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By Leonard J. Friedman

The contact process for the production of sulfuric acid has been used commercially since before the turn of the century (1880?s), and rapidly replaced the chamber process after the development of vanadium catalysts in the early 1900's (1910's - 1920's). Plant size has increased from a few tons per week to single train units in excess of 4,000 tons per day. Much of the history of the contact process is in the minds of the few remaining early process pioneers that started in the industry in the 1920's and 1930?s, and in sulfuric acid industry books published in 1921, 1925, 1936, and the last Deucker and West in 1959. Since those not familiar with history are doomed to repeat the failures and mistakes of the past, this paper includes a brief history of the contact process along with the history and development of equipment and materials in each equipment area of the process. The main focus of the paper is to present the development and analysis of equipment and materials in the contact section of the sulfuric acid plant - from the dry tower to stack.

Jan 1, 1999

By Bora Derin

Optimization of slag composition has great importance on effective and clean metal production technologies. Reddy-Blander (RB) model, a priori, is very useful tool for prediction of impurity capacities of industrial slags. In this study, sulfide capacities (Cs) of 19 lead smelter slags indicated in the literature were calculated and effects of Cs values on sulfur content of lead bullions were discussed.

Jan 1, 2006

By Norihiro Murayama

The hydrothermal syntheses of zeolites from coal fly ash were carried out using NaOH and KOH as an alkali source. The cation exchange capacity (CEC) and the ion exchange selectivity were investigated for the zeolites synthesized by a hydrothermal treatment. The effective usage of the zeolite as a cation exchanger was considered from the viewpoint of engineering. Zeolite P, HS (hydroxysodalite) and K-CHA (potassium-chabazite) are mainly formed as zeolite species in NaOH or KOH solution at 393K. The zeolite P and K-CHA have a large exchange capacity as a cation exchanger. The cation exchange isotherms of various monovalent and divalent cations with various zeolites are investigated. The order of selectivity of the zeolites is as follows, NH4+> K+> Li+.For the divalent cation, the largest removal amount is obtained for Pb2+ in the low equilibrium concentrations below 0.2mmol/dm3, and almost perfect removal can be achieved for Pd2+. The order of selectivity of zeolites in low concentration is expressed in the following order; Pb2+> Co2+> Cd2+> Ca2+> Mg2+> Ni2+. Ii is considered the zeolites obtained from coal fly ash can be used as an excellent cation exchanger.

Jan 1, 2006

By Samson Adeosun, Sanmbo Balogun, David Esezobor

"In a typical year, approximately 1.7 million tons of residues and wastes are expected from Ajaokuta integrated steel plant, Nigeria. They will be generated mainly from sinter plant, blast furnace (BF), and basic oxygen furnace (BOF) operations and during rolling and finishing. The residues and wastes include slag, dust, sludge and slurries from gas cleaning, waste water, mill scales and other associated scraps. In this paper concepts for the utilization of residues and wastes in Ajaokuta Steel Plant where no reclamation routines have been provided for in the first and second phases of its project implementation is designed. The paper analyses the sources of the iron oxide wastes and evaluates the quantities expected from the main production facilities of the plant which include the two 312 m2 capacity sintering machines, the two 2000 m3 blast furnaces and two 130-T BOF (of the 2nd phase expansion of the Steel Plant). A reclamation routine designed for Ajaokuta residues and wastes is presented.IntroductionIn the steel industry, approximately 550kg of residues per ton of crude steel arise from the production processes and from pollution control facilities [1- 4]. These residues consist of slag, dusts and sludge, mill scale, spent pickle liquor, and other iron bearing materials. The main by – products generated in the steel industry are listed in Table I.Although major progress has been made in the recycling and use of some of these residues, particularly flue dust, blast furnace and steel making slag, yet a significant quantity are land filled or stockpiled. These unsightly stockpiles occupy valuable real estate and may become a source of environmental pollution if not otherwise disposed. In any case, the dumping option has become quite costly. For instance, one ton of iron ore costs between 28 and 34 US dollar, whereas as much as $20 per ton of steel produced is required to meet environmental compliance obligation in the USA [5, 6]."

Jan 1, 2008

By A. D. Besser

The world production of lead has been growing continuously and reached over 7 million tonnes in 2005. At the same time, the structure of lead consumption has changed: the use of lead compounds to liquid fuel has been virtually terminated; the proportion of lead for manufacture of lead-acid batteries has been growing and reached 76.7% of the overall world production of this metal. This has taken place against the background of increasingly stringent environmental norms and environmental legislation. This is due to the lack of an alternative for lead in manufacture of local power sources. A solution to the problem of meeting the industrial demand for lead with simultaneous reduction in the primary lead production is in recycling. A large amount of batteries manufactured worldwide and their short life cycle, as well as the positive economics and a possibility to comply with the environmental requirements encourage the development of secondary lead production. Currently, over 60% of the world demand for lead is met due to recycling. The current situation with collection, transportation, storage and processing of spent lead-acid batteries has been analyzed in this paper. Examples are given to illustrate technological and equipment solutions and trends for improvement of secondary lead production discussed.

Jan 1, 2006

The entrainment of copper matte in the slag during the slag skimming stage of a Peirce-Smith converter was studied with a dam break model. Experiments were carried out with a range of fluid pairs where the lighter fluid was allowed to overflow a weir and the amount of entrained heavier fluid measured. The resulting entrainment is measured as the ratio of the heavy to light fluid withdrawn. The fluids include oil-water, water- glycerol and salt solutions-water pairs to cover a wide range of densities and viscosities. It was found that the Richardson number, Ri, correlates the entrainment well. For the case of the liquid-liquid interface initially at the same height as the weir, the entrainment was found to vary with Ri-1/3. The transient flow was simulated with a volume of fluid (VOF) code written in-house and used a stairstep approach to represent flow obstacles. The code was validated against the experimental results with good agreement for the variation of the heights of the two fluid with time. The simulation showed that the prevailing mechanism for entrainment is due to a pressure differential created across the liquid in the converter during pouring resulting in the heavier liquid being rotated upwards and over the weir.

Jan 1, 1999

By Daojin Cao

Aiming at many controversial reports on Raman spectral pattern of octamolybdate ion in aqueous solution appearing in the literature, a new method for the establishment of corresponding relation between Raman spectral pattern and chemical components of aqueous molybdate solution was put forward using spectroscopy measure and component analyses of saturated solution of ammonium octamolybdate hydrate known structure. It was found that the main characteristic of Raman spectral pattern of the saturated solution was described as the same ?double-peaks, hereinto a weak peak at the boundary? as some literature, but chemical components of the saturated solution were affirmed to be octamolybdate ion (Mo8O264-) and double protonated heptamolybdate ion (H2Mo7O244-), which were in equilibrium in aqueous solution each other. The authors propose that the pattern of the saturated solution can be regarded as the standard pattern of primiparous octamolybdate ion during acidified molybdate solution. It is satisfying that the standard pattern is applied to the identification of primiparous octamolybdate ion during acidified molybdate solution.

Jan 1, 2006

Accretions of dust on the walls of the offtakes from furnaces and in the waste heat boiler are a cause of significant operating and maintenance problems in non-ferrous smelters. The dust originates from entrained solids in the gas stream and vaporised species that condense during gas cooling. Control of dust formation is very important for minimising the formation of accretions and reducing the severity of environmental problems caused by toxic species, such as those containing arsenic, in the dust. The present paper discusses the formation of accretions and the condensation of dust in copper smelting from a thermodynamic viewpoint. Changes, in gas composition and the amounts and identities of the condensed species in the dust are calculated using computational thermodynamics. Interactions between dust species to form accretions are considered in the light of appropriate phase equilibria. The results show that the nature of the dust formed varies greatly, depending on the temperature and the amount of oxygen present during cooling. Control of the amount of oxygen is required if offtake and waste heat boiler accretion problems are to be minimised.

Jan 1, 2002

By D. L. Stewart

"Melt loss is usually one of the highest individual cost items in the operation of ah ingot casting facility. While melt loss and the resulting cost for the entire facility is usually well known (at least via standard cost accounting), dross generation and melt loss for individual unit operations within the plant are usually not known. Thus, the financial impact of various practices, alloys and scrap types is not known. Development of an accurate, relatively low-cost technique for measurement of melt loss at commercial scale would aid in understanding melt loss for existing units, as well as evaluation of the melt loss impact of alternate processes.This paper will describe a methodology developed at Alcoa for accurate and inexpensive measurement of melt loss at commercial scale. The methodology has been used to evaluate the impact of scrap type, melting practices, and dross treatment technology on melt loss."

Jan 1, 2000

By Naoki Hiroyoshi

It is generally accepted that ferric ions are effective for leaching chalcopyrite as an oxidant and ferrous ions contribute to the leaching only as a source of the oxidant ferric ions. However, this paper shows that ferrous ions are more useful for leaching chalcopyrite than oxidant ferric ions in sulfuric acid solutions in air at ambient temperatures. Leaching experiments and dissolved oxygen consumption measurements were carried out with a very pure chalcopyrite and 0.001 - 1 mol dm-3 sulfuric acid solutions containing 0 - 0.1 mol dm-3 ferric or ferrous ions at 303 K. Chalcopyrite oxidation with dissolved oxygen was promoted by ferrous ions but suppressed by ferric ions. As a result, the amount of extracted copper was larger with ferrous ions than with ferric ions. Effects of Thiobacillus ferrooxidans on the ferrous promoted chalcopyrite leaching were also investigated and discussed based on the experimental data.

Jan 1, 1999

By Admire Chaendera

A gas jet was blown through submerged nozzles to stir the bath in the presence and absence of slag. Mixing and mass transfer rates were then studied. Water and kerosene (10% by volume) were used to simulate the metal and slag phases respectively in the cold model. The mixing time (Tmix), defined at 99.66% bath homogeneity level, increased with bath height and decreased with an increase in the gas injection rate. Its value in the model vessel was related to gas flow rate (Q), bath weight (W), and bath height (H) by, Tmix = 4.39Q-0.73W0.24H1.12. Inclusion of the slag phase increased Tmix by about 16% and the mass transfer parameter, [(Reloc,r)0.25(Ret)0.32], values by about 32%. Mass transfer rates were higher near the bath surface and in the gas-liquid plume region. They increased with gas flow rate but decreased with an increase in bath height. The relationship, K Q0.08, showing derived mass transfer coefficient (K) dependence on the gas injection rate (Q) was established. The proportionality constant in the equation varied with gas flow rate and sample location.

Jan 1, 2006

By Florian Kongoli

The so-called "fayalite" slag, despite problems associated with it, is the most widely used slag in copper smelting processes. Thirty years ago, in order to overcomes some drawbacks of this slag a new "calcium ferrite" slag was proposed especially for continuous copper converting. Since both slags have strong and weak points depending on the field of their application about 8 years ago another new "ferrous calcium silicate" slag was proposed that is expected to solve the drawbacks of each slag. This new slag is defined as mainly consisting of FeOx, CaO and SiO2 as its main components but it can practically have several combinations of these constituents. In order to determine the best area of this slag for possible industrial application the quantification of phase relations is an important subject. In this paper the work carried out by the authors in quantifying through an original physical model the phase relations, liquidus surface, liquidus regions, behavior of solid phases and the effect of minor components is reviewed. Several special compositions of this slag have been identified and discussed for possible applications in the industrial practice.

Jan 1, 2006

By V. L. Richards, S. N. Lekakh, S. A. Dutler

"This study presents determination on the thermal properties of investment casting shell molds used in casting process modeling. Superheat and latent heat from solidification and cooling of a casting can either be accumulated by ceramic shell for thin-walled casting or transfer to environment for massive casting. Heat capacity and thermal conductivity both play important roles in casting solidification. Thermal properties of ceramic shell depend on shell composition and fabrication techniques as well as thermal history during shell preparation process due to multiple phase transformations. Inverse modeling was combined with corrected Laser Flash method to determine the applicable thermal properties of the shell during casting solidification. Pure nickel was poured into ceramic shells containing two thermocouples and experimental cooling curves were obtained. These curves were then fitted to the model by adjusting temperature dependent heat capacity and thermal conductivity.IntroductionCasting solidification in investment casting shell affected by shell thermal properties including specific heat capacity and thermal conductivity. For relatively thin walled casting, most of the melt superheat and part of latent heat are accumulated by the shell. This process is mainly controlled by shell heat capacity. In the case of massive casting, significant part of latent heat transfers to environment through the shell so that this process is mainly controlled by shell thermal conductivity."

Jan 1, 2012

By A. G. Guézennec

Electric Arc Furnace (EAF) steelmaking co-produces amounts of dust (15 to 25 kg per ton of steel), which require to be collected and stored in specific landfills. The collection, handling, and possible beneficiation of EAF dust depend on its composition and morphology. We first studied theoretically the chemical evolution of dust particles along the fume extraction system, from the furnace down to the filters, using thermodynamic calculations of the Fe-Zn-O system. We show how it would be possible to favor zincite formation in dust and therefore increase further zinc recovery. Then, we developed a new morphological model, based on population balances, for predicting the granulometric evolution of dust particles as a result of agglomeration and sintering in the fume extraction ducts. The contribution of the various mechanisms (Brownian, turbulent, and sedimentary agglomeration; thermophoretic deposition; coalescence and sintering) is assessed. The influence of the exhausting conditions on dust granulometry is detailed. For the extraction system studied, intense agglomeration of the sub-micronic particles and complete coalescence take place inside the furnace; micronic particles then undergo little evolution from the elbow to the water-jacket, whereas big agglomerates are formed downstream. These results are in good agreement with dust particle observations.

Jan 1, 2006

By Erik Olsson, Gunilla Hyllander, Stefan Schuster, Lena Sundqvist Ökvist, Maria Lundgren, Michael Hensmann, Olavi Antila

"Residual materials from the integrated steel plant itself or other sources often contain valuable compounds of e.g. C and Fe. Dust and sludge have to be agglomerated to be able to recycle to the blast furnace (BF) via top-charging. By injection of the materials, preparation methods in terms of e.g. drying and/or screening only, can be used. Alternative carbon materials (ACM) in terms of BF dust and sludge have been successfully injected up to levels of 60 kg/tHM in the LK.AB Experimental Blast Furnace (LKAB EBF®). Efficiency in recovery of valuable compounds as well as the behavior of undesired elements have been evaluated and are discussed.IntroductionTraditionally, recycling of steel in-plant fines is made via the sinter plant and blast furnace route. Steel plants operating with 100% pellet as ferrous burden and have no sinter plant. There are limited areas for land fill and costs are caused for preparation of landfills and deposit fees. Very fine paniculate dusts or sludges cause decreased productivity and increased coke rate in the sinter plant, and therefore other ways for recycling must be considered. Injecting them into the BF could be an economically and technically feasible alternative. Additionally, as the materials contain valuable compounds of e.g. C and Fe."

Jan 1, 2012

The reported values of the standard reduction potentials of the Au(NH3)2+/Au(0) and Au(S2O3)23-/Au(0) couples are reviewed to emphasise the experimental difficulties associated with the measurement of reliable values for these quantities. The standard reduction potential for Ag(I)/Ag(0) in ammonia and thiosulphate solutions measured at ionic strength 0.1 and 25oCis used to predict the following relevant stability constants () for gold complexes based on the linear free energy correlations: Au(NH3)2+2 = 1013, Au(S2O3)23-2 = 1024 and Au(NH3)43+4 = 1033. The equilibrium constant ( 10-11) for the reaction Au(S2O3)23- + 2NH3 = Au(NH3)2+ + 2S2O32- based on these stability constants is in reasonable agreement with the measured value (10-9) based on potentiometric and spectroscopic data when excess ammonia was added to a solution of Na3Au(S2O3)2. This also indicates that the stability constant of Au(NH3)2+ is 9 to11 orders of magnitude less than that of Au(S2O3)23-. Relevant species distribution and Eh-pH diagrams based on the revised data are presented.

Jan 1, 2003

By S. de Vries, B. Wasmund, J. Metric, N. Voerrnann, S. Kasinger

Gulf Chemical & Metallurgical Corporation (GCMC) operates a circular DC electric smelting furnace to treat nickel and cobalt bearing residues at its plant in Freeport, Texas. The furnace, originally built by others, has experienced problems including runouts through the hearth and the lower sidewall. Hatch has designed several improvements to the furnace to alleviate these problems. The single anode at the centre of the hearth was replaced with a patented system of twelve air-cooled copper anodes evenly spaced around the furnace lower sidewall. The DC power supply comprises two transformers and two rectifiers operating in parallel. The water-cooling system on the bottom and lower sidewall shell plates was replaced with an air-cooling system using copper cooling fins. The existing row of water-cooled copper coolers in the metal bath zone was re-designed for greater heat removal capacity and better element joint sealing, and a new row of water-cooled copper coolers was added to cool both the alumina bath and freeboard zones. The existing water-cooled metal and alumina tapblocks were also re-designed for more robust cooling. A binding system was added to provide refractory compression that reduces the risk of liquid leaks. Finally, the furnace tilting frame was relocated to the top of the furnace where it is less likely to be damaged.

Jan 1, 2000

By T. Lezhava

Recycling technology of spent Mn-Zn system batteries has been worked out and tested in laboratory scale. The proposed technological scheme includes the following basic operations: breakage of batteries, hydro-vibrated treatment of broken up mass, electrolysis by using alkali electrolyte. This method enables extracting of 200-220 kg zinc in powder form, of 300-350 kg manganese concentrate and of 130 kg steel in the form of scrap per tone of broken up batteries.

Jan 1, 2006

By M. D. Crites

As part of a multi-year program for assessing the viability of chrome-free refractories in copper smelting, converting and refining furnaces, dynamic corrosion tests have been conducted on a series of refractories from the magnesia-alumina system, using a ferrous silicate slag. The corrosion rates of the test refractories are compared with those of a reference mag-chrome brick, and recommendations are made for more in-depth evaluations of the more corrosion-resistant materials.

Jan 1, 1999

By Batric Pesic

Dissolution of gold with sodium bromate solutions of various compositions was studied by using a rotating disc technique. The role of bromide ion, acid and externally added bromine was examined. It was found that sodium bromate could not dissolve gold in the absence of either acid or bromide ion, or both. When acid was absent, no bromine necessary for gold dissolution could be produced. When bromide ion was absent, formation of soluble gold bromide species, AuBr,-, was not possible. Bromate concentration had a complex effect, and it was dependant on bromide ion concentration. For fixed initial bromide ion concentration, gold dissolution rate increased with sodium bramate concentration increase until certain level, beyond which further increase of bromate concentration decreased the gold dissolution rate. The negative effect of bromate was explained by the depletion of necessary bromide ion. Sulfuric acid concentration effect was a function of initially present bromine.

Jan 1, 1992