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By Kyong-Hwan Lee

This paper is focused on describing the pilot and demonstration plants for pyrolysis process of mixed plastic wastes developed at Korea Institute of Energy Research (KIER). These plants were constructed at KIER (300 ton/yr) and also Korea R & D Company (3,000 ton/yr) in Kimjae city, in Korea. The raw material used was mixed plastic wastes that were generated from household and industry, etc. The liquid products obtained by pyrolysis at around 400°C were used as an alternative fuel oil. These processes were controlled by automatic control system with continuous operation in a control room. Main process units consist of automatic feeding, melting, thermal cracking systems and vacuum distillation. Their characteristics were automatic pyrolysis operation under vacuum atmospheric pressure, continuous control in feeding of raw material and discharging of solid residue, the recirculation of cracked reactant with a high temperature into the melting reactor and continuous pyrolysis of reactant in circulation thermal cracking system such as constant stirred tank reactor (CSTR), plug flow reactor and light/heavy oil separator, in order to maximize the efficiency of light oil products like kerosene and diesel. In addition, the process performance of pilot plant was described.

Jan 1, 2006

By V. L. Stolyarova

As part of an effort to develop the fluoride electrolysis route for the production of rare earth metals and alloys, a study of the thermodynamic properties of DyF3 has been carried out by Knudsen cell mass spectrometry. A quadrupole mass spectrometer QMS 420 was used in conjunction with the Knudsen cell arrangement. The experiments were carried out in the temperature range 1280-1440 K. Vaporization was carried out from platinum, molybdenum and tantalum cells. The Dy*, DyF+, DyF2+ fragment ions and the DyF3 parent ion were identified in the mass spectrum of the DyF3 vapour. The DyF, vapour pressure was obtained by the complete isothermal vaporizadon method as well as the ion current comparison method, and the enthalpy of sublimation of DyF3 was evaluated. From the DyF3 vapour pressure data obtained at different temperatures, the enthalpies of formation of DyF3 in the gaseous as well as condensed phases have been evaluated. The experimental data are compared with the thermodynamic information available in literature.

Jan 1, 1995

By Ron H. Schonewille

Experiments were conducted by injecting air-oxygen gas mixtures through a ceramic lance into molten copper matte and measuring the sulphur dioxide content of the offgas. The injection conditions were characterized by measuring pressure fluctuations immediately upstream of the lance and capturing the information on an oscilloscope screen. The parameters investigated were gas flowrate, lance geometry, lance immersion, orifice diameter and melt composition. An overhead nitrogen lance was used in specific tests to create an inert gas blanket directly above the bath surface to inhibit reaction in this region. The extent of oxidation was modeled by separating the gas-liquid contact into three stages; bubble growth, bubble rise and bubble rupture. The contribution of each stage to oxygen utilization was determined by varying the lance immersion and by performing tests both with and without an inert gas blanket. Bubble rise was found to be relatively unimportant, accounting for less than 5% of the total oxygen utilization. Bubble rupture and bubble growth were found to contribute approximately equally, with bubble rupture becoming more important with increasing gas flow rate. This study highlights the importance of reactions taking place above the bath surface in a copper converter.

Jan 1, 1999

By David G. Dixon, Ahmad Ghahremaninezhad, Edouard Asselin

"In this study pertaining to the electrochemistry of chalcopyrite, the active/passive behavior of a chalcopyrite electrode in 0.5M sulfuric acid solution was investigated. Potentiostatic and potentiodynamic polarization and multi-cyclic voltanunetry were conducted to analyze the electrodissolution parameters of the electrode.The potentiodynamic and potentiostatic polarizations of chalcopyrite revealed the formation of a passive film on the surface of chalcopyrite. From the potentiostatic study in the passive potential region, a decrease in the dissolution current density by increasing the potential was observed. From this, it was concluded that the passive film is an n-type semiconductor and cation interstitial defects or anion vacancies are the charge carriers. From multi-cyclic voltammetry studies, four cathodic peaks at - 0.37, 0.30, -0.10 and-0.20 YsHE were detected on the surface of a passivated chalcopyrite electrode. The cathodic peaks at 0.37 and 0.30 V were connected to ferric to ferrous reduction and copper sulfide formation, respectively. The peaks at -0.10 and - 0.20 were related to chalcopyrite reduction. The products of the chalcopyrite reduction reactions were suggested to be Cu2S, Cu9fesS16 and Cu5feS4 and evolution of hydrogen sulfide gas (H2S).IntroductionChalcopyrite is the most abundant copper bearing mineral in the world and its dissolution behavior represents the most important technological consideration in the hydrometallurgical extraction of copper [I]. Since the current pyrometallurgical methods for copper extraction from chalcopyrite have environmental issues, many studies have considered the leaching and dissolution of CuFeS2 in different aqueous media [2-5]. The main problem associated with leaching processes is the slow dissolution rate of the mineral [6]. During the dissolution process, increasing the potential of the chalcopyrite in the anodic direction will cause the formation of surface layers which hinder the dissolution rate of the mineral [7]. The precise composition of the layers is in dispute. Previous studies have concluded that these layers could be sulfur [8-9], precipitated iron compounds [8], a solid electrolyte interphase (SEI) - which slows the rate of electron transfer- [10], a metal deficient sulfide [ll], or polysulfidic in nature [12-13]. In order to increase the leaching kinetics of chalcopyrite, the characterization of the layers formed during dissolution is essential and electrochemical methods are important to this end. Studies by Biegler [14] show nucleation and growth of a thin two-dimensional sulfide phase on the surface of chalcopyrite during the exposure of a polished sample in HzS04 solution or air. More studies by Biegler and Swift [15] have shown evidence for nucleation and growth of a 3-dimensional phase at low anodic potentials (around 200 mV vs. OCP). The current-time behavior of the dissolution process in this potential area has the characteristics of expansion and overlap of localized dissolution centers."

Jan 1, 2012

By K. Noda

Tamano Smelter of Hibi Kyodo Smelting Co., Ltd. is carrying out a low cost production using a Tamano Type Flash Smelting Furnace (T-FSF), which is an improved version of Outokumpu Type Flash Smelting Furnace but without slag cleaning furnace and also by developing its own coke combustion technology. Coke combustion technology that is the basis of the system has been improved several times and, at present, it has evolved to a stage where it can be reproduced on the Computer guided system for Coke Combustion in the T-FSF (CCCT) using a general- purpose computer. This CCCT is featured by 'its trend control and predicting function, and an operator can freely control the operation parameters so as to control the operation flexibly. We have recently developed an overall energy reduction system covering the Smelting Plant to Sulfuric Acid Plant, which we call an Optimum Low Cost Operation System (OLCO) to reconsider the energy costs including coke, heavy fuel oil, and electric power. In this report, we would like to present the recent operation of T-FSF based on CCCT as well as the optimum energy operation utilizing OLCO system.

Jan 1, 2002

By Donald O. Voit

A BASIC language program has been written that simulates the performance of an integrated solvent extraction circuit consisting of an extractor, a reflux fed scrubber, and a stripper. The program is designed to simulate the performance of a circuit having an aqueous feed containing each of the lanthanides as well as yttrium. The Kremser equation is used to determine the separation occuring in each section of the circuit. The required input variables are the feed composition, the separation factors, the light key extraction factors and extractor feed zone distribution coefficient, the number of stages, and the reflux ratios. The program calculates the composition of the streams at each node in the circuit, the total loading, and the remaining distribution coefficients. User interaction with the program is essential. The program has no capability to determine if the calculated values are consistent with various real restraints. Knowledge of the physical, chemical, and equilibrium behavior is essential to successfully utilize the program. The number of iterations required to achieve steady-state provides insight to the circuit response times. With suitable supervision the program can be used as a simulator for operator training.

Jan 1, 1989

By Damien Wagner

To reduce the emission of greenhouse gases by the steel industry, particularly for ironmaking, the production of DRI (Direct Reduced Iron) using hydrogen as the reducing gas instead of carbon monoxide is being considered. In this context, the reduction of pure hematite by hydrogen was studied at the laboratory scale, varying the experimental conditions and observing the rate and the course of the reaction. All the reduction experiments were performed in a thermobalance and supplementary characterization methods were used like scanning and transmission electron microscopy, X-ray diffraction, and Mössbauer spectrometry. The influence of rising temperature in the range 550-900°C is to accelerate the reaction; no slowing down was observed, contrary to some literature conclusions. A series of experiments consisted in interrupting the runs before complete conversion, thus enabling the characterization of partially reduced samples. Interpretation confirms the occurrence of three successive and rather separate reduction steps, through magnetite and wustite to iron, and illustrates a clear structural evolution of the samples. Finally, the influence of the sample type was revealed comparing a regular powder, a nanopowder and a sintered sample. The regular powder proved to be the most reactive despite its larger grain size, due to a more porous final structure.

Jan 1, 2006

By S. C. Grand, T. J. Auping, K. Born

Process control, environmental monitoring, budgeting and accounting are based on process data. Without appropriate tools for data analysis, the process data could remain unused and wasted. This paper demonstrates how data reconciliation can be used as a tool to develop closed mass balances. Mass balances are the initial step in plant optimisation (technical, economical or environmental). From mass balances, fundamental process models can be developed. These balances link process parameters (e.g., feed materials) to process performance (e.g., recovery of valuable elements). Some of these models could find their way into simulators useful to plant operators. Classical regression methods regularly fail when they are applied to complex non-linear problems involving a large number of variables. Alternatively, multiparametrical regression analysis can be successfully applied with the aid of neural networks based on reconciled data. Both methods have been applied to plant data originating from the hydrometallurgical zinc plant at Ruhr-Zink, which in this paper serves as a case study. Very promising and useful results were obtained from this study.

Jan 1, 2000

By Rainer Köster, Tobias Wagner, Markus Delay, Fritz Hartmann Frimmel, Wolfgang Ferstl, Wolfgang Höll

"The mobilization of contaminants from industrial residues like ashes from municipal solid waste incinerators in case of leaching is investigated world wide. In classical leach tests only soluble species are considered. In addition the geochemical behaviour of residues has to be completed by assessing the mobilization via colloidal particles. This transport is well known from natural aquatic systems. Quantification of aquatic colloids is associated with considerable difficulties, because they are often found in low concentrations and in a size distribution where small particles with diameters below 0.1 µm predominate. In the past years, the Laser-induced Breakdown Detection (LIBD) has been developed as a novel sensitive method for quantifying colloids. Column leaching experiments with directly coupled LIBD were used to quantify the release of heavy metals and colloids out of bottom ashes. Some typical colloid bound heavy metal concentrations in the leachate are in some cases exceeding the limits defined by German authorities. The LIBD with a flow-through cell allowed to assign absolute values to colloid size and concentration."

Jan 1, 2008

By Lanre Oshinowo

The trend in process engineering is to design compact, more efficient processes, there is the paramount requirement to get the job done right the first time going from the drawing board to full-scale commercial operation. To accomplish this goal, there is also the need for tools beyond the traditional engineering toolkit to evaluate designs through virtual prototyping, thereby reducing the risks associated with making design decisions. One of the most important tools that has recently come to the forefront of process design and development is Computational Fluid Dynamics (CFD). CFD has been used at HATCH to address the key process parameters that drive the design of hydrometallurgical unit operations. This paper will detail the role of CFD at HATCH in achieving a superior level of confidence in the process design of autoclave circuits. Specifically, the optimum application of multiphase modeling including hydrodynamic, heat and mass transfer to hydrometallurgy operations, the impact of non-Newtonian slurry rheology on autoclave performance, and the challenges of optimizing the mixing of key reactants into slurries in autoclave reactors, is discussed.

Jan 1, 2003

By John E. Dutrizac, Tzong T. Chen

"Laboratory experiments were undertaken to ascertain the behaviour of various ""impurity"" species during the precipitation of hematite directly from ferric sulphate solutions at 225°C and in the presence of 40 or 50 g/L of hematite seed. Copper, nickel and zinc are not significantly incorporated in hematite precipitates. Although the nickel contents increase to 0.22% as the Ni concentration increases to 60 g/L, the solid solution Ni contents are low relative to the bulk Ni contents. Thus, part of the Ni may be present as tiny particles of poorly soluble NiS04.H20. Increasing germanium concentrations to 2,000 mg/L result in products containing up to 0.59% Ge. The Ge occurs either in solid solution in the hematite or is adsorbed on the nanometer-size hematite crystallites. Increasing As(V) concentrations to 10 g/L increase the AsO4 contents of the products up to 16%. However, the products consist of hematite together with As04-containing Fe(SO4)(OH) and an unknown Fe-AsO4 species. All the hematite products contain - 1% SO4 which appears to be adsorbed on the nanometer-size hematite crystallites.IntroductionDissolved iron is a common impurity in most hydrometallurgical processing circuits and, generally, the iron must be eliminated prior to the subsequent recovery of the sought after metals. Simple neutralization of iron-rich solutions yields slurries which are difficult to thicken and filter. To address these concerns, the jarosite, goethite and hematite processes have been developed, and these technologies are able to reject the dissolved iron in a readily filterable form [1]. Despite its higher cost, the hematite process offers several potential advantages. Because hematite is an iron-rich, high-density compound, its formation would reduce the mass of residue and the size of a residue storage pond. Hematite is the thermodynamically stable form of iron under ambient conditions, and this stability would facilitate the impoundment of hematite precipitates. Furthermore, hematite has some market potential for cement manufacture and even for iron making [2]. In all the commercial hematite processes, the dissolved ferric ions are first reduced to the ferrous state. Subsequently, the pH of the solution is adjusted and the solution is then oxidized. The ferric ions gradually generated during solution oxidation hydrolyze and precipitate mostly as hematite, although commercial hematite products also contain trace or minor amounts of jarosite-type compounds. However, there are potential advantages in precipitating hematite directly from ferric ion solutions, as the reduction and subsequent oxidation of the iron are not required. Although the precipitation of hematite directly from relatively concentrated ferric sulphate solutions (up to 0.5 M Fe(SO4)is) was recently demonstrated [3], the behaviour of impurity species during hematite precipitation is largely unknown. To address this issue, systematic laboratory experiments were undertaken to ascertain the behaviour of a number of ""impurity"" species during the precipitation of hematite directly from ferric sulphate solutions at 225°C, and the results are presented in this paper."

Jan 1, 2012

By E. J. Peuraniemi

Recently commissioned Kennecott-Outokumpu flash converting was developed to replace the approved but environmentally outdated Peirce-Smith -converting to satisfy the globally tightening emission regulations. In the present study, dust formation and reaction mechanisms of two copper mattes with different experimental parameters were studied in lean suspension conditions. Both mattes had very high copper content of approximately 75 wt% and low iron content of 4.5 wt% and 1.2 wt% Fe. A laboratory scale, vertical laminar-flow furnace with a low feeding rate was used to simulate the phenomena taking place in the reaction shaft of a flash converter. Experimental conditions included temperature of 1300 °C with reaction gas oxygen contents of 20 vol%, 50 vol%, and 75 vol%. In the experiments, sieved particle fractions were fed to the furnace and sampled after short reaction time intervals by quenching them into a water film. Collected particles were analysed chemically for their main elements to define their removal rates. Also, optical and scanning electron microscopy with EDS-analyser were applied to determine phenomena occurring during reactions. Kinetics of oxidation as well as ignition of particles are discussed. Changes in particle morphology, size, and composition are reviewed to describe dust formation and reaction mechanisms.

Jan 1, 1999

By Jeaneth S. Benedetto

The physical and chemical processes developed for recovery of uranium and phosphor from phosphoro-uraniferous ore bodies consists of three basic steps: concentration of the phosphate bearing uranium by flotation, chemical dissolution of the concentrate by wet phosphoric acid and extraction of uranium by solvent. In this process two products are obtained: 1) uranium and 2) phosphoric acid. The purpose of this work was to develop technological know-how of phosphoric acid purification though an extraction of P2O5 by solvents. It was investigated by two lines of research. In the first one the uranium was extracted before the phosphoric acid purification. In the second, the phosphoric acid was extracted before uranium recovery. The comparison of the two processes is shown in this paper. Experimental work was developed on a laboratory scale to select and optimize the process variables. After the laboratory study, the research of extraction and stripping was continued on a pilot scale in pulsed perforated-plate columns in order to investigate the main operational and process conditions. The first phosphoric acid extraction experiments showed good results using a raffinate sample obtained from the uranium extraction process. It was possible to obtain a high purity phosphoric acid.

Jan 1, 2003

By Pekka Taskinen, Hannu Johto

"Copper sulfide concentrates often contain impurities such as lead and iron. The phase stabilities of the sulfide impurity systems in metallurgical process conditions are in many cases unsatisfactorily known. Thermodynamic information of a system gives better understanding of its behavior of metal making processes, but also has effects on the economic and environmental factors of the production process. In this study, isothermal equilibrium and quenching experiments of the stable phases of the system Cu2S-FeS-PbS at 700 and 900 °C were carried out and based on the experimental results, Gibbs triangle of equilibrium phases of the system was outlined.IntroductionThe knowledge of stabilities of phases and the thermodynamic properties of many sulfide systems in the temperature range of 500-1200 °C are quite limited. Especially, the knowledge of liquidus surfaces of multicomponent sulfide systems is essential for making many metallurgical processes more environmental friendly and allowing the utilization of complex concentrates. In this work, the aim was to investigate the phase stabilities of the quasiternary system CU2SFeS- PbS using evacuated silica ampoules. Of greatest interest were the properties of the liquidus surface in the system, in order to be able to predict better the formation of a liquid phase in metallurgical processes."

Jan 1, 2012

By Peter G. Smith

Tri-calcium aluminate (TCA) is a dominant alkaline component of the red mud residue from the Bayer process. A method being considered for industrial implementation partially neutralizes the residue by contacting it with gaseous CO2. This paper outlines the chemistry of CO2neutralisation of TCA under conditions relevant to the treatment of Bayer residue. CO2 neutralisation of the liquor is fast. It results in the formation of amorphous aluminium hydroxide and dawsonite that agglomerate together. Neutralisation of solid TCA is slower and leads to the formation of calcite, dawsonite and amorphous aluminium hydroxide. The dissolution of TCA in partially neutralised slurries causes pH reversion. However the carbonated solutions contain a store of bicarbonate that can supply aqueous carbon dioxide to complete the transformation. The pH at which the carbonation is carried out will affect the degree of TCA transformation during the carbonation process. In particular, if the pH of the carbonation is too low (near 7.0), calcite precipitation is inhibited and the degree of transformation is low. Controlling the carbonation pH helps to optimise the neutralisation process.

Jan 1, 2003

By Yoshio Waseda

A laser flash method has been applied to obtain the thermal diffusivity values of Zr55Al10Ni5Cu30 alloy in the liquid, glassy, crystallized and supercooled liquid states. The electrical resistivity of this particular alloy was measured in the glassy, and crystallized states by a direct current four probe technique. A specific heat of Zr55Al10Ni5Cu30 alloy was also determined by a differential scanning calorimeter in the glassy state. On the other hand, thermal diffusivity values for two alloys of Zr60Al15Ni25 and Zr65Al7.5Cu27.5 were measured in the crystallized and liquid states. The thermal diffusivity values of three Zr-based alloys in the liquid state are summarized in the linear equations with positive temperature dependency and it is noted that the lower the thermal diffusivity values of Zr-based alloys at liquidus temperature, the lower the critical cooling rate to obtain metallic glass phase becomes. The thermal diffusivity values of Zr-based alloys were compared with those of Pd-based alloy case. These results suggest that thermal diffusivity of alloy liquids might be an indicator of the glass-forming ability of Zr-based and Pd-based alloys.

Jan 1, 2006

By Teruo Tanabe

The hydrogen-absorbing materials are expected to have the following properties at moderate conditions, (a) a large capacity of hydrogen absorption, (b) the absorption rate of hydrogen is large and (c) hydrogen-absorbed materials can easily desorb hydrogen. Thus the three concepts of capacity, rate and reversibility seem to be indispensable to clarify the mechanism of hydrogen absorption by the materials. In this work, the amount of absorbed hydrogen, the absorption rate and the reversibility of hydrogen absorption- desorption reaction were measured for binary R-M systems (R = Y, La, Ce; M = Co, Ni). These experimental results were discussed by the following three physical properties that were calculated by the extended Hückel method, i.e. the density of states unoccupied by electrons, the cohesive energy and the energy fluctuation. The major results are as follows: (a) the amount of absorbed hydrogen increases with the density of states in the energy range between -9 and -4 eV, (b) the R-M compounds of which energy fluctuations are large show a large value of rate of hydrogen absorption, and (c) when the cohesive energy is large, the compound has a tendency not to easily desorb hydrogen, i.e. its reversibility is poor.

Jan 1, 2006

By R. D. MacDonald

The papers presented in this chapter cover a wide range of hydrometallurgical topics and might be considered to be unrelated to each other. All of the authors, however, utilized the basic methods of process mineralogy to characterize the reactants in their experiments and the products produced. The wide range of research topics which can be pursued successfully by the use of the methods of process mineralogy is a matter of interest in itself. One might speculate that the methods could be even more widely applied if only their utility were better recognized. These methods for characterizing reactants and products include principally x-ray diffraction, optical micros-copy, wet chemical analyses, instrumental chemical analyses, high intensity magnetic separation, micro-scale gravity separation, differential thermal analysis, micro-hardness testing, and judicious use of the sledgehammer and cold chisel. It is perhaps not by coincidence that most of the papers in this chapter were prepared not by mineralogists, but by hydrometallurgists, who are recognizing the importance of thinking in terms of mineral phases, and not just assays! It appears that the gap between process mineralogy and the mineral industry is closing, and that future AIME sessions promise to become established forums where mutual discussion of such topics as metallurgical "troubleshooting" and process design may become commonplace between plant engineer and process mineralogist.

Jan 1, 1981

By Yong Hack Lee

Electric Arc Furnace (EAF) dust is generated when scraps are treated in the electric arc furnace and usually classified as hazardous industrial waste in most countries. EAF dust usually contains 15 to 25% of zinc and 3% of lead. It is usually treated in rotary kiln (Waelz process) or landfilled after a solidification and stabilization treatment. Numerous methods have been proposed as the EAF dust treatment technology, but few of them are in operation as a commercial scale except the Waelz process. Korea Zinc performed a plant test in which 600 tons of EAF dust was treated using TSL (Top Submerged Lance) technology. The TSL technology is a low cost, proven technology for processing zinc-bearing residues. The EAF dust was first de-chlorinated and fed to the TSL furnace. Finally, clean slag satisfying toxicity criteria was generated and valuable metals such as zinc and lead were recovered as fume oxide. The fume oxide was de-halogenated by sodium carbonate and sent to zinc refinery to recover zinc and lead. The recovery of zinc and lead was 90% and 93%, respectively. Most of the dioxin in the EAF dust was discomposed so dioxin less than the Korean regulation limit was detected in the offgas, which proves that the TSL technology is the best solution to treat EAF dust.

Jan 1, 2006

Plastics recycling has become an established national industry in Korea. However, it is still in its infant stage and experiences growing pains. In Korea, mixed plastic wastes generated from households after hand picking and/or mechanical sorting processes amount to 1,700,000 ton per year in 2005, and most of these waste are finally end up with landfill and/or incineration due to lacks of separation technologies and economical reasons. These plastic wastes can not be used as raw materials for chemical and/or thermal recycling because of their high content of PVC (upto 4.0 wt.%). In the present work, gravity separation system has been developed to remove PVC from the mixed plastic waste and recover the individual plastics. The separation system mainly consists of air classification, crushing, feeding system at fixed rate and wet-type gravity separation system. The gravity system based on centrifugal separation also consists of mixing, precleaning, separation, dewatering, recovery system, wastewater treatment system, etc. The main objective of this process to be developed is to achieve high separation efficiency of polyolefins (PE, PP, PS) with less than 0.3 wt.% PVC content and less than 10% moisture content in the final products. The system with a capacity of 0.5 ton per hour is developed and operational results are presented.

Jan 1, 2006