction liquid to form aluminum salt precipitates, so as to obtain the reaction liquid with the aluminum salt precipitates;
fourthly, natural settlement: maintaining the temperature of the reaction liquid precipitated by the aluminum salt precipitate obtained in the step three to be 0-40 ℃, controlling the sedimentation stirring speed, continuing stirring for 5-45 hours, stopping stirring, naturally settling the precipitate for 3-15 hours, and taking the supernatant of the sediment for later use;
fifthly, membrane separation: precisely filtering the settled supernatant obtained in the step four by using microporous membrane equipment to obtain dealuminizing acid liquor of an aluminum profile anodic oxidation tank for later use;
sixthly, component adjustment: analyzing and determining the mass percent of sulfuric acid of the dealuminizing acid solution for the aluminum profile anodic oxidation tank obtained in the step fifthly, adding concentrated sulfuric acid and a LY-920 wide-temperature oxidizing agent special for aluminum profile anodic oxidation according to the mass percent of sulfuric acid of the aluminum profile anodic oxidation tank acid solution for the aluminum profile anodic oxidation process, and uniformly stirring to obtain the recyclable anodic oxidation tank acid solution for anodic oxidation of the next batch of aluminum profiles.
2. The treatment method for recycling waste acid from the aluminum profile anodic oxidation tank, according to claim 1, is characterized in that: the waste acid of the aluminum profile anodic oxidation tank is residual acid liquor used for anodic oxidation of aluminum profiles in the oxidation tank, which has high aluminum ion content, cannot be reused and needs to be discarded, and comprises the following components: 10-30% of sulfuric acid, 0.8-3.0% of aluminum ions, 0.1-5% of LY-920 wide-temperature oxidant special for anodic oxidation of aluminum profiles and 68-86% of water; the dissociation reaction temperature of the chemical-mixture agent is the temperature capable of promoting the generation of corresponding aluminum salt, and the range of the dissociation reaction temperature is 15-120 ℃.
3. The treatment method for recycling waste acid from the aluminum profile anodic oxidation tank, according to claim 1, is characterized in that: the solid aluminum salt in the step II is any one of analytically pure or chemically pure aluminum dodecylbenzene sulfonate, aluminum phytate, aluminum oxalate, aluminum phosphate, aluminum silicate, aluminum polysilicate, aluminum fluosilicate and aluminum hydrofluoride, or a mixture of two to eight of the aluminum dodecylbenzene sulfonate, the aluminum phytate, the aluminum oxalate, the aluminum phosphate, the aluminum silicate, the aluminum polysilicate, the aluminum fluosilicate and the aluminum hydrofluoride in any proportion; the screening is 40-600 meshes.
4. The treatment method for recycling waste acid from the aluminum profile anodic oxidation tank, according to claim 1, is characterized in that: and the mass fraction capable of playing an inducing role in the step three is the mass fraction capable of playing a role in inducing crystallization, and the range of the mass fraction is 0.05-5%.
5. The treatment method for recycling waste acid from the aluminum profile anodic oxidation tank, according to claim 1, is characterized in that: the sedimentation stirring speed in step four is a stirring speed at which the aluminum salt can sediment, and is in a range of 1 to 50 rpm.
6. The treatment method for recycling waste acid from the aluminum profile anodic oxidation tank, according to claim 1, is characterized in that: in the microporous membrane equipment obtained in the step, the membrane material is silicon carbide, the membrane component is a honeycomb coal type inner tubular membrane, and the sizes of the membrane pores are 1, 0.5, 0.1 and 0.04 mu m.
7. The treatment method for recycling waste acid from the aluminum profile anodic oxidation tank, according to claim 1, is characterized in that: the concentrated sulfuric acid obtained in the step VI is analytically pure or chemically pure sulfuric acid with the mass fraction of 98%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810901764.6A CN110820028B (en) | 2018-08-09 | 2018-08-09 | Treatment method for recycling waste acid of aluminum profile anodic oxidation tank |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810901764.6A CN110820028B (en) | 2018-08-09 | 2018-08-09 | Treatment method for recycling waste acid of aluminum profile anodic oxidation tank |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110820028A CN110820028A (en) | 2020-02-21 |
| CN110820028B true CN110820028B (en) | 2021-07-30 |
Family
ID=69541304
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810901764.6A Active CN110820028B (en) | 2018-08-09 | 2018-08-09 | Treatment method for recycling waste acid of aluminum profile anodic oxidation tank |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110820028B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111778535A (en) * | 2020-06-23 | 2020-10-16 | 孔瑞扬 | Aluminum profile surface oxidation treatment method |
| CN113584567B (en) * | 2021-07-14 | 2022-09-27 | 佛山市三水凤铝铝业有限公司 | Recovery processing method of aluminum profile surface oxidation treatment tank liquor |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5543519B2 (en) * | 1976-01-17 | 1980-11-06 | ||
| JPH05228471A (en) * | 1992-02-18 | 1993-09-07 | Nittetsu Mining Co Ltd | Treatment of aluminum phosphate-containing monobasic acid waste liquid |
| CN103030123A (en) * | 2012-12-27 | 2013-04-10 | 苏州浩中环保设备有限公司 | Recovery and treatment equipment and process of waste diluted phosphoric acid containing metal salt |
| CN103911651A (en) * | 2014-03-28 | 2014-07-09 | 佛山市三水雄鹰铝表面技术创新中心有限公司 | Process for recovering aluminum ions and sulfuric acid from aluminum alloy anodic oxidation tank |
| CN104098076A (en) * | 2014-07-29 | 2014-10-15 | 四川立业电子有限公司 | Method for reclaiming phosphoric acid and aluminium phosphate in formation waste liquid |
| CN204824284U (en) * | 2015-08-13 | 2015-12-02 | 唐山紫天化工防腐有限公司 | Sulphuric acid and aluminium ion recovery unit of aluminum alloy oxidation groove waste liquid |
| CN105692950A (en) * | 2014-11-28 | 2016-06-22 | 中国科学院金属研究所 | Treatment method for titanium-aluminum intermetallic compound chemical milling waste liquid |
| CN107879536A (en) * | 2017-12-07 | 2018-04-06 | 乳源瑶族自治县东阳光化成箔有限公司 | A kind of processing method of the waste water of nitric acid containing aluminium |
| CN108070892A (en) * | 2017-12-04 | 2018-05-25 | 佛山市三水雄鹰铝表面技术创新中心有限公司 | A kind of oxidized aluminum alloy slot aluminium ion and retrieval of sulfuric acid and washing medicament retention system and technique |
-
2018
- 2018-08-09 CN CN201810901764.6A patent/CN110820028B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5543519B2 (en) * | 1976-01-17 | 1980-11-06 | ||
| JPH05228471A (en) * | 1992-02-18 | 1993-09-07 | Nittetsu Mining Co Ltd | Treatment of aluminum phosphate-containing monobasic acid waste liquid |
| CN103030123A (en) * | 2012-12-27 | 2013-04-10 | 苏州浩中环保设备有限公司 | Recovery and treatment equipment and process of waste diluted phosphoric acid containing metal salt |
| CN103911651A (en) * | 2014-03-28 | 2014-07-09 | 佛山市三水雄鹰铝表面技术创新中心有限公司 | Process for recovering aluminum ions and sulfuric acid from aluminum alloy anodic oxidation tank |
| CN104098076A (en) * | 2014-07-29 | 2014-10-15 | 四川立业电子有限公司 | Method for reclaiming phosphoric acid and aluminium phosphate in formation waste liquid |
| CN105692950A (en) * | 2014-11-28 | 2016-06-22 | 中国科学院金属研究所 | Treatment method for titanium-aluminum intermetallic compound chemical milling waste liquid |
| CN204824284U (en) * | 2015-08-13 | 2015-12-02 | 唐山紫天化工防腐有限公司 | Sulphuric acid and aluminium ion recovery unit of aluminum alloy oxidation groove waste liquid |
| CN108070892A (en) * | 2017-12-04 | 2018-05-25 | 佛山市三水雄鹰铝表面技术创新中心有限公司 | A kind of oxidized aluminum alloy slot aluminium ion and retrieval of sulfuric acid and washing medicament retention system and technique |
| CN107879536A (en) * | 2017-12-07 | 2018-04-06 | 乳源瑶族自治县东阳光化成箔有限公司 | A kind of processing method of the waste water of nitric acid containing aluminium |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110820028A (en) | 2020-02-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102154673B (en) | Method for preparing environment-friendly micro-arc oxidation black ceramic film on aluminum alloy surface | |
| CN110820028B (en) | Treatment method for recycling waste acid of aluminum profile anodic oxidation tank | |
| CN103332666B (en) | Sinking agent in a kind of wet-process phosphoric acid concentration treating processes | |
| CN112456502A (en) | Preparation process of high-efficiency, energy-saving and environment-friendly high-purity quartz sand | |
| Song et al. | Study of the formation process of titanium oxides containing micro arc oxidation film on Mg alloys | |
| CN101391847B (en) | Method for treating tailing water from mineral processing plant by microwave | |
| CN102786096A (en) | Iron oxide for lithium iron phosphate battery, and its preparation method | |
| CN112551658A (en) | High-alumina fly ash defluorination flocculant and preparation method and application thereof | |
| CN1772963A (en) | Common-battery deposition producing method for Mg La Pr Ce intermediate alloy | |
| CN100448781C (en) | Method for mixed acid hydrolysis of acid-soluble titanium slag and ilmenite | |
| CN103539183A (en) | Acid method for preparing aluminum polychlorid and high-purity nanoscale white carbon black through ash of oil shale | |
| CN101058536A (en) | Method of preparing ultramicro ferrous oxalate | |
| CN105401166A (en) | Method for preparing L-cysteine hydrochloride anhydrous substances | |
| CN102191519A (en) | Method for preparing molten salt electrodeposition aluminium membrane on surface of aluminium based composite material | |
| CN101759315B (en) | Method for recycling waste diluted sulfuric acid from acid washing solution of steel | |
| CN110818157B (en) | Treatment method for recycling waste acid of aluminum profile chemical polishing tank | |
| JP5096260B2 (en) | Method for purifying tin-containing waste and method for reusing tin-containing waste | |
| CN112058106A (en) | Composite MOF (Metal organic framework) derived seawater desalination membrane and preparation method thereof | |
| CN102952419A (en) | Preparation method of modified titanium oxide coating applied to metal matrix corrosive protection | |
| CN107473486B (en) | Combined treatment method of desulfurization wastewater | |
| CN104014300B (en) | Diatomite preparation is with the method for drainage functional beer stabilizing agent | |
| CN109250795B (en) | Method for rapidly preparing poly-silicate aluminum ferric sulfate by one-pot microwave radiation method | |
| CN102605222B (en) | La, Ce, Pr and Nd-containing aluminum titanium alloy wire and production method thereof | |
| CN107500364A (en) | A kind of high-purity FeCl2·4H2O preparation method | |
| CN102492319B (en) | A kind of corrosion resistant coating, its preparation method and using method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |