CN1129194A - Aluminium hydroxide and preparation method thereof - Google Patents

Aluminium hydroxide and preparation method thereof Download PDF

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Publication number
CN1129194A
CN1129194A CN 95109122 CN95109122A CN1129194A CN 1129194 A CN1129194 A CN 1129194A CN 95109122 CN95109122 CN 95109122 CN 95109122 A CN95109122 A CN 95109122A CN 1129194 A CN1129194 A CN 1129194A
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aluminium hydroxide
weight
sodium
sulfuric acid
crystal seed
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CN 95109122
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CN1075043C (en
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冈本英俊
石川功
大西孝幸
川合康夫
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Resonac Holdings Corp
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Showa Denko KK
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Abstract

The present invention purposes to reduce a fixed sodium and an undissolved residue amount to acid. The aluminum hydroxide separates out from the sodium aluminate by CO[2] gas decomposition method of adding seed crystal, in order to provide aluminum hydroxide with low content of an undissolved residue amount to acid and a fixed sodium.

Description

Aluminium hydroxide and manufacture method thereof
The present invention relates to aluminium hydroxide, possess the aluminium hydroxide that institute does not in the past have characteristic, especially relate to the aluminium hydroxide that is suitable for water conditioner usefulness raw material.
As the industrial making method of aluminium hydroxide, main method is a bayer's process, forms sodium aluminate solution by handling bauxitic clay with the sodium hydroxide solution heat treated, utilizes to wherein feeding CO in the past 2Make it to separate out, and do not feed CO recently with aluminium hydroxide 2, but add aluminium hydroxide as crystal seed, separate out aluminium hydroxide by means of stirring, to make aluminium hydroxide.
Aluminium hydroxide is sintered into aluminum oxide, and it is used on various uses, but among the aluminum hydroxide compound purposes, maximum purposes is the raw material as Tai-Ace S 150 or poly aluminium chloride and inorganic water conditioner.
As the aluminium hydroxide with this kind of work raw material, its important prerequisite is its this characteristic of solvability in mineral acid.That is, from reaction yield, undissolved residue is few more good more, if there is residue that slagging-off operation in reaction back then must be set, if solubilizing reaction speed is too fast, owing to have the danger of bumping, so wish the sort of aluminium hydroxide with the not too little and characteristic that solubilizing reaction is fast of granularity.
In addition, also must reduce the foreign matter content in the aluminium hydroxide sometimes, need be as the few aluminium hydroxide of sodium content of maximum impurity in the impurity.
But still there is not the aluminium hydroxide that can satisfy solvability and these two characteristics of low impurity content of aluminium hydroxide simultaneously in the past.
Therefore, the object of the invention is to provide a kind of few and sodium impurity content is low this and the aluminium hydroxide of common opposite characteristic in the past of in acid undissolved residue that have.
The inventor etc. carry out for achieving the above object meticulously, deep research, and the result has finished the present invention.
That is, as fixed sodium (Fix-Na 2O) content is lower than 0.22 weight %, record sulfuric acid insoluble sludge content with the sulfuric acid dissolution rate assay method of following regulation and be lower than aluminium hydroxide and the manufacturing process thereof that 0.12 weight % is a feature, a kind of aluminium hydroxide manufacture method has been proposed, it is characterized in that: with bauxitic clay, calcium cpd, sodium compound and coal mix, pulverize the back sintering, add entry then, at least a water or solution in sodium hydroxide or the sodium aluminate, extract the soluble part of sinter, separate residue, after further desiliconization is handled, the preparation sodium aluminate solution, in this solution, add the aluminium hydroxide fine powder as crystal seed, and feed CO 2, make it to separate out aluminium hydroxide.
Wherein, above-mentioned sulfuric acid dissolution rate assay method is as follows: with 195 grams through 110 ℃ down dry 2 hours aluminium hydroxide mixes with the 250 gram distilled water and the 375 gram vitriol oils, the limit is stirred (rotating speed is 240 rev/mins) limit and was dissolved 60 minutes under 105-107 ℃.Then, with 1 liter of hot water dilution lysate, and, use 1 liter of hot wash again with the filtration of C type qualitative filter paper.Filter paper and residue are weighed after dry 30 minutes down at 100 ℃, and the dried filter paper weight of measuring in advance before deduction filters is calculated residue weight Xg, with (Xg/195) * 100 as sulfuric acid undissolved residue amount (weight %).
In addition, above-mentioned fixed sodium (Fix-Na 2O) content is: the whole sodium from the aluminium hydroxide impurities are converted into Na 2The O value is promptly from total sodium (T-Na 2O) in, deduction is converted into the numerical value that NaO obtains, i.e. solubility sodium (W-Na by following condition by the solubility Na of stripping in aluminium hydroxide amount 2O), the Na that tries to achieve 2The O amount.Promptly by formula: (Fix-Na 2O)=(T-Na 2O)-(W-Na 2O) numerical value of obtaining.
Total sodium (T-Na 2O) amount is obtained by the following method.That is, restrain the accurate weighing of sodium hydroxide samples in the 100ml beaker with 1.000.
In this beaker, add 10ml dilution heat of sulfuric acid (special grade chemical sulfuric acid is prepared with (1: 1) distilled water).In the temperature of not emitting the white cigarette of sulfuric acid (about 250 ℃) reinforced beaker was heated 15 minutes.To do solid sample water then and move in the 250ml volumetric flask, water cooling to 20 ℃.After the water-cooled, accurately add the 0.2mgLi/ml lithium internal standard solution of 25ml, add distilled water again and make the total amount constant volume at 250ml.Then, press the method for JIS H1901-1977 defined,, and be converted into Na with flame spectrophotometer measuring Na amount 2O is with as T-Na 2O.
Soluble sodium (W-Na below is described 2O) quantitative determination process.Take by weighing 5 gram (being accurate to 1mg) aluminium hydroxides in the 100ml beaker, add 50~60 ℃ of warm water of 50ml, insulation is 2 hours under 80~90 ℃ of temperature.Then, with 5B filter paper filtering beaker content, with warm water washing 4 times.
This filtrate is cooled to 20 ℃, adds the 0.2mgLi/ml lithium internal standard solution of 10ml, make total amount reach 100ml with distilled water again, press the method for JIS H1901-1977 regulation and measure, and be converted into Na with flame spectrophotometer measuring Na 2O is as W-Na 2O.
Aluminium hydroxide of the present invention is gibbsite Al (OH) 3(Al 2O 33H 2O).
Below explanation is as the characteristic of aluminium hydroxide feature of the present invention.At first, Fix-Na 2The O value is below the 0.22 weight %, and stable lower value of making is about 0.03 weight %.Secondly, sulfuric acid undissolved residue amount is 0.12 weight %, can make the product of this lower value near 0 weight %.
In addition, the characteristic as the maximum feature of aluminium hydroxide of the present invention is that primary particle and secondary particle have both.
Utilize the An Delie Ash to drip and move the secondary grain diameter d that the pipe method records 50Be 18~110 μ m, isodisperse n value is 4-9 when mapping on RRS granulometric curve figure, and the secondary particle granularity of aluminium hydroxide of the present invention is complete.
Manufacture method of the present invention below is described.
Use bauxitic clay, calcium cpd, sodium compound and coal as raw material.Calcium cpd refers to oxide compound, oxyhydroxide and the carbonate etc. of calcium; Sodium compound is meant the oxyhydroxide and the carbonate of sodium.The two uses under the situation of Wingdale and yellow soda ash, by weight 1.5~1.8: 2: 0.1: 0.2 ratio is with bauxite raw material, Wingdale, yellow soda ash and coal mix, it is crushed in 1~5mm scope, equal 1200~1300 ℃ of sintering 1-2 hours with rotary kiln, add entry then, at least a water or solution in sodium hydroxide or the sodium aluminate, under 90~100 ℃, extract the soluble part of sinter, separate residue, handled 30 minutes~1 hour down in 150~200 ℃ again, the silicon composition is separated out with the sodium silicoaluminate form finish the desiliconization processing, to make sodium aluminate solution.
Add aluminium hydroxide crystal seed in this sodium aluminate solution, its purpose will be illustrated.
As the aluminium hydroxide that crystal seed uses, its preferred median size is less than 3 μ m; If be higher than 3 μ m, then must strengthen the crystal seed add-on, the sulfuric acid undissolved residue amount of the aluminium hydroxide of separating out also increases simultaneously, thereby bad.
If the add-on of crystal seed is with following formula, promptly by When defined crystal seed rate is represented, 0.15-15% preferably.The crystal seed rate is lower than at 0.15% o'clock, can not stably make Fix-Na 2Low and the also low aluminium hydroxide of sulfuric acid undissolved residue amount of O, and the crystal seed rate surpasses at 15% o'clock, even owing to be higher than this amount and add again and also can not produce the effect that meets this ratio and do not have good and economic, so bad.
After adding above-mentioned crystal seed, feed carbonic acid gas under the following conditions, make it branch and parse aluminium hydroxide.The sodium aluminate solution of ventilation solution preferably, is converted into Al 2O 3, contain and be equivalent to 70-90 gram Al 2O 3/ liter, and in NaOH, preferably contain 90-110 gram A1 2O 3/ liter concentration; Preferred temperature when decomposing with carbonic acid gas is 50-95 ℃, is more preferably 60-90 ℃.Fix-Na 2The O measurer has the trend that reduces with increase in temperature, and sulfuric acid undissolved residue measurer has the tendency that reduces with the temperature reduction.
Carbon dioxide gas is diluted to CO with air 2Gas concentration reaches 20-40%, be equivalent to 1 go up state in the sodium aluminate solution optimizing breathing amount that feeds above-mentioned gas be 0.3-3NL (standard liter)/minute.If not enough 0.3NL/ branch, then desire obtains high eduction rate length consuming time; Otherwise it is, then bring obstacle, thereby all bad to stable operation if surpass the 3NL/ branch.
The feeding time of carbon dioxide gas is generally preferably in 1-5 hour scope.
Manufacture method of the present invention is compared with the bayer's process that adds crystal seed, because reaction times of the present invention weak point and eduction rate are up to 70-90 weight %, so the production of aluminum hydroxide rate height of unit volume reactive tank.And making it the round-robin bayer's process as the adding crystal seed of present main stream approach, eduction rate is 40-60 weight %.
The present invention is if be in below the 80 weight % eduction rate, and then impurity silicone content in the aluminium hydroxide is pressed SiO 2Count below the 0.04 weight %.Though along with SiO is pressed in the raising of eduction rate 2The sila matter content of meter has the trend that increases, but does not find when following to increase in this ratio when eduction rate is in 50 weight %, to reaching below the 80 weight % little increasing before, and sharply increases during above 80 weight %.Though the impurity silicone content is subjected to the very big influence of above-mentioned eduction rate in the aluminium hydroxide, work as eduction rate one and regularly also be subjected to separating out Temperature Influence, it is high more to separate out temperature, and the impurity silicone content is big more.
Just make below that used condition describes in the above-mentioned manufacture method of aluminium hydroxide of the present invention.
The high person of crystal seed rate for example works as d for well 50When the crystal seed rate of=2 μ m crystal seeds is 0.5 weight %, be lower than 80 ℃ as if the evolution reaction temperature, then Fix-Na 2O is higher than 0.2 weight %.Only attenuate hour when the particle diameter of crystal seed, can find that just crystal seed rate lower value has the trend of reduction.
In addition, when the decomposition reaction temperature is 80 ℃, d 50The crystal seed of=3.0 μ m, bad if the crystal seed rate is not more than 8 weight %.If d 50The crystal seed of=0.5 μ m, and the crystal seed rate then can be made Fix-Na when being higher than 0.2 weight % 2O is below the 0.22 weight % and the sulfuric acid undissolved residue is the following aluminium hydroxide of 0.12 weight %.
Below elaborate with embodiment and reference examples.
Embodiment 1~13
Will in homemade bauxitic clay, Wingdale, yellow soda ash and coal (coal-tar pitch) by 1.5: 2: 0.1: 0.2 weight ratio is mixed, and is crushed to the 2mm degree, and 1250 ℃ of following sintering are 1 hour in rotary kiln.Add water and make it to become the sodium aluminate solution with following composition in this sinter, 95 ℃ dissolved 1 hour down, told residue, handled 40 minutes in 150 ℃ of following silica removals, removed solidss such as sodium aluminium silicate, made sodium aluminate solution.Consisting of of this sodium aluminate solution:
Free NaOH 110 grams per liters
Al 2O 3(scaled value) 90 grams per liters
Na 2CO 330 grams per liters
K 2O 8 grams per liters
SiO 20.3 grams per liter
According to condition shown in the table 1, i.e. crystal seed particle diameter d 50, the crystal seed rate, separate out under the temperature, 240 rev/mins stirrer is installed, the speed of dividing with 5.5NL/ 10 going up and state sodium aluminate solution and feed CO in placing reaction vessel with the air dilution in 10 liters of reaction vessels that place thermostatic bath 2Concentration is 40% gas, carries out 3 hours, decomposes, to separate out aluminium hydroxide.This moment, eduction rate was 80 weight %.
The characteristic of resulting aluminium hydroxide is shown in Table 1.
Wherein, the hydrogen-oxygen aluminium that uses as crystal seed is the material with following properties.
Crystal seed A Crystal seed B Crystal seed C
Secondary particle diameter d 50(μm) ???3.0 ???2.0 ???0.5
Isodisperse n ???1.7 ???2.3 ???2.5
?Fix-Na 2O ????(wt%) ???0.29 ???0.27 ???0.23
Sulfuric acid undissolved residue amount (wt%) ???0.1 ???0.0 ???0.0
Table 1
Embodiment No. Crystal seed particle diameter (μ m) Crystal seed rate (%) Separate out temperature (℃) Aluminium hydroxide
Fix-Na 2O (wt%) Undissolved residue amount (wt%) Secondary particle footpath (μ m) Isodisperse n ?SiO 2Conversion amount (wt%)
Embodiment 1 embodiment 2 embodiment 3 embodiment 4 embodiment 5 embodiment 6 implement 7 embodiment, 8 embodiment, 9 embodiment, 10 embodiment, 11 embodiment, 12 embodiment 13 ???2.0 ???2.0 ???2.0 ???2.0 ???2.0 ???2.0 ???2.0 ???2.0 ???3.0 ???0.5 ???0.5 ???0.5 ???0.5 ????0.5 ????0.5 ????1.5 ????1.5 ????1.5 ????3.0 ????3.0 ????3.0 ???10.0 ????0.5 ????1.0 ????3.0 ????8.0 ???90 ???95 ???80 ???90 ???95 ???60 ???80 ???90 ???80 ???80 ???80 ???80 ???80 ???0.18 ???0.14 ???0.18 ???0.12 ???0.07 ???0.20 ???0.14 ???0.09 ???0.20 ???0.15 ???0.11 ???0.09 ???0.03 ????0.10 ????0.12 ????0.02 ????0.08 ????0.11 ????0.02 ????0.02 ????0.05 ????0.05 ????0.03 ????0.02 ????0.02 ????0.01 ?????81 ?????88 ?????57 ?????58 ?????63 ?????44 ?????43 ?????42 ?????51 ?????70 ?????53 ?????33 ?????19 ??????5.3 ??????6.1 ??????5.0 ??????5.1 ??????6.0 ??????8.2 ??????8.3 ??????8.6 ??????7.3 ??????8.6 ??????6.0 ??????8.8 ??????7.2 ????0.022 ????0.024 ????0.020 ????0.021 ????0.022 ????0.006 ????0.008 ????0.014 ????0.009 ????0.009 ????0.008 ????0.006 ????0.006
So-called undissolved residue amount in the ※ table is meant the undissolved residue amount that records by above-mentioned sulfuric acid dissolution rate assay method.
Embodiment 14~19
Though manufacture method of the present invention is the method for embodiment, but just puts down in writing by reference examples as the method for aluminium hydroxide.
For decomposing the sodium aluminate solution that uses among the embodiment 1~13, feed CO by the crystal seed particle diameter shown in the table 2, crystal seed rate and decomposition temperature condition 2Gas makes it to separate out aluminium hydroxide.The eduction rate of this moment is 80 weight %.The characteristic of the aluminium hydroxide that is obtained is shown among the table 2.
Except that creating conditions shown in the table 2, by having carried out same operation with embodiment 1~13 similarity condition.
Table 2
Embodiment No. Crystal seed particle diameter (μ m) Crystal seed rate (%) Separate out temperature (℃) Separate out aluminium hydroxide
?Fix-Na 2O ??(wt%) Undissolved residue amount (wt%) Secondary particle footpath (μ m) Isodisperse n ?SiO 2Conversion amount (wt%)
Embodiment 14 embodiment 15 embodiment 16 embodiment 17 embodiment 18 embodiment 19 ????2.0 ????2.0 ????2.0 ????3.0 ????3.0 ????0.5 ????0.5 ????0.5 ????1.5 ????3.0 ????5.0 ????0.1 ????60 ????80 ????60 ????80 ????80 ????80 ???0.45 ???0.29 ???0.27 ???0.38 ???0.29 ???0.31 ????0.04 ????0.05 ????0.02 ????0.12 ????0.10 ????0.05 ???????87 ???????84 ???????52 ???????75 ???????67 ??????105 ????8.9 ????8.7 ????5.9 ????6.8 ????7.0 ????8.9 ????0.017 ????0.019 ????0.018 ????0.014 ????0.012 ????0.010
Reference examples 1~3
For embodiment 1~13, do not add aluminium hydroxide crystal seed, carry out CO by condition shown in the table 3 2Decompose, obtained the aluminium hydroxide of characteristic shown in the table 3.
The eduction rate of the aluminium hydroxide of this moment also is 80 weight %.
Table 3
Reference examples No. Crystal seed particle diameter (μ m) Crystal seed rate (%) Separate out temperature (℃) Separate out aluminium hydroxide
??Fix-Na 2O ???(wt%) Undissolved residue amount (wt%) Secondary particle footpath (μ m) Isodisperse n ?SiO 2Conversion amount (wt%)
Reference examples 1 reference examples 2 reference examples 3 ???- ???- ???- ????0 ????0 ????0 ????60 ????80 ????90 ????0.72 ????0.58 ????0.38 ????0.02 ????0.62 ????0.87 ????60 ????85 ????85 ????6.4 ????7.8 ????8.0 ????0.031 ????0.033 ????0.035
Embodiment 20~23
At the eduction rate of aluminium hydroxide is in all conditions of embodiment 1 of 80 weight %, regulates and separates out the time, make eduction rate become 12,45,68 and 90 weight % respectively, and other condition and operation and embodiment 1 is identical, make it to separate out aluminium hydroxide.The characteristic of resulting aluminium hydroxide is shown among the table 4.
Table 4
Embodiment No. Eduction rate (wt%) Aluminium hydroxide
Fix-Na 20 (wt%) Insoluble residual molten amount (wt%) SiO 2Conversion amount (wt%)
Embodiment 20 ?12 ?0.21 ????0.06 ????0.010
Embodiment 21 ?45 ?0.17 ????0.08 ????0.013
Implement 22 ?68 ?0.17 ????0.09 ????0.018
Embodiment 23 ?90 ?0.22 ????0.12 ????0.078
Reference example 1~10
Shown in the table 5 is the characteristic of the commercially available product aluminium hydroxide goods of separating out with the bayer's process that adds crystal seed.
Table 5
Reference example No. The goods trade mark ?Lot ?No. Separate out aluminium hydroxide
?Fix-Na 2O ??(wt%) Undissolved residue amount (wt%) Number of times particle footpath (μ m) Isodisperse n ??SiO 2Conversion amount (wt%)
Reference example 1 reference example 2 reference examples 3 reference examples 4 reference examples 5 Clear and electrician's (strain) makes HWA ??A ??B ??C ??D ??E ???0.30 ???0.26 ???0.26 ???0.30 ???0.27 ????0.19 ????0.38 ????0.08 ????0.05 ????0.26 ????53 ????59 ????59 ????50 ????57 ???2.5 ???2.6 ???2.7 ???2.8 ???2.7 ????0.009 ????0.007 ????0.008 ????0.009 ????0.006
Reference example 6 Clear and electrician's (strain) makes HWB ??A ???0.15 ????0.92 ????60 ???2.3 ????0.007
Reference example 7 Clear and electrician's (strain) makes HWC ??A ???0.11 ????1.64 ????80 ???2.4 ????0.008
Reference example 8 Clear and electrician's (strain) makes HWP ??A ???0.45 ????0.03 ????55 ???3.8 ????0.008
Reference example 9 The system A-30 of Alcoa society ??A ???0.23 ????1.23 ????94 ???3.2 ????0.017
Reference example 10 Sumitomo Chemical (strain) system C-14S ??A ???0.15 ????0.20 ????60 ???3.4 ????0.004
Make for the first time so a kind of aluminium hydroxide according to the present invention, this aluminium hydroxide has in acid the characteristics such as insoluble residue amount few and impurity Na, especially fixed sodium content is low. Aluminium hydroxide of the present invention also possesses the complete characteristics of particle diameter of primary particle and secondary. Aluminium hydroxide of the present invention is suitable for using with raw material as high-grade inorganic water treatment agent.

Claims (4)

1. an aluminium hydroxide is characterized in that fixed sodium (Fix-Na 2O) content is below the 0.22 weight %, and the sulfuric acid undissolved residue amount that records by following sulfuric acid dissolution rate assay method is lower than 0.12 weight %.
Sulfuric acid dissolution rate assay method: will mix with the 250 gram distilled water and the 375 gram vitriol oils by 2 hours 195 gram aluminium hydroxides of drying under 110 ℃, dissolved 60 minutes in 105~107 ℃ on stirring (rotating speed is 240 rev/mins) limit, limit.1 liter of hot water dilution lysate filters through C type qualitative filter paper then, uses 1 liter of hot wash again.Filter paper and residue were weighed after under 100 ℃ dry 30 minutes, and the dry filter paper weight that deduction was measured before filtering is in advance obtained residue weight Xg, and (Xg/195) * 100 are defined as sulfuric acid undissolved residue amount (weight %).
2. the aluminium hydroxide of claim 1 is characterized in that the impurity silicone content is scaled SiO 2The time be below the 0.04 weight %.
3. the manufacture method of an aluminium hydroxide, it is characterized in that bauxitic clay, calcium cpd, sodium compound and coal are mixed, pulverize the back sintering, add at least a water or solution in entry, sodium hydroxide or the sodium aluminate then, extract the soluble part of sinter, separate residue, and then do desiliconization and handle back manufacturing sodium aluminate solution, in this solution, add fine aluminium hydroxide as crystal seed, and feed CO 2Gas makes it to separate out aluminium hydroxide.
4. the aluminium hydroxide manufacture method of claim 3, the eduction rate that it is characterized in that aluminium hydroxide is below the 80 weight %.
CN95109122A 1995-05-26 1995-06-27 Aluminium hydroxide and preparation method thereof Expired - Lifetime CN1075043C (en)

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JP7128468A JPH08325011A (en) 1995-05-26 1995-05-26 Aluminum hydroxide and its production
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JP5179095B2 (en) * 2006-06-14 2013-04-10 裕子 石栗 Method for producing high-purity aluminum hydroxide and high-purity aluminum hydroxide obtained by the method
CN100378000C (en) * 2006-08-25 2008-04-02 中国铝业股份有限公司 Method for producing micropowder aluminium hydroxide by neutralization method
TW200909356A (en) * 2007-07-09 2009-03-01 Aditya Birla Sci & Tech Co Ltd Extraction of alumina
CN114130382B (en) * 2021-12-14 2023-11-21 河南能源化工集团研究总院有限公司 Aluminum hydroxide powder and preparation method thereof

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CN1031689A (en) * 1987-09-02 1989-03-15 山东铝厂 Producing sandy alumina through continuous stirring and decomposition of seed technology
CN1032650A (en) * 1987-10-17 1989-05-03 全苏铝镁电极工业科学研究设计院 The preparation method of aluminium hydroxide

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