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By Gordon A. Irons

"Powder injection for melt refining is widely practiced in the steel industry, and is gaining acceptance in the non-ferrous industries. In these commercially-important systems, the thermodynamics and kinetics may be very complicated. More than one element may be removed by refining, and often the refining agents are not just one compound. In this paper, the thermodynamic and kinetic aspects of these processes are reviewed. A number of examples are given, such as the desulphurization of iron with a variety of reagent mixtures, and selenium removal from copper with several different reagent combinations.IntroductionI am very pleased and honored to present a paper at this Symposium recognizing the many contributions of Professor Howard Womer. Even at the time I was an undergraduate student, the WORCRA process was part of the curriculum. I remember at the time that I was fascinated by the concept, and due to it and the many other rapid developments in Process Metallurgy, I chose it as my field of study. I think the Symposium is testimony that Professor Womer has touched the lives of many others as well.My original assignment was an overview of the basic aspects of gas and solids injection. However, I reviewed most of this material at the Savard/Lee Symposium [1]. In the present paper, I will present some of the basic issues related to refining with powder injection, using work that we have recently completed in both ferrous and non-ferrous systems."

Jan 1, 1996

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 Mark Kramer

This paper is limited to treatment of bottom and fly ash waste resulting from WTE and RTE Cogeneration plants, commonly known as trash burners. The body of the paper defines waste generation and conventional treatment schemes. This paper does not identify a best treatment, however, it does offer a general perspective of the treatments to lead the reader to further investigation. Advantages and disadvantages of the ash treatments Is discussed in each treatment section.

Jan 1, 1996

By P. Thapliyal

The petroleum refining industry generates over a million tons of spent catalyst per year, containing valuable metals. Currently, these materials are recycled to smelting furnaces, but the fundamental mechanisms controlling the recovery processes are poorly understood. Furthermore, submerged injection of finely divided materials is potentially a means to obtain high recoveries of pay metals. In this study, a catalyst containing 10% Ni and 1% Co was injected into 45 kg heats of matte. A copper matte was chosen so that the nickel and cobalt recoveries were measurable. It was found that the recovery ranged from 40 to 700Al, increasing with catalyst feed rate, decreasing with catalyst particle size and decreasing with the oxygen content of the carrier gas. A mathematical model was developed to account for the results, and to permit extrapolation to nickel mattes. The industrial implications are discussed.

Jan 1, 1996

By Ikuhiro Sumi

A new steelmaking process, in which manganese ore was intentionally reduced, was developed to achieve a higher manganese Yield using a combined blowing converter. In this study, manganese behavior was discussed through the introduction of a model. Apparent reduction rates of manganese were calculated by the two terms that were determined experimentally, with SOkg and 2S0ton combined blowing converters. The model calculated manganese changes during the operation. We applied the model to the actual operation and found that manganese behavior was predicted fairly well by this model.

Jan 1, 1996

By Douglas K. Modrow

In the fall of 1993, construction was completed on a state of the art industrial waste water treatment plant at Asarco's East Helena Lead Smelter. Purpose of the plant was to remove arsenic and metals using hydroxide precipitation. Completing of the plant culminated a lengthy process of laboratory bench-scale test work, engineering, construction, and Environmental Protection Agency (EPA) oversight. Unfortunately, the effiuent requirements for the plant were made significantly more stringent as construction was rearing completion. As a result, optimization activities were initiated to determine and implement measures to substantially improve effiuent quality so the new discharge limits could be met. These activities consisted of acquiring a thorough understanding of process chemistry and plant operations, and developing simple, practical methods of automating unit operations associated with the treatment plant. Implementation of these modifications in the second half of 1996 will not only significantly improve the constancy and reliability of treatment plant operations, but also result in operating cost savings and reduced need for increased operator attention at capacity flows, plus allow the treatment plant to meet the new discharge limits.

Jan 1, 1996

By William Petruk

An investigation was conducted to determine whether mineral liberation data obtained by one image analysis technique are the same as data obtained by another image analysis technique. The liberated vs non-liberated, volume % and weight % techniques for measuring mineral liberations by image analysis were tested. The results show significant differences between the values obtained by the different techniques. The lowest liberation values were obtained by the liberated vs non-liberated technique and highest by the weight % technique. It is interpreted that the weight % technique produces the most realistic results. The weight % technique also produces data that can define mineral associations for the unliberated grains. These include (1) mineral quantities in particles that contain different amounts of unliberated mineral, (2) mineral quantities in particles that have different size ranges, and (3) mineral quantities and degrees of liberation for specific minerals in particles of different size ranges.

Jan 1, 1996

By K. Sanjay

Factorial optimisation technique has been used to develop regression equations at different time intervals for extraction of manganese from precipitated manganese oxide/hydroxide in sulphuric acid using charcoal as the reductant. The three parameters chosen for a 23 full factorial design were : acid concentration, amount of carbon and temperature. The regression equations were used to predict >> 90% extractions as well as kinetic data.

Jan 1, 1996

By Zhenglong Li

A process has been developed to recover titanium from a blast-furnace slag which contains about 20-25% Ti02 and 12% Fe. In this process. "hot" slag from the blast furnace is directed to a separate furnace where it is reheated with additives to form two simple slag phases: one is titanium enriched anosovite (Ti3O5) and the other is a titanium lean non-crystal glass phase. The modified slag is then processed by conventional beneficiation techniques to produce a marketable titanium concentrate and a usable slag material. This paper focus on separating anosovite from glass by electrostatic separation and froth flotation.

Jan 1, 1996

By Rui-Qing Li, John G. Peacey, Peter J. Hancock

"Noranda has been investigating a pyrometallurgical process for the direct recovery of zinc from zinc concentrate and zinc and iron containing residues. The process consists of injecting dry zinc concentrate and secondary zinc materials into a molten iron oxysulphide bath, volatilizing metallic zinc into furnace off gas essentially free of sulphur or S02, fixing sulphur contained in the feed materials as iron oxysulphide matte which is disposed, and recovering metallic zinc in an ISP type lead splash condenser. Combustion of petroleum coke with air or oxygen enriched air inside the oxygen containing matte supplies part of the heat, and the products of combustion dilute the zinc-laden gas to a desired level.This paper describes the process concept, thermodynamic background, experimental tests, mass and heat balance calculation for a conceptual flowsheet, environmental stability of the residue and advantages and disadvantages of the process. Experimental tests have successfully proved the process concept and thermodynamic predictions. Direct smelting of zinc concentrate and residues inside an iron oxysulfide bath has a great potential to become a cost effective and flexible zinc smelting process.1. INTRODUCTIONZinc is mainly produced by a roast-leach-electrowinning process route, which accounts for about 80% of the world primary zinc production. This process produces high quality zinc with very high zinc recovery (>95%) but suffers from several major drawbacks such as using high cost electricity as reductant, producing environmentally problematic iron containing leach residue (jarosite or goethite) and the difficulty in treating secondary zinc feed materials containing high impurity levels, such as electric arc furnace dusts from the steel industry, and other complex sources. Also in some areas, markets for sulphuric acid are distant resulting in negative realizations on acid sales.The Imperial Smelting Furnace (ISF) process is the major pyrometallurgical process to treat zinc-lead concentrate. The advantage of this process over the electrolytic zinc process is its flexibility in treating high-lead, bulk concentrates with high recoveries of lead, copper and precious metals. However, this is a two-stage process involving sintering of Zn-Pb concentrates followed by blast furnace reduction. The process requires large amounts of high-quality coke which is a major operation cost, and the sintering process which results in serious environmental problems."

Jan 1, 1996

By J. F. White

An experimental study was undertaken to evaluate the feasibility of a selective chloridizing roasting pre?treatment process for the elimination of impurities from zinc feed?stocks prior to recovering zinc by conventional unit operations. In this investigation, a number of chemistries that might serve as a basis for such a pre? treatment process were examined. A variety of chloridizing agents were admixed with EAF dust to promote the selective removal of lead and cadmium by the formation of volatile metal chlorides, he results of the experimentation firmly establish that selective chloridizing roasting is a technically feasible means of eliminating lead and cadmium from EAF dust. Excellent extraction efficiencies were accomplished with a number of chloride additives; as high as 98 percent lead extraction and 88 percent cadmium extraction were attained with minimal zinc losses, Continuous pilot?scale tests reinforced the trends established by laboratory?scale experimentation, Attempts of chlorine elimination using pyrohydrolysis were less successful. The extent of chlorine elimination was found to be highly dependent upon EAF dust sample type and treatment temperature.

Jan 1, 1996

By J. Bostjancic

As wastewater discharge regulations become more stringent, power plants, manufacturing plants and other industrial sites are looking for ways to reduce makeup water requirements and to recycle and reuse as much wastewater as possible. In some cases, environmental regulations require zero liquid discharge, meaning all wastewater must either be retained on site or reduced to solids for disposal off site. Zero liquid discharge or "closed-loop" wastewater treatment systems using evaporators and other process equipment have been well-accepted in recent years. Often overlooked is the fact that zero discharge is not just the latest fashion--many commercial zero liquid discharge systems have been in operation since the mid-70's. This paper will give specific examples of zero liquid discharge operations from 1974 to the present, showing how evaporation equipment and processes have changed to meet the requirements of industry and environmental regulations.

Jan 1, 1996

By John L. Watson

The dewatering of steel industry waste sludges prior to discard or recycling often presents significant problems due to the fineness of the sludge particles, which may blind the filter medium and/or produce a cake with limited porosity, Several steel plant wastes, such as sludges from BOF and EAF gas cleaning operations exhibit not only a very fine particle size, but also some degree of magnetic character, A novel process has been developed to utilize the magnetic character of such sludges to enhance dewatering through a multi-force operation involving magnetic, chemical and vacuum forces, The process consists essentially of undertaking vacuum filtration of a flocculated sludge in a magnetic field, This is achieved by installing a permanent magnetic in a fixed position on the axis of a vacuum drum filter, thus effecting filtration of magnetic and non- magnetic particles, bound together in flocs, in a magnetic field, Previous tests using a modified laboratory vacuum drum filter treating artificial (magnetite) and industry waste (BF sludge) feeds have demonstrated that filtration capacity may be enhanced significantly with increases of up to 3000/0, An explanation of the mechanisms associated with the enhanced filtration was not obvious, and this research was undertaken to permit the cake formation in the magnetic field to be monitored to provide an insight into the manner in which particles agglomerate to form the cake. These tests revealed that the magnetic field caused magnetic particles to be aligned perpendicular to the filter surface and to form channels through which filtrate could freely pass thus increasing capacity, The effects of various magnetic fields and field strengths on the filtration process were also investigated. A simple computer model was constructed to demonstrate the proposed theory of multi-force dewatering, The model output graphically illustrated the suggested mechanism and confirmed the enhanced capacity of the novel dewatering process,

Jan 1, 1996

By A. K. Kyllo, G. G. Richards

"The formation and control of accretions is an important aspect of process operation for gas injection. The nature of the accretion formed can have a considerable effect on a process, especially on the life of the lance or the refractories in the tuyere region. There are three basic shapes of accretion formed on tuyeres; pipes, hemispheres and hollow-cored hemispheres. However, there are wide variations within these shapes. Generally, the type of accretion formed will depend on the injector design, certain operating parameters and the physical properties of the bath materials. This paper seeks to collect the results of previous and current physical and mathematical modelling together with data gathered from operating furnaces, to obtain a better understanding of the effects of process design and operating variables on accretion formation.IntroductionAn important consideration in the design of a gas injection process is the possible freezing of the bath either around the tuyere or on the lance. With proper design, freezing may be controlled to provide protection of the lance or refractory, and to avoid blockage. Improper design may lead to tuyere blockage and significant refractory or lance erosion. In view of this, a good understanding of the heat transfer in the injection region is essential.While tuyere blockage has been a persistent problem since the inception of submerged gas injection processes, the problem of accretion formation was not studied in detail until the development of the shrouded tuyere by Savard and Lee. A number of studies relating to accretion formation have been carried out since then, but there is still little information available relating the nature of the accretion formed to the design of the injection system.The build up of materials on lances is a similar problem, and may also be either beneficial or detrimental, depending on circumstances. Unfortunately, there is even less information available regarding build up on lances than there is relating to tuyere accretions. While the form of build up on lances is generally a simple coating of the lance, accretions on tuyeres tend to be more complex. Tuyere accretions tend to occur in one of three basic forms: pipe, hemispherical and hollow-cored hemispherical (Figure 1). However, there appears to be a considerable variation within these forms."

Jan 1, 1996

By D. M. Jones

Dust generation data have been obtained from 19 industrial Outokumpu flash furnaces. Statistical analyses of the data have been carried out and the most significant factors affecting dust generation evaluated. The results indicate that dust production may most effectively be minimized by: 1) Minimizing the distance between the molten slag and the furnace roof 2) Optimizing burner design and combustion parameters.

Jan 1, 1996

By N. B. Gray, I. F. Taylor

"Gas injection to promote chemical reactions or mixing is a feature of many metallurgical processes. Often the aim of gas injection is to bring about a chemical reaction between the gas and liquid but most of the past physical and mathematical modelling work has ignored the influence of such reactions. In the work reported here, cold model studies have been conducted in which gas reacts with the liquid into which it was injected. The rate of liquid mixing has been measured as an indication of the mechanical energy transfer. It has been found that gas generated chemically within the liquid is significantly less effective at promoting mixing than the equivalent volume of inert gas. The relative ineffectiveness of chemically produced gas is thought to be due to smaller bubble sizes in comparison to the inert gas case. Small bubbles characteristic of chemically generated gas move with low slip velocities relative to the liquid and lead to different turbulence generation mechanisms.IntroductionIn processes such as steelmaking, copper conversion, bath smelting and ladle steel finishing gas is injected into liquid metal where it reacts chemically or simply serves as a source of agitation. An understanding of fluid flow phenomena in such situations is an essential pre-requisite to the calculation of process intensity and the optimisation of vessel productivity. Traditional physical cold modelling approaches to prediction of liquid flow in such situations are now often augmented by the techniques of computational fluid dynamics. Even with the availability of numerical modelling techniques cold physical models continue to have an important role for validation because it is generally difficult to obtain quantitative data from high temperature processes.Almost all previous cold modelling work has been based on the injection of an inert gas into water or some other non-reactive liquid. Such models do not include the significant increase in gas volume inherent in some processes. For example the oxidation of carbon in steelmaking leads to a twofold increase in molar gas flux through the reaction:"

Jan 1, 1996

By F. Patisson

During exothermic gas-solid reactions, heat generation makes temperature rise and modifies the rate of the various mass transfer processes, namely the chemical reaction itself, the pore diffusion and the external transfer. We have investigated this thermal effect during the oxidation of zinc sulfide porous pellets in a thermo balance furnace, between 550 and 900°C-and under O2-N2 atmosphere. The results have been' analyzed by using, firstly, the law of additive reaction times derived from the isothermal Grainy Pellet Model, and, secondly, a new numerical model taking into account non-isothermal conditions. Both the models can satisfactorily simulate conversion versus time, but the numerical model also depicts the temperature evolution within the pellet. Finally it is shown that owing to the heat generation the zinc sulfide oxidation takes place under diffusion control (3/4 internal, 114 external) in all the cases studied. During the course of reaction, the. pellet undergoes strong temperature variations, with thermal gradients confined to a shell oxide layer.

Jan 1, 1996

By Guy L. Fredrickson

A modified transpiration reactor was used to measure the composition of the equilibrium gas phase formed above compounds in the Hg-O-S system at high temperatures (600 to 900K). A thermodynamic database {(AGo°f AH°t. AS°t)} for-HgO, HgS, HgSO4, Hg2SO4, HgSO4?HgO, and HgSO4?2HgO was developed based on the experimental results. Prior to this study, only estimated data were available in the literature for the sulfates and oxysulfates at temperatures above 298K. A series of vapor pressure' stability diagrams were constructed from 473 to 973K with isobars of Hg(g), HgO(g), S2(g), and SO3(g). These diagrams were found to be significantly different than those available previously and do provide insight to the phase relations of importance during the thermal processing of Hg-containing wastes. The thermodynamic results were used to conduct a series of Gibbs energy minimization calculations for a thermal processor' afterburner system for the treatment of HgS-containing wastes. The retention of Hg in the discharge calcine was examined as a function of temperature and excess air. Hg was found to report to the calcine as HgSO4, Hg2SO4, or HgSO4 HgO depending on the process conditions, and Hg retention occurs at temperatures as high as 930K. The precipitation of Hg-containing phases from cooled afterburner discharge gas starts at approximately 900K and the cooling of the gas an additional 30K (to 870K) results in over 50% of the Hg being preCipitated as HgS04?HgO. It was also determined that for small amounts of Hg present in sulfide concentrates during roasting, the Hg will be retained as HgSO4 or HgSO4?HgO at temperatures as high as 870K.

Jan 1, 1996

By Rejane Tubino Geyer

The volume of electric arc furnace (EAF) plus oxygen (BOF) slag produced yearly in the world is about 84 million ton. Because of this, the study of recycling processes as a way to solve the storage problem of these slags rise in importance. There are, however, some inconvenients on using this byproduct: lime, which takes part of the process of steel production, remains as a non-reactive raw product in the slag. Since lime reacts in presence of humidity, forming expansive compounds, slag use is strongly limited. There are some utilizations for the electric arc furnace and oxygen slag in the Civil Construction Industry, mainly as base, subbase and asphalt covering in highways. However, independently of the type of recycling, a period of "cure" of about six months is necessary. Because of this slow cure process this byproduct may turn non-competitive in some regions if compared, for example, with the natural aggregate. The objective of this work is to present the flowsheet of the slags production as a residue both at the electric and oxygen steel plants and, through a bibliographic review, to analize the possibilities and limiting factors for the use of steelmaking slags in the Civil Construction Industry.

Jan 1, 1996

By K. Abe

Onahama Smelter has two green-charge reverberatory furnaces and the annual smelting capacity is 600 thousand tons copper concentrate. In addition to the concentrate, various kind of industrial wastes has been processed and utilized. First, the brick waste from converter is ground and used as raw material of castable for repairing the copper melt launders. Second, the slag containing calcium-sulfide from other foundry is fed to the reverberatory furnaces. Calcium sulfide is oxidized to CaO. The melting rate of concentrate is accelenlled and the slag loss is decreased. Third, the tip tire made of waste car tire is charged into the reverberatory furnaces as fuel. The steam of waste heat boiler for turbine generators has been increased so as to decrease the electricity cost. Fourth, the sulfur accretion from other chemical plant is blended into the copper concentrate and the sulfur is recovered as the gypsum for sale. Fifth, the processed waste oil has been utilized in the copper concentrate dryer by which the smelting capacity was increased effectively. Consequently, Onahama smelter contributes to the society by processing the wastes to the harmless slag and utilizing them as fuel through the copper smelting.

Jan 1, 1996