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By H. Y. Sohn

The purpose of this article is to analyze critically and quantitatively the effect of chemical equilibrium on the overall rates of fluid-solid reactions. It is shown through a mathematical analysis that a reaction with a small equilibrium constant (a positive standard free energy of reaction) is more likely to be rate-controlled by pore diffusion or mass transfer than a reaction with a large equilibrium constant. The overall reaction rate of the former also tends to be slow. Furthermore, the apparent activation energy of such a reaction approaches the standard enthalpy of reaction (M-f'), rather than the true activation energy of the chemical reaction. The Law of Additive Reaction Times developed by the author is shown to apply to equilibrium-limited fluid-solid reactions and to be useful in quantitatively analyzing the behavior of such reactions.

Jan 1, 2003

By R. M. Taylor

Lime addition to acid mine drainage (AMD) leads to precipitation, predominantly of metal hydroxides and calcium sulfate, and is the benchmark for remediation by precipitation. Geo2 Limited of Melbourne, Australia has developed and patented a novel alternative precipitation scheme based on the formation of mixed valency, M(I1)-M(III), hydroxide sulfate salts. When the composition of AMD is appropriate, the Green Precipitate Process provides a useful and more effective alternative to conventional liming. The characteristics and utility of the Green Precipitate Process are described in terms of the underlying chemistry, and a case study where the Green Precipitate process outperforms conventional liming. A mobile pilot pipe reactor rig which was built by Geo2 to demonstrate the process, and used successfully in both Australia and the United States, is described.

Jan 1, 1998

By Houyuan Liu

A new process was developed to recover nickel and cobalt by leaching laterite ore at atmospheric pressure and.95"-105" C. The nickel-containing goethite in limonite was first leached with sulphuric acid to liberate over 90% of nickel, cobalt and iron. The dissolved iron was then precipitated as Ni-free goethite by the additioil of saprolite. The acid released during iron precipitation as goethite was simultaneously used as lixiviant to leach saprolite to recover more nickel. With this process the limonite and saprolite were essentially converted into goethite-, gypsum- and silica- containing tailings. Twenty bench scale tests and two campaigns of pilot plant operation were carried out at BHP Billiton's Newcastle Technology Centre (NTC) from January to August 2002. The overall nickel and cobalt extractions were 81 to 90% and 91 to 100% respectively. The average plant availability was 99%. The advantages of this process over existing processes include high plant availability, high consistency, robustness and simplicity of the operation.

Jan 1, 2004

By Pertti Koukkari, Nagendra Tripathi, Karri Penttilä, Justin Salmine

ChemSheet is a thermodynamic multi‐phase multi‐component simulation software, which is used as an Add‐in in Microsoft Excel. In ChemSheet, the unique Constrained Gibbs free energy method can be used to include dynamic constraints and reaction rates of kinetically slow reactions, yet retaining full consistency of the multiphase thermodynamic model. With appropriate data, ChemSheet models can be used to simulate reactors and processes in all fields of thermochemistry. The presentation will cover off‐line modeling of Cu‐flash smelters and advanced thermochemical simulation coupled with on‐line process control of Cu‐Ni smelting. The presentation will describe an off‐line model of Cu‐smelter based on critically assessed properties of the Al-Ca-Cu-Fe-O-S-Si –system (slag, matte and liquid metal) by using the quasichemical model. A four‐stage reactor model (shaft, settler, uptake and bath) is used for optimizing process parameters and feed particle distribution. As a second example, an advanced thermochemical model of a Ni-Cu sulphide smelting plant will be given. The on‐line model covers the operation of treating Ni-Cu-S concentrate via roasters, electric furnace and converters, producing a high grade Bessemer matte product for further refining. The model integrates the thermochemistry of the roasters and electric furnace, and predicts important process parameters such as degree of sulphur elimination in the fluid‐bed roasters, matte grade, iron metallization, slag losses and the iron to silica ratio in the electric furnace slag. Both models can be used to assist process engineers and operators in calculating the addition rates of coke, flux and air for different feed scenarios.

Jan 1, 2014

By Eddie C. Chou

Phelps Dodge, Inc. (PD) is currently developing a lateritic nicke/Vcobalt deposit in Madagascar. Hazen Research, Inc. provides technical assistance to PD to investigate recovery processes for nickel and cobalt. Various process options were evaluated in laboratory experiments and pilot plant operations. The process selected for the feasibility study consists of feed preparation, high-pressure acid leach, countercurrent decantation wash, sulfide precipitation, sulfide dissolution, solvent extraction, ion exchange, and electrowinning. Among these unit processes, high-pressure acid leach, sulfide precipitation, and sulfide dissolution are applications of pressure technologies. Process development work and design criteria for commercial operations of these unit processes are presented in this paper. Concerns related to scaling in the high-pressure acid leach and the sulfide precipitation processes are discussed. Corrosion of various metal coupons under these environments was examined.

Jan 1, 2000

By C. S. Ek

Tests have been performed to recover silver and lead from residues produced after a super-hot leaching in a zinc hydrometallurgical plant operating with jarosite precipitation. When this residue is leached in ammoniaammonium sulfate or in diethylenetriamine solutions, lead dissolution is not complete and its recovery from the aqueous solutions is either difficult, due to the operating conditions, either expensive due to the amount of added reagents. In both cases, silver is partly dissolved, partly left in a new residue still containing lead and baryum sulfates. The best treatment seems to include a selective flotation producing first a silver concentrate assaying about I % Ag, then a 50 % lead concentrate collecting the baryum salts, and a final quartz-gypsum tailing. Metal recoveries can reach 50 % and 80 %, respectively.

Jan 1, 1989

By H. Y. Sohn

The purpose of this article is to analyze critically and quantitatively the effect of chemical equilibrium on the overall rates of fluid-solid reactions. It is shown through a mathematical analysis that a reaction with a small equilibrium constant (a positive standard free energy of reaction) is more likely to be rate-controlled by pore diffusion or mass transfer than a reaction with a large equilibrium constant. The overall reaction rate of the former also tends to be slow. Furthermore, the apparent activation energy of such a reaction approaches the standard enthalpy of reaction (Mf'), rather than the true activation energy of the chemical reaction. The Law of Additive Reaction Times developed by the author is shown to apply to equilibrium-limited fluid-solid reactions and to be useful in quantitatively analyzing the behavior of such reactions.

Jan 1, 2003

By Pengfu Tan

In order to understand and control the formation of dioxins and furans in iron ore sinter plants and to possibly avoid expensive end-of-pipe removal stages, thermodynamic calculations on the stability of PCDD/Fs have been combined with sinter process modeling by means of kinetic simulations and computational fluid dynamics. Three thermodynamic databases of PCDD/Fs, derived using the Group Additivity approach and two computational molecular modeling methods, MNDO and PM3, respectively, combined with the SGTE database have been used to model the PCDDIF formation and the PCDD/F isomer distributions in iron ore sintering. The results show very similar conditions for the PCDD/F formation using the different databases. Concerning the isomer distributions of toxic PCDD/Fs, the calculated data derived from the MNDO method showed optimum agreement with measured values from industrial furnaces. The thermodynamic calculations also proved that the isomer distributions found in combustion processes are equilibrium values, while the concentration ratio of PCDDs and PCDFs in the wind boxes does not represent an equilibrium state. A CFD model of iron ore sintering was developed including the kinetics of 15 relevant chemical reactions with the aim of describing the temperature fields and the gas flow patterns in the sintering bed. On the basis of these information and experimental observations reported in the literature possible pathways for the PCDD/F formation in sinter plants have been identified: PCDD/Fs are formed in the critical temperature region of 250 to 450°C below the combustion zone, are then carried downwards with the gas and condensed close to the bottom of the sinter bed. Transported to the discharge end with the solid mixture, they are again released into the gas phase when the flame front approaches the bottom. PCDD/Fs are also formed in the last wind boxes when the hot off-gases cool down and reach the critical temperature range. Consequently, methods to reduce the dioxin formation reactions are proposed including inhibitor addition to the sinter feed and off-gas quenching.

Jan 1, 2003

By Michael J. McGuire

Rostoker, Inc. has developed a process to smelt solid hazardous/non-hazardous inorganic wastes. Near seven hundred experiments were performed. Actual industrial wastes as well as reagent grade chemicals were used. By mixing a multiplicity of these wastes to proper formulations, then furnacing them, it was determined that saleable end products could be reclaimed; metal, fume and slag. The slag, due to its siliceous structure was tested to be leach resistant (40 CFR). This formed the essence of our patent, #5,180,421 "Method and Apparatus for Recovering Useful Products from Waste Streams". What is unique is that a HTMR (High Temperature Metal Recovery) process has been developed that can treat a multiplicity of wastes within the same furnace. The discussion will include a list of waste streams we have treated, details of proper waste formulation and experimental results.

Jan 1, 1994

By A. P. Pavia

Investigation on profitable ways to recover significant quantities of silver remaining dissolved in highly concentrated chloride solutions frequently pass through the development of solvent extraction (SX) routes. In this work, the general pathways involving Ag(I) extraction by dibutylthiourea (DBT) or tetraethylthiuram disulfide (disulfiram, DSF), from concentrated acidic chloride solutions, are investigated. With this purpose, the dependence of Ag(I) distribution coefficient on ligand and chloride concentrations has been analysed. Furthermore, in order to check whether there is some protonation at any site of DBT or DSF after contact with adequate chloride phases, lH NMR has also been used. The collected spectroscopic data suggest that anionic Ag(I) extraction reactions are not likely to occur. Based on the overall results achieved, proposals for the most probable Ag(I) extraction reactions are made.

Jan 1, 2001

By C. P. Snyman

Three independent methods of coal classification can be distinguished, namely on the basis of grade, type and rank. The latter two can be determined accurately and unambiguously only by means of microscopical techniques. These three independent variables affect all the coal properties and therefore also the technological behaviour of a particular coal. The influence of the inorganic constituents of coal on the fusibility of the ash and on the length of the slag, and also on fouling and slagging, is discussed. The fractionation of the ash-forming constituents during combustion and gasification of pulverised coal shows that fouling and slagging are not related directly to the fusibility and composition of ash of the coal as a whole. The results of combustion experiments using a drop furnace technique indicate that the ignition temperatures of the light volatiles in the coal, and of the formed char, as well as the burn-out time of the char are more dependent on the rank than on the type or grade of the original coal. High-ash coals, however, apparently ignite at lower temperatures and are more reactive than low-ash coals of similar type and rank. The surface properties of coal, which are important in froth flotation and oil agglomeration, correlate well with the inherent moisture content (and by inference with the heat of wetting and the calorific value) and therefore with the type and rank of the coal. In coal exploration, variations of rank offer the possibility of predicting the presence of an intrusion near the seam, thus contributing to more effective exploration and mine planning.

Jan 1, 1991

By Fathi Habashi

The recovery of uranium from wet process phosphoric acid was applied on industrial scale in the 1940's by using octylpyrophosphoric acid as an extractant. Later, more efficient reagents were used, e.g., di(2-ethylhexyl) phosphoric acid and actylphenyl phosphoric acid. In the 1970's the rare earths in Kola phosphate were recovered in Finland and recently (1997) in Norway using HNO, as a leaching agent and di(2-ethylhexyl) phosphoric acid as solvent. It was demonstrated later on laboratory scale that both uranium and rare earths could be extracted from the rock by tributyl phosphate but at different pH values provided that the rock is leached with nitric or hydrochloric acids instead of the commonly used sulfuric. This new concept opens the way to the possibility of treating phosphate rock by in-situ, dump, or vat leaching for the recovery of phosphate values as well as uranium and the rare earths. Another solvent extraction process is used industrially for the purification of phosphoric acid using butyl and amyl alcohols.

Jan 1, 1998

By L. Evrard, S. Brouwer, E. Bosly, E. Boydens

"A partial desulfurization roasting process has been tested on a typical copper-zinc sulfide concentrate in a Nichols Herreshoff monohearth pilot furnace whereby the su!fµr is partially removed and iron is to a certain degree preferentially oxidized. The phase changes that occur in the particles during selective roasting at 650°C and 800°C over a range of residence times were investigated by the use of chemical analysis, optical microscopy, X-ray diffraction and electron microprobe analyses. The purpose of this work was to get an insight into the mineral assemblages formed by controlled oxidation roasting and to evaluate if this non traditional approach could be afterwards used to recover zinc, copper and iron by a physical separation method. IntroductionThere has been considerable interest over the years in improving extraction and processing procedures for recovering non ferrous metals especially from polymetallic ores containing copper, lead, zinc and iron sulfides with very fine intergrown phases. Complex sulfide ores, which represent considerable reserves and resources in copper, lead and zinc, as well as precious metals and sulfur, are difficult to treat by conventional physical processes, leading to impure concentrates at low metal recovery. Some methods that can be used to treat such ores were described by G. Barbery (1). Various metallurgical routes generally combining pyro- and hydrometallurgical methods have been explored to develop new processes to recover the metals from zinc-bearing sulfidic ores and concentrates (2, 3, 4). The feasibility of partitioning complex sulfide minerals to simpler phases in order to improve selective extraction of mineral constituents has also been investigated (5)."

Jan 1, 1999

By T. R. A. Davey

The technologies of lead, zinc and tin extraction have made varying degrees of progress over the past twenty years. Producers of all metals have faced increasing demands for reduction of pollution and environmental degradation, and the level of public concern is rising rather than abating. New processing techniques must therefore be not only economically feasible, but politically acceptable, even when the demands of "conservationists" and ?environmentalists? are unreasonable. A new generation of processing techniques has come into being, which do not rely on an expensive sintering stage, nor use metallurgical coke, which is difficult to make without serious pollution. They utilise intense reactors, conveying materials from one stage to the next preferably within an enclosed space, obviating fume emissions, and avoiding heat losses as far as possible. The acceptability of the new techniques? is increased if lowgrade or complex materials can be treated, along with a variety of returns and wastes. In addition, a good selling and servicing organisation seems to be as important as good process technology in determining the spread of the new processes. In the field of pyrometallurgical refining the need is for more general application of several recently developed techniques rather than a search for alternatives to the existing process technologies. However, there is a need for fundamental work investigating the phenomenon of oxygen anode overvoltage in the electrolytic zinc process, in order to make progress in the further reduction of energy consumption. There is also scope for further development and application of vacuum distillation to up-grade thermally produced zinc. This paper presents a personal view of processes which should be developed to overcome existing problems, as we approach the turn of the century,

Jan 1, 1990

By S. Ajima

The Naoshima Smelter and Refinery is the most important copper operation of Mitsubishi Materials Corporation. There are a Mitsubishi Continuous smelter and a conventional type of copper tankhouse. The continuous smelter with 240,000 mtpy of anode production was commissioned in May 19914 replacing two existing smelters, i.e an original Mitsubishi Process line and a conventional reverberatory furnace line. In July 1992, the copper tankhouae was expanded for the purpose to close the gap of production capacity between the smelter and the tankhouse. The cathode production capacity was increased from 13,800 to 15,800 mtpm. By these plant modifications, the distribution of minor elements was significantly changed and the impurities load is getting on increase reflecting recent shortage of clean copper concentrates supply. The paper discusses the distribution of minor elements and the impurity control strategy at the smelter end the refinery.

Jan 1, 1995

By P. N. Anyalebechi

The effects of application of steady and pulsed electric current on the cast microstructures of ingots of a 7050 type aluminum alloy have been experimentally investigated over a solidification rate range of 0.1-10 K/s. This involved the application of an electric current of 465-930 mA/cm2 of melt surface area to laboratory-size ingots solidified in a unidirectional manner. Within the ranges of electric current density and solidification rate investigated, the applied electric current reduced the average dendrite, grain, and second-phase particle size. It also made the size distribution of the second-phase particles more uniform. The mechanism for the observed refinement of the cast microstructure by the applied electric current is not well understood. The potential effects of heat-induced local convections, shear stress-induced fragmentation of dendrites, increased temperature gradient due to Joule heating and the thermal and constitutional supercooling engendered by Peltier, Thompson, and Joule heating are discussed.

Jan 1, 2009

By Kazuya Koyama

We are studying the hydrometallurgical recycling process of indium from an Indium-Tin-Oxide(ITO) target. For this process, it is necessary to remove Sn(IV) ions from the aqueous hydrochloric acid solutions containing In(III). In this study, the removal of Sn(IV) ions by a potentiostatic electrolysis method was examined. The polarization measurements and potentiostatic electrolyses were carried out under a nitrogen atmosphere. In the Sn(IV) solution, current begins to rise at the cathode potential of -0.26 V vs. SHE, and increases with a reduction in the cathode potential. In the In(III) solution, current begins to rise at a cathode potential of -0.43 V vs. SHE. Metallic tin was electrodeposited without indium electrodeposition at the cathode potentials of -0.30 and -0.40V vs. SHE. More than 98% of the Sn(IV) was removed at the cathode potential of -0.40 V after the electrolysis for 3hrs. Both tin and indium were electrodeposited at the cathode potential of -0.50V vs. SHE.

Jan 1, 2006

By Chao Li, Shuai Wang, Hongxu Li, Lifeng Zhang, Xie Yang

The method of chloride-hypochlorite leaching has the advantages of short process, low pollution and higher in reaction rate compared with the traditional leaching method. In this research, NaCl - NaClO solution is used to leaching gold from a refractory gold concentrate, and the influence of NaCl and NaClO concentration, reaction time to the leaching rate were investigated in this experiment. The raw materials and the leaching residue were characterized by a series of analysis methods such as XRD, XRF, SEM and EDS. Results indicate that the leaching rate and the desulfurization rate can be achieved at 96.26% and 98% with most optimum conditions as follows: NaCl concentration 50g/L, NaClO concentration 200g/L, Liquid-solid ratio 10:1, the best reaction time was 150 mins. And these conditions should be guaranteed pH<8.0, ORP>900mV.

Jan 1, 2015

By Marietta Canty

A paper is presented in which an innovative biological process is described for the treatment of cyanide-, metals-, and nitrate-contaminated mine process water. The technology was tested for its ability to detoxify cyanide and nitrate and immobilize metals in wastewater from agitation cyanide leaching. A pilot-scale demonstration is described in which a pilot plant was constructed to demonstrate the technology on a mine process waste stream at a mine in Nevada. The demonstration was performed Jointly under the Mine Waste Technology Program (MWTP), which is funded by the U.S. Environmental Protection Agency (EPA) and is jointly administered by the U.S. Department of Energy&apos;s (DOE) Western Environmental Technology Office (WETO) and the Superfund Innovative Technology Evaluation (SITE) Demonstration Program under Interagency Agreement Number DW89938513-0 I-0. MSE Technology Applications, Inc. (MSE) located in Butte. Montana, was the contractor responsible for conducting the project, and Pintail Systems, Inc., of Aurora. Colorado, was the technology provider. The pilot-scale unit was field-tested at the Echo Bay McCoy/Cove Mine southwest of Battle Mountain, Nevada. The biotreatment process was considered to be successful in destroying cyanide in the mine process water. The process was also determined to be effective in removing metals. The pH was consistently neutralized, and nitrates were successfully removed from the mine process water. As a result of conducting these pilot-scale tests, the biotreatment process was concluded to be an innovative, cost-effective alternative for the treatment of mining wastewaters.

Jan 1, 1998

By A. A. el-Geassy

High-grade iron ore fines rejected from the DRl plants (>96%Fe20) were isothermally reduced in 30-60%COIH2 gas mixtures at 973-1273K. The freshly reduced reaction products were then subsequently carburised in either H2/CO or H2/CO/S mixtures at 823-1073K for 30-120 min. The thermogarvimetric technique was used to follow up both of reduction and carburisation reactions as a function of time. The carburised samples were characterized by X-ray and Mossbauer techniques. Chemical and carbon analyses were also applied. The influence of temperature and gas composition on the reduction behavior was investigated. The calculated values of apparent activation energy, application of gas-solid mathematical formulations were correlated with the microstructures to predict the reduction mechanism, The influence of carburization time, temperature, CO contents in H2/CO or H2/CO/S were investigated. A conversion extent of Fe to Fe3C was taken as a measurable index for the efficiency of carburization reaction under the different experimental conditions.

Jan 1, 2003