CN104760979B - A kind of preparation technology of high-purity alumina powder - Google Patents
A kind of preparation technology of high-purity alumina powder Download PDFInfo
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Abstract
The invention discloses the preparation technology of a kind of high-purity alumina powder, with industrial sodium aluminate solution as raw material, or with the molten sodium aluminate solution being deployed into of industrial aluminium hydroxide alkali as raw material, purified by solution two-stage nitration, it is thus achieved that fine aluminium acid sodium solution；In fine aluminium acid sodium solution, add crystal seed initiator and sodium separates out inhibitor, prepare seed slurry；Adding sodium in fine aluminium acid sodium solution and separate out inhibitor and other impurity inhibitor, add seed slurry, high temperature is sowed point, obtains pure cerium hydroxide aluminum；Pure cerium hydroxide aluminum high-temperature calcination, shrend, washing, obtain high-purity alumina powder, product purity>99.99%, mean diameter<10 μm, pure α Al2O3Phase.Solution purification slag, seed precipitation solution, washing liquid enter Bayer process system.The present invention can low cost, high efficiency, environmentally friendly prepare high-purity alumina powder.
Description
Technical field
The invention belongs to metallurgy of aluminium technical field, be specifically related to the preparation technology of a kind of high-purity alumina powder.
Background technology
High-purity alumina powder is of many uses, price is high, dimensions of market is relatively large, and various countries use different production technologies competitively
Produce.At present, have by the high-purity alumina powder main production process of raw material classification:
(1) with rafifinal (aluminium powder) as raw material, react with water, or add Organic substance (such as choline) formation Organic substance, then water
Solving, the aluminium hydroxide of precipitation is through calcining to obtain high-purity alumina powder.The purity of the alumina powder that the method prepares depends on aluminum or aluminum
The purity of powder, reacts the factor being also to affect purity with water.Though such method technique is simple, but there is process control
Difference, product purity are difficult to ensure card, high in cost of production shortcoming.
(2) with aluminium salt (such as aluminum sulfate, aluminum chloride, aluminum nitrate) as raw material, by solution purification or repeatedly crystallize, it is thus achieved that pure
Solution, then adds alkali (such as ammonia, sodium hydroxide etc.) and neutralizes, separate out aluminium hydroxide, calcine to obtain pure zirconia aluminium powder.Such method is produced
Product purity is easy to control, but flow process compared with long, cost of material is high, waste residue and waste water is many, advantage of lower cost.
(3) with industrial aluminium hydroxide as raw material, by sulphuric acid or dissolving with hydrochloric acid, aluminum sulfate, liquor alumini chloridi are prepared, then
Solution purification or multiple steps of crystallization, it is thus achieved that pure solution, add ammonia, multiple steps of crystallization, obtains Burnt ammonium alum, or is converted into aluminium carbonate
Ammonium, then thermally decompose, obtain high-purity alumina powder.Such method is industrial main method, and product purity is controlled, but during
Waste residue, waste water and waste gas are many, and environmental pollution is serious.
(4) with aluminium alcoholates as raw material, pass through more purification, it is thus achieved that pure aluminium alcoholates, then hydrolyze to obtain aluminium hydroxide, calcine to obtain high pure oxygen
Changing aluminium powder, the method product purity is high, quality controllable, but long flow path, cost are high.(5) with Alumina Enterprise sodium aluminate solution it is
Raw material, desiliconization purified solution, then low concentration solution carbon is got aluminium hydroxide, is changed thing mutually for after boehmite, roasting
Wash with concentrated acid, obtain high-purity alumina powder (CN102602968A, CN201410110524.6), or get hydroxide by planting
Aluminum, then change thing mutually for boehmite removing sodium, wash to obtain high purity aluminium oxide (CN200410023998.3), or plant get hydrogen-oxygen
Change aluminum, acid dissolve, again alkali neutralize aluminium hydroxide, roasting obtain high purity aluminium oxide (US2013/0052124A).Such cost of material
Low, but solution purification flow process is simple, and in solution, impurity is many.In calcining, add additive, be easily introduced new impurity；Calcination product
Regrind, time concentrated acid processes again, the impurity entered in lattice is difficult to remove, thus product purity is low, and useless concentrated acid processes difficulty；Another
Aspect, during powder body grinds, pattern difficulty controls, and product applications is restricted.
Summary of the invention
The technical problem to be solved is that to there is cost for the existing technique preparing high-purity alumina powder high, dirty
The shortcomings such as dye is serious, production procedure is complicated, it is provided that the preparation technology of a kind of high-purity alumina powder, the present invention can low cost, efficiently
Rate, environmentally friendly prepare high-purity superfine alumina powder, meet current efficiently, economy, the requirement of environmental protection.
For solve above-mentioned technical problem, the present invention by the following technical solutions:
The present invention is with industrial sodium aluminate solution as raw material, or with industrial aluminium hydroxide as raw material, the molten dissolving of alkali is deployed into height
Concentration sodium aluminate solution；Based on ionic valence condition regulation and control and precipitation adsorption principle, carry out solution two-stage nitration purification, it is thus achieved that pure sodium aluminate solution
Liquid；Sodium aluminate solution is joined inversely preparation seed slurry in hydrogen peroxide (or sodium bicarbonate, aluminum sulfate) solution；At fine aluminium
Acid sodium solution adds sodium and separates out inhibitor and other impurity inhibitor, add seed slurry, at high temperature approximate homogeneous phase condition
Sow point, obtain pure cerium hydroxide aluminum；Then under the conditions of high-temperature calcination, volatilization removes impurity, high-temperature oxydation aluminium powder shrend, adds
Chelating agent washs, and obtains high-purity alumina powder, product purity > 99.99%.Solution purification slag, seed precipitation solution, washing liquid enter the Bayer genealogy of law
System.
A kind of preparation technology of high-purity alumina powder, step is as follows:
(1) one section of solution purification: with sodium aluminate solution as raw material, it is clean that addition oxidant and calcareous material carry out one section of solution
Change, desiliconization, except ferrum, except Organic substance, be subsequently adding flocculant and carry out settling, filtering；Add oxidant, make low valence metal ion oxygen
Chemical conversion high volence metal ion, beneficially generates the precipitation that dissolubility is little, granularity is superfine, oxidation operation becomes colourless having simultaneously
Machine thing or portions turn are carbanion；Add Calx or other calcareous material, make silicon dioxide in solution generate slaked lime
Garnet, calcium carbonate, and simultaneously as adsorbent, precipitation that the metal ion that in adsorbent solution, granularity is superfine generates, Organic substance；Again
Add flocculant, settle, filter；
(2) two-stage nitration solution purification: add precipitant in the solution after (1) one section of solution purification of step, at 40 ~ 70 DEG C
Under the conditions of, in solution, zinc, calcium, lead, antimony, lithium, magnesium etc. generate water-fast precipitation；It is subsequently adding segregative adsorbent, inhales
Enclose and state impurity, filter after standing, it is thus achieved that fine aluminium acid sodium solution, alkali concn 10 ~ 170g/L, Crater corrosion is 1.3 ~ 2.5；
(3) prepared by crystal seed: take the fine aluminium acid sodium solution that step (2) obtains, and is added thereto to crystal seed initiator and sodium separates out
Inhibitor, prepares seed slurry；Add sodium and separate out inhibitor, sodium aluminate solution is added in the solution containing initiator inversely,
Under the conditions of lower temperature, strong mixing, prepare active aluminium hydroxide seed slurry；
(4) solution kind is divided: take the fine aluminium acid sodium solution that step (2) obtains, and is added thereto to sodium and separates out inhibitor and metal
Elemental release inhibitor obtains seed liquor, seed slurry is poured in seed liquor, seed slurry and the ratio of seed liquor
Dissolved to be capable of most crystal seed, in the short time, solution is limpid, reaches to approximate homogeneous system and is as the criterion, controls crystal seed
Dissolution degree, starts when 70 ~ 90 DEG C kind point under conditions of approximation is homogeneous, plants point end temperature at 50 ~ 65 DEG C, plants between timesharing 24 ~ 46
Hour, resolution ratio, more than 20%, is planted point product and is obtained pure cerium hydroxide aluminum after fully washing；
(5) preparation of high-purity alumina powder:: pure cerium hydroxide aluminum is at the bar of 1100 ~ 1600 DEG C (preferably 1300 ~ 1400 DEG C)
Calcine 30 ~ 240min(under part and be preferably 60 ~ 90min), fully volatilize during calcining the impurity such as sodium, lithium, zinc, antimony, lead, reduces oxidation
Impurity in aluminum product, calcined oxide aluminium powder is cooled in 1000 DEG C, then adds chelating agent after shrend, washs to obtain pure α-Al2O3
The high-purity alumina powder of phase；
Wherein purification slag, seed precipitation solution and washing liquid enter Bayer process system.
Oxidant in described step (1) is at least one in hydrogen peroxide, sodium peroxide or sodium peroxydisulfate, and addition is
0.1~20g/L。
Flocculant in described step (1) is at least in the flocculant containing hydroximic acid or polyacrylamide flocculant
Kind, the weight concentration of described flocculant is 1 ‰, and addition is 1 ~ 5mL/L.
Precipitant in described step (2) is at least two in sodium phosphate, sodium fluoride, sodium sulfide, sodium carbonate or hexafluosilicic acid
Kind, wherein sodium sulfide addition 0.1 ~ 5g/L, sodium phosphate addition 0.1 ~ 5g/L, sodium fluoride addition is 0.1 ~ 10g/L, carbonic acid
Sodium addition 0.1 ~ 5g/L, hexafluosilicic acid addition is 0.1 ~ 10g/L.
Adsorbent in described step (2) is activated carbon, the flue dust of alumina roasting furnace or 400 ~ 800 DEG C of calcined aluminas
One or both mixture in powder, addition is 1 ~ 10g/L.
In described step (3), crystal seed initiator is at least one in hydrogen peroxide, sodium bicarbonate, aluminum sulfate or sulphuric acid, adds
Entering amount is 2 ~ 10g/L.
In described step (3) and step (4), sodium separates out inhibitor is a kind of or many in stearic acid, mannitol, beta-schardinger dextrin-
Planting mixture, addition is 0.05 ~ 1g/L, preferably 0.1 ~ 0.2g/L.
In described step (4) metal ion separate out inhibitor be citric acid, ethylenediaminetetraacetic acid, sodium ethylene diamine tetracetate or
One or more mixtures in tartaric acid, addition is 0.05 ~ 2g/L, preferably 0.5 ~ 1g/L.
Approximating homogeneous condition in described step (4) is: after seed slurry adds to seed liquor, most crystal seeds
Being dissolved, in the short time, solution is limpid, approximates homogeneous system, separates out aluminium hydroxide the most in a large number, enters a normal kind point state.
Described step (5) complexing agent is at least one in oxalic acid, ethylenediaminetetraacetic acid, citric acid or tartaric acid, adds
Entering amount is 0.01 ~ 5g/L, preferably 0.01 ~ 2g/L.
Washing in described step (5) is to wash in the dilute sulfuric acid of 0.1 ~ 10%, and dilute sulfuric acid concentration is preferably 0.5 ~ 5%.
Beneficial effects of the present invention: (1) present invention, with cheap Alumina Enterprise sodium aluminate solution as raw material, divides by planting
Producing high purity aluminium hydroxide, then calcining produces high purity aluminium oxide, and seed precipitation solution enters alumina producing flow process, and wash water enters oxidation
Aluminum laterite washing system, thus this technique non-environmental-pollution, have cost advantage simultaneously.Directly use industrial sodium aluminate solution,
Low cost；Waste residue or waste back-cycling alumina producing flow process in the most high-purity powder, constitute side line production technology, be to metallurgical grade oxygen
The high value changing aluminum production is supplemented.
(2) in the present invention, in concentrated base, solution purification is not only Calx desiliconization, removes silicon dioxide in solution, in addition it is also necessary to remove
Remove the various impurity in solution；Therefore hydroxide based on foreign ion or other insoluble compound dissolubility are little, and seldom
Amount precipitation can not generate the corase particles that can settle, easily filter separation, need to adsorb the principle on easily separated material, adds oxidant
And Calx, by Fe (OH) bigger for dissolubility2It is converted into Fe (OH)3, and utilize the impurity such as a large amount of desiliconization slag generated absorption ferrum,
Simultaneous oxidation removes partial organic substances, is allowed to be converted into the Organic substance of sodium carbonate or other small-molecular-weight；Add flocculant, formed
Floc sedimentation, removes impurity further, obtains one section of purified solution.Then in one section of purified solution, add precipitant, generate sulfuration
The indissoluble precipitations such as thing, phosphate, carbonate, fluoride, wherein remove in lithium, one section of scavenging solution of precipitation with composite form and remain
Calcium be the impurity-removing method of non-the normally off key, add adsorbent, adsorb above-mentioned contamination precipitation thing, be isolated by filtration removing impurity,
Obtain two-stage nitration purified solution.
(3) in concentrated base, metal ion precipitation is difficult to regulate and control, and the new surface of aluminum hydroxide that separates out can be high, easy to be adsorbed or coprecipitated
Separate out；Particularly sodium ion separates out, and has no the report that suppression separates out at present.On the other hand, traditional adds crystal seed, passes through out-phase
The mode kind of nucleation is divided, it is impossible to obtain Na2The O aluminium hydroxide less than 0.09%, the most homogeneous spontaneous nucleation, obtain under high concentration
In aluminium hydroxide, Na2O content is also greater than 0.15%, and therefore the present invention uses approximation homogeneous nucleation mode kind to divide, available Na2O contains
Measure the aluminium hydroxide about 0.04%.
(4), during high-temperature calcination aluminium hydroxide, sodium, lithium, zinc etc. are volatile, can remove partial impurities；Meanwhile, high temperature oxygen
Change aluminum, during shrend, occurs particle refinement process, beneficially impurity to remove；Again in washing process, add diluted acid, add
Chelating agent, is conducive to improving the dissolubility of impurity, improves the efficiency of washing impurity-removing.
(5) in all technique of the present invention, purification slag, seed precipitation solution and washing liquid all enter in alumina producing flow process, will not produce
Raw environmental pollution, will not dramatically increase cost, because above-mentioned purification slag, seed precipitation solution and washing liquid are all in alumina producing flow process
Necessary, can play a role in alumina producing flow process, bring benefits.
Figure of description
Fig. 1 is the process chart that the present invention prepares high-purity alumina powder.
Detailed description of the invention
Below, will in conjunction with specific embodiments, the present invention will be described further.
As it is shown in figure 1, sodium aluminate solution adds oxidant, at a low price after iron tramp reaction, generate the hydrogen-oxygen that dissolubility is less
Change ferrum etc.；The oxidable Organic substance of remaining oxidant, not only plays decolorization, and partial organic substances can be oxidized to carbonic acid
Sodium；Adding Calx, generate calcium aluminosilicate hydrate, both carried out desiliconization, de-carbon acid ion, newly-generated product again can be in adsorbent solution
Impurity；Add flocculant, generate floc sedimentation, be on the one hand conducive to filtering, be on the other hand conducive to remove impurity.Thus constitute one section
Solution purification technique.Add precipitant, in sodium aluminate solution generate zinc sulfide, calcium phosphate, calcium carbonate, vulcanized lead, lithium fluoride,
The insoluble compound such as lithium phosphate or lithium fluorosilicate, adds adsorbent, adsorbs above-mentioned insoluble compound, filters, it is achieved solution is deep
The purpose that degree purifies, thus constitute two-stage nitration solution purification technique, it is thus achieved that fine aluminium acid sodium solution.One section of purification slag is the most impure
Calcium aluminosilicate hydrate, two-stage nitration purification slag is salic, all can return to Bayer Process digestion system recycling.
Fine aluminium acid sodium solution is added inversely in the solution containing crystal seed initiator, and add sodium precipitation inhibitor, at height
Under conditions of speed stirring, prepare the seed slurry of aluminium hydroxide.In fine aluminium acid sodium solution, add sodium separate out inhibitor, metal
Elemental release inhibitor, adds seed slurry when 70-90 DEG C, and under high temperature, most seed crystal of aluminium hydroxide are dissolved, solution
Short time is more limpid, for approximation homogeneous system, then occurs aluminium hydroxide to separate out in a large number, enters kind of a point process.Controlling final temperature
When about 60 DEG C, terminating kind point, plant point serosity and take out, carry out solid-liquid separation, solid phase adds hot wash, to final washing liquid pH 8 ~
Between 9, obtain pure cerium hydroxide aluminium powder；
By the high-temperature calcination in high temperature furnace of pure cerium hydroxide aluminium powder, under high temperature, the impurity such as sodium, lithium, zinc, antimony is volatile, in removing
State partial impurities；Then, alumina powder shrend under high temperature, make particle refinement, make impurity the most exposed, it is simple to remove impurity further；?
Solution adds dilute sulfuric acid, adds chelating agent, washing, obtain high-purity alumina powder.
Embodiment 1
The preparation technology of the present embodiment high-purity alumina powder is as follows:
(1) one section of solution purification: dissolve industrial aluminium hydroxide with industrial sodium hydroxide, obtains alkali, aluminium oxide dense after dilution
Degree is respectively the sodium aluminate solution of 150g/L, 165g/L.In this sodium aluminate solution, the hydrogen peroxide of concentration 10% is added at 90 DEG C
10mL/L, reacts 30min；Then 10g/L quick lime, 90 DEG C of strong agitation 1h are added；Add 1 ‰ polypropylene of 5ml/L
Snf S. A. S. of amide flocculant KM800(France) and containing Qing Te company of the hydroximic acid Organic substance HX300(U.S.), take out after sedimentation 1h
Filter, obtains primary purification clear liquid；
(2) two-stage nitration solution purification: at 70 DEG C, adds 0.5g/L Na in primary purification clear liquid respectively2S、1g/L
Na3PO4, 2g/L NaF, after reaction 30min, be subsequently adding activated alumina and activated carbon powder 5g/L, 70 DEG C of stirring 2h, after terminating
Sucking filtration；Filtrate adds 15g/L macroanion resin mixing 20min, the most again sucking filtration, obtains fine aluminium acid sodium solution；
(3) prepared by crystal seed: above-mentioned fine aluminium acid solution 50mL, add pure water 150mL, at 40 DEG C be incubated, add mannitol and
Stearic acid mixture 0.03/L, is then slowly added dropwise 10% hydrogen peroxide 100mL, strong agitation 0.5h, obtains seed slurry；
(4) solution kind is divided: take fine aluminium acid sodium solution 600mL, adds pure water 200mL, adds manna and stearic acid at 80 DEG C
Mixture 0.02g/L, ethylenediaminetetraacetic acid and tartaric acid 0.05g/L obtain seed liquor, then it is former that seed slurry is poured into kind point
In liquid, starting to plant to divide under conditions of approximation is homogeneous, initial temperature is set as 80 DEG C, and final temperature is set as 65 DEG C, and kind point terminates for 24 hours
After, sucking filtration serosity, a large amount of pure water of solid product, last wash water pH is to terminate washing during 7-8, dries, obtains pure hydrogen
Alumina product, whole kind divides procedure decomposition rate to be about 51%；
(5) preparation of high-purity alumina powder: take the pure cerium hydroxide aluminum product 8g that above-mentioned warp is cleaned, dried, be placed in high pure oxygen
Change in aluminum crucible, chamber type electric resistance furnace calcined at 1600 DEG C 0.5h, after product is cooled to 1000 DEG C, add to normal-temperature water,
Carry out shrend；Again with mixed solution 100mL strong agitation washing 2h at 80 DEG C of 5% sulphuric acid with 1g/L citric acid, filter, Gu
Body redistilled water washs post-drying, obtains high-purity α-Al2O3Powder body, purity more than 99.99%, mean diameter 9.5 μm.
Embodiment 2
The preparation method of the high purity alumina powder of the present embodiment: the pure cerium hydroxide aluminum that Example 1 step (4) obtains produces
Product 8g, is placed in high purity aluminium oxide crucible, calcines 1h, after product is cooled to 1000 DEG C, add in chamber type electric resistance furnace at 1300 DEG C
Enter to normal-temperature water, carry out shrend；Exist with 1g/L ethylenediaminetetraacetic acid and tartaric mixed solution 100mL with 10% sulphuric acid again
At 100 DEG C, strong agitation washing 2h, filters, the redistilled water washing post-drying of solid heat, obtains high-purity α-Al2O3Powder body,
Purity more than 99.99%, mean diameter 8.2 μm.
Embodiment 3
The preparation technology of the present embodiment high-purity alumina powder is as follows:
(1) one section of solution purification: taking industry high-concentration sodium aluminate solution, alkali is (with Na2O count), alumina concentration be respectively
155g/L、180g/L.In this sodium aluminate solution, hydrogen peroxide 50mL and the 10g/L sodium peroxide of concentration 20% is added, instead at 90 DEG C
After answering 30min；10g/L quick lime, strong agitation 1h is added at 100 DEG C；Add the 1 ‰ polyacrylamide flocculations of 2ml/L
Agent and hydroxyl oximes flocculant HX600, sucking filtration after flocculating sedimentation 1h, obtain primary purification clear liquid；
(2) two-stage nitration solution purification: at 50 DEG C, adds 0.5g/L Na in above-mentioned primary purification liquid respectively2S、1g/L
Na3PO4, 2g/LNaF, process the flue dust 5g/L adding alumina roasting furnace after 10min, 50 DEG C of stirring 30min, take out after terminating
Filter；Under quantitative filter paper, it is encased inside macroanion resin the most again, again filters, obtain fine aluminium acid sodium solution；
(3) prepared by crystal seed: take above-mentioned fine aluminium acid sodium solution 50mL, adds pure water 100mL, is incubated at 25 DEG C, adds manna
Alcohol and beta-schardinger dextrin-0.5g/L, be then slowly added dropwise the NaHCO of concentration 50g/L3Solution 40mL, strong agitation 0.5h, obtain crystal seed
Serosity；
(4) solution kind is divided: take fine aluminium acid sodium solution 600mL, adds pure water 250mL, is incubated at 90 DEG C, add mannitol and
Beta-schardinger dextrin-0.5 g/L, citric acid and ethylenediaminetetraacetic acid 2g/L obtain seed liquor, pour seed slurry into seed liquor
In, starting to plant under conditions of approximation is homogeneous to divide, initial temperature is set as 90 DEG C, and final temperature is set as 65 DEG C, after kind point terminates for 46 hours,
Sucking filtration serosity, a large amount of pure water of solid product, last wash water pH is to terminate washing during 7-8, dries, obtains pure cerium hydroxide
Aluminum product, whole kind divides procedure decomposition rate to be about 55%；
(5) preparation of high-purity alumina powder: take the pure cerium hydroxide aluminum product 10g that above-mentioned warp is cleaned, dried, be placed in high pure oxygen
Change in aluminum crucible, chamber type electric resistance furnace is calcined at 1400 DEG C 1h, after product cooling, with 0.5% sulphuric acid and 1g/L ethylenediamine tetrem
The mixed solution 100mL of acid is strong agitation washing 3h at 50 DEG C, filters, the redistilled water washing post-drying of filter cake heat,
Obtain high-purity α-Al2O3Powder body, purity more than 99.99%, mean diameter about 4.6 μm.
Embodiment 4
The preparation method of the high purity alumina powder of the present embodiment: the pure cerium hydroxide that Example 3 step (4) prepares
Aluminum product 80g, is placed in high purity aluminium oxide crucible, calcines 2h in chamber type electric resistance furnace at 1300 DEG C, and product is cooled to 1000 DEG C
After, add to normal-temperature water, carry out shrend；With the mixed solution 100mL of 5% sulphuric acid and 0.01g/L oxalic acid at 80 DEG C strong
Agitator treating 3h, filters, and solid redistilled water washs post-drying, obtains high-purity α-Al2O3Powder body, purity more than 99.99%,
Mean diameter 5.1 μm.
Embodiment 5
The preparation technology of the present embodiment high-purity alumina powder is as follows:
(1) one section of solution purification: taking industry high-concentration sodium aluminate solution, alkali is (with Na2O count), alumina concentration be respectively
163g/L、180g/L.In this sodium aluminate solution, hydrogen peroxide 2mL and the 5g/L sodium peroxydisulfate of concentration 20%, reaction is added at 90 DEG C
After 30min；10g/L quick lime, strong agitation 1h is added at 90 DEG C；Add 1 ‰ polyacrylamide flocculants of 2ml/L
Snf S. A. S. of KM800(France), sucking filtration after flocculating sedimentation 1h, obtain primary purification clear liquid；
(2) two-stage nitration solution purification: at 70 DEG C, adds 1g/L Na in above-mentioned primary purification liquid respectively2S、3g/L
Na3PO4, 6g/L NaF, 4g/L sodium carbonate, 6g/L hexafluosilicic acid, process the flue dust 10g/L adding roaster after 10min, 50 DEG C
Stirring 30min, terminates rear sucking filtration；Under quantitative filter paper, it is encased inside macroanion resin the most again, again filters, obtain pure sodium aluminate solution
Liquid；
(3) prepared by crystal seed: take above-mentioned fine aluminium acid sodium solution 50mL, adds pure water 200mL, is incubated at 40 DEG C, adds tristearin
Acid 0.2g/L, is then slowly added dropwise the hydrogen peroxide solution 100mL of 10%, strong agitation 0.5h, obtains seed slurry；
(4) solution kind is divided: take fine aluminium acid sodium solution 600mL, adds pure water 200mL, is incubated at 80 DEG C, adds stearic acid
0.2 g/L, citric acid and ethylenediaminetetraacetic acid 1g/L, obtain seed liquor, seed slurry is poured in seed liquor, in approximation
Starting under conditions of Jun Xiang to plant and divide, initial temperature is set as 80 DEG C, and final temperature is set as 60 DEG C, after planting point end in 36 hours, and sucking filtration serosity,
The a large amount of pure water of solid product, last wash water pH is to terminate washing during 7-8, dries, obtains pure cerium hydroxide aluminum product, whole
Individual kind divides procedure decomposition rate to be about 51%；
(5) preparation of high-purity alumina powder: take the pure cerium hydroxide aluminum product 10g that above-mentioned warp is cleaned, dried, be placed in high pure oxygen
Change in aluminum crucible, chamber type electric resistance furnace is calcined at 1100 DEG C 4h, after product cooling, with 5% sulphuric acid and 1g/L ethylenediaminetetraacetic acid
Mixed solution 100mL at 50 DEG C strong agitation washing 3h, filter, filter cake heat redistilled water washing post-drying, obtain
To high-purity α-Al2O3Powder body, purity more than 99.99%, mean diameter about 4.6 μm.
Embodiment 6
The preparation technology of the present embodiment high-purity alumina powder is as follows:
(1) one section of solution purification: taking industry high-concentration sodium aluminate solution, alkali is (with Na2O count), alumina concentration be respectively
163g/L、180g/L.In this sodium aluminate solution, hydrogen peroxide 2mL and the 5g/L sodium peroxide of concentration 20%, reaction is added at 90 DEG C
After 10min；5g/L quick lime, strong agitation 1h is added at 100 DEG C；Add the 1 ‰ hydroxyl oximes flocculant HX600 of 1ml/L
(Qing Te company of the U.S.), sucking filtration after flocculating sedimentation 1h, obtain primary purification clear liquid；
(2) two-stage nitration solution purification: at 70 DEG C, adds 0.5g/L Na in above-mentioned primary purification liquid respectively2S、1g/L
Na3PO4, 2g/LNaF, process and add active oxidation aluminium powder 1g/L after 10min, 70 DEG C of stirring 30min, terminate rear sucking filtration；The most again
Under quantitative filter paper, it is encased inside macroanion resin, again filters, obtain fine aluminium acid sodium solution；
(3) prepared by crystal seed: take above-mentioned fine aluminium acid sodium solution 50mL, adds pure water 150mL, is incubated at 40 DEG C, adds β-ring
Dextrin and stearic acid 0.2g/L, be then slowly added dropwise the aluminum sulfate solution 100mL of concentration 40g/L, strong agitation 0.5h, obtain crystal seed
Serosity；
(4) solution kind is divided: take fine aluminium acid sodium solution 600mL, adds pure water 200mL, is incubated at 70 DEG C, adds beta-schardinger dextrin-
With stearic acid 0.2 g/L, tartaric acid and ethylenediaminetetraacetic acid 0.2g/L, obtain seed liquor, seed slurry is poured kind point into former
In liquid, starting to plant to divide under conditions of approximation is homogeneous, initial temperature is set as 70 DEG C, and final temperature is set as 55 DEG C, and kind point terminates for 30 hours
After, sucking filtration serosity, a large amount of pure water of product, last wash water pH is to terminate washing during 7-8, dries, obtains pure cerium hydroxide
Aluminum product, whole kind divides procedure decomposition rate to be about 55%；
(5) preparation of high-purity alumina powder: take the pure cerium hydroxide aluminum product 80g that above-mentioned warp is cleaned, dried, be placed in high pure oxygen
Change in aluminum crucible, chamber type electric resistance furnace is calcined at 1400 DEG C 1h, after product cooling, with 0.5% sulphuric acid and 5g/L ethylenediamine tetrem
The mixed solution 100mL of acid is strong agitation washing 2h at 100 DEG C, filters, the redistilled water washing post-drying of filter cake heat,
Obtain high-purity α-Al2O3Powder body, purity more than 99.99%, mean diameter about 4.6 μm.
Claims (9)
1. the preparation technology of a high-purity alumina powder, it is characterised in that step is as follows:
(1) one section of solution purification: with industrial sodium aluminate solution as raw material, it is clean that addition oxidant and calcareous material carry out one section of solution
Change, desiliconization, except ferrum, except Organic substance, be subsequently adding flocculant and carry out settling, filtering；
(2) two-stage nitration solution purification: add precipitant and adsorbent in the solution after (1) one section of solution purification of step, after standing
Filter and obtain fine aluminium acid sodium solution；
(3) prepared by crystal seed: take the fine aluminium acid sodium solution that step (2) obtains, and is added thereto to crystal seed initiator and sodium separates out suppression
Agent, prepares seed slurry；
(4) solution kind is divided: take the fine aluminium acid sodium solution that step (2) obtains, and is added thereto to sodium and separates out inhibitor and metal ion
Separate out inhibitor and obtain seed liquor, seed slurry is poured in seed liquor, control the dissolution degree of crystal seed, when 70 ~ 90 DEG C
Starting under conditions of approximation is homogeneous kind point, plant point end temperature at 50 ~ 65 DEG C, plant between timesharing 24 ~ 46 hours, resolution ratio is more than 20%,
Plant point product and obtain pure cerium hydroxide aluminum after fully washing；
(5) preparation of high-purity alumina powder: pure cerium hydroxide aluminum calcines 30 ~ 240min under conditions of 1100 ~ 1600 DEG C, then through water
Add chelating agent after quenching, wash to obtain pure α-Al2O3The high-purity alumina powder of phase；
Approximating homogeneous condition in described step (4) is: after seed slurry adds to seed liquor, most crystal seeds are molten
Solving, in the short time, solution is limpid, approximates homogeneous system, separates out aluminium hydroxide the most in a large number, enters a normal kind point state.
The preparation technology of high-purity alumina powder the most according to claim 1, it is characterised in that: the oxygen in described step (1)
Agent is at least one in hydrogen peroxide, sodium peroxide or sodium peroxydisulfate, and addition is 0.1 ~ 20g/L.
The preparation technology of high-purity alumina powder the most according to claim 1, it is characterised in that: the wadding in described step (1)
Solidifying agent is at least one in the flocculant containing hydroximic acid or polyacrylamide flocculant, and the weight concentration of described flocculant is
1 ‰, addition is 1 ~ 5mL/L.
The preparation technology of high-purity alumina powder the most according to claim 1, it is characterised in that: sinking in described step (2)
Shallow lake agent is at least two in sodium phosphate, sodium fluoride, sodium sulfide, sodium carbonate or hexafluosilicic acid, and addition is 0.2-20g/L.
The preparation technology of high-purity alumina powder the most according to claim 1, it is characterised in that: the suction in described step (2)
Attached dose is one or both mixture in activated carbon, the flue dust of alumina roasting furnace or 400 ~ 800 DEG C of calcined oxide aluminium powders, adds
Entering amount is 1 ~ 10g/L.
The preparation technology of high-purity alumina powder the most according to claim 1, it is characterised in that: crystal seed in described step (3)
Initiator is at least one in hydrogen peroxide, sodium bicarbonate, aluminum sulfate or sulphuric acid, addition 2 ~ 10g/L.
The preparation technology of high-purity alumina powder the most according to claim 1, it is characterised in that: described step (3) and step
(4) in, sodium separates out inhibitor is at least one in stearic acid, mannitol or beta-schardinger dextrin-, and addition is 0.05 ~ 1g/L；Described
In step (4) metal ion separate out inhibitor be in citric acid, ethylenediaminetetraacetic acid, sodium ethylene diamine tetracetate or tartaric acid extremely
Few one, addition is 0.05 ~ 2g/L.
The preparation technology of high-purity alumina powder the most according to claim 1, it is characterised in that: complexation in described step (5)
Agent is at least one in oxalic acid, ethylenediaminetetraacetic acid, citric acid or tartaric acid, and addition is 0.01 ~ 5g/L.
The preparation technology of high-purity alumina powder the most according to claim 1, it is characterised in that: washing in described step (5)
Wash is to wash in the dilute sulfuric acid of 0.1 ~ 10%.
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| CN107285348A (en) * | 2017-07-14 | 2017-10-24 | 杭州智华杰科技有限公司 | A kind of method that water quenching prepares Ultrafine Aluminium Oxide Particle |
| CN107337223B (en) * | 2017-08-04 | 2019-04-30 | 大连交通大学 | The water quenching preparation process of high purity aluminium oxide particle |
| CN107500324A (en) * | 2017-08-16 | 2017-12-22 | 云南铝业股份有限公司 | The method for preparing high purity aluminium oxide |
| CN109399677B (en) * | 2018-12-10 | 2021-04-13 | 贵州博汇联润铝业有限公司 | Method for preparing aluminum hydroxide by using aluminum rock as raw material cell grinding and water milling seed crystal |
| CN115535982B (en) * | 2022-11-09 | 2023-04-14 | 上海太洋科技有限公司 | Preparation method of optical-grade aluminum dihydrogen phosphate |
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| CN1579941A (en) * | 2004-05-14 | 2005-02-16 | 山东铝业股份有限公司 | Method for preparing high-pruity alumina powder |
| CN102398914A (en) * | 2010-09-10 | 2012-04-04 | 中国科学院过程工程研究所 | Method for modifying Bayer process, processing low-grade diaspore bauxite and producing alumina |
| CN104045100A (en) * | 2014-06-27 | 2014-09-17 | 中国铝业股份有限公司 | Preparation method of aluminum hydroxide |
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| CN1579941A (en) * | 2004-05-14 | 2005-02-16 | 山东铝业股份有限公司 | Method for preparing high-pruity alumina powder |
| CN102398914A (en) * | 2010-09-10 | 2012-04-04 | 中国科学院过程工程研究所 | Method for modifying Bayer process, processing low-grade diaspore bauxite and producing alumina |
| CN104045100A (en) * | 2014-06-27 | 2014-09-17 | 中国铝业股份有限公司 | Preparation method of aluminum hydroxide |
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