It is necessary to clarify the influence of thermal history on the conversion of aluminate species in sodium aluminate solution in order to optimize Bayer alumina production. The interconversion of various solution species in the systems was investigated by measuring the infrared spectra of sodium aluminate solution with different compositions after separate heat treatment, dilution and concentration. The results show that increasing temperature or prolonging holding time favors the transformation of Al2O（OH）2- to Al—OH vibration（condensed Al O4 tetrahedral aluminate ion） at about 880 cm-1 and Al（OH）-4. A12O（OH）2-66 and Al—OH tetrahedral dimer ions convert rapidly to Al（OH）-4 during the dilution process; however, the back transformation of Al（OH）-4 to the Al—OH tetrahedral dimer ions can occur in diluted sodium aluminate solution. As for the concentration process, the transformation of Al（OH）-4 to A12O（OH）2-6 and Al—OH tetrahedral dimer ions can take place, while it is relatively difficult to transform to A12O（OH）2-6.
Pyrochlore-type tungsten oxide (PTO), WO3·0.5H2O, is an emerging material with very wide potential applications. The influences of iron valences and the additive amount of ferrous ion on tungsten crystallization ratio and the acceleration mechanism of ferrous ion were investigated when PTO was hydrothermally prepared in aqueous ammonium tungstate solution containing ammonium carbonate. The results show that ferrous ion can remarkably accelerate tungsten crystallization while both elemental iron and ferric ion have little influence on the crystallization. Moreover, the tungsten crystallization ratio increases with increasing the amount of ferrous ions added and reaches the maximum of about 60% with ferrous ion concentration of 16 g/L. FTIR analysis of the spent solution after PTO crystallization shows that ferrous ion can accelerate the conversion of WO4 tetrahedral to WO6 octahedron. Combined with XPS and XRD analyses of the hydrothermal product, the acceleration effect of ferrous ion on tungsten crystallization could basically be attributed to the increase in the interplanar spacing of PTO lattice caused by the incorporation of ferrous ion into PTO crystal lattice. The results presented is conducive to the efficient preparation of PTO powder and cleaner tungsten metallurgy.
Qiu-sheng ZHOUMin XIANGDong LIXiao-bin LITian-gui QIZhi-hong PENGGui-hua LIU
Pure compounds and kaolin were employed to investigate the reaction behavior of ferric oxide in thetrinarysystem Fe2O3?SiO2?Al2O3 during reductive sintering process. The thermodynamic analyses and reductive sintering experimental results show that ferrous oxide generated from the reduction of ferric oxide by carbon can react with silicon dioxide and aluminum oxide to form ferrous silicate and hercynite at 1173 K, respectively. In the trinary system Fe2O3?SiO2?Al2O3, ferrous oxide obtained from ferric oxide reduction preferentially reacts with aluminum oxide to form hercynite, and the reaction of ferrous oxide with silicon dioxide occurs only when there is surplus ferrous oxide after the exhaustion of aluminum oxide. When sintering temperature rises to 1473 K, hercynite further reacts with silicon dioxide to form mullite and ferrous oxide. Results presented in this work may throw a new light upon the separation of alumina and silica present in Al/Fe-bearing materials with low mass ratio of alumina to silica in alumina production.
The reaction behaviors of silicate species in （NH4）2WO4-（NH4）2CO3-NH3-H2O system are crucial to developing a greenmanufacture technique for ammonium paratungstate. In order to efficiently remove silicon from the system, the reaction behaviors ofsilicate species were systematically investigated by thermodynamic analysis. The thermodynamic analysis shows that silicate in thetungstate clinker partly decomposes in the leaching process, with 150-160 mg/L silicon thermodynamically at 25 ℃. The dissolvedsilicon can be removed by magnesium salts via forming insoluble MgSiO3. The low carbonate and high ammonia concentrations inthe system are beneficial to the removal of silicon, with silicon concentration reaching 8-10 mg/L thermodynamically, whereasMgSiO3 precipitation is hardly formed when the concentration of total carbonate is more than 1.5 mol/L. The reaction behaviors ofcalcium and magnesium were also studied in the system. The results in the verification experiments consist with the theoreticalcalculation.
