CN110820028A - 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
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- 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
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- 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
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- C25D21/00—Processes for servicing or operating cells for electrolytic coating
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Abstract
The invention discloses a treatment method for recycling waste acid of an aluminum profile anodic oxidation tank, which comprises the steps of ⑴ heating reaction, namely taking the waste acid of the aluminum profile anodic oxidation tank into a strong acid resistant reaction kettle, starting cooling water to reflux, continuously stirring, adding a chemical mixture, heating the mixture to the reaction temperature, maintaining the reaction temperature, continuously heating and stirring, ⑵ seed crystal preparation, namely taking solid aluminum salt which is difficult to dissolve in water and dilute sulfuric acid and consists of chemical mixture acid radicals and aluminum ions, crushing and screening by using a stainless steel crusher, ⑶ seed crystal induction, namely utilizing aluminum salt in seed crystal induction reaction liquid to form aluminum salt precipitate, ⑷ natural settling, wherein the temperature of the obtained aluminum salt precipitate reaction liquid is controlled, stirring is continuously carried out, settling supernatant is taken, ⑸ membrane separation is carried out, the obtained settling supernatant is precisely filtered by using microporous membrane equipment, an aluminum profile anodic oxidation tank dealuminizing acid liquid is obtained, ⑹ component adjustment, cost is low, no pollution is caused, aluminum ions are fully removed, the acid can be recycled, the utilization rate of raw materials is high, and the process is simple and.
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:
⑴ heating reaction, namely putting the waste acid of the aluminum profile anodic oxidation tank into a strong acid resistant reaction kettle or other container, starting cooling water for reflux, adding a chemical mixture with the mass of 0.3-25% of the waste acid under the condition of continuous stirring, heating the mixture to the chemical mixture dissociation reaction temperature and maintaining the chemical mixture dissociation reaction temperature, and continuing heating and stirring for reaction 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 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 ℃.
⑵ seed crystal preparation, which is to take solid aluminum salt which is composed of corresponding chemical mixture acid radical and aluminum ion and is difficult to be dissolved in water and dilute sulfuric acid, crush the aluminum salt by a stainless steel crusher, and screen the crushed product by a standard sieve to obtain the 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.
⑶ seed crystal induction, namely, reducing the temperature of the reaction liquid obtained in the step ⑴ to 0-45 ℃, maintaining the temperature at 0-45 ℃, adding the seed crystal obtained in the step ⑵ with mass fraction capable of playing an induction role into the reaction liquid under the condition of continuous stirring, and continuously stirring for 1.0-25 hours to enable aluminum salt in the seed crystal induction reaction liquid to form aluminum salt precipitate, thereby obtaining the reaction liquid with the aluminum salt precipitated.
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%.
⑷, naturally settling, namely maintaining the temperature of the reaction liquid precipitated by the aluminum salt precipitate obtained in the step ⑶ at 0-40 ℃, controlling the settling and stirring speed, continuing stirring for 5-45 hours, stopping stirring, naturally settling the precipitate for 3-15 hours, and taking the supernatant of the settling 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.
⑸ and (3) membrane separation, namely precisely filtering the settled supernatant obtained in the step ⑷ 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.
⑹, analyzing and measuring the mass percent of sulfuric acid of the dealuminizing acid solution of the aluminum profile anodic oxidation tank obtained in the step ⑸, 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 of 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 is the heating reaction of the step ⑵, the seed induction of the step ⑶ and the membrane separation of the step ⑷, and the technical problems and difficulties that the acid which can generate insoluble aluminum salt with aluminum is dissociated to generate insoluble aluminum salt are solved mainly through the heating reaction of controlling the temperature, the crystallization of the insoluble aluminum salt is induced by using the seed of the insoluble aluminum salt to solve the solid phase precipitation of the insoluble aluminum salt, and the filtration of insoluble impurities in the dealuminizing waste acid of the aluminum profile chemical polishing tank with high acid concentration and strong acidity is solved through the filtration of a strong corrosion resistant silicon carbide membrane.
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:
⑴ heating reaction, namely taking 500 grams of waste acid of the aluminum profile anodic oxidation tank, the waste acid mainly comprising 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 water, adding 1.5 percent of dodecylbenzene sulfonic acid by mass 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 heating and stirring for reaction for 8 hours, and reacting the dodecylbenzene sulfonic acid with the aluminum ions to generate corresponding dodecylbenzene sulfonic acid aluminum to obtain reaction liquid for later use.
⑵ seed crystal preparation, the solid analytically pure dodecylbenzene sulfonic acid aluminum is taken and crushed by a stainless steel crusher, and the crushed material is sieved by a standard sieve of 200 meshes to obtain the dodecylbenzene sulfonic acid aluminum seed crystal.
⑶ seed crystal induction, namely, reducing the temperature of the reaction liquid obtained in the step ⑴ to 25 ℃, maintaining the temperature at 25 ℃, adding 0.5 mass percent of aluminum dodecylbenzene sulfonate seed crystal into the reaction liquid under the stirring condition with the stirring speed of 200rpm, and continuing stirring for 15 hours to ensure that aluminum salt in the seed crystal induction reaction liquid fully forms aluminum dodecylbenzene sulfonate precipitate to obtain the reaction liquid with the aluminum salt precipitated.
⑷ and naturally settling, namely maintaining the temperature of the reaction solution precipitated by the aluminum salt obtained in the step ⑶ 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 a settled supernatant for later use.
⑸ Membrane separation, namely, finely filtering the settled supernatant fluid obtained in the step ⑷ by using microporous membrane equipment with a membrane material of silicon carbide, a membrane hole of 0.04 mu m and a membrane component form of a honeycomb briquette type inner tubular membrane to obtain 493 g of the dealuminizing acid solution in 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).
⑹, adjusting the components, namely adding analytically pure concentrated sulfuric acid and LY-920 wide-temperature oxidizing agent special for aluminum profile anodic oxidation according to the requirement of sulfuric acid mass percentage content of the aluminum profile anodic oxidation tank acid liquid required by the aluminum profile anodic oxidation process, 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:
⑴ heating reaction, namely putting 650 g of waste acid of the aluminum profile anodic oxidation tank, which mainly comprises 16 percent (mass fraction) of sulfuric acid, 2.1 percent (mass fraction) of aluminum ions, 1.3 percent (mass fraction) of LY-920 wide-temperature oxidant special for aluminum profile anodic oxidation and 80.6 percent (mass fraction) of water, into a ground triangular flask, adding 2.5 percent (mass) of phytic acid under the stirring condition of the stirring speed of 130rpm, starting cold water reflux, heating the mixture to 90 ℃ and maintaining the temperature at 90 ℃, and continuing heating and stirring for reaction for 9 hours to enable the phytic acid in the mixture to react with the aluminum ions to generate corresponding aluminum phytate, thereby obtaining reaction liquid for later use.
⑵ seed crystal preparation, the solid analytically pure aluminum phytate is taken and crushed by a stainless steel crusher, and the crushed product is sieved by a 160-mesh standard sieve to obtain the aluminum phytate seed crystal.
⑶ seed crystal induction, namely, reducing the temperature of the reaction solution obtained in the step ⑴ to 30 ℃, maintaining the temperature at 30 ℃, adding 0.3 mass percent of phytic acid aluminum seed crystal into the reaction solution under the stirring condition that the stirring speed is 200rpm, and continuing stirring for 15 hours to ensure that the aluminum salt in the seed crystal induction reaction solution fully forms phytic acid aluminum precipitate to obtain the reaction solution precipitated by the aluminum salt.
⑷ and naturally settling, namely maintaining the temperature of the reaction solution precipitated by the aluminum salt obtained in the step ⑶ at 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 a settling supernatant for later use.
⑸ Membrane separation, namely, precisely filtering the settled supernatant fluid obtained in the step ⑷ by using microporous membrane equipment with a membrane material of silicon carbide, a membrane hole of 0.1 mu m and a membrane component form of a honeycomb briquette type inner tubular membrane to obtain 639 g of dealuminizing acid solution in the aluminum profile anodic oxidation tank, wherein the content of aluminum ions is less than or equal to 0.20 percent (mass fraction) and the content of sulfuric acid is 14.9 percent (mass fraction).
⑹, adjusting the components, namely adding analytically pure concentrated sulfuric acid and LY-920 wide-temperature oxidizing agent special for aluminum profile anodic oxidation according to the requirement of sulfuric acid mass percentage content of the aluminum profile anodic oxidation tank acid liquid required by the aluminum profile anodic oxidation process, 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:
⑴ heating reaction, namely, 832 grams of waste acid of an 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, are taken to be put into a ground triangular flask, oxalic acid with the mass fraction of 3.0 percent is added under the stirring condition with the stirring speed of 150rpm, cold water reflux is started, the mixture is heated to 80 ℃ and maintained at 80 ℃, the heating stirring reaction is continued for 12 hours, the oxalic acid and the aluminum ions react to generate corresponding aluminum oxalate, and the reaction liquid is obtained for standby.
⑵ seed crystal preparation, namely crushing solid analytically pure aluminum oxalate by a stainless steel crusher, and sieving the crushed material by a 300-mesh standard sieve to obtain the aluminum oxalate seed crystal.
⑶ seed crystal induction, namely, reducing the temperature of the reaction liquid obtained in the step ⑴ to 15 ℃, maintaining the temperature at 15 ℃, adding 0.25 mass percent of aluminum oxalate seed crystal into the reaction liquid under the stirring condition that the stirring speed is 160rpm, and continuing stirring for 20 hours to ensure that aluminum salt in the seed crystal induction reaction liquid fully forms aluminum oxalate precipitate to obtain the reaction liquid of aluminum salt precipitate.
⑷ and naturally settling, namely maintaining the temperature of the reaction solution precipitated by the aluminum salt obtained in the step ⑶ at 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 a settled supernatant for later use.
⑸ Membrane separation, namely, finely filtering the settled supernatant fluid obtained in the step ⑷ 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 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 19.2 percent (mass fraction).
⑹, adjusting the components, namely adding analytically pure concentrated sulfuric acid and LY-920 wide-temperature oxidizing agent special for aluminum profile anodic oxidation according to the requirement of sulfuric acid mass percentage content of the aluminum profile anodic oxidation tank acid liquid required by the aluminum profile anodic oxidation process, 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:
⑴ heating reaction, namely taking 500 grams of waste acid of an aluminum profile anodic oxidation tank, which mainly comprises 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 water, into a ground triangular flask, 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 and stirring for reaction for 8 hours, and enabling the phosphoric acid in the mixture to react with the aluminum ions to generate corresponding aluminum phosphate to obtain reaction liquid for later use.
⑵ seed crystal preparation, which is to take solid analytically pure aluminum phosphate, crush the solid analytically pure aluminum phosphate by a stainless steel crusher, and screen the crushed material by a 200-mesh standard sieve to obtain the aluminum phosphate seed crystal.
⑶ seed crystal induction, namely, reducing the temperature of the reaction liquid obtained in the step ⑴ to 25 ℃, maintaining the temperature at 25 ℃, adding aluminum phosphate seed crystals with the mass fraction of 0.5 percent into the reaction liquid under the stirring condition with the stirring speed of 200rpm, and continuing stirring for 15 hours to ensure that aluminum salt in the seed crystal induction reaction liquid fully forms aluminum phosphate precipitate to obtain the reaction liquid with aluminum salt precipitated.
⑷ and naturally settling, namely maintaining the temperature of the reaction solution precipitated by the aluminum salt obtained in the step ⑶ 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 a settled supernatant for later use.
⑸ Membrane separation, namely, finely filtering the settled supernatant fluid obtained in the step ⑷ by using microporous membrane equipment with a membrane material of silicon carbide, a membrane hole of 0.04 mu m and a membrane component form of a honeycomb briquette type inner tubular membrane to obtain 493 g of the dealuminizing acid solution in 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).
⑹, adjusting the components, namely adding analytically pure concentrated sulfuric acid and LY-920 wide-temperature oxidizing agent special for aluminum profile anodic oxidation according to the requirement of sulfuric acid mass percentage content of the aluminum profile anodic oxidation tank acid liquid required by the aluminum profile anodic oxidation process, 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:
⑴ heating reaction, namely taking 500 grams of waste acid of the aluminum profile anodic oxidation tank, the waste acid mainly comprising 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 water, adding 6.5 percent (mass fraction) of silicic acid 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 heating, stirring and reacting for 8 hours to ensure that the silicic acid in the mixture reacts with the aluminum ions to generate corresponding aluminum silicate, and obtaining reaction liquid for later use.
⑵ seed crystal preparation, the analytical pure aluminum silicate is taken, crushed by a stainless steel crusher, and the crushed material is sieved by a 200-mesh standard sieve to obtain the aluminum silicate seed crystal.
⑶ seed crystal induction, namely, reducing the temperature of the reaction liquid obtained in the step ⑴ to 25 ℃, maintaining the temperature at 25 ℃, adding aluminum silicate seed crystals with the mass fraction of 0.5 percent into the reaction liquid under the stirring condition with the stirring speed of 200rpm, and continuing stirring for 15 hours to ensure that aluminum salt in the seed crystal induction reaction liquid fully forms aluminum silicate precipitate to obtain the reaction liquid with the aluminum salt precipitated.
⑷ and naturally settling, namely maintaining the temperature of the reaction solution precipitated by the aluminum salt obtained in the step ⑶ 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 a settled supernatant for later use.
⑸ Membrane separation, namely, finely filtering the settled supernatant fluid obtained in the step ⑷ by using microporous membrane equipment with a membrane material of silicon carbide, a membrane hole of 0.04 mu m and a membrane component form of a honeycomb briquette type inner tubular membrane to obtain 493 g of the dealuminizing acid solution in 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).
⑹, adjusting the components, namely adding analytically pure concentrated sulfuric acid and LY-920 wide-temperature oxidizing agent special for aluminum profile anodic oxidation according to the requirement of sulfuric acid mass percentage content of the aluminum profile anodic oxidation tank acid liquid required by the aluminum profile anodic oxidation process, 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:
⑴ heating reaction, namely taking 500 grams of waste acid of the aluminum profile anodic oxidation tank, which mainly comprises 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 water, in a ground triangular flask, adding 8.5 percent of polysilicic acid 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 heating and stirring for reaction for 8 hours, and enabling the polysilicic acid and the aluminum ions to react to generate corresponding aluminum polysilicate to obtain reaction liquid for later use.
⑵ seed crystal preparation, namely crushing the solid analytically pure aluminum polysilicate by a stainless steel crusher, and sieving the crushed material by a 200-mesh standard sieve to obtain the aluminum polysilicate seed crystal.
⑶ seed crystal induction, namely, reducing the temperature of the reaction solution obtained in the step ⑴ to 25 ℃, maintaining the temperature at 25 ℃, adding 0.5 mass percent of aluminum polysilicate seed crystal into the reaction solution under the stirring condition that the stirring speed is 200rpm, and continuing stirring for 15 hours to ensure that the aluminum salt in the seed crystal induction reaction solution fully forms aluminum polysilicate precipitate to obtain the reaction solution in which the aluminum salt precipitates.
⑷ and naturally settling, namely maintaining the temperature of the reaction solution precipitated by the aluminum salt obtained in the step ⑶ 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 a settled supernatant for later use.
⑸ Membrane separation, namely, finely filtering the settled supernatant fluid obtained in the step ⑷ by using microporous membrane equipment with a membrane material of silicon carbide, a membrane hole of 0.04 mu m and a membrane component form of a honeycomb briquette type inner tubular membrane to obtain 493 g of the dealuminizing acid solution in 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).
⑹, adjusting the components, namely adding mass analytically pure concentrated sulfuric acid and LY-920 wide-temperature oxidizing agent special for aluminum profile anodic oxidation according to the requirement of sulfuric acid mass percentage content of the aluminum profile anodic oxidation tank acid liquid required by the aluminum profile anodic oxidation process, 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:
⑴ heating reaction, namely taking 500 grams of waste acid of an aluminum profile anodic oxidation tank, the waste acid mainly comprising 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 water, adding 15.5 percent (mass fraction) of fluosilicic acid (mass fraction of fluosilicic acid is 30 percent) into a ground triangular flask 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 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.
⑵ seed crystal preparation, namely crushing the solid analytically pure fluoaluminum silicate by a stainless steel crusher, and sieving the crushed material by a 200-mesh standard sieve to obtain the aluminum fluosilicate seed crystal.
⑶ seed crystal induction, namely, reducing the temperature of the reaction liquid obtained in the step ⑴ to 25 ℃, maintaining the temperature at 25 ℃, adding 0.5 mass percent of aluminum fluosilicate seed crystal into the reaction liquid under the stirring condition with the stirring speed of 200rpm, and continuing stirring for 15 hours to ensure that aluminum salt in the seed crystal induction reaction liquid fully forms aluminum fluosilicate precipitate to obtain the reaction liquid separated out by the aluminum salt precipitate.
⑷ and naturally settling, namely maintaining the temperature of the reaction solution precipitated by the aluminum salt obtained in the step ⑶ 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 a settled supernatant for later use.
⑸ membrane separation, namely, finely filtering the settled supernatant fluid obtained in the step ⑷ 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 solution 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).
⑹, adjusting the components, namely adding analytically pure concentrated sulfuric acid and LY-920 wide-temperature oxidizing agent special for aluminum profile anodic oxidation according to the requirement of sulfuric acid mass percentage content of the aluminum profile anodic oxidation tank acid liquid required by the aluminum profile anodic oxidation process, 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:
⑴ heating reaction, namely 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 oxidizing agent special for aluminum profile anodic oxidation and 77.5 mass percent of water, adding hydrofluoric acid (aqueous solution with the mass percentage concentration of the hydrofluoric acid) with the mass percent of 2.5 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 ℃, continuing heating and stirring for reaction for 8 hours to enable the hydrofluoric acid and the aluminum ions to react to generate corresponding aluminum fluoride, and obtaining reaction liquid for later use.
⑵ seed crystal preparation, the solid analytically pure aluminum fluoride is taken and crushed by a stainless steel crusher, and the crushed material is sieved by a 200-mesh standard sieve to obtain the aluminum fluoride seed crystal.
⑶ seed crystal induction, namely, reducing the temperature of the reaction solution obtained in the step ⑴ to 25 ℃, maintaining the temperature at 25 ℃, adding 0.5 mass percent of aluminum fluoate seed crystal into the reaction solution under the stirring condition with the stirring speed of 200rpm, and continuing stirring for 15 hours to ensure that the aluminum salt in the seed crystal induction reaction solution fully forms aluminum fluoate precipitate to obtain the reaction solution in which the aluminum salt precipitates.
⑷ and naturally settling, namely maintaining the temperature of the reaction solution precipitated by the aluminum salt obtained in the step ⑶ 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 a settled supernatant for later use.
⑸ Membrane separation, namely, finely filtering the settled supernatant fluid obtained in the step ⑷ 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 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 16.8 percent (mass fraction).
⑹, adjusting the components, namely adding analytically pure concentrated sulfuric acid and LY-920 wide-temperature oxidizing agent special for aluminum profile anodic oxidation according to the requirement of sulfuric acid mass percentage content of the aluminum profile anodic oxidation tank acid liquid required by the aluminum profile anodic oxidation process, 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:
⑴ heating reaction, namely adding 1760 g of waste acid of an aluminum profile anodic oxidation tank, which mainly comprises 16.5 percent (mass fraction) of sulfuric acid, 2.0 percent (mass fraction) of aluminum ions, 0.9 percent (mass fraction) of LY-920 wide-temperature oxidant special for aluminum profile anodic oxidation and 80.6 percent (mass fraction) of water, into a ground triangular flask, adding 0.5 percent (mass fraction) of dodecylbenzene sulfonic acid and 7.5 percent (mass fraction) of fluosilicic acid (mass fraction of fluosilicic acid is 30 percent aqueous solution) under the stirring condition of the stirring speed of 100rpm, starting cold water for refluxing, heating the mixture to 89 ℃, maintaining the temperature at 89 ℃, continuing heating and stirring for reaction for 12 hours, and enabling the dodecylbenzene sulfonic acid and the fluosilicic acid in the mixture to react with the aluminum ions to generate corresponding aluminum dodecylbenzene sulfonate and aluminum fluosilicic acid, thereby obtaining a reaction solution for later use.
⑵ seed crystal preparation, 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 aluminum dodecylbenzene sulfonate and aluminum fluosilicate.
⑶ seed crystal induction, namely, reducing the temperature of the reaction liquid obtained in the step ⑴ to 25 ℃, maintaining the temperature at 15 ℃, adding mixed seed crystals with the mass fraction of 0.3 percent into the reaction liquid under the stirring condition with the stirring speed of 200rpm, and continuing stirring for 18 hours to ensure that aluminum salt in the seed crystal induction reaction liquid fully forms aluminum dodecylbenzenesulfonate and aluminum fluosilicate precipitates to obtain the reaction liquid separated out by the aluminum salt precipitates.
⑷ and naturally settling, namely keeping the temperature of the reaction solution precipitated by the aluminum salt obtained in the step ⑶ at 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 a settled supernatant for later use.
⑸ membrane separation, namely precisely filtering the settled supernatant fluid obtained in the step ⑷ 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 solution 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).
⑹, adjusting the components, namely adding analytically pure concentrated sulfuric acid and LY-920 wide-temperature oxidizing agent special for aluminum profile anodic oxidation according to the requirement of sulfuric acid mass percentage content of the aluminum profile anodic oxidation tank acid liquid required by the aluminum profile anodic oxidation process, 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:
⑴ heating reaction, namely taking 5280 grams of aluminum profile anodic oxidation tank waste acid mainly comprising 17.2 percent (mass fraction) of sulfuric acid, 2.2 percent (mass fraction) of aluminum ions, 1.1 percent (mass fraction) of LY-920 wide-temperature oxidizing agent special for aluminum profile anodic oxidation and 79.5 percent (mass fraction) of water, adding 5.5 percent (mass fraction) of phosphoric acid and 3.5 percent (mass fraction) of fluosilicic acid (mass fraction of fluosilicic acid is 30 percent) into a ground triangular flask under the stirring condition of the stirring speed of 100rpm, starting cold water to reflux, heating the mixture to 95 ℃ and maintaining the temperature at 95 ℃, continuing heating and stirring for reaction for 11 hours, and enabling the phosphoric acid and the fluosilicic acid in the mixture to react with the aluminum ions to generate corresponding aluminum phosphate and aluminum fluosilicate, thus obtaining reaction liquid for later use.
⑵ seed crystal preparation, mixing solid analytically pure aluminum phosphate and aluminum fluosilicate at a mass ratio of 2:1, crushing by a stainless steel crusher, and sieving the crushed material by a 300-mesh standard sieve to obtain the mixed aluminum seed crystal consisting of the aluminum phosphate and the aluminum fluosilicate.
⑶ seed crystal induction, namely, reducing the temperature of the reaction liquid obtained in the step ⑴ to 10 ℃ and maintaining the temperature at 10 ℃, adding mixed seed crystals with the mass fraction of 0.3 percent into the reaction liquid under the stirring condition with the stirring speed of 220rpm, and continuing stirring for 16 hours to ensure that aluminum salt in the seed crystal induction reaction liquid fully forms aluminum phosphate and aluminum fluosilicate precipitates to obtain the reaction liquid separated out by the aluminum salt precipitates.
⑷ and naturally settling, namely keeping the temperature of the reaction solution precipitated by the aluminum salt obtained in the step ⑶ at 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 a settling supernatant for later use.
⑸ Membrane separation, namely, precisely filtering the settled supernatant obtained in the step ⑷ 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 dealuminized acid liquor 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 15.3 percent (mass fraction).
⑹, adjusting the components, namely adding analytically pure concentrated sulfuric acid and LY-920 wide-temperature oxidizing agent special for aluminum profile anodic oxidation according to the requirement of sulfuric acid mass percentage content of the aluminum profile anodic oxidation tank acid liquid required by the aluminum profile anodic oxidation process, 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:
⑴ heating reaction, namely putting the waste acid of the aluminum profile anodic oxidation tank into a strong acid resistant reaction kettle or other container, starting cooling water for reflux, adding a chemical mixture with the mass of 0.3-25% of the waste acid under the condition of continuous stirring, heating the mixture to the chemical mixture dissociation reaction temperature and maintaining the chemical mixture dissociation reaction temperature, and continuing heating and stirring for reaction 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;
⑵ preparing seed crystal by pulverizing solid aluminum salt composed of corresponding complexing agent acid radical and aluminum ion and difficult to be dissolved in water and dilute sulfuric acid with stainless steel pulverizer, and sieving the pulverized product with standard sieve to obtain aluminum salt seed crystal;
⑶ seed crystal induction, namely, reducing the temperature of the reaction liquid obtained in the step ⑴ to 0-45 ℃, maintaining the temperature at 0-45 ℃, adding the seed crystal obtained in the step ⑵ with mass fraction capable of playing an induction role into the reaction liquid under the condition of continuous stirring, and continuously stirring for 1.0-25 hours to enable aluminum salt in the seed crystal induction reaction liquid to form aluminum salt precipitate so as to obtain the reaction liquid separated out by the aluminum salt precipitate;
⑷, naturally settling, namely maintaining the temperature of the reaction liquid precipitated by the aluminum salt precipitate obtained in the step ⑶ at 0-40 ℃, controlling the settling and stirring speed, continuing stirring for 5-45 hours, stopping stirring, naturally settling the precipitate for 3-15 hours, and taking the supernatant of the settling for later use;
⑸ membrane separation, namely precisely filtering the supernatant fluid obtained in the step ⑷ by microporous membrane equipment to obtain dealuminizing acid liquor in an aluminum profile anodic oxidation tank for later use;
⑹, analyzing and measuring the mass percent of sulfuric acid of the dealuminizing acid solution of the aluminum profile anodic oxidation tank obtained in the step ⑸, 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 of 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 method for recycling the waste acid from the aluminum profile anodic oxidation tank in the step ⑴ is the residual acid from the aluminum profile anodic oxidation tank used for anodic oxidation of the aluminum profile in the oxidation tank, which has high aluminum ion content, can not be reused and needs to be discarded, and comprises the components of 10-30% by mass of sulfuric acid, 0.8-3.0% by mass of aluminum ions, 0.1-5% by mass of LY-920 wide-temperature oxidant special for anodic oxidation and 68-86% by mass of water, wherein the chemical mixture is one of analytically pure or chemically pure dodecylbenzene sulfonic acid, phytic acid, aluminum profile, phosphoric acid, silicic acid, polysilicic acid, fluosilicic acid and hydrofluoric acid, or a mixture of two to eight of the two or more in any proportion, and the dissociation reaction temperature of the chemical mixture is the temperature capable of promoting the generation of the corresponding aluminum salt and ranges from 15-120 ℃.
3. The method for treating the waste acid from the aluminum profile anodizing tank in the recycling mode according to claim 1, wherein the solid aluminum salt in the step ⑵ is any one of analytically pure or chemically pure aluminum dodecylbenzenesulfonate, aluminum phytate, aluminum oxalate, aluminum phosphate, aluminum silicate, aluminum polysilicate, aluminum fluorosilicate and aluminum hydrofluoride, or a mixture of two or more of the aluminum salts in any proportion, and the screening is 40-600 meshes.
4. The processing method for recycling the waste acid from the aluminum profile chemical polishing tank as claimed in claim 1, wherein the mass fraction capable of inducing the crystallization in the step ⑶ is 0.05-5%.
5. The processing method for recycling the waste acid from the aluminum profile anodic oxidation tank is characterized in that the sedimentation stirring speed in the step ⑷ is the stirring speed at which the aluminum salt can be sedimented, and the range of the stirring speed is 1-50 rpm.
6. The method for recycling waste acid from the anodic oxidation tank of aluminum profile according to claim 1, wherein the microporous membrane device of step ⑸ has a membrane material of silicon carbide, and the membrane component is in the form of honeycomb briquette type inner tubular membrane with membrane pores of 1, 0.5, 0.1 and 0.04 μm.
7. The method for recycling waste acid from the anodic oxidation tank of aluminum profiles as claimed in claim 1, wherein said concentrated sulfuric acid of step ⑹ is sulfuric acid with 98% mass fraction of analytical or chemical purity.
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