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By Stephan Mulch, Christian His, Patrick M. Stephan, Thibault Champion

"When fuel costs increase dramatically, waste to energy (WTE) conversion technologies become a good alternative to produce energy. The potential energy available in domestic wastes, in developed countries, could be upwards of 4% of their total energy needs. Due to low energy recovery and low level of treated domestic wastes in many countries, the energy coming from waste is generally less than 0.5% of the country needs.Domestic waste incineration can convert heat to electricity for industry and housing and allow waste volume reduction in countries where land fills are a scarce resource.There is a request to improve existing combustion technology by increasing energy recovery with better heat transfer in the boiler and also by increasing lining durability with more resistant materials and technologies.The knowledge of corrosion phenomena and material performance allows Saint-Gobain Group to develop and propose high performance refractory lining solutions.IntroductionThe interest in alternative energy has been growing dramatically in the two last decades due to several combined factors, such as global energy demand, fuels prices evolution (e.g. crude oil, Figure 1) or environmental and geopolitics factors"

Jan 1, 2008

By Jamil M. Khalifeh, Shadia J. Ikhmayies, Bothina A. Hamad

"We computed the optical properties of the cubic niobium nitride (o-NbN) compound using the full potential linearized augmented plane wave (FL-LAPW) method within density functional theory (DFT). The complex dielectric function and optical constants, such as optical absorption coefficient, refractive index, extinction coefficient, energy-loss spectrum, and reflectivity, are all calculated and compared with experimental results. The behavior of the computed quantities is similar to that obtained experimentally, but the optical positions are shifted to lower energies. This shift was related to the strong interband transitions, which are located at energies higher than 5 eV for NbN- as they are for IV B transition-metal mononitrides- and they appear in the computed spectra and not in the experimental spectra. These interband transitions simply shift the position of the reflectivity edge or the screened plasma frequency to the longer wavelength side.IntroductionIn recent years, NbN, as a transition metal nitride, has become a very popular material due to its high hardness, melting point, wear resistance, chemical inertness and temperature stability, which makes it suitable for use as emission cathodes in microelectronics and sensors, optical films and micro-mechanics etc [l]. Niobium nitride has long been known as highly polymorphic material, for which several crystalline structures have been reported in the literature [2]. These structures include the well known super-conducting rock-salt (Fm-3m, or Bl) structure (o-NbN), the hexagonal structure with space group p63/mmc and prototype Fe2N (18fuN), the hexagonalstructure with space group p63/mmc and prototype NiAs ~-NbN) and others.There has been a lot of computational studies for the structural and electronic properties ofNbN [3, 4-7], but according to our knowledge there is not any computational work that has been devoted to study the optical properties of this transition metal compound. At the same time a number of authors had performed experimental work in this direction. For example, Xin-kang et. al [l] studied the microstructure and optical properties of magnetron sputtered NbN thin films. Torche et. al [8] studied the composition, structure, electrical and optical properties of nonstoichiometric niobium nitrides. Newport et. al [9] investigated the reflection and transmission spectra of cubic niobium nitride films, and Tanabe et. al [10] had investigated the optical parameters and reflectivity of reactively sputtered NbN thin films by using in situ ellipsometry."

Jan 1, 2013

By A. Cullaj

During a period of 15 years the metallurgical and chemical complex of Elbasan containing more than 15 principal plants, producing cast-iron, steel, coke, nickel carbonate, nickel, cobalt, chromium and other products, discharged into air, river water and soil an extensive amount of hazardous wastes containing high toxic substances. A monitoring study for the levels of heavy metals in soils nearby the former plant is carried out for the first time. Very high levels (total and extractable) of contaminants such as nickel, cobalt and chromium are found in samples taken from a relatively vast territory including the city of Elbasan, situated 8 kilometres far from the plant. The most polluted samples present a total content of 1211.8 ? 2949.6 mg/kg Ni, 97.0 ? 181.2 mg/kg Co and 1358.7 ? 4130 mg/kg Cr. These levels exceed several times the phytotoxic thresholds and present a potential hazard for the inhabitants. This study, as part of a bigger multinational project on solid decontamination, will also serve to the possible application of the new phytoremediation and phytoextraction technologies, being developed in parallel in this project.

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 Jhon Cuya

Titanium dioxide is the well-known catalyst for the photodecomposition of water in UV region and its nanoparticles show better performance than its bulk materials. Furthermore, partially sulfurized TiO2 is expected to be chemically stable and have an enhanced photocatalytic activity compared with TiO2. For this purpose, the sulfurization behavior ofTiO2 nanopartic1es was thermogravimetrically (TG) studied by a thermo-balance with a quartz spring using CS2. From the TG curve of TiO2 nanopartic1es, first, the weight decrease appeared down to around 8 wt% and then sulfurization reaction started at around 500°C at a heating rate of 1 C°/min. The weight increase curve showed a maximum of ca 30 wt% at around 750°?C and then gradually decreased to ca 12 wt% at 1000°C. This would be caused by the formation of TiS2 followed by the decomposition ofTiS2 to lower sulfides, such as Tit.0.8S2 and Ti3S4. From the comparison of the sulfurization of TiO2 nanoparticles with that of anatase, rutile and Ti(OH)4, it was found that TiO2 nanoparticles showed a similar behavior to that of Ti(OH)4.

Jan 1, 2003

By M. J. Perpich

Electrochemical and chemical leaching tests were carried out on chalcocite, covellite and chalcopyrite in acidified iron sulfate solutions sparged with a mixture of O2 - SO2. The gas mixture catalyzed the ferrous to ferric oxidation reaction in situ and, therefore, increased the redox potential and oxidizing strength of the solution. Anodic polarization curves in dilute sulfuric acid on copper sulfide electrodes showed that chalcopyrite passivates and dissolves at current densities orders of magnitude less than chalcocite and covellite. The addition of a depassivating agent (Ag+) increased the passive current density of chalcopyrite and caused breakdown near 0.625 V (SCE). The depassivating effect was also observed during the leaching of chalcopyrite particulate samples as small amounts of Ag+ added to acidified iron sulfate solutions in the presence of O2 - SO2 mixtures greatly increased the leaching rate and the total amount of Cu oxidized (> 90%). Passivation was prevented in the absence of Ag+ by decreasing the initial oxidizing power of the solution and by pretreating the sample in a reductive leach. Both of these methods resulted in transformation of the chalcopyrite surface from its characteristic greenish-gold into deep black. Increased concentrations of Fe+++ due to 02 - S02 sparging were then able to oxidize the transformation product.

Jan 1, 1999

By David Ellis

The next generation of Reusable Launch Vehicle (RLV) will utilize regeneratively cooled combustion chamber liners in the engines. The current design calls for using a new Cu-8 at. % Cr-4 at. % Nb (Cu-8 Cr-4 Nb) alloy for the liners. Work is ongoing to characterize the thermophysical and mechanical properties of the alloy from - 253 to 800°C, the temperature range to which the alloy will be subjected during service. The alloy has been commercially produced in quantity for NASA. The powder size has been characterized and the microstructure examined. The powder was extruded into bar using a commercial extrusion press. In addition, samples have been hot isostatically pressed (HIPed) at NASA Glenn Research Center. Both processing methods produced fully consolidated material. Transmission electron microscopy (TEM) revealed highly faulted Cr2Nb and some elemental precipitates. Cryogenic tensile testing showed the extruded specimens had significantly higher strengths than NARloy-Z (Cu-3 wt % Ag-0.5 wt % Zr) even after being subjected to a simulated braze cycle. The Young's moduli (Cu-8 Cr-4 Nb) were lower than NARloy-Z. The lower moduli is highly beneficial for reducing thermally induced stresses in rocket engine combustion chamber liners and similar applications.

Jan 1, 1999

By H. Bernier

The Noranda Inc., CCR Division, copper refinery located in Montreal-East, Québec, Canada, has expanded over the years to reach a capacity of 410,000 metric tons of cathode production per year. The expansion process resulted in nine, parallel, 200 m. long bays each equipped with its overhead cranes and manually operated washing machines. Anode scrap washing and piling was done manually. The mechanization of the tank house involved the elimination of 18 cells at one end of each of the bays in order to install transfer conveyors where anode scrap and cathode loads are deposited by the bay cranes. The cathode loads are brought by new transverse cranes to new machines where cathodes are washed, piled in predetermined bundle weights, check weighed, strapped then shipped in trucks or railroad cars. Suspension bars are automatically removed, stacked in magazines and sent back to the starting sheet machines. Anode scrap loads are brought to machines located near the anode furnaces where they are washed and piled in bundles for easy charging. The mechanization has eliminated numerous hazardous jobs and has realized a reduction of 0.2 man-hours/ton. After these modifications, the refinery production capacity now stands at 370,000 metric tons per year.

Jan 1, 1987

By A. V. Tarasov

The nonferrous metals industry has been a sector with one of the highest growth rates during the recent years. The prospects for the Russian metals industry during the period until 2010 are associated first of all with a growing domestic demand for its products. The technological level of the metallurgical operations in Russia is relatively low in comparison with industrially developed countries: the average energy requirement is higher by 20% to 30%; the amount of generated waste in the process of rolled products manufacture is twice as high; the average labor productivity is lower by 2.5 to 3.0 times; the overall negative environmental impact is twice as high. Improvement of the technological level of the nonferrous metals production under the conditions of market economy is possible by application of innovative technologies for the development of this sector. The main trends for development of the nonferrous metals sector are: - meeting of more stringent requirements to the quality of concentrates; - more complete recovery of associated elements as commercial-grade products; - development of continuous process lines based on autogenous, resource-saving and environmentally safe processes; - use of combined technologies, including pyrometallurgical, hydrometallurgical and upgrading processes; - expansion of the fields of application for nonferrous metals and their alloys.

Jan 1, 2006

By M. C. Ruiz

The conventional pyrometallurgical methods to treat copper sulfide concentrates include generally, one or more oxidizing steps where the formation of SO2 gas can not be prevented. From the economical point of view and the nature of some of the processes in which SO2 is produced, its complete capture is not feasible; therefore an important fraction is released to the atmosphere as fugitive emissions. In this research, the reduction of chalcocite was studied in the presence of lime as an alternative method, which overcomes the pollution problems related to SO2 emissions. The effect of temperature, time, concentration of carbon and CaO on the reduction rate were studied. Among these variables, temperature affects most the reduction rate. Conversions over 95 % can be obtained in less that 20 minutes at temperatures over 1000 ° C. The measured partial pressures of the gaseous components indicated that the chalcocite reduction proceeded through the gaseous intermediate species CO, C02, and the overall kinetics was controlled by the Boudouard reaction. The kinetic model In(1-X)= kt fits well the experimental data. Apparent activation energy of 3 14 kJ/mol was calculated for the temperature range of 900 0C-1050 °C.

Jan 1, 1999

By Kenshi Kawabata, Mitsuji Ueda, Junko Umeda, Katsuyoshi Kondoh, Kantarou Kaneko

Solid-state recycling process of in-house scraps of machined magnesium (Mg) alloy wastes has been established to directly produce wrought materials via the repetitively plastic deformation by Roll-compaction (RCP) and the conventional hot extrusion. The coarse chips, wasted in machining AMX602 (Mg-6Al-0.2Mn-2Ca) cast billets used for the gate bar used in Electronic Toll Collection (ETC) of the high-way system, were employed as the input materials in this study. RCP process enabled to serve coarse Mg alloy powder consisting of refined grains and intermetallics with no re-melting. They were easily consolidated by hot extrusion, and their wrought alloys showed both homogeneously refined grains less than 1~2 µm by dynamic recrystallization and randomized texture by repetitive plastic deformation on the input wastes. These materials revealed extremely advanced mechanical properties of high tensile strength of 356MPa and high ductility of 14.8%, compared to the originally virgin materials with 270MPa TS and 5% elongation. When applying the same Mg alloy wastes via RCP process to the mass production in the company, the large-scale extruded materials also indicated the superior tensile properties. It means that this direct solid-state process is held as “Up-grade recycle of metal wastes”.

Jan 1, 2008

By Jeffrey F. Adams

Gypsum fouling is a common problem in the hydrometallurgical industry. It is a particular problem in free sulphuric acid neutralization, or iron removal operations where sulphates are removed from aqueous solutions by the addition of calcium-containing bases. Previous work revealed a strong correlation between the degree of gypsum supersaturation in the reactor and the rate of scale growth indicating that scale formation and growth are primarily controlled by chemical phenomena. However, the chemical behaviour of gypsum is variable and unpredictable with solution chemistry and temperature. Many of the "rules of thumb" that are used to predict its behaviour (and avoid fouling) are in fact based on gypsum solubility in water, rather than on real mixed metal sulphate systems. However, despite this unconventional solubility behaviour, we have been able to accurately model it in Ni, Mg, and Zn containing solutions over a wide range of temperature (25°C-90°C) and solution concentration (0-6 m) using the OLI simulation software. Furthermore, by studying fouling rates in a simulated continuous neutralization reactor, the relationship between process conditions and fouling rates were explained for the first time. This has led to an understanding of how techniques for minimizing gypsum fouling work.

Jan 1, 2003

By R. Upadhyaya

Aluminium alloy matrix cast composites have been synthesised by incorporating fine graphite powders (0.5 - 20 µm size) and chopped carbon fibres (6.5 pm P). 3-6 mm length) by liquid metallurgy technique. Incorporation of these second phase materials exceeding 6-8 wt% invariably resulted in agglomeration of the dispersoids and sometimes leading to even total rejection. It was found that small additions of mischmetal (1-3 wt%) during dispersion resulted in better incorporation without much agglomeration of the dispersoid as evident from the macro and micro structures of the composites. Further, the additions of mischmetal increased the volume of the effective incorporation of the dispersoid even to the extent 50- 60%. The mischmetal addition results in a significant increase in the power factor of the stirrer motor indicating an apparent increase in the viscosity of the system. The higher viscosity of the melt increase the shear transmission conditions within the melt during stirring thereby breaking the agglomerates of the dispersoids. The increased viscosity of the melt seems to be due to the formation rare earth - aluminium inter metallics precipitation, as observed in the metallographic studies, thereby making the process a "pseudorheocasting? technique. A provisional patent has been filed based on this work.

Jan 1, 1989

By Berndt Moeller

Mercury-cell chlor-alkali production plants generate mercury contaminated wastewater streams from which mercury must be precipitated and filtered, resulting in a sludge containing 2% mercury (designated KI06) that cannot be landfilled in the United States without treatment. REMERC is a chemical treatment process used to recover 99% of the mercury from wastewater sludge generated at these plants. The process uses leaching to oxidize mercury compounds to mercuric chloride, washing and filtration to separate mercuric chloride from the treated sludge, and cementation to reduce the mercuric chloride to metallic mercury. Mercury not recovered in cementation is recycled to the wastewater process for precipitation and filtration. Treated sludge contains less than 260 ppm total mercury and 0.2 ppm TCLP, meeting the USEPA low mercury subcategory specifications that allow landfill disposal. REMERC uses readily available chemicals, is straightforward to control and inexpensive to operate, has no mercury emissions to air, and recovers metallic mercury. REMERC enabled significant cost savings including lower solids disposal costs, recovery and reuse of metallic mercury in the chlor-alkali process, and ability to treat non-wastewater sludge. No new EPA permits were required. REMERC was shown to be a viable process for recovery of metallic mercury from K106 designated sludge.

Jan 1, 2003

By María Cristina Ruiz

In the processing of copper concentrates by the conventional smelting-converting technology, complying with the increasingly severity of environmental legislation in some countries has become difficult, mainly due to severe fugitive emissions of gases produced during the batch PS (Peirce-Smith) converting step. In this work, the results of an investigation on the pressure leaching with sulfuric acid and oxygen of white metal (produced in a Teniente Converter reactor) are discussed. The study was carried out at laboratory scale and the main variables studied were temperature, concentration of sulfuric acid and partial pressure of oxygen. The experimental results indicated that most of the sulfur in the white metal was oxidized to sulfate in the whole range of temperature studied (105ºC to 150 ºC). The concentration of sulfuric acid over 0.05 M, and oxygen partial pressure over 6 atm had little effect on the dissolution of copper from the white metal. On the other hand, temperature had the most significant effect on copper dissolution; below 130 ºC copper dissolution was incomplete after 5 hours of leaching while at 150 ºC the dissolution was complete in 90 minutes and 10 atm of partial pressure of oxygen

Jan 1, 2006

By Marco A. S. Aguiar, Luis G. S. Sobral, Vânia Mori, Paulo A. Medeiros da Silva

"Copper occurs in the crust of the earth, predominantly, as sulphides. Among the copper sulphide minerals, the chalcopyrite is the most abundant and the most refractory to the conventional oxidative processes. This work aims at developing an electrolytic process for treating a copper sulphides flotation concentrate, more precisely chalcopyrite (CuFeS2) and bornite (Cu5FeS4) in the percentages of 70 and 30%, respectively.This paper presents a low-cost operational electroleaching process for treating copper sulphides flotation concentrates, with a high chalcopyrite content. This research practical work aims at improving the copper extraction from that sulphide mineral, in a relatively short time with low-operating cost taking into consideration the influence of a cationic surfactant. The electrolyte of the electrolytic reaction system was a 2,0 mol.L-1 NaCl solution containing CTAB, a cationic surfactant. The electroleaching system contains one DSATM (dimensionally stable anode) anode and two nickel or copper foams (threedimension electrodes. During the electroleaching process the chloride ions are oxidized to chlorine at the anode surface, which in contact with the aqueous phase generate enough hypochlorite ions to oxidize chalcopyrite.The copper ions released from the chemical oxidation process are reduced at the cathode surface as metallic copper."

Jan 1, 2008

By V. A. Bryukvin

It has been found that by superimposing symmetric alternating current over the process, the rate of nickel and cobalt leaching from metallized products with copper sulfate solutions increases by a factor of 1.5 to 2.0 and the apparent activation energy of the process investigated is reduced from 12 down to 6.6 kcal/mole. It appears especially attractive to use alternating current for anodic dissolution (oxidation) of metallic scrap of refractory metals and their alloys in ammonia electrolytes permits production of high-grade commercial products in the form of respective ammonium salts using a short and virtually reagent-free process flowsheet. Similar approaches can be applied also for electrochemical processing of nickel and copper scrap in sulfuric acid media with subsequent recovery of pure sulfate salts or electrolytic processing. Electrochemical technology for recycling of tungsten-cobalt (WC 15) and tungsten-rhenium (WR 20) alloys has been also investigated. In the former case, anodic oxidation of carbide alloy was carried out in nitric acid electrolyte with production of pure tungstic acid. The research conducted has indicated that the physicochemical effect of alternating current results in a lower activation energy of electrode reactions due to changes in the mechanisms of the electrode reactions themselves.

Jan 1, 2006

Many studies have been conducted over the past 3 decades on the leaching of gold in solutions containing thiosulfate, ammonia and copper. However, most of these studies have been carried out using ore samples, with very few fundamental studies of this system being attempted. The majority of the published studies have failed to acknowledge the undesirable side reaction between copper(H) and thiosulfate, let alone account for its effect. The fact that the solution chemistry is constantly changing makes it very difficult to perform a fundamental study of gold leaching. With the advent of the rotating electrochemical quartz crystal microbalance (REQCM), such fundamental studies are possible as this instrument measures mass in real time. This has allowed leach kinetics to be measured in a matter of minutes and hence at essentially constant solution conditions; The present paper highlights that a sufficient concentration of copper(II) and ammonia are required in order to achieve appreciable gold leach rates. However, the use of air (oxygen) to maintain the copper(Il) concentration catalyses the undesirable copper(II) reaction with thiosulfate. The presence of ammonium ions is shown to have an effect on this undesirable reaction as well as on the gold leaching ?reaction. Preliminary electrochemical studies into .gold electrowinning using the REQCM show that gold(I) thiosulfate cannot be readily reduced to metallic gold in the potential region at which cementation usually occurs. However, it is well known that gold cementation onto copper occurs rapidly. The current study addresses this discrepancy by studying the effect that copper and silver have on the reduction of gold thiosulfate. It has been found that the presence of both silver and copper enhance gold deposition, particularly at low over potentials. While this is beneficial in cementation, the presence of copper and silver in solution has been found to cause passivation of the cathode surface during electrowinning at 'higher overpotentials.

Jan 1, 1998

By William J. Mallio

Substantial differences between in situ and conventional technology require that in situ ore grade be established for deposit as distinct from the total contained metal value. Establishing an in situ ore grade involves determining the fraction' of the contained metal that can be leached by the fluid. This depends on the proportion of the ore minerals that occur on fluid flow paths as defined by the permeability distribution. Mechanisms involved in the in situ mining of sulfides are: oxidation of the sulfur, solution of the metals, complexing of the released metals, and a transport to a recovery point. Metal ions may be delayed or lost due to inefficiencies in these pro-cess steps or by reactions of the metal ions in solution with the rock. These reactions can involve precipitation of new phases, exchange of the metals of the interest with Ca or Na in clays or zeolites, retention of metals in oxidized mineral grains, or secondary enrichment of other sulfides along the paths of the solution flow. The efficiency of solution of metals and potential loss or delay mechanisms are controlled by local equilibria (the Eh, pH conditions) present in different parts of the ore zone. Permeability distribution in the rock mass and the coincidence of ore minerais with flow channels must be determined before a deposit can be judged suitable for in situ mining. Laboratory studies indicate that the natural permeability system is dependent on the degree of cementation of veins by late generation hydrothermal activities. The major conclusions of the study are:, 1. Deposit selection is critical; suitable deposit types include deep lying sedimentary deposits, selected zones of porphyry systems and vein controlled hydrothermal deposits; 2. Adequate laboratory and geochemical analyses should be undertaken through quantitative petrographic study and permeability mapping; and 3. Economic incentives for in situ mining must consider limitations of recovery caused by inefficiencies in dissolution and transport associated with particular deposits.

Jan 1, 1981

By Anestis Vlyssides, Elli Maria Barampouti, Sofia Mai, ?postolos Vlyssides

"A new anaerobic reactor variation, the UASB/CO2-stripper reactor was conceived. It consisted of a conventional UASB reactor that recirculated the biogas produced. The sludge characteristics of this system were examined when treating high strength wastewater. From the data collected, it was obvious that the UASB/CO2-stripper system can satisfactorily operate at higher loading rates (25 g COD·L-1·d-1). A pronounced effect on the quality of the granular sludge was observed. The VSS/TSS ratio decreased sharply. A considerable decrease in the mean granule diameter was observed, while the specific gravity of the granules increased. The sludge bed porosity increased significantly leading to a considerable expansion of the sludge bed. These changes in the sludge properties led to a gradual shift of the system towards a fluidized bed process as far as its hydraulic characteristics were concerned.IntroductionIn recent years energy considerations and environmental concerns have increased the interest in direct anaerobic treatment of industrial wastes. The anaerobic method of waste treatment offers, under the present circumstances, a number of significant advantages with trivial or more serious drawbacks over other treatment methods. The major obstacle to the application of the process for this specific purpose is perhaps the difficulty of extending it to a stable and simple operational form. A number of reactor configurations has been developed leading to high biomass concentrations, e.g. the contact process, the filter reactor, the UASB reactor, and the fluidized bed systems, but the process stability problem still remains [1].A prime objective in the operation of anaerobic waste treatment process is the maintenance of a proper pH range. Thus, a possible solution to the process stability problem could be obtained by increasing alkalinity in the anaerobic systems. Therefore, the main objective of this paper is to present and evaluate the results of a system (UASB/ CO2-stripper) with increased alkalinity concentrations."

Jan 1, 2008