CN104760979A - Preparation technology of highly pure alumina powder - Google Patents
Preparation technology of highly pure alumina powder Download PDFInfo
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Abstract
The invention discloses a preparation technology of highly pure alumina powder. The technology comprises the following steps: carrying out solution two-stage purification on a raw material industrial sodium aluminate solution or sodium aluminate solution obtained through alkali dissolution blending of the industrial aluminum hydroxide to obtain a pure sodium aluminate solution; adding a crystal seed initiator and a sodium precipitation inhibitor into the pure sodium aluminate solution to prepare a crystal seed slurry; adding the sodium precipitation inhibitor and other impurity inhibitors into the pure sodium aluminate solution, adding the crystal seed slurry, and carrying out species separation at a high temperature to obtain pure aluminum hydroxide; and carrying out high temperature calcining on the pure aluminum hydroxide, carrying out water quenching, and washing to obtain the highly pure alumina powder with the purity of above 99.99% and the average particle size of below 10[mu]m, wherein the highly pure alumina powder is pure alpha-Al2O3 phase. The technology comprises the processes of solution purification to remove slag, species separation of a mother liquor, and entrance of a washing liquid to a Bayer process system. The highly pure alumina powder can be prepared in a low cost, high efficiency and environmental protection manner.
Description
Technical field
The invention belongs to metallurgy of aluminium technical field, be specifically related to a kind of preparation technology 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 adopt different production technique competitively to produce.At present, have by the high-purity alumina powder main production process of raw material classification:
(1) with rafifinal (aluminium powder) for raw material, react with water, or add organism (as choline) and form organism, then be hydrolyzed, the aluminium hydroxide of precipitation is through calcining to obtain high-purity alumina powder.The purity of the aluminum oxide powder that the method obtains depends on the purity of aluminium or aluminium powder, and reacting with water is also the factor affecting purity.Though this class methods technique is simple, there is poor process control, product purity is difficult to ensure card, high in cost of production shortcoming.
(2) with aluminium salt (as Tai-Ace S 150, aluminum chloride, aluminum nitrate) for raw material, by solution purification or repeatedly crystallization, obtain pure solution, then add alkali (as ammoniacal liquor, sodium hydroxide etc.) neutralization, separate out aluminium hydroxide, calcine to obtain pure zirconia aluminium powder.This class methods product purity is easy to control, but flow process compared with long, raw materials cost is high, waste residue and waste water is many, advantage of lower cost.
(3) take industrial aluminium hydroxide as raw material, by sulfuric acid or dissolving with hydrochloric acid, obtained Tai-Ace S 150, liquor alumini chloridi, then solution purification or multiple steps of crystallization, obtain pure solution, then add ammoniacal liquor, multiple steps of crystallization, obtain exsiccated ammonium alum, or be converted into aluminium carbonate ammonium, then thermolysis, obtain high-purity alumina powder.These class methods are industrial main method, and product purity is controlled, but in process, waste residue, waste water and waste gas are many, and environmental pollution is serious.
(4) be raw material with aluminium alcoholates, by more purification, obtain pure aluminium alcoholates, then be hydrolyzed to obtain aluminium hydroxide, calcine to obtain high-purity alumina powder, the method product purity is high, quality controllable, but long flow path, cost are high.
(5) with Alumina Enterprise sodium aluminate solution for raw material, desiliconization cleansing soln, then low concentration solution carbon being got aluminium hydroxide, being changed thing mutually for washing with concentrated acid after boehmite, roasting again, obtain high-purity alumina powder (CN102602968A, CN201410110524.6), or get aluminium hydroxide by planting, change thing mutually for boehmite takes off sodium, washs to obtain high purity aluminium oxide (CN200410023998.3), or kind gets aluminium hydroxide, acid dissolve, again alkali neutralize aluminium hydroxide, roasting obtain high purity aluminium oxide (US2013/0052124A).Such raw materials cost is low, but solution purification flow process is simple, and in solution, impurity is many.In calcining, add additive, easily introduce new impurity; Calcination product is regrinded, again concentrated acid process time, the impurity entered in lattice is difficult to removing, and thus product purity is low, and useless concentrated acid process is difficult; On the other hand, powder grinds pattern difficulty in process and controls, and product applications is restricted.
Summary of the invention
Technical problem to be solved by this invention there is the shortcomings such as cost is high, seriously polluted, Production Flow Chart is complicated for the existing technique preparing high-purity alumina powder, a kind of preparation technology of high-purity alumina powder is provided, the present invention can low cost, high-level efficiency, environmentally friendly prepare high-purity superfine alumina powder, meet the requirement of current efficient, economy, environmental protection.
For solving the problems of the technologies described above, the present invention by the following technical solutions:
The present invention is raw material with industrial sodium aluminate solution, or is raw material with industrial aluminium hydroxide, and the broad solution of alkali is deployed into high-concentration sodium aluminate solution; Based on ionic valence condition regulation and control and precipitation adsorption principle, carry out solution two sections purification, obtain fine aluminium acid sodium solution; Sodium aluminate solution is joined inversely in hydrogen peroxide (or sodium bicarbonate, Tai-Ace S 150) solution and prepare seed slurry; In fine aluminium acid sodium solution, add sodium separate out inhibitor and other impurity inhibitor, add seed slurry, at high temperature approximate homogeneous phase condition is sowed point, obtains pure cerium hydroxide aluminium; Then volatilization removing impurity under high-temperature calcination condition, the shrend of high temperature oxidation aluminium powder, then add complexing agent washing, obtain high-purity alumina powder, product purity >99.99%.Solution purification slag, seed precipitation solution, washing lotion enter Bayer process system.
A preparation technology for high-purity alumina powder, step is as follows:
(1) one section of solution purification: be raw material with sodium aluminate solution, adds oxygenant and calcareous material carries out one section of solution purification, desiliconization, deironing, organic matter removal, then adds flocculation agent and carries out sedimentation, filtration; Add oxygenant, make low valence metal ion be oxidized to high volence metal ion, be conducive to generating the precipitation that solubleness is little, granularity is superfine, become by oxidation operation colourless organism or portions turn to be carbanion simultaneously; Add lime or other calcareous material, make silicon-dioxide in solution generate calcium aluminosilicate hydrate, calcium carbonate, and simultaneously as sorbent material, precipitation, organism that the metal ion that in adsorbent solution, granularity is superfine generates; Add flocculation agent again, sedimentation, filtration;
(2) two sections of solution purifications: add precipitation agent in the solution after step (1) one section of solution purification, under the condition of 40 ~ 70 DEG C, in solution, zinc, calcium, lead, antimony, lithium, magnesium etc. generate water-fast precipitation; Then add segregative sorbent material, adsorb above-mentioned impurity, filter after leaving standstill, obtain fine aluminium acid sodium solution, alkali concn 10 ~ 170g/L, Crater corrosion is 1.3 ~ 2.5;
(3) JZPD capsule: get the fine aluminium acid sodium solution that step (2) obtains, adds crystal seed initiator wherein and sodium separates out inhibitor, preparation seed slurry; Add sodium and separate out inhibitor, sodium aluminate solution is added inversely in the solution containing initiator, under lesser temps, strong mixing condition, prepare active aluminium hydroxide seed slurry;
(4) solution kind is divided: get the fine aluminium acid sodium solution that step (2) obtains, add sodium wherein to separate out inhibitor and metal ion and separate out inhibitor and obtain seed liquor, seed slurry is poured in seed liquor, the ratio of seed slurry and seed liquor is dissolved can realize most crystal seed, in short period of time, solution is limpid, reach approximate homogeneous system to be as the criterion, control the dissolution degree of crystal seed, start when 70 ~ 90 DEG C to plant under the condition of approximate homogeneous phase and divide, plant point end temperature at 50 ~ 65 DEG C, plant point 24 ~ 46 hours time, rate of decomposition is greater than 20%, plant point product and obtain pure cerium hydroxide aluminium after fully washing,
(5) preparation of high-purity alumina powder:: pure cerium hydroxide aluminium calcining 30 ~ 240min(under the condition of 1100 ~ 1600 DEG C (being preferably 1300 ~ 1400 DEG C) is preferably 60 ~ 90min), fully volatilize during calcining the impurity such as sodium, lithium, zinc, antimony, lead, reduce the impurity in alumina product, calcined oxide aluminium powder is cooled in 1000 DEG C, after shrend, add complexing agent again, wash to obtain pure α-Al
2o
3the high-purity alumina powder of phase;
Wherein purification slag, seed precipitation solution and washing lotion enter Bayer process system.
Oxygenant in described step (1) is at least one in hydrogen peroxide, sodium peroxide or Sodium Persulfate, and add-on is 0.1 ~ 20g/L.
Flocculation agent in described step (1) is that the weight concentration of described flocculation agent is 1 ‰, and add-on is 1 ~ 5mL/L containing at least one in the flocculation agent of hydroximic acid or polyacrylamide flocculant.
Precipitation agent in described step (2) is at least two kinds in sodium phosphate, Sodium Fluoride, sodium sulphite, sodium carbonate or silicofluoric acid, wherein sodium sulphite add-on 0.1 ~ 5g/L, sodium phosphate add-on 0.1 ~ 5g/L, Sodium Fluoride add-on is 0.1 ~ 10g/L, sodium carbonate add-on 0.1 ~ 5g/L, silicofluoric acid add-on is 0.1 ~ 10g/L.
Sorbent material in described step (2) is one or both mixtures in activated carbon, the flue dust of alumina roasting furnace or 400 ~ 800 DEG C of calcined oxide aluminium powders, and add-on is 1 ~ 10g/L.
In described step (3), crystal seed initiator is at least one in hydrogen peroxide, sodium bicarbonate, Tai-Ace S 150 or sulfuric acid, and add-on is 2 ~ 10g/L.
It is one or more miscellanys in stearic acid, N.F,USP MANNITOL, beta-cyclodextrin that described step (3) and the middle sodium of step (4) separate out inhibitor, and add-on is 0.05 ~ 1g/L, is preferably 0.1 ~ 0.2g/L.
In described step (4), metal ion precipitation inhibitor is one or more miscellanys in citric acid, ethylenediamine tetraacetic acid (EDTA), sodium ethylene diamine tetracetate or tartrate, and add-on is 0.05 ~ 2g/L, is preferably 0.5 ~ 1g/L.
In described step (4), the condition of approximate homogeneous phase is: seed slurry is added to after in seed liquor, and most crystal seed is dissolved, and in the short period of time, solution is limpid, and approximate homogeneous system, then separates out aluminium hydroxide in a large number, enters normal kind point state.
Described step (5) complexing agent is at least one in oxalic acid, ethylenediamine tetraacetic acid (EDTA), citric acid or tartrate, and add-on is 0.01 ~ 5g/L, is preferably 0.01 ~ 2g/L.
Washing in described step (5) is washed in the dilute sulphuric acid of 0.1 ~ 10%, and dilute sulphuric acid concentration is preferably 0.5 ~ 5%.
Beneficial effect of the present invention: (1) the present invention with the Alumina Enterprise sodium aluminate solution of cheapness for raw material, by planting a point production high purity aluminium hydroxide, then high purity aluminium oxide is produced in calcining, seed precipitation solution enters alumina producing flow process, wash water enters alumina laterite washing system, thus this technique non-environmental-pollution, has cost advantage simultaneously.Direct employing industrial sodium aluminate solution, cost is low; Waste residue or waste back-cycling alumina producing flow process in high-purity powder, form side line production technique simultaneously, is to supplement the high value that metallurgical-grade aluminum oxide is produced.
(2) in the present invention, in concentrated base, solution purification is not only lime desiliconization, silicon-dioxide in removing solution, also needs to remove the various impurity in solution; Therefore based on the oxyhydroxide of foreign ion or other insoluble compound solubleness little, and minute quantity precipitation can not generate can the coarse particle of sedimentation, easily filtering separation, the principle on easily separated material need be adsorbed on, add oxygenant and lime, by Fe (OH) larger for solubleness
2be converted into Fe (OH)
3, and utilizing the impurity such as a large amount of desiliconization slag absorption iron generated, simultaneous oxidation remove portion organism, makes it the organism being converted into sodium carbonate or other small-molecular-weight; Add flocculation agent, form floc sedimentation, remove impurity further, obtain one section of cleansing soln.Then in one section of cleansing soln, precipitation agent is added, generate the indissoluble precipitations such as sulfide, phosphoric acid salt, carbonate, fluorochemical, wherein removing remaining calcium in lithium, precipitation one section of scavenging solution with composite form is very crucial impurity-removing method, add sorbent material, adsorb above-mentioned contamination precipitation thing, remove impurity by filtering separation, obtain two sections of cleansing solns.
(3) in concentrated base, metal ion is separated out and is difficult to regulation and control, and new surface of aluminum hydroxide of separating out can be high, is easily adsorbed or coprecipitatedly to separate out; Particularly sodium ion is separated out, and has no the report suppressing to separate out at present.On the other hand, traditional adds crystal seed, is divided, can not obtain Na by the mode kind of heterogeneous nucleation
2o lower than 0.09% aluminium hydroxide, simultaneously homogeneous phase sporadic nucleation, obtain Na2O content in aluminium hydroxide under high density and be also greater than 0.15%, therefore the present invention adopts approximate homogeneous nucleation mode kind to divide, and can obtain Na
2o content about 0.04% aluminium hydroxide.
(4) in high-temperature calcination aluminium hydroxide process, sodium, lithium, zinc etc. are volatile, can remove portion impurity; Meanwhile, in shrend process, there is particle refinement process in high temperature alumina, is conducive to impurity removing; Again in washing process, add diluted acid, then add complexing agent, be conducive to the solubleness improving impurity, improve the efficiency of washing impurity-removing.
(5) in all technique of the present invention, purification slag, seed precipitation solution and washing lotion all enter in alumina producing flow process, environmental pollution can not be produced, significantly can not increase cost, because above-mentioned purification slag, seed precipitation solution and washing lotion are all necessary in alumina producing flow process, can play a role in alumina producing flow process, bring benefits.
Figure of description
Fig. 1 is the process flow sheet that the present invention prepares high-purity alumina powder.
Embodiment
Below, will in conjunction with specific embodiments, the present invention will be described further.
As shown in Figure 1, sodium aluminate solution adds oxygenant, at a low price after iron contamination reaction, generates the ironic hydroxide etc. that solubleness is less; The oxidable organism of remaining oxygenant, not only plays decolorization, and partial organic substances can be oxidized to sodium carbonate; Add lime, generate calcium aluminosilicate hydrate, both carried out desiliconization, except carbanion, newly-generated product again can impurity in adsorbent solution; Add flocculation agent again, generate floc sedimentation, be conducive on the one hand filtering, be conducive to removal of impurities on the other hand.Thus form one section of solution purification technique.Add precipitation agent, the insoluble compounds such as zinc sulphide, calcium phosphate, calcium carbonate, lead sulfide, lithium fluoride, Trilithium phosphate or lithium fluosilicate are generated in sodium aluminate solution, add sorbent material again, adsorb above-mentioned insoluble compound, filter, realize the object of solution deep purification, thus form two sections of solution purification techniques, obtain fine aluminium acid sodium solution.The calcium aluminosilicate hydrate that one section of purification slag is mainly impure, two sections of purification slags are salic, all can return Bayer Process digestion system recycling.
Fine aluminium acid sodium solution is added in the solution containing crystal seed initiator inversely, and adds sodium precipitation inhibitor, under the condition of high-speed stirring, the seed slurry of obtained aluminium hydroxide.In fine aluminium acid sodium solution, add sodium separate out inhibitor, metal ion precipitation inhibitor, seed slurry is added when 70-90 DEG C, under high temperature, most seed crystal of aluminium hydroxide is dissolved, the solution short period of time is more limpid, for approximate homogeneous system, then there is aluminium hydroxide to separate out in a large number, enter kind of a point process.When controlling final temperature about 60 DEG C, terminating to plant and dividing, plant point slurries and take out, carry out solid-liquid separation, the washing of solid phase heating water, extremely final washing lotion pH is between 8 ~ 9, obtains pure cerium hydroxide aluminium powder;
By the high-temperature calcination in High Temperature Furnaces Heating Apparatus of pure cerium hydroxide aluminium powder, under high temperature, the impurity such as sodium, lithium, zinc, antimony is volatile, removes above-mentioned partial impurities; Then, under high temperature, aluminum oxide powder shrend, makes particle refinement, makes impurity easily exposed, is convenient to further removal of impurities; Add dilute sulphuric acid in the solution, add complexing agent, washing, obtains 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, obtain alkali after dilution, sodium aluminate solution that alumina concentration is respectively 150g/L, 165g/L.In this sodium aluminate solution, the hydrogen peroxide 10mL/L of concentration 10% is added, reaction 30min at 90 DEG C; And then add 10g/L unslaked lime, 90 DEG C of violent stirring 1h; Add 1 ‰ Snf S. A. S. of polyacrylamide flocculant KM800(France of 5ml/L again) and containing Qing Te company of the hydroximic acid organism HX300(U.S.), suction filtration after sedimentation 1h, obtains primary purification clear liquid;
(2) two sections of solution purifications: at 70 DEG C, add 0.5g/L Na respectively in primary purification clear liquid
2s, 1g/L Na
3pO
4, 2g/L NaF, reaction 30min after, then add activated alumina and activated carbon powder 5g/L, 70 DEG C stir 2h, terminate rear suction filtration; Add 15g/L macroanion resin in filtrate and mix 20min, and then suction filtration, obtain fine aluminium acid sodium solution;
(3) JZPD capsule: above-mentioned fine aluminium acid solution 50mL, adds pure water 150mL, be incubated at 40 DEG C, add N.F,USP MANNITOL and stearic acid miscellany 0.03/L, then slowly drip 10% hydrogen peroxide 100mL, violent stirring 0.5h, obtains seed slurry;
(4) solution kind is divided: get fine aluminium acid sodium solution 600mL, add pure water 200mL, sweet dew and stearic acid miscellany 0.02g/L is added at 80 DEG C, ethylenediamine tetraacetic acid (EDTA) and tartrate 0.05g/L obtain seed liquor, again seed slurry is poured in seed liquor, start to plant under the condition of approximate homogeneous phase and divide, initial temperature is set as 80 DEG C, final temperature is set as 65 DEG C, after planting point end in 24 hours, suction filtration slurries, the a large amount of pure water of solid phase prod, last wash water pH terminates washing when being 7-8, dry, obtain pure cerium hydroxide aluminium product, whole kind divides procedure decomposition rate to be about 51%,
(5) preparation of high-purity alumina powder: get the pure cerium hydroxide aluminium product 8g that above-mentioned warp is cleaned, dried, be placed in high purity aluminium oxide crucible, calcine 0.5h at 1600 DEG C in chamber type electric resistance furnace, after product is cooled to 1000 DEG C, be added in normal-temperature water, carry out shrend; Wash 2h by mixing solutions 100mL violent stirring at 80 DEG C of 5% sulfuric acid and 1g/L citric acid again, filter, solid second distillation water washing post-drying, obtains high-purity α-Al
2o
3powder, purity more than 99.99%, median size 9.5 μm.
Embodiment 2
The preparation method of the high purity alumina powder of the present embodiment: the pure cerium hydroxide aluminium product 8g that Example 1 step (4) obtains, be placed in high purity aluminium oxide crucible, in chamber type electric resistance furnace, calcine 1h at 1300 DEG C, after product is cooled to 1000 DEG C, be added in normal-temperature water, carry out shrend; Wash 2h by 10% sulfuric acid and 1g/L ethylenediamine tetraacetic acid (EDTA) and tartaric mixing solutions 100mL violent stirring at 100 DEG C again, filter, the second distillation water washing post-drying that solid is warm, obtain high-purity α-Al
2o
3powder, purity more than 99.99%, median size 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: get industry high-concentration sodium aluminate solution, alkali is (with Na
2o counts), alumina concentration is respectively 155g/L, 180g/L.In this sodium aluminate solution, hydrogen peroxide 50mL and the 10g/L sodium peroxide of concentration 20% is added, after reaction 30min at 90 DEG C; 10g/L unslaked lime is added, violent stirring 1h at 100 DEG C; Add 1 ‰ polyacrylamide flocculants and the hydroxyl oximes flocculation agent HX600 of 2ml/L again, suction filtration after flocculating settling 1h, obtains primary purification clear liquid;
(2) two sections of solution purifications: at 50 DEG C, add 0.5g/L Na respectively in above-mentioned primary purification liquid
2s, 1g/L Na
3pO
4, 2g/LNaF, add the flue dust 5g/L of alumina roasting furnace after process 10min, 50 DEG C are stirred 30min, terminate rear suction filtration; And then macroanion resin is encased inside under quantitative paper, again filter, obtain fine aluminium acid sodium solution;
(3) JZPD capsule: get above-mentioned fine aluminium acid sodium solution 50mL, add pure water 100mL, is incubated at 25 DEG C, adds N.F,USP MANNITOL and beta-cyclodextrin 0.5g/L, then slowly drips the NaHCO of concentration 50g/L
3solution 40mL, violent stirring 0.5h, obtain seed slurry;
(4) solution kind is divided: get fine aluminium acid sodium solution 600mL, add pure water 250mL, be incubated at 90 DEG C, add N.F,USP MANNITOL and beta-cyclodextrin 0.5 g/L, citric acid and ethylenediamine tetraacetic acid (EDTA) 2g/L obtain seed liquor, seed slurry is poured in seed liquor, start to plant under the condition of approximate homogeneous phase and divide, initial temperature is set as 90 DEG C, final temperature is set as 65 DEG C, after planting point end in 46 hours, suction filtration slurries, the a large amount of pure water of solid phase prod, last wash water pH terminates washing when being 7-8, dry, obtain pure cerium hydroxide aluminium product, whole kind divides procedure decomposition rate to be about 55%,
(5) preparation of high-purity alumina powder: get the pure cerium hydroxide aluminium product 10g that above-mentioned warp is cleaned, dried, be placed in high purity aluminium oxide crucible, 1h is calcined at 1400 DEG C in chamber type electric resistance furnace, after product cooling, 3h is washed by mixing solutions 100mL violent stirring at 50 DEG C of 0.5% sulfuric acid and 1g/L ethylenediamine tetraacetic acid (EDTA), filter, the second distillation water washing post-drying of filter cake heat, obtains high-purity α-Al
2o
3powder, purity more than 99.99%, median size about 4.6 μm.
Embodiment 4
The preparation method of the high purity alumina powder of the present embodiment: the pure cerium hydroxide aluminium product 80g that Example 3 step (4) prepares, be placed in high purity aluminium oxide crucible, in chamber type electric resistance furnace, calcine 2h at 1300 DEG C, after product is cooled to 1000 DEG C, be added in normal-temperature water, carry out shrend; Wash 3h by mixing solutions 100mL violent stirring at 80 DEG C of 5% sulfuric acid and 0.01g/L oxalic acid, filter, solid second distillation water washing post-drying, obtains high-purity α-Al
2o
3powder, purity more than 99.99%, median size 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: get industry high-concentration sodium aluminate solution, alkali is (with Na
2o counts), alumina concentration is respectively 163g/L, 180g/L.In this sodium aluminate solution, hydrogen peroxide 2mL and the 5g/L Sodium Persulfate of concentration 20% is added, after reaction 30min at 90 DEG C; 10g/L unslaked lime is added, violent stirring 1h at 90 DEG C; Add 1 ‰ Snf S. A. S. of polyacrylamide flocculant KM800(France of 2ml/L again), suction filtration after flocculating settling 1h, obtains primary purification clear liquid;
(2) two sections of solution purifications: at 70 DEG C, add 1g/L Na respectively in above-mentioned primary purification liquid
2s, 3g/L Na
3pO
4, 6g/L NaF, 4g/L sodium carbonate, 6g/L silicofluoric acid, add the flue dust 10g/L of stoving oven after process 10min, 50 DEG C are stirred 30min, terminate rear suction filtration; And then macroanion resin is encased inside under quantitative paper, again filter, obtain fine aluminium acid sodium solution;
(3) JZPD capsule: get above-mentioned fine aluminium acid sodium solution 50mL, add pure water 200mL, is incubated at 40 DEG C, adds stearic acid 0.2g/L, and then slowly drip the hydrogen peroxide solution 100mL of 10%, violent stirring 0.5h, obtains seed slurry;
(4) solution kind is divided: get fine aluminium acid sodium solution 600mL, add pure water 200mL, be incubated at 80 DEG C, add stearic acid 0.2 g/L, citric acid and ethylenediamine tetraacetic acid (EDTA) 1g/L, obtain seed liquor, seed slurry poured in seed liquor, start to plant under the condition of approximate homogeneous phase and divide, initial temperature is set as 80 DEG C, final temperature is set as 60 DEG C, after planting point end in 36 hours, suction filtration slurries, a large amount of pure water of solid phase prod, last wash water pH terminates washing when being 7-8, dry, obtain pure cerium hydroxide aluminium product, whole kind divides procedure decomposition rate to be about 51%;
(5) preparation of high-purity alumina powder: get the pure cerium hydroxide aluminium product 10g that above-mentioned warp is cleaned, dried, be placed in high purity aluminium oxide crucible, 4h is calcined at 1100 DEG C in chamber type electric resistance furnace, after product cooling, 3h is washed by mixing solutions 100mL violent stirring at 50 DEG C of 5% sulfuric acid and 1g/L ethylenediamine tetraacetic acid (EDTA), filter, the second distillation water washing post-drying of filter cake heat, obtains high-purity α-Al
2o
3powder, purity more than 99.99%, median size 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: get industry high-concentration sodium aluminate solution, alkali is (with Na
2o counts), alumina concentration is respectively 163g/L, 180g/L.In this sodium aluminate solution, hydrogen peroxide 2mL and the 5g/L sodium peroxide of concentration 20% is added, after reaction 10min at 90 DEG C; 5g/L unslaked lime is added, violent stirring 1h at 100 DEG C; Add the 1 ‰ Qing Te companies of the hydroxyl oximes flocculation agent HX600(U.S. of 1ml/L again), suction filtration after flocculating settling 1h, obtains primary purification clear liquid;
(2) two sections of solution purifications: at 70 DEG C, add 0.5g/L Na respectively in above-mentioned primary purification liquid
2s, 1g/L Na
3pO
4, 2g/LNaF, process 10min after add active oxidation aluminium powder 1g/L, 70 DEG C stir 30min, terminate rear suction filtration; And then macroanion resin is encased inside under quantitative paper, again filter, obtain fine aluminium acid sodium solution;
(3) JZPD capsule: get above-mentioned fine aluminium acid sodium solution 50mL, add pure water 150mL, is incubated at 40 DEG C, adds beta-cyclodextrin and stearic acid 0.2g/L, and then slowly drip the alum liquor 100mL of concentration 40g/L, violent stirring 0.5h, obtains seed slurry;
(4) solution kind is divided: get fine aluminium acid sodium solution 600mL, add pure water 200mL, be incubated at 70 DEG C, add beta-cyclodextrin and stearic acid 0.2 g/L, tartrate and ethylenediamine tetraacetic acid (EDTA) 0.2g/L, obtain seed liquor, seed slurry is poured in seed liquor, start to plant under the condition of approximate homogeneous phase and divide, initial temperature is set as 70 DEG C, final temperature is set as 55 DEG C, after planting point end in 30 hours, suction filtration slurries, the a large amount of pure water of product, last wash water pH terminates washing when being 7-8, dry, obtain pure cerium hydroxide aluminium product, whole kind divides procedure decomposition rate to be about 55%,
(5) preparation of high-purity alumina powder: get the pure cerium hydroxide aluminium product 80g that above-mentioned warp is cleaned, dried, be placed in high purity aluminium oxide crucible, 1h is calcined at 1400 DEG C in chamber type electric resistance furnace, after product cooling, 2h is washed by mixing solutions 100mL violent stirring at 100 DEG C of 0.5% sulfuric acid and 5g/L ethylenediamine tetraacetic acid (EDTA), filter, the second distillation water washing post-drying of filter cake heat, obtains high-purity α-Al
2o
3powder, purity more than 99.99%, median size about 4.6 μm.
Claims (10)
1. a preparation technology for high-purity alumina powder, is characterized in that step is as follows:
(1) one section of solution purification: be raw material with industrial sodium aluminate solution, adds oxygenant and calcareous material carries out one section of solution purification, desiliconization, deironing, organic matter removal, then adds flocculation agent and carries out sedimentation, filtration;
(2) two sections of solution purifications: add precipitation agent and sorbent material in the solution after step (1) one section of solution purification, filter after leaving standstill and obtain fine aluminium acid sodium solution;
(3) JZPD capsule: get the fine aluminium acid sodium solution that step (2) obtains, adds crystal seed initiator wherein and sodium separates out inhibitor, preparation seed slurry;
(4) solution kind is divided: get the fine aluminium acid sodium solution that step (2) obtains, add sodium wherein to separate out inhibitor and metal ion and separate out inhibitor and obtain seed liquor, seed slurry is poured in seed liquor, control the dissolution degree of crystal seed, start when 70 ~ 90 DEG C to plant under the condition of approximate homogeneous phase and divide, plant and divide end warm at 50 ~ 65 DEG C, kind point 24 ~ 46 hours time, rate of decomposition is greater than 20%, plants point product and obtain pure cerium hydroxide aluminium after fully washing;
(5) preparation of high-purity alumina powder: pure cerium hydroxide aluminium calcines 30 ~ 240min under the condition of 1100 ~ 1600 DEG C, then adds complexing agent after shrend, washs to obtain pure α-Al
2o
3the high-purity alumina powder of phase.
2. the preparation technology of high-purity alumina powder according to claim 1, is characterized in that: the oxygenant in described step (1) is at least one in hydrogen peroxide, sodium peroxide or Sodium Persulfate, and add-on is 0.1 ~ 20g/L.
3. the preparation technology of high-purity alumina powder according to claim 1, it is characterized in that: the flocculation agent in described step (1) is containing at least one in the flocculation agent of hydroximic acid or polyacrylamide flocculant, the weight concentration of described flocculation agent is 1 ‰, and add-on is 1 ~ 5mL/L.
4. the preparation technology of high-purity alumina powder according to claim 1, is characterized in that: the precipitation agent in described step (2) is at least two kinds in sodium phosphate, Sodium Fluoride, sodium sulphite, sodium carbonate or silicofluoric acid, and add-on is 0.2-20g/L.
5. the preparation technology of high-purity alumina powder according to claim 1, it is characterized in that: the sorbent material in described step (2) is one or both mixtures in activated carbon, the flue dust of alumina roasting furnace or 400 ~ 800 DEG C of calcined oxide aluminium powders, and add-on is 1 ~ 10g/L.
6. the preparation technology of high-purity alumina powder according to claim 1, is characterized in that: in described step (3), crystal seed initiator is at least one in hydrogen peroxide, sodium bicarbonate, Tai-Ace S 150 or sulfuric acid, add-on 2 ~ 10g/L.
7. the preparation technology of high-purity alumina powder according to claim 1, is characterized in that: described step (3) and step (4) middle sodium precipitation inhibitor are at least one in stearic acid, N.F,USP MANNITOL or beta-cyclodextrin, and add-on is 0.05 ~ 1g/L; In described step (4), metal ion precipitation inhibitor is at least one in citric acid, ethylenediamine tetraacetic acid (EDTA), sodium ethylene diamine tetracetate or tartrate, and add-on is 0.05 ~ 2g/L.
8. the preparation technology of high-purity alumina powder according to claim 1, it is characterized in that: in described step (4), the condition of approximate homogeneous phase is: seed slurry is added to after in seed liquor, most crystal seed is dissolved, in short period of time, solution is limpid, approximate homogeneous system, then separate out aluminium hydroxide in a large number, enter normal kind point state.
9. the preparation technology of high-purity alumina powder according to claim 1, is characterized in that: described step (5) complexing agent is at least one in oxalic acid, ethylenediamine tetraacetic acid (EDTA), citric acid or tartrate, and add-on is 0.01 ~ 5g/L.
10. the preparation technology of high-purity alumina powder according to claim 1, is characterized in that: the washing in described step (5) is washed in the dilute sulphuric acid of 0.1 ~ 10%.
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| CN106745126A (en) * | 2017-01-13 | 2017-05-31 | 山东鲁北企业集团总公司 | A kind of method with phosphoric acid seed production ultrafine aluminium hydroxide |
| 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 |
| CN107337223A (en) * | 2017-08-04 | 2017-11-10 | 大连交通大学 | The water quenching preparation technology 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 |
| CN109399677A (en) * | 2018-12-10 | 2019-03-01 | 贵州博汇联润铝业有限公司 | One kind grinding water mill crystal seed as raw cell using pelite and prepares aluminium hydroxide method |
| CN115535982A (en) * | 2022-11-09 | 2022-12-30 | 上海太洋科技有限公司 | Preparation method of optical-grade aluminum dihydrogen phosphate |
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