CN108178174A - A kind of method that sapphire grade high purity aluminium oxide is prepared using anodic oxidation of aluminiun materials waste liquid - Google Patents
A kind of method that sapphire grade high purity aluminium oxide is prepared using anodic oxidation of aluminiun materials waste liquid Download PDFInfo
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- CN108178174A CN108178174A CN201611125207.7A CN201611125207A CN108178174A CN 108178174 A CN108178174 A CN 108178174A CN 201611125207 A CN201611125207 A CN 201611125207A CN 108178174 A CN108178174 A CN 108178174A
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- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
- C01F7/30—Preparation of aluminium oxide or hydroxide by thermal decomposition or by hydrolysis or oxidation of aluminium compounds
- C01F7/32—Thermal decomposition of sulfates including complex sulfates, e.g. alums
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Abstract
The present invention relates to anodic oxidation of aluminiun materials devil liquor recoveries to utilize field, and in particular to the method that sapphire grade high purity aluminium oxide is prepared using anodic oxidation of aluminiun materials waste liquid.The present invention is using anodic oxidation of aluminiun materials waste liquid as raw material, the foreign ion removed in anodic oxidation of aluminiun materials waste liquid is pre-processed by waste liquid first, then it is 1.5~3.0 to adjust pH by ammonium hydroxide, prepare alum crude product, alum is further purified by repeated recrystallize again, sapphire grade high purity aluminium oxide can be made finally by sintering.The preparation method of the present invention is cheap with raw material, simple for process, and turns waste into wealth, and meets the theory of " environmentally protective " and " sustainable development " that country advocates energetically, and large-scale use has preferable social benefit.
Description
Technical field
The present invention relates to anodic oxidation of aluminiun materials devil liquor recoveries to utilize field, and in particular to utilizes anodic oxidation of aluminiun materials waste liquid system
The method of standby sapphire grade high purity aluminium oxide.
Background technology
With the high speed development of industry, application of the aluminium section bar in industrial production, building and civil use material is more and more extensive.
There is a procedure to be referred to as anodization in aluminium section bar production.Pickling is needed before anodization, is exactly the corrosiveness using acid solution
Derust, depending on its corrosion degree using the dipping cleaning of sulfuric acid liquid to surface smooth pieces, the maceration extract use after a certain period of time into
It is replaced for waste liquid, waste liquid and clear water dual disposal form pickling waste waters containing aluminium.In aluminium section bar used, about 65%
Will pass through surface treatment, and building industry, aerospace industry, automobile industry al member and part, Ji Huquan
Portion will pass through anodized or coating treatment.The existing nearly hundred anodic oxidation production lines of aluminum fabrication industry in China, can generate
A large amount of waste liquid and waste water, average often production 1t aluminium section bars generate 0.05t waste water, and the aluminum content in waste water per ton reaches
20kg.The waste liquid majority factory of generation is all unprocessed and discharges, and not only polluted environment, also wastes bauxite resource, therefore contains
How high added value recycling is a very important research to aluminium waste water.
Sapphire is α-Al2O3Monocrystalline, also known as " corundum " have unique physics, chemistry, optical electron and mechanical property,
For a kind of important technology crystal, it has been widely used in science and technology, national defence and civilian industry and telecommunications field at present,
The particularly optimal substrate material such as LED light emitting diodes, large scale integrated circuit SOI, SOS and superconducting nano structural membrane
Material.Sapphire may further be used to manufacture other active equipments, to being used for luminescent crystal Al other than it can be used as base material2O3
The many new applications of sapphire have been expanded in the research of itself or impurity defect.As countries in the world are to sapphire growth Technique Popularizing
The attention of application, large scale, the demand of sapphire crystal of high quality increase rapidly, promote the research and growth of sapphire crystal
As most one of industry of development vitality at present.
Raw material for growing sapphire monocrystalline is the Highly pure alumina micro-powder of purity >=99.995%, as sapphire needs
The amount of asking it is growing day by day, the market prospects of high purity aluminium oxide will be very extensive.Existing high purity alumina powder technology of preparing master
There are alkoxide hydrolysis, Al (OH)3Sintering process, AlCl3Gas phase synthesis method, sol-gal process, improvement Bayer process, alum heat
Solution etc., wherein alkoxide hydrolysis product purity are high, but complicated for operation, and the time of required consumption is long, are hardly formed and criticize
Measure production scale；Al(OH)3Sintering process is although simple for process, but it is difficult to clean；AlCl3Gas phase synthesis method product particle size is uniform,
Grain is tiny, and reaction process is pollution-free, but reaction condition requirement is harsh, needs professional equipment, and production cost is high；Sol-gal process raw material
It derives from a wealth of sources, low production cost, no exhaust emission, but during gel is formed by colloidal sol, technological parameter is difficult to control；Change
Good Bayer process can generate high-purity alpha-alumina powder, but production process is complicated, and required condition is harsh in industry；Alum heat
Solution is one of main method for producing high purity alumina powder, and technology maturation is easy to operate, and product purity is high, but is produced
Cost is higher, and the production cycle is long.At present, there are no prepare sapphire grade high-purity powder method using anodic oxidation of aluminiun materials waste liquid
Relevant report.
Invention content
The object of the present invention is to provide a kind of sides that sapphire grade high purity aluminium oxide is prepared using anodic oxidation of aluminiun materials waste liquid
Method, this method are raw material using anodic oxidation of aluminiun materials waste liquid, turn waste into wealth, reduce the production cost of aluminium oxide, are had good
Economic benefit.
To achieve these goals, the technical scheme is that：
A kind of method that sapphire grade high purity aluminium oxide is prepared using anodic oxidation of aluminiun materials waste liquid, is included the following steps：
1) anodic oxidation of aluminiun materials waste liquid pre-processes
By the Ca in anodic oxidation of aluminiun materials waste liquid2+、Fe2+、Mg2+、Si4+It removes, obtains pretreatment fluid；
2) alum crude product is prepared
The pH to 1.5~3.0 of pretreatment fluid is adjusted with ammonium hydroxide, is cooled to -20~5 DEG C of precipitation crystal, separation of solid and liquid obtains sulphur
Sour aluminium ammonium crude product；
3) purifying aluminum ammonium sulfate is recrystallized
The obtained alum crude product of step 2) is subjected to recrystallization processing：The recrystallization processing includes：By sulfuric acid
Aluminium ammonium crude product is added to the water, and being heated to 50~70 DEG C is completely dissolved alum, adds in screener and is uniformly mixed, heat filtering obtains
Filtrate, filtrate are cooled to -20~5 DEG C of precipitation solids, separation of solid and liquid, and solvent washs to obtain recrystallization alum fine work for the first time
Above-mentioned recrystallization processing procedure n times are repeated, obtain (N+1) secondary recrystallization alum fine work；
4) (N+1) secondary recrystallization alum fine work thermal decomposition is prepared into sapphire grade high purity aluminium oxide.
Aluminium oxide prepared by the present invention is configured as α-Al2O3, i.e. sapphire configuration reaches sapphire rank in purity.
Ammonium hydroxide is added in into pretreatment fluid, can be generated ammonium sulfate with the sulfuric acid in neutralization pretreatment liquid, further generate sulphur
Sour aluminium ammonium.The pH of solution is adjusted to 1.5~3.0, Al (OH) can be precipitated to avoid alum aqueous hydrolysis3。
Anodic oxidation of aluminiun materials waste liquid removes impurity F e with activated carbon2+, impurity Mg is removed with D001 ion exchange resins2+；With hydrogen fluorine
Acid removes impurity Ca2+And Si4+After obtain.
Determine first in anodic oxidation of aluminiun materials waste liquid other than sulfate radical and aluminium ion the type of other contained ions and from
Sub- concentration selects corresponding removal of impurities mode to clean, obtains anodic oxidation of aluminiun materials waste liquid according to the type of ion and concentration
Pretreatment fluid.The present invention choose certain aluminium section bar production process in anodic oxidation waste liquid, by detection understand waste liquid it is main into
Part is Al2(SO4)2And H2SO4, the content of aluminium is 0.58%, and impurity content is respectively Ca2+：3.4ppm, Fe2+：6.4ppm, Mg2+：
1.0ppm, Na+：2.8ppm, Si4+:1.4ppm.The activated carbon of 5.0~15.0g/L is added in into waste liquid, 10~60min of stirring is gone
Except impurity Fe2+；The D001 ion exchange resins of 0.4~0.8g/L are subsequently added into, stir 30~50min, remove Mg2+Impurity；Again to every
1.0~10mL hydrofluoric acid is added in 100mL anodic oxidation waste liquids, the control reaction time is 50~60min, removes impurity Ca2+With
Si4+Ion obtains the pretreatment fluid of anodic oxidation of aluminiun materials waste liquid after removal of impurities.
Anodic oxidation of aluminiun materials waste liquid pretreatment further preferred embodiment be：The activity of 10.0g/L is added in into waste liquid
Charcoal, mixing time 30min；It is subsequently added into the D001 ion exchange resins of 0.6g/L, reaction time 40min；Again to every 100mL anodic oxygens
Change and 6mL hydrofluoric acid is added in waste liquid, reaction time 50min, the pretreatment fluid of treated anodic oxidation of aluminiun materials waste liquid.
Screener described in step 3) is citric acid, and dosage needs 0.3~0.6g citric acids for every liter of waste liquid, further excellent
It selects in scheme, the dosage of screener is every liter of waste liquid 0.5g.Its effect is：Insoluble network is formed with the foreign ion in solution
Object is closed, the impurity in alum crude product can be further removed by heat filtering.
Described washed with solvent of step 3) is to be washed after being first washed with water with ethyl alcohol, and alum can be drawn by being washed with water
The impurity for being dissolved in water in crystallization, then ethyl alcohol cleaning can remove the impurity for being dissolved in ethyl alcohol, and the volatility of ethyl alcohol and boiling
Point is lower than water, and ethyl alcohol can be miscible with water, and the product after being recrystallized after being cleaned with ethyl alcohol is easily dried.
In order to obtain high-purity alum fine work, knot operation again can be carried out repeatedly to alum, step 3) is preferred
The number of recrystallization be N be 1,2 or 3.
Filter device is heated during heat filtering, it is possible to reduce filtered when hot aluminum ammonium sulfate solution is dashed forward to the cold
It being precipitated on device, the filtering mouth of blocking filtering device, the temperature of filter device used in the heat filtering process is preferably 50~
70℃。
Step 4) the thermal decomposition includes the following steps：With 2 DEG C/min from room temperature to 250 DEG C；Again with 5 DEG C/min from
250 DEG C are warming up to 550 DEG C；30min is kept the temperature at 550 DEG C；Again 900 DEG C are warming up to from 550 DEG C with 5 DEG C/min；In 900 DEG C of heat preservations
2h；1200 DEG C~1300 DEG C are warming up to 5 DEG C/min, keep the temperature 2h, be down to room temperature to obtain the final product.
Compared with prior art, the present invention it the advantage is that：
(1) the raw materials used in the present invention is anodic oxidation of aluminiun materials waste liquid and ammonium hydroxide, and one side ammonium hydroxide raw material is simple, adds in ammonium hydroxide
The spent acid in waste liquid is eliminated, on the other hand industrial aluminum waste liquid is turned waste into wealth, reduces production cost, there is good economy
Benefit.
(2) present invention prepares alum using anodic oxidation of aluminiun materials waste liquid, through repeated recrystallize purifying aluminum ammonium sulfate, sulphur
The purity of sour aluminium ammonium is up to 99.995%, can so that high-temperature calcination prepare sapphire grade high purity aluminium oxide, entire technological process letter
Single, repeatability is strong, and production process pollution is small, and less energy consumption has preferable social effect, it can be achieved that large-scale production.
(3) characteristics such as economical, functional and environment compatibility of process of the invention meet country's promotion
" environmentally protective " and the theory of " sustainable development ", by process modification, improves production efficiency, at entire aluminium industry sewage
The development of reason plays a role.
Description of the drawings
Fig. 1 is the XRD spectrum of alum crude product obtained under condition of different pH in embodiment 1-4, and wherein a is embodiment
4, pH=1.5；B is embodiment 3, pH=2.0；C is embodiment 2, pH=2.5；D is embodiment 4, pH=3.0；
Fig. 2 is the XRD diagram of the aluminium oxide of embodiment 1-2 and the preparation in comparative example 1-2；
The SEM that Fig. 3 is embodiment 1-2 schemes；Wherein a is that the SEM of embodiment 1 schemes, and b is that the SEM of embodiment 2 schemes.
Specific embodiment
To make the object, technical solutions and advantages of the present invention clearer, embodiment of the present invention will be made into one below
Step ground detailed description.
Embodiment 1
A kind of method that sapphire grade high purity aluminium oxide is prepared using anodic oxidation of aluminiun materials waste liquid is present embodiments provided, is had
Body step is as follows：
1) anodic oxidation of aluminiun materials waste liquid pre-processes
The anodic oxidation of aluminiun materials waste liquid in certain aluminium section bar production process is taken, the main ingredient for understanding waste liquid by detection is
Al2(SO4)2And H2SO4, the content of aluminium is 0.58wt%, and impurity content is respectively Ca2+：3.4ppm, Fe2+：6.4ppm, Mg2+：
1.0ppm, Na+：2.8ppm, Si4+:1.4ppm；
By taking 1L waste liquids as an example, 10g activated carbon stirring 30min is added in into waste liquid, by filtering removal adsorbing contaminant Fe2+
Activated carbon；Then 0.6gD001 ion exchange resins are added in, stir 40min, ion exchange resin and Mg ions are removed by suction filtration
The complex compound of formation；60ml hydrofluoric acid (a concentration of 400g/L) is added, 50min is reacted, is filtered to remove CaF2Insoluble matters are waited, are obtained
To pretreatment fluid；
2) alum crude product is prepared
With ammonium hydroxide regulating step 1) in the obtained pH of pretreatment fluid to 3.0, be cooled to -10 DEG C of precipitation crystal, filtering obtains
To alum crude product；
The mass fraction of ammonium hydroxide used in this step is 25%~28%；
3) purifying aluminum ammonium sulfate is recrystallized
The obtained alum crude product of step 2) is subjected to recrystallization processing：The recrystallization processing procedure is by sulfuric acid
Aluminium ammonium crude product is added to the water, and being heated to 60 DEG C is completely dissolved alum, adds in 0.5g citric acid screeners and stirs evenly, adds
For hot heat filtering device to 60 DEG C, heat filtering obtains filtrate, and filtrate is cooled to -5 DEG C of precipitation solids, and separation of solid and liquid is first washed with water, then
Wash to obtain recrystallization alum fine work for the first time with ethyl alcohol；
The above-mentioned recrystallization processing procedure of repetition 2 times, obtains the 3rd recrystallization alum fine work, and purity may be up to
99.998%；
4) alum thermal decomposition prepares sapphire grade high purity aluminium oxide
The alum product for weighing the 3rd recrystallization of step 3) is put into crucible, and heat is carried out using following heating gradient
It decomposes：With 2 DEG C/min from room temperature to 250 DEG C；Again 550 DEG C are warming up to from 250 DEG C with 5 DEG C/min；30min is kept the temperature at 550 DEG C；Again
With 5 DEG C/min 900 DEG C are warming up to from 550 DEG C；2h is kept the temperature at 900 DEG C；1200 DEG C are warming up to 5 DEG C/min, 2h is kept the temperature, is down to room
Temperature is up to sapphire grade high purity aluminium oxide, and purity is up to 99.997%.
Embodiment 2
A kind of method that sapphire grade high purity aluminium oxide is prepared using anodic oxidation of aluminiun materials waste liquid is present embodiments provided, is had
Body step is as follows：
1) anodic oxidation of aluminiun materials waste liquid pre-processes
The anodic oxidation of aluminiun materials waste liquid in certain aluminium section bar production process is taken, the main ingredient for understanding waste liquid by detection is
Al2(SO4)2And H2SO4, the content of aluminium is 0.58%, and impurity content is respectively Ca2+：3.4ppm, Fe2+：6.4ppm, Mg2+：
1.0ppm, Na+：2.8ppm, Si4+:1.4ppm；
By taking 1L waste liquids as an example, 12g activated carbon stirring 30min is added in into waste liquid, by filtering removal adsorbing contaminant Fe2+
Activated carbon；Then 0.8gD001 ion exchange resins are added in, stir 50min, ion exchange resin and Mg ions are removed by suction filtration
The complex compound of formation；80ml hydrofluoric acid (a concentration of 400g/L) is added, 50min is reacted, is filtered to remove CaF2Insoluble matters are waited, are obtained
To pretreatment fluid；
2) alum crude product is prepared
With ammonium hydroxide regulating step 1) in the obtained pH of pretreatment fluid to 2.5, be cooled to 0 DEG C of precipitation crystal, filtering obtains
Alum crude product；
The mass fraction of ammonium hydroxide used in this step is 25%~28%；
3) purifying aluminum ammonium sulfate is recrystallized
The obtained alum crude product of step 2) is subjected to recrystallization processing：The recrystallization processing procedure is by sulfuric acid
Aluminium ammonium crude product is added to the water, and being heated to 50 DEG C is completely dissolved alum, adds in 0.6g citric acid screeners and stirs evenly, adds
For hot heat filtering device to 70 DEG C, heat filtering obtains filtrate, and filtrate is cooled to 0 DEG C of precipitation solid, and separation of solid and liquid is first washed with water, then
Wash to obtain recrystallization alum fine work for the first time with ethyl alcohol；
The above-mentioned recrystallization processing procedure of repetition 3 times, obtains the 4th recrystallization alum fine work, and purity may be up to
99.998%；
4) alum thermal decomposition prepares sapphire grade high purity aluminium oxide
The alum product for weighing step 3) the 4th recrystallization is put into crucible, and heat is carried out using following heating gradient
It decomposes：With 2 DEG C/min from room temperature to 250 DEG C；Again 550 DEG C are warming up to from 250 DEG C with 5 DEG C/min；30min is kept the temperature at 550 DEG C；Again
With 5 DEG C/min 900 DEG C are warming up to from 550 DEG C；2h is kept the temperature at 900 DEG C；1300 DEG C are warming up to 5 DEG C/min, 2h is kept the temperature, is down to room
Temperature is up to sapphire grade high purity aluminium oxide, and purity is up to 99.997%.
Embodiment 3
A kind of method that sapphire grade high purity aluminium oxide is prepared using anodic oxidation of aluminiun materials waste liquid is present embodiments provided, is had
Body step is as follows：
1) anodic oxidation of aluminiun materials waste liquid pre-processes
The anodic oxidation of aluminiun materials waste liquid in certain aluminium section bar production process is taken, the main ingredient for understanding waste liquid by detection is
Al2(SO4)2And H2SO4, the content of aluminium is 0.58%, and impurity content is respectively Ca2+：3.4ppm, Fe2+：6.4ppm, Mg2+：
1.0ppm, Na+：2.8ppm, Si4+:1.4ppm；
By taking 1L waste liquids as an example, 5g activated carbon stirring 10min is added in into waste liquid, by filtering removal adsorbing contaminant Fe2+
Activated carbon；Then 0.4gD001 ion exchange resins are added in, stir 50min, ion exchange resin and Mg ions are removed by suction filtration
The complex compound of formation；100ml hydrofluoric acid (a concentration of 400g/L) is added, 60min is reacted, is filtered to remove CaF2Wait insoluble matters,
Obtain pretreatment fluid；
2) alum crude product is prepared
With ammonium hydroxide regulating step 1) in the obtained pH of pretreatment fluid to 2.0, be cooled to 5 DEG C of precipitation crystal, filtering obtains
Alum crude product；
The mass fraction of ammonium hydroxide used in this step is 25%~28%；
3) purifying aluminum ammonium sulfate is recrystallized
The obtained alum crude product of step 2) is subjected to recrystallization processing：The recrystallization processing procedure is by sulfuric acid
Aluminium ammonium crude product is added to the water, and being heated to 60 DEG C is completely dissolved alum, adds in 0.3g citric acid screeners, stirs evenly,
Heat filtering device is heated to 70 DEG C, heat filtering obtains filtrate, and filtrate is cooled to -20 DEG C of precipitation solids, and separation of solid and liquid is first washed with water
It washs, then washs to obtain recrystallization alum fine work for the first time with ethyl alcohol；
The above-mentioned recrystallization processing procedure of repetition 1 time, obtains the 2nd recrystallization alum fine work, and purity may be up to
99.995%；
4) alum thermal decomposition prepares sapphire grade high purity aluminium oxide
The alum product for weighing the 2nd recrystallization of step 3) is put into crucible, and heat is carried out using following heating gradient
It decomposes：With 2 DEG C/min from room temperature to 250 DEG C；Again 550 DEG C are warming up to from 250 DEG C with 5 DEG C/min；30min is kept the temperature at 550 DEG C；Again
With 5 DEG C/min 900 DEG C are warming up to from 550 DEG C；2h is kept the temperature at 900 DEG C；1200 DEG C are warming up to 5 DEG C/min, 2h is kept the temperature, is down to room
Temperature is up to sapphire grade high purity aluminium oxide, and purity is up to 99.993%.
Embodiment 4
A kind of method that sapphire grade high purity aluminium oxide is prepared using anodic oxidation of aluminiun materials waste liquid is present embodiments provided, is had
Body step is as follows：
1) anodic oxidation of aluminiun materials waste liquid pre-processes
The anodic oxidation of aluminiun materials waste liquid in certain aluminium section bar production process is taken, the main ingredient for understanding waste liquid by detection is
Al2(SO4)2And H2SO4, the content of aluminium is 0.58%, and impurity content is respectively Ca2+：3.4ppm, Fe2+：6.4ppm, Mg2+：
1.0ppm, Na+：2.8ppm, Si4+:1.4ppm；
By taking 1L waste liquids as an example, 15g activated carbon stirring 60min is added in into waste liquid, by filtering removal adsorbing contaminant Fe2+
Activated carbon；Then 0.8gD001 ion exchange resins are added in, stir 50min, ion exchange resin and Mg ions are removed by suction filtration
The complex compound of formation；10ml hydrofluoric acid (a concentration of 400g/L) is added, 55min is reacted, is filtered to remove CaF2Insoluble matters are waited, are obtained
To pretreatment fluid；
2) alum crude product is prepared
With ammonium hydroxide regulating step 1) in the obtained pH of pretreatment fluid to 1.5, be cooled to -10 DEG C of precipitation crystal, filtering obtains
To alum crude product；
The mass fraction of ammonium hydroxide used in this step is 25%~28%；
3) purifying aluminum ammonium sulfate is recrystallized
The obtained alum crude product of step 2) is subjected to recrystallization processing：The recrystallization processing procedure is by sulfuric acid
Aluminium ammonium crude product is added to the water, and being heated to 60 DEG C is completely dissolved alum, adds in screener citric acid 0.4g/L and stirs evenly,
Heat filtering device is heated to 60 DEG C, heat filtering obtains filtrate, and filtrate is cooled to -5 DEG C of precipitation solids, and separation of solid and liquid is first washed with water,
It is washed to obtain the 1st recrystallization alum fine work with ethyl alcohol again；
The above-mentioned recrystallization processing procedure of repetition 2 times, obtains the 3rd recrystallization alum fine work, and purity may be up to
99.996%；
4) alum thermal decomposition prepares sapphire grade high purity aluminium oxide
The alum product for weighing the 3rd recrystallization of step 3) is put into crucible, and heat is carried out using following heating gradient
It decomposes：With 2 DEG C/min from room temperature to 250 DEG C；Again 550 DEG C are warming up to from 250 DEG C with 5 DEG C/min；30min is kept the temperature at 550 DEG C；Again
With 5 DEG C/min 900 DEG C are warming up to from 550 DEG C；2h is kept the temperature at 900 DEG C；1300 DEG C are warming up to 5 DEG C/min, 2h is kept the temperature, is down to room
Temperature is up to sapphire grade high purity aluminium oxide, and purity is up to 99.996%.
Comparative example 1
This comparative example is identical with the method for embodiment 1, and difference lies in step 4) differences, specially weigh step 3) the 2nd
The alum product of secondary recrystallization is put into crucible, is thermally decomposed using following heating gradient：With 2 DEG C/min from room temperature to
250℃；Again 550 DEG C are warming up to from 250 DEG C with 5 DEG C/min；30min is kept the temperature at 550 DEG C；It is warming up to again with 5 DEG C/min from 550 DEG C
900℃；2h is kept the temperature at 900 DEG C；1000 DEG C are warming up to 5 DEG C/min, keeps the temperature 2h.
Comparative example 2
This comparative example is identical with the method for embodiment 2, and difference lies in step 4) differences, specially weigh step 3) the 2nd
The alum product of secondary recrystallization is put into crucible, is thermally decomposed using following heating gradient：With 2 DEG C/min from room temperature to
250℃；Again 550 DEG C are warming up to from 250 DEG C with 5 DEG C/min；30min is kept the temperature at 550 DEG C；It is warming up to again with 5 DEG C/min from 550 DEG C
900℃；2h is kept the temperature at 900 DEG C；1100 DEG C are warming up to 5 DEG C/min, keeps the temperature 2h.
Test example
1) the embodiment 1-4 alums prepared are analyzed with XRD, the results are shown in Figure 1, can from Fig. 1
Go out, the structure of ten sulfate dihydrate aluminium ammoniums prepared by embodiment 1-4 is identical, and as pH=3.0, crystallization effect is preferable.
2) the embodiment 1-2 and comparative example 1-2 aluminium oxide prepared is analyzed with XRD, the results are shown in Figure 2,
Figure it is seen that comparative example 1-2 is different from the crystalline form of the aluminium oxide of embodiment 1-2, only forged in 1200 DEG C or more high temperature
It burns, α-Al could be obtained2O3Powder.
3) the sapphire grade high purity aluminium oxide that embodiment 1 and embodiment 2 obtain is analyzed with SEM figures, as a result such as Fig. 3
Shown, the alumina particle that as can be seen from the figure prepared by embodiment 1 and embodiment 2 is uniform, but the crystallite dimension at 1300 DEG C
Increase, exacerbates α-Al2O3Reunion, the α-Al obtained at 1200 DEG C2O3Powder dispersity is good.
4) elemental analysis, elemental analysis result such as table 1 have been carried out to the embodiment 1-4 sapphire grade high purity aluminium oxides prepared
It is shown：
1 sapphire grade high purity aluminium oxide elemental analysis result of table
Claims (7)
- A kind of 1. method that sapphire grade high purity aluminium oxide is prepared using anodic oxidation of aluminiun materials waste liquid, it is characterised in that：Including such as Lower step：1) anodic oxidation of aluminiun materials waste liquid pre-processesBy the Ca in anodic oxidation of aluminiun materials waste liquid2+、Fe2+、Mg2+、Si4+It removes, obtains pretreatment fluid；2) alum crude product is preparedThe pH to 1.5~3.0 of pretreatment fluid is adjusted with ammonium hydroxide, is cooled to -20~5 DEG C of precipitation crystal, separation of solid and liquid obtains aluminum sulfate Ammonium crude product；3) purifying aluminum ammonium sulfate is recrystallizedThe obtained alum crude product of step 2) is subjected to recrystallization processing：The recrystallization processing includes：By alum Crude product is added to the water, and being heated to 50~70 DEG C is completely dissolved alum, adds in screener and is uniformly mixed, heat filtering must be filtered Liquid, filtrate are cooled to -20~5 DEG C of precipitation solids, and separation of solid and liquid washs to obtain recrystallization alum essence for the first time with solvent Product；First time recrystallization alum fine work is repeated into above-mentioned recrystallization processing procedure n times, obtains (N+1) secondary recrystallization sulphur Sour aluminium ammonium fine work；4) sapphire grade high purity aluminium oxide is made in (N+1) secondary recrystallization alum fine work thermal decomposition.
- 2. the method for sapphire grade high purity aluminium oxide is prepared using anodic oxidation of aluminiun materials waste liquid according to claim 1, it is special Sign is that anodic oxidation of aluminiun materials waste liquid removes impurity F e with activated carbon2+, impurity is removed with the cation exchange resin of D001 models Mg2+；Impurity Ca is removed with hydrofluoric acid2+And Si4+。
- 3. the method for sapphire grade high purity aluminium oxide is prepared using anodic oxidation of aluminiun materials waste liquid according to claim 1, it is special Sign is that the screener described in step 3) is citric acid, and the dosage that every liter of waste liquid needs is 0.3~0.6g.
- 4. the method for sapphire grade high purity aluminium oxide is prepared using anodic oxidation of aluminiun materials waste liquid according to claim 1, it is special Sign is that described washed with solvent of step 3) is to be washed after being first washed with water with ethyl alcohol.
- 5. the method for sapphire grade high purity aluminium oxide is prepared using anodic oxidation of aluminiun materials waste liquid according to claim 1, it is special Sign is that the N described in step 3) is 1,2 or 3.
- 6. the method for sapphire grade high purity aluminium oxide is prepared using anodic oxidation of aluminiun materials waste liquid according to claim 1, it is special Sign is：The temperature of filter device used in the heat filtering process is 50~70 DEG C.
- 7. the method for sapphire grade high purity aluminium oxide is prepared using anodic oxidation of aluminiun materials waste liquid according to claim 1, it is special Sign is that the step 4) thermal decomposition includes the following steps：With 2 DEG C/min from room temperature to 250 DEG C；Again with 5 DEG C/min from 250 DEG C are warming up to 550 DEG C；Keep the temperature 30min；Again 900 DEG C are warming up to from 550 DEG C with 5 DEG C/min；Keep the temperature 2h；It is heated up with 5 DEG C/min To 1200 DEG C~1300, heat preservation 2h to get.
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