Herstellung und Eigenschaften von Aluminiumaquoxid. II. Böhmit aus Natriumaluminat und Salpetersäure

Preparation and Properties of Aluminium Hydroxide. II. Boehmite from Sodium Aluminate and Nitric Acid A report is given on the physical-chemical characteristics of aluminium hydroxide which contain mainly boehmite, having been obtained by continuous precipitation from sodium aluminate solution with nitric acid using technical raw materials and conditions being very similar to those applied in production. The influence of the reaction conditions (pH value, temperature, concentration and residence time in the precipitation suspension) on the chemical composition, structure and texture of the hydrogels is studied. With rising precipitation temperature the pH range extends, within which already after short residence times pure-phase, relatively well crystalline boehmite hydrogels are obtained in the precipitated solution.     

Herstellung und Eigenschaften von geformtem Aluminiumoxid. I. Einfluß der Fällbedingungen des Böhmithydrogels auf die Porenstruktur des geformten Aluminiumoxids

Preparation and Properties of Formed Aluminium Oxide. I. Influence of the Precipitation Conditions of the Boehmite Hydrogel on the Pore Structure of Formed Aluminium Oxide A report is given on the influence of the precipitation conditions of boehmite (pH value, temperature, concentration and residence time in the precipitation suspension) on the cavity structure of aluminium oxide spheres, made by coagulation of boehmite hydrosol in ammonia liquor and subsequent thermal treatment at 110 and 600°C. The boehmite hydrogel was obtained at continuous precipitation conditions by neutralisation of sodium aluminate solution with nitric acid. It is shown that the difference in the pore structure of the formed aluminium oxide obtained by varying the precipitation conditions were caused by the special morphological features of the boehmite crystallization in the precipitation process.     

Herstellung und Eigenschaften von geformtem Aluminiumoxid. II. Einfluß der mechanischen Zerkleinerung gefällten Böhmithydrogels auf die Porenstruktur und die Abriebfestigkeit des geformten Aluminumoxids

Preparation and Properties of Formed Aluminium Oxide. II. Influence of the Mechanical Comminution of Precipitated Boehmite Hydrogel on the Pore Structure and Abrasion Resistance of the Aluminium Oxide A report is given on the physical-chemical characteristics of formed aluminium oxide on the basis of boehmite which had been continuously precipitated with nitric acid from sodium aluminate solution, subsequently filtrated, dried at 110°C and ground prior to moulding. In double dependence on the grinding intensity (type of mill, grinding time) and on the precipitation conditions (pH value, temperature) the changes of the morphology and the texture of the boehmite hydrogel are investigated. According to the particles constituting the precipitated boehmite hydrogel is made in two stages. In dependence on the grinding intensity a maximum correlation is observed for the abrasion resistance.     

Herstellung und Eigenschaften von Aluminiumaquoxid. III. Peptisierung von Böhmit mit Salpetersäure

Preparation and Properties of Aluminium Hydroxide. III. Peptization of Boehmite with Nitric Acid A reaction of the aluminium oxide hydroxide boehmite with nitric acid in dependence on the temperature and the molar ratio HNO₃/Al₂O₃ is studied. The effect of the acid results in the formation of basic aluminium nitrates, which can change the rheological properties of the boehmite hydrogel due to redispersion or desaggregation up to its ?liquefaction”? to boehmite hydrosol. For the dependence of the flow velocity of the boehmite hydrosol on the molar ration HNO₃ Al₂O₃ a maximum correlation is characteristic. It can also be interpreted from the colloid-chemical point of view and it is a technically relevant indicator for the optimization of the peptization. By the peptization conditions of the boehmite hydrogel the pore structure of the Al₂O₃ can be varied in a carefully directed way.     

Influence of aluminium precursor on physico-chemical properties of aluminium hydroxides and oxides

An attempt to obtain aluminium hydroxide that could give aluminium oxides of increased thermal stability was made. Aluminium hydroxide was precipitated during a hydrolysis of aluminium chloride in ammonia medium. The influence of preparative conditions, such as a dosing rate of aluminium precursor, pH, duration of the precipitate refluxing and temperature of calcination, on the properties of obtained hydroxides and oxides was investigated. The materials were studied with the following methods: thermal analysis, IR spectroscopy, low-temperature nitrogen adsorption and adsorption–desorption of benzene vapours. Precipitated boehmites had high values of S _BET determined from nitrogen adsorption (220–300 m²g^–1), good sorption capacity for benzene vapours, developed mesoporous structure and hydrophilic character. It has been proved that a high pH value during the precipitation of aluminium hydroxide favoured better crystallisation of boehmite structure, higher temperature of its dehydroxylation into γ-Al₂O₃, and delayed transformation of γ phase into α-Al₂O₃. Aluminium oxides derived from the hydroxides precipitated at a high pH were the most stable at high temperatures, and were characterised with the best surface properties. The online version of the original article can be found at     

Electron microscope investigations on the morphology of aluminium hydroxides

Summary The results are given of an investigation by means of the electron microscope and electron diffraction of the morphology of amorphous aluminium hydroxide and boehmite. The ageing process of amorphous aluminium hydroxide prepared from aluminium nitrate, ammonium alum and amalgamated aluminium was studied.

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Zusammenfassung Untersuchungen im Elektronenmikroskop und mit Elektronenbeugung über die Morphologie vom amorphen Aluminiumhydroxyd und B?hmit werden beschrieben. Die Alterung von amorphem Aluminiumhydroxyd, hergestellt aus Aluminiumnitrat, Ammoniumalaun und amalgamiertem Aluminium wurde untersucht.

     

Preparation of aluminas

Aluminium hydroxide was prepared by precipitation from aluminium nitrate solution with ammonia solution. Thermal decomposition of the solid hydroxide was studied by means of TG, DTG and DTA. The sample was thermally treated in the temperature interval between 200 °C and 1000 °C. X-ray phase analysis was used to study the phase compositions of the resulting products, and their surface areas were compared.     

Die Bildung von kristallinem Böhmit in gemeinsam gefällten AlFe(III)-Hydroxiden unter hydrothermalen Bedingungen

Under mild hydrothermal conditions originally amorphous aluminium hydroxide coprecipitated with iron(III)ions as Al_0,5Fe_0,5(OH)₃ transforms into aluminium hydroxide crystalline phases which are not observed in products of ageing of pure aluminium hydroxide.By X-ray diffraction analysis, IR spectroscopic studies and microscopic observations it has been found that due to the presence of iron(III) hydroxide it is possible to stabilize the trihydoxide of aluminium i.e. bayerite until 130–140°C. Moreover, with increasing temperature well crystallized boehmite is obtained instead of the usually formed pseudoboehmite.Experiments revealed that the formation of crystalline boehmite does not take place as a process of pseudoboehmit crystallites growth but only as a result of bayeriteboehmite transformation.

     

Über basische Aluminiumsalze und ihre Lösungen. VII. Zum Einfluß der Herstellungsbedingungen,der Konzentration und der Alterungszeit auf die Zusammensetzung von Lösungen basischer Aluminiumsalze

Basic Aluminium Salts and their Solutions. VII. Influence of Preparation, Concentration, and Aging on the Constitution of Solutions of Basic Aluminium Salts 0.1 to 4 molar basic aluminium chloride solutions – prepared by dissolving aluminium metal in substoichiometric quantities of hydrochloric acid and 10^?4 to 0.2 molar basic solutions of aluminium chloride and perchlorate – prepared by adding alkali to the solutions of the neutral salts were investigated for the kinetics of their reactions with ferrone and by ²⁷Al NMR spectroscopy. In all solutions the contents of polymeric species decreases at equal basicity with increasing aluminium concentration. On the other hand the Al₁₃O₄₀ complex is only formed in solutions prepared by addition of alkali. The differences of composition are confirmed by the aging behaviour of the solutions.     

以拟薄水铝石为铝源合成的β沸石的表征和催化性能(英文)

考察了以拟薄水铝石为铝源、固体硅胶为硅源、四乙基氢氧化铵为模板剂时不同晶化混合液ＳｉＯ２／Ａｌ２Ｏ３比和不同晶化温度对β沸石合成的影响。ＸＲＤ、ＴＧＡ、ＩＣＰ及ＳＥＭ研究结果表明,在晶化混合液ＳｉＯ２／Ａｌ２Ｏ３比为２０至５０之间、晶化温度为１４０℃～１６０℃范围内能合成出高结晶度的β沸石,且β沸石硅铝比与晶化混合液硅铝比呈良好的线性关系：ＴＧＡ总失重量随β沸石硅铝比增加而增加,晶化温度对β沸石的晶粒度没有明显影响。此外,所制备的Ｈβ沸石对甲苯与Ｃ９芳烃歧化和烷基转移反应具有良好的催化性能。     

Adsorption of organic matter at mineral/water interfaces. IV. Adsorption of humic substances at boehmite/water interfaces and impact on boehmite dissolution

The adsorption of Suwannee River fulvic acid (SRFA) and Pahokee peat humic acid (PPHA) at the boehmite (gamma-AlOOH)/water interface and the impact of SRFA on boehmite dissolution have been examined over a wide range of solution pH conditions (pH 2-12), SRFA surface coverages (Gamma(SRFA), total SRFA binding site concentration normalized by the boehmite surface area) of 0.0-5.33 micromol m(-2), and PPHA surface coverages (Gamma(PPHA), PPHA binding site concentration normalized by boehmite surface area) of 0.0-4.0 micromol m(-2), using macroscopic adsorption and in situ attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopy. At relatively high SRFA surface coverages (Gamma(SRFA) = 5.33 micromol m(-2)), in situ ATR-FTIR spectral features of adsorbed SRFA are very similar to those measured for SRFA in solution at approximately 1-3 pH units higher. At sub-monolayer surface coverages (Gamma(SRFA) = 1.20 and 2.20 micromol m(-2)), several new peaks and enhancements of the intensities of a number of existing peaks are observed. The latter spectral changes arise from several nonorganic extrinsic species (i.e., adsorbed carbonate and water, for alkaline solution conditions), partially protonated SRFA carboxyl functional groups (near-neutral pH conditions), and small quantities of inner-spherically adsorbed SRFA carboxyl groups and/or Al(III)-SRFA complexes (for acidic conditions). The spectra of PPHA adsorbed at boehmite/water interfaces also showed changes generally consistent with our observations for SRFA sorbed on boehmite. These observations confirm that SRFA and PPHA are predominantly adsorbed at the boehmite/water interface in an outer-sphere fashion, with minor inner-sphere adsorption complexes being formed only under quite acidic conditions. They also suggest that the positively charged boehmite/water interface stabilizes SRFA and PPHA carboxyl functional groups against protonation at lower pH. Measurements of the concentration of dissolved Al(III) ions in the absence and presence of SRFA showed that the boehmite dissolution process is clearly inhibited by the adsorption of SRFA, which is consistent with previous observations that outer-spherically adsorbed organic anions inhibit Al-(oxyhydr)oxide dissolution.     

Influence of aluminium precursor on physico-chemical properties of aluminium hydroxides and oxides Part II. Al(ClO4)3·9H2O

Aluminium hydroxide was precipitated during a hydrolysis of aluminium perchlorate in ammonia medium. The materials were studied with the following methods: thermal analysis, IR spectroscopy, X-ray diffraction, low-temperature nitrogen adsorption and adsorption–desorption of benzene vapours. Freshly precipitated boehmite had a high value of S_BET=211 m² g^–1 determined from nitrogen adsorption, good sorption capacity for benzene vapours, developed mesoporous structure and hydrophobic character. After prolonged refluxing at elevated temperature its crystallinity increased which was accompanied by an increase of specific surface determined from nitrogen adsorption up to 262m²g^–1 , decrease of sorption capacity for benzene vapours and stronger hydrophobic character. The calcinations of all boehmites at temperature up to 1200°C resulted in formation of à-Al₂O₃ via transition form of γ-, δ- and θ-Al₂O₃. The samples of aluminium oxides obtained after calcination at 550 and 900°C were characterised with high values of specific surface area of 205–220 and 138–153 m² g^–1 , respectively. The SBET values calculated for the oxide samples derived from aged hydroxides and calcined at 1200°C are higher than for the analogous sample prepared without the ageing step. It was concluded that the process of ageing at elevated temperature developed thermal stability of aluminium oxides.     

Coagulation by hydrolysing metal salts

Aluminium and iron salts are widely used as coagulants in water and wastewater treatment and in some other applications. They are effective in removing a broad range of impurities from water, including colloidal particles and dissolved organic substances. Their mode of action is generally explained in terms of two distinct mechanisms: charge neutralisation of negatively charged colloids by cationic hydrolysis products and incorporation of impurities in an amorphous hydroxide precipitate (‘sweep flocculation’). The relative importance of these mechanisms depends on factors such as pH and coagulant dosage. Alternative coagulants, based on prehydrolysed forms of aluminium and iron, are more effective than the traditional additives in many cases, but their mode of action is not completely understood, especially with regard to the role of charge neutralisation and hydroxide precipitation. Some basic features of metal hydrolysis and precipitate formation are briefly reviewed and the action of hydrolysing coagulants is then discussed, with examples from the older literature and from some recent studies on model systems. Dynamic monitoring of floc formation and breakage can give useful insights into the underlying mechanisms. Although the results can be reasonably well explained in terms of established ideas, a detailed understanding of the ‘sweep flocculation’ mechanism is not yet available. There are also still some uncertainties regarding the action of pre-hydrolysed coagulants.     

Dosage acidimétrique de l'ion aluminium

Acid titration of aluminium salts consists of two stages.1. Titration of the free acid. Complex ions are formed of aluminium with oxalatē of hydrofluorideions. 'I'he precipitation of aluminium hydroxide is retaided. Consequently the neutralisatiom of the free acid by the base is quite clear.2. Simultaneous titration of the acid and the aluminium ions. The solution with NaOH is neutralised until all the aluminium hydroxide is just precipitated. To avoid errors due to the formation of adsorption compounds, an excess of base is added and back-titrated with hydrochloric acid at the boiling point.These two titrations permit the determination of XXX acid and the aluminium content of the solution to approximately 0,3%.The influence of disturbing ions is studied.     

Über basische Aluminiumsalze und ihre Lösungen. XIX. Zur Art der Al-Kationen in hochbasischen,hochkonzentrierten Aluminiumchloridlösungen

Basic Aluminium Salts and their Solutions. XIX. Nature of Aluminium Cations in Highly Basic Highly Concentrated Aluminium Chloride Solutions It is shown that in highly concentrated basic aluminium chloride solutions (c_Al ≈ 7.7 mol · l^?1; r = OH/Al = 2.48), prepared by dissolving aluminium metal in substoichiometric quantities of hydrochloric acid, polymeric aluminium cations (Al_poly) dominate. By dilution of these solutions also increasing amounts of monomeric cations (Al_mono) occur. On aging Al_mono reacts with Al_poly forming small portions of tridecameric Al₁₃O₄₀ cations (Al₁₃). On the basis of these results literature data, after which corresponding commercial basic aluminium chloride solutions contain essentially Al₁₃ cations, are critically discussed.     

Thermal transformations of the products of partial hydrolysis of hydrous aluminium nitrate

Thermal analysis, mass spectrometry, infrared spectrophotometry, X-ray phase analysis, scanning electron microscopy, and sorption methods were used in the study of thermal transformations of the products of partial hydrolysis of hydrous aluminium nitrate in ammonia medium. It has been found that the process of aluminium nitrate hydrolysis under the conditions applied and in the presence of ammonia gives boehmite as the main product, with some admixture of a basic salt.Aluminium oxide obtained from the products of partial hydrolysis of hydrous aluminium nitrate in ammonia medium at 550°C has a crystalline -Al₂O₃ structure. Its specific surface, as determined by low-temperature adsorption of nitrogen, exceeds 200 m²g^–1. Features of the products are well developed mesopore structure and considerable ability of benzene adsorption. Calcination of the obtained aluminium oxide for 2 h at 900°C reduces its specific surface to about 110 m² g^–1.This revised version was published online in November 2005 with corrections to the Cover Date.     

Uranium sorption on oxyhydroxide minerals by surface complexation and precipitation

During the chemical weathering of the uranium mill tailings, released uranium could be immobilized by the newly formed secondary minerals such as oxyhydroxides. A deeper understanding of the interaction between uranium and common oxyhydroxides under environmental conditions is necessary. In this work, uranium sorption behaviors on Al-, Mn- and Fe-oxyhydroxide minerals (boehmite, manganite, goethite, and lepidocrocite) were investigated by batch experiments. Results showed that the uranium sorption on Al-oxyhydroxide behaved significantly differently from the other three minerals. The sorption edge of the Mn- and Fe-oxyhydroxides located around pH 5, while the sorption edge of boehmite shifted about 1.5 pH unit to near neutral. The sorption isotherms of uranium on manganite, goethite and lepidocrocite at pH 5.0 could be well fitted by the Langmuir model. Instead of surface complexation, sorption on boehmite happened mainly by uranium-bearing carbonates and hydroxides precipitation as illustrated by the characterization results. Both carbonate and phosphate strongly affected the uranium sorption behavior. The removal efficiency of uranium by boehmite exceeded 98% after three sorption-desorption cycles, indicating it may be a potential material for uranium removal and recovery.     

Thermal stability and flame retardancy of polyester fabrics sol–gel treated in the presence of boehmite nanoparticles

Polyester fabrics have been treated with hybrid organic-inorganic sols containing aluminium hydroxide, namely a synthetic boehmite. The treated fabrics have been thoroughly investigated by infrared spectroscopy, scanning electron microscopy coupled to elemental analysis and thermogravimetry. Furthermore, the flammability of the coated fabrics has been assessed and compared with that achieved by applying the two components separately. More specifically, flammability tests have shown that the sol–gel treatment in the presence of boehmite nanoparticles is able to suppress the dripping phenomenon, which represents the main issue to fulfil for polyester fabrics.     

Control of the morphology and particle size of boehmite nanoparticles synthesized under hydrothermal conditions

The spontaneous nucleation under hydrothermal conditions often leads to aggregation of crystallizing particles, which is an undesired phenomenon when the goal is the preparation of nanocrystals with narrow particle size distribution. The present paper reports on the synthesis of boehmite nanocrystals under hydrothermal conditions. An aqueous aluminum chloride salt solution was first prepared, and the pH was increased to 11 using a 5 M sodium hydroxide solution. The hydrothermal treatment was performed at 160 degrees C for different periods of time. The system yielded relatively small (15-40 nm) boehmite crystallites aggregated into larger (160 nm) particles. To avoid the aggregation, a biocompatible polymer, sodium polyacrylate (NaPa) 2100, was employed as a size-/morphology-controlling agent. Thus, stable colloidal suspensions of rounded boehmite nanoparticles having a size between 15 and 40 nm were obtained at 160 degrees C for 24 h. Further, the effect of synthesis time on the morphological features of boehmite synthesized in such a NaPa-containing system was investigated. The increase of the synthesis time from 24 to 168 h resulted in the formation of very long boehmite fibers (1000-2000 nm) with an average diameter of about 10 nm. The boehmite samples were characterized by XRD, DLS, TEM, IR, N2 adsorption, and zeta potential measurements. The colloidal stability of the obtained suspension was also studied.     

Efficiency of some phenylthiosemicarbazide derivatives in retarding the dissolution of Al in NaOH solution

Five derivatives of phenylthiosemicarbazide have been prepared and treated as inhibitors for the corrosion of aluminium in 2M sodium hydroxide. All the five substances afford 98.5 to 75% protection to aluminium in sodium hydroxide. 1(-Methoxybenzoyl)-4-phenyl-3-thiosemicarbazide being the most efficient inhibitor. Thermometric and weight loss methods indicate that the inhibition is principally governed by the adsorption of these compounds on the surface of the aluminium metal and the adsorbability of inhibitors is dependent on the basicity of the oxygen and sulphur sites involved.

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Die Effizienz einiger Phenylthiosemicarbazid-Derivate in der Verzögerung der Auflösung von Al in NaOH-Lösung

Zusammenfassung Es wurden fünf Derivate von Phenylthiosemicarbazid hergestellt und als Inhibitoren für die Korrosion von Aluminium in 2M NaOH eingesetzt. Die Substanzen ergaben 98.5 bis 75% Schutz für Aluminium in NaOH. Dabei war 1-(Methoxybenzoyl)-4-phenyl-3-thiosemicarbazid der effizienteste Inhibitor. Thermometrische und Gewichtsverlustmethoden zeigten, daß die Inhibition prinzipiell von der Adsorption dieser Verbindungen auf der Metalloberfläche gesteuert wird, wobei die Adsorbierbarkeit der Inhibitoren von der Basizität der teilnehmenden Sauerstoff- und Schwefelfunktionen abhängt.