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By Z. R. Llanos, W. G. Deering

Gulf Chemical and Metallurgical Corporation (GCMC) has been operating facility for treatment of spent catalysts in Freeport, Texas since 1974. Recently, GCMC expanded its operations with the addition of an electric furnace for the production of fused alumina and mixed alloys. GCMC and its affiliate Sadaci, started up a new pre-treatment facility in Ghent, Belgium in 1998. GCMC is also part owner of Bear Metallurgical Corporation, a major producer of ferroalloys in the United States. This paper reviews the processes at these facilities. Changes in the management of hydrotreating and hydrorefining spent catalysts are discussed in light of recently issued federal regulations that made the majority of spent catalysts a listed hazardous waste.

Jan 1, 2000

By Tamas Kekesi

Anion exchange in HCl media is considered an efficient alternative to the combination of the conventional purification methods. Anion-exchange distribution functions have been determined for cobalt and the main impurity elements by the technique of batch equilibration. Results were confirmed by spectrophotometric investigations and elution tests. Based on the new and the available distribution functions, combined with the assessment of thermodynamic stability, a procedure of anion exchange separation has been devised to eliminate virtually all the impurities from the cobalt-chloride solution. Separation of copper has been enhanced by the introduction of a preliminary step under reduced conditions. The rest of the impurities are eliminated in a second anion-exchange step applying rinsing and elution stages under oxidized conditions. The optimum parameters of the procedure have been determined according to performance characteristics (purification ratios, yields and volume efficiencies) derived from the analysis of elution curves obtained with laboratory scale ion-exchange columns. Special computer programs have been developed to facilitate thermodynamic simulation, analytical correction and data processing.

Jan 1, 2003

By Michael P. Heisel

Solinox is a physical scrubbing process capable of removing a number of noxious materials from off-gasses, especially SO2, hydrocarbons, halogens, heavy metals such as dust, etc. As these materials are dissolved physically, (not chemically bound), the solvent is absolutely stable and no by-products are formed in the scrubbing cycle. The process has? been installed in three plants up to now, treating from approximately 30 MMSCFD to approximately 100 MMSCFD. These installations are in a non ferrous metal smelting operation, in a cellulose factory, and in a roasting process.

Jan 1, 1992

By W. J. Guay

Scrubbing of simulated copper reverberatory furnace gases containing 1.0 percent sulfur dioxide with the minus 74 ~m fraction of the San Manuel tailings has shown sulfur dioxide removals of almost 100 percent over an effluent pH range of 3.1 to 4.6 and a wide range of liquid to gas ratios with absorptions of 11 to 17 Kg of sulfur dioxide per tonne of minus 74 um slimes. The high reactivity of the tailings slimes with S02 indicates that the reaction rate is not controlled by the slow dissolution of calcium carbonate in sulfurous acid which characterizes scrubbers using ground limestone. The interpretation of these results has been considerably enhanced by wet chemical analysis and emission spectrographic analysis which show that calcium and iron account for about 90 percent of the SO2 absorption with the rest being accounted for by aluminum, magnesium, potassium, and sodium. Mineralogic examination confirms the, chemical and spectrographic analyses showing that the major constituent removed from the slimes is calcium carbonate, with lesser amounts of chlorite and montmorillonite (silicates containing iron, magnesium, aluminum, and calcium) being removed.

Jan 1, 1981

By Zhang Huaiwei, Shi Xiaoyan, Li Xinlin, Sun Fei, Hong Xin

"The control of the slag properties has become very essential in improving the separation between the slag and the matte in the copper slag cleaning process. The goal of the present work is to characterize the copper converting slag through chemical analysis (XRF), X-ray diffraction (XRD), scanning electron microscopy (SEM) coupled with energy dispersive spectroscopy detection (EDS) and thermal analysis (DSC). The majority of the identified elements were Fe, Cu, Si and 0. The XRD has presented compounds such as Fe2Si04, Si02, CuFe204, Fe304, and Cu. The main existence of copper element was the metallic copper due to the entrainment loss. Slight amounts of copper were existed as the CuFe204 in the slag. The density, viscosity, electric conductivity and the thermodynamic property of the molten copper converting slag were also investigated in the study.IntroductionCopper slag, which is produced during pyrometallurgical production of copper from ores, contains materials like iron, alumina, calcium oxide, silica etc. For every tonne of metal production about 2.2 ton of slag is generated [l]. The slags of copper converting process contain about 5% of copper and about 20% magnetite. The copper are present in the slags either as physically entrapped or in chemically dissolved [2-3]. The traditional slag cleaning method is electric furnace process including two steps, intensive slag reduction and quiet sedimentation. Although the process is suitable for the various copper slags, it is also with the higher energy consumption [ 4-7]. The slag characterization studies are the fundamental step in the definition of an appropriate recycling process for saving the energy consumption."

Jan 1, 2013

By WenCai Li, Yong Ren, Shuai Niu, Xin Hong

"Temperature measurement is very important in metal smelting process. Many devices are used to realize non-contact temperature measurements. Compared to conventional thermocouple, infrared temperature measurement has it's unique advantages. However, using an infrared temperature measurement at the top of the furnace can not obtain the desired optical signal because of disturbance from slag layer, high-temperature gases and other effects. A real time thermometry system with dual-wavelength radiation was presented to get optical signal emitted from molten metal through bottom-blowing nozzle. Taking into account the advantages and disadvantages of bottom-blowing devices, a MHP (Multiple Hole Plug) bottom-blowing device was used, through which the optical signal was transferred to the infrared thermometer by use of optical fiber. After conversion and analysis in real-time, the result was displayed and recorded in computer. After calibration, it could be a good predictor of temperature trend in a metallurgical process. IntroductionAt the refining stage of steelmaking, in order to achieve predetermined chemical composition and temperature, high-temperature molten steel is refined in a furnace such as converter. Because the refining process involved with chemical components and reaction velocities in the furnace rely on the temperature of steel, it is necessary to know the temperature accurately in real time during the process. And temperature measurement is also helpful for the end-point judgment. The temperature in the refining process changes quickly, for instance, in a converter, 300t molten steel is processed in only about half an hour.At present, traditional way of temperature measurement is using a thermocouple probe mounted on a lifter called a sub-lance. The thermocouple is immersed in molten steel and its temperature is measured during the short period until the thermocouple is fused. Accurate and reliable temperature can be obtained by this method, but in consideration of the discontinuous measurement and the costs, missing the end-point temperature may sometimes occur.According to the above background, a method in which a temperature-sensing element such as a thermocouple is immersed directly in molten steel is not suitable for the continuous temperature measurement because materials having such stability are not available. Therefore, radiation thermometry is promising. There have been some reports on radiation thermometry through an observation nozzle through the bottom or side of a refining furnace [1, 2]."

Jan 1, 2014

By Norihiko Fukatsu, Takashi Iwamoto, Noriaki Kurita, Koji Katahira, Kunihiro Koide, Teruo Ohashi

"The galvanic cell-type hydrogen sensor employing CaZro.9Ino.t03-a. as the solid electrolyte was designed for the measurement of hydrogen activities in molten copper under industrial .conditions. The sensor probe consists of the cap-shaped solid electrolyte with porous platinum electrode on the inside and alumina refractory tube. The gas mixture of the composition 4%H2-0.5%02-Ar was made to flow on the inside electrode. The hydrogen sensor probe was inserted directly into molten copper and the melt was used as the outer electrode. The effect of oxygen activity gradient to EMF was eliminated theoretically by measuring the oxygen activity in the melt simultaneously with an oxygen sensor. The high stability of output and excellent response to the change of hydrogen activity were obtained over the wide range of industrial copper melting conditions.IntroductionIn the metal casting process, hydrogen easily dissolves in molten metals from water vapor in the surrounding atmosphere. Owing to the large difference in hydrogen solubility between liquid and solid metal, dissolved hydrogen becomes a cause of the defects of blowholes in castings or ingots. It is necessary to control the hydrogen content in the molten metals [l]. Using proton-conducting ceramics as a solid electrolyte, high temperature-type hydrogen sensor can be constructed [2]. SrCe03- and BaCe03-based perovskite-type oxides exhibit appreciable proton conduction under hydrogen containing atmosphere at high temperature [3-5]. A hydrogen sensor for molten aluminum using CaZro.91no.103-a. has been developed and widely used in the ·process control in the aluminum melting industry [6,7]. The same type of hydrogen sensor has also been expected in the copper melting industry. .. However, CaZro.91no.103-a shows ·not only proton but also oxide ion conduction in the high temperature and at low oxygen activies like the copper melting· conditions. Then we studied the oxide ion conduction in CaZro.91no.103-a. iit · detail [8]. From the consideration on the EMF of the galvanic cell employing this material as electrolyte, it was shown that the unknown hydrogen activity may be precisely determined from cell potential which is corrected for the effect of oxygen potential gradient And the hydrogen sensor based in this principle was constructed and tested in laboratory-scale [9,10]. We repeated the similar tests in factory-scale and developed the sensor system for practical uses [11, 12]. In this report, the structure and system of the hydrogen sensor for molten copper will be introduced first. The reliability of the sensor will then be demonstrated from the results of experiments for sensor probes carried out in TYK's laboratory."

Jan 1, 2000

By M. A. Verhaege, Stanislav S. Naboychenko, Vladimir I. Skorohodov, Olga Yu. Goriaeva

A new technology for the processing of secondary raw materials containing precious and Platinum Group Metals (PGMs) has been designed at the Laboratory of Heavy Metals at USTU. The technology is based on hydrometallurgical processing of the materials followed by sorption separation of the PGMs from the leach solution. Different versions of the technology can be realised depending on the type of processed material but the fundamentals are similar. Some parts of the technology can easily be integrated into existing flowsheets. The stage of sorption removal of platinum and palladium was tested on the site of the Joint Stock Company (JSC) "Uralelectromed" on pilot plant scale. A process was developed to obtain fine gold, silver, platinum and palladium. No waste is produced because all solutions are recycled. There are no gas emissions. Selective sorption of platinum and palladium from silver-containing solutions is possible even if the concentration ratio of silver to PGMs is one thousand to one. Sorption behaviour of the PGMs as a function of the bulk metal concentrations was studied. Recovery of 90-95% of platinum and 70-80% of palladium is possible.

Jan 1, 2000

By S. B. . Tyrrell

This paper describes research carried out to develop and optimise a process to extract lithium from the processed waste of spent lithium ution of lithium salts can be used to produce a pure lithium hydroxide solution, From this, lithium carbonate is produced, the major precursor for other lithium chemicals and for new lithium batteries. Hence, the recycle loop can be closed. Significant variation in the composition of the battery waste has been observed. Small amounts of metals other than lithium and certain anions can present technical difficulties such as electrode dissolution and membrane fouling. Pre-treatment of the waste, together with an optimum combination of cell materials and operating parameters has been found to enhance separation and alter the energy consumption of the process.

Jan 1, 1999

By Go-Gi Lee, Jae-Young Jung, Myung-Duk Seo, Hyun-Na Bae, Seon-Hyo Kim

"Bubbles form at the anode during the electrowinning of magnesium and cause hydrodynamic acceleration and electrical field disturbance. A three-dimensional computational model was developed to investigate the effects of the geometry of the electrochemical chamber and the size distribution of bubbles on the fluid flow in the pilot plant. The results are validated by measurements of the surface characteristics of molten salt and the bubbles formed. Fluid flow at the surface was recorded with a high speed camera, and the distribution of bubble size is determined by inspecting the video images frame by frame. The measured size distribution of the bubbles is entered into the computer simulation of a multi-phase flow. A sloped roof is installed above the electrodes, to enhance the flow of the molten salt, thus resulting in higher current efficiency, lower energy consumption, and higher quality of magnesium metal.IntroductionTitanium's excellent properties of low density, high specific strength, high temperature strength, and exceptional resistance to corrosion are highly beneficial to diverse applications including aerospace, automotive, construction, and medical implants. Although the Kroll process[l] and Hunter process have been used for the extraction of titanium in the 20th century, their complicated engineering stages and high production cost, have led to further research into new processes such as FCC Cambridge, Armstrong and TiRO. Despite these intense research efforts, no process has yet been developed that is more economical than the Kroll process, by which most of the global commercial titanium is still being produced."

Jan 1, 2011

By Klaus-Markus Peters, James G. Hemrick, John Damiano

"Work was performed by Oak Ridge National Laboratory (ORNL), in collaboration with industrial refractory manufacturers, refractory users, and academic institutions, to employ novel refractory systems and techniques to reduce energy consumption of molten material processing vessels found in industries such as aluminum, glass and pulp and paper. The energy savings strategies discussed are achieved through reduction of chemical reactions, elimination of mechanical degradation caused by the service environment, reduction of temperature limitations of materials, and elimination of costly installation and repair needs. Key results of several case studies resulting from US Department of Energy (DOE) funded research programs are discussed with emphasis on applicability of these results to high temperature processing industries.IntroductionRefractory materials are limited in their application by many factors including chemical reactions between the service environment and the refractory material, mechanical degradation of the refractory material by the service environment, temperature limitations on the use of a particular refractory material, and the inability to install or repair the refractory material in a cost effective manner or while the vessel is in service. All of these limitations reduce the energy efficiency of the process as degraded refractory materials lead to loss of process heat (reduced insulation by refractories) and the need for maintenance through repair or replacement of refractory linings.This situation is conceptualized in Figure 1 which shows that when the thickness of the refractory wall is reduced by chemical or mechanical degradation, the heat losses through the wall increase exponentially. The subsequent maintenance to repair such conditions often requires cooling of the furnace or refractory lined vessel which entails loss of energy due to cooling and consumption of energy due to reheating. Additionally, production time and capability are sacrificed.Additionally, in most applications where refractories are used (metal melting furnaces, glass furnaces, steel making furnaces, gasifiers, etc.) wear of the refractory lining is not uniform. Very often, specific areas will wear (become thinner) more rapidly due to exposure to more corrosive or erosive conditions. This concept is illustrated in Figure 2, through the example of excessive metal line corrosion."

Jan 1, 2009

By Ragnhild E. Aune, Shahid Akhtar, Reza Beheshti

"The potential use of Black Dross (BD) as a raw material for the production of refractories, fluxing agents and glasses is the main motivation of the present study. Heat treatment experiments were carried out in Ar, and under reduced pressure (20 Pa), to evaluate the salt removal efficiency. The chemical composition of the BD after heat treatment was investigated by SEM-EDS and XRD analyses. Based on the present results, it is established that the salt starts to evaporate at ˜1273 K in Ar, and under reduced pressure. The salt removal efficiency in a 20 g sample was found to increase in both cases as a function of time and temperature. Moreover, in Ar the chlorine concentration was lowered to 0.3 wt% after heat treatment at 1523 K for 10 hours. Under reduced pressure, however, 0.2 wt% residual chlorine was obtained after 8 hours at 1473 K.IntroductionIt is believed that aluminum recycling in the near future will become the main route of aluminum production [1]. Black dross (BD) that is produced during this process contains, among other things, high amount of salts like NaCl and KCl [2, 3]. Almost 800,000 tons of BD is annually land filled in United States and this number continues to grow with the increase in aluminum recycling [2]. The BD should be dumped in controlled land field and it is costly procedure [4, 5].The water-soluble compounds in BD react with water or environmental humidity and release chlorides into the water and/or generate toxic gases such as H2, CH4, NH3 and H2 S [6-8]. In the Europe, BD is considered as toxic waste and its disposal as landfill is forbidden [8, 9]. After salt removal, the BD is considered to be non-hazardous and can be buried under ground [10].On the other hand, BD do also contains many relatively valuable compounds that may be changed in to useful materials as a result of further treatment [11, 12]"

Jan 1, 2012

By Niander A. Cerqueira, Pâmela Berçot, Afonso G. Azevedo, Victor B. Souza, Victor T. Bartolazzi, Bruno Padilha

In recent years, concern about environmental issues has become a parameter to consider in the projects in engineering. In order to reduce the impact that the tire improper disposal may result for the environment, we sought a solution to this problem. This article proposes the use of rubber scrap tires as fine aggregate in concrete production. The material produced was analyzed by a bending test, resulting in product quality, in particular for application in situations requiring a more ductile material.

Mar 1, 2017

By Junji Shibata

Zeolite synthesized from coal fly ash has many intelligent properties such as cation exchange, adsorption, catalyst and so on. The suitable use of the zeolite, however, is not established in an actual commercial scale yet. From the viewpoints of an effective usage of coal fly ash and the zeolite obtained from coal fly ash, we propose the new concept for environmentally friendly usage of zeolite, in which coal fly ash safely returns to the soil with growing plants and purifying wastewater. This method can make great contribution to recycle of coal fly ash, to purification of high nutritious water and to tree planting.

Jan 1, 2002

By K. Dzieciol

The paper presents a study about three image correlation methods ?common cross-correlation, mutual information and phase-correlation ? applied to characterize microstructures reconstructed with X-ray tomography. It is shown that phase correlation is not only the fastest, but also the most sensitive method for detection of similar microstructure features, cavities in the present case. A new image correlation indicator is proposed, which takes into account both the phase shift and the amplitude of similar features in compared images. Some preprocessing aspects related to the tomographic reconstruction and filtering out of characteristic noise are also discussed.

Jan 1, 2009

By Y. Takasaki

For zinc hydrometallurgical extraction, reducing the electric power consumption of the electrowinning process is an important issue for energy savings. At the Zinc & Lead 2000 symposium, the authors suggested that by using the Pb-0.5%Ag-0.6%Ca alloy, the electrolysis energy can be decreased compared to the conventional Pb-0.9%Ag alloy. In this study, the corrosion behaviors of the Pb-Ag-Ca electrode in a sulfuric-acid electrolyte were investigated. Based on the results Or me Pb-0.5%Ag-0.6%Ca anode after 20 days of electrolysis, the bath voltage and the quantity of anode slime decreased compared to the Pb-I%Ag anode. Subsequently, beta-PbO2 on the electrode surface was detected by XRD and its peaks were sharper than the Pb-1 %Ag anode. Moreover, a dense beta-PbO2 layer on the 0.6%Ca a anode surface was observed. Therefore, it was suggested that the dense beta-PbO2 layer on the anode surface is one of the factors that leads to a lower bath voltage and decreasing quantity of anode slime.

Jan 1, 2003

By Wenqiang Bao, Qijie Zhai, Ting Wang, Shaobo Zheng, Huigai Li

The type of inclusions with different sizes in as-cast low carbon steel strip which is deoxidized by Si–Mn has been characterized by scanning electron microscope (SEM) and transmission electron microscopy (TEM). SEM observation and analysis suggested that the type of inclusions larger than 1 μm is manganese silicate. TEM analysis was carried out to investigate the composition and structure of nano-inclusions. Inclusions with diameter about 100 nm are manganese silicate, MnS–Si(Mn)Ox complex particles and isolated cubic Al2O3. Furthermore, HREM observations have revealed that there were two kinds of ultrafine particles in size range of 5–10 nm. One is spherical monoclinic Cu2S; the other is silicon-iron oxide particles with morphology of long strip. In addition, some thermodynamic calculations were performed to explain the corresponding relation between the type of inclusions and their size.

Mar 1, 2017

By Takao Mori

Novel rare earth boron icosahedral compounds are investigated as potential high temperature thermoelectric materials. REB50-type compounds and REB22C2N compounds were synthesized and the thermoelectric properties measured. Seebeck coefficients in excess of 200 V/K are observed at temperatures above 1000 K for the REB50-type compounds. Strikingly, n-type behavior was observed for REB22C2N. Up to now, non-doped B12 icosahedral compounds have all been p-type. The discovery of an n-type compound is extremely important in terms of the potential development of this class of compounds as viable thermoelectric materials. Low thermal conductivities of < 0.03 W/cm/K at room temperature was observed for these rare earth boron cluster compounds.

Jan 1, 2006

By Wufeng Jiang, Jiann-Yang Hwang, Suju Hao, Yuzhu Zhang

Magnetite powder and coke powder were used as experimental materials and H2 as reducing agent in a high temperature vacuum tube furnace. The change rules of magnetite powder (MP), mixed coke powder and magnetite powder (MCMP), and carbon coated magnetite powder (CCMP) in the process of reduction were studied. The samples were determined by field emission scanning electron microscopy and X-ray diffraction. The results show that, with the increase of reduction time, the reduction degree of magnetite powder is improved. Under the same reduction conditions, the addition of coke powder improves the reduction rate. Compared with MP, when the reduction time was 120 min, the reduction degree of MCMP was 30% greater; and the reduction degree of CCMP was 39% greater. The mixed grinding of magnetite powder and coke powder is a better way to add carbon. Under the same reduction conditions, compared with MCMP, the reduction degree of CCMP was 9% greater when the reduction time was 120 min. After the reduction of CCMP, the number of pores in the sample increased and the structure was loose. The results of this study have some reference value for improving the reduction rate of magnetite powder.

Mar 1, 2018

By Wantae Kim

In order to establish the optimized recovery process for heavy minerals from Korean beach sand, we investigated the several physical separation methods such as gravity and magnetic separation followed by mineralogical characterization. There was clear relationship between the particle size and heavy mineral content that heavy minerals were mostly concentrated in the particles below 100mesh. Gravity separation using the spiral and shaking table separators made it possible to concentrate heavy minerals by rejecting the light and coarse particles consist mainly of quartz and other non-valuable minerals. The high-intensity magnetic roll separator and subsequent induced magnetic separator were applied to fractionate magnetic particles according to their magnetic susceptibility. The content of TiO2 of high susceptible ilmenite-rich fraction was 43.98wt.% while those of ZrO2 of non-magnetic and magnetic residue were 6.78wt.% and 3.11wt.%, respectively.

Jan 1, 2006