基于六水铝酸三钙的双电层调控从铝酸钠溶液中短流程脱除有机物

从铝酸钠溶液中经济地脱除有机物是长期以来的研究重点。基于叶滤环节将六水铝酸三钙(TCA)作为助滤剂的工艺,提出一种短流程同时滤除杂质颗粒和吸附脱除有机物的新方法。在浓缩铝酸钠溶液中制备结晶度低、TCA含量高、表面能高、晶格畸变大的超细TCA样品。同时,TCA样品在碱性溶液中的Zeta电位线性依赖于TCA含量,揭示二元混合物Zeta电位的可加性。描述在碱性溶液中TCA二元混合物双电层的演化规律。此外,超细TCA样品对长烷基链及高相对分子质量有机物具有较高的吸附容量,对腐殖酸钠的吸附容量可达69.69mg/g(以有机碳计),而高温溶出过程会显著降低TCA的吸附容量。

Effect of inorganic salt impurities on seeded precipitation of silica hydrate from sodium silicate solution

To clarify the precipitation of silica hydrate from the real desilication solutions of aluminosilicate solid wastes by adding seeds and improve integrated waste utilization,the seeded precipitation was studied using synthesized sodium silicate solution containing different inorganic salt impurities.The results show that sodium chloride,sodium sulfate,sodium carbonate,or calcium chloride can change the siloxy group structure.The number of high-polymeric siloxy groups decreases with increasing sodium chloride or sodium sulfate concentration,which is detrimental to seeded precipitation.Calcium chloride favors the polymerization of silicate ions,and even the chain groups precipitate with the precipitation of high-polymeric sheet and cage-like siloxy groups.The introduced sodium cations in sodium carbonate render a more open network structure of high-polymeric siloxy groups,although the carbonate ions favor the polymerization of siloxy groups.No matter how the four impurities affect the siloxy group structure,the precipitates are always amorphous opal-A silica hydrate.

铝酸钠对铬铁矿无钙焙烧过程中铬氧化的影响

研究Na_(2)O·Al_(2)O_(3)与铬尖晶石及铬铁矿的氧化焙烧反应行为,揭示Na_(2)O·Al_(2)O_(3)对铬氧化的影响。结果表明:Na_(2)O·Al_(2)O_(3)与MgO·Cr_(2)O_(3)的氧化焙烧过程中,MgO·Cr_(2)O_(3)中仅有约50%的铬被氧化转化为Na_(2)CrO_(4),其余的铬转化为含铝尖晶石Mg(CrAl)O_(4)。Mg(CrAl)O_(4)在铬铁矿氧化焙烧条件下很难与Na_(2)O·Al_(2)O_(3)进一步反应。Na_(2)O·Al_(2)O_(3)与铬铁矿氧化焙烧进一步证实了Na_(2)O·Al_(2)O_(3)不能与部分铬尖晶石充分反应,从而揭示了传统铬铁矿无钙焙烧生产铬盐过程中铬氧化转化率低的原因。根据实验结果,提出了一种消除Na_(2)O·Al_(2)O_(3)对无钙焙烧过程影响的新策略,即在炉料中增加Na_(2)CO_(3)的配量以满足形成Na_(2)O·Al_(2)O_(3)的需要,新策略可使铬氧化率提高至近100%。本研究更新了人们对铝酸钠在铬铁矿无钙焙烧过程作用机理的认识,为开发高效清洁的铬盐生产技术提出了新思路。

Reaction behavior of kaolinite with ferric oxide during reduction roasting

The pre-separation of silica and alumina in aluminosilicates is of great significance for efficiently treating alumina-/ silica-bearing minerals for alumina production. In this work, the reaction behavior of kaolinite with ferric oxide during reduction roasting was investigated. The results of thermodynamic analyses and reduction roasting experiments show that ferrous oxide obtained from ferric oxide reduction preferentially reacts with alumina in kaolinite to form hercynite, meanwhile the silica in kaolinite is transformed into quartz solid solution and/or cristobalite solid solution. With increasing roasting temperature, fayalite formed by reaction of surplus ferrous oxide with silica at low temperature is reduced to silica and metallic iron in the presence of sufficient carbon dosage. However, increasing roasting temperature and decreasing Fe2O3/Al2O3 molar ratio favor mullite formation. The complete conversion of kaolinte into free silica and hercynite can be obtained by roasting raw meal of kaolin, ferric oxide and coal powder with Fe2O3/Al2O3/C molar ratio of 1.2:2.0:1.2 at 1373 K for 60 min. This work may facilitate the development of a technique for comprehensively utilizing silica and alumina in aluminosilicates.

Efficient separation of alumina and silica in reduction-roasted kaolin by alkali leaching

Alkali leaching was employed to investigate the separation of alumina and silica in roasted kaolin obtained by roasting kaolin alone in air at 1273 K for 60 min and in clinker prepared by roasting the mixed raw meal of kaolin,ferric oxide and coal powder with Fe2O3/Al2O3/C molar ratio of 1.2:2.0:1.2 in reducing atmosphere at 1373 K for 60 min.The thermodynamic analyses and alkali leaching results show that the composition of the Al-Si spinel in roasted kaolin is close to that of 3Al2O3·2SiO2 and the spinel is dissolved with increasing leaching time,resulting in difficulty in deeply separating alumina and silica in kaolin by the traditional roasting-leaching process.On the contrary,the efficient separation of alumina and silica in kaolin can be reached by fully converting kaolinite into insoluble hercynite and soluble free silica,namely quartz solid solution and cristobalite solid solution,during reduction roasting,followed by alkali leaching of the obtained clinker.Furthermore,experimental results from treating high-silica diasporic bauxite indicate that the reduction roasting-alkali leaching process is potential to separate silica and alumina in aluminosilicates.

Transformation of hematite in diasporic bauxite during reductive Bayer digestion and recovery of iron

The reductive Bayer digestion by using iron powder as reductant is proposed to convert hematite to magnetite and further to dissociate iron minerals from sodium aluminosilicate hydrate(desilication product,DSP)based on the differences of their surface properties.The results show that the differences of surface properties between magnetite and DSP in zeta potential,wettability and solvation trend facilitate magnetite to agglomerate,grow up and thus to dissociate from DSP.The increments of reductant amount and alkali concentration favor the transformation of hematite in digestion with the relative alumina recovery of98.91%.Processing the resultant red mud can obtain qualified iron concentrate with iron grade of approximate60%and recovery of about86%through magnetic separation,resulting in reduction of red mud emission higher than70%.The results are potential to develop a novel technology for processing high iron diasporic bauxite efficiently and provide references for comprehensive utilization of high iron red mud.

Molybdenite-limestone oxidizing roasting followed by calcine leaching with ammonium carbonate solution

Oxidizing roasting of molybdenite with lime can significantly reduce SO2pollution compared with the traditional roastingwithout lime.However,the calcine is subsequently leached by sulfuric acid,resulting in serious equipment corrosion and abundantnon-recyclable CaSO4slag.In this work,a novel process,in which the molybdenite was roasted with CaCO3followed by(NH4)2CO3solution leaching,was proposed to improve the art of lime roasting-sulfuric acid leaching.Oxidizing roasting of molybdenite withCaCO3was investigated through thermodynamic calculation,thermogravimetric analysis and roasting experiments.The results showthat the products of the oxidizing reaction of MoS2in the presence of CaCO3and O2are CaSO4,CaMoO4and CO2at573-1000K.The MoS2conversion rate achieves approximately99%and the sulfur-retained rate attains approximately95%with aCaCO3-to-MoS2molar ratio of3.6at500°C for1h by adding5%mineralizer A(mass fraction).The leaching results show that theleaching rate of Mo reaches98.2%at85°C for7h with a(NH4)2CO3concentration of600g/L and a liquid-solid ratio of10mL/g.The results presented are potential to develop a novel cleaner technique for ammonium molybdate production.

Enrichment and separation of iron minerals in gibbsitic bauxite residue based on reductive Bayer digestion

The mineralogical characteristics of three kinds of gibbsitic high-iron bauxite and the effects of various digestion conditions on the enrichment and separation of iron minerals were investigated. The results show that adding an appropriate organic reductant such as glycerol can promote the digestion of concomitant diaspore, boehmite and alumogoethite as well as the conversion of goethite to hematite in the reductive Bayer digestion. Processing Bauxite A with A/S of 25.41 can directly produce qualified iron concentrates(TFe>56%) by the reductive Bayer digestion, and thus realize the zero red mud discharge. For Bauxite B and Bauxite C with A/S of 7.82 and 3.35, the iron recoveries of 65.13% and 79.13% can be achieved with the corresponding TFe of 52.05% and 50.16% in the iron concentrates by gravity separation, respectively, resulting in the red mud discharge reduction of ~50% or above.

Kinetics of oxidation roasting of molybdenite with different particle sizes

The kinetics of oxidation roasting of molybdenum concentrate was studied by differential thermal−gravimetric experiments and non-isothermal analysis methods.The results show that high temperature is beneficial for oxidation of molybdenum concentrate.The initial oxidation temperature of the molybdenum concentrate is 450℃,and the rapid oxidation occurs above 500℃.The oxidation process conforms to the unreacted shrinking nucleus model.The early stage of the oxidation is controlled by chemical reaction with the apparent activation energy of 123.180 kJ/mol,while the later stage is controlled by internal diffusion with the apparent activation energy of 80.175 kJ/mol.Moreover,the oxidation rate is closely related to particle size of the concentrate.The smaller the particle size is,the larger the oxidation rate is.

Precipitation of spherical boehmite from concentrated sodium aluminate solution by adding gibbsite as seed

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.

Effects of iron-containing phases on transformation of sulfur-bearing ions in sodium aluminate solution

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.

Behavior of calcium oxalate in sodium aluminate solutions

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.

Effect of lithium ion on seed precipitation from sodium aluminate solution

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.

Surface properties of superfine alumina trihydrate after surface modification with stearic acid

The surface properties of superfine alumina trihydrate （ATH） after surface modification were studied by measuring the contact angle, active ratio, oil adsorption, total organic carbon, adsorption ratio, and Fourier transform infrared （FTIR） spectrum. The contact angle increased initially and then slowly decreased with an increase of the amount of stearic acid. However, the surface flee energy decreased ini- tially and then increased. Surface modification with stearic acid or sodium stearate can benefit from elevating temperature. The base surface tension component and the free energy of Lewis acid-base both declined sharply following the surface modification. Excess stearic acid was physically adsorbed in the form of multilayer adsorption, and an interaction between oxygen on the ATH surface and hydroxyl in stearic acid was subsequently determined. Our results further indicated that the contact angle and adsorption ratio can be used as control indicators for surface modification compared with active ratio, oil adsorption and total organic carbon.

Preparation of spherical cobalt carbonate from cobalt sulfate solution

A precursor of cobaltous dihydroxycarbonate was firstly prepared by precipitation reaction of cobalt sulfate solution and ammonium carbonate solution,and then a hydrothermal process for the precursor was conducted to obtain the spherical cobalt carbonate with low sulfur content.The experimental results show that the feeding method,final p H value of the precipitation reaction slurry and the concentration of the cobalt sulfate solution have obvious effects on the sulfur content,morphology and particle size distribution of the precursor.The sulfur content of the precursor is 0.0115 wt.%under the optimized conditions.The hydrothermal treatment with temperatures of 125-150℃can transform the precursor of cobaltous dihydroxycarbonate into spherical cobalt carbonate and decrease the sulfur content to 0.0030 wt.%in the obtained product.

Properties of low-modulus sodium silicate solution in alkali system

The properties of low-modulus(m≤1)sodium silicate and pre-desilication solutions in alkali systems were studied by measuring their electrical conductivity,viscosity,and surface tension.The results show that the property of high concentration pre-desilication solution is similar to that of sodium silicate solution.The electrical conductivity of sodium silicate solution increases with increasing the temperature and silica concentration but decreases with increasing the modulus.Further,the viscosity of the solution increases with increasing the silica concentration and linearly decreases with increasing the temperature,whereas its surface tension gradually decreases with increasing silica concentration and temperature,indicating that the sodium silicate solution is an oligomer with strong surface activity.At room temperature,the electrical conductivity and surface tension of sodium silicate solution are higher than those of pre-desilication solution,whereas its viscosity is smaller than that of pre-desilication solution.A turning point exists at a silica concentration of 44.7 g/L.When the silica concentration is less than 44.7 g/L,the ionic structure of the solution is dominated by monomeric silicate ions.In contrast,when the silica concentration changes from 44.7 to 50 g/L,the migration number of silicate anions significantly decreases.

Dissolving behavior of ammonium paratungstate in(NH_4)_2CO_3-NH_3?H_2O-H_2O system

The effects of temperature, ammonia concentration and ammonium carbonate concentration on the dissolving behavior of ammonium paratungstate were studied in（NH4）2CO3-NH3？H2O-H2O system. The results show that rising temperature, prolonging duration, increasing ammonia concentration and decreasing ammonium carbonate concentration favor dissolving of ammonium paratungstate at temperature below 90 ℃, while the WO3 concentration decreases after a certain time at temperature above 100 ℃. Furthermore, the undissolved tungsten exists in the form of either APT·4 H2O below 90 ℃ or pyrochlore-type tungsten trioxide above 100℃. In dissolving process, the ammonium paratungstate dissolves into paratungstate ions followed by partially converting to tungstate ion, resulting in the coexistence of the both ions. This study may provide a new idea to exploit a novel technique for manufacturing ammonium paratungstate and pyrochlore-type tungsten trioxide.

Effect of iron valence on hydrothermal preparation of pyrochlore-type tungsten oxide

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.

Enhanced conversion mechanism of Al-goethite in gibbsitic bauxite under reductive Bayer digestion process

The conversion mechanism of Al-goethite under the action of different additives(lime or reductant for typical or reductive Bayer digestion)was investigated by thermodynamic calculation,XRD,and SEM-EDS.The results show that the formation of Fe-substituted hydrocalumite is crucial to converting Al-goethite to hematite during Bayer digestion by adding lime.However,the conversion proceeds more easily under the action of reductant due to the rapid formation of magnetite.Additionally,Bayer liquor composition significantly affects the product composition and also the conversion rate of Al-goethite.Compared to typical Bayer digestion with Al-goethite containing gibbsitic bauxite as raw material,the red mud yield of reductive Bayer digestion decreases from 39.02%to 31.19%,and the grade of TFe in red mud increases from 41.66%to 53.80%.

Thermodynamic analysis on reaction behaviors of silicates in (NH_4)_2WO_4-(NH_4)_2CO_3-NH_3-H_2O system

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.