Dissolution kinetics of aluminum and iron from coal mining waste by hydrochloric acid☆

The extraction of aluminum from coal mining waste (CMW) is an important industrial process. The two major problems in applications are low aluminum dissolution efficiency and high iron content in the r...     

Effect of reaction temperature on Fe–Al analcime formation

The effects of reaction period, temperature, and iron species on the zeolite framework type were studied in this work. Gismondine (GIS) is usually synthesized by hydrothermal method at 80°C from sodium metasilicate and aluminum nitrate as starting materials preferentially independent of the presence/absence of iron source. However, the present work revealed that pure analcime (ANA) could be formed at temperatures more than 120°C. A large polyhedral ANA crystal with a diameter of 180 μm was obtained even at a comparatively low temperature such as 150°C at a short reaction period of 1 week. The presence of iron source promoted the formation of pure ANA. Infrared spectroscopy, X-ray diffraction, and ICP-OES analysis suggested that the iron component added as a reactant was incorporated into the ANA framework through the isomorphous substitution for Al.     

蠕虫形管状镧铝复合介孔材料的合成及表征

The lanthanum aluminum mesoporous materials were synthesized using sodium dodecyl sulfate as a template agent by ultrasonic hydrothermal method.The resulting samples were characterized by low angle X-ray diffraction(XRD),N2 adsorption-desorption studies,transmission electron microscopy(TEM)and surface morphology analysis(SEM),surface acid(NH3-TPD),reducibility properties(TPR),X-ray energy dispersive spectrometer(EDS)and thermogravimetric analysis(TG/DTG).A l/La composite mesoporous material were synthesized with n(Al)︰n(La)=70︰1.0,80°C of reaction temperature,20 h of reaction time,12 h of crystallization time,650°C of calcination temperature.The specific surface area of the sample is 273.90 m 2 ·g ?1 ,with the average diameter 5.642 nm and pore volume 0.2354 cm 3 ·g ?1 .The samples have mesoporous structure and its particles are similar to a worm-shaped tubular structure.The influence of calcination temperature on the surface physical and chemical properties of Al/La composited mesoporous materials was examined,and the results showed that the acid strength was increased but the amount of acidic sites is decreased as the calcination temperature increased.It was found that the sample calcined at 650°C had appropriate acid content,acid strength and better reducibility.     

Effects of mechanical activation on the digestion of ilmenite in dilute H2SO4

The commercial sulfate process for pigment production uses concentrated sulfuric acid(N 85 wt% H_2SO_4) as feeding material and discharges 8–10 tons of spend dilute acid(20 wt% H_2SO_4) per ton of product. Re-using spend acid to leach ilmenite can cut the waste emission and save fresh feeding acid. However, the leaching reaction with dilute acid is very slow and the digestion efficiency is fairly low. This paper describes a wet-milling process to enhance the dilute-acid leaching of ilmenite that makes it possible to produce TiO_2 pigment in a more environmentally benign routine. The leaching kinetic study of unmilled ilmenite, dry milled 60 min ilmenite and wet milled 60 min ilmenite was conducted by revision of the shrinking core model(SCM), incorporation of particle size distribution(PSD) into SCM. The results revealed that mechano-chemical activation method significantly increased the leaching efficiency of titanium from 36% to 76% by reducing the particle size and increasing the reaction contact area. On the other hand, the milling process increased the lattice deformation and amorphization of crystalline, which lowered the activation energies in the leaching process. Compared with dry milling operation, wet milling is more effective, the particle size distribution of wet-milled ilmenite was much narrower, smaller, and more uniform. Wet milling of ilmenite makes the leaching reaction with dilute acid(60 wt% H_2 SO_4) practicable and the re-use of spend acid becomes possible and economical.     

An investigation on dissolution kinetics of single sodium carbonate particle with image analysis method

Dissolution kinetics of sodium carbonate is investigated with the image analysis method at the approach of single particle. The dissolution experiments are carried out in an aqueous solution under a series of controlled temper-ature and pH. The selected sodium carbonate particles are al spherical with the same mass and diameter. The dissolution process is quantified with the measurement of particle diameter from dissolution images. The concentration of dissolved sodium carbonate in solvent is calculated with the measured diameter of particle. Both surface reaction model and mass transport model are implemented to determine the dissolution mecha-nism and quantify the dissolution rate constant at each experimental condition. According to the fitting results with both two models, it is clarified that the dissolution process at the increasing temperature is controlled by the mass transport of dissolved sodium carbonate travelling from particle surface into solvent. The dissolution process at the increasing pH is control ed by the chemical reaction on particle surface. Furthermore, the dissolution rate constant for each single spherical sodium carbonate particle is quantified and the results show that the disso-lution rate constant of single spherical sodium carbonate increases significantly with the rising of temperature, but decreases with the increasing of pH conversely.     

Electrodeposition of aluminum on needle cathode using AlCl3/urea molten salts at low-temperature and its application to hydrogen generation

The electrodeposition of aluminum(Al) was studied using two electrolyte solutions, such as anhydrous AlCl_3-urea and hydrated AlCl_3·6 H_2 O-urea. A systematic examination using cell voltages 1.0–2.0 V was carried out at temperatures((50–100) ± 2) °C. A needle-shaped cathode was employed for the deposition of aluminum. A dendrite and particulate microstructure of Al were observed on the needle-shaped cathode. An improved condition for the manufacturing of small sizes and high purity of aluminum deposits was obtained. Pure Al with a current efficiency(yield) of 84%–99% was obtained from those of non-aqueous electrolytes and only of 8.6%–9.3% from those of hydrated electrolytes. The electrical conductivities of electrolytes remained considerable at((50–100)± 2) °C. The improved aluminum powders were used for the reaction with water. The aluminum reacts with water at room temperature, producing pure H_2 with 100% yield. The electrodeposited aluminum metal can be used as an excellent energy carrier.     

Leaching Kinetics of Calcium Vanadate by Na2CO3 Solution

Leaching kinetics of calcium vanadate by Na2CO3 solution was studied. Kinetic equation was established according to the variation of VO3-concentration with time during the leaching process. The influences of initial pH value and stirring speed on reaction rate constant were examined and the corresponding apparent activation energy was calculated. The results indicate that the leaching process is a 0.68 order reaction, and the reaction rate constant 8.64×10-6 mol/(L-s). It increases with the increase of pH value and stirring speed. And the dissolution rate of calcium vanadate also increases. The apparent activation energy is 38.98 kJ/mol, and temperature has great influence on the leaching rate of calcium vanadate.     

硫酸-糖蜜酒精废液浸出软锰矿的动力学(英文)

The kinetics of reductive leaching of manganese from low grade pyrolusite in dilute sulfuric acid in the presence of molasses alcohol wastewater was investigated. The shrinking core model was applied to quantify the effects of reaction parameters on leaching rate. The leaching rate increases with reaction temperature, concentrations of H 2 SO 4 and organic matter in molasses alcohol wastewater increase and ore particle size decreases. The leaching process follows the kinetics of a shrinking core model and the apparent activation energy is 57.5 kJ·mol –1 . The experimental results indicate a reaction order of 0.52 for H2SO4 concentration and 0.90 for chemical oxygen demand (COD) of molasses alcohol wastewater. It is concluded that the reductive leaching of pyrolusite with molasses alcohol wastewater is controlled by the diffusion through the ash/inert layer composed of the associated minerals.     

Long-term nitritation performance of ammonium-rich landfill leachate☆

This study presents a biological system combined upflow anaerobic sludge bed (UASB) with sequencing batch reactor (SBR) to treat ammonium-rich landfill leachate. The start-up and operation of the nitritation at low temperatures were investigated. The synergetic interaction of free ammonia (FA) inhibition on nitrite-oxidizing bacteria (NOB) and process control was used to achieve nitritation in the SBR. It is demonstrated that nitritation was successful y started up in the SBR at low temperatures (14.0 °C–18.2 °C) by using FA inhibition coupled with process control, and then was maintained for 482 days at normal/low temperature. Although ammonia-oxidizing bacteria (AOB) and NOB co-existed within bacterial clusters in the SBR sludge, AOB were confirmed to be dominant nitrifying population species by scanning electron microscopic (SEM) observation and fluorescence in situ hybridization (FISH) analysis. This confirmation not only emphasized that cultivating the appropriate bacteria is essential for achieving stable nitritation performance, but it also revealed that NOB activity was strongly inhibited by FA rather than being eliminated altogether from the system.     

Integration of coal pyrolysis process with iron ore reduction:Reduction behaviors of iron ore with benzene-containing coal pyrolysis gas as a reducing agent☆

An integrated coal pyrolysis process with iron ore reduction is proposed in this article. As the first step, iron oxide reduction is studied in a fixed bed reactor using simulated coal pyrolysis gas with benzene as a model tar compound. Variables such as reduction temperature, reduction time and benzene concentration are studied. The carbon deposition of benzene results in the retarded iron reduction at low temperatures. At high temperatures over800 °C, the presence of benzene in the gas can promote iron reduction. The metallization can reach up to 99% in20 min at 900 °C in the presence of benzene. Significant increases of hydrogen and CO/CO2 ratio are observed in the gas. It is indicated that iron reduction is accompanied by the reforming and decomposition of benzene. The degree of metallization and reduction increases with the increasing benzene concentration. Iron oxide can nearly completely be converted into cementite with benzene present in the gas under the experimental conditions. No sintering is found in the reduced sample with benzene in the gas.     

N-methyl-2-(2-nitrobenzylidene) hydrazine carbothioamide-A new corrosion inhibitor for mild steel in 1 mol·L-1 hydrochloric acid

The corrosion inhibition of mild steel in 1 mol·L?1 hydrochloric acid by N-methyl-2-(2-nitrobenzylidene) hydrazine carbothioamide (MNBHC) was studied using weight loss and electrochemical studies. Results obtained indicate that the inhibitor is effective in hydrochloric acid medium and the efficiency decreases with increase in temperature. Added halide additives improve the efficiency of the inhibitor. The AC impedance studies reveal that the process of inhibition is through charge transfer. Polarization studies indicate the mixed nature of the in-hibitor. From the thermodynamic, spectral and surface analyses the nature of adsorption has been found out. The adsorption of the inhibitor on mild steel follows the Langmuir isotherm.     

Mechanism and kinetics study on removal of Iron from phosphoric acid by cation exchange resin

Iron element is one of the main impurities in wet-process phosphoric acid and it has a significant impact on the subsequent phosphorus chemical products. This paper studied the feasibility of using Sinco-430 cation exchange resin for iron removal from phosphoric acid. The specific surface area and the total exchange capacity of resin were 8.91 m~2·g~(-1) and 5.18 mmol·g~(-1), respectively. The sorption mechanism was determined by FTIR and XPS and the results indicated that iron was combined with-SO_3 H in resin. The removal process was studied as a function of temperature, H_3 PO_4 content and mass ratio between resin and solution. The unit mass of resin to remove iron was 0.058 g·g~(-1) resin when the operating parameters were T = 50 ℃, H_3 PO_4 content = 27.61 wt%and S/L = 0.1, respectively. Kinetics study demonstrated that pseudo-second-order reaction model fits this study best and the calculated activation energy of overall reaction is 29.10 kJ·mol~(-1). The overall reaction process was mainly controlled by pore diffusion.     

Effects of Sn residue on the high temperature stability of the H_2-permeable palladium membranes prepared by electroless plating on Al_2O_3 substrate after SnCl_2–PdCl_2 process: A case study

The stability of composite palladium membranes is of key importance for their application in hydrogen energy systems. Most of these membranes are prepared by electroless plating, and beforehand the substrate surface is activated by a SnCl_2–PdCl_2 process, but this process leads to a residue of Sn, which has been reported to be harmful to the membrane stability. In this work, the Pd/Al_2O_3 membranes were prepared by electroless plating after the SnCl_2–PdCl_2 process. The amount of Sn residue was adjusted by the SnCl_2 concentration, activation times and additional Sn(OH)_2coating. The surface morphology, cross-sectional structure and elemental composition were analyzed by scanning electron microscopy(SEM), metallography and energy dispersive spectroscopy(EDS), respectively. Hydrogen permeation stability of the prepared palladium membranes were tested at450–600 °C for 400 h. It was found that the higher SnCl_2 concentration and activation times enlarged the Sn residue amount and led to a lower initial selectivity but a better membrane stability. Moreover, the additional Sn(OH)_2coating on the Al_2O_3 substrate surface also greatly improved the membrane selectivity and stability.Therefore, it can be concluded that the Sn residue from the SnCl_2–PdCl_2 process cannot be a main factor for the stability of the composite palladium membranes at high temperatures.     

Kinetic analysis of experiment data for the formation of C.I.Acid Blue 9 leuco compound

A systematic study of the synthesis of C.l.Acid Blue 9 leuco compound in water is reported.The kinetic analysis of experimental data for the condensation reaction between 2-formylbenzenesulfonic acid sodium and N-ethyl-N-(3'-sulfonic acid benzyl) aniline obtained at four different temperatures ranging between 85 and 100 ℃ is discussed.It is shown that the reaction followed second-order rate kinetics.The overall rate constant (k) increased with the increase of temperature.On the basis of the value of k,activation energy (Ea) of the reaction was evaluated.Importantly,it is found that reactant concentration has great effect on the formation of C.I.Acid Blue 9 leuco compound,implying that it is not enough to improve the conversion of N-ethyl-N-(3'-sulfonic acid benzyl) aniline by only prolonging reaction time in the late period of the reaction.     

Study on reactions of gaseous P2O5 with Ca3(PO4)2 and SiO2 during a rotary kiln process for phosphoric acid production

In a rotary kiln process for phosphoric acid production,the reaction between gaseous phosphorus pentoxide(P_2O_5)and phosphate ore and silica contained in feed balls(the so-called P_2O_5"absorption")not only reduces phosphorous recovery but also generates a large amount of low melting-point side products.The products may give rise to formation of kiln ring,which interferes with kiln operation performance.In this study,the reactions of gaseous P_2O_5with solid calcium phosphate(Ca_3(PO_4)_2),silica(SiO_2)and their mixture,respectively,were investigated via combined chemical analysis and various characterizations comprised of X-ray diffraction(XRD),Fourier-transform infrared(FT-IR)spectroscopy,thermogravimetric analysis and differential scanning calorimeter(TGDSC),and scanning electron microscopy and energy dispersive spectrometer(SEMEDS).Attentions were focused on apparent morphology,phase transformation and thermal stability of the products of the P_2O_5"absorption"at different temperatures.The results show that the temperature significantly affected the"absorption".The reaction between pure Ca_3(PO_4)_2 and P_2O_5 occurred at 500°C.Calcium metaphosphate(Ca(PO_3)_2)was the primary product at the temperatures≤900°C with its melting point≤900°C while calcium pyrophosphate(Ca_2P_2O_7)was obtained over 1000°C,which has a melting point≤1200°C.The"absorption"by pure SiO_2 started at 800°C and the most significant reaction occurred at 1000°C with formation of silicon pyrophosphate(SiP_2O_7)product of melting point≤1000°C.Using mixed Ca_3(PO_4)_2and SiO_2as raw material,the"absorption"by Ca_3(PO_4)_2 was enhanced due to existence of silica.At 600–700°C,silica was inert to P_2O_5and thus formed a porous structure in the raw material,which accelerated diffusion of gaseous P_2O_5inside the mixture.At higher temperatures,the combined"absorption"by calcium phosphate and reaction between silicon dioxide and the"absorption"product calcium pyrophosphate,reinforced the"absorption"by the mixture.Besides,it was found that both Ca(PO_3)_2and SiP_2O_7were unstable at high temperatures and would decompose to Ca_2P_2O_7and SiO_2,respectively,at over 1000°C and 1100°C with the release of gaseous P_2O_5at the same time.     

Extraction of Alumina from Coal Fly Ash with Sulfuric Acid Leaching Method

Coarse g-Al2O3 powder was prepared through acid leaching, solid-liquid separation, crystallizing and aluminum sulfate decomposing processes using coal fly ash and concentrated sulfuric acid as raw materials. The metallurgy level Al2O3 can be obtained by disposing coarse g-Al2O3 powder with Bayer process. The optimum conditions of acid leaching process were determined by experiments. The extraction rate of Al2O3 can be stabilized at about 87% under these conditions. The thermodynamics and kinetics of sulfuric acid leaching process were studied with irreversible thermodynamics.     

CO2-hierarchical activated carbon prepared from coal gasification residue: Adsorption equilibrium,isotherm, kinetic and thermodynamic studies for methylene blue removal

Mineral matter in a residue(RC G) from coal gasification(CG) was removed by two-stage acid leaching. Hierarchical activated carbon(HAC) was prepared by activating RC Gwith CO_2. The performance of HAC on removing methylene blue(MB) from an aqueous solution was investigated. HAC was characterized by N_2 adsorption–desorption isotherm, Fourier transform infrared spectroscopy, and scanning electron microscopy. The results show that HAC exhibits hierarchical pore structure with high specific surface area(862.76 m~2·g~(-1)) and total pore volume(0.684 cm~3·g~(-1)), and abundant organic functional groups. The adsorption equilibrium data of MB on HAC are best fitted to the Redlich-Peterson. The kinetic data show that the pseudo-first-order model is more suitable at low MB concentration, while the advantages of the pseudo-second-orderand the Elovich models are more obvious as the concentration increases. According to the thermodynamic parameters, the HAC-MB adsorption process is spontaneous and endothermic.     

Studies of Heterogeneous Hydrothermal Stripping from Iron-loaded Naphthenic Acid–Alcohol–Kerosen

The technique of hydrothermal stripping from mixed aqueous-organic systems is a promising method for synthesizing oxide ceramic powders for high-performance applications. Some factors influencing heterogeneous hydrothermal stripping with water from iron-loaded organic phase of naphthenic acid–isooctyl alcohol–kerosene, such as initial concentrations of iron and naphthenic acid, concentration of Fe2O3 “seed”, temperature and time, were investigated. Based on the experimental results, the rate equation was established. Nano-ferric oxide powders were obtained by the technique of hydrothermal stripping from the iron-loaded organic phase. The results suggest that the heterogeneous hydrothermal stripping proceeds in 3 steps: adsorption of naphthenic acid dimers and naphthenic complex of iron onto the surface of “seed”, hydrolysis of adsorbed complex of iron, and condensation of hydrolyzed complex. The process activation energy is 115 kJ/mol and the heterogeneous hydrothermal stripping is controlled by a chemical reaction (the hydrolysis of naphthenic complex of iron).     

Anodic Reaction of Arsenopyrite in Ammoniacal Solutions

Anodic dissolution of arsenopyrite in ammoniacal solution has been investigated by electrochemical methods. The process is an irreversible reaction with formation of a ferric oxidized film and is retarded by the film. The process rate is controlled by the electrochemical reaction on the electrode surface in the lower temperature range, or alternatively by the diffusion through the film in the higher temperature range. The overall reaction has 14 electron transferred and can be expressed by     

Ultrasonic Electro-oxidation Process of Molybdenite Concentrate

The oxidation of MoS2 concentrate in NaCl solution electrolysis environment and the impact of ultrasonic field on the leaching process of Mo were investigated. The decomposition process of MoS2 can be accelerated by ultrasonic field. When there are iron ions, anode potential is decreased about 0.7 V than that without iron ions, iron ions in the solution play an electronic transmission role by directly joining the electrode reaction of anode and oxidation leaching process. The results indicate that the leaching rate of Mo can achieve 99.5% with ultrasonic field exertion working 4 min in every 5 min under the conditions that the liquid-solid ratio is 20, mixing rate 500 r/min, iron ion concentration 6%, leaching temperature 40℃, pH (initialization) 1, and leaching time 4 h, respectively.