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By Keizo Uematsu, Satoshi Tanaka, Nozomu Uchida, Yutaka Saito

"Effect of moisture content must be fully understood for controlling the granule compaction of ceramics. It changes the mechanical behavior of spray-dried granules applied for compaction process, and governs the structure and properties of .ceramics. To understand the time-dependent change in processing, the kinetics was examined for change of moisture content for granules placed in a die and the pressed compacts also. The results were explained in terms of apparent moisture diffusion coefficients. They varied non-linearly with the PVA content in the granules. The results were explained through the non-uniform PVA distribution in the granules.IntroductionMoisture must be controlled in compaction process to produce the green compacts having uniform structure. It affects glass transition temperature of binder and thus the deformation behavior of powder granules under an applied stress. Several studies [1-7] have clarified the effect of moisture content on the compaction behavior of granules and the structure of resultant compacts for both die pressing and cold isostatic pressing (CIP) of pre-formed compacts. In these studies, the moisture contents in the system were equilibrated with the humidity in the atmosphere before compaction. In practice, however, the moisture content in the system may vary with time if the relative humidity of surrounding atmosphere is different from what the granules were equilibrated previously. This is very likely case in real production processes. However, the kinetics of moisture change in the granules as well as in the pre-formed powder compacts have not been well studied. For controlling the microstructure in a system, it is necessary to fully understand the kinetics of moisture change and its relevance to packing structure of powders."

Jan 1, 2000

By Juergen Antrekowitsch, Stephan R. Steinacker

The main aim of the electric furnace treatment in the primary copper industry is the reduction of valuable metals such as zinc, lead or copper itself. On the one hand legal restrictions for the further use of the treated slag are constantly getting stricter while on the other every type of loss in the oxidic phase leads to economic disadvantages. In order to fully understand and to improve the process, kinetics during the reduction play an essential role. In the first part, this paper highlights the theoretical background of the reduction process, while the following chapters present experimental aspects and results from laboratory scale trials at the Montanuniversitaet Leoben. In addition, the comparison between the chemical reaction and the diffusion model plays a continuously important role. By investigating the reducibility of electric furnace slag, process adaptions and ameliorations are developed.

Jan 1, 2016

By Xianzhong Hu, Qingbo Yu, Qin Qin

"Oxy-fuel combustion is one promising option among different CO2 capture technologies. The object of this work is to show the effect of CO2 dilution on the laminar flame speed, flame structure and reaction pathway for methane oxidation at O2/CO2 atmosphere. In this paper, kinetic simulations were made using CHEMKIN with GRI-Mech 3.0 mechanism, which was validated by experimental data of laminar flame speeds. The reaction pathway of CH4/O2/CO2 mixture was derived from reaction flow analysis. Results showed that CO2 decreased the flame speeds, lowed concentration of major intermediates and increased flame thickness. The major chemical pathways of CH4 to CO2 have not changed at O2/CO2 atmosphere comparing with O2/N2 atmosphere, but contributions to major intermediates formation from each related elementary reaction have changed a lot. In addition, the secondary chemical pathways of CH3 oxidation became different at O2/CO2 atmosphere.IntroductionNowadays, as the global economy is developing fast and the pollutant levels (especially global warming gases) are increasing, a lot of researches are focusing on new technologies which can cut greenhouse gas emissions [1]. New technologies have been developed, such as high Mild combustion, flameless combustion and Integrated Gasification Combined Cycle (IGCC) technology. Oxy-fuel combustion using carbon dioxide as dilution of oxygen is considered as a promising approach for reducing CO2 emission. The properties of CO2 in flue gas are different from N2 in air. On one side, the transport, thermal and radiative properties of CO2 are different from N2 in air. On the other side, CO2 is not inert but directly participates in chemical reactions and recent researches [2-5] also present the chemical effects of CO2 on oxy-combustion. For these differences above, the characteristics of oxy-combustion are not alike with traditional combustion. It is necessary to develop the investigation of oxy-combustion.In all combustion processes, laminar flame speed is an important parameter, which links to combustion behavior. Analysis of this parameter can provide a better understanding of the effect of CO2 dilution in the process of oxy-combustion. Several investigations of laminar flame speeds of oxy-fuel flame have been improved, including experimental measurements and numerical computations. A.A.Konnov et al. measured the flame speeds of oxy-methane and oxy-ethane mixture using the heat flux method with a flat burner [6-8]. V. Ratna Kishore et al. used heat flux method to measure the adiabatic laminar flame speeds of hydrogen [9] and H2/CO mixture [10]. Adiabatic laminar flame speeds of hydrogen in O2/CO2 atmosphere are much smaller than in O2/N2 or in O2/Ar. The burning velocity of H2/CO mixture decreased with increase in CO2 content in mixture. Jeongseog Oh et al. [11] used Bunsen flame to measure the laminar flame speeds of premixed oxy-methane mixture with angle methods in atmospheric condition (300k, 1atm). The results were SL=29.1cm/s and SL=29.5cm/s respectively derived from oxy-methane from CH* images and Schlieren photos."

Jan 1, 2014

By Jafar Safarian

A new kinetic modelling technique has been applied to study the rate of MnO reduction from slags by dissolved carbon in liquid iron. Based on a consideration of the fundamental reaction kinetics, a general differential equation for the slag reduction process has been formulated, which then is solved analytically for certain special cases. By re-writing the solutions in a dimensionless form the poorly known kinetic constants are eliminated, which makes the model both flexible and applicable to a wide range of experimental conditions. For example, changes in process parameters such as temperature, metal composition, slag composition, gas composition can readily be captured along with variations in the crucible geometry. Based on a comparison with a series of experimental reduction curves being reported in the literature, it is concluded that the predictive power of the model is surprisingly good, yielding outputs that are both reliable and physically reasonable. An attractive feature of the model is that it provides an alternative way of calculating the activation energies from experimental reductions curves. For example, it suggests that the activation energy for the reduction of MnO by dissolved carbon in liquid iron is about 90 kJ/mol, which is different from the previously reported activation energies. The model also suggests that the crucible geometry, which affects both slag the volume and the resulting slag/metal interfacial area, has a significant influence on the overall reduction kinetics. This design parameter is a key to further optimisation of the process on an industrial scale.

Jan 1, 2006

By Alexandre Bonan

The paper reports on the results of a kinetic study on the oxidation reaction of aqueous free cyanide ions with H202, in the presence of Cu(2+) catalyst. The variables and respective ranges studied were the following: (CN) ° = 10 -100 mg/l pH = 10 -11 (H202/CN) mol ratio = 1 -3 (Cu/CN) mol ratio = 0 -0.25 The results lead to the development of a semi-empirical model whish incorporates both the useful oxidation reaction and the parallel alkaline decomposition of H202.

Jan 1, 1992

By Zengjie Wang

Kinetic study of hydrochloric acid leaching of Panzhihua ilmenite from China is presented. Both temperature and concentration of hydrochloric acid have significant effects on the rate process of Fe dissolution from ilmenite ore, while the ratio of liquid to solid has little effect on the Fe dissolution. The Fe dissolution is found to follow the spherical model f (??) =1-(1- ??)1/3 and the apparent activation energy is calculated as 47.21 KJ/mol, suggesting a chemical reaction controlled mechanism. The dissolving behaviors vary at different kinetic stages. At the beginning the amount of the dissolved Fe and Ti increased monotonically with leaching time, while about 15 minutes later the dissolved Ti in the form of TiOCl2 began hydrolyzed into TiO2 fines reunited on the ilmenite ore surface, as observed by SEM and EDS technique. For the unreacted ilmenite particles covered by a layer of hydrolyzed TiO2, the leaching seemed to be as a selective leaching of iron and because Ti dissolved from and hydrolyzed rapidly again into the unreacted ilmenite particles. The leaching process can be ended 4 hour later when almost of Fe has dissolved into the solution and TiO2 remains as solid residues. The effects of acid concentration and leaching temperature were also investigated.

Jan 1, 2009

By Du Sichen, S. Seetharaman, J. A. Bustnes

"The present study deals with the kinetic studies of reduction of some selected transition metal tungstates with hydrogen. The measurements were carried out by the isothermal thermogravimetric method. Shallow powder beds were employed in order to avoid the effects due to transport phenomena affecting the reaction rate. In this way, the chemical reaction rates could be selectively studied. The experiments were carried out in the temperature range 873 - 1173 K. From the experimental data, the activation energies were evaluated and were found to be around 88 kJ / mol in the case of both iron as well as cobalt tungstates indicating the similarities in W-O bonds in both cases. The activation energies obtained are discussed in the light of the position of the transition metal in the periodic table as well as the thermodynamic stabilities of the various tungstates.IntroductionThe tungsten containing hard metals, characterized by high density, belong to a class of two-phase metal matrix composites. While these types of materials have traditionally found their applications within the defence industry as armour-piercing projectiles, counterbalance in helicopters and military aircrafts, outer casings of hand-grenades, etc., commercial applications for this class of alloys also exist, including radiation shields, penetrators for the oil industry, turbines for turbo-jet engines and a wide range of sports related parts. A possible route to the production of these alloys is to reduce the tungstates such as FeW04, Co W04 and NiW04 using a reductant like hydrogen or carbon monoxide. In order to have a better understanding of the processes involved in the production, it is important to have a knowledge of the reduction kinetics for these tungstates. According to the knowledge of the present authors, while the reduction ofNiW04 by hydrogen gas has been investigated earlier in the present laboratorypl no systematic reduction study has been carried out previously for the tungstates of iron, cobalt."

Jan 1, 1996

By G. A. Irons, D. Guo, D. Angheiina

To produce low-carbon (<30 ppm) steel in the tank degassing process, a ladle of steel with an oxidizing slag is placed in a vacuum tank equipped with bottom bubbling. The kinetics of this process are slow compared to the more prevalent RH degassing process, providing the impetus for the present work. There are several aspects to this work: water models of the fluid flow in the ladle; simulation of the decarburization (CO evolution) with C02 desorption in water; pilot-plant (60 kg) studies of the decarburization kinetics; mathematical modelling of the fluid flow in the ladle; mathematical models for each of the kinetic sites (plume, top slag and auto-nucleation); and full-scale trials. The results show that during the refining cycle the contribution from each reaction site changes, suggesting avenues for reducing cycling time and final carbon contents.

Jan 1, 2000

By J. A. Bustnes

The present work deals with kinetic studies of the reduction of molybdenum- and tungsten oxides by hydrogen. The experimental method used was therrnogravimetry under isothermal as well as non-isothermal conditions. The non-isothermal kinetics in the case of the reduction of MOO, to Moo2 has been modeled considering surface reaction as rate- controlling. In the case of the reduction of W02 to W a model was developed on the basis of the movement of the reaction front. The activation energies calculated on the basis of the models were in good agreement with those derived from isothermal experiments.

Jan 1, 1994

By Filippos Patsiogiannis

Laboratory size (4.5 kg) low carbon steel melts were deoxidized using Al and FeAl (33% Al), with and without synthetic fluxes, in alumina and zirconia crucibles. The dissolved oxygen, total oxygen, soluble aluminum, insoluble aluminum, silicon and carbon contents in the melt were determined as a function of refining time and temperature. It was observed that the reaction between aluminum and oxygen in solution closely follows thermodynamic equilibrium. Silica present in the alumina crucibles was found to be a source of oxygen for the melt, while this was not the case for zirconia crucibles. Reoxidation of the melt occurred through oxygen pick-up from the atmosphere. The extent of this reoxidation was found to be a function of oxygen content of the bath and the slag cover on the surface of the melt. The effectiveness of calcium-aluminate based fluxes in protecting the melt from the reoxidation and in increasing the rate of removal of inclusions was evaluated.

Jan 1, 1992

By Filippos Patsiogiannis

Laboratory size (5 kg) aluminum killed low carbon steel melts were desulfurized with synthetic fluxes in zirconia crucibles. The sulfur, oxygen, aluminum, silicon, and manganese contents in the melt were determined as a function of refining time and temperature. With a good argon shield and synthetic flux cover, melt reoxidation was not observed. Sulfur removal followed first order reaction kinetics. The effectiveness of calcia saturated calcium-aluminate (12CaO.7Al2O3) based fluxes in desulfurizing the steel melts was evaluated. The effects of initial sulfur level of the melt, weight of the flux (slag), and additions of tellurium, fluorspar, and barium oxide to the melt on the kinetics of desulfurization were also studied.

Jan 1, 1993

By José Roberto de Oliveira

Based on literature review one can see that the main objectives of MnO reduction is the comprehension of slag interactions and reactions with other elements beyond carbon. That&apos;s because it is worthwhile to study pure MnO reduction, where there will be not oxides interaction and just carbon will be the reduction agent. By a thermodynamic analysis we know that Si can react with MnO, then it&apos;s important to study this influence, so as Mn content. Our work aims to develop kinetics parameters for the MnO reduction, varying Mn and Si contents in bath. This has been given by pressure measure of CO in a Fe-C bath. The CO is generated by the oxide reduction with carbon. It has been proved that: - Mn content decreases the MnO reduction; - the MnO reduction is mainly influenced by Si content in a bath containing Iron, Carbon and Manganese so as Silicium

Jan 1, 1997

By Jorge Alberto Soares Tenório, Viviane Tavares de Moraes, Denise Crocce Romano Espinosa, Franco Alves Lavacchini Ramunno

"The traditional process for recovery of metals from waste electric and electronic equipment (WEEE) usually involves pyrometallurgical processing. However, the application of this technology to processing waste printed circuit boards (WPCBs) might lead to the formation of dioxins and furans, due to thermal degradation of flame-retardants and polymeric resins present in the board substrate. Therefore, this paper proposes a hydrometallurgical route for the recovery of copper. The acid leaching behavior of copper has been investigated at three different temperatures (25°C, 50°C and 75°C) with and without the addition of an oxidizing agent (hydrogen peroxide - H202). The dissolution kinetics for acid copper leaching was calculated based on chemical analysis by ICP-OES (Inductively Coupled Plasma - Optical Emission Spectroscopy). At 50°C with 1 mol/L H2S04 added 10 mL H202 (30%) each half hour under pulp density of 1 g I 10 mL, 100% of copper was extracted after 3 hours. The dissolution kinetics of copper with H2SO4-H2O 2 followed 1 - (1 - X)113 =Ket, i.e. chemically controlled reaction model.IntroductionThe information regarding the generation of waste electric and electronic equipment (WEEE) are still difficult to obtain because the estimates should take into consideration the historical production and sale of various products and the rate at which they reach the end of their life cycle, whose duration depends on the behavior of consumers [1]. Thus, the estimated overall WEEE generation varies between 25 and 50 million tons each year, which corresponds to more than 5% of all municipal waste generated [2], and this amount will increase at a rate of 3 to 5% per year, approximately three times faster than other individual types of waste [3].Printed circuit boards (PCBs) are essential parts of electric and electronic equipment (EEE), being found in virtually all electronic products, as well as in weapons systems [4]. A PCB is a basic component, which consists of a board where copper tracks are deposited. While the board behaves as an electrical insulator, the tracks connect electrically the various components attached to the board [ 5]. In addition to glass fibers, paper and resins, the PCBs contain significant amounts of metals, such as copper, iron, nickel, lead, stain, silver, gold and palladium [6]. In general, the weight fraction of metal is around 28% and the remainder of the boards is composed of plastic (19%), bromine (as flame retardant - 4%) and ceramic material (49%) [7]."

Jan 1, 2014

By Baozhong Zhao

Laboratory experiments have been conducted on the removal of As, Sb and Bi from molten copper by SF 6 injection. The results showed that the impurities can be removed by SF6 injection in the? sequence of Sb >As >,Bi and the rate of Bi removal is affected significantly by the concentration levels of As and Sb in the copper melt. Analysis of the experimental data indicates that the impurity removal process is under chemical reaction control rather than by mass transfer of impurity through the molten copper phase. On the basis of experimental results, a kinetic model was developed and the order of chemical reaction and the volumetric chemical reaction rate coefficients of impurity removal were determined.

Jan 1, 1996

By Gerald Onyedika, Tochi Onwumere, Martin Ogwuegbu

"The kinetic study for the leaching of iron from cassiterite ore in KOH solution was studied. The effects of KOH concentration, particle size and reaction temperature on the leaching rate of iron were also examined. The results of leaching studies showed that the leaching of iron from cassiterite ore in KOH solution is significantly influenced by the reaction temperature, KOH concentration, and decrease in particle size. The study showed that 90.62% of iron ore was leached in 8M KOH solution at 80°C within 120 minutes. The experimental data were well evaluated using the shrinking model for surface chemical reaction and diffusion control through the product layer. The activation energies for the iron ore dissolution using the two models were calculated to be 32.06KJmor1 and 97.97 KJmor' respectively.IntroductionIn recent times, there has been increasing attention on the kinetic study of mineral dissolution. In most of these studies, the experimental results were analyzed with a suitable shrinking core model under the assumption that the ore is a homogeneous spherical solid phase [1-4]. A study of the dissolution kinetics of a Nigerian cassiterite ore by hydrochloric acid showed that increase in the hydrochloric acid concentration is accompanied with increase in the amount of cassiterite ore dissolved at various times [4]. The optimal concentration was found to be 4.0M HCl, after which there was a decline in the amount of the ore dissolved, which showed that the concentration of the reagent has a significant effect on the leaching rate of the ore. Also in studying the effect of stirring speed on the rate of cassiterite ore dissolution while keeping other conditions constant for 120 minutes, the result showed that the rate of cassiterite ore dissolution was dependent on the stirring speed over a range of 0 to 630 rpm. Above 360 rpm, the stirring speed no longer had any effect on the solid dissolution. The dissolution rates of cassiterite were analyzed using a suitable shrinking model. The results showed that the reaction was controlled by the diffusion of tin through the porous product layer, a reaction order with respect to hydrogen ion concentration of 0.92 M and activation energy of 50.05KJmor'. In another kinetic study on the leaching of a low grade niobium-tantalum ore with concentrated KOH solution the effect ofreaction temperature, KOH concentration, agitation speed, particle size and alkali-to-ore mass ratio on the dissolution rate of niobium were examined [5]. The result of niobium leaching from low grade niobium-tantalum ore with concentrated KOH, solution at different agitation speeds showed that the dissolution rate increased with increase in agitation rate. In the case of particle size effect, the results show that small particles require much shorter time for complete dissolution than the large ones."

Jan 1, 2013

By José Roberto de Oliveira

In a smelting reduction process the reduction reaction occurs predominantly in the liquid state. The main reduction agent is the carbon from the carbon saturated iron bath. The aim of the present work was to determine the velocity equation and the rate constant of the reduction rate of MnO content in a Mn0-SiO2-Fe0 slag by iron saturated carbon and the carbon dissolution rate in a Fe-Mn bath. The manganese content in the iron bath was in the range of 5 to 15 wt.%. It was observed that the rates of carbon dissolution in all Fe-Mn baths are faster than the rates of MnO reduction by the carbon saturated liquid iron.

Jan 1, 1999

By M. C. Ruiz

The conventional pyrometallurgical methods to treat copper sulfide concentrates include generally, one or more oxidizing steps where the formation of SO2 gas can not be prevented. From the economical point of view and the nature of some of the processes in which SO2 is produced, its complete capture is not feasible; therefore an important fraction is released to the atmosphere as fugitive emissions. In this research, the reduction of chalcocite was studied in the presence of lime as an alternative method, which overcomes the pollution problems related to SO2 emissions. The effect of temperature, time, concentration of carbon and CaO on the reduction rate were studied. Among these variables, temperature affects most the reduction rate. Conversions over 95 % can be obtained in less that 20 minutes at temperatures over 1000 ° C. The measured partial pressures of the gaseous components indicated that the chalcocite reduction proceeded through the gaseous intermediate species CO, C02, and the overall kinetics was controlled by the Boudouard reaction. The kinetic model In(1-X)= kt fits well the experimental data. Apparent activation energy of 3 14 kJ/mol was calculated for the temperature range of 900 0C-1050 °C.

Jan 1, 1999

By R. Cheng

The kinetics of the solvent extraction of ythium from HCl solution with mono-2-ethyl hexyl phosphonic acid mono-2-ethyl hexyl ester (HEHEHP) have been studied using a rotating diffusion cell (RDC). The effects of rotation speed, pH, ymium and extractant concentrations and temperature on the rate of extraction were examined. The rate of extraction of ythium appears to be controlled by an interfacial reaction of metal ion and extractant. The concentration of the latter is determined mainly by diffusion through the membrane. The contributions of the rates of diffusion in the diffusion layer, diffusion in the membrane and chemical reaction at the interface to the overall rate have been calculated on the basis of a kinetic model.

Jan 1, 1992

By Aiyuan Ma, Tu Hu, Chenyu Sun, Yonggang Zuo, Hongying Xia, Jinhui Peng, Libo Zhang, Yongguang Luo

"In this study, the adsorption characteristics of tannin acid in aqueous solution were investigated using regenerated activated carbon (AC), with the aim to remove the tannin acid organic matter from the solution after zinc hydrometallurgy and Ge precipitation. Results showed the temperature has little effect on the adsorption ability (q.) of the regenerated activated carbon. The experimental equilibrium data were tested for the Langmuir and Freundlich isotherms. The adsorption equilibrium was better described by the Langmuir isotherm (R2 > 0.99). Pseudo first- and second-order kinetic models were used for describing kinetic data. It was determined that the kinetics of tannin acid removal was well fitted by second-order reaction.IntroductionGermanium recovery is a complex processes [1]. Hydrometallurgical processes are favoured and these are based on the precipitation of germanium as hydroxide or sulphide or alternately with tannic acid [2]. However, in the germanium recovery process, too much tannin is consumed by the germanium-tannins complexation process, and results in a high content of tannic acid remaining in solution, which is harmful to the valuable metal recovery [3]."

Jan 1, 2014

By David Langberg

Recovery of dissolved copper from discard slags is a critical consideration affecting the economics of copper smelting. Slag cleaning is frequently carried out in electric furnaces, however reduction by injection of natural gas in a holding furnace may offer a lower cost alternative in some circumstances. As the residence time of the injected gas is short, the factors controlling the rate of reduction need to be clarified in order to optimise the design of the slag cleaning furnace. A series of medium scale (200 kg) reduction tests to investigate the rate of reduction of copper-containing slags by injection of natural gas-nitrogen mixtures between 1150-1250C was carried out by CSIRO Minerals. The composition of the gas in the top-space of the reactor was found to be significantly more reducing than the slag, indicating that thermodynamic equilibrium was not established between the slag and the gas in the bubble plume. An apparent first order rate law was observed between the rate of oxygen elimination from the bath and the magnetite concentration of the bath. The dissolved copper concentration was closely correlated with the oxygen potential of the slag, suggesting a partial equilibrium between the dissolved components of the slag. The utilisation efficiency of the natural gas decreased as the natural gas flow rate was increased. The results of the tests tend to indicate that the rate is controlled by a mixed reaction kinetics/ mass transport mechanism. The work was supported by Xstrata Copper ? Mt Isa Mines.

Jan 1, 2006