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By Steven M. Puricelli

Sulfuric acid plants associated with smelters, have historically been an overworked and often neglected pollution control device. They could do little more than manage the wide fluctuations in gas flow and SO2 strength from the smelter. With the introduction of flash smelting, the picture began to change, but the fluctuating batch converters continued to dictate acid plant design. More recently, the commercial use of continuous converting processes utilizing high levels of oxygen enrichment has dramatically upgraded the SO2 strength and stabilized the gas flow to the acid plant. The SO2 gas now issues continuously and at concentrations that allow for compact and, cost effective acid plants. Relieved of the burden of excessive dilution air, the heats of reaction can also be recovered as medium pressure steam and used to drive a generator, making the acid plant a net producer of power and a valuable asset to balance sheets. This concept was put into practice at the Kennecott Utah Copper Corporation smelter modernization project, located in Salt Lake City, Utah. The new acid plant, which was commissioned in June of 1995, is a sophisticated, low environmental impact, energy producing plant, worthy of review. This paper examines the key features of this acid plant, such as controlling its tail gas, by catalysis alone, to an environmentally friendly, 100 ppm of SO2, while feeding the acid plant converter with an efficient 14% SO2. The acid plant is also a prudent steward of energy resources, recovering 220,000 lb/hr of 140 psig steam from process heat which is used to generate a substantial 20 MW of gross power. Also discussed will be some of the ongoing issues, such as handling of selenium and fluorine in the gas cleaning sections, as well as a review of some. of the problems that were identified and resolved. Today's modem acid plants, by necessity, are becoming a producer of quality, valuable products, making the acid plant an asset and not a liability. Plants like Kennecott are already gaining wider acceptance and are expected to be the vision of the future.

Jan 1, 1998

By Jing Zhang, Qing Xiao, Xulong Liu, Qiuju Li

"Pickling sludge generated from stainless steel production process contains large quantity of Cr, Ni, and Fe. The disposal of and fill sludge directly not only leads to the heavy metal dissolves in the soil and underwater, but also loss value metals. However, the major mineral phases of value metal are hydroxides and there are lots of calcium fluoride and water in the sludge. So the pickling sludge has to be pretreated before reduction-magnetic separation. The TG analysis, reduction reaction and magnetic separation were all used to study the pickling sludge. The result indicated that up to 900°C the total weight loss of pickling sludge was 22.32%. The mass contents of Fe, Cr and Ni in the tailings (non-magnetic) were 4.27%, 0.067% and 0.041% respectively.IntroductionSince 21st century, the stainless steel production in the world has been continuously increasing because of its excellent performance [1]. However, high stainless steel production means a high pickling sludge production. For example, in a stainless steel plant with waste water quantity of 100m3 /h, the production of pickling sludge will exceed 15 Kt/a. Pickling is essential for generating of a homogeneous and corrosion-resistant surface during stainless steel production subsequent process. Pickling of stainless steels is predominantly carried out with an aggressive solution, sulfuric acid H2S04 or composed of nitric acid HN03 and hydrofluoric acid HF [2]. During the pickling process, the pickling acids are recovered through ion exchange and metal ions such as Fe3+, Cr3+ and Ni2+ get into the acids forming the pickling waste water [3]. Then, the pickling waste water is precipitated with lime, forming pickling hydroxide sludge. It is not feasible to recycle or treat the pickling sludge using conventional methods, because the sludge has high contents of calcium fluoride and water but low contents of iron, chromium and nickel. However, it would also pose a potential environmental problem if deposited outdoors over a long term because it contains heavy metals such as Cr and Ni. At present, solidification/stabilization (S/"

Jan 1, 2014

By M. Goto, T., Matsutani, T. Igarashi

"PT. Smelting was established in February 1996 as a company to· construct the first copper Smelter and Refinery in Indonesia with US$500 million direct construction cost and operate it. The plant is located in Gresik, East Java, Indonesia and 20km northwest from Surabaya, 2nd largest city in Indonesia. The site was selected due to following .advantages.1. Adjacent PT: Petrokimia Gresik, - a fertilizer company, purchases all sulfuric acid produced through pipeline.2. Facing on the seashore of the Madura Strait, it is possible to unload copper concentrate from West Papua (3,000km from Gresik) and load granulated slag to the market.3. Close to the good harbor facilities at Surabaya for export the products.4. Gresik Industrial Area has adequate infrastructure.5. Surabaya is a quite nice city to live for people from abroad.The shareholder of PT. Smelting are Mitsubishi Materials Corporation (60.5%), PT. Freeport Indonesia (25:0%), Mitsubishi Corporation (9.5%) and Nippon Mining and Metals Co. Ltd. (4.5%).The Gresik Copper Smelter and Refinery is designed to produce 200,000 tpy of copper cathode from 660,000 tpy of copper concentrates supplied 100% by 'Grasberg Mine of PT. Freeport, Indonesia in West Papua (former Irian Jaya). Other by products are 600,000 tpy of sulfuric acid, 30,000 tpy of gypsum, 509 tpy of precious metal slime and 400,000 tpy of granulated slag. These are sold to domestic and international markets.This project adopted the Mitsubishi Continuous Copper Smelting and Converting Process in the Smelter for anode casting, Contilanod process comprising Hazelett twin belt caster and a Mannesmann's travelling shear were selected. ISA stainless steel cathode process is applied in refinery. The combination of contilanod anode and stainless steel cathode ensured good cathode quality from the very beginning of start-up SO2 gas generated from Smelter is treated by Lurgi-Mitsubishi double contact/absorption acid plant. All contact. wastewater from the plant is treated in multistage wastewater treatment plant.Electricity and oxygen are ·supplied ""over the fence"" by a company which is located in the site of the Gresik Smelter and Refinery."

Jan 1, 2000

By Gabriel Riveros

Fire refining of copper consists of two stages copper oxidation and copper reduction. Very frequently the capacity of the anode furnace is determined by the rate of copper reduction, The analysis of factors affecting the rate of the oxygen reduction from a liquid copper with solid carbon or injected hydrocarbons pointed out the role of the mass transfer in a liquid copper in final stage of the reduction. Experimental results of copper reduction with graphite and injected natural gas in laboratory-scale crucibles showed two stages of the reduction process with a sharp change of the controlling mechanism. The estimated dynamic surface area of gas bubbles based on the measured bubble frequency and the gas flowrate allowed for the determination of the reaction constant as a degree of the partial pre-combustion of the air/natural gas mix. The variation of the used reductant as a function of the oxygen concentration and temperature has been evaluated based on the determined kinetic model. The intensification of copper reduction in fire refining has been discusses on the basis of obtained kinetic data and analysis of various factors determining the time of reduction.

Jan 1, 2003

By John A. Vallomy

"The CONSTEEL Process introduces a new concept in electric steelmaking by continuously feeding-preheating-melting and refining ferrous scrap or direct reduced iron. The process uses the furnace off-gas and fuel to preheat the scrap in a specially designed preheater. Thermal incineration of the flue gas reduces the carbon monoxide level to the more stringent requirements. Hot water or steam production from heat of flue gas is optional. The tap-to-tap time is set to match the cycle of the caster. The steel is treated via ladle metallurgy. The environment inside and outside of the steelplant is improved by decreasing levels of noise and hazardous emissions. Energy consumption decreases and disturbance to the electric network is eliminated. A CONSTEEL prototype was tested at Nucor Steel, Darlington, SC. A greenfield project is in the completion stage at the Florida Steel plant of Charlotte, NC, USA. The Process PhilosophyThe philosophy of the CONSTEEL Process is not solely to enhance efficiency; this was just a natural result of the change from a batch to a continuous practice. The primary objective in development was four-fold:1) 100% process control2) Rational use of available energy3) Improved environment inside and outside the plant4) Stability of energy input from the power systemIt was to make electric steelmaking more a science than an art and amenable to modern automation.The Basic Concept of CONSTEELThe concept of the process is shown in figure and includes basically a continuous feeding system, a preheater and a melting - refining furnace. A pre-established amount of heat is introduced into the scrap while traveling through the preheater using the sensible and chemical heat contained in the furnace off-gas and additional fuel. Melting-refining is carried out in the electric furnace. Slag formers, slag foaming additions and oxygen are injected to refine the melted steel continuously, to minimize the refractory erosion, to shield the arc, thus optimizing the transfer to the metal bath of the heat generated in the arc, to keep the bath homogeneous in composition and temperature and to produce carbon monoxide (CO) which is fuel for the preheater."

Jan 1, 1988

By Mark Tjerkstra

In ,1993, the WMC Resources Ltd.-owned Kalgoorlie Nickel Smelter, underwent a capacity upgrade. This capacity increase was offset by .air quality control restrictions limiting the smelter's availability to 80%. As the direct. result of this limitation, WMC Resources Ltd commissioned a double absorption contact ,acid ,plant for the desulphurisation of furnace waste gas in August 1996. The history and the impact of the acid plant on S02 emissions and air quality is reviewed. General descriptions of the other aspects of the Kalgoorlie Nickel Smelter's Environmental Project are also included in the paper. Information on 'the design features? and operating practices that relate to or contrast with practices at operations visited by KNS personnel prior to acid plant commissioning provide the paper's focus. Smelter operation has changed markedly from unstable operation prior to 1997 to continuous" operation with little down time due to mechanical or process failures resulting in increased smelter availability to more than 90%

Jan 1, 1998

By Andrey V. Tarasov

To carry out a physicochemical substantiation of a transition to ?soft? modes of reduction of calcine obtained by desulfurizing roasting of nickel concentrate produced as a result of copper-nickel converter matte separation in a nickel anode production circuit, an analysis has been conducted of the macrokinetic behavior of actual calcine samples in the presence of gaseous H2-CO mixtures and solid reductant additives. Within a temperature range of 900°C to 1100°C the main regularities typical of the calcine reduction process with individual gases (H2, CO) also take place when using a gaseous mixture. Under the conditions of low-temperature (900°C to 1000°C) nickel oxide reduction with products of fuel oil conversion in the presence of coke, the role of the latter is insignificant from the technological viewpoint. As a result of the present investigations, we have obtained analytical expressions of macrokinetic parameters of the reaction interaction within the [NiO] calcine-H2-CO-C-CO2-H2O-O2-N2 system.

Jan 1, 2005

By Jay. M. Khodadadi, Josef Štetina, František Kavicka

"With the aid of the proper original numerical model of solidification the instruction for preparation of input parameters for numerical simulation of technological processes, with change of the phase or structure, will be presented. A method of calculation analysis of influence of therrpophysical properties of materials entering the system of casting-mould-cores environment, and also of boundary conditions on the required simulation accuracy will be suggested. For the cast material, the influence of heat .conductivity, specific heat capacity, density and latent heat of phase transformation also has been analysed. For metallic or non-metallic moulding material"" the influence of the see main parameters has been analysed and, furthermore, their combination, influence of thermal conductivity, and of heat storage. The order of influence of all quoted parameters of a casting and moulding material was established. For example heat conductivity in the liquid state is on the last place. From the boundary conditions the -most important influence on the total solidification time and · on the mechanism of forming of temperature field has the ·boundary condition on the casting mould boundary, then follows the boundary condition on the level of a molten metal. The negligible influence has the boundary condition on the mould frame and on the bottom.IntroductionThe original and universal mathematical model of solidification, cooling and heating has been set up and checked, in order to be capable of analysing a one- to three-dimensional steady or unsteady temperature field of the casting-mould-environment system and, namely, of the system as a whole or its arbitrary parts, during any industrial technological process whose individual processes could be solidification, cooling, heating, refrigeration and others, in any sequence or singly. The model enables the simulation of traditional and also non-traditional technologies of casting in foundries, metallurgical plants, forging operations, heat treatment processes, etc. If solidification is not the matter, the metal part of the system need not be called the casting but a component, a block, a forging and the like."

Jan 1, 2000

By Ramana G. Reddy

Thermodynamic modeling and experimental study on impurity capacities and their distribution between mattes or metal and slags in smelting, converting and refining of non-ferrous metals was discussed. A brief review on the recent developments in copper smelting and converting is presented. The analysis showed that, copper smelting capacity increased by a factor of 10 since 60's, smelting rate increased by a factor of more than 5 and process fuel equivalent decreased by a factor of 2. A thermodynamic model for prediction of impurities capacities in slags and their distribution in mattes and slags was developed. The impurities capacities (i.e. sulfur and arsenic) of slags were calculated a priori with no adjustable parameters using the Reddy-Blander model. The capacities predictions were made in a wide range of matte and slag compositions, PSo, and temperatures in conditions pertaining to copper and lead industrial slags. The calculated results for sulfide and arsenate capacities are in good agreement with the available experimental and industrial copper and lead industrial slags data. The sulfide and arsenate capacities in copper slags (fayalite, ferrite and olivine) and lead slags are reviewed. The application of RB model predicted ratios of O2 and S2 partial pressures in industrial copper smelting processes are discussed. Application of this model for the prediction of Sb, Bi and other impurity capacities and their distribution ratios in mattes or metal and slags, in industrial smelting and refining processes is discussed.

Jan 1, 2003

By Albert Wraith, Thomas Price, Wayne Boyd, Skip (I. E. ) Hills, Cameron Harris

Most Peirce-Smith converters inject air through tuyeres, with nitrogen representing the majority of gas passing through the process. The nitrogen controls the temperature of the vessel by carrying away heat from the reactions, both globally and locally at the tuyere tip. However, nitrogen adds energy to the bath and contributes to splashing and limits the blowing rate. High oxygen smelting has made streams of gas containing high concentrations of sulphur dioxide commonplace, which can be used to substitute SO2 for nitrogen and drastically changes Peirce- Smith converting (and all other smelting/converting processes as well). Less SO2 is required to carry away the same quantity of heat, which allows higher concentrations of oxygen and leads to the possibility of increased production. The paper investigates this substitution, its impact on converter productivity, and on the remainder of the plant. 181

Jan 1, 2009

By C. B. Solnordal, R. N. Taylor

"The heat transfer conditions on the outer side of a Sirosmelt lance have been determined using experimental measurements in combination with a mathematical model. By measuring the temperature distribution along the wall of an operating Sirosmelt lance, as well as the thickness of the slag layer on it, it was possible to use the model to determine both the heat transfer coefficient between the vessel contents and the lance, as well as the effective thermal conductivity of the slag layer. The effective thermal conductivity of the slag layer was found to be within the range 0.7-1.3 W.m-1. ºCl, which was in good agreement with measured values for magnetite. The outside heat transfer coefficient varied from 80 to ISO W.m-2. ºC1, which was smaller than quoted in the literature for metal/slag systems. The discrepancy was attributed to the high thermal resistance experienced between the lance wall and the slag layer, as well as the large quantities of combustion gases that envelop the lance tip and reduce convection and conduction from the melt to the lance. INTRODUCTIONThe Sirosmelt submerged combustion smelting process [1] utilizes top injection lances to deliver fuel and air into a metallurgical melt. To help prevent lance failure from attack by liquid slag, helical vane swirlers are used within the annular lance to impart swirl to the flowing air and enhance the heat transfer from the lance wall to the air. The swirlers thus cool the wall, and enable a frozen layer of slag to form on its outer surface. This solid layer ensures liquid slag cannot reach the lance surface, and the lance is protected.A mathematical model of the heat transfer processes associated with the lance has been developed, which combines heat balance equations with engineering correlations to predict the wall and cooling air temperature of the lance, as well as the air pressure distribution. An account of the model was given by Rankin et al. [2]. To further enhance the model and enable it to predict the thickness of slag accumulating on the lance, a detailed analysis of the heat flow through the slag layer commenced in 1992. By far the most complex aspect of the model, the flow of heat from the vessel contents to the outside of the lance was dependent on many factors, including:-"

Jan 1, 1996

By David Cocke

Study of surface and subsurface interfacial chemistry of metallic and similar systems has its enormous technological importance. Copper, for example, is a common component of many alloys and bulk amorphous systems. It is being increasingly studied today because of its use for electronic interconnect systems where processing is done below 200 ºC. Since several types of copper oxides exist, and the degree of their formation is dependent on temperature, perhaps characterization by EDS-SEM depth profiling and EIS might delineate one type of oxide from another. In this paper, we described our work on transformation of copper oxides with temperature ranging from 70 to 350 °C and their characterization by SEM, EDS, and XRD. We also showed the use of the phase angle portion of the impedance as a means to identify the predominant structure and the transition through Cu3O2 between the predominant stable CuO and Cu2O.

Jan 1, 2009

At its Copper Cliff Smelter, Inco Limited processes a bulk copper-nickel concentrate in two Inco oxygen flash furnaces. The furnace matte is converted to low iron matte for further processing, and the molten converter slag is recycled to the flash furnaces. The flash furnace slag is discarded. Natural gas or coke supplies a minor proportion of the process heat requirements, thus limiting the flash furnace matte grade to the target 45% CuNiCo. Coke addition to the furnace offers a potential means of establishing a reducing barrier on the surface of the molten bath. Such a practice would be conducive to producing sulfur deficient (partially metallized) matte. At the same iron content, the iron activity of sulfur deficient matte is higher than that of regular matte. A supernatant coke barrier could, therefore, be expected to lead to higher nickel and cobalt recoveries, reduction or even elimination of magnetite furnace bottom build-up and increased sulfur elimination as SO2 in the flash furnace. Preliminary experiments were conducted in a mini plant flash furnace to investigate the effect on process metallurgy of the suggested modified scheme. This paper presents the experimental results and discusses key aspects of the possible operation of the Inco flash furnace with a coke barrier separating the freeboard from the molten bath.

Jan 1, 2003

By H. C. Roland Kammel

Stannous sulfate electrolytes are widely used nowadays in electrolytic tin production. Characteristic features of this electrolysis process are that dense cathode deposits can only be obtained by additions of organic additives and that so called ?black mud is formed on the anode surface which leads to an increase in cell-voltage. In order to prevent excessive cell-voltages or oxygen evolution the black mud has to be removed periodically. Studies in laboratory scale have been performed about the effect of different organic additives on electrolytic tin deposition and the formation of surface layers on pure and industrial tin anodes. Results reveal that organic addition agents are effective in reducing cathode roughening as well as extending the covering time of the anode ?by black muds.

Jan 1, 1985

By Qiang Zhong, Qian Li, Yongbin Yang, Tao Jiang

Thermogravimetric analysis (TGA) has been used to research the pyrolysis and combustion processes of coal used in rotary kiln of iron ore oxide pellet. Furthermore, the effects of air flow and oxygen concentration on the combustion behavior of coal were examined with TGA. The results showed that two individual stages can be distinguished for the pyrolysis of coal, the water evaporation stage and the de-volatilization stage. And the information on ignition and burnout characteristics can be obtained from the combustion process analyzed by TGA. Large air flow almost has no effect to the combustion process except that it enhances combustion intensity. However, the combustion process is further accelerated under oxygen-enriched conditions. With all experimental results, it could provide an attractive approach of analyzing coal for the rotary kiln process.

Jan 1, 2016

By Gabriel Riveros

Fire refining of copper consists of two stages copper oxidation and copper reduction. Very frequently the capacity of the anode furnace is determined by the rate of copper reduction. The analysis of factors affecting the rate of the oxygen reduction from a liquid copper with solid carbon or injected hydrocarbons pointed out the role of the mass transfer in a liquid copper in final stage of the reduction. Experimental results of copper reduction with graphite and injected natural gas in laboratory- scale crucibles showed two stages of the reduction process with a sharp change of the controlling mechanism. The estimated dynamic surface area of gas bubbles based on the measured bubble frequency and the gas flowrate allowed for the detennination of the reaction constant as a degree of the partial pre-combustion of the air/natural gas mix. The variation of the used reductant as a function of the oxygen concentration and temperature has been evaluated based on the detennined kinetic model. The intensification of copper reduction in fire refining has been discusses on the basis of obtained kinetic data and analysis of various factors detennining the time of reduction.

Jan 1, 2003

By Bogdan Petkovic, Boban Todorovic

In the early 90's a completely unknown problem was encountered at the converter Department: it was a chronic shortage of the cold copper charge needed for the second operating period. A high temperature operating regime was caused which further provoked a chain of consequences such as a drastic drop of the number of operations in campaigns. The consumption of repair bricks reached the quantity of 8.3955 kg / tonne of anode Cu. In 1994, we won the process of cold material smelting during the "copper" blowing [2]. The number of operations per campaign reached 180-200 again. Also in 1994 we won the process of smelting cold materials to obtain "tin" blowing with the purpose of completing their processing cycle [2]. During the period 1994 – 2007 a total of 107,845 tonnes of cold material were remelted to make copper and 56,794 tonnes were re-smelted to obtain "tin". Upon synthesizing these two processes, a completely new model was achieved in 2005, by Bogdan Petkovic, which entirely utilized all available energy of the Peirce-Smith (PS) converters of the Bor Copper Smelter and now represents the basis of the time cycle. The cold material now enters the converter plant, copper recovery is increased and the method itself is environmentally friendly. 167

Jan 1, 2009

By Kafui Nyavor

The indirect, and the direct contact mechanisms of bacteria oxidation of sulfides were studied using Thiobacillus ferrooxidans and pyrite. The aim was to determine which of the two generally aeeepted mechanisms played a dominant role, if any, during acid mine drainage (AMD) formation from the oxidation of sulfide minerals. The results show that at a pH of 4.5 where T. ferrooxidans are quite active, but where initial chemical oxidation of pyrite to Fe2+ is limited, the bacteria were unable to directly oxidize pyrite to any significant extent. Whereas, in the presence of Fe2+, T. ferrooxidallS assisted oxidation of pyrite by the indirect mechanism was observed and sustained over the pH and Eb range where the bacteria is active. The results lead to the conclusion that the direct contactmechanism of pyrite oxidition by T. ferrooxidans is insignificant. The predominant, and possibly the only, pathway involves the indirect bacteria oxidation of available Fe2+ to Fe3+, which in turn oxidizes FeS2 to generate additional Fe2+ and acidity in a cyclic process.

Jan 1, 1996

By N. Kanari

One of the criteria to define the market value of chromite concentrate is its chromium to iron ratio. Changing this ratio for a definite chromite mineral is impossible by physical processing. This study investigated the possibility of increasing this ratio through the carbochlorination and the oxychlorination of chromite concentrates. Experiments are carried out up to 1000 °C. The characteristics of samples and reaction products are determined by SEM, XRD and chemical analysis. The carbochlorination of a chromite concentrate at about 600 °C leads to the . selective partial elimination of iron allowing a higher Cr/Fe ratio of the treated concentrate. Selective extraction of iron could also be achieved at about 950 °C by oxychlorination. In this case, a part of chromium contained in the concentrate is recovered as chromium oxychloride. The obtained residue had high content of Cr, Mg and A1 oxides. Such material has probably better chemical and thermal properties that may. be useful for foundary and refractory applications. Two flow-sheets for the beneficiation of the chromite concentrates using carho- and oxychlorination are suggested.

Jan 1, 1997

By Demaerel. J. P.

Arsenic plays a major role during electroreflning of copper. Both the arsenic content in the anode and the arsenic concentration of the electrolyte have, in conjunction with other impurities such as lead, antimony, bismuth and oxygen, a direct influence on the quality of the cathode. The mechanisms are currently slime. inclusion and precipitation of insoluble compounds in the bulk of the electrolyte. Arsenic has also been reported to have a depassivating effect on the anode. An influence on the anode slime adhesion has also been found. A literature survey is given and these data are compared with and completed by our own results based on lab and pilot scale experiments as well as on Olen tank.house practice.

Jan 1, 1987