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By V. Ramachandran

In view of the increasing environmental regulations that have been promulgated in the last 30 years, non-ferrous smelters and refineries have learnt to handle effectively the process waste streams that need to be bled from the system for impurities' control The cations of concern are copper, lead, zinc, cadmium, mercury, thallium, nickel, silver, sodium and potassium. Anionic species of arsenic and selenium also need to be addressed, Sulfates and chlorides-not a major concern at present-have come under scrutiny in the recent past. The current paper reviews several treatment options with reference to a) types of waste streams processed b )process chemistry c)discharge options and recovery of treated water and d) sludge disposal The long term goal of any smelter and/lor refinery should be to achieve zero liquid discharge from the plant. Methods to obtain zero discharge are discussed.

Jan 1, 2003

By P. Chris Pistorius

"Ilmenite smelting involves partial reduction of iron oxide from a slag consisting mainly of T1O2, T12O3 and FeO, yielding as products iron (with approximately 2% carbon) and titanium slag. Slag purity requirements preclude any fluxing additions, and the aggressive nature of the slag necessitates a furnace freeze lining. Large departures from thermal and chemical equilibrium hold in the smelter, with possible implications for process stability. The slag is approximately 150K. hotter than the metal, which means that the metal temperature is below the slag melting point; this difference in temperature has been shown to lead to formation of a solid TisOs-rich layer between the slag and metal. Recent equilibrium measurements have confirmed that the slag and metal are not in chemical equilibrium either, with significantly more reducing conditions in the metal than in the slag. After solidification, the pseudobrookite slag structure is metastable below approximately 1400K, and may transform upon slight oxidation.IntroductionThe natural mineral ilmenite is the main source of titanium, which is mainly used to produce Ti02-based pigments. Ilmenite has the ideal formula FeTiC>3, but natural minerals can be partially oxidized (to contain some Fe3+), and typically contain MnO and MgO as well, together with associated silicate minerals. Smelting is one of the methods to upgrade ilmenite for subsequent T1O2 pigment production; smelting involves partial reduction of FeO to form metallic iron as a byproduct and titanium slag as the main product. Reduction is typically controlled to yield a slag which contains around 10% FeO, 85% (Ti02+Tij03) and 5% impurity oxides (mainly MnO, AI2O3 and S1O2). An example of a typical average slag composition from reduction of South African ilmenite is shown in Table I. As this indicates, a significant side reaction is reduction of some T1O2 to T12O3. The relative extents of reduction of FeO to Fe and of Ti02 to T12O3 are such that the slag stoichiometry is close to that of the pseudobrookite phase [1]. Pseudobrookite has the structure AB2O5 (where ""A"" and ""B"" are different cation sites); the phase which makes up the bulk of solidified titanium slag has the AB2O5 structure and stoichiometry [2], and can be viewed as a solid solution of FeTi20s, T13O5, ÌçÔÀ2è5, MgTi20s, AI2T1O5 and C^TiOs [1]. This solid-solution phase is referred to as ""pseudobrookite"" or ""M3O5"" in this paper."

Jan 1, 2012

By Takamitsu Nakasuga, Haiping Sun, Kyushu University, Katsumi Mori

"The kinetic behavior of reduction of chromite ore by liquid iron containing carbon and silicon has been investigated under various experimental conditions to clarify the reduction mechanism. It was found that the reduction rate of chromium ore by liquid Fe-C alloy was very slow. In addition, when carbon and silicon coexisted in the iron melt, silicon was found to preferentially oxidized to form silica, which favored for the fonnation of liquid slag and the rate of reduction was considerably accelerated. The similar effect was obtained by the addition of some fluxes, such as SiO2, Na2B407, CaO-SiO2, which also promoted the formation of a liquid slag and thus the reduction rate in the early stage also increased.IntroductionThe reduction of Cr2O3 is a basic reaction for production of ferro-chromium from chromite ore and for chromium recovery from the slag fonned during the decarburization period of a stainless steel-making process. The reduction of chromite ore consumes much energy and its reaction rate is not so high. Thus, in order to increase the reduction efficiency, it is strongly desired to clarify its reduction mechanism from the practical and the theoretical points of view."

Jan 1, 2000

By Rzyman Michal, Nakamura Takashi, Shibata Etsuro, Grabda Mariusz, Oleszek-Kudlak Sylwia

"Tetrabromobisphenol A (TBBPA) and many systems based on the synergistic effect of brominated organic compounds with Sb2O3 are extensively used as effective brominated flame retardants (BFRs) in many materials such as plastics and textiles. Thermal degradation of BFR containing plastics leads to the formation of hydrocarbons and gaseous compounds such as HBr and SbBr3. Our thermodynamic considerations indicate that these gases can act as bromination agents for metallic oxides such as ZnO, Cu2O, CuO, PbO and FeO. Moreover, these metallic oxides have the thermodynamic tendency to brominate easier than does Sb2O3. The aim of this study was to investigate experimentally the reactivity of ZnO with 1) HBr originating from the thermal decomposition of TBBPA and 2) SbBr3, which is formed during thermal degradation of brominated flame retardant plastics. The thermal treatments of the mixture of compounds of interest were investigated by thermogravimetry coupled with mass spectrometry.IntroductionTetrabromobisphenol A (TBBPA) and many systems based on the synergistic effect of brominated organic compounds with Sb2O3 are extensively used as effective brominated flame retardants (BFRs) in materials such as plastics and textiles. For instance, 4.5 million tons of flame retardant plastics containing BFRs are produced in Japan each year. Thus, in thermal treatments such as the incineration and melting of solid wastes, BFR containing plastics are intentionally or unintentionally included in the wastes. Thermal degradation of BFR-containing plastics leads to the formation of hydrocarbons and gaseous compounds such as HBr and SbBr3 [1-5]. Our thermodynamic considerations [6] indicate that heavy metal oxides such as ZnO, Cu2O, CuO, PbO and FeO should easily react with HBr prior to Sb2O3 and also with SbBr3, the main gaseous product in the thermal decomposition of TBBPA, forming low boiling point metallic bromides suitable for the volatile separation of heavy metals. The metal oxides are also expected to qualitatively and quantitatively affect debromination and decomposition of the flame retardant."

Jan 1, 2008

By Rachel De Lucas

In recent years, as the price of oil soars upward, scientists have started to focus on other energy sources, such as hydrogen. As magnesium can be used for hydrogen storage by forming MgH2, industry will see a growing demand for the hydride. In hydrogen storage and release cycles using magnesium, hydrogen is released from magnesium hydride through hydrolysis and magnesium hydroxide is produced. Therefore, recycling magnesium hydroxide back to magnesium becomes important. The solid oxide membrane (SOM) process is an emerging technology for this process. In the SOM process, MgF2-CaF2-MgO flux is contained in a stainless steel crucible, which works as the cathode. An ionic-conducting YSZ membrane, connected to a liquid metal anode, is partially immersed in the flux. During electrolysis, when the voltage between anode and cathode is higher than the dissociation potential of magnesium oxide, magnesium ions move toward the cathode and are reduced into magnesium vapor. The oxygen ions move toward the anode, passing through the YSZ membrane. They are then oxidized, forming pure oxygen, CO/CO2 or steam (by reaction with hydrogen). The magnesium vapor, generated at the cathode, is collected in the condenser as high purity magnesium. SOM experiments have been conducted with different liquid metal anodes and without reductants. The SOM technique is a highly energy efficient process and with by-products being oxygen or steam, it is also an environmentally friendly green process. A 2-D electrostatics mathematical model was developed as an initial step towards optimizing the design for a three-tube scale-up SOM electrolysis cell. Several possible geometries were examined to develop the scale-up model and convergence of the model was achieved.

Jan 1, 2006

By Shubin Wang

Copper(II) and nickel(II) are often recovered from ammoniacal alkaline solutions by solvent extraction using hydroxyoxime extractants: both copper(II) and nickel(II) are extracted from ammoniacal alkaline solutions and, from the loaded organic phase, nickel(II) is selectively stripped with a dilute acid followed by copper(II) stripping with an acid of higher concentration. Since a small portion of ammonia is co-extracted with copper and nickel, the extracted ammonia should be scrubbed using a dilute acid before metal stripping. In the present study, a mechanistic model has been developed in order to support design and control of this process. The equilibrium distribution ratios of copper(II), nickel(II), and ammonia at 298 K using LIX® 84-I (active component, 2-hydroxy-5-nonylacetophenone oxime) as the extractant are successfully correlated by considering the relevant equilibria. Based on these results, quantitative prediction of equilibrium distribution ratios in the process has been made possible, and suitable conditions for the efficient separation of copper(II) and nickel(II) are discussed.

Roasting treatments were investigated to remove arsenic from a nickel concentrate. The main arsenic minerals and their proportions in the concentrate were niccolite (NiAs)-50%, gersdorffite (NiAsS)-40% and arsenopyrite (FeAsS)-10%. Thermal analysis showed that gersdorffite and niccolite began decomposing when heated above 640 and 830°C respectively. The maximum roasting temperature was limited by agglomeration of the concentrate above 900°C. A small vibrated bed reactor was used to investigate the effects of temperature and gas flowrate, the latter to sweep away evolved arsenic. At 900°C, 24% of the original arsenic remained in the concentrate. SEM examination of the calcine showed that the residual arsenic was associated with the calcium in the gangue minerals. Additions of sulphur (either as elemental sulphur or from pyrite) facilitated the decomposition of the arsenic-containing minerals, decreased reaction with calcium in the gangue and produced calcine containing 4-6% of the original arsenic. Treatment with chlorine during roasting was effective in reducing the arsenic content to similar levels. Generation of chlorine in the bed by sulphation of CaC12 also produced encouraging results. Arsenic, Nickel Concentrate, Roasting, Chlorine, Sulphur, Gersdorffite, Niccolite

Jan 1, 2005

By Leonard J. Friedman

There have been considerable changes in systems, equipment design and materials used in the modern Sulfuric Acid process. Many of these will shape the metallurgical sulfuric acid plant for the year 2000 and beyond. Advances have come from all over the world, and include new scrubbing area designs, catalyst contacting devices, silicon stainless alloys for unlined acid systems, energy recovery from acid heat, stainless converters and heat exchangers, etc. This paper describes each of the process "advances" and presents a review and analysis indicating advantages, operating experience and limitations.

Jan 1, 1988

By S. C. Sharma

The aluminium matrix composites with ceramic dispersoids can be separated by density difference concept. In the proposed work composite scrap is recycled using an oil fired furnace. The scrap is melted in the furnace and temperature is maintained below 740 degree centigrade. Because of the density difference the lighter dispersoids will float and heavier dispersoids will settle down. The clean melt is separated be removing the floating and settled disperssoils, and then filtering using ceramic filters.

Jan 1, 1995

By C. J. Beyke

Slags and/or mattes from three secondary lead producers were studied as part of an effort to develop treatment methods for these lead-bearing residues. Each company used a somewhat different production process. Company A used a reverberatory furnace followed by a blast furnace. Company B used only a blast furnace. Company C used both a reverberatory and a blast furnace, and the scrap material was desulfurized with sodium carbonate prior to smelting. The slag matrix produced from sulfur-bearing scrap consisted mainly of iron-calcium silicates; the slag from desulfurized material was similar, but also contained sodium. In all the slags most lead was present in metallic form, often alloyed with tin, antimony, arsenic, and/or iron. Slag from Company B contained the most alloying elements, often as discrete subparticles within the lead droplets. Mattes were produced at Companies A and B; predominant phases were pyrrhotite and magnetite, while lead was present in metallic form and as galena.

Jan 1, 1995

By R. S. Krarner

Fly ash, a by-product of coal burning power plants, poses a major problem for the utility industry since most fly ash must be landfilled. These quantities may represent as much as 20% of the total material going into landfills. A major problem with fly ash utilization is that although the ash consists of useable components, ash composition can vary depending on the types of coal burned and plant operating conditions. Ash is first characterized using SEM, image analysis, and chemical methods. Processing techniques were developed to separate ash into various components including cenospheres, magnetic spheres, carbon, and clean ash. These products are again evaluated for various utilizations before being used to produce valuable products such as mullite, activated carbon, fillers in plastics, and concrete.

Jan 1, 1994

By Guilian Gao

TbFeCo is a common choice for many rare-earth transition metal films currently used as the magneto-optic layer for magneto-optical: recording devices. Since the environmental stability of RE-TM alloys is typically poor compared with traditional metal oxide particle media, such devices rely on multiple functional overlayers (metallic and/or dielectric) and organic coatings for durability. This paper presents an electrochemical evaluation of the degree of protection of several candidates for the reflective layer, Al, AlCr and AIPt and for the dielectric layer, SiN, AISIN and AIN. Cyclic voltammetry In 0.2M K2SO4 solutions at room temperature revealed that AIPt film offers superior corrosion protection compared to Al and AICr films. Of the three dielectric layers examined, SIN seems to be the most corrosion resistant. Examination by optical and scanning electron microscope confirm the findings of electrochemical experiments. The corrosion resistance of single layers of Al, AICr and AIPt has also been examined and factors affecting their performance are discussed.

Jan 1, 1992

By G. Scavino

A 0.5 wt.% C, 22 wt.% Mn austenitic steel, recently proposed for fabricating automotive body structures by cold sheet forming, due to favorable overall strength and ductility, exhibits plastic localizations during uniaxial tensile tests, whereas no localization happens during biaxial Erichsen cupping tests. Full-thickness tensile and Erichsen specimens, cut from as-produced sheets, were polished and tested at different strain rates. During the tensile tests, the plastic localization phenomena consist first of macroscopic deformation bands traveling along the tensile axis, and then of series of stationary deformation bands, each adjacent to the preceding ones; both types of bands involve the full specimen width and yield macroscopically observable surface relief. No comparable surface relief was observed during the standard Erichsen tests. The stress state being known to influence plastic localization phenomena, reduced-width Erichsen tests were performed with 10 to 30 mm width polished specimens, in order to explore the transition from biaxial to uniaxial loading.

Jan 1, 2009

By Sergei A. Degterov

A thermodynamic database for the slag, matte and liquid copper phases in the Cu-Ca-Fe-Pb-Zn-Si-O-S system has been developed for the ranges of compositions of importance to the production of copper. When used with the Gibbs energy minimization software and other databases of the F*A*C*T thermodynamic computing system, this database will permit the calculation of matte-slag-copper-gas phase equilibria that take place during copper smelting and converting. The calculations reproduce within experimental error limits all available experimental data on phase diagrams, activities of components, enthalpies of mixing, matte - alloy miscibility gap and tie-lines. The calculated solubilities of Cu in both S-free slag and slag equilibrated with matte are also in good agreement with experiment under all studied conditions, such as at SiO2 saturation, in equilibrium with Fe, Cu or Cu-Au alloys, at fixed oxygen or SO2 partial pressures and at different contents of Pb, Zn and CaO in the slag. Sulfide contents (sulfide capacities) of the slags are predicted within experimental error limits. The distribution of Pb and Zn among matte, slag, copper and gas has been calculated. The calculations are in good agreement with experimental data and predict the distributions under conditions which are difficult to study experimentally, such as at magnetite saturation or under various oxygen partial pressures and iron to silica ratios in the slag.

Jan 1, 1999

By Tomoya Nihei, Hiroshi Hayashi

"A novel selenium removal process called Recycled Green rust/Ferrite Process is developed by MMC. In this process, a mixed Fe2+-Fe3+ hydroxide compound, green rust (GR), reduces selenate to elemental selenium, while GR is consequently oxidized to magnetite Fe3O4. Sequencing batch-mode experiment showed that the residual selenium concentration gradually decreased with the number of batch test increased. Stable selenium removal was achieved when the number of batch test exceed 15 times. Optimum selenium removal ratio reached 99.95% where initial Se concentration 2.1mg/L decreased to 0.001mg/L. Furthermore, the continuous feeding test carried out through a pilot-scale plant with a feeding capacity 600 L/hr. Approximately 860-hour-feeding test was carried out for the selenium-contaminated groundwater which had an averaged selenium concentration of 0.88 mg/L. Selenium concentration in the effluent from thickener maintained less than 0.01 mg/L (selenium removal rate of 99%) until a net operating time reached 800 hours.IntroductionJapan is one of the largest producers of selenium, and thus there are potential environmental impacts of selenium on soil and aquatic environments. The Mitsubishi Material Corporation (MMC) owns some real estate properties whose soil and groundwater was polluted by selenium and other heavy metals. These sites include former industrial plants: a smelter for nonferrous metal and a fabricating semiconductors and pigments. Selenium in aquatic environment commonly exists in four oxidation states, namely, VI, IV, 0 and -II. Selenate ion (SeO4 2-), the most oxidized form of selenium, and selenite ion (SeO3 2-) are highly soluble and mobile. Elemental selenium (Se0) is insoluble in water and therefore has much lower toxicity. Because selenium is carcinogenic and teratogenic at high concentration, the national effluent standard in Japan is fixed at 0.1 mg/L and the environmental standard at 0.01 mg/L. Although there are several selenium removal techniques, the most conventional process is coprecipitation with a ferric hydroxide because of its simplicity and low cost. It is known that selenite is adsorbed strongly on the surface of ferric hydroxide, but selenate is not. The low affinity of selenate on oxide mineral surfaces was demonstrated by the fact that selenate could be easily displaced by adding competing anions, particularly sulfate ion. Selenate removal from polluted water is one of the most difficult techniques, and more effective methods are desired. MMC developed a novel selenium removal process [1]. In this process, the concentrated slurry that contains Fe(II)-Fe(III) hydroxyl-salts known as Green Rusts (GRs) contributes to selenate removal. The main components of the iron precipitate in the reactor are GRs and their oxidation product, magnetite (Fe3O4)."

Jan 1, 2008

By Michael F. Kitto

The production of sulphuric acid at base metals smelters is predominantly an involuntary activity and now comprises approximately 17% of all-forms sulphur supply in world terms. The majority of elemental sulphur is also produced involuntarily in response to environmental regulations regarding emissions from hydrocarbon processing plants. The paper examines the points of similarity and difference in the sulphur and smelter acid markets, and reviews their interactions. The reasons for the merchant acid market collapse of 1993 are analyzed, and the prospects of a recurrence are considered.

Jan 1, 1996

By Katsutoshi Komeya

Aluminum nitride(A1N) is a theoretically high thermal conductive ceramic, but is a poor sinterable one because of its covalent bond structure. The densification of A1N had to be done first. It was found in 1968 that rare earth compounds as yttria were an excellent sintering aids. Recently more improvement of conductivity was attained by following effects of yttria: (1) trapping of oxygen in A1N sources to form yttrium aluminates, (2)elimination of the aluminates by heating in carbo-reductive atmosphere. Consequently very high thermal conductivity of up to 270W/mK has been developed. Thus A1N applications for substrates and packages have been opened.

Jan 1, 1992

By K. Itagaki, H. Henao

"The experimental study on the phase equilibrium and distribution of minor elements such as chromium and copper between magnesia saturated FeOx-MgO-SiO2 slag and Fe-Ni alloy were carried out under controlled oxygen partial pressure between 10-6-5 and 10-10 using CO and CO2 mixed gas at 1773 and 1873 K.The effect of slag additives such as lime (CaO/SiO2 molar ratio: 1) and alumina (AlO1.5/SiO2 molar ratio: 0.1) on the distribution behavior of the minor elements was also investigated.The value of distribution ratio for chromium, defined by (%Cr in slag)/[%Cr in alloy], is larger than 70 at the pO2 region conducted in the present study for the MgO saturated FeOx-MgO-SiO2 slag at 1773K. These value are almost 4-order higher then that of nickel though the distribution ratio of copper shows similar values with nickel. Analysis of the data indicates that addition of lime in the slag and the increase of temperature reduce the dissolution of chromium into the slag and the addition of aluminum increases the dissolution of chromium into the slag while reduces the dissolution of copper and nickel.IntroductionChromium. is a minor element in a nickel oxide ore but a Japan major component in the secondary material of stainless steel and is also introduced in the Fe-Ni production process due to dissolving bricks of a furnace. Chromium is a concerned matter for the beneficial utilization and disposition of ·slag because Cr6+ is a harmful element. Considering Fe-Ni as an alloy component in steel making, and the demand of high purity nickel, chromium is an -undesirable element that has to be eliminated into slag prior to the steel making, or the production of high temperature refractory alloys. On · the other ·hand chromium is an element of steel alloy for many applications, thus Fe-Ni containing chromium in minor element is desirable in some stainless steel making."

Jan 1, 2000

By Y. Maeda

Non-ferrous smelting furnaces generally lnstal1 a gas cooling system for treatment of waste gas containing S02. From the point of view of corrosion resistance and recovery of waste heat, the high pressure boiler system Is the best way to cool gas, however this system requires high Initial investment and relatively higher operating costs. Because the feasibility of this boiler system greatly depends on the smelting process and scale, other lower temperature systems, e.g. water-cooled Jacket system, are more suitable If the smelting process does not produce enough steam nor generate enough electricity to compensate operating cost. In addition, the water-cooled Jacket system Is simple in structure and easy to operate. For those reasons, it is applied widely. A new smelting furnace. was planned tin our factory and It was necessary to install waste gas cooling equipment. In our case, a water-cooled Jacket system was mo11e feasible because of the low gas volume and high dust content. H was also expected to operate without maintenance for ten years. On the other hand, some leakage problems with the water-cool1ed Jacket had been experienced In the past. That is because S02 in the waste gas changed into sulfuric acid which corroded the Jacket material, As the first step, several data from actual usage were reviewed to throw light on the corrosion process, and an appropriate procedure to determine the operating temperature of cooling water was obtained. For the basis of this study, a water-cooled Jacket system was newly designed and tested for three months in a pilot plant. After this system's performance was confirmed, It was installed In a new furnace as a commercial pl.ant. After one year of operation, the initial thickness of carbon steel Jacket remains almost the same.

Jan 1, 1992

By Jing Zhong, Yugang Li, Chen Yan, Shaoda Zhang, Qian Wang

Online surface quenching technology has been developed for the hot charging process to prevent the surface cracks in high strength low-alloy steel slabs. In this paper, a two-dimensional heat transfer model of surface quenching process was presented. This finite element model includes nonlinear thermodynamic properties, by which the slab temperature distributions were computed. The model predicted temperatures show reasonable agreement with the measurements. The effects of the water flow rate and slab movement velocity on temperature variation during the quenching and subsequent tempering process were investigated. The result shows that the temperature drop increases but the tempering temperature changes slightly with increasing water flow rate and decreasing slab velocity. Keeping the slab movement velocity at 1.2-2.1m/min and the water flow rate at 55-70m3/h, the slab surface experiences a temperature drop of 400-600 firstly, then recovers above 650, the quenching and energy-saving effect are remarkable.

Jan 1, 2015