CN108178174B - Method for preparing sapphire-grade high-purity aluminum oxide by using aluminum anodic oxidation waste liquid - Google Patents
Method for preparing sapphire-grade high-purity aluminum oxide by using aluminum anodic oxidation waste liquid Download PDFInfo
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Abstract
The invention relates to the field of recycling of aluminum product anodic oxidation waste liquid, in particular to a method for preparing sapphire grade high-purity aluminum oxide by using the aluminum product anodic oxidation waste liquid. According to the invention, the waste liquid of the anodic oxidation of the aluminum material is used as a raw material, firstly impurity ions in the waste liquid of the anodic oxidation of the aluminum material are removed through waste liquid pretreatment, then the pH value is adjusted to be 1.5-3.0 through ammonia water, a crude product of aluminum ammonium sulfate is prepared, the aluminum ammonium sulfate is further purified through repeated recrystallization, and finally the sapphire grade high-purity aluminum oxide can be prepared through sintering. The preparation method has the advantages of cheap raw materials, simple process, and changing waste into valuable, accords with the ideas of green environmental protection and sustainable development vigorously advocated by China, is used in a large scale, and has better social benefit.
Description
Technical Field
The invention relates to the field of recycling of aluminum product anodic oxidation waste liquid, in particular to a method for preparing sapphire grade high-purity aluminum oxide by using the aluminum product anodic oxidation waste liquid.
Background
With the rapid development of industry, the application of aluminum profiles in industrial production, buildings and civil materials is more and more extensive. One process in the production of aluminum profiles is called anodization. Before anodizing, it needs pickling, i.e. using the corrosive action of acid liquor to remove rust, according to its rust-resisting degree adopting sulfuric acid liquor to make soaking and cleaning to make its surface smooth and clean, after said soaking liquor is used for a certain time, it can be changed into waste liquor, and the waste liquor and clean water can be mixed and discharged so as to form the aluminium-containing pickling waste water. Of the aluminium profiles used, approximately 65% are surface-treated, whereas the aluminium components and parts for the construction industry, the aeronautics and astronautics industry, the automotive industry are almost entirely anodized or coated. A large amount of waste liquid and waste water are generated in the existing nearly hundred anode oxidation production lines in the aluminum processing industry in China, 0.05t of waste water is generated in each 1t of aluminum profile production on average, and the aluminum content in each ton of waste water reaches 20 kg. Most factories of the generated waste liquid are discharged without treatment, so that the environment is polluted, and the aluminum resource is wasted, and therefore, the high-added-value resource utilization of the aluminum-containing waste water is a very important research.
The sapphire is α -Al2O3Single crystal, also called corundum, has unique physical, chemical, optical electronic and mechanical characteristics, is an important technical crystal, and is widely applied to the fields of scientific technology, national defense and civil industry and electronic communication at present, in particular to L ED light-emitting diodes, large-scale integrated circuit SOI, SOS, superconducting nanostructure film and other ideal substrate materials2O3Research on defects per se or impurities has expanded many new applications of sapphire. With the attention paid to the popularization and application of sapphire growth technology in various countries in the world, the demand for large-size and high-quality sapphire crystals is rapidly increased, and the research and growth of sapphire crystals are promoted to become one of the most active industries at present.
The raw material for growing the sapphire single crystal is high-purity alumina micropowder with the purity of more than or equal to 99.995 percent, and the market prospect of the high-purity alumina is very wide with the increasing demand of sapphire. The existing preparation technology of high-purity alumina powder mainly comprises alkoxide hydrolysis method and Al (OH)3Sintering process, AlCl3The method comprises the following steps of (1) performing a gas phase synthesis method, a sol-gel method, an improved Bayer method, an aluminum ammonium sulfate pyrolysis method and the like, wherein the product obtained by the alkoxide hydrolysis method is high in purity, but the operation is complex, the consumed time is long, and the mass production scale is difficult to form; al (OH)3Although the sintering method has simple process, the impurity removal is difficult; AlCl3The product of the gas phase synthesis method has uniform granularity, fine particles and no pollution in the reaction process, but the reaction condition is strict, professional equipment is required, and the production cost is high; the sol-gel method has wide raw material sources, low production cost and no waste gas pollution, but the technological parameters are difficult to control in the process of forming gel by sol; the improved Bayer process can generate high-purity alumina powder, but the production process is complex and the required conditions in the industry are harsh; the ammonium aluminum sulfate pyrolysis method is one of the main methods for producing high-purity aluminum oxide powder, and has the advantages of mature technology, simple operation, high product purity, higher production cost and long production period. At present, no report related to a method for preparing sapphire grade high-purity powder by using aluminum material anodic oxidation waste liquid exists.
Disclosure of Invention
The invention aims to provide a method for preparing sapphire grade high-purity aluminum oxide by using aluminum material anodic oxidation waste liquid.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a method for preparing sapphire grade high-purity aluminum oxide by using aluminum material anodic oxidation waste liquid comprises the following steps:
1) pretreatment of waste anodic oxidation liquid of aluminum material
Ca in the waste liquid of anodic oxidation of aluminum material2+、Fe2+、Mg2+、Si4+Removing to obtain a pretreatment solution;
2) preparation of crude aluminum ammonium sulfate
Adjusting the pH value of the pretreatment solution to 1.5-3.0 by using ammonia water, cooling to-20-5 ℃ to precipitate crystals, and performing solid-liquid separation to obtain a crude product of aluminum ammonium sulfate;
3) recrystallization purification of aluminum ammonium sulfate
Recrystallizing the crude product of the aluminum ammonium sulfate obtained in the step 2): the recrystallization treatment comprises the following steps: adding the crude product of aluminum ammonium sulfate into water, heating to 50-70 ℃ to completely dissolve the aluminum ammonium sulfate, adding a shielding agent, uniformly mixing, carrying out hot filtration to obtain a filtrate, cooling the filtrate to-20-5 ℃ to separate out a solid, carrying out solid-liquid separation, and washing with a solvent to obtain a first refined product of recrystallized aluminum ammonium sulfate
Repeating the recrystallization process for N times to obtain an (N +1) th recrystallized fine aluminum ammonium sulfate product;
4) thermally decomposing the (N +1) th recrystallized ammonium aluminum sulfate fine product to prepare the sapphire grade high-purity alumina.
The alumina prepared by the invention has the configuration of α -Al2O3I.e., sapphire configuration, to sapphire grade in purity.
Ammonia water is added to the pretreatment solution to neutralize sulfuric acid in the pretreatment solution to produce ammonium sulfate and further produce aluminum ammonium sulfate. The pH value of the solution is adjusted to 1.5-3.0, so that the hydrolysis of the ammonium aluminum sulfate aqueous solution to separate out Al (OH) can be avoided3。
Removing impurity Fe from aluminum anode oxidation waste liquid by using activated carbon2+Removing Mg impurity by D001 ion resin2+(ii) a Removal of Ca impurity by hydrofluoric acid2+And Si4+And then obtaining the compound.
Firstly, determining the types and ion concentrations of other ions except sulfate radicals and aluminum ions in the aluminum material anodic oxidation waste liquid, and selecting a corresponding impurity removal mode according to the types and the concentrations of the ions to remove impurities, thereby obtaining a pretreatment liquid of the aluminum material anodic oxidation waste liquid. The invention selects the anodic oxidation waste liquid in the production process of certain aluminum profile, and the detection shows that the main component of the waste liquid is Al2(SO4)2And H2SO4The content of aluminum is 0.58 percent, and the content of impurities is respectively Ca2+：3.4ppm，Fe2+：6.4ppm，Mg2+：1.0ppm，Na+：2.8ppm，Si4+1.4ppm, adding 5.0-15.0 g/L g of activated carbon into the waste liquid, stirring for 10-60 min to remove Fe impurity2+Then adding 0.4-0.8 g/L g D001 ion resin, stirring for 30-50 min, removing Mg2+Adding 1.0-10 m of L hydrofluoric acid into every 100m of L anodic oxidation waste liquid, controlling the reaction time to be 50-60 min, and removing Ca impurities2+And Si4+And (4) carrying out ion removal to obtain pretreatment liquid of the aluminum material anodic oxidation waste liquid.
A further preferable scheme of the pretreatment of the aluminum material anodic oxidation waste liquid is that 10.0 g/L of activated carbon is added into the waste liquid, the stirring time is 30min, then 0.6 g/L of D001 ionic resin is added, the reaction time is 40min, then 6m L of hydrofluoric acid is added into every 100m L of the anodic oxidation waste liquid, the reaction time is 50min, and the treated pretreatment liquid of the aluminum material anodic oxidation waste liquid is obtained.
The shielding agent in the step 3) is citric acid, the dosage of the shielding agent is 0.3-0.6 g of citric acid per liter of waste liquid, and in a further preferable scheme, the dosage of the shielding agent is 0.5g per liter of waste liquid. The function is as follows: forming insoluble complex with impurity ion in the solution, and further removing impurities in the crude aluminum ammonium sulfate by hot filtration.
And 3) washing with the solvent is to wash with water and then with ethanol, wherein the impurities dissolved in the water in the aluminum ammonium sulfate crystals can be absorbed by washing with water, then the impurities dissolved in the ethanol can be removed by washing with ethanol, the volatility and the boiling point of the ethanol are lower than those of the water, the ethanol can be mutually dissolved with the water, and the product recrystallized after washing with the ethanol is easy to dry.
In order to obtain high-purity refined aluminum ammonium sulfate, the aluminum ammonium sulfate can be subjected to multiple times of recrystallization, and the preferable number of times of recrystallization in the step 3) is 1, 2 or 3.
The filtering device is heated in the hot filtering process, the phenomenon that a hot aluminum ammonium sulfate solution is separated out on the filtering device when being suddenly cooled and blocks a filtering opening of the filtering device can be reduced, and the temperature of the filtering device used in the hot filtering process is preferably 50-70 ℃.
Step 4) the thermal decomposition comprises the following steps: heating from room temperature to 250 deg.C at 2 deg.C/min; then the temperature is raised from 250 ℃ to 550 ℃ at the speed of 5 ℃/min; preserving the heat at 550 ℃ for 30 min; then raising the temperature from 550 ℃ to 900 ℃ at a speed of 5 ℃/min; preserving heat for 2 hours at 900 ℃; heating to 1200-1300 ℃ at the speed of 5 ℃/min, preserving the heat for 2h, and cooling to room temperature to obtain the product.
Compared with the prior art, the invention has the advantages that:
(1) the raw materials used by the invention are the aluminum product anodic oxidation waste liquid and the ammonia water, on one hand, the ammonia water raw material is simple, the waste acid in the waste liquid is removed by adding the ammonia water, on the other hand, the industrial aluminum waste liquid is changed into valuable, the production cost is reduced, and the invention has good economic benefit.
(2) The method prepares the ammonium aluminum sulfate by using the aluminum anodic oxidation waste liquid, purifies the ammonium aluminum sulfate through repeated recrystallization, has the purity of the ammonium aluminum sulfate as high as 99.995 percent, can further prepare the sapphire grade high-purity aluminum oxide through high-temperature calcination, has simple whole process flow, strong repeatability, small pollution in the production process, low energy consumption, can realize large-scale production, and has better social effect.
(3) The process method has the characteristics of economy, functionality, environmental harmony and the like, accords with the concepts of green environmental protection and sustainable development advocated by the state, improves the production efficiency through process improvement, and plays a certain role in the development of sewage treatment in the whole aluminum industry.
Drawings
Fig. 1 is an XRD pattern of crude aluminum ammonium sulfate prepared under different pH conditions of examples 1-4, wherein a is example 4 and pH is 1.5; b is example 3, pH 2.0; c is example 2, pH 2.5; d is example 4, pH 3.0;
FIG. 2 is an XRD pattern of the alumina prepared in examples 1-2 and comparative examples 1-2;
FIG. 3 is an SEM photograph of example 1-2; wherein a is the SEM image of example 1 and b is the SEM image of example 2.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, embodiments of the present invention will be described in further detail below.
Example 1
The embodiment provides a method for preparing sapphire grade high-purity alumina by using aluminum anodic oxidation waste liquid, which comprises the following specific steps:
1) pretreatment of waste anodic oxidation liquid of aluminum material
Taking the waste liquid of anodic oxidation of aluminum material in the production process of certain aluminum profile, and detecting the main component of the waste liquid is Al2(SO4)2And H2SO4The aluminum content was 0.58 wt%, and the impurity contents were Ca, respectively2+：3.4ppm，Fe2+：6.4ppm，Mg2+：1.0ppm，Na+：2.8ppm，Si4+:1.4ppm；
Taking waste liquid 1L as an example, adding 10g of activated carbon into the waste liquid, stirring for 30min, and removing the adsorbed impurity Fe by suction filtration2+Adding 0.6g of D001 ion resin, stirring for 40min, filtering to remove complex formed by ion exchange resin and Mg ions, adding 60ml of hydrofluoric acid (400 g/L), reacting for 50min, filtering to remove CaF2Obtaining a pretreatment solution by the insoluble substances;
2) preparation of crude aluminum ammonium sulfate
Adjusting the pH value of the pretreatment liquid obtained in the step 1) to 3.0 by using ammonia water, cooling to-10 ℃ to separate out crystals, and filtering to obtain a crude product of aluminum ammonium sulfate;
the mass fraction of the ammonia water used in the step is 25-28%;
3) recrystallization purification of aluminum ammonium sulfate
Recrystallizing the crude product of the aluminum ammonium sulfate obtained in the step 2): adding the crude product of aluminum ammonium sulfate into water, heating to 60 ℃ to completely dissolve the aluminum ammonium sulfate, adding 0.5g of citric acid shielding agent, uniformly stirring, heating a hot filtering device to 60 ℃, carrying out hot filtering to obtain a filtrate, cooling the filtrate to-5 ℃ to precipitate a solid, carrying out solid-liquid separation, washing with water, and then washing with ethanol to obtain a first refined product of recrystallized aluminum ammonium sulfate;
repeating the recrystallization process for 2 times to obtain a 3 rd recrystallized fine aluminum ammonium sulfate product with the purity of 99.998%;
4) preparation of sapphire grade high-purity alumina by thermal decomposition of aluminum ammonium sulfate
Weighing the aluminum ammonium sulfate product recrystallized for the 3 rd time in the step 3), putting the aluminum ammonium sulfate product into a crucible, and performing thermal decomposition by adopting the following temperature rise gradient: from room temperature to 250 ℃ at 2 ℃/min; then the temperature is raised from 250 ℃ to 550 ℃ at the speed of 5 ℃/min; preserving the heat at 550 ℃ for 30 min; then raising the temperature from 550 ℃ to 900 ℃ at a speed of 5 ℃/min; preserving heat for 2 hours at 900 ℃; raising the temperature to 1200 ℃ at a speed of 5 ℃/min, preserving the temperature for 2h, and reducing the temperature to room temperature to obtain the sapphire grade high-purity alumina, wherein the purity of the alumina can reach 99.997%.
Example 2
The embodiment provides a method for preparing sapphire grade high-purity alumina by using aluminum anodic oxidation waste liquid, which comprises the following specific steps:
1) pretreatment of waste anodic oxidation liquid of aluminum material
Taking the waste liquid of anodic oxidation of aluminum material in the production process of certain aluminum profile, and detecting the main component of the waste liquid is Al2(SO4)2And H2SO4The content of aluminum is 0.58 percent, and the content of impurities is respectively Ca2+：3.4ppm，Fe2+：6.4ppm，Mg2+：1.0ppm，Na+：2.8ppm，Si4+:1.4ppm；
Taking waste liquid 1L as an example, adding 12g of activated carbon into the waste liquid, stirring for 30min, and removing the adsorbed impurity Fe by suction filtration2+Adding 0.8g of D001 ion resin, stirring for 50min, filtering to remove complex formed by ion exchange resin and Mg ions, adding 80ml of hydrofluoric acid (400 g/L), reacting for 50min, filtering to remove CaF2Obtaining a pretreatment solution by the insoluble substances;
2) preparation of crude aluminum ammonium sulfate
Adjusting the pH value of the pretreatment liquid obtained in the step 1) to 2.5 by using ammonia water, cooling to 0 ℃ to separate out crystals, and filtering to obtain a crude product of aluminum ammonium sulfate;
the mass fraction of the ammonia water used in the step is 25-28%;
3) recrystallization purification of aluminum ammonium sulfate
Recrystallizing the crude product of the aluminum ammonium sulfate obtained in the step 2): adding the crude product of aluminum ammonium sulfate into water, heating to 50 ℃ to completely dissolve the aluminum ammonium sulfate, adding 0.6g of citric acid shielding agent, uniformly stirring, heating a hot filtering device to 70 ℃, carrying out hot filtering to obtain a filtrate, cooling the filtrate to 0 ℃ to separate out a solid, carrying out solid-liquid separation, washing with water, and then washing with ethanol to obtain a first refined product of recrystallized aluminum ammonium sulfate;
repeating the recrystallization process for 3 times to obtain a 4 th recrystallized fine aluminum ammonium sulfate product with the purity as high as 99.998%;
4) preparation of sapphire grade high-purity alumina by thermal decomposition of aluminum ammonium sulfate
Weighing the ammonium aluminum sulfate product recrystallized for the 4 th time in the step 3), putting the product into a crucible, and performing thermal decomposition by adopting the following temperature rise gradient: from room temperature to 250 ℃ at 2 ℃/min; then the temperature is raised from 250 ℃ to 550 ℃ at the speed of 5 ℃/min; preserving the heat at 550 ℃ for 30 min; then raising the temperature from 550 ℃ to 900 ℃ at a speed of 5 ℃/min; preserving heat for 2 hours at 900 ℃; heating to 1300 ℃ at the speed of 5 ℃/min, preserving the heat for 2h, and cooling to room temperature to obtain the sapphire grade high-purity alumina with the purity of 99.997 percent.
Example 3
The embodiment provides a method for preparing sapphire grade high-purity alumina by using aluminum anodic oxidation waste liquid, which comprises the following specific steps:
1) pretreatment of waste anodic oxidation liquid of aluminum material
Taking the waste liquid of anodic oxidation of aluminum material in the production process of certain aluminum profile, and detecting the main component of the waste liquid is Al2(SO4)2And H2SO4The content of aluminum is 0.58 percent, and the content of impurities is respectively Ca2+：3.4ppm，Fe2+：6.4ppm，Mg2+：1.0ppm，Na+：2.8ppm，Si4+:1.4ppm；
Taking waste liquid 1L as an example, adding 5g of activated carbon into the waste liquid, stirring for 10min, and removing the adsorbed impurity Fe by suction filtration2+Adding 0.4g of D001 ion resin, stirring for 50min, filtering to remove complex formed by ion exchange resin and Mg ions, adding 100ml of hydrofluoric acid (400 g/L), reacting for 60min, filtering to remove CaF2Obtaining a pretreatment solution by the insoluble substances;
2) preparation of crude aluminum ammonium sulfate
Adjusting the pH value of the pretreatment liquid obtained in the step 1) to 2.0 by using ammonia water, cooling to 5 ℃ to separate out crystals, and filtering to obtain a crude product of aluminum ammonium sulfate;
the mass fraction of the ammonia water used in the step is 25-28%;
3) recrystallization purification of aluminum ammonium sulfate
Recrystallizing the crude product of the aluminum ammonium sulfate obtained in the step 2): adding the crude product of aluminum ammonium sulfate into water, heating to 60 ℃ to completely dissolve the aluminum ammonium sulfate, adding 0.3g of citric acid shielding agent, uniformly stirring, heating a hot filtering device to 70 ℃, carrying out hot filtering to obtain a filtrate, cooling the filtrate to-20 ℃ to separate out a solid, carrying out solid-liquid separation, washing with water, and then washing with ethanol to obtain a first refined product of recrystallized aluminum ammonium sulfate;
repeating the recrystallization process for 1 time to obtain a 2 nd-time recrystallized fine aluminum ammonium sulfate product with the purity as high as 99.995 percent;
4) preparation of sapphire grade high-purity alumina by thermal decomposition of aluminum ammonium sulfate
Weighing the ammonium aluminum sulfate product recrystallized for the 2 nd time in the step 3), putting the product into a crucible, and performing thermal decomposition by adopting the following temperature rise gradient: from room temperature to 250 ℃ at 2 ℃/min; then the temperature is raised from 250 ℃ to 550 ℃ at the speed of 5 ℃/min; preserving the heat at 550 ℃ for 30 min; then raising the temperature from 550 ℃ to 900 ℃ at a speed of 5 ℃/min; preserving heat for 2 hours at 900 ℃; raising the temperature to 1200 ℃ at a speed of 5 ℃/min, preserving the temperature for 2h, and reducing the temperature to room temperature to obtain the sapphire grade high-purity alumina, wherein the purity of the alumina can reach 99.993%.
Example 4
The embodiment provides a method for preparing sapphire grade high-purity alumina by using aluminum anodic oxidation waste liquid, which comprises the following specific steps:
1) pretreatment of waste anodic oxidation liquid of aluminum material
Taking the waste liquid of anodic oxidation of aluminum material in the production process of certain aluminum profile, and detecting the main component of the waste liquid is Al2(SO4)2And H2SO4The content of aluminum is 0.58 percent, and the content of impurities is respectively Ca2+：3.4ppm，Fe2+：6.4ppm，Mg2+：1.0ppm，Na+：2.8ppm，Si4+:1.4ppm；
Taking waste liquid 1L as an example, adding 15g of activated carbon into the waste liquid, stirring for 60min, and removing the adsorbed impurity Fe by suction filtration2+The activated carbon of (1); then add 0.8gD001 ionophoreStirring for 50min, filtering to remove complex formed by ion exchange resin and Mg ion, adding 10ml hydrofluoric acid (400 g/L), reacting for 55min, filtering to remove CaF2Obtaining a pretreatment solution by the insoluble substances;
2) preparation of crude aluminum ammonium sulfate
Adjusting the pH value of the pretreatment liquid obtained in the step 1) to 1.5 by using ammonia water, cooling to-10 ℃ to separate out crystals, and filtering to obtain a crude product of aluminum ammonium sulfate;
the mass fraction of the ammonia water used in the step is 25-28%;
3) recrystallization purification of aluminum ammonium sulfate
Adding the crude product of the aluminum ammonium sulfate obtained in the step 2) into water, heating to 60 ℃ to completely dissolve the aluminum ammonium sulfate, adding 0.4 g/L g of citric acid serving as a shielding agent, uniformly stirring, heating a hot filtering device to 60 ℃, carrying out hot filtering to obtain a filtrate, cooling the filtrate to-5 ℃ to separate out a solid, carrying out solid-liquid separation, washing with water, and then washing with ethanol to obtain a refined product of the aluminum ammonium sulfate recrystallized for the 1 st time;
repeating the recrystallization process for 2 times to obtain a 3 rd recrystallized fine aluminum ammonium sulfate product with the purity as high as 99.996%;
4) preparation of sapphire grade high-purity alumina by thermal decomposition of aluminum ammonium sulfate
Weighing the aluminum ammonium sulfate product recrystallized for the 3 rd time in the step 3), putting the aluminum ammonium sulfate product into a crucible, and performing thermal decomposition by adopting the following temperature rise gradient: from room temperature to 250 ℃ at 2 ℃/min; then the temperature is raised from 250 ℃ to 550 ℃ at the speed of 5 ℃/min; preserving the heat at 550 ℃ for 30 min; then raising the temperature from 550 ℃ to 900 ℃ at a speed of 5 ℃/min; preserving heat for 2 hours at 900 ℃; heating to 1300 ℃ at the speed of 5 ℃/min, preserving the heat for 2h, and cooling to room temperature to obtain the sapphire grade high-purity alumina with the purity of 99.996 percent.
Comparative example 1
The comparative example is the same as the method of example 1, and is different from the method of step 4), specifically, the ammonium aluminum sulfate product recrystallized for the 2 nd time in the step 3) is weighed and put into a crucible, and thermal decomposition is carried out by adopting the following temperature rise gradient: from room temperature to 250 ℃ at 2 ℃/min; then the temperature is raised from 250 ℃ to 550 ℃ at the speed of 5 ℃/min; preserving the heat at 550 ℃ for 30 min; then raising the temperature from 550 ℃ to 900 ℃ at a speed of 5 ℃/min; preserving heat for 2 hours at 900 ℃; raising the temperature to 1000 ℃ at a speed of 5 ℃/min, and preserving the temperature for 2 h.
Comparative example 2
The comparative example is the same as the method of example 2, and is different from the method of step 4), specifically, the ammonium aluminum sulfate product recrystallized for the 2 nd time in the step 3) is weighed and put into a crucible, and thermal decomposition is carried out by adopting the following temperature rise gradient: from room temperature to 250 ℃ at 2 ℃/min; then the temperature is raised from 250 ℃ to 550 ℃ at the speed of 5 ℃/min; preserving the heat at 550 ℃ for 30 min; then raising the temperature from 550 ℃ to 900 ℃ at a speed of 5 ℃/min; preserving heat for 2 hours at 900 ℃; heating to 1100 deg.C at 5 deg.C/min, and maintaining for 2 hr.
Test examples
1) The results of the analysis of the aluminum ammonium sulfate prepared in examples 1 to 4 by XRD are shown in fig. 1, and it can be seen from fig. 1 that the aluminum ammonium sulfate dodecahydrate prepared in examples 1 to 4 has the same structure and is superior in crystallization effect at pH 3.0.
2) The alumina prepared in examples 1-2 and comparative examples 1-2 was analyzed by XRD, and the results are shown in FIG. 2. As can be seen from FIG. 2, the alumina of comparative examples 1-2 has a different crystal form from that of examples 1-2, and α -Al can be obtained only by calcining at a high temperature of 1200 ℃ or more2O3And (3) powder.
3) The analysis of the sapphire grade high purity aluminas obtained in examples 1 and 2 using SEM images is shown in FIG. 3, in which it can be seen that the aluminas prepared in examples 1 and 2 have uniform grain size, but the grain size increases at 1300 ℃ to increase α -Al2O3Of α -Al obtained at 1200 deg.C2O3The powder has good dispersibility.
4) Elemental analysis was performed on the sapphire grade high purity alumina prepared in examples 1-4, and the elemental analysis results are shown in table 1:
TABLE 1 elemental analysis results for sapphire grade high purity alumina
Claims (5)
1. A method for preparing sapphire grade high-purity alumina by using aluminum material anodic oxidation waste liquid is characterized by comprising the following steps: the method comprises the following steps:
1) pretreatment of waste anodic oxidation liquid of aluminum material
Ca in the waste liquid of anodic oxidation of aluminum material2+、Fe2+、Mg2+、Si4+Removing to obtain a pretreatment solution; wherein the impurity Fe in the waste liquid of aluminum anodic oxidation is removed by activated carbon2+Removing Mg impurity by using cation exchange resin D0012+Removing Ca impurity with hydrofluoric acid2+And Si4+；
2) Preparation of crude aluminum ammonium sulfate
Adjusting the pH value of the pretreatment solution to 1.5-3.0 by using ammonia water, cooling to-20-5 ℃ to precipitate crystals, and performing solid-liquid separation to obtain a crude product of aluminum ammonium sulfate;
3) recrystallization purification of aluminum ammonium sulfate
Recrystallizing the crude product of the aluminum ammonium sulfate obtained in the step 2): the recrystallization treatment comprises the following steps: adding the crude product of aluminum ammonium sulfate into water, heating to 50-70 ℃ to completely dissolve the aluminum ammonium sulfate, adding a shielding agent, uniformly mixing, carrying out hot filtration to obtain a filtrate, cooling the filtrate to-20-5 ℃ to separate out a solid, carrying out solid-liquid separation, and washing with a solvent to obtain a first recrystallized fine product of aluminum ammonium sulfate; repeating the recrystallization treatment process for N times on the first recrystallized fine aluminum ammonium sulfate product to obtain an (N +1) th recrystallized fine aluminum ammonium sulfate product;
4) thermally decomposing the (N +1) th recrystallized ammonium aluminum sulfate fine product to prepare sapphire grade high-purity alumina; the thermal decomposition comprises the following steps: heating from room temperature to 250 deg.C at 2 deg.C/min; then the temperature is raised from 250 ℃ to 550 ℃ at the speed of 5 ℃/min; preserving the heat for 30 min; then raising the temperature from 550 ℃ to 900 ℃ at a speed of 5 ℃/min; preserving the heat for 2 hours; heating to 1200-1300 ℃ at the speed of 5 ℃/min, and preserving the heat for 2 h.
2. The method for preparing sapphire grade high-purity aluminum oxide by using aluminum material anodic oxidation waste liquid according to claim 1, wherein the shielding agent in the step 3) is citric acid, and the dosage of the shielding agent per liter of waste liquid is 0.3-0.6 g.
3. The method for preparing the sapphire grade high-purity aluminum oxide by using the aluminum material anodic oxidation waste liquid as claimed in claim 1, wherein the washing with the solvent in the step 3) is washing with water and then washing with ethanol.
4. The method for preparing the sapphire grade high-purity aluminum oxide by using the aluminum material anodic oxidation waste liquid according to claim 1, wherein N in the step 3) is 1, 2 or 3.
5. The method for preparing the sapphire grade high-purity aluminum oxide by using the aluminum material anodic oxidation waste liquid according to claim 1, which is characterized by comprising the following steps of: the temperature of the filtering device used in the hot filtering process is 50-70 ℃.
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| CN102795722A (en) * | 2012-08-15 | 2012-11-28 | 张宏智 | Method for treating waste water generated from surface treatment of aluminum products |
| 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 |
| CN104591245A (en) * | 2014-12-23 | 2015-05-06 | 贵州师范大学 | Method for extracting high-purity alumina by adsorbing impurities with activated carbon |
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| CN102795722A (en) * | 2012-08-15 | 2012-11-28 | 张宏智 | Method for treating waste water generated from surface treatment of aluminum products |
| 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 |
| CN104591245A (en) * | 2014-12-23 | 2015-05-06 | 贵州师范大学 | Method for extracting high-purity alumina by adsorbing impurities with activated carbon |
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