WO1994024048A1 - Production d'hydroxyde d'aluminium - Google Patents

Production d'hydroxyde d'aluminium Download PDF

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Publication number
WO1994024048A1
WO1994024048A1 PCT/US1993/003474 US9303474W WO9424048A1 WO 1994024048 A1 WO1994024048 A1 WO 1994024048A1 US 9303474 W US9303474 W US 9303474W WO 9424048 A1 WO9424048 A1 WO 9424048A1
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WO
WIPO (PCT)
Prior art keywords
aluminum hydroxide
aluminum
particles
choline
alumina
Prior art date
Application number
PCT/US1993/003474
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English (en)
Inventor
Edward S. Martin
Mark L. Weaver
John E. Marhanka
Alan Pearson
Masaki Madono
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Aluminum Company Of America
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US07/601,654 external-priority patent/US5225229A/en
Application filed by Aluminum Company Of America filed Critical Aluminum Company Of America
Priority to AU42849/93A priority Critical patent/AU4284993A/en
Priority to PCT/US1993/003474 priority patent/WO1994024048A1/fr
Publication of WO1994024048A1 publication Critical patent/WO1994024048A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F7/00—Compounds of aluminium
    • C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
    • C01F7/42—Preparation of aluminium oxide or hydroxide from metallic aluminium, e.g. by oxidation
    • C01F7/428—Preparation of aluminium oxide or hydroxide from metallic aluminium, e.g. by oxidation by oxidation in an aqueous solution
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/10—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminium oxide
    • C04B35/111—Fine ceramics
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/45—Aggregated particles or particles with an intergrown morphology
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/14—Pore volume
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/16—Pore diameter

Definitions

  • This invention relates to the production of aluminum trihydroxide.
  • Figure 1 depicts the structural formula of tetramethylammonium hydroxide.
  • Figure 2 depicts the structural formula of choline.
  • Figures 3, 4 and 5 are 5000x scanning electron micrographs of aluminum hydroxide particles of the present invention.
  • Figures 6 and 7 are 5000X scanning electron micrographs of alumina calcined from aluminum hydroxide particles precipitated respectively in the presence and absence of an alpha alumina promoter.
  • aluminum hydroxide is produced, as in Keith and Comely, by the reaction of water with aluminum metal.
  • An attraction of producing aluminum hydroxide in this way lies in the fact that aluminum metal of very high purity is available in the marketplace at reasonable prices as compared to the cost of obtaining similar purity aluminum hydroxide by direct production from bauxite.
  • Choline concentrations of about 0.05 to 2 mole per liter (M) are effective for promoting the reaction of water and aluminum metal according to the present invention.
  • the range of 0.05 to 1 mol per liter is preferred when ceramic aluminas are the desired end product.
  • Higher choline concentrations yield products having morphologies suitable, for example, for sorbent applications, as discussed below. Concentrations above about 2.0M are not preferred, as decreased reaction rates seem to be found at such concentrations.
  • the lower end of this concentration range causes a pH of about 12.7, and pH rises to above 13 as one exceeds around 0.1 M.
  • Example IV of Keith and Comely's 3,494,733 is the example where tetramethylammonium hydroxide is used
  • pH used in Example IV of Keith and Comely's 3,494,733 is 9.5, this indicating a tetramethylammonium hydroxide concentration in the neighborhood of 3.2 ⁇ 10 -5 M.
  • Temperature of the aqueous solution used in the invention is preferably kept above about 40oC, in order to prevent scale adhesion on the aluminum metal being reacted.
  • the temperature also is preferably kept relatively low, for example in the range of about 40°C to 70oC, preferably about 50°C, which results in a final product of improved translucency.
  • Stirring provides intimate contact of metal and solution and maintains a homogenous concentration in the solution.
  • the stirring need not be so vigorous as blender, or high shear, mixing.
  • Stirring reduces scale adhesion on the vessel containing the reactants.
  • Stirring also enhances autoprecipitation, i.e., precipitation without any need for seeding.
  • a reaction mixture to which alpha alumina promoter has been added for example in an amount of about 0.01-10% by weight based on the amount of equivalent alpha alumina in the precipitate obtained, preferably about 0.01-5%, more preferably about 0.01-1%, yields a precipitate containing mixed hydrate (Gibbsite) and alpha alumina crystals. These amounts correspond to about 0.1 to 100 g/l, 0.1 to 50 g/l and 0.1 to 10 g/l, respectively.
  • Advantages flowing from this mixed precipitate include lower temperatures for converting the Gibbsite to alpha alumina, with correspondingly smaller alpha alumina crystallites and improved grindability. Also, the calcined final product from precipitation in the presence of an alpha alumina promoter shows improved translucence, especially when coupled with the lower precipitation temperature discussed above. These advantages can be obtained in the presence of dissolving additives other than choline in the reaction mixture.
  • the promoter material should be of high purity, but need only be pure enough to meet the purity requirements of the final product. Examples of maximum impurity limits are 100 ppm SiO 2 , 50 ppm Na 2 O, 30 ppm Fe 2 O 3 and 50 ppm total for any remaining impurities.
  • the promoter material should generally be submicron in size. Material having a median particle size of about 0.5 ⁇ is suitable. For example, a suitable material may have a particle size distribution with a d90 value of 1.66 ⁇ , a d50 value of 0.54 ⁇ and a d10 value of 0.33 ⁇ , as tested on a Micromeritics Sedigraph ® .
  • the d90, d50 and d10 values are points on the particle size distribution curve at which, respectively, 90, 50 and 10% of the material is finer than the stated particle size. For instance, 90% of the particles have diameters smaller than the d90 value of 1.66 ⁇ .
  • Precipitation also can be carried out in the presence of an aluminum hydroxide seed.
  • the aluminum metal dissolves in the choline solution readily enough to drive the precipitation so that the aluminum hydroxide seed is not necessary for the precipitation, some advantages in the form of improved particle size control may arrive from use of the seed.
  • Reaction time is in general 4 to 6 hours, with up to two days being required for very coarse metal.
  • the longer reaction times for the coarser metal is not necessarily of disadvantage, since coarser metal is cheaper and batch operation permits one to simply load the reactants into a vessel and permit the reaction to go to completion. Continuous operation is, of course, also possible.
  • impurities can also result from contaminants in the water and the choline. Deionized, or perhaps double-deionized, and distilled water is suitable. Depending on the end use of the aluminum hydroxide, different impurities are of concern to different end uses. Iron and copper impurities in the aluminum are disadvantageous to the invention, because these impurities retard the aluminum-water reaction.
  • the aluminum hydroxide product of the invention will, in general, have an average particle size of at least about 1 micron, preferably about 4 to 12 microns, with higher choline concentrations giving the larger average particle sizes.
  • Aluminum hydroxide produced according to the present invention can be calcined to produce high purity alumina useful, for example, in the manufacture of high intensity sodium vapor discharge lamps.
  • Aluminum hydroxide precipitated in the presence of an alpha alumina promoter as discussed above can be calcined to form alpha alumina at lower temperatures, for example less than 1100°C, preferably about 1050°C. Any remnant choline is driven off or destroyed in the calcination, and other impurity concentrations can be reduced, depending on their vapor pressures or the vapor pressures of their oxides.
  • calcined product of the invention uses for the calcined product of the invention are as polishing compound, in cutting tools, in bioceramics, in electronic substrates, synthetic jewels, watch covers, special windows (such as the window of the bar-code readers of checkout counters), encapsulating lids of various types, etc.
  • a solution of choline in water was made using Eastman practical grade 45% choline in methanol to yield a solution concentration of 0.05 mols choline per liter of solution.
  • the solution was brought to a temperature of 40°C and stirred using an air stirrer.
  • 40.5 grams of aluminum powder namely Alcoa High-Purity Atomized Powder Grade 7123 powder (minimum aluminum content of 99.97%) having an average particle size of 17 microns and a surface area of 250,000 mm 2 /gm, first mixed with a small amount of deionized water to guard against dusting, was mixed with the choline solution.
  • the 40.5 grams of aluminum provided a metal concentration of 2 mols per liter of choline solution.
  • Table I presents a summary of the experimental conditions used for this example.
  • Table IV presents the types of aluminum hydroxide detected by X-ray diffraction analysis.
  • Example II The purpose of this example was to determine the effect of solution metal concentration. Procedure was as in Example I, except that 101.1 grams of aluminum was used, this amounting to a metal concentration of 5 mols per liter of choline solution. Temperature control became more difficult (the larger amount of aluminum resulted in increased heat evolution), as evidenced by the greater temperature range in Table I. However, the process, as embodied in this Example, is still well within the capabilities of any of a multitude of temperature control techniques familiar to chemical engineers. Aluminum hydroxide types recovered were as presented in Table IV.
  • Example I a granular aluminum metal of lower surface area was used to provide an idea of the effect of surface area, by comparison with Examples I-IV.
  • the metal measured 99.7% Al in purity. Choline concentration was also varied, to develop an indication of its effect on reaction time.
  • Procedure was as in Example I, with parameter and result differences as noted in Table II.
  • Example V and VI 61 grams of aluminum were charged, and the experiments were stopped before complete reaction.
  • Example VII all of the aluminum charged was reacted.
  • Aluminum hydroxide types recovered were as presented in Table V.
  • the reactor was a packed-bed-type formed by the pebbles in a vertical tube of 11 ⁇ 2-inch internal diameter and 18-inches height. Choline solution circulated upflow through the bed, at a 1 liter per minute flow rate, 5 cm/sec average flow velocity, to provide the contact achieved by stirring in Examples I-VII. Hydrogen gas was vented at the top of the tube.
  • the choline solution was circulated into the bottom of the tube from a holding tank, brought off the top of the tube, and recirculated back to the holding tank.
  • the holding tank was sufficiently large that the aluminum hydroxide product coming from the top of the tube settled to the bottom of the tank, with the circulation to the bottom of the tube being from clarified solution above the bottom of the tank.
  • Experimental conditions and results are presented in Tables II and V. Temperature was measured in the holding tank.
  • Example II aluminum surface area was further decreased.
  • Solutions of choline in water were made as in Example I to yield solution concentrations as given in Table III. The solutions were brought to the temperatures indicated in Table III.
  • Aluminum rods having initial dimensions of 9.3 mm diameter by 33 to 35 mm length were then added to the liquid and the liquid was stirred above the immersed rods. The rods were about 99.99% pure aluminum metal. Reaction times and weight of aluminum reacted were as given in Table III. Unlike Examples X-XIII, there was no stirring in Example IX. Weight of aluminum hydroxide recovered, and the identity of the aluminum hydroxide - gibbsite - appears in Table VI.
  • Example IX was varied as follows: Instead of a stagnant solution, the solution was continuously stirred. The surface area of the aluminum was 335 mm 2 /gram. For a charge of 25.1 grams, 2.56 grams of aluminum reacted in 6.5 hours. The weight of recovered aluminum hydroxide product was 6.34 grams, a little less than stoichiometric due to scale formation on the reactor walls. The product contained bayerite and nordstrandite.
  • Tables IIIA show that there is no consistent difference in rate of the choline-water-aluminum reaction at 60°C between choline solutions which contain methanol and those which do not.
  • the methanol-free choline was prepared by passing choline chloride through a strong-base ion-exchange resin, Rexyn 201 of Fisher Scientific.
  • the aluminum hydroxide particles of the present invention particularly those produced using a solution containing methanol as well as more than 1.0M choline, show unusual morphologies, as seen in the examples of Figs. 3,4 and 5.
  • the sample of Fig. 3 was prepared with a choline concentration of 2.0M, a reaction temperature of 75oC and a reaction time of about 6.2 hrs, and has a surface area of about 32.2 m 2 /gm and average pore diameter of about 227 angstroms (BET 4V/A).
  • the sample of Fig. 4 was prepared with a choline concentration of 2.0M, a reaction temperature of 60°C and a reaction time of about 30 hours.
  • the material has a surface area of about 40 m 2 /gm.
  • the sample of Fig. 5 was prepared with a choline concentration of 1.5M, a reaction temperature of 60°C and a reaction time of about 7.4 hours.
  • the material has a surface area of about 21.1 m 2 /gm and an average pore diameter of about 280.4 angstroms. In each case, the methanol concentration was about 4.6 times greater than the choline concentration. The surface areas and pore sizes were determined through BET nitrogen sorption analysis.
  • the particles are formed from a plurality of randomly-oriented platelets, resulting in a sponge-like morphology.
  • the platelets are about 0.1 to 0.3 ⁇ thick.
  • the spacing and orientation of the platelets is such that the particles have a large number of "macro" openings about 0.05-2.5 ⁇ , preferably about 0.1-1 ⁇ in size.
  • the aluminum hydroxide particles have a surface area of at least about 1.5 m 2 /gm, preferably at least about 5 m 2 /gm, more preferably about at least 10 m 2 /gm.
  • the aluminum hydroxide particles of the present invention may be calcined to form alumina particles.
  • the calcining can be carried out at, for example, 400 to 800oC. A time of one to three hours is usually sufficient to ensure dehydroxylation.
  • the lower calcining temperatures appear to provide higher surface areas as shown in Tables VII to X.
  • the alumina particles generally have a surface area of at least 375 m 2 /gm, preferably at least 425 m 2 /m.
  • the morphologies of the aluminum hydroxide particles are retained in the alumina particles. With respect to crystal structure, the calcined particles assume the transition (i.e., chi, gamma, or mixtures thereof) alumina phases. As noted above the aluminum hydroxide particles of the present invention are substantially free from alkali metal (especially sodium) contamination. This benefit likewise is retained in the calcined particles.
  • the amount of sodium in the aluminum hydroxide particles is less than 0.01% by weight, preferably less than 0.001%. Similar levels are found for sodium oxide in the calcined particles.
  • the calcined particles also have a large number of relatively large pores, with at least about 30% being at least about 100 angstroms in diameter. The average pore diameter should be 100 angstroms or larger (as determined by the BET method), preferably at least 200 angstroms.
  • the high surface area range renders the alumina particles suitable for heterogenous catalyst support and absorbent applications.
  • the large pore sizes are particularly useful in allowing transport of very high molecular weight compounds into and out of the pore structure.
  • Such compounds include, for example, heavy compounds in petroleum, peptides and proteins in sorbent applications in biological systems, and synthetic polymers.
  • the aluminum hydroxide particles of this invention can be calcined to form alpha alumina, which in turn can be pressed and sintered. Particles formed at low choline concentrations are particularly useful in this regard. Examples of calcining to form alpha alumina are found in Table XI. Sample 21886-4 was prepared with 0.125M choline and Sample 21886-6 with 0.50M choline. In each case the reaction temperature was 60°C, with a reaction time of 30.4 hrs for the former and 24 hrs for the latter. The Alpha Alumina % column reflects the X-ray diffraction intensity of the samples as compared to that of Alcoa Standard SRPA 87. The results show that alpha alumina was produced.
  • the calcined product obtained can be sintered to form ceramics.
  • Al(OH) 3 produced in a 30 gallon reactor, 0.125 M choline, 75°C, was calcined for 4 hours at 1150°C, and the resulting alpha alumina was given a so-called "ACMA" grind, i.e., 4 kg of grinding balls and 125 gm of the alpha alumina at 62 rpm rotation rate in a 1.3 gallon mill.
  • the ground product was pressed at 5000 psig to form a green body of 2.088 gm/cc density.
  • the pressed alumina compact was then heated to progressively higher temperatures, finishing with one hour at 1540°C, providing an average fired density of 3.943 gm/cc, based on two samples, one 3.942, the other 3.994.
  • the material of the present invention can be sintered to high densities, i.e., greater than 3.9 gm/cc, using conventional techniques. This provides more efficiency in the sintering operation, allowing either the production of higher density material for given sintering conditions or the use of more economical conditions to provide a given density.
  • Material formed from higher choline concentrations also can be sintered, although the "macroporous" structure of the material limits its use as a ceramic. Such sintered material can be used, for example, in high temperature insulation applications.
  • Run 1- Aluminum hydrate is prepared by reacting 1000g high purity aluminum metal in 10 liters of 1.4M choline at 50°C. 20 g/l finely ground alpha alumina (d90-1.66 ⁇ , d50-0.54 ⁇ , d10- 0.33 ⁇ ) is added to the reaction mixture as the hydrate is precipitating. The resulting material is then dried, split into three batches, and the individual portions calcined for 2 hrs at 1050, 1150 or 1250oC.
  • Run 2 is identical to run 1 except no alpha alumina promoter material is added during precipitation.
  • the surface areas and alumina phase compositions obtained after calcining are as follows:
  • Figs. 6 and 7 are scanning electromicrographs of the products calcined at 1050°C from Runs 1 and 2, respectively. It can be seen that the calcined material from the precipitation in the presence of the alpha alumina promoter (Fig. 6) shows a smaller crystallite size, even though the particle size is not significantly changed. The smaller crystallite size allows the product to be ground finer, and thus green bodies formed from the ground product can be sintered at lower temperatures.
  • Translucence is evaluated by the optical transmission of white light in a brightness meter.
  • Run 1 Aluminum hydrate is prepared by reacting 1000 g high purity aluminum metal in 10 liters of 1.4M choline at 50°C. 20 g/l finely ground alpha alumina promoter (d90-1.66 ⁇ , d50-0.54 ⁇ , d10-0.33 ⁇ ) is added to the reaction mixture as the hydrate is precipitating. The precipitate is collected and calcined for two hours at 1250oC. The resulting product shows a particle size distribution of d90- 1.31 ⁇ , d50- 0.62 ⁇ , and d10- 0.35 ⁇ , and a translucence (absorbance) value of 12.
  • Run 2 is identical to Run 1 except no promoter material is added during precipitation.
  • the resulting material shows a particle size distribution of d90- 0.91 ⁇ , d50- 0.48 ⁇ and d10-0.35 ⁇ , and a translucence value of 17.
  • Run 3 is identical to Run 2, except the precipitation temperature is 75°C.
  • the resulting product shows a particle size distribution of d90- 1.33 ⁇ , d50- 0.53 ⁇ and d10- 0.31 ⁇ , and a translucence value of 26.
  • HPA-CHV2 0.05 78-89 250,000** 3.70 101.0
  • HPA-CHV3 0.05 54-67 250,000** 4.92 40.5
  • HPA-CHV4 0.05 55-65 250,000** 5.50 101.0

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)

Abstract

Procédé de production d'hydroxyde d'aluminium qui consiste à faire réagir de l'eau en phase liquide et de l'aluminium à un pH supérieur à environ 12,4. Dans cette plage de pH, l'hydroxyde d'aluminium est produit à des vitesses acceptables, à la fois pour des surfaces spécifiques d'aluminium supérieures à 75 000 mm2 par gramme et pour des surfaces spécifiques d'aluminium inférieures à environ 50 000 mm2 par gramme, allant même jusqu'à 20 mm2 par gramme. Selon un autre mode de réalisation de la présente invention, le procédé de production d'hydroxyde d'aluminium consiste à faire réagir de l'aluminium avec de l'eau liquide contenant de la choline. On obtient des particules d'hydroxyde d'aluminium ayant des morphologies uniques en leur genre.
PCT/US1993/003474 1990-03-05 1993-04-14 Production d'hydroxyde d'aluminium WO1994024048A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
AU42849/93A AU4284993A (en) 1993-04-14 1993-04-14 Aluminum hydroxide production
PCT/US1993/003474 WO1994024048A1 (fr) 1990-03-05 1993-04-14 Production d'hydroxyde d'aluminium

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US07/601,654 US5225229A (en) 1986-07-18 1990-03-05 Aluminum hydroxide production
PCT/US1993/003474 WO1994024048A1 (fr) 1990-03-05 1993-04-14 Production d'hydroxyde d'aluminium

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112174177A (zh) * 2020-10-13 2021-01-05 中国铝业股份有限公司 一种水硬性氧化铝及其制备方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0263810A2 (fr) * 1986-10-03 1988-04-13 Treibacher Chemische Werke Aktiengesellschaft Matériau abrasif fritté à base d'alumine alpha
US5225229A (en) * 1986-07-18 1993-07-06 Aluminum Company Of America Aluminum hydroxide production

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5225229A (en) * 1986-07-18 1993-07-06 Aluminum Company Of America Aluminum hydroxide production
EP0263810A2 (fr) * 1986-10-03 1988-04-13 Treibacher Chemische Werke Aktiengesellschaft Matériau abrasif fritté à base d'alumine alpha

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112174177A (zh) * 2020-10-13 2021-01-05 中国铝业股份有限公司 一种水硬性氧化铝及其制备方法

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