The adsorption isotherm of sodium polyacrylate on dicalcium silicate(2CaO-SiO2) in sodium aluminate solution at 80 ℃ was studied.The type of surface adsorption of sodium polyacrylate is saturated adsorption,and the...The adsorption isotherm of sodium polyacrylate on dicalcium silicate(2CaO-SiO2) in sodium aluminate solution at 80 ℃ was studied.The type of surface adsorption of sodium polyacrylate is saturated adsorption,and the adsorption behavior belongs to L-type,according with the monolayer adsorption model of Langmuir equation.The surface coverage of sodium polyacrylate is 1.06 mol/μm2.The relation curve between the surface pressure and the molecular area of adsorption film was obtained by Gibbs formula.The variation of interfacial energy caused by adsorption as well as the relationship between the relation curve and the type of adsorption was discussed.展开更多
The synthesis of sodium ferrite and its desulfurization performance in S2 -bearing sodium aluminate solutions were investigated. The thermodynamic analysis shows that the lowest temperature is about 810 K for synthesi...The synthesis of sodium ferrite and its desulfurization performance in S2 -bearing sodium aluminate solutions were investigated. The thermodynamic analysis shows that the lowest temperature is about 810 K for synthesizing sodium ferrite by roasting the mixture of ferric oxide and sodium carbonate. The results indicate that the formation process of sodium ferrite can be completed at 1173 K for 60 min, meanwhile raising temperature and reducing NazCO3 particle size are beneficial to accelerating the formation of sodium ferrite. Sodium ferrite is an efficient desulfurizer to remove the S2- in aluminate solution, and the desulfurization rate can reach approximately 70% at 373 K for 60 min with the molar ratio of iron to sulfur of 1:1-1.5:1. Furthermore, the desulfurization is achieved by NaFeS2·2H2O precipitation through the reaction of Fe(OH)4 and S^2- in aluminate solution, and the desulfurization efficiency relies on the Fe(OH)4^- generated by dissolving sodium ferrite.展开更多
The mechanism of seeded precipitation of sodium aluminate solution was studied by measuring the seeded-precipitation rate and electrical conductivity online, as well as calculating the activity and fraction of ion pai...The mechanism of seeded precipitation of sodium aluminate solution was studied by measuring the seeded-precipitation rate and electrical conductivity online, as well as calculating the activity and fraction of ion pair. The results show that the electrical conductivity of sodium aluminate slurry linearly decreases with increasing aluminum hydroxide addition. Moreover, both the electrical conductivity of slurry and the difference in electrical conductivity between sodium aluminate solution and slurry remarkably decline in the first 60 min before gradually increasing in the preliminary 10 h and finally reaching almost the same level after 10 h. In low Na2 O concentration solution the activities of Na OH and Na Al(OH)4 in seeded precipitation are high, which can enlarge the difference in conductivity between slurry and solution. Additionally, more ion pairs exist in solution in preliminary seeded precipitation, and the adsorption of Na+Al(OH)4- on seed surface is likely to break the equilibrium of ion pair formation and to decrease the difference in conductivity in preliminary seeded precipitation.展开更多
1.IntroductionSodium aluminate solutions are veryimportant intermediate products in alumin-ium metallurgy.The physico-chemicalproperties of sodium aluminate solutions areconcerned by metallurgists and engineersdealing...1.IntroductionSodium aluminate solutions are veryimportant intermediate products in alumin-ium metallurgy.The physico-chemicalproperties of sodium aluminate solutions areconcerned by metallurgists and engineersdealing with alumina production[1].Thedata of viscosity,electroconductivity,UV展开更多
The precipitation of spherical boehmite was studied by surface energy calculations, measurements of precipitation ratios, Fourier transform infrared spectroscopy, X-ray diffraction, scanning electron microscopy, and t...The precipitation of spherical boehmite was studied by surface energy calculations, measurements of precipitation ratios, Fourier transform infrared spectroscopy, X-ray diffraction, scanning electron microscopy, and transmission electron microscopy. The surface energy calculation results show that the(001) and(112) planes of gibbsite surfaces are remarkably stable because of their low surface energies. In addition, the(010) plane of boehmite grows preferentially during precipitation because of its low surface energy. Thus, we propose a method to precipitate spherical boehmite from a supersaturated sodium aluminate solution by adding gibbsite as seed in a heterogeneous system. In this method, gibbsite acts as the preliminary seed and saturation modifier. The results show that the fine boehmite first nucleates on the(001) and(112) planes of gibbsite and then grows vertically on the(001) and(112) basal planes of gibbsite via self-assembly, thereby forming spherical boehmite. Simultaneously, gibbsite is dissolved into the aluminate solution to maintain the saturation for the precipitation of boehmite. The precipitation ratio fluctuates(forming an M-shaped curve) because of gibbsite dissolution and boehmite precipitation. The mechanism of boehmite precipitation was further discussed on the basis of the differences in surface energy and solubility between gibbsite and boehmite. This study provides an environmentally friendly and economical method to prepare specific boehmite in a heterogeneous system.展开更多
The liquor concentration, mineral proportion, crystal parameters and micro morphology of various desilication products(DSPs) precipitated in silica-supersaturated sodium aluminate solution at 95 ℃ under different r...The liquor concentration, mineral proportion, crystal parameters and micro morphology of various desilication products(DSPs) precipitated in silica-supersaturated sodium aluminate solution at 95 ℃ under different reaction conditions were systematically researched. The DSPs formed under atmospheric pressure comprise amorphous phase, zeolite A, zeolite and sodalite, and the DSPs concentration and crystallinity increase with the increase of initial silica concentration, initial molar ratio of caustic Na2O to Al2O3(αK) and desilication duration. Decreasing the initial silica concentration, initial αK and increasing the desilication duration can reduce the proportion of zeolite A. The zeolite and sodalite are the stable DSPs, while the precipitation of zeolite A occurs at a high silica-supersaturated state in sodium aluminate solution. The DSPs are precipitated in the form of agglomerates, but the morphologies of various DSPs are quite different. Both the molar ratios of Na2O to Al2O3 and SiO-2 to Al2O3 in DSPs increase with the increasing desilication duration, resulting in the increase of the cell volumes of various DSPs. The precipitation sequence of DSPs under atmospheric pressure is: amorphous phase→zeolite A→zeolite→sodalite.展开更多
It has been found that samples of sodium aluminate solutions with the same composition but different preparative history may have difTerent structure and physico-chemical properties.The structure of sodium-bearing alu...It has been found that samples of sodium aluminate solutions with the same composition but different preparative history may have difTerent structure and physico-chemical properties.The structure of sodium-bearing aluminate solutions change very slowly during the storage after preparation.Sodium aluminate solutions contain several ammunium-bearing anisons such as Al(OH)^(-)_(4),Al(OH)^(3-)_(6)and[(HO)_(3)Al-O-Al(OH)_(3)]^(2-),etc.These anions can convert to each other but the reactions are very slow owing to the formation or breakage of covalent Al-O bond.Hence the ratio between these anions approaches equilibrium very slowly after the preparation,and the structure or properties of these solution samples before equilibrium is reached depend on their preparative histosive.展开更多
The formation kinetics and mechanism of tricalcium aluminate hydrate and calcium oxalate in dilute sodium aluminate solution and sodium oxalate solution were studied respectively based on the lime causticization, and ...The formation kinetics and mechanism of tricalcium aluminate hydrate and calcium oxalate in dilute sodium aluminate solution and sodium oxalate solution were studied respectively based on the lime causticization, and the optimal conditions for removing the oxalate in dilute sodium aluminate solution as well as the mechanism were finally obtained.The formation processes of tricalcium aluminate hydrate and calcium oxalate are mainly controlled by the chemical reaction and the inner diffusion respectively,and the corresponding reaction rate equations as well as the apparent activation energy were calculated. The hydrocalumite with a spatially interleaved structure will form in dilute sodium aluminate solution with sodium oxalate, greatly removing the oxalate impurity by absorption. Calcium oxalate can be converted to tricalcium aluminate hydrate with the increasing reaction time. The oxalate causticization efficiency and the alumina loss rate can be over 90% and below 31% respectively when reacted at 50℃ with a stirring rate of 200 r/min.展开更多
Periodical attenuation of particles,which interferes seriously the normal alumina production,exists in Bayer process.In order to solve this problem,the rule of periodical attenuation of Al(OH) 3 particles was investig...Periodical attenuation of particles,which interferes seriously the normal alumina production,exists in Bayer process.In order to solve this problem,the rule of periodical attenuation of Al(OH) 3 particles was investigated by laboratory experiments under simulated industrial conditions.The results show that at higher temperature the variation period of particle size is shortened,while prolongs with more solid content.Particle size fluctuation amplitude reduces with the temperature rising but increases with the solid content increasing.Particle size distribution becomes more uniform by replenishing fine seeds,enabling the periodical fluctuation of Al(OH)3 particle size to be attenuated.Combining properly the additives with controlling the seed size is able to reduce the amplitude of periodical fluctuation and shorten the attenuation time.With unbalance of particle size distribution,the particles gradually become bigger,even inducing the decrease of the specific surface area of seeds,which is the major reason causing explosive attenuation of Al(OH)3 particles in seed precipitation process.展开更多
Excess lithium in alumina is significantly bad for aluminum reduction.In this study,the concentration variation of lithium ion in sodium aluminate solution with addition of synthetic lithium aluminate was investigated...Excess lithium in alumina is significantly bad for aluminum reduction.In this study,the concentration variation of lithium ion in sodium aluminate solution with addition of synthetic lithium aluminate was investigated.Elevating temperature,increasing caustic soda concentration,reducing alumina concentration or raising molar ratioαk improved equilibrium concentration of lithium ion in sodium aluminate solution.Agitation speed had a minimal effect on lithium ion concentration.Over 0.65 g/L lithium ion equilibrium concentration was observed in digestion process,whereas 35 mg/L lithium ion concentration remained in solution after precipitation time of 9 h.Moreover,equilibrium concentration decreased sharply from digestion of boehmite or diaspore to seed precipitation,about 95%lithium was precipitated into red mud(bauxite residue)and aluminum hydroxide.This study provides a valuable perspective in removal or extraction of lithium from sodium aluminate solution in alumina refineries.展开更多
A series of low-temperature phase transitions of sodium aluminate solutions were studied by differential scanning calorimetry (DSC) and Raman spectroscopy. The results indicate that NaOH concentration is a primary imp...A series of low-temperature phase transitions of sodium aluminate solutions were studied by differential scanning calorimetry (DSC) and Raman spectroscopy. The results indicate that NaOH concentration is a primary impact factor for the binary eutectic point and ice melting temperature of sodium aluminate solutions with low NaOH concentration. In addition, the phase transition process of sodium aluminate solutions with low NaOH concentration from 123.15 to 283.15 K is divided into four steps: non-crystal to crystal, ternary eutectic reaction, binary eutectic reaction and ice melt. The projection phase diagram of NaOH-Al(OH)3-H2O system at low temperature was plotted, in which the ternary eutectic temperature for sodium aluminate solutions is 183.15 K.展开更多
The structural changes of silicate anions in the desilication process with the addition of calcium hydrate alumino-carbonate were studied by measuring Raman spectra, infrared spectra and corresponding second derivativ...The structural changes of silicate anions in the desilication process with the addition of calcium hydrate alumino-carbonate were studied by measuring Raman spectra, infrared spectra and corresponding second derivative spectra. The results show that the desilication ratio in the solution prepared by the addition of sodium silicate(solution-SS) is much greater than that in the solution by the addition of green liquor(solution-GL), and low alumina concentration in the sodium aluminate solutions facilitates the desilication process. It is also shown that alumino-silicate anions in the solution-GL, and Q^3 polymeric silicate anions in solution-SS are predominant, respectively. In addition, increasing the concentration of silica favors respectively the formation of the alumino-silicate or the Q^3 silicate anions in the solution-GL or the solution-SS. Therefore, it can be inferred that the low desilication ratio in the silicate-bearing aluminate solution is mainly attributed to the existence of alumino-silicate anions.展开更多
The precipitation performance and kinetics of gibbsite from sodium aluminate solution with different sodium oxalate concentrations as well as the corresponding influence mechanism of oxalate during the seed precipitat...The precipitation performance and kinetics of gibbsite from sodium aluminate solution with different sodium oxalate concentrations as well as the corresponding influence mechanism of oxalate during the seed precipitation process were systematically investigated by physicochemical properties test,using SEM and Raman spectra.As the concentration of sodium oxalate increases,both the precipitation rate and particle size of gibbsite decrease.The presence of sodium oxalate not only increases the viscosity of sodium aluminate solution,but also promotes the transformation of Al(OH)4^? to Al2O(OH)6^2?.The overall reaction rate constant decreases and the apparent activation energy of gibbsite increases with the increasing sodium oxalate concentration,the rate controlling step of which is chemical reaction.The needle-like sodium oxalate precipitates on the gibbsite crystals and covers the active Al(OH)3 seed sites,which leads to the lower precipitation rate and the finer particle size of gibbsite during the seed precipitation process.展开更多
The constitution of high-caustic ratio and highly concentrated sodium aluminate solutions has been investigated by Raman spectra method.By comparison with the Raman spectra of crystalline solids of Ca_3[Al(OH)_6]_2 an...The constitution of high-caustic ratio and highly concentrated sodium aluminate solutions has been investigated by Raman spectra method.By comparison with the Raman spectra of crystalline solids of Ca_3[Al(OH)_6]_2 and Ba_2[Al_2(OH)_(10)],it can be concluded that AI(OH)_6^(3-)ion and perhaps its polymers may be formed in these solutions.展开更多
Sulfides in the high-sulfur bauxite lead to serious steel equipment corrosion and alumina product degradation via theBayer process,owing to the reactions of sulfur and iron-containing phases in the sodium aluminate so...Sulfides in the high-sulfur bauxite lead to serious steel equipment corrosion and alumina product degradation via theBayer process,owing to the reactions of sulfur and iron-containing phases in the sodium aluminate solution.The effects ofiron-containing phases on the transformation of sulfur-bearing ions(S2?,223S O?,23SO?and24SO?)in sodium aluminate solutionwere investigated.Fe,Fe2O3and Fe3O4barely react with23SO?and24SO?,but all of them,particularly Fe,can promote theconversion of223S O?to23SO?and S2?in sodium aluminate solution.Fe can convert to3Fe(OH)?in solution at elevatedtemperatures,and further react with S2?to form FeS2,but Fe2O3and Fe3O4have little influence on the reaction behavior of S2?insodium aluminate solution.Increasing temperature,duration,dosage of Fe,mole ratio of Na2Ok to Al2O3and caustic sodaconcentration are beneficial to the transformation of223S O?to23SO?and S2?.The results may contribute to the development oftechnologies for alleviating the equipment corrosion and reducing caustic consumption during the high-sulfur bauxite treatment bythe Bayer process.展开更多
Effect of lithium ion in sodium aluminate solution on precipitation rate,lithium content,morphology,and crystallization of alumina trihydrate(ATH) was investigated. Results showed that increasing lithium ion concentra...Effect of lithium ion in sodium aluminate solution on precipitation rate,lithium content,morphology,and crystallization of alumina trihydrate(ATH) was investigated. Results showed that increasing lithium ion concentration in solution improved the precipitation rate and lithium content in ATH,whereas reduced the mass fraction of lithium precipitation from solution. Lithium ion in solution generated the fine ATH, and thereafter significantly increased the total particle number due to the preferential nucleation.Elevating temperature or reducing lithium ion concentration decreased lithium content in ATH and reduced the fine particle amount.Moreover, lithium ion in the solution changed the morphology of ATH by improving the growth of the(110) and(200) planes of gibbsite.A large amount of fine bar-or flake-shaped ATH attached on the coarse particles also benefited the secondary nucleation and led to the poor strength of alumina.All results will further contribute to improving the quality of alumina.展开更多
The stability of calcium oxalate is critical for the removal of sodium oxalate from sodium aluminate solutions.This studyinvestigated the behavior of calcium oxalate in sodium aluminate solution containing sodium carb...The stability of calcium oxalate is critical for the removal of sodium oxalate from sodium aluminate solutions.This studyinvestigated the behavior of calcium oxalate in sodium aluminate solution containing sodium carbonate.Results show that calciumoxalate can be converted to tricalcium aluminate hydrate(TCA)and calcium carbonate in sodium aluminate solution and sodiumcarbonate solution,respectively.Elevating temperature,extending residence time,or increasing caustic soda concentration enhancesthe conversion ratio of calcium oxalate in sodium aluminate solution;as a consequence,anti-causticisation occurs.Stability ofcalcium-containing compounds in sodium aluminate solution containing sodium carbonate differs from that in sodium aluminatesolution or sodium carbonate solution.Na2CO3in aluminate solution accelerates the transformation of calcium oxalate;thus,aluminais lost because of4CaO·Al2O3·CO2·11H2O and TCA formation.Calcium carbonate,4CaO·Al2O3·CO2·11H2O and calcium oxalatecan change into TCA in sodium aluminate solution at elevated temperature.Calcium oxalate remains relatively stable in dilutealuminate solution within a short residence time at low temperature.Thus,a novel process for removal of sodium oxalate by limecausticisation was presented and employed in an alumina refinery in China.展开更多
The effects of frequency of ultrasound on the precipitation process of prepared supersaturated sodium aluminate solutions of practical concentration were studied experimentally under seeded, isothermal, batch crystall...The effects of frequency of ultrasound on the precipitation process of prepared supersaturated sodium aluminate solutions of practical concentration were studied experimentally under seeded, isothermal, batch crystallization conditions at various temperatures and initial ak(mole ratio of Na2O/Al2O3). The decomposition and the particle number percentage for size below 2 mm at time of 15 h were compared, particle size distribution and SEM photos of the product aluminum hydroxide were also analyzed. The results indicate that the ultrasonic treatment at 16 kHz can enhance the decomposition rate of sodium aluminate solutions, and also has effects on particle morphology and particle size distribution of aluminum hydroxide precipitated.展开更多
Na4EDTA and EDTA were adopted as new additives to intensify the seeded precipitation process of sodium aluminate solution. The effects of the two additives at certain concentrations on the seeded precipitation rate of...Na4EDTA and EDTA were adopted as new additives to intensify the seeded precipitation process of sodium aluminate solution. The effects of the two additives at certain concentrations on the seeded precipitation rate of sodium aluminate solution, particle size distribution (PSD) and morphology of precipitated gibbsite were investigated using titration method, particle size analyzer and scanning electron microscope (SEM), respectively. The results show that the two additives can accelerate the seeded precipitation rate of sodium aluminate solution. At relatively high concentration, the facilitative effect of EDTA on sodium aluminate solution is more obvious than that of Na4EDTA. EDTA makes gibbsite particles thinner than Na4EDTA. The Na+ and H+ result in the different effects on the seeded precipitation rate of sodium aluminate solution in spite of the same EDTA anion in the two additives.展开更多
The anionic species of the SiO_2-containing sodium aluminate solutions prepared by different methods have been investigated by Raman spectra and ultraviolet spectra.It was found that these solutions have different SiO...The anionic species of the SiO_2-containing sodium aluminate solutions prepared by different methods have been investigated by Raman spectra and ultraviolet spectra.It was found that these solutions have different SiO_2-containing anions.The solution prepared by leaching in- dustrial sinter of soda-lime sintering process contains polvsilicate ions with Si-O-Si radicals.展开更多
基金Project(50974036)supported by the National Natural Science Foundation of China
文摘The adsorption isotherm of sodium polyacrylate on dicalcium silicate(2CaO-SiO2) in sodium aluminate solution at 80 ℃ was studied.The type of surface adsorption of sodium polyacrylate is saturated adsorption,and the adsorption behavior belongs to L-type,according with the monolayer adsorption model of Langmuir equation.The surface coverage of sodium polyacrylate is 1.06 mol/μm2.The relation curve between the surface pressure and the molecular area of adsorption film was obtained by Gibbs formula.The variation of interfacial energy caused by adsorption as well as the relationship between the relation curve and the type of adsorption was discussed.
基金Project(51374239)supported by the National Natural Science Foundation of China
文摘The synthesis of sodium ferrite and its desulfurization performance in S2 -bearing sodium aluminate solutions were investigated. The thermodynamic analysis shows that the lowest temperature is about 810 K for synthesizing sodium ferrite by roasting the mixture of ferric oxide and sodium carbonate. The results indicate that the formation process of sodium ferrite can be completed at 1173 K for 60 min, meanwhile raising temperature and reducing NazCO3 particle size are beneficial to accelerating the formation of sodium ferrite. Sodium ferrite is an efficient desulfurizer to remove the S2- in aluminate solution, and the desulfurization rate can reach approximately 70% at 373 K for 60 min with the molar ratio of iron to sulfur of 1:1-1.5:1. Furthermore, the desulfurization is achieved by NaFeS2·2H2O precipitation through the reaction of Fe(OH)4 and S^2- in aluminate solution, and the desulfurization efficiency relies on the Fe(OH)4^- generated by dissolving sodium ferrite.
基金Project(51274242)supported by the National Natural Science Foundation of China
文摘The mechanism of seeded precipitation of sodium aluminate solution was studied by measuring the seeded-precipitation rate and electrical conductivity online, as well as calculating the activity and fraction of ion pair. The results show that the electrical conductivity of sodium aluminate slurry linearly decreases with increasing aluminum hydroxide addition. Moreover, both the electrical conductivity of slurry and the difference in electrical conductivity between sodium aluminate solution and slurry remarkably decline in the first 60 min before gradually increasing in the preliminary 10 h and finally reaching almost the same level after 10 h. In low Na2 O concentration solution the activities of Na OH and Na Al(OH)4 in seeded precipitation are high, which can enlarge the difference in conductivity between slurry and solution. Additionally, more ion pairs exist in solution in preliminary seeded precipitation, and the adsorption of Na+Al(OH)4- on seed surface is likely to break the equilibrium of ion pair formation and to decrease the difference in conductivity in preliminary seeded precipitation.
文摘1.IntroductionSodium aluminate solutions are veryimportant intermediate products in alumin-ium metallurgy.The physico-chemicalproperties of sodium aluminate solutions areconcerned by metallurgists and engineersdealing with alumina production[1].Thedata of viscosity,electroconductivity,UV
基金financially supported by the National Natural Science Foundation of China (No.51274242)the Fundamental Research Funds for the Central Universities of Central South University (No.2016zzts038)
文摘The precipitation of spherical boehmite was studied by surface energy calculations, measurements of precipitation ratios, Fourier transform infrared spectroscopy, X-ray diffraction, scanning electron microscopy, and transmission electron microscopy. The surface energy calculation results show that the(001) and(112) planes of gibbsite surfaces are remarkably stable because of their low surface energies. In addition, the(010) plane of boehmite grows preferentially during precipitation because of its low surface energy. Thus, we propose a method to precipitate spherical boehmite from a supersaturated sodium aluminate solution by adding gibbsite as seed in a heterogeneous system. In this method, gibbsite acts as the preliminary seed and saturation modifier. The results show that the fine boehmite first nucleates on the(001) and(112) planes of gibbsite and then grows vertically on the(001) and(112) basal planes of gibbsite via self-assembly, thereby forming spherical boehmite. Simultaneously, gibbsite is dissolved into the aluminate solution to maintain the saturation for the precipitation of boehmite. The precipitation ratio fluctuates(forming an M-shaped curve) because of gibbsite dissolution and boehmite precipitation. The mechanism of boehmite precipitation was further discussed on the basis of the differences in surface energy and solubility between gibbsite and boehmite. This study provides an environmentally friendly and economical method to prepare specific boehmite in a heterogeneous system.
基金Projects(51774079,51674075,51104041)supported by the National Natural Science Foundation of ChinaProject(N130402010)supported by the Fundamental Research Funds for the Central Universities,China
文摘The liquor concentration, mineral proportion, crystal parameters and micro morphology of various desilication products(DSPs) precipitated in silica-supersaturated sodium aluminate solution at 95 ℃ under different reaction conditions were systematically researched. The DSPs formed under atmospheric pressure comprise amorphous phase, zeolite A, zeolite and sodalite, and the DSPs concentration and crystallinity increase with the increase of initial silica concentration, initial molar ratio of caustic Na2O to Al2O3(αK) and desilication duration. Decreasing the initial silica concentration, initial αK and increasing the desilication duration can reduce the proportion of zeolite A. The zeolite and sodalite are the stable DSPs, while the precipitation of zeolite A occurs at a high silica-supersaturated state in sodium aluminate solution. The DSPs are precipitated in the form of agglomerates, but the morphologies of various DSPs are quite different. Both the molar ratios of Na2O to Al2O3 and SiO-2 to Al2O3 in DSPs increase with the increasing desilication duration, resulting in the increase of the cell volumes of various DSPs. The precipitation sequence of DSPs under atmospheric pressure is: amorphous phase→zeolite A→zeolite→sodalite.
基金supported by the National Natural Science Foundation of China
文摘It has been found that samples of sodium aluminate solutions with the same composition but different preparative history may have difTerent structure and physico-chemical properties.The structure of sodium-bearing aluminate solutions change very slowly during the storage after preparation.Sodium aluminate solutions contain several ammunium-bearing anisons such as Al(OH)^(-)_(4),Al(OH)^(3-)_(6)and[(HO)_(3)Al-O-Al(OH)_(3)]^(2-),etc.These anions can convert to each other but the reactions are very slow owing to the formation or breakage of covalent Al-O bond.Hence the ratio between these anions approaches equilibrium very slowly after the preparation,and the structure or properties of these solution samples before equilibrium is reached depend on their preparative histosive.
基金Project(2018YFC1901903)supported by the National Key R&D Program of ChinaProjects(51774079,51674075)supported by the National Natural Science Foundation of ChinaProject(N182508026)supported by the Fundamental Research Funds for the Central Universities,China
文摘The formation kinetics and mechanism of tricalcium aluminate hydrate and calcium oxalate in dilute sodium aluminate solution and sodium oxalate solution were studied respectively based on the lime causticization, and the optimal conditions for removing the oxalate in dilute sodium aluminate solution as well as the mechanism were finally obtained.The formation processes of tricalcium aluminate hydrate and calcium oxalate are mainly controlled by the chemical reaction and the inner diffusion respectively,and the corresponding reaction rate equations as well as the apparent activation energy were calculated. The hydrocalumite with a spatially interleaved structure will form in dilute sodium aluminate solution with sodium oxalate, greatly removing the oxalate impurity by absorption. Calcium oxalate can be converted to tricalcium aluminate hydrate with the increasing reaction time. The oxalate causticization efficiency and the alumina loss rate can be over 90% and below 31% respectively when reacted at 50℃ with a stirring rate of 200 r/min.
基金Project(50804031) supported by the National Natural Science Foundation of China
文摘Periodical attenuation of particles,which interferes seriously the normal alumina production,exists in Bayer process.In order to solve this problem,the rule of periodical attenuation of Al(OH) 3 particles was investigated by laboratory experiments under simulated industrial conditions.The results show that at higher temperature the variation period of particle size is shortened,while prolongs with more solid content.Particle size fluctuation amplitude reduces with the temperature rising but increases with the solid content increasing.Particle size distribution becomes more uniform by replenishing fine seeds,enabling the periodical fluctuation of Al(OH)3 particle size to be attenuated.Combining properly the additives with controlling the seed size is able to reduce the amplitude of periodical fluctuation and shorten the attenuation time.With unbalance of particle size distribution,the particles gradually become bigger,even inducing the decrease of the specific surface area of seeds,which is the major reason causing explosive attenuation of Al(OH)3 particles in seed precipitation process.
基金Project(2015BAB04B01)supported by the National Key Technology R&D Program of ChinaProject(FA2017029)supported by Science and Technology Program of Chongzuo,ChinaProject(CSUZC201811)supported by the Open-End Fund for the Valuable and Precision Instruments of Central South University,China
文摘Excess lithium in alumina is significantly bad for aluminum reduction.In this study,the concentration variation of lithium ion in sodium aluminate solution with addition of synthetic lithium aluminate was investigated.Elevating temperature,increasing caustic soda concentration,reducing alumina concentration or raising molar ratioαk improved equilibrium concentration of lithium ion in sodium aluminate solution.Agitation speed had a minimal effect on lithium ion concentration.Over 0.65 g/L lithium ion equilibrium concentration was observed in digestion process,whereas 35 mg/L lithium ion concentration remained in solution after precipitation time of 9 h.Moreover,equilibrium concentration decreased sharply from digestion of boehmite or diaspore to seed precipitation,about 95%lithium was precipitated into red mud(bauxite residue)and aluminum hydroxide.This study provides a valuable perspective in removal or extraction of lithium from sodium aluminate solution in alumina refineries.
基金Project(51374251)supported by the National Natural Science Foundation of China
文摘A series of low-temperature phase transitions of sodium aluminate solutions were studied by differential scanning calorimetry (DSC) and Raman spectroscopy. The results indicate that NaOH concentration is a primary impact factor for the binary eutectic point and ice melting temperature of sodium aluminate solutions with low NaOH concentration. In addition, the phase transition process of sodium aluminate solutions with low NaOH concentration from 123.15 to 283.15 K is divided into four steps: non-crystal to crystal, ternary eutectic reaction, binary eutectic reaction and ice melt. The projection phase diagram of NaOH-Al(OH)3-H2O system at low temperature was plotted, in which the ternary eutectic temperature for sodium aluminate solutions is 183.15 K.
基金Project(51274242)supported by the National Natural Science Foundation of ChinaProject(2015CX001)supported by the Innovation-driven Plan in Central South University,China
文摘The structural changes of silicate anions in the desilication process with the addition of calcium hydrate alumino-carbonate were studied by measuring Raman spectra, infrared spectra and corresponding second derivative spectra. The results show that the desilication ratio in the solution prepared by the addition of sodium silicate(solution-SS) is much greater than that in the solution by the addition of green liquor(solution-GL), and low alumina concentration in the sodium aluminate solutions facilitates the desilication process. It is also shown that alumino-silicate anions in the solution-GL, and Q^3 polymeric silicate anions in solution-SS are predominant, respectively. In addition, increasing the concentration of silica favors respectively the formation of the alumino-silicate or the Q^3 silicate anions in the solution-GL or the solution-SS. Therefore, it can be inferred that the low desilication ratio in the silicate-bearing aluminate solution is mainly attributed to the existence of alumino-silicate anions.
基金Projects(51774079,51674075)supported by the National Natural Science Foundation of ChinaProject(N182508026)supported by the Fundamental Research Funds for the Central Universities,China。
文摘The precipitation performance and kinetics of gibbsite from sodium aluminate solution with different sodium oxalate concentrations as well as the corresponding influence mechanism of oxalate during the seed precipitation process were systematically investigated by physicochemical properties test,using SEM and Raman spectra.As the concentration of sodium oxalate increases,both the precipitation rate and particle size of gibbsite decrease.The presence of sodium oxalate not only increases the viscosity of sodium aluminate solution,but also promotes the transformation of Al(OH)4^? to Al2O(OH)6^2?.The overall reaction rate constant decreases and the apparent activation energy of gibbsite increases with the increasing sodium oxalate concentration,the rate controlling step of which is chemical reaction.The needle-like sodium oxalate precipitates on the gibbsite crystals and covers the active Al(OH)3 seed sites,which leads to the lower precipitation rate and the finer particle size of gibbsite during the seed precipitation process.
文摘The constitution of high-caustic ratio and highly concentrated sodium aluminate solutions has been investigated by Raman spectra method.By comparison with the Raman spectra of crystalline solids of Ca_3[Al(OH)_6]_2 and Ba_2[Al_2(OH)_(10)],it can be concluded that AI(OH)_6^(3-)ion and perhaps its polymers may be formed in these solutions.
基金Project(51604309)supported by the National Natural Science Foundation of ChinaProject(201509048)supported by the Environmental Protection’s Special Scientific Research for Chinese Public Welfare IndustryProject(2015CX001)supported by the Innovation-driven Plan in Central South University,China
文摘Sulfides in the high-sulfur bauxite lead to serious steel equipment corrosion and alumina product degradation via theBayer process,owing to the reactions of sulfur and iron-containing phases in the sodium aluminate solution.The effects ofiron-containing phases on the transformation of sulfur-bearing ions(S2?,223S O?,23SO?and24SO?)in sodium aluminate solutionwere investigated.Fe,Fe2O3and Fe3O4barely react with23SO?and24SO?,but all of them,particularly Fe,can promote theconversion of223S O?to23SO?and S2?in sodium aluminate solution.Fe can convert to3Fe(OH)?in solution at elevatedtemperatures,and further react with S2?to form FeS2,but Fe2O3and Fe3O4have little influence on the reaction behavior of S2?insodium aluminate solution.Increasing temperature,duration,dosage of Fe,mole ratio of Na2Ok to Al2O3and caustic sodaconcentration are beneficial to the transformation of223S O?to23SO?and S2?.The results may contribute to the development oftechnologies for alleviating the equipment corrosion and reducing caustic consumption during the high-sulfur bauxite treatment bythe Bayer process.
基金Project(2015BAB04B01)supported by the National Key Technology Research&Development Program of ChinaProject(CSUZC201811)supported by the Open-End Fund for the Valuable and Precision Instruments of Central South University,China
文摘Effect of lithium ion in sodium aluminate solution on precipitation rate,lithium content,morphology,and crystallization of alumina trihydrate(ATH) was investigated. Results showed that increasing lithium ion concentration in solution improved the precipitation rate and lithium content in ATH,whereas reduced the mass fraction of lithium precipitation from solution. Lithium ion in solution generated the fine ATH, and thereafter significantly increased the total particle number due to the preferential nucleation.Elevating temperature or reducing lithium ion concentration decreased lithium content in ATH and reduced the fine particle amount.Moreover, lithium ion in the solution changed the morphology of ATH by improving the growth of the(110) and(200) planes of gibbsite.A large amount of fine bar-or flake-shaped ATH attached on the coarse particles also benefited the secondary nucleation and led to the poor strength of alumina.All results will further contribute to improving the quality of alumina.
基金Project(51274242) supported by the National Natural Science Foundation of ChinaProject(2015CX001) supported by the Innovation-driven Plan of Central South University,China
文摘The stability of calcium oxalate is critical for the removal of sodium oxalate from sodium aluminate solutions.This studyinvestigated the behavior of calcium oxalate in sodium aluminate solution containing sodium carbonate.Results show that calciumoxalate can be converted to tricalcium aluminate hydrate(TCA)and calcium carbonate in sodium aluminate solution and sodiumcarbonate solution,respectively.Elevating temperature,extending residence time,or increasing caustic soda concentration enhancesthe conversion ratio of calcium oxalate in sodium aluminate solution;as a consequence,anti-causticisation occurs.Stability ofcalcium-containing compounds in sodium aluminate solution containing sodium carbonate differs from that in sodium aluminatesolution or sodium carbonate solution.Na2CO3in aluminate solution accelerates the transformation of calcium oxalate;thus,aluminais lost because of4CaO·Al2O3·CO2·11H2O and TCA formation.Calcium carbonate,4CaO·Al2O3·CO2·11H2O and calcium oxalatecan change into TCA in sodium aluminate solution at elevated temperature.Calcium oxalate remains relatively stable in dilutealuminate solution within a short residence time at low temperature.Thus,a novel process for removal of sodium oxalate by limecausticisation was presented and employed in an alumina refinery in China.
基金Supported by the Key Program of National Fundamental Research Development(No. G1999064892-2)National Natural Science Foundation(No. 59874031)
文摘The effects of frequency of ultrasound on the precipitation process of prepared supersaturated sodium aluminate solutions of practical concentration were studied experimentally under seeded, isothermal, batch crystallization conditions at various temperatures and initial ak(mole ratio of Na2O/Al2O3). The decomposition and the particle number percentage for size below 2 mm at time of 15 h were compared, particle size distribution and SEM photos of the product aluminum hydroxide were also analyzed. The results indicate that the ultrasonic treatment at 16 kHz can enhance the decomposition rate of sodium aluminate solutions, and also has effects on particle morphology and particle size distribution of aluminum hydroxide precipitated.
基金Project(20476107) supported by the National Natural Science Foundation of ChinaProject(2005CB623702) supported by the National Basic Research Program of China
文摘Na4EDTA and EDTA were adopted as new additives to intensify the seeded precipitation process of sodium aluminate solution. The effects of the two additives at certain concentrations on the seeded precipitation rate of sodium aluminate solution, particle size distribution (PSD) and morphology of precipitated gibbsite were investigated using titration method, particle size analyzer and scanning electron microscope (SEM), respectively. The results show that the two additives can accelerate the seeded precipitation rate of sodium aluminate solution. At relatively high concentration, the facilitative effect of EDTA on sodium aluminate solution is more obvious than that of Na4EDTA. EDTA makes gibbsite particles thinner than Na4EDTA. The Na+ and H+ result in the different effects on the seeded precipitation rate of sodium aluminate solution in spite of the same EDTA anion in the two additives.
文摘The anionic species of the SiO_2-containing sodium aluminate solutions prepared by different methods have been investigated by Raman spectra and ultraviolet spectra.It was found that these solutions have different SiO_2-containing anions.The solution prepared by leaching in- dustrial sinter of soda-lime sintering process contains polvsilicate ions with Si-O-Si radicals.