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By M. Kinne

Catalyst preparation/ characterization Slightly modified DP (~Schumacher et al. Catal. Lett. 89, 109, 2003) CeO2 HAS 15 from Rhodia calcined in air for~ 2h BET: ~188m2/g, particles size: 5.7nm (TEM, XRD) + HAuCl4 at pH of 6.5-7, (>95% of the Au was deposited) ? Au/CeO2 (2.6wt% Au, ICP-AES) A new conditioning procedure was applied, including heating at low temperature in N2 and H2/N2 mixtures) Patent DE 10205873A1. Very small Au particles <2nm, for CO oxidation catalyst as Au/TiO2, Au/Fe2O3, and Au/Co2O3 Here Au particles size <3.5nm (XRD) Summary ? CO is nearly exclusively adsorbed on the Au particles ? Positive reaction orders of 0.5 are found for CO and H2O ? Ea= 40kJ/mol ? The catalyst is very active and stable ? During WGS reaction huge amounts of formates are formed and cover the surface ? The activity of the catalyst seems to be correlated with the formate species.

Oct 1, 2003

By K. M. Parida

The kinetics of dissolution of manganese dioxide in dilute sulphuric acid solution have been investigated using iron pyrites as a reductant. The dissolution rate of manganese is independent of the speed stirring but depends upon temperature, particle size, specific surface area of manganese ore, acid concentration, Fe(II) concentration and amount of pyrite. The activation energy is 43.6 KJ/mol and the linear relationship between the rate of dissolution and lido indicates that the reaction is chemically-controlled. The redox reactions of MnO2 with iron pyrites and Fe(II) are the rate-controlling reactions.

Jan 1, 1990

By Glastonbury J. R

The kinetics of the direct chlorination of, zircon in the presence of carbon was studied at temperatures between 9000C and 12000 C. From the experimental data it is prop- osed that the most likely mechanism for metal oxide (MeO2) chlorination is as follows: At I Surfaceon zMeO2+ZMeCl - MeOC12 (1) At Carbon MeOC12+C+Cl MeC14+CO (2) Surface It.is envisaged that this type of mechan- ism would occur for both the zirconium and, silicon. constituents of the ore. In the above mechanism; the surface re- actions appear to be fast and not rate controll- ing. In a carbon surface deficient bed the diff- usion of oxychloride intermediate through the boundary layer to the carbon surface becomes the rate controlling step. In a zircon surface deficient bed the diffusion of oxychloride away from the zircon surface controls the reaction. This postulated mechanism can be used to ex-, plain the observed experimental effects.

Jan 1, 1973

By C. F. Ferron

A process has been developed to treat the copper gold ores from the Guelb Moghrein mine in Mauritania. The process consists of pressure leaching the sulphide concentrate, neutralising with the oxide ore, recovery of copper by SX/EW and of gold by cyanidation of the autoclave residue. This paper focuses on the pressure leaching step, and presents data from bench and pilot plant test programs. In particular, attention is drawn to the effects of temperature, grind size, neutralisation, retention time and solution recycle on the kinetics of copper dissolution from various flotation concentrates. Likely leach mechanisms are briefly discussed.

Jan 1, 2000

By José Carlos Abreu

This work presents a kinetics study covering the effects of temperature over the reduction rates of a carbon composite briquette, aiming its use as burden in some of the new alternate ironmaking technologies, such as the Tecnored process. It is reported that increases in the temperature increases the reaction rate. Additionally, the morphology of the iron phase generated during the reduction of these briquettes is presented. It was possible to verify that three types of iron morphology occurred during the process: an external, dense and continuous iron layer, the presence of iron globules at the center of the briquettes and whiskers at the briquette&apos;s core. The measurement of the carbon content on the globules and the external iron layer is also presented.

Jan 1, 2003

By José Carlos Abreu

This work presents a kinetics study covering the effects of temperature over the reduction rates of a carbon composite briquette, aiming its use as burden in some of the new alternate ironmaking technologies, such as the Tecnored process. It is reported that increases in the temperature increases the reaction rate. Additionally, the morphology of the iron phase generated during the reduction of these briquettes is presented. It was possible to verify that three types of iron morphology occurred during the process: an external, dense and continuous iron layer, the presence of iron globules at the center of the briquettes and whiskers at the briquette&apos;s core. The measurement of the carbon content on the globules and the external iron layer is also presented

Jan 1, 2003

By Zhou A, Cadogan J. M

Direct reduction of iron ore (DR) is one of the promising technology emerging in the world&apos;s steel industry. Kinetics and Mossbauer studies of DR with hydrogen have been carried out at two temperatures of 600¦C and 800¦C in this investigation. The results show that different controlling steps govern the reduction rate at different temperatures. The mechanism was also found to vary during the reduction. The Mossbauer spectra of the samples reduced in various time intervals were studied to determine the phase changes during reduction.

Jan 1, 1997

By Shengli Wu, Feng Chang, Hua Lu, Jianliang Zhang

Kinetic studies of the blast furnace dust (BFD) reduction process have been carried out under non-isothermal conditions. BFD pellets were made with bentonite as the binder. A Comprehensive Thermal Analyzer (TG-DSC) was used to determine the mass loss of pellets, which were heated at three heating rates of 10, 20, 30 K/min up to 1493 K. Furthermore, the metallization rate and mineral composition of BFD pellets heated to several different temperatures were analyzed by chemical analysis and X-ray diffraction (XRD). It was found that, with its inherent carbon resources as the reducing agent, the metallization rate of BFD pellets could reach 88% at most. The reduction and weight loss process of iron oxides mainly happens above 1273 K. In addition, from application of the Coats-Redfern equation the apparent activation energy of the reduction from wustite to Fe was 443 kJ/mol and the mechanism was interface reaction R..

Mar 1, 2017

By C. J. Pretorius

More than 30 percent of the global demand for zircon (ZrSi04) is supplied by South Africa. A significant amount of the zircon is exported, and beneficiated products are then imported for industrial applications locally. Beneficiating the zircon locally could have a positive impact on the local market, since zircon is only one of many such cases. Ammonium acid fluoride serves as an alternative anhydrous fluorinating agent for zircon in the synthesis of several metal fluoridesl.2. It provides an effective dry fluorinating method and is easier to handle than hydrogen fluoride or fluorine gas. Zircon exposed to extreme plasma temperatures dissociates and becomes more reactive. The reaction of the plasma-dissociated zircon (Zr02?SiO2) with the ammonium acid fluoride (NH4F?XHF, where x= 1 to 5) forms two main intermediate compounds (NH4)3ZrFr(s) and (NH4) 2SiF6(s), the latter decomposing to form volatile products at relatively low temperatures, providing easy separation of the silicon and zirconium compounds. The ammonium zirconate compound decomposes to form zirconium tetrafluoride (ZrF4), which can be further manufactured into zirconium metal, to name but one product. Data on the kinetics of the reaction of ammonium acid fluoride with zircon and plasma-dissociated zircon, combined with the thermo-dynamic parameters of the reaction, is essential for the development of an industrial process for the production of a precursor for the manufacturing of zirconium metal, namely anhydrous ZrF4. Both the reaction kinetics and reaction parameters will be included in this study, as well as some proof that the reaction proceeds to ZrF4 on a small batch scale. If the exact reaction parameters can be pinned down, a wide spectrum of anhydrous metal fluorides can be synthesized through this fluorination route.

Jan 1, 2012

By C. J. Pretorius

More than 30 percent of the global demand for zircon (ZrSi04) is supplied by South Africa. A significant amount of the zircon is exported, and beneficiated products are then imported for industrial applications locally. Beneficiating the zircon locally could have a positive impact on the local market, since zircon is only one of many such cases. Ammonium acid fluoride serves as an alternative anhydrous fluorinating agent for zircon in the synthesis of several metal fluorides1,2. It provides an effective dry fluorinating method and is easier to handle than hydrogen fluoride or fluorine gas. Zircon exposed to extreme plasma temperatures dissociates and becomes more reactive. The reaction of the plasma-dissociated zircon (Zr02.SiO2) with the ammonium acid fluoride (NH4F.XHF, where x= 1 to 5) forms two main intermediate compounds (NH4)3ZrFr(s) and (NH4) 2SiF6(s), the latter decomposing to form volatile products at relatively low temperatures, providing easy separation of the silicon and zirconium compounds. The ammonium zirconate compound decomposes to form zirconium tetrafluoride (ZrF4), which can be further manufactured into zirconium metal, to name but one product. Data on the kinetics of the reaction of ammonium acid fluoride with zircon and plasma-dissociated zircon, combined with the thermo¬dynamic parameters of the reaction, is essential for the development of an industrial process for the production of a precursor for the manufacturing of zirconium metal, namely anhydrous ZrF4. Both the reaction kinetics and reaction parameters will be included in this study, as well as some proof that the reaction proceeds to ZrF4 on a small batch scale. If the exact reaction parameters can be pinned down, a wide spectrum of anhydrous metal fluorides can be synthesized through this fluorination route.

Jan 1, 2012

By P. C. Chaubal

The overall kinetics of oxidation of single partic1es of chalcopyrite have been studied for temperatures up to 1273 K. The experiments were conducted in a stationary bed reactor using a non-isothermal technique. Any mass and heat transfer effects on the kinetics of oxidation were eliminated by using a high-enough gas flowrate. Up to temperatures of 873 K, pore-bl1ocking kinetics were applicable, whereas above 873 K, power-law kinetics gave a satisfactory fit of the data. The activation energy was 215 kJ/mol below 754 Kand 23.7 kJ/mol above 1,060 K. Predominance area diagrams were constructed at various temperatures and used in conjunction with X-ray analyses of partially oxidized samples to determine the intermediate phases formed during the reaction. The analysi1s also provides a justification for the kinetic models used. The results indicate that the reaction rate is first order with respect to oxygen concentration and inversely proportional to the square of the particle size throughout the ranges of temperature studied.

Jan 1, 1985

By Xiang Ma, Halvor Dalaker, Kai Tang, Stefan Andersson

Silicon carbide (SiC) is one of the most important non-oxide ceramic materials for many industrial applications and is mainly synthesized by carbothermic reduction of silicon oxide by coke above 2200°C. Replacing natural gas (mostly methane, CH4) for coke in SiC synthesis could considerably reduce energy consumption and CO2-emissions owing to higher carbon activity of CH4 at lower temperature. The generally accepted reaction mechanism is that SiC is synthesized through gaseous intermediate silicon monoxide, SiO. In the present study, the reaction mechanism for the SiO and CH4 gaseous mixture has been examined using atomic scale modelling. Molecular dynamics (MD) using a reactive force field (ReaxFF) has been utilized to examine the initial stages of reactions involving a gas mixture of SiO and CH4 and surfaces of SiC. The MD results revealed some interesting SiC formation mechanisms. The reaction energies of the critical intermediate species were also estimated by density functional theory (DFT) calculations and the implications for the force field parameters used in ReaxFF was discussed.

Jan 1, 2015

By Michael Nicol

A quantitative description of hydrometallurgical operations depends primarily on an understanding of the kinetics of the chemical and physical processes that take place in such operations. This paper will review the current status of kinetics in hydrometallurgy in terms primarily of the author’s experience in diverse unit operations. A distinction will be made between the popular use of models based on limited kinetic data and mechanisms which reflect the actual elementary chemical or physical steps involved in an overall process. Several examples will be used to illustrate this distinction. The proliferation of published papers of declining quality has resulted in the bequest to later researchers of outdated and often incorrect conclusions by a process that is often difficult to reverse. Some examples of these mysterious concepts will be examined and hopefully reversed. Finally, several examples will be given that identify significant gaps in our understanding of the kinetics of important processes that remain unresolved.

Jan 1, 2014

By C. Hecker, J. A. Garcia

To determine the kinetic reaction mechanism, electrochemical experimental techniques of stationary polarization, linear voltammetry and faradaic impedance were used. Gold electrodeposition experiments were realized using an electrolysis cell, provided· by a rotary disk of vitreous carbon and or' platinum counter electrode of platinum mesh and reference electrode. Using an automatic measurement system voltarnmograrns and Nyquist faradaic impedance spectra were obtained. In this paper, responses for different cases were analyzed through faradaic impedance criteria, considering several kinds of diagrams obtained. The importance diffusion influence of aurocyanide ions and adsorption as controlling steps previous charge transfer was verified. A model of proposed mechanism is discussed.

Jan 1, 1997

By C. E. Jordan

Direct digestion of phosphate ores by the acid-alcohol method offers improved leaching selectivity for the exclusion of iron and aluminum in the product acid. The leaching kinetics of this process will have a major role in the eventual application of this technology. The Bureau of Mines investigated apatite dissolution to determine the reaction rate and mechanisms of the leaching kinetics. The dissolution kinetics were monitored on various sized fractions of pure apatite. The "shrinking-core" kinetics model was applied to the data to determine the rate controlling mechanisms. For each size fraction, the initial reaction rate was controlled by the dissolution reaction. After an hour the dissolution rate slowed indicating a diffusion controlled reaction caused by the formation of calcium sulfate hemi-hydrate coating on each particle. For complete dissolution of the apatite, the phosphate rock should be ground to near 10 µ m size.

Jan 1, 1993

By Happ J. V

Factors affecting the rate of arsenic removal from lead bullion during softening processes were studied. Very high rates of removal could be obtained under conditions of intense agitation and ready availability of oxidant. Reaction mechanisms were proposed to explain the sequences observed. Selective removal of arsenic with minimal loss of antimony from bullion was favoured by a low temperature Harris process and oxidizing via a caustic soda medium.

Jan 1, 1987

By Baozhong Zhao

Experimental results have shown that fluxing with soda ash (Na:zC03) can remove As and Sb from molten copper at the rate of As>Sb, but is relatively ineffective in removing Hi. The rate of impurity removal is controlled by impurity mass transfer in the metal phase. In this paper, a mathematical model was developed to describe the impurity removal phenomena. The model incorporates the effects of molten bath mixing intensity, soda ash feeding rate, oxygen content in the molten copper and soda ash fluxing by surface addition and injection. The model predictions are in good agreement with experimental results and may be used in designing large scale tests.

Jan 1, 1996

By S. D. F. Rocha, A. L. A. SANTOS, E. M. A. BECHELENI, R. M. Papini, P. R. M. Viana, F. P. C. Silvas

The kinetics of atmospheric sulfuric acid leaching from a Brazilian nickel laterite ore was assessed using distinct reducing agents and ore mineralogy. This transitional ore contains 1.63% Ni distributed as 1.27% in coarse size (− 500 + 150 μm), mainly as silicates (lizardite and chlorite—28.6%), and 2.06%in the fines fraction (− 75 μm), mainly as iron oxy-hydroxides (goethite and hematite—49%). The effects of temperature, acid concentration, reducing reagent type, and concentration were evaluated. The − 75 μm fraction limited the leaching efficiency and the use of reducing media with thiosulfate improved leaching and Ni-Fe selectivity. However, at constant Eh of 626–743 mV and a pH range between 0.2 and 1.1, no substantial rise in metals extraction, except for Co and Mn, has been observed. In order to determine the process control at 95 °C, two regions in the extraction curves were used in combination with the shrinking core model. Control by porous diffusion was observed and the kinetic constant was found to be in the order kFe<kNi<kMn<kCo<kMg for atmospheric leaching without Eh control. In reducing media for the first 15 min of leaching, the kinetic constant was found to be kFe<kNi<kMg≅kCo<kMn as derived from Ni disseminated into iron oxides structures.

Oct 7, 2020

By S. D. F. Rocha, A. L. A. SANTOS, E. M. A. BECHELENI, F. P. C. Silvas

Hydrometallurgical processes are needed to extract nickel (Ni) when it is disseminated in mineral matrix. High-pressure acid leaching (HPAL) and atmospheric acid leaching (AAL) are alternatives, and AAL has the advantage of requiring mild temperatures and pressure. Reducing-reagent tests improved the extraction of metals for the specific limiting portion of the ore. Low dosage of sodium thiosulfate presented better selectivity and safer operating conditions, allowing metal extractions of 50–62 percent at 95 °C. However, the low extraction rate obtained for Ni and the similar levels of impurities — magnesium (Mg), manganese (Mn), cobalt (Co) and iron (Fe) — extracted may represent economical and technological challenges in the downstream process.

By E. V. Konopleva, H. J. McQueen

"The isothermal bainite transformation kinetics of low- and medium-carbon alloy steels after hot deformation and the rmocycling treatment (TC) has been studied by the magneto - metric method. Deformation was produced by rolling at 800°C-1000°C. TC included three cycles of rapid (30°C/s) electro-heating up to 900°C-1000°C followed by quenching.Hot deformation retards bainite transformation in the lower part of bainite range (<400°C) and accelerates it in the upper part (>400°C). The effect is greater for higher strain and lower deformation temperature. Deformation also diminishes the overall bainite fraction below 400°C and increases the completeness of reaction above 400°C.Thermocycling provides more uniform ultrafine austenite grains with average size of 3 µm -4 µm compared to 12 µm -14 µm after conventional heating. The transformation rate after TC was almost the same as after conventional heating in low-carbon steel but was faster in medium-carbon with no change in the completeness of reaction. The degree of acceleration increased with rise of transformation temperature.There are a number of factors which are responsible for a change in bainite transformation kinetics in austenite deformed at high temperatures or subjected to TC. One of the most important factors is the refinement of structure, another one is structural and chemical inhomogenity of austenite due to deformation or to rapid heating. To estimate the contribution of these factors, ?-transformation was studied after different austenitizing conditions (low-temperature heating at 850°C- 950°C; high-temperature heating at 1100°C; step treatment – austenitizing at 1100°C, then cooling to 950°C-850°C). The results obtained make it possible to conclude that the structural and chemical inhomogeneity of austenite activate the bainite reaction while the grain refinement retards it. Intensity of the effect produced by each factor depends strongly on the steel composition."

Jan 1, 1997