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By Noriaki Kurita, Norihiko Fulcatsu, Teruo Ohashi

"An electrochemical sensing device for hydrogen in molten metal has now been available owing to the development of the proton conducting solid electrolyte made of ceramics of metal oxide. The structure of the sensor and the theoretical limitations of its applications are discussed based on the electrochemical properties of the electrolyte used. The practical performance of the sensor is reviewed from the results of test measurements at the plants of aluminum and copper melting industries. The effectiveness of the sensor to the process control of continuous casting of copper is also discussed.IntroductionSince the in-line monitoring of the amount of oxygen dissolved in molten metal was realized by using the oxygen concentration cell based on zirconia solid electrolyte a similar method has been expected to be developed for sensing of hydrogen, which is a very important element of gas species in liquid metals, especially, in aluminum and copper. In 1981; Iwahara and coworkers found the dominant proton conduction at a high temperature in some perovskite-type oxide (1). Since then, the effort has been made to apply this proton conducting material as the electrolyte of the hydrogen concentration cell for high temperature use. The hydrogen sensor for liquid aluminum of this kind was first produced in 1991 (2) and released commercially from TYK Co., Ltd. Recently, we have developed the mother one usable at higher temperature such as copper and silver melting processes (3). In this note we discuss their structure, design and applicable limitations based on the electrochemical properties of this new type electrolyte. The performance of the sensor and benefit to use it to control the melting process is also discussed"

Jan 1, 2000

By P. A. Davidson

"We discuss the influence of a static magnetic field on jets, vortices and turbulence. This is particularly relevant to D.C. braking in slab casting. Our main conclusion is that, typically, the magnetic field destroys mechanical energy, via joule dissipation, but is unable to destroy momentum. Rather, it continually rearranges the momentum in such a way that the energy falls.IntroductionIt is well-known that a static magnetic field can suppress motion of a liquid metal. That is to say, movement of the liquid across the magnetic field lines induces a current. This leads to Joule dissipation and the resultant rise in thermal energy is accompanied by a corresponding fall in kinetic energy.This phenomenon has been exploited in a range of metallurgical processes. For example, in the continuous casting of large steel slabs, an intense, static magnetic field is commonly used to suppress motion within the mould. The objective is to keep the free surface of the liquid quiescent, thus avoiding the entrainment of surface debris. In other solidification processes, such as techniques for growing semi-conductor crystals, it is widely believed that natural convection has a detrimental effect on the metallurgical structure of the solid. Again, the imposition of a static magnetic field is seen as one means of suppressing these unwanted motions. Finally, magnetic damping is used in the laboratory measurements of chemical and thermal diffusivities, particularly where solutal or thermal buoyancy can disrupt the measurement technique.In this paper we shall look at the damping of jets, vortices and turbulence. Our aim is to present a unified theoretical framework from which the many published studies may be viewed."

Jan 1, 1999

By Zenon R. Llanos

"The disposal of spent hydroprocessing (HDP) catalysts in the petroleum refining industry has been a concern in the past due to their classification as listed hazardous wastes. However, because these catalysts have higher metal concentrations than regular ores, and the recent surge in prices for molybdenum, vanadium, nickel and cobalt what used to be considered as a liability for generators is now viewed as a valuable renewable source of strategic metals. At the same time the generation of spent catalysts has steadily risen due to new environmental regulations for low sulfur fuels and an increased appetite of gasoline consumers. This paper will examine spent catalyst market and the role played by Gulf Chemical & Metallurgical Corporation in the reclamation of metals over the last sixty years. Introduction Hydroprocessing (HDP) catalysts are used in petroleum refineries for two main applications: desulfurization and cracking. The catalyst support is alumina or mixtures of alumina and silica. Active metals include molybdenum, nickel, cobalt and tungsten. The selection of catalysts depends on the application and sometimes the cost. The life cycle of HDP catalysts is represented in Figure 1. The catalyst cycle in a reactor varies from continuous to one-two years. Catalysts used in various refining processes are deactivated by coke, sulfur, vanadium and other impurities in the refinery feedstocks and become spent. Refineries can optionally send the spent catalysts for regeneration, metals reclamation or landfilling. Catalysts used for refining heavy crudes often can not be regenerated. Catalysts used with light oils can be reused twice or three times after regeneration. When the option for regeneration is not viable, spent catalysts are send metal reclamation facilities or landfills."

Jan 1, 2008

By Wang Haibei

China is the important country in terms of Ga, Ge reserves and products. These elements usually associate with lead and zinc ores such as in Fankou, Dachang and Lanping mines. Until now these metals could not be extracted from zinc residues effectively. The main reason is that it is difficult to separate zinc and iron. BGRIMM has carried out considerable research on this subject and some hydrometallurgical processes were developed. Zinc residues were pressure leached with a reducing agent such as zinc concentrates or SO2 at 110~130C. The final concentrate of H2SO4 was 30~50g/L. The metals such as Zn, Fe, Ga and Ge were dissolved into solution. In the leaching residue Pb and Ag could reach 20% and 2000g/t. The feed of solvent extraction was prepared from the leaching solution by pre-neutralization ? precipitation of Ga, Ge and acid dissolving. Then Ga and Ge were extracted by solvent extraction through P204 and G315 produced by BGRIMM. After stripping, metallic Ga was produced by electrowinning. GeO2 was produced by precipitation. The iron in raffinate was removed by the hematite process. The solution after removal of iron came back at the zinc neutral leaching stage. In 2003-2004, pilot tests were finished in BGRIMM in cooperation with Fankou Lead and Zinc Mine Ltd. And the extraction rate of Ga and Ge in the leaching stage was 94% and 83% respectively. The total recovery rate was 90% and 80%. It is estimated that the technology has a wide commercial use in the coming five years.

Jan 1, 2006

By Esa J. Peuraniemi

Copper smelting to form blister in one single step has been possible for a long time even from low grade concentrates. In spite of obvious benefits, it has been economically viable only with few special raw materials having high enough Cu/Fe and Cu/S ratio. Outokumpu Blister Flash Smelting is currently applied at three operations, and three others will be commissioned in the near future. With typical chalcopyrite concentrates two main obstacles have prevented wider adaptation of direct blister processing: slag formation and heat generation. Oxygen potential in the reaction shaft must be high in order to produce blister with targeted sulfur content below 1%. When large amount of iron is oxidized, as well as sulfur, copper is inevitably also oxidized into slag. High copper amount in substantial tonnages of slag lead on to costly down stream recovery operations to obtain discardable slag. Almost complete oxidation of sulfur and iron releases a high amount of heat which traditionally has been solved by lowering oxygen enrichment of the blast leading on to oversized off-gas line and acid plant. One challenge in direct blister smelting relates to the attack of aggressive high-copper containing slag against furnace refractory lining. In continuously operated Outokumpu Direct Blister Flash Smelting this is taken care of by preventing vigorous melt movement in the settler. Stable bath conditions and stationary slag against refractory lining enable the formation of a protective autogenous layer between aggressive slag and vulnerable refractory. These direct blister smelting challenges are addressed from equipment and process development point of view. New solutions to overcome the obstacles are presented and discussed.

Jan 1, 2006

By V. A. Luganov

During the treatment of raw materials containing arsenic and antimony, problems in the distribution of these elements in the process products occur. In a number of cases in processing of copper-bearing materials, it is possible (or necessary) to obtain speiss. The purpose of the present research is to study the theoretical aspects and analyze the technological possibilities of producing copper-bearing speiss and the subsequent electrometallurgical processing with copper extraction as well as arsenic and antimony utilization. Copper arsenide (Cu3As) and copper antimonide (Cu3Sb) are the main components of the speiss. A thermodynamic analysis of the electrochemical oxidation of Cu3As and Cu3Sb, carried out using Pourbaix diagrams, showed that in a pH range from 0 to 2, oxidation potential 0.45-0.55V, ions of copper and arsenic and antimony trioxide are in the equilibrium. The kinetic study has shown, that with an increase in the polarization potential, the dissolution process changes from chemical to diffbsion control. An increase in temperature stabilizes the electrolysis process due to dissolution of arsenic trioxide forming on the anode. Electrolysis of speiss using a cathode diaphragm with the solution pH = 1-2, current density 150-200 A/m2 and temperature 60-70°C makes it possible to obtain cathode copper with a current efficiency of 95-96% and to remove the arsenic from the process during the electrolyte cleaning process. The arsenic content in the cathode copper did not surpass 0.002%. As the result of the research, a technological flowsheet for copper-lead speiss processing was developed. At the present time this technology is undergoing pilot testing.

Jan 1, 1999

By Fiseha Tesfaye, Pekka Taskinen

"A thermodynamic study of the equilibrium phase assemblage AgBi3S5-Bi2S3-S was made by an EMF-technique, using the RbAg4l5 solid electrolyte. The ternary phase was synthesized from the pure Ag2S and Bi2S3 in an evacuated silica ampoule and grinded into powder and mixed with appropriate compositions of B12S3 and S, in a series of experiments, for pressing in to pellets. The pellets were assembled to form the galvanic cells Pt (-) | Ag ] RbAg4ls | AgBi3S5+ Bi2S3 + S + (C) I Pt (+). The EMF-measurements were made in the temperature range 299 - 460 K.In this paper, thermodynamic functions of the ternary phase AgBi3S5 (pavonite) have been determined. The agreement between the obtained results and the literature values were established.IntroductionThe complex group of ore minerals constitutes from trace amounts to a major proportions of sulfosalts. Although the sulfosalts rarely form massive ore bodies, they are commonly associated with rich sulfide ore minerals for the base and precious metals and widely distributed in a metal poor sulfide minerals [1]. For instance, Ag-bearing sulfosalts are encountered in ore minerals for the production of the base metals and are common sources of silver. Nevertheless, thermodynamic properties of the sulfosalts are poorly known.Reliable thermochemical data are essential for quantitative modeling of the chemical behavior of the sulfosalts in equilibrium with sulfides, which in turn would promote the optimization of complex minerals treatment and extractive metallurgy of the valuable metals."

Jan 1, 2012

By Han-Tao Hu

Keywords: RH refining process, flow of molten steel, two-phase flow, gas holdup, circulation rate, mathematical modeling A three-dimensional mathematical model for the flow of the molten steel in the whole degasser during the RH refining process has been proposed and developed with considering the physical characteristics of the process, particularly the behaviors of gas-liquid two-phase flow in the up-snorkel and the momentum exchange between the two phases. The fluid flow fields and the gas holdups of liquid phases and others respectively in a 90 t RH degasser and its water model unit with a 1/5 linear scale have been computed using this model. The results showed that the flow pattern of molten steel in the whole RH degasser could be well modeled by the model. The liquid can be fully mixed during the refining process except the area close to the free surface of liquid and zone between the two snorkels in the ladle, but there is a boundary layer between the descending liquid stream from the down-snorkel and its surrounding liquid, which is a typical liquid-liquid two phase flow, and the molten steel in the ladle is not in a perfect mixing state. The lifting gas blown is rising mostly near the up-snorkel wall, which is more obvious under the conditions of a practical RH degasser, and the flow pattern of the bubbles and liquid in the up-snorkel is closer to an annular flow. The calculated circulation rates for the model unit at different lifting gas rates are in good agreement with the determined values.

Jan 1, 2005

By Serge Lavoie

Alcan's Guillaume-Tremblay plant, located in Jonquiere, Quebec, has been in operation since 1990. This was the first plasma dross processing plant ever built. In addition to the use of the plasma heating technology, Guillaume-Tremblay has other unique features making it a modern and efficient dross processing facility. This paper presents a general overview of the practical experience at the Guillaume-Tremblay plant. In particular, the utilization of plasma heating in industrial conditions, the metallurgical performance, the unique dross handling system, the control and information management system and the reclaiming of the by-products will be discussed. Finally, the use of the plasma process for salty dross will be addressed' briefly.

Jan 1, 1995

By Yoshinao Kobayashi

he removal of oxygen from titanium and zirconium is important for use in application because it significantly affects the mechanical and physical properties such as ductility and toughness. However, thermodynamic properties of oxygen in molten titanium and zirconium have not been clarified and the effective deoxidation process of molten titanium and zirconium has not been established. In this study, the standard Gibbs energy of reaction of oxygen and yttrium in molten titanium and zirconium have been measured by a chemical equilibrium technique. Molten titanium, zirconium, and their alloys with aluminum were equilibrated with a Y2O3, A12O3, or Zr02 pellet in a cold crucible. The results are summarized as follows:

Jan 1, 2000

By Jing Zhan, Tian-zu Yang, Wei-feng Li, Li-Hua Jiang, Shi-yan Xu, Jian-yang Huang, Chuan-fu Zhang, Yan-qing Fan

The amount and activity of coal, reduction temperature and other parameters of the process of bottom-blown reduction of liquid high lead slag were investigated in laboratory. Methods to strengthen the bottom-blown reduction process were studied by industrial production. The results were in the follows: the reduction temperature was 1150℃; reduction time was 1.5h; the reductant was anthracite; lead content in slag was controlled to 2%; the rate of coal was 7% and gasification loss of coal in high temperature was severe; liquid lead slag reduction rate was faster with coal; prolonging the reaction size had little effect on reducing lead in slag; the size of the reactor can be further reduced.

Jan 1, 2015

By Kezhuan Gu

Data on the kinetics and thermodynamics of dephosphorization are analyzed in terms of the dynamic partition ratio, determined by a combination of slag thermodynamic properties and the balance of oxygen supply and consumption. A recently developed phosphate capacity correlation is combined with data on kinetics to quantify the most significant parameters in controlling the interfacial oxygen potential. The role of slag composition, entrained gas fraction and temperature are discussed in addition to metal carbon and sulfur content. It is demonstrated that the mass transport of oxygen in the slag is enhanced by factors increasing conductivity and inhibited by entrained gas. The mass transfer of phosphorus in the metal is described considering surface renewal induced by CO bubbles.

By Milan Lj. Stamatovic

The hydrometallurgical recovery of zinc from recycled blast furnace dust from a steel plant (Smederevo Metallurgical Company, Yugoslavia) was investigated. The dust contained 22% Fe, 17% Zn and 0.2% Pb. X-Ray diffractometry showed that the main components were hematite and magnetite, in combination with zinc oxide. Individual particles were generally spherical and ranged in size from 10 to 150 microns; 63% were less than 33 microns in diameter. An effective hydrometallurgical approach proved to be by caustic leaching and electrowinning. Recovery of zinc in the form of zinc powder was over 90%; this material can be used for the cementation of impurities in the conventional hydrometallurgical process for zinc production.

Jan 1, 1994

By Grigore Matei

The thermodynamic properties of CuzS-FeS system are important not only in the ease of copper smelting but also in the case of general pyro-metallurgy. However there arc not many reported activity data In this study, activities of FeS and CU2S in the Cu2S-FeS system were calculated using the Darken's method from the activity data of the Cu2S-FeS-Sb2S3 systems measured by the transportation method at 1050°C. The activities of Cu2S and FeS in the Cu2S-FeS system showed negative deviation from the ideal behaviour and satisfied the relation of the Gibbs-Duhem equation.

Jan 1, 2003

By Yushiro Hirai

Saganoseki smelter & refinery had operated two flash smelting furnaces from 1973, attaining 330,000 mtpy of copper production in 1989. In 1996, however, it carried out a "integration of two flash furnaces". That is, it doubled the feeding capacity to one flash furnace to shut down another furnace while maintaining the same production. Single flash furnace operation has successfully started in March 1996 accomplishing a great reduction of the total production cost. The production had reached to 350,000 mtpy in 1997, and further increased to 450,000 mtpy by executing the expansion program with single flash furnace in 1998. This paper introduces results of the single flash furnace operation and describes about an outline of the expansion.

Jan 1, 1999

By Donald R. Sadoway

Fused salt electrolysis is used extensively in the primary extraction of metals (electrowinning), in the refining of metals (electrorefining), and in the formation of coatings (electroplating). In the case of rare earths, fused salt electrolysis competes with nonelectrochemical processes to make the same products. However, fused salt electrolysis has the potential to produce these metals in a variety of technologically useful forms: thin films and epitaxial layers, powders, and a variety of nonequilibrium structures. The theory and practice of fused salt electrolysis as it applies to the extraction, refining and plating of rare earth metals are described. The potential of fused salt electrolysis to synthesize advanced materials containing the rare earth elements is assessed.

Jan 1, 1989

By Fuxing Yin, Akira Sato, Yoshiaki Ohsawa, Kohji Kawaharai

"INCRAMUTE alloy (nominally 45Mn-53Cu-2Al wt. %) has a specific damping capacity as high as 0.4, through a solid-solution and aging treatment. The damping behavior of the alloy is highly temperature-dependent and shows a peak near room temperature. The inadequate strength in the high damping condition restrains the practical application of the alloy, as structural components. Ferromagnetic MnB particles are dispersed in the alloy during induction remelting the matrix alloy in an argon atmosphere. Surface modification of the MnB particles by mechanical alloying (MA) and suitable control of the addition process cause a homogeneous distribution of MnB particles in the alloy. In the composite containing 2 wt. % MnB particles, temperature dependence of damping capacity is improved, and higher damping capacity is still retained in the temperatures over 60 °C. Meanwhile, the Young's modulus and tensile strength were also increased by about 20%. The roles of the MnB particles in improving both damping behavior and mechanical properties were also discussed.IntroductionMany viscoelastic materials, such as rubbers, polymers and plastics, have the superior ability to damp vibration and noise. However, in the applications as structural materials the high damping capacities of materials are pursued upon the satisfactory mechanical properties, especially those at elevated temperatures. Damping alloys are finding more and more applications in structures where noise and vibration ·should be ·eliminated. Specific damping capacity (SDC), defined as the ratio of the energy dissipated to the maximum vibration energy stored per cycle, is usually used to evaluate the damping capacity of alloys. INCRAMUTE damping alloy, developed by the International Copper Research Association, Inc., has a nominal composition of 45Mn-53Cu-2Al in weight percent. The high damping· microstructure of this alloy is obtained through the solution treatment at 820 °C followed by a water quench and aging at 400°C for 10 hours followed by cooling to room temperature [1]. With the heat treatment, a SDC peak ·vs. temperature of as high as 0.4 was observed in the alloy at the strain amplitude of about 10-3 while a tensile strength of about 500MPa was sustained."

Jan 1, 2000

By Qingchun Yu, Bin Yang, Yong Deng, Heng Xiong, Fei Wang, Minxiu Chen

"Metal aluminum produced by non-electrolysis process received much attention due to its lower energy consumption. In this paper, carbothermic reduction and carbothermic-chlorination of alumina in normal pressure and vacuum were studied. The products were examined by means of XRD, EDS and SEM. During the carbothermic reduction process using carbon reductant in normal pressure, no metal aluminum was found. However, when coal was used as reductant, a mixture containing metallic aluminum, A14C3, and silicon was obtained, but metallic aluminum couldn't be separated from the mixture. During the carbothermic-chlorination process in vacuum, Al404C and Al4C3 were produced by the reaction between alumina and carbon, and Al Ch gas reacted with Al404C and Al4C3 to produce Al Cl gas. Metallic aluminum was produced due to the disproportionation of A!Cl gas and condensed on the collecting plate. Meanwhile, the initial temperature of carbothermic reduction of alumina reduced in vacuum compared with that in normal pressure.IntroductionIndustrial production of primary aluminum is carried out in alumina cell by the so-called Hall- Heroult process, necessitating the use of very high currents of low voltage. The alumina from which metallic aluminum is gained must be chemically pure, otherwise impure metal results. The main drawbacks of the electrolytic production are its very high energy consumption, the release ofperfluorocarbons, and the high specific C02 emissions [1]. During the past years, there were a lot of attempts to produce metallic aluminum by carbothermic reduction of A1203 [2, 3]. Cox [4] determined the vapor pressure over the A1203-C system and performed X-ray diffraction analysis of condensed products. It was demonstrated that an increase in the carbon content in the system leaded to the sequence of transitions: A1203~Al404C~A1zoc~A14C3 ~AI [5]. In any carbothermic reduction process for aluminum, extremely high temperatures (2000 °C ) were required [6]. In spite of considerable effort, the carbothermic reduction of alumina to aluminum remains a formidable technical challenge, due to the high temperatures required, and to the formation of aluminum carbide and oxycarbide byproducts [7]."

Jan 1, 2013

By Qingchun Yu, Bin Yang, Yong Deng, Heng Xiong, Fei Wang, Minxiu Chen

"Metal aluminum produced by non-electrolysis process received much attention due to its lower energy consumption. In this paper, carbothermic reduction and carbothermic-chlorination of alumina in normal pressure and vacuum were studied. The products were examined by means of XRD, EDS and SEM. During the carbothermic reduction process using carbon reductant in normal pressure, no metal aluminum was found. However, when coal was used as reductant, a mixture containing metallic aluminum, A14C3, and silicon was obtained, but metallic aluminum couldn't be separated from the mixture. During the carbothermic-chlorination process in vacuum, Al404C and Al4C3 were produced by the reaction between alumina and carbon, and Al Ch gas reacted with Al404C and Al4C3 to produce Al Cl gas. Metallic aluminum was produced due to the disproportionation of A!Cl gas and condensed on the collecting plate. Meanwhile, the initial temperature of carbothermic reduction of alumina reduced in vacuum compared with that in normal pressure.IntroductionIndustrial production of primary aluminum is carried out in alumina cell by the so-called Hall- Heroult process, necessitating the use of very high currents of low voltage. The alumina from which metallic aluminum is gained must be chemically pure, otherwise impure metal results. The main drawbacks of the electrolytic production are its very high energy consumption, the release ofperfluorocarbons, and the high specific C02 emissions [1]. During the past years, there were a lot of attempts to produce metallic aluminum by carbothermic reduction of A1203 [2, 3]. Cox [4] determined the vapor pressure over the A1203-C system and performed X-ray diffraction analysis of condensed products. It was demonstrated that an increase in the carbon content in the system leaded to the sequence of transitions: A1203~Al404C~A1zoc~A14C3 ~AI [5]. In any carbothermic reduction process for aluminum, extremely high temperatures (2000 °C ) were required [6]. In spite of considerable effort, the carbothermic reduction of alumina to aluminum remains a formidable technical challenge, due to the high temperatures required, and to the formation of aluminum carbide and oxycarbide byproducts [7]."

Jan 1, 2013

By P. C. A. Maia, J Alexandre, F. A. J. Saboya, A. R. G. Azevedo, G. C. Xavier

"This work shows the characterization of clay and the granite waste by-product from the sawing process of the granitic blocks, used as raw material for brick ceramic. Besides, shows the degradation of the ceramic material obtained with different by-product contents in the waste after lab test degradation, is investigated. The clay is obtained from mine use areas of ceramic industry in Campos-RI and the waste is originating from of the area of Cachoeiro-ES, an important center of decorative stone in Brazil. The mixes were made by the addition of 0% up to 10% of the waste in the raw material. After drying and firing up to 900°C, obtained prismatic pieces were considered intact. Physico-mechanical properties were obtained from wet and drying tests in laboratory considering 50 and 150 cycles. The results showed that the use of powder byproduct has a considerably influence on the weathering and strength of the material.IntroductionThe ornamental rocks and coating defines the most promising areas of business in the mineral sector [l]. In this context, the Espirito Santo appears as the main Brazilian state in production and export of ornamental rocks, representing 47% of national production [2] which in tum is one of the economic sectors most representative of this State, due of its transport logistics and port vocation that facilitates the export of such products.It is estimated that the state of Espirito Santo there are approximately 1,200 companies dedicated to the activities of ornamental rock by providing 20,000 direct jobs [ 1]. These mobilize support activities, such as companies that provide machinery, equipment and supplies for industries, including service providers for maintenance.However, the production of rocks produces about 15,000 tons of granite waste/month [3] only in the municipality of Cachoeiro ltapemirim-ES. This is justified by the presence of more than 500 extraction industries, cutting and processing of stone, with about 900 looms, waste generators.According to [4], there is great potential for the use of granite waste in red ceramics introduced for the manufacture of bricks, blocks structural ceramics. and other ceramic products, especially when evaluated on exposure to weathering."

Jan 1, 2014