CN101607730A - A kind of preparation method of sandy alumina - Google Patents
A kind of preparation method of sandy alumina Download PDFInfo
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- CN101607730A CN101607730A CNA2008101151304A CN200810115130A CN101607730A CN 101607730 A CN101607730 A CN 101607730A CN A2008101151304 A CNA2008101151304 A CN A2008101151304A CN 200810115130 A CN200810115130 A CN 200810115130A CN 101607730 A CN101607730 A CN 101607730A
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- aluminate solution
- sodium aluminate
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Abstract
The present invention relates to a kind of preparation method of sandy alumina, comprising: the volume ratio by methyl alcohol and water is 1: 0.1-1: 1 comes the mixed solvent of compounding methanol and water; Mol ratio according to sodium oxide and aluminum oxide is dissolved in the water for the 1.3-2.0 weighing, prepares to such an extent that contain the sodium aluminate solution of sodium oxide concentration 80-230g/L, alumina concentration 70-240g/L, molecular ratio 1.3-2.0; The mixed solvent of methyl alcohol and water is dripped in sodium aluminate solution, and should the dropping process place airtight, 30-75 ℃ water bath with thermostatic control to carry out, obtain separating out the suspension of aluminium hydroxide after stirring reaction 3-24 hour; Reacted suspension is carried out liquid-solid separation, the solid phase that obtains adopt 70-100 ℃ hot wash at least once, and, obtain the aluminium hydroxide product in 80-100 ℃ of drying; Aluminium hydroxide promptly obtains sandy alumina through roasting.Adopt the inventive method, the reaction times shortens greatly than the prior seed decomposition method, also need not add aluminium hydroxide crystal seed, and rate of decomposition can improve more than 20%, and the decomposition nut liquid cycle efficiency improves greatly; Product granularity-45 μ m＜12%.
Description
Technical field
The present invention relates to a kind of preparation method of sandy alumina, specifically relate to a kind of from sodium aluminate solution like the industrial sodium aluminate seminal fluid constituent class prepare the method for sandy alumina.
Background technology
Aluminum oxide is the main production raw material of electrolytic aluminum, and global aluminum oxide output about 90% is used to produce electrolytic aluminum.Aluminum oxide industry has vital role as the upstream basic raw material industry of aluminium industry to development and national economy.
Bayer process is the main method that aluminum oxide industry is produced, and associated viscera sees " process for making alumina " (Bi Shiwen chief editor) for details, and the aluminum oxide of the whole world more than 90% all adopts Bayer process production.Development through over one hundred year, the technology of alumina producing have made significant progress and the greatly improvement, perfect of degree.But in aluminium producing Bayer process, a series of problems such as rate of decomposition is low, decomposition rate is slow, decomposition process is tediously long because of existing for decomposition process of sodium aluminate solution seed, a large amount of solid accumulation, product granularity are restive, and become the technology " bottleneck " of alumina producing.For this reason, numerous investigators have also done number of research projects to enhancement method, mainly be that physics outfield (as magnetic field and ultrasonic wave) method is strengthened, inorganic and organic additive reinforcement etc. are strengthened, added to activation crystal seed method, but because above enhancement method all fails to change the essential mechanism that sodium aluminate solution crystal seed decomposes, the decomposition balance still is subjected to the thermodynamical restriction of dissolution equilibrium, and effect is very unobvious.
Summary of the invention
The objective of the invention is in the existing aluminium producing Bayer process, rate of decomposition is low, decomposition rate is slow, decomposition process is tediously long because of existing for decomposition process of sodium aluminate solution seed, a large amount of solid accumulation, the restive existing problem of product granularity, thereby provide a kind of under the control reaction conditions, drip the mixed solvent of methyl alcohol and water in the sodium aluminate solution, utilize methyl alcohol to promote the decomposition of sodium aluminate solution, obtain the effect of aluminium hydroxide fast, and the method for preparing sandy alumina that need not to add crystal seed, this method reaction times is short, rate of decomposition is high; The low defective of alumina product fine size, intensity of also having avoided carbon method to obtain simultaneously.
The objective of the invention is to be achieved through the following technical solutions:
The preparation method of sandy alumina provided by the invention comprises the steps:
1) mixed solvent of compounding methanol and water at first: is 1 by methyl alcohol with the volume ratio of water: 0.1-1: 1 mixes;
2) get that to contain sodium oxide concentration 80-230g/L, alumina concentration 70-240g/L, sodium oxide and alumina molar ratio be the sodium aluminate solution of 1.3-2.0;
3) with the methyl alcohol of step 1) preparation and the mixed solvent and the step 2 of water) sodium aluminate solution, volume ratio according to the mixed solvent of sodium aluminate solution and methyl alcohol and water is 1: 0.5-1: 2.5 batchings, the mixed solvent of described methyl alcohol and water is dripped in sodium aluminate solution, till the mixed solvent of methyl alcohol and water drips;
This dropping process places airtight water bath with thermostatic control to carry out, and temperature remains on 30-75 ℃ under normal pressure, and stirring reaction 3-24 hour, obtains separating out the suspension of aluminium hydroxide;
4) suspension that step 3) is obtained carries out liquid-solid separation, and solid phase is used 70-100 ℃ of hot wash at least once, and places 80-100 ℃ of drying, obtains the aluminium hydroxide product, and liquid phase is carried out fractionation, isolates the methanol loop utilization;
5) aluminium hydroxide that step 4) is obtained is calcined, and wherein the incinerating temperature is 950-1100 ℃, 2 hours time, promptly obtains the sandy alumina product.
In above-mentioned technical scheme, the preparation of described sodium aluminate solution: the mol ratio according to sodium oxide and aluminum oxide is 1.3-2.0, and weighing sodium hydroxide and aluminium hydroxide are dissolved in the water, and until the limpid after-filtration twice of solution, promptly gets sodium aluminate solution.
In above-mentioned technical scheme, the mixed solvent of described methyl alcohol and water is 60.0mL/h-420.0mL/h toward the sodium aluminate solution rate of addition.
In above-mentioned technical scheme, described material purity is to get final product more than the technical grade.
The invention has the advantages that:
The method for preparing sandy alumina of the present invention is different from traditional decomposition of crystal seed, and system becomes present quaternary system from original ternary.Though have U.S. Pat 4900537 to relate to a kind of method of adding pure methyl alcohol in the sodium aluminate solution, but its pure consumption is far smaller than the consumption in present method, and also needs to add a large amount of crystal seeds simultaneously, the purpose that this method is added methyl alcohol is to change crystal formation.Method of the present invention is different from the method (Wang Xue that Chinese Academy Of Sciences Process Engineering Research Institute explores out again, Zheng Shili, to open virtuous. methyl alcohol dissolved sodium aluminate prepares aluminium hydroxide. the process engineering journal, 2008,8:72-77.), because it adds a large amount of pure methyl alcohol, cause the rapid variation of system character, what obtain is flaky, irregular aluminum hydroxide crystals, does not far meet the physical index of the sandy alumina of Aluminum Electrolysis Production requirement.Among the preparation method of sandy alumina of the present invention, plus solvent is to add in the mode of alcohol-water mixed solvent, not only made full use of alcohol to the alkali dissolution in the Sodium Aluminate Solution System, and the not dissolved characteristic of aluminium, regulate and control its influence by proportioning and the rate of addition of regulating alcohol-water simultaneously to the degree of supersaturation and the supersaturated solution stability of system, thereby controlling suitable crystallization speed (separates out slowly than adding pure methyl alcohol, but it is much rapider than the decomposition of crystal seed method), thereby obtain macrobead, the aluminium hydroxide product of good flowing properties, can obtain the second best in quality sandy alumina after the calcining, this sandy alumina meets the desired physical index of Aluminum Electrolysis Production.
Utilize the method for preparing sandy alumina of the present invention, can realize that the bayer's process kind divides that seminal fluid is efficient to be decomposed fast, the time can shorten to 1/3 of decomposition of crystal seed method, and very the person is shorter; Simultaneously can in system, not add crystal seed, greatly improved the utilising efficiency of aluminium, also saved cost; Rate of decomposition can improve more than 20% than the decomposition of crystal seed method, thereby improves equipment capacity greatly, and the decomposition nut liquid cycle efficiency improves greatly simultaneously; Product granularity-45 μ m＜12%; And the methyl alcohol boiling point is low, is easy to separate.The method technology for preparing sandy alumina of the present invention is simple, regulation and control effectively.
And the method for preparing sandy alumina of the present invention also can realize the utilization again of methyl alcohol, both has been beneficial to the protection environment, can save cost again.
Description of drawings
Below, describe embodiments of the invention in conjunction with the accompanying drawings in detail, wherein:
Fig. 1 is the SEM picture of the aluminium hydroxide of the embodiment of the invention 2 preparations;
Fig. 2 is that the SEM of the aluminium hydroxide of the embodiment of the invention 2 preparations amplifies picture;
Fig. 3 is the SEM picture that the aluminium hydroxide of the embodiment of the invention 3 preparations is calcined the sandy alumina that obtains;
Fig. 4 is the SEM amplification picture that the aluminium hydroxide of the embodiment of the invention 3 preparations is calcined the sandy alumina that obtains.
Embodiment
Embodiment 1
Get sodium aluminate solution (take by weighing 21.94g sodium hydroxide and 32.12g aluminium hydroxide, place the tetrafluoroethylene bottle to be dissolved in 100mL water in 120 degree, treat that twice of the limpid after-filtration of the solution promptly) 75mL of present embodiment preparation, its composition is Na
2O concentration 170.6g/L, Al
2O
3Concentration 209.5g/L, Na
2O and Al
2O
3Mol ratio (molecular ratio) 1.34;
The mixed solvent of compounding methanol and water again is 1: 0.1 according to the volume ratio of methyl alcohol and water, gets the methyl alcohol for preparing and the mixed solvent 150mL of water;
Then the mixed solvent of above-mentioned methyl alcohol and the water speed with 60mL/min is dripped in sodium aluminate solution, wherein the volume ratio of the mixed solvent of sodium aluminate solution and methyl alcohol and water is 1: 2.0, till the mixed solvent of methyl alcohol and water drips; The dropping process of the mixed solvent of above-mentioned methyl alcohol and water is carried out in 75 ℃ water bath with thermostatic control, and the airtight stirring reaction of normal pressure stopped after 9 hours; And slowly separate out the suspension of aluminium hydroxide; The suspension that obtains is carried out liquid-solid separation, isolate aluminium hydroxide solid phase and mother liquor; Na in the mother liquor
2O concentration is 65.8g/L, Al
2O
3Concentration 18.6g/L, molecular ratio is 5.81, liquid phase is carried out fractionation again, also isolates methyl alcohol; Solid phase with 80 ℃ of hot washes once and places 90 ℃ of dryings, the aluminium hydroxide product, and promptly obtained sandy alumina in 2 hours in 950 ℃ of calcinings.The rate of decomposition of present embodiment sodium aluminate solution is 76.93%, the sandy alumina leading indicator granularity-45 μ m=8.74% that obtains.
Wherein the raw material in the present embodiment all adopts chemical pure.
The liquid phase of present embodiment is through fractionation, isolate methyl alcohol after, methyl alcohol can utilize through subsequent disposal again.
The preparation process of following examples is with embodiment 1, and difference only is that concrete proportioning is different with condition, describes in detail no longer one by one.
Embodiment 2
To Na
2O concentration is 171.3g/L, Al
2O
3Concentration is that 183.0g/L, molecular ratio are the mixed solvent (V that drips methyl alcohol and water in 1.54 the sodium aluminate solution with the speed of 300.0mL/min
Methyl alcohol: V
Water=1: 0.5), the volume ratio of sodium aluminate solution and mixed solvent is 1: 1; Said process airtight stirring reaction of normal pressure in 55 ℃ of waters bath with thermostatic control is carried out, stop after 12 hours; Reacted suspension is carried out liquid-solid separation, obtain aluminium hydroxide solid phase and mother liquor; Na in the mother liquor
2O concentration is 92.33g/L, Al
2O
3Concentration 27.12g/L, molecular ratio is 5.60, liquid phase is carried out fractionation, isolates methyl alcohol; Solid phase is with 70 ℃ of hot washes twice, and places 90 ℃ of dryings, the aluminium hydroxide product, 1000 ℃ of calcinings promptly obtained sandy alumina in 2 hours.The rate of decomposition of present embodiment sodium aluminate solution is 72.51%, the sandy alumina leading indicator granularity-45 μ m=6.62% that obtains, and aluminium hydroxide product pattern is seen accompanying drawing 1 and accompanying drawing 2.What wherein the raw material in the present embodiment all adopted is analytically pure.
Embodiment 3
To Na
2O concentration is 87.3g/L, Al
2O
3Concentration is that 72.2g/L, molecular ratio are the mixed solvent (V that drips methyl alcohol and water in 1.99 the sodium aluminate solution with the speed of 420.0mL/min
Methyl alcohol: V
Water=1: 0.8), the volume ratio of sodium aluminate solution and mixed solvent is 1: 2.5; With said process airtight stirring reaction of normal pressure 18 hours in 60 ℃ of waters bath with thermostatic control; Reacted suspension is carried out liquid-solid separation, obtain aluminium hydroxide solid phase and mother liquor; Na in the mother liquor
2O concentration is 28.3g/L, Al
2O
3Concentration 4.5g/L, molecular ratio is 10.35; Solid phase with 85 ℃ of hot washes once and places 80 ℃ of dryings, the aluminium hydroxide product, 1100 ℃ of calcinings promptly obtained sandy alumina in 2 hours.The rate of decomposition of present embodiment sodium aluminate solution is 80.68%, the sandy alumina leading indicator granularity-45 μ m=5.51% that obtains, and the product pattern after the calcining is seen accompanying drawing 3 and accompanying drawing 4.What wherein the raw material in the present embodiment all adopted is commercially pure.
Embodiment 4
To Na
2O concentration is 153.9g/L, Al
2O
3Concentration is that 142.2g/L, molecular ratio are the mixed solvent (V that drips methyl alcohol and water in 1.78 the sodium aluminate solution with the speed of 240.0mL/min
Methyl alcohol: V
Water=1: 0.3), the volume ratio of sodium aluminate solution and mixed solvent is 1: 0.75; With said process airtight stirring reaction of normal pressure 6 hours in 45 ℃ of waters bath with thermostatic control; Reacted mixed solution is carried out liquid-solid separation, obtain aluminium hydroxide solid phase and mother liquor; Na in the mother liquor
2O concentration is 82.65g/L, Al
2O
3Concentration 25.65g/L, molecular ratio is 5.30, liquid phase is carried out fractionation, isolates methyl alcohol; Solid phase with 90 ℃ of hot washes once and places 80 ℃ of dryings, the aluminium hydroxide product, in 1000 ℃ down calcining promptly obtained sandy alumina in 2 hours.The rate of decomposition of present embodiment sodium aluminate solution is 66.84%, the sandy alumina leading indicator granularity-45 μ m=9.47% that obtains.What wherein the raw material in the present embodiment all adopted is commercially pure.
Embodiment 5
To Na
2O concentration is 229.6g/L, Al
2O
3Concentration is that 240.6g/L, molecular ratio are the mixed solvent (V that drips methyl alcohol and water in 1.57 the sodium aluminate solution with the speed of 120.0mL/min
Methyl alcohol: V
Water=1: 1), the volume ratio of sodium aluminate solution and mixed solvent is 1: 1; With said process airtight stirring reaction of normal pressure 24 hours in 40 ℃ of waters bath with thermostatic control; Reacted mixed solution is carried out liquid-solid separation; Na in the mother liquor that obtains
2O concentration is 83.28g/L, Al
2O
3Concentration 30.88g/L, molecular ratio is 4.44; Solid phase with 80 ℃ of hot washes once and places 80 ℃ of dryings, the aluminium hydroxide product, 1100 ℃ of calcinings promptly obtained sandy alumina in 2 hours.The rate of decomposition of present embodiment sodium aluminate solution is 64.64%, the sandy alumina leading indicator granularity-45 μ m=6.53% that obtains.What wherein the raw material in the present embodiment all adopted is analytically pure.
Embodiment 6
To Na
2O concentration is 102.4g/L, Al
2O
3Concentration is that 110.1g/L, molecular ratio are the mixed solvent (V that drips methyl alcohol and water in 1.53 the sodium aluminate solution with the speed of 180.0mL/min
Methyl alcohol: V
Water=1: 0.45), the volume ratio of sodium aluminate solution and mixed solvent is 1: 0.5; With said process airtight stirring reaction of normal pressure 3 hours in 30 ℃ of waters bath with thermostatic control; Reacted mixed solution is carried out liquid-solid separation; Na in the mother liquor that obtains
2O concentration is 83.53g/L, Al
2O
3Concentration 28.39g/L, molecular ratio is 4.84; Solid phase with 85 ℃ of hot washes once and places 90 ℃ of dryings, the aluminium hydroxide product, 950 ℃ of calcinings promptly obtained sandy alumina in 2 hours.The rate of decomposition of present embodiment sodium aluminate solution is 68.31%, the sandy alumina leading indicator granularity-45 μ m=11.47% that obtains.What wherein the raw material in the present embodiment all adopted is chemical pure.
Claims (4)
1. the preparation method of a sandy alumina may further comprise the steps:
1) mixed solvent of compounding methanol and water at first: the volume ratio by methyl alcohol and water is 1: 0.1-1: 1;
2) get that to contain sodium oxide concentration 80-230g/L, alumina concentration 70-240g/L, sodium oxide and alumina molar ratio be the sodium aluminate solution of 1.3-2.0;
3) with the methyl alcohol of step 1) preparation and the mixed solvent and the step 2 of water) sodium aluminate solution, volume ratio according to the mixed solvent of sodium aluminate solution and methyl alcohol and water is 1: 0.5-1: 2.5 batchings, the mixed solvent of described methyl alcohol and water is dripped in sodium aluminate solution, till the mixed solvent of methyl alcohol and water drips;
This dropping process places airtight water bath with thermostatic control to carry out, and temperature remains on 30-75 ℃ under normal pressure, and stirring reaction 3-24 hour, obtains separating out the suspension of aluminium hydroxide;
4) suspension that step 3) is obtained carries out liquid-solid separation, and solid phase is used 70-100 ℃ of hot wash at least once, and places 80-100 ℃ of drying, obtains the sandy aluminium hydroxide product, and liquid phase is carried out fractionation, isolates methyl alcohol;
5) aluminium hydroxide that step 4) is obtained is calcined, and wherein the incinerating temperature is 950-1100 ℃, 2 hours time, promptly obtains the sandy alumina product.
2. press the preparation method of the described sandy alumina of claim 1, it is characterized in that, the preparation of described sodium aluminate solution: the mol ratio according to sodium oxide and aluminum oxide is 1.3-2.0, weighing sodium hydroxide and aluminium hydroxide are dissolved in the water, until the limpid after-filtration twice of solution, promptly get sodium aluminate solution.
3. by the preparation method of the described sandy alumina of claim 1, it is characterized in that the mixed solvent of described methyl alcohol and water rate of addition in the sodium aluminate solution is 60.0mL/h-420.0mL/h.
4. by the preparation method of the described sandy alumina of claim 1, it is characterized in that described material purity is more than the technical grade.
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| CN2008101151304A CN101607730B (en) | 2008-06-17 | 2008-06-17 | Method for preparing sandy alumina |
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| CN2008101151304A CN101607730B (en) | 2008-06-17 | 2008-06-17 | Method for preparing sandy alumina |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102432051A (en) * | 2010-09-29 | 2012-05-02 | 中国科学院过程工程研究所 | Method for preparing spherical Bayer stones |
| CN110436496A (en) * | 2019-08-30 | 2019-11-12 | 贵州大学 | A method of Ultrafine High-purity Alumina is prepared using industrial sodium aluminate solution |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4900537A (en) * | 1986-12-11 | 1990-02-13 | Biotage, Inc. | Control of form of crystal precipitation of aluminum hydroxide using cosolvents and varying caustic concentration |
-
2008
- 2008-06-17 CN CN2008101151304A patent/CN101607730B/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102432051A (en) * | 2010-09-29 | 2012-05-02 | 中国科学院过程工程研究所 | Method for preparing spherical Bayer stones |
| CN102432051B (en) * | 2010-09-29 | 2013-10-16 | 中国科学院过程工程研究所 | Method for preparing spherical Bayer stones |
| CN110436496A (en) * | 2019-08-30 | 2019-11-12 | 贵州大学 | A method of Ultrafine High-purity Alumina is prepared using industrial sodium aluminate solution |
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