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By Semih Perdahcioglu, Arthur E. Morris

"The curricula for the majority of Materials Science and Engineering programs is devoid of all but the most rudimentary coverage of the principles of material and energy balance calculations. As a result, graduated engineers that need to make such calculations are faced with three unpalatable options. First, attempt to learn the subject by attending workshops or short courses sponsored by corporations or industry groups. Second, outsource the needed work to a consulting engineering company. Third, purchase a software package that's capable of simulating a process. Each of these options require a considerable investment of employee time and effort. The first option might be the best if suitable computational software was readily available. We review the recent development of such software, which is entirely based in Excel. The software tools include a thermodynamic database, tools for multiple computations, and a flowsheet simulation program. These tools employ teaching by simulation.IntroductionPracticing engineers often come up with situations where they must learn a technical subject that they didn't cover in their college classes. One possibility is to obtain a couple of texts on the subject, and delve in. Or, they may sign up for an intensive short course where they can get personal instruction and guidance. But the first option requires a lot of study time, and the second option may not provide the specific instruction (or intensity of instruction) required to appropriately master the subject. Here we look at ways of using simulation techniques to learn the methodology for making material and energy balances on industrial processes.Industrial heating processes have undergone many changes over the past dozen years, as vendors have introduced new heating equipment designed to recover the greatest possible amount of heat from the fuel, and to meet stringent environmental challenges for emissions (especially NOx). Even though the recent unprecedented drop in price of natural gas may have altered the urgency for improving a plant's energy efficiency, the need is still there. Until recently, there was a dearth of readily-available software for process engineers to use for simulating a plant's flowsheet. The good news now is the existence of several Excel-based software tools that make the calculational process much easier. [ 1]. Plant engineers may also be interested in a DOEsponsored program[2] which allows plant-wide and ""what-if' analyses of the energy balance."

Jan 1, 2013

By A. Siegmund, R. D. Prengaman

Lead anodes used in zinc electrowinning generally contain 0.5 - 1.0 % silver to reduce the rate of corrosion over the service life. For good quality zinc, the cathodes must contain less than 10 ppm lead. In order to reduce the lead contamination of the cathode, the lead anode must become coated with a protective layer of Pb02/Mn02. The formation of this layer may take as long as 30 - 60 days, during which time zinc production is substantially reduced and the cathodes are contaminated with lead. To improve the mechanical properties of Pb-Ag-anodes alloying elements such as calcium, strontium, barium and others are added. The production of cast lead-silver or lead-silver-calcium anodes often results in the formation of numerous holes, voids or laps in the anode surface that can initiate localized internal corrosion. Based on the experience as the major supplier of rolled anodes for copper electrowinning, RSR Technologies has developed an improved anode for zinc electrowinning. The anode consists of a rolled Pb- Ag-Ca-alloy with a controlled surface grain structure. It forms an adherent protective oxide coating within 2 - 3 days when placed in an electrowinning cell. The preferred calcium and silver contents of the alloy are 0.03 - 0.08 % and 0.3 - 0.4%, respectively. Rolling sheets significantly reduces the presence of internal porosity or laps. The lack of defects results in long anode life. The rolling also produces a uniform grain structure to which the corrosion product readily adheres, thus significantly reducing the conditioning period.

Jan 1, 2000

By C. A. Pickles

Microwave processing is a relatively new technology that has been successfully applied in a number of industries. However, in the field of metal extraction, there is a paucity of success, despite considerable hype in the early years. Increased reaction rates, lowered reaction temperatures and higher energy efficiencies were some of the advantages claimed. Even with over almost two decades of research and some pilot plant studies, microwave metal extraction remains essentially a laboratory technique. In this paper, the research performed over the last few decades will be reviewed and some reasons for the lack of success in developing microwave metal extraction processes will be discussed. Based on the knowledge gained from these experiences, a more informed view of microwave heating can lead to the realization that there is still some untapped potential for this heating technique in metal extraction processes.

By Sheng Dai, Yuan Lee, Haiming Xiao, J. P. Young

"There are numerous analytical applications of scatter-emission and/or absorption spectroscopy applied to liquids and solids in the temperature range of 0 to 350°C. In this paper an all-silica fiberoptic probe is described which is useful for spectral analyses from 0 to 1600 K and can be used in harsh chemical environments. The probe has been used for Raman spectral analyses of many molten salt and solid material systems to 1000°C. It has applications for such studies at higher temperature ranges. The instrumentation required along with the demonstrated and proposed applications of the all-silica probe are presented and discussed.IntroductionThere are many kinds of scatter-emission spectroscopies that are of value for analytical measurements. Fluorescence, reflectance, arc or spark emission are descriptors for some of these. Raman scatter spectroscopy is also quite a useful technique for analytical measurements.In Figure 1, we give a simplified explanation of the Raman effect. If one shines monochromatic light into a sample, light may be absorbed, exciting the sample to some virtual state. We know from experience that almost all of the light is re-emitted in the same wavelength range. This is called Rayleigh or Mei scattering and is designated in the figure by the arrows in both examples that point up and down from the same lower energy state. A very small percentage (the order of 10-4%) of the monochromatic light is re-emitted leaving the sample at a vibrationally-excited state. Thus, this light is at a distinctly lower energy compared to the exciting radiation. This is called a Stokes shift and is represented in the left-hand example by an arrow descending to a more energetic vibrational state. If the sample is not at a temperature of absolute zero, some of this vibrationally excited state will be thermally populated. That portion of the sample still absorbs and re-emits exciting radiation as Rayleigh scattered light, but a small percentage of the exciting light is re-emitted as the sample relaxes to the lower vibrational state. The energy of this light is of higher energy and is called an anti-Stokes shift, depicted in the example to the right. Notice that the energy separation of the Stokes or anti-Stokes shifted emission from that of the exciting radiation is the same, and expressed in ~cm-I. The intensity of either shifted emission is a function of the population of the vibrational energy states; therefore, the ratio of the intensity of Stokes to anti-Stokes signal varies with absolute temperature. We will come back to this point later."

Jan 1, 1997

By G. B. Harris

Much has been written over the past decade concerning the disposal of arsenic from metallurgical processes. In Canada, there are proposed regulations which would classify arsenic in the Primary Group of twenty one persistent, toxic pollutants to be banned or phased out. Since many nickel and cobalt ores, not to mention those of copper, gold and uranium, contain significant amounts of arsenic, it is pertinent to assess the current state-of-the-art of its disposal. The literature is reviewed, and it is demonstrated that from a purely chemical point of view, the family of ferric arsenates largely immobilize arsenic. There is clear evidence from laboratory studies that both crystalline ferric arsenate (scorodite) and amorphous ferric arsenates in which the molar Fe/As ratio is at least three (Fe/As = 3) have very low arsenic solubility; plant data are given to support this. The debate over the long term stability of these compounds continues however; the evidence presented for long term stability and for compound breakdown is critically reviewed in the light? of the recent structural studies, and the role of base metals in these compounds evaluated. Finally, conclusions are drawn as to the viability of a purely chemical process for the long term disposal of arsenic from metallurgical processes.

Jan 1, 1993

By F. Ajersch, P: Tsantrizos, K: Shanker

"TiN films have been deposited on various substrates by a novel reactive plasma technology. In this process, a nitrogen source (NH3 or N2) and TiCl4 are reacted in the jet of a plasma torch, and are deposited onto a substrate forming TiN films at a high growth rate ( > 2µm/min). It was found that the process parameters strongly affect the microstructure, thickness, density, and growth rate of the TiN films. These parameters include source of nitrogen (NH3 or N2, N/Ti ratio, temperature of substrate, and spray distance. In general, it was found that thick and dense coatings were deposited when the N:Ti ratio was kept low, and the substrate temperature was high. Also, for the series of conditions investigated, NH3 was found to give much better results than N2•. The limitations and advantages of this technique are also discussed in this paper.IntroductionTiN is an extremely hard material and is used in many wear applications, particularly as a protective coating on cutting tools to extend their Iife(1.2). Owing to its excellent chemical stability, TiN is also frequently used as a diffusion barrier in the electronics industry for sub-micron Al/TiN/Si ohmic contact systems (3) or as a coating on high-temperature resistant alloys in gas turbine applications (4), based on its good resistance to oxidation. Other applications include decorative coatings in the jewelry industry, and specialized applications such as solar energy absorbers and transparent heat mirrors(5).TiN films can be deposited/formed using various techniques. The main techniques of deposition are CVD (Chemical Vapour Deposition) and PVD (Physical Vapour Deposition). Each of these techniques can have many variations in equipment characteristics, reactants as well as a range of process parameters (pressure and temperature). In the CVD process, TiN is generally deposited onto a heated substrate where a chemical reaction takes place. The reaction can be one of reduction(6) (e.g.: TiCI4 + 0.5N2 + 2H2 --> TiN + 4HCI), of thermal decomposition(7) (e.g. decomposition of titanium dialkylamide), or of displacement (e.g. TiCI4 + NH3 --> TiN + 3HCI + 0.5CI2)' The displacement and reduction reactions are the most common."

Jan 1, 1994

By Zhao-cheng Liu

Iron oxide red pigment powders of high quality were synthesized from pyrite cinders. Iron ox-ide red pigment powders were synthesized by hydrothermal method from the precursor of Fe(OH)3 and Fe(OH)2 colloid, which were obtained after ammonia solution reacted with acidic leaching solution produced by the reaction of pyrite cinders with sulfuric acid. Effects of reaction concentration, reaction temperature, reaction time, pH value and n(Fe2+)/n(Fe3+) on main properties of oxide iron red were studied by experiments. The prepared particles were characterized by means of X-ray diffraction (XRD) and scanning electron microscope(SEM). The results revealed that the synthesized iron oxide red particles were _-Fe2O3 and pseudocubic with particle size of 0.50~0.75µm. Furthermore, the quality of iron oxide red pigment powders reached the first grade of national standard (GB1863-89 ).

Jan 1, 2009

By Pengfu Tan

A thermodynamic model of KIVCET lead smelting process has been developed. The model has the capability to predict the distribution behaviors of Pb, Zn, Fe, S, O, As, and heat balance in KIVCET direct lead smelting furnace. The compositions of lead bullion, matte, slag and gaseous phases, and heat balance are calculated. The effect of the ratio between oxygen and feed on the chemistry of the smelt and heat balance of the coke checker has been simulated and discussed. The thermodynamic model also helps to understand the tapping issue of the lead bullion. In this paper, some applications of this model in the industry have been presented.

Jan 1, 2006

By R. Winand, M. Degrez, C. Temmerman

"The influence of the copper electro crystallization inhibitors (mainly thiourea, gelatin and chloride ions) is studied in a new fully automatic pilot plan. This paper describes the conception and the building of this plan. The new approach is to reproduce the experimental conditions observed in the industry with the three additives present simultaneously in the electrolyte and secondly to study the influence of a slight modification of the concentration of one inhibitor, the others being present in the electrolyte with their industrial nominalconcentrations.1. INTRODUCTIONDespite the fact that gelatine, thiourea and chloride ions have been used in copper electrorefining for a long time, precise knowledge concerning their influence on the cathode deposit, metallographic structure and associated properties is still lacking.Many authors studied the influence of each additive separately, or of two added at a time. Only a few authors studied the combined influence of the three additives added simultaneously. The general conclusion that can be drawn is that the combined influence is far from that forseen from the influence of each additive separately, or even from two additives used at a time. Moreover most of the experiments described in the literature were performed by adding all additives at once initially. It is however, well known that gelatine looses a great part of its activity during the first half hour due to degradation by sulfuric acid (as shown by the cathode overpotential drop). Thiourea is rapidly replaced by a number of degradation mole,cules and complex ions including cations from the solution, changing even the equilibrium between Cu, Cu(I) and Cu(II).Chloride ions are consumed by precipitation.A number of successive research projects [1-9] led pregressively to the concept that, in order to obtain reproducible results representative of industrial cathodes, it was necessary to simulate as far as possible industrial conditions. It was essential that all additives were added continuously during the electrolysis, with, as consequence, a continuous bleed.The purpose of this paper is to describe the concept of a new fully automatic pilot plan for copper electrorefining and to present the first results."

Jan 1, 1997

By J. -P. Nepper

It has been possible to largely contain converter aisle emissions of SO2 and fumes in the case of batch-wise operated Peirce Smith converters during normal blowing periods with the help of suitably designed primary hoods. Controlling the escape of off-gas during the periods of turning the converter in or out of the stack has been problematic in the past. Effective automated control systems have been developed for the purpose and successfully applied in smelter operations in Spain, Taiwan and Germany. This has led not only to an effective reduction of emissions in the converter environment but also to an improvement in the converter operation.

Jan 1, 1992

By Lin Li, Xiang Li, Yifang Zheng, Jilai Xue, Jun Zhu

"Al drops and gas bubbles in the anode-cathode space of aluminum electrolysis cell are of great importance for cell operation improvement in metal loss, current efficiency and energy consumption. A direct observation on the Al drop, gas bubble and ultrasound was carried out through a see-through cell. The Al drop immersed into the cryolitic melt was found moving up and down irregularly in the anode-cathode space without electrolysis, which was then completely dissolved into the melt. During electrolysis, the Al drop came to the anode area and reacted with the gas bubbles generated on the anode. Under ultrasound, the gas bubbles were removed from the anode surface while the Al drop was kept on the side of anode. The observed phenomena were useful for technology improvement in reducing the anode-cathode distance or lowering the energy consumption in aluminum electrolysis.IntroductionDuring aluminum electrolysis, aluminum metal drop and anodic gas bubble are in close contact each other within the anode-cathode space, and the interaction between them can produce significant impact on metal loss, current efficiency and energy consumption. The motions of the Al drop and the gas bubble are also related to the dissolution of aluminum metal into cryolitic melt and the cell voltage drop due to the bubble layer covering the anode surface.A number of studies have been carried out using different types of see-through cells, where the dissolving process of metal Al into cryolitic melts (metal fog) in the anode-cathode space was directly observed and photographed [1, 2]. With the similar method, some direct observations on the anodic bubble behaviors with and without ultrasound were performed during aluminum electrolysis [3-6]. However, to our best knowledge, there is no published work on direct observation on the behavior of Al drops and anodic gas bubbles staying together within the same anode-cathode space, as well as the motion and interaction of them in cryolite-alumina melts."

Jan 1, 2011

By H. J. Garcia

Biodegradation of cyanide by microorganisms isolated from solids previously exposed to cyanide has been investigated. Initial sodium cyanide concentration was 300 ppm at pH 10.5. The kinetics of biodegradation were found to be first order with respect to cyanide concentration, and the overall reaction rate constant is k = 0.102 day-1. The activation energy and the frequency factor were determined to be { A }Ea = 5.45 Kcal/mol and A = 1.28 x 10-2 sec-1, respectively. Based on these values, thermodynamic properties of an intermediate activated complex were assessed. All tests resulted in cyanide concentrations less than 0.1 ppm in about 35 days at 250C, whereas at 350C the time of biodegradation to reach this cyanide level was 30 days. Kinetic data were also established to relate biodegradation to amount of inoculum. The maximum theoretically-attainable rate, Vm , and the optimum amount of inoculum, K , were determined to be 4.8 x 10-4 M NaCN/day and 7.5 % of amount of inoculum. With respect to the mechanism of biodegradation, cyanide was shown to decompose to carbonate, bicarbonate and ammonia. Titrimetric analyses revealed concentrations of 5.6 x 10-3, 4.8 x 10-3 M, and 70.2 ppm for carbonate, bicarbonate and ammonia, respectively. The average cell population was determined to be 3.75 x 108 cells/mL.

Jan 1, 1994

By F. A. Steward

Copper is one of the trace minerals essential to life. It is added, usually in the form of copper sulfate, to virtually all formulated feedstuffs and to dietary supplements fed to animals on forage. Over the past five years, an improved inorganic copper source trademarked Micronutrients TBCC™, has been developed, tested and commercially introduced. TBCC is a crystalline form of basic copper chloride. Synthesis is accomplished in a continuous neutralization I crystallization process. In current commercial production, the primary sources of copper currently used as feedstocks are the etching solutions used to manufacture electronic printed wiring boards. These solutions have traditionally been managed as hazardous wastes, but their use to manufacture TBCC™ exempts them from regulation as wastes under the "Use/Reuse" provisions of RCRA. Research conducted over five years at multiple universities has shown that animals are healthier when fed this source of copper and that vitamin losses in feed are reduced by its use.

Jan 1, 2000

By Daniel Gauthier, Patrick Sharrock, Cedric Verwilghen, Gilles Flamant, Ange Nzihou, Jocelyn Ramaroson

Clean processes are needed to dispose of many wastes. The incineration of 1 ton of municipal solid waste generates 6000 Nm3 of combustion gases contaminated with heavy metals and other pollutants. Gas scrubbing processes are required to clean incineration fumes in order not to transfer pollution to the atmosphere. We are investigating the use of Hydroxylapatite (Ca-HA) particles for use as sorbent for the removal of volatile heavy metals. We have carried out the synthesis of Ca-HA by two precipitation methods from solution and obtained solids with specific surface areas reaching more than 100 m2/g. Preliminary adsorption experiments were conducted in a horizontal furnace by mixing Ca-HA with 5% by weight of cadmium chloride in solid state. The mixture was heated to 600°C under air atmosphere during 6 hours. Chemical analysis of the solids confirmed that 85 % of the cadmium was retained in the solid phase. Such laboratory results showed that Ca-HA is capable of adsorbing cadmium chloride vapors, and pilot scale studies confirmed cadmium abatement in an industrial context.

Jan 1, 2008

By Zhihong Liu

In recent years, the removal of arsenic from different types of high arsenic containing materials produced in nonferrous metallurgical processes have been experimentally studied in the complex materials processing research group from Central South University. These materials include arsenic and antimony bearing flue dust, arsenic sulfide residue and arsenate bearing flue dust. The separation of arsenic from other valuable metals was carried out hydrometallurgically; for each type of arsenic bearing material, different processes have been employed individually to remove the arsenic effectively. In this paper, the flowsheets and typical experimental results have been summarized.

By P. N. Anyalebechi

The effects of solidification rate (0.4-26.1 K/s) and alloying elements on the cast microstructures of aluminum alloy 5182 have been investigated with directionally cooled laboratory-size ingots. The alloying elements examined included Mg (3.6-4.7 wt.%), Mn (0.35-0.75 wt.%), Fe (0.11- 0.42 wt.%), Cu (0.03-0.25 wt.%), and Si (0.11-0.28 wt.%). These reflect the chemical compositions of AA 5182 end stocks with high recycled used beverage container (UBC) content. For a given chemical composition, the average dendrite cell and constituent phase particle size decreased with increase in average solidification rate. In general, within the level investigated, Mg did not have a significant effect on the types, volume fractions, and average sizes of the constituent phase particles. However, increase in Mn, Si, Fe, and Cu increased average sizes and volume fractions of the constituent phase particles.

Jan 1, 2010

By Xue Ping

Sm2Fe17 alloy is an important precursor for the preparation of Sm2Fe17Nx magnet, which possesses a higher Curie temperature, larger anisotropy field, better resistance to oxidation and thermal stability. In this paper, the wet chemical co-precipitation was developed for synthesis of the Sm-Fe alloy oxide precursor. Based on the principles of simultaneous equilibrium and mass balance, a series of thermodynamic equilibrium equations of Sm(III)-Fe(II)-NH3-C2O4 2--H2O system at ambient temperature were deduced theoretically and the thermodynamic diagrams of lg[M2+]T (M=Sm, Fe) versus pH at different solution compositions were drawn. Then, the experiments were done to address the various effects on the wet chemical process, including solution pH value, reactant concentration, reaction temperature and aging time, etc. It is found that by precise control of the process, the Sm-Fe alloy oxide precursor was synthesized with fine crystallization and special size &size distribution.

Jan 1, 2008

By M. Hashiuchi

In 1972, the tankhouse of the Tamano Smelter adopted a high current density electrolysis operation applying the PRC (Periodic Reverse Current) method. In 1994, the phase four production expansion project, which incorporated significant re-structuring of the organization, was completed and we have achieved an annual production capacity of 191,000 tons. The target of this project, the production capacity, was increased by 1'8% and labor productivity by 25%. After the expansion, some improvements in the starting sheet section and the verticality of the electrodes were carried out, and the efficiency of the operation was greatly enhanced, including the improvement of the quality of the electrolytic copper.

Jan 1, 1999

By Masao Miyake, Eiichiro Matsubara, Tetsuji Hirato, Yasuhiro Awakura

"Zn-Cr alloy coating with around 15 wt% Cr has been found to have much higher chemical corrosion-resistance to steel than conventional zinc plating, while· its structure has not been clarified. The Zn-Cr alloy plating is performed at high current densities around 1 A cm-2 and for 10 to 20 sec using acidic aqueous sulfate solutions with some additives in the iron-steel industry. Due to the high current densities, it seems reasonable to consider that the Zn-Cr alloy plating proceeds under an unsteady-state condition and that the resulting coatings have a non-equilibrium phase and have a structure change in the .direction of thickness. In this research, the crystal structure of the Zn-Cr alloy coating electrodeposited at high current densities and change of the structure in the direction of thickness were examined by X-ray diffraction. The coatings containing under 20 and 35-40 wt% Cr had hcp and bee structure, respectively, while the coatings containing 20-35 wt% Cr comprised two phases with the hcp and the bee structure. The structure of the coating varied in the direction of thickness; both the hcp and bcc phases coexisted in the vicinity of the substrate, while the hcp phase became predominant with increasing distance from the substrate.IntroductionRecently it has been reported that Zn-Cr alloy coating containing around 15 wt% Cr has much higher corrosion-resistance to steel than conventional zinc plating.1-3) The corrosion-resistanc·e of Zn-Cr alloy plated steel sheet with a plating amount of 20 g m·2 is, for example, superior to that of Zn plated steel with a plating amount in the range 60 to 90 g m·2 , which is widely used for automotive bodies today.4l The Zn-Cr alloy plating is obtained by electrodeposition at current densities over 0.5 A cm·2 from a sulfate solution containing zinc and trivalent chromium ions and some additives.5•6) The deposition current densities mentioned above are much higher than those for usual electroplating processes, e.g., Zn, Cu and Ni plating, carried out about 0.05 A cm·2 • Therefore, the time required for plating is very short; around 10-20 sec. Due to the high current densities, it seems reasonable to consider that the· Zn-Cr alloy plating proceeds under an unsteady-state condition and that the resulting coatings do not have a phase expected from equilibrium diagrams; no phase diagram of the Zn-Cr system with a full composition range has been available. 7). In other words, the alloy phase plated would be a non-equilibrium phase with unknown structures."

Jan 1, 2000

By F. E. Pawlek

Copper concentrates can be comminuted in an attritor within a very short time to a particle size of 1 - 0.1 um. Addition of sodium hydroxide enhances commninution. The concentrates, suspended only in water, can be completely dissolved under oxygen over pressure and temperatures ranging from 120 - 180°C (248 - 356°F), because the surface area of the concentrate has been significantly increased by the ultra fine grinding. Addi¬tion of a small amount of silver ions to leach liquor containing sulfuric acid acted as a catalyst for the dissolution of chalcopyrite, because of the formation of local elements on the surface. The addition of C1- ions was also catalytically very effective. With this method it is possible to completely dissolve the copper contained in chalcopyrite concentrates after ultra fine grinding within 30 min at 110°C (230°F) under an oxygen partial pressure of 1 atm (14 psig). Several flowsheets demonstrate the industrial feasibility.

Jan 1, 1976