Thermodynamics and kinetics of extracting zinc from zinc oxide ore by the ammonium sulfate roasting method

Thermodynamic analyses and kinetic studies were performed on zinc oxide ore treatment by （NH4）2SO4 roasting technology. The results show that it is theoretically feasible to realize a roasting reaction between the zinc oxide ore and （NH4）2SO4 in a temperature range of 573-723 K. The effects of reaction temperature and particle size on the extraction rate of zinc were also examined. It is found that a surface chemical reaction is the rate-controlling step in roasting kinetics. The calculated activation energy of this process is about 45.57 kJ/mol, and the kinetic model can be expressed as follows： 1 - （1 - α）1/3 = 30.85 exp（-45.57/RT）·t. An extraction ratio of zinc as high as 92% could be achieved under the optimum conditions.

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 experi-mentally. Thermodynamic calculations show that mullite present in the fly ash can react with NH4HSO4 in the 298-723 K range. Process op-timization 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）], whereαis the extraction rate and t is the roasting temperature.

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, sulfitric 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 leach- ing efficiency of manganese and superior selectivity against calcium compared to hydrochloric acid. The optimal leaching conditions in sul- furic acid media were determined; under the optimal conditions, the leaching efficiencies of Mn and Ca were 92.42% and 9.61%, respec- tively. Moreover, the kinetics of manganese leaching indicated that the leaching follows the diffusion-controlled model with an apparent ac- tivation energy of 12.28 kJ·mol-l. 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 MnSOa4·H20.

Adsorption equilibrium and kinetics studies of divalent manganese from phosphoric acid solution by using cationic exchange resin

There are numerous impurities in wet-process phosphoric acid,among which manganese is one of detrimental metallic impurities,and it causes striking negative effects on the industrial phosphoric acid production and downstream commodity.This article investigated the adsorption behavior of manganese from phosphoric acid employing Sinco-430 cationic ion-exchange resin.Resorting FT-IR and XPS characterizations,the adsorption mechanism was proved to be that manganese was combined with sulfonic acid group.Several crucial parameters such as temperature,phosphoric acid content and resin dose were studied to optimize adsorption efficiency.Through optimization,removal percentage and sorption capacity of manganese reached 53.12 wt%,28.34 mg·g^-1,respectively.Pseudo-2nd-order kinetic model simulated kinetics data best and the activation energy was evaluated as 6.34 kJ·mol^-1 for the sorption reaction of manganese.In addition,the global adsorption rate was first controlled by film diffusion process and second determined by pore diffusion process.It was found that the resin could adsorb up to 50.24 mg·g^-1 for manganese.Equilibrium studies showed that Toth adsorption isotherm model fitted best,followed by Temkin and Langmuir adsorption isotherm models.Thermodynamic analysis showed that manganese adsorption was an endothermic process with enhanced randomness and spontaneity.

Kinetics Analyzing of Direction Reduction on Manganese Ore Pellets Containing Carbon

Using high temperature carbon tube furnace, reduction of manganese ore pellets containing carbon was investigated. The reaction was divided into two stages at five minutes after reaction, and the kinetics model of reduction process was established. The experimental results showed that, the reaction rate in the earlier stage was controlled by the chemical reactions between FeO, MnO and carbon reductant, and the activation energy was 28.85 KJ/mol. In the later stage, as the carbon reductant replaced by CO, the reaction rate was controlled by CO-diffusing in solid products, and the cor- responding activation energy was 86.56 KJ/mol. Reaction rate of the later stage was less than the earlier one.

Kinetics of Manganese Oxides Dissolution in Sulphuric Acid Solutions Containing Oxalic Acid

The kinetics of the interaction of MnO2, Mn2O3, and Mn3O4, with sulphuric acid solutions and the effect of oxalic acid on this process are studied. As the sulphuric acid concentration is increased from 0.1 to 5 N, the dissolution rate of Mn2O3, Mn3O4 to MnO2 and Mn2+ ions decreases, whereas it increases with the concentration of Mn2+ ions. Upon the addition of H2Ox, the complete dissolution of Mn3O4 occurs more quickly. The reaction order with respect to the H+ and O x2- ions is +0.5 ± 0.1. A mechanism of MnO2 dissolution promotion by?O x2- is proposed. The dissolution rate was found to depend on the concentrations of?MnHOx - ions and was highest at pH 1.6 ± 0.2. A rate law and mechanism are suggested for manganese oxides dissolution.

The Effect of Additives on Calcium Sulfate Dihydrate Crystallization Kinetics in Gypsum Type Brine System

1 Introduction There exist calcium and sulfate ions outside sodium chloride in solution mining for calcium sulfate brine.The calcium and sulfate ions not only affect the purity of the vacuum salt products,but also increase the scaling of vacuum evaporation tanks and brine reusing pipes.Additives have certain impacts on the crystallization dynamics(Randolph et al.,1971).The crystallization

IMPROVED LEACHING METHOD AND KINETICS OF MANGANESE CARBONATE ORE AT ROOM TEMPERATURE

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Kinetics of reductive leaching of manganese oxide ore using cellulose as reductant

The kinetics of reductive leaching of manganese from a low-grade manganese oxide ore were studied using cellulose as reductant in dilute sulfuric acid medium.It was found that when the stirring speed was higher than 200 r/min,the effect of gas film diffusion on manganese extraction efficiency could be neglected,and the kinetic behavior was investigated under the condition of elimination of external diffusion influence on the leaching process.Effects of leaching temperature,mass ratio of cellulose and ore,and the sulfuric acid concentration on manganese extraction efficiency were discussed.The kinetic data were analyzed based on the shrinking core model,which indicated that the leaching process was dominated by both ash layer diffusion and chemical reaction at the initial stage,with the progress of leaching reaction,the rate-controlling step switched to the ash layer diffusion.It was also concluded that the sulfuric acid concentration had the most significant influence on the leaching rate,the reaction orders with respect to the sulfuric acid concentration were 2.102 in the first 60 min,and 3.642 in the later 90 min,while the reaction orders for mass ratio of cellulose and ore were 0.660 and 0.724,respectively.An Arrhenius relationship was used to relate the temperature to the rate of leaching,from which apparent activation energies were calculated to be 46.487 kJ/mol and 62.290 kJ/mol at the two stages,respectively.Finally,the overall leaching rate equations for the manganese dissolution reaction with cellulose in sulphuric acid solution were developed.The morphological changes and mineralogical forms of the ore before and after the chemical treatment were discussed with the support of SEM and XRD analyses.

Study on hydrometallurgical process and kinetics of manganese extraction from low-grade manganese carbonate ores

In order to utilize low-grade manganese ore resources effectively, a hydrometallurgical process was developed for manganese extraction in dilute sulfuric acid medium, and the kinetics of leaching manganese was also investigated. At room temperature, manganese from low-grade manganese carbonate ores was extracted by sulfuric acid leaching without reductants. During the extracting process, single-factor analysis method was used to evaluate the effects of grinding fineness, sulfuric acid concentration,liquid-to-solid ratio, agitation rate and leaching time on the leaching efficiencies of Mn and Fe. The optimal leaching conditions are determined as coarse particles of below 2 mm size(without ball-milling),sulfuric acid concentration of 0.86 mol/L, liquid-to-solid ratio of 5:1, agitation rate of 150 r/min and leaching for 180 min at room temperature. Under the optimal conditions, the leaching efficiencies of Mn and Fe are 96.21% and 13.35%, respectively. In addition, through the experiments at different temperatures, it is found that the leaching process follows the shrinking core model under the conditions of changing acid concentration and intermittent reaction device. Moreover, the apparent activations of effective diffusion and chemical reaction in the kinetic model are calculated to be 18.83 and27.15 kJ/mol, respectively.

Leaching process and kinetics of manganese in low-grade manganese ore

Manganese was extracted from leaching low-grade manganese ore in sulfuric acid medium. The effects of granule diameter, leaching time, liquid/solid ratio (V/W) and the concentration of sulfuric acid were investigated through orthogonal and single factor experiments. The experimental results showed that the optimal leaching conditions are, size of 0.054mm, 120 minutes of reaction time, 3(V/W) of liquid/solid ratio and 30% of the concentration of sulfuric acid (g/g). Under those conditions, the leaching efficiency is 96.73%. The kinetics of the leaching process is in accordance with the characteristics of fractal reaction.

Sulfation Kinetics in the Preparation of Cellulose Sulfate

In the established apparatus, the converaion ratios of cellaloee sulfation (X) under dif-ferent salfation conditlons were measured. The range of temperature was from -5℃ to +5℃, and the H2SO4 concentration was from 3.1 mol.L^-1 to 4.5 mol.L^-1. The experimental results were used for the establishment of the kinetic model for cellulose sulfation. With the model, X values and the yield of NaCS (Y) can be calculated, thus the reaction with respect to H2SO4 concentration is determined to be third order.

Kinetics of discontinuous precipitation in Cu–20Ni–20Mn alloy

The morphology and growth kinetics of discontinuous precipitation （DP） in a Cu-20Ni-20Mn alloy were investigated in the tem- perature range of523-573 K by optical microscopy, scanning electron microscopy, and transmission electron microscopy. A lamellar mixed structure consisting of alternating larnellae of a matrix and NiMn phase was observed in DP colonies. The volume fraction of regions formed by a DP reaction was determined by quantitative metallographic measurements. The kinetics of DP was evaluated on the basis of the John- son-MehI-Avrami Kohnogorov equation, which resulted in a time exponent of approximately 1.5. We confirmed that the nucleation of the discontinuous precipitate was confined to grain edges or boundaries at an early stage of the reaction. The activation energy of DP process was determined to be approximately （72.7 ± 7.2） kJ/mol based on the Arrhenius equation; this result suggests that DP is controlled by gn-ain boundary diffusion. The hardness values exhibited good correlation with the volume fraction of DP; this correlation was attributed to the plvsence of the ordered N iMn phase.

Reaction Kinetics for Heterogeneous Oxidation of Mn(III) ～Toluene

The reaction kinetics of the heterogeneous oxidation of toluene with Mn 3+ was studied by considering the effects of disproportionation of Mn 3+ in reaction system, a 'parallel' modulus was set up. And then the concentration of Mn 3+ in disproportionation and the concentration of benzaldehyde in oxidation were respectively determined in turn, the rate constant, order and pseudo activation energy of the heterogeneous oxidation were obtained by mathematical deduction and the kinetic equation was concluded. In addition, the reaction mechanism was analyzed. It shows that the results are completely consistent with modulus.

Simulation Experiments and Kinetics for the Formation of Organic Sulfide in Marine Carbonate Reservoirs

Thermal simulation experiments on the system of gasoline and magnesium sulfate were carried out using an autoclave operating at high temperature and high pressure in the presence of water. Properties of the gas-oil-solid 3-phase products were analyzed by some advanced analytical methods including gas chromatography, microcoulometry, capillary gas chromatography in combination with a pulsed flame photometric detector, FT-IR and X-ray diffraction. The results showed that the reaction could proceed at 450℃ - 550℃ to produce MgO, S, C, H2S, CO2 and a series of organic sulfides such as mercaptans, sulfoethers and thiophenes as the main products. According to the reaction kinetics, the calculated activation energy of the reaction is 68.9 kJ·mol-1.

The Study of Dissolution Kinetics of K_2SO_4 Crystal in Aqueous Ethanol Solutions with a Statistical Rate Theory

Dissolution kinetics of K2SO4 crystal in aqueous ethanol solutions was studied on-line with ion selective electrode. The concentration of K2SO4 was calculated from the determined electromotive force in which the activity coefficient of components in the liquid phase was calculated with the Pitzer equation. Dissolution kinetic parameters in the modified statistical rate theory were regressed. The correlation results show that dissolution rate of K2SO4 is slower in aqueous ethanol solutions than that in aqueous solutions. The two most important reasons are as follows: (1) The solubility of K2SO4 in aqueous ethanol solutions is lower than that in aqueous solutions, which causes a decrease of the driving force of mass transfer. (2) The process of surface reaction of K2SO4 became slower due to the addition of ethanol, so that the whole process is mainly dominated by the surface reaction instead of mass transfer.

Modeling and Estimation of the Kinetics of Seeded Solvent-mediated Phase Transformation in a Batch Crystallizer

Modeling the kinetics of the preparing process is necessary to produce a product with the appropriate particle properties and minimum production cost.Owing to the lackness of crystal size distributor （CSD） information,however,solvent-mediated phase transformation encounters difficulty in modeling the kinetics as compared to solution crystallization.Consequently,a model was established by making the product CSD to move along by horizontal translation to obtain the CSDs of the stable phase in the process of transformation.Then the moment method was used to solve the popular balance equation,and the least square nonlinear regression method was applied to estimate the kinetics parameters.The model has been successfully used to simulate the transformation of CaSO4？2H2O to α-CaSO4？1/2H2O in an isothermal seeded batch crystallizer with different stirring speeds,and it is beneficial to producing high performance α-CaSO4？1/2H2O crystals which have the right particle characteristics.

Study of Thermodynamics and Kinetics of CH_4-CaSO_4 and H_2S-Fe_2O_3 Systems

The destruction of hydrocarbon in deep carbonate diagenetic environment is one of problems on the formation of oil and gas. Organic-inorganic reactions in the process of TSR(Thermochemical Sulfate Reduction) are the main reason to make disappearance of the hydrocarbons. The work in this field has often been the subject of much research work in recent years. In this paper, the thermodynamics of CH4-CaSO4 and H2S-Fe2O3 systems is discussed to investigate the possibility of reactions. It is found that these two reactions can proceed spontaneously.Increasing temperature is favorite for CH4-CaSO4 system but disfavorite for H2S-Fe2O3 system. Thermal simulation experiments were carried out using autoclave at high temperature and high pressure. The properties of the products were characterized by microcoulometry, FT-IR and XRD methods. On the basis of the experimental data, a reaction kinetic model is developed and kinetic parameters are determined.

Insertion/removal kinetics of lithium ion in spinel LiCu_xMn_(2-x)O_4

The insertion/removal processes of lithium ion in spinel lithium manganese oxide(LiMn2O4) and copper doped spinel lithium manganese oxide (LiCuxMn2-xO4) on a powder microelectrode were studied by electrochemical impedance spectroscopy(EIS), cyclic voltammetry(CV) and X-ray diffractometry(XRD). The insertion/removal process of lithium ion in the spinel oxides consists of three steps: charge transfer of lithium ion on the surface of the spinel oxides, diffusion and occupation of lithium ion in the lattice of the spinel oxide. Similar to chromium, the doping of copper in spinel lithium manganese oxide results in the increase of the charge transfer resistance and the double layer capacitance for lithium insertion or removal, and the decrease of the diffusion coefficient of lithium ion in the lattice of spinel oxide. However, the insertion capacitance, a parameter reflecting the occupation of lithium ion in the lattice of the spinel oxide, is hardly influenced by the doping of copper. The influence of the doped copper on the kinetic process of lithium insertion/removal in spinel lithium manganese oxide is related to the contraction of spinel lattice.

Kinetics of Nitrogen Diffusion in Granular Manganese

The kinetics and the influence of time on granular manganese nitriding were studied by means of a vacuum resistance furnace,X-ray diffraction technique,and LECO TC-436 oxygen/nitrogen determinator.The longer the nitriding time,the more the nitrogen pickup.Except for a trace of oxide MnO that developed,the metal manganese could thoroughly be nitrided to form Mn4N and a little ζ-phase（the stoichiometric components as Mn2N）with the nitriding time lasting.A kinetic model is developed to reveal the nitriding situation and agrees well with the experimental results.