Thermodynamics and kinetics of alumina extraction from fly ash using an ammonium hydrogen sulfate roasting method

A novel method was developed for extracting alumina (Al₂O₃) from fly ash using an ammonium hydrogen sulfate (NH₄HSO₄) roasting process, and the thermodynamics and kinetics of this method were investigated. The thermodynamic results were verified experimentally. Thermodynamic calculations show that mullite present in the fly ash can react with NH₄HSO₄ in the 298–723 K range. Process optimization reveals that the extraction rate can reach up to 90.95% when the fly ash reacts with NH₄HSO₄ at a 1:8 mole ratio of Al₂O₃/NH₄HSO₄ at 673 K for 60 min. Kinetic analysis indicates that the NH₄HSO₄ roasting process follows the shrinking unreacted core model, and inner diffusion through the product layer is the rate-controlling step. The activation energy is calculated to be 16.627 kJ/mol; and the kinetic equation can be expressed as 1 ? (2/3)α ? (1 ? α)2/3 = 0.0374t exp[?16627/(RT)], where α is the extraction rate and t is the roasting temperature.     

纤维素在1-丁基-3-甲基咪唑系列离子液体中的溶解性能研究

合成了1丁基-3-甲基咪唑的乙酸盐（[bmim][Ac]）、乳酸盐（[bmim][La]）、乙醇酸盐（[bmim][Ga]）以及二氰胺盐（[bmim][Dca]）4种离子液体．测定了70℃时纤维素在这些离子液体中的溶解度，并利用。HNMR核磁研究了其溶解规律．借助傅里叶转换红外光谱（FTIR）、热重分析（TGA），对从[bmim][Ac]／纤维素溶液中再生纤维素的结构和热稳定性进行了表征．结果表明，4种离子液体中，乙酸根的氢键形成能力最强，离子液体[bmim][Ac]对纤维素的溶解效果最佳，而且在纤维素的溶解以及再生过程中，纤维素与[bmim][Ac]溶剂没有发生化学反应，与原料纤维素相比，再生纤维素大分子结构没有被破坏，热稳定性稍有降低．     

Effects of the mineral phase and valence of vanadium on vanadium extraction from stone coal

The influence of roasting on the leaching rate and valence of vanadium was evaluated during vanadium extraction from stone coal. Vanadium in stone coal is hard to be leached and the leaching rate is less than 10% when the raw ore is leached by 4 mol/L H₂SO₄ at 90℃ for 2 h. After the sample is roasted at 900℃ for 2 h, the leaching rate of vanadium reaches the maximum, and more than 70% of vanadium can be leached. The crystal of vanadium-bearing mica minerals decomposes and the content of V(V) increases with the rise of roasting temperature from 600 to 900℃, therefore the leaching rate of vanadium increases significantly with the decomposition of the mica minerals. Some new phases, anorthite for example, form when the roasting temperature reaches 1000℃. A part of vanadium may be enwrapped in the sintered materials and newly formed phases, which may impede the oxidation of low valent vanadium and make the leaching rate of vanadium drop dramatically. The leaching rate of vanadium is not only determined by the valence state of vanadium but also controlled by the decomposition of vanadium-bearing minerals and the existence state of vanadium to a large extent.     

Mesoporous fibrous silicon nitride by catalytic nitridation of silicon

The catalytic effect of metal oxide/alumina whiskers(CeO_2, Mn_3O_4, NiO, Co_3O_4, Fe_2O_3, Cr_2O_3/AW) was evaluated on their ability to drive the nitridation of silicon and to generate mesoporous fibrous silicon networks.Silicon powder with different particles size along with the catalyst was nitridized at 1300 °C for 5 h in nitrogen and nitrogen diluted with 10 vol% ammonia atmospheres. Nitridation degree of silicon up to 99% was recorded using 1.5 wt% CeO_2 and Fe_2O_3 catalysts in nitrogen-ammonia atmosphere. The catalyzed samples contain submicronic silicon nitride fibres with a diameter of 400–500 nm and a length of up to few micrometers. The compressive strength of 46 ± 1 MPa was measured for silicon samples catalyzed with nickel oxide/alumina whiskers and nitridized in N_2/10 vol%NH_3 atmosphere. Porous silicon nitride networks were produced with 45–52% porosity, pore sizes in the range of 370–1200 nm and median pore in the range of 495–1655 nm.     

Alkaline digestion behavior and alumina extraction from sodium aluminosilicate generated in pyrometallurgical process

In pyrometallurgical process, Al-and Si-bearing minerals in iron and aluminum ores are easily transformed into sodium aluminosilicates in the presence of Na₂O constituents, which alters the leaching behaviors of Al₂O₃ and SiO₂. It was confirmed that sodium aluminosilicates with different phase compositions synthesized at various roasting conditions were effectively digested in the alkaline digestion process. Under the optimum conditions at temperature of 100-120℃, liquid-to-solid ratio (L/S) of 10:2 mL/g, caustic ratio of 4, and Na₂O concentration of 240 g/L, the actual and relative digestion ratio of Al₂O₃ from the synthesized sodium aluminosilicates reached maximums of about 65% and 95%, respectively, while SiO₂ was barely leached out. To validate the superior digestion property of sodium aluminosilicate generated via an actual process, the Bayer digestion of an Al₂O₃-rich material derived from reductive roasting of bauxite and comprising Na_1.75Al_1.75Si_0.25O₄ was conducted; the relative digestion ratio of Al₂O₃ attained 90% at 200℃.     

Comparative analysis of the dissolution kinetics of galena in binary solutions of HCl/FeCl<Subscript>3</Subscript> and HCl/H<Subscript>2</Subscript>O<Subscript>2</Subscript>

A comparative study of the dissolution kinetics of galena ore in binary solutions of FeCl₃/HCl and H₂O₂/HCl has been undertaken. The dissolution kinetics of the galena was found to depend on leachant concentration, reaction temperature, stirring speed, solid-to-liquid ratio, and particle diameter. The dissolution rate of galena ore increases with the increase of leachant concentration, reaction temperature, and stirring speed, while it decreases with the increase of solid-to-liquid ratio and particle diameter. The activation energy (E _a) of 26.5 kJ/mol was obtained for galena ore dissolution in 0.3 M FeCl₃/8.06 M HCl, and it suggests the surface diffusion model for the leaching reaction, while the E _a value of 40.6 kJ/mol was obtained for its dissolution in 8.06 M H₂O₂/8.06 M HCl, which suggests the surface chemical reaction model for the leaching reaction. Furthermore, the linear relationship between rate constants and the reciprocal of particle radius supports the fact that dissolution is controlled by the surface reaction in the two cases. Finally, the rate of reaction based on the reaction-controlled process has been described by a semiempirical mathematical model. The Arrhenius and reaction constants of 11.023 s⁻¹, 1.25×10⁴ and 3.65×10² s⁻¹, 8.02×10⁶ were calculated for the 0.3 M FeCl₃/8.06 M HCl and 8.06 M H₂O₂/8.06 M HCl binary solutions, respectively.     

UV/visible spectroscopic analysis of CO<Superscript>3+</Superscript> and CO<Superscript>2+</Superscript> during the dissolution of cobalt from mixed Co-Cu oxidized ores

The leaching of cobalt from four-mixed Co-Cu oxidized ores containing cobalt at levels ranging from 0.5wt% to 34wt% was studied and the results has been reported. Conventional dissolution of these oxidized Co-Cu ores with diluted H₂SO₄ and SO₂ as a reducing agent resulted in a substantial improvement in the solution based recovery of cobalt. UV/visible spectroscopic analysis of the leached solutions indicated that the increased cobalt content in the solution was a result of flushing the acidified cobalt leaching solution with SO₂. Furthermore, UV/visible spectroscopy confirmed that as SO₂ was flushed into the acidified leaching solution, Co³⁺ bearing minerals were reduced to the readily soluble Co²⁺ bearing minerals, and this resulted in the increase of total cobalt in the collected solution. The mechanism of the reduction of Co³⁺ to Co²⁺ bearing minerals when SO₂ is flushed during the leaching of mixed Co-Cu oxidized ores, including the stability trends of Co³⁺, Co²⁺, and Cu²⁺ complexes, as shown by their UV/visible spectra, are also discussed.     

Extraction of Aluminum and Iron from Boiler Slag by Sulfuric Acid

This paper presents a new method of recycling aluminum and iron in boiler slag derived from plants that use coal as fuel. The new method integrates efficient extraction and reuse of the leached pellets together. An elemental analysis of aqueous solutions leached by sulfuric acid was determined by EDTA-Naz-ZnCl2 titration method. The components and microstructures of the samples were examined by means of XRF, XRD and SEM. An aluminum extraction efficiency of 86.50% was achieved when the sintered pellets were leached using 4 mol · L^- 1 H2SO4 at solid/ liquid [m（g）/V（mL）] ratio of 1 ： 5 at 80 ℃ for 24 h. An iron extraction efficiency of 94.60% was achieved in the same conditions for the maximum extraction efficiency of Al. The extraction efficiencies of Al and Fe increased with an increase in temperature, leaching time and acidity. The concentration of alumina and iron hydroxide in the final product was determined to be 99.12% and 92.20% respectively. This product of alumina would be used directly for the production of metallic aluminum.     

CO2和O2共注入下方解石溶解对黄铁矿氧化固铀的影响

我国大型可地浸砂岩型铀矿床普遍存在黄铁矿和方解石与铀矿物密切共生现象。中性地浸采铀过程中O₂和CO₂的共注入会诱导黄铁矿氧化和方解石溶解,目前针对二者共存体系中方解石溶解对黄铁矿氧化固铀的影响尚不明确。本文通过静态批实验和数值模拟的方法对比研究了CO₂和O₂条件下方解石溶解对黄铁矿氧化固铀的影响。结果表明:无CO₂分压下中性Tris缓冲体系中黄铁矿氧化对U(VI)的吸附率高达90%,有CO₂分压下碳酸铀酰体系中铀的固定率明显降低,约有32%的铀被吸附。在方解石和黄铁矿共存体系中,单独通O₂条件下铀的吸附率为27%,CO₂和O₂共通时黄铁矿氧化对铀的吸附率仅为2%,结合数值模拟结果表明O₂₊黄铁矿+方解石体系和CO₂₊O₂₊黄铁矿+方解石体系中Ca₂(UO₂)(CO₃)₃质量比分别为80%和95%。X射线衍射(X-ray diffraction,XRD)、X射线光电子能谱(X-ray photoelectron spectroscopy,XPS)和傅里叶红外光谱(Fourier transform infrared,FT-IR)结果表明黄铁矿表面发生微氧化形成针铁矿和纤铁矿会增加U(VI)的吸附,方解石溶解促进Ca-UO₂-CO₃络合物的形成影响了黄铁矿及其氧化产物对U(VI)的固定,提高了U(VI)的迁移能力。     

Efficient and selective recovery of Ni,Cu, and Co from low-nickel matte via a hydrometallurgical process

Low-nickel matte was intensively characterized, and Ni, Cu, and Co were determined to exist mainly as (Fe,Ni)₉S₈ and FeNi₃, Cu₅FeS₄, and (Fe,Ni)₉S₈ and Fe₃O₄ (in isomorphic form), respectively. The efficient and selective extraction of Ni, Cu, and Co from the low-nickel matte in an (NH₄)₂S₂O₈/NH₃·H₂O solution system was studied. The effects of (NH₄)₂S₂O₈ and NH₃·H₂O concentrations, leaching time, and leaching temperature on the metal extraction efficiency were systematically investigated. During the oxidative ammonia leaching process, the metal extraction efficiencies of Ni 81.07%, Cu 93.81%, and Co 71.74% were obtained under the optimal conditions. The relatively low leaching efficiency of Ni was mainly ascribed to NiFe alloy deactivation in ammonia solution. By introducing an acid pre-leaching process into the oxidative ammonia leaching process, we achieved the high extraction efficiencies of 98.03%, 99.13%, and 85.60% for the valuable metals Ni, Cu, and Co, respectively, from the low-nickel matte.     

Thermodynamics and phase transformations in the recovery of zinc from willemite

Willemite is a common component of zinc and lead metallurgical slags that, in the absence of effective utilization methods, cause serious environmental problems. To solve this problem and increase zinc recovery, we proposed a novel extraction method of zinc from willemite by calcified roasting followed by leaching in NH₄Cl-NH₃·H₂O solution. The thermodynamics and phase conversion of Zn₂SiO₄ to zinc oxide (ZnO) during calcified roasting with CaO were investigated. The mechanism of mineralogical phase conversion and the effects of the CaO-to-Zn₂SiO₄ mole ratio (n(CaO)/n(Zn₂SiO₄)), roasting temperature, and the roasting time on zinc-bearing phase conversion were experimentally investigated. The results show that Zn₂SiO₄ was first converted to Ca₂ZnSi₂O₇ and then to ZnO. The critical step in extracting zinc from willemite is the conversion of Zn₂SiO₄ to ZnO. The zinc percent leached in the ammonia leaching system rapidly increased because of the gradual complete phase conversion from willemite to ZnO via the calcified roasting process.     

A new process of extracting vanadium from stone coal

A new process of extracting vanadium from the stone coal vanadium ore in Fangshankou, Dunhuang area of Gansu Province, China was introduced. Various leaching experiments were carried out, and the results show that the vanadium ore in Fangshankou is difficult to process due to its high consumption of acid and the high leaching rate of impurities. However, the leaching rate can be up to 80% and the content of V₂O₅ in the residue can be between 0.22%–0.25% in the process of ore fine grinding→oxidation roasting→mixing and ripening→aqueous leaching→P₂O₄ solvent extraction→sulfuric acid stripping→oxidation and precipitation→decomposition by heat. Also, the quality of flaky V₂O₅ produced by this process can meet the requirements of GB3283–87. The total leaching rate of vanadium is 70%. Also, three types of wastes are easy to treat. The vanadium extraction process is better in relation to the aspect of environmental protection than the sodium method.     

Development of high volume rice husk ash alumino silicate composites

The development of high volume rice husk ash (RHA) alumino silicate composites (ASC) was studied. RHA was used as the source of silica and aluminium in the ASC. The mass ratios of RHA:Al(OH)3 of 70:30 to 99:1 were tested. The results indicate that the obtained ASC mortars are not stable and disintegrate in water. Boric acid was introduced to the mixture to overcome this problem. Stable ASC mortars with high RHA:Al(OH)₃ mass ratios of 90:10 to 97.5:2.5 were obtained with the use of boric acid and 115℃ curing. The compressive strength of the mortar of 20 MPa was gained. The immersion test indicates that high volume RHA ASC mortars show good resistance in 3vol% H₂SO₄ solution, but is slightly less durable in 5wt% MgSO₄ solution.     

硫氧混合铅锌矿中锌的氧化氨浸动力学

常压低温条件下在NH3-(NH4)2 SO4体系中使用过硫酸铵作为氧化剂对硫氧混合铅锌矿中的锌进行浸出实验,系统研究了搅拌速度、浸出剂浓度、氧化剂浓度与温度对于锌浸出率的影响.结果表明,在最优条件下锌的浸出率可达93.2%,且浸出过程中几乎没有其他离子进入溶液,实现了锌的选择性高效浸出,从而简化了后续的浸出液净化与材料制备过程.动力学研究表明,硫氧混合铅锌矿中锌的氧化氨浸过程遵循固体产物层扩散控制的未反应核收缩模型,浸出反应的表观活化能为17.89 kJ·mol-1.     

Preparation of manganese sulfate from low-grade manganese carbonate ores by sulfuric acid leaching

In this study, a method for preparing pure manganese sulfate from low-grade ores with a granule mean size of 0.47 mm by direct acid leaching was developed. The effects of the types of leaching agents, sulfuric acid concentration, reaction temperature, and agitation rate on the leaching efficiency of manganese were investigated. We observed that sulfuric acid used as a leaching agent provides a similar leaching efficiency of manganese and superior selectivity against calcium compared to hydrochloric acid. The optimal leaching conditions in sulfuric acid media were determined; under the optimal conditions, the leaching efficiencies of Mn and Ca were 92.42% and 9.61%, respectively. Moreover, the kinetics of manganese leaching indicated that the leaching follows the diffusion-controlled model with an apparent activation energy of 12.28 kJ·mol-1. The purification conditions of the leaching solution were also discussed. The results show that manganese dioxide is a suitable oxidant of ferrous ions and sodium dimethyldithiocarbamate is an effective precipitant of heavy metals. Finally, through chemical analysis and X-ray diffraction analysis, the obtained product was determined to contain 98% of MnSO₄·H₂O.     

HSO3-functionalized Brønsted acidic ionic liquids promote esterification of aromatic acid

Esterification of aromatic acid can be promoted via HSO3-functionalized Br nsted acidic ionic liquids (ILs). Under the optimum conditions, using 1-(3-sulfonic acid) propyl-3-methylimidazolium hydrogen sulfate ([MimC3SO3H][HSO4]) and 1-(4-sulfonic acid) butyl-3-methylimidazolium hydrogen sulfate ([MimC 4 SO 3 H][HSO4 ]) as dual solvent-catalysts, the conversion of esterification of aromatic acid was determined to be more than 90%, indicating that HSO3-functionalized ILs show much better catalytic ability than those of non-functionalized ionic liquids. The separation of desired product was easily performed by extraction with diethyl ether and these HSO3-functionalized ILs could be reused 7 times after vacuum drying. Our data represent an environmentally friendly method for the preparation of aromatic esters.     

Kinetic modeling of copper bioleaching from low-grade ore from the Shahrbabak Copper Complex

The copper recovery from low-grade copper sulfide ore was investigated using microbial leaching. Several parameters substantially affect the bioleaching of copper; among them, pulp density and nutrient media were selected for investigation. The optimum conditions for copper recovery were a pulp density of 5 g/mL, a mixed-mineral salt medium of Acidithiobacillus thiooxidans (70vol%) and Acidithiobacillus ferrooxidans (30vol%), and 10vol% of inoculum. Under these conditions, the maximum bioleaching capacity of the medium for copper recovery was determined to be approximately 99%. The effect of pulp density on the kinetics of the bioleaching process was surveyed using both da Silva's method and constrained multilinear regression analysis. The kinetics of copper dissolution followed the shrinking core model, and the process was diffusion controlled at a pulp density of 5 g/mL. Nevertheless, at higher pulp densities, the process was controlled by chemical reaction.     

添加剂对准东煤灰熔融特性影响的研究

以四种典型的准东煤为煤样,利用SiO₂-CaO-Al₂O₃三元系统相图分析了准东煤结渣倾向性的变化,并采用灰熔融温度测试仪研究煤灰化学成分和灰熔融性的关系,寻求提高准东煤灰熔融温度的方法。结果表明,根据三元相图的灰熔融性趋势,添加适量的氧化物添加剂可以提高煤灰的熔融温度,实验中神华煤添加5%的CaO,5% Al₂O₃的可以显著的提高煤灰熔融温度。研究结果为准东煤在实际工业应用提供理论依据。     

Up-grading of natural ilmenite ore by combining oxidation and acid leaching

Rutile (TiO₂) is heavily used in pigments and colorants, and the most abundant source of rutile is ilmenite. Upon oxidation of ilmenite, rutile can be formed with modest energy consumption; furthermore, after leaching, only a few byproducts are formed. Unfortunately, one drawback is the necessarily long oxidative process of typically used methods. In this study, we show that a fluidized bed reactor can be used to oxidize ilmenite ore to rapidly form rutile and pseudobrookite (Fe₂TiO₅) phases. Ilmenite was oxidized with 5vol% O₂ in Ar at temperatures of 1173 K or 1223 K and subsequently leached using a diluted H₂SO₄ solution to dissolve the pseudobrookite phase. The effects of acid concentration, temperature, and cooling rate after oxidation were investigated. We show that the ilmenite was rapidly oxidized to form rutile and pseudobrookite phases at 1173 and 1223 K in a 5vol% O₂/95vol% Ar environment within 40 min. The final maximum rutile yield was 84.2mol% after leaching in (1 + 1) H₂SO₄ solution at 393 K for 12 h.     

The comparative investigation on redox property and second-order nonlinear response of Keggin-type α-[PM12O39NPh]3− (M = W and Mo) and Mo6NPh

Keggin-type phenylimido-polyoxometalates α-[PM₁₂O₃₉NPh]³⁻ (M = W and Mo) have been systematically investigated on the electronic structures, redox as well as nonlinear optical (NLO) properties by density functional theory (DFT). The strong M≡N bond confirmed by natural bond orbital (NBO) analysis comprises one s bond and two π bonds, the same as Mo≡N in [Mo₆O₁₈NPh]²⁻. Furthermore, phenylimido segment effectively modifies the electronic properties of α-[PM₁₂O₃₉NPh]³⁻. On one hand, when enlarging the inorganic cluster from {Mo₆O₁₈} to {PMo₁₂O₃₉}, the energy gap between HOMO and LUMO in α-[PMo₁₂O₃₉NPh]³⁻ decreased, resulting in enormously anodic shift for the reduction potential, while the excitation energy is less and the total second-order polarizability β ₀ is up to 438-3×10⁻³⁰ esu, which is nearly 10 times larger than that of [Mo₆O₁₈NPh]²⁻. On the other hand, when metal W in α-[PM₁₂O₃₉NPh]³⁻ is substituted by Mo, the interaction between Mo and N is enhanced and the redox ability becomes stronger. The β ₀ value for α-[PMo₁₂O₃₉NPh]³⁻ is more than 5 times higher than that of α-[PW₁₂O₃₉NPh]³⁻. It indicates that changing appropriate metal or enlarging the inorganic cluster will improve the redox properties and second-order nonlinear response. Moreover, the electron transition for three compounds mentioned above occurred mainly from organoimido segment (as the electron donor) to polyanion cluster (as the acceptor). As a result, α-[PMo₁₂O₃₉NPh]³⁻ may be a promising candidate for oxidant and nonlinear optical material. Electronic Supplementary Material  Supplementary material is available for this article at and is accessible for authorized users. Supported by National Natural Science Foundation of China (Grant No. 20573016), Training Fund of NENU’s Scientific Innovation Project (Grant No. NENUSTC07017), Science Foundation for Young Teachers of Northeast Normal University (Grant No. 20070304) and Program for Changjiang Scholars and Innovative Research Team in University (PCSIRT)