Search Documents

By Benjamin P. Hay

Complexation of a metal ion to a ligand often results in structural changes that introduce steric strain within the ligand. A design criterior:1 for ligands that will complex metal ions more strongly is to choose Iigar:1d architecture, that minimizes this strain. This paper describes how molecular mechanics models can be used to define the degree of ligand binding site organization in terms of' ,strain energies associated with conformational reorganization and distortion of the binding conformer. This approach yields a method to predict how modifications to ligand structure will affect metal binding affinity.

Jan 1, 1999

By C. A. Pickles

At the present time, pyrometallurgical processes are employed for the recovery of lead from battery scrap. These processes have serious pollution problems, primarily due to the emfssion of sulphur dioxide and airborne lead in the form of dust and fume. In addition it is necessary to dispose of solid wastes and liquid effluents which contain lead and in some cases sodium sulfide-containing compounds. In this work an improved process was investigated for the recovery of lead from battery residue. This involved pelletization of the residue with sodium carbonate and moisture. Then, the pellets were melted without carbon and the .sodium sulphate salt was removed. Subsequently, the molten lead oxide was reduced with carbon. This process minimizes the sulphur dioxide emissions and leads to very low sulfide contents of the sodium sulfate salt

Jan 1, 1992

By Pengfu Tan

In order to understand and control the formation of dioxins and furans in iron ore sinter plants and to possibly avoid expensive end-of-pipe removal stages, thermodynamic calculations on the stability of PCDD/Fs have been combined with sinter process modeling by means of kinetic simulations and computational fluid dynamics. Three thermodynamic databases of PCDD/Fs, derived using the Group Additivity approach and two computational molecular modeling methods, MNDO and PM3, respectively, combined with the SGTE database have been used to model the PCDDIF formation and the PCDD/F isomer distributions in iron ore sintering. The results show very similar conditions for the PCDD/F formation using the different databases. Concerning the isomer distributions of toxic PCDD/Fs, the calculated data derived from the MNDO method showed optimum agreement with measured values from industrial furnaces. The thermodynamic calculations also proved that the isomer distributions found in combustion processes are equilibrium values, while the concentration ratio of PCDDs and PCDFs in the wind boxes does not represent an equilibrium state. A CFD model of iron ore sintering was developed including the kinetics of 15 relevant chemical reactions with the aim of describing the temperature fields and the gas flow patterns in the sintering bed. On the basis of these information and experimental observations reported in the literature possible pathways for the PCDD/F formation in sinter plants have been identified: PCDD/Fs are formed in the critical temperature region of 250 to 450°C below the combustion zone, are then carried downwards with the gas and condensed close to the bottom of the sinter bed. Transported to the discharge end with the solid mixture, they are again released into the gas phase when the flame front approaches the bottom. PCDD/Fs are also formed in the last wind boxes when the hot off-gases cool down and reach the critical temperature range. Consequently, methods to reduce the dioxin formation reactions are proposed including inhibitor addition to the sinter feed and off-gas quenching.

Jan 1, 2003

By Li Qian

Mechanisms of bio-dephosphorization from iron ore was investigated in this Paper. The results show that there are two bio-dephosphorization ways from iron ore, the one is that Acidithiobacillus ferrooxidans directly derive phosphorus from the ore, the other is phosphorus is able to be leached acid produced during metabolizing of Acidithiobacillus ferrooxidans, and the latter is more important than the other. Adding suitable pyrite can enhance the bio- dephosphorization process through providing nourishment and producing acid directly due to S 3oxidized or indirectly due to Fe3 as oxidant. The potential varies in the range of 0.434~0.498V and pH is in the range of 2.5 ~ 1.25 during bio-leaching process. It can be founded that, according 2+to the E-pH graph of Fe-H2O system, Fe wouldn?t be oxidized under sterile system in this potential and pH ranges. It can be obviously concluded that the Acidithiobacillus ferrooxidans are 2+able to reduce the potential for the oxidization of Fe and make the oxidization occur in the above pH and potential zone, so the bio-leaching process can proceed. the investigation of E-pH graph of P-H2O system show that H3PO4 can exist steadily.

Jan 1, 2009

By M. Cavallini, G. Cannavale, P. P. Milella, A. Pescetelli, C. Lupi

Ni-Cd sealed and vented cells have been widely used in the last few years. The environmental hazard related to the heavy metals contained in Ni-Cd batteries is well known. Therefore, a number of scientific studies and commercial processes have been implemented in order to recycle them. Since spent batteries are a heterogeneous and complex material, any kind of recovery process needs some preliminary treatments. The proposed process described in this paper has been tested in laboratory and further developed in a pilot plant. It consists of a combination of mechanical and hydrometallurgical treatment steps, and is able to treat all type of Ni-Cd batteries. In particular, the mechanical treatments have to be done separately on vented and sealed cells, while the hydrometallurgical step is performed on a mixture of the two products obtained from mechanical steps. A fully automated dismantling line would allow the separate recovery of the plastic or metallic casing, terminals, KOH electrolyte, and electrodes to be further processed· for Ni and Cd recovery. The electrodes coming from dismantling line and sealed batteries are submitted separately to an original crushing and elutriation treatment to separate metallic and active paste in the first case and metallic, plastic and active paste in the second case. The hydrometallurgical treatment is carried out on active paste bearing product to produce Ni, Cd, and Fe comn1ercial salts through acidic leaching followed by a multi-step solvent extraction operation to obtain pure solutions.

Jan 1, 2000

By G. Glinski, K. A. Pericleous

"Recent advances in new computational modelling techniques such as Lattice-Boltzmann and Dissipative Particle methods offer the prospect of simulating complex fluids such as colloidal and dense suspensions in industrial processes. They are referred to as mesoscopic methods since they lie between molecular dynamics at a microscopic atomistic scale «lO-9m) and traditional macroscopic CFD methods (> 1O-2m). The models behave like a 'coarse-grained' gas consisting of fictitious interacting particles, which are much larger than the real molecules of the actual fluid they represent. Inter-particle forces are set so that the collisions collectively mimic the phenomenological transport properties and flow of the underlying fluid at a macroscopic scale.Much of the developmental work to date has focused on laying theoretical foundations based on thermodynamic and kinetic theory. Successful applications include predictions of macroscopic transport properties of complex fluids and flows in porous media and filters. With the constant increase in computational power, these mesoscopic methods are now sufficiently developed to determine their suitability to simulate complex fluid flows in real industrial processes. This work describes the application of meso scopic methods to the stencil printing of solder pastes in the assembly of electronic components. The aim of this work is to assess the ability of these methods to study the transport mechanisms of individual solder particles suspended in the flux solvent as they enter and fill the micro-apertures of a stencil. This paper demonstrates the coupling of such mesoscopic methods to continuum CFD methods to predict the flow of dense suspensions (i.e. solder paste) in industrial processes."

Jan 1, 2001

By Xiao-hui Fan, Xu-ling Chen, Zhi-yuan Yu1, Guanghui Li, Min Gan, Yun-song Huang, Tao Jiang

Compared with the traditional de-NOx processes by cleaning the waste gas, a new approach for reducing the formation of NOx during sintering process is proposed. Since more than 90vol% of NOx comes from the fuel combustion, the influence of sintering coke breeze pretreated by CO(NH2)2 additive on the NOx emission is researched. As adding CO(NH2)2, the reduction agents (NHi) are generated during the pyrolysis of CO(NH2)2, which reinforce the NOx reduction, And the appropriate content of CO(NH2)2 is 1.0 mass% of coke breeze.

Jan 1, 2015

By E. James Quinn

Solvent extraction technology using EHEHPA (2-ethylhexyl phosphonic acid, 2-ethyhexyl mono ester) is the norm for industrial separations of rare earth elements. This process has some shortcomings, including a large number of stages compared to most SX processes and high acid requirement for stripping of the heavy rare earths. In this work, we examine a number of alternative mixed solvent extraction systems: (i) Mixtures of organophosphonic and phosphinic acids such as EHEHPA/Cyanex 272 or Cyanex 572; (ii) Ionic liquid mixtures of EHEHPA with quaternary ammonium chloride (Aliquat 336); and (iii) Mixtures of carboxylic acids for yttrium/lanthanide separations. We discuss and compare the efficacy of these systems with reference to the Nd/Sm separation, which is of industrial significance. Based on the extraction chemistry and the use of modelling tools to define the counter-current solvent extraction circuit, we present a techno-economic analysis of a separation plant and discuss the impact of various solvent systems on the capital expenditure (CAPEX) and operating costs (OPEX).

By G. Belardi

The purpose of the study was to check on the level of environmental contamination and to design a project for cleaning up the Abetina Mine area at Piancastagnaio (Grosseto, Italy). Contamination of this area had occurred during the mining and treatment of cinnabar (HgS) over a prolonged period. The aim of the project is to remove the sources of contamination or render them harmless. Mining of the Piancastagnaio deposit started in 1840, mercury metal being extracted from the ore by thermal treatment. Together with Spain, Italy was the first country to produce this metal and was the world leader in this field between 1936 and 1943. Though mercury production in the Monte Amiata region of Tuscany ceased in 1974 the ensuing environmental impact is very evident, taking the form of rusty old mining and processing works, plus waste tips which still contain considerable amount of mercury even after the ore had been subject to thermal extraction treatment. The research which has been conducted included mapping the area to identify the main sources of mercury and arsenic pollution, as well as the level of environmental contamination. Mercury and arsenic values in excess of 16,000 and 150 ppm respectively are encountered in the most highly-contaminated places. The cleanup project has been drawn up on the basis of the field and laboratory investigations. This provides for a combination of remediation measures on the land concerned, as well as in situ inertization of contaminating elements by means of mixtures of chemical compounds such as cyclosiloxanes. Due account has been taken of Italian and EU environmental regulations when establishing the measures for rendering the various polluting element innocuous. 'The efficacy of the inertization techniques has been checked by yield tests in acetic acid and carbon dioxide, reducing the Hg and As contents of the material in the untreated and treated states from maximum values of 7 mgll to minima close to zero.

Jan 1, 1996

By John Dasher

One of our War Plants processed Bolivian concentrates as low as 17% Sn by the Arnhem process (pressure leach with HCL) and sent the waste acid down a ditch to Galveston Bay where the chlorides, mostly iron, hydrolyzed. Oyster men, and Texas, demandedimpoundment until a disposal process could be developed. A recycle process found by lab work was recommended, piloted and a plant built. This involved cementation of As Sb, Cu, Bi and Ag on light moving scrap iron and of Sn & Pb on Al turnings (then not recyclable), evaporation and crystallization of hydrous FeCl2, roasting crystals in a muffle furnace and absorbing HCI for reuse. The residue from leaching the low grade concentrates was floated to remove undissolved sulfides, classified and passed over sand and slimes tables to get a smeltable concentrate, a discardable sand tail and a slimes tail worth treating After desliming at 2 micro meters cassiterite, oxide flotation gave good, lab results; but commercial equipment wasn't adequate then. Chloride volatilization, with or without smelting gave high recoveries of Sn as SnCl2, whose marketing was questionable. I have heard this was finally fluxed and smelted.

Jan 1, 1992

By Olexandr Gydin

The evolution of grain and dislocation structures during cold deformation of the new steel LH800 of Salzgitter AG is investigated in the frame of this work. The main feature of this material is its ability to air-harden by carbon content of about 0.1%. The initial ferrite structure of the metal provides high plasticity at cold deformation and subsequent heat treatment increases tensile strength approximately two times. Described are results of in-situ tensile tests in the SEM. SEM and TEM analysis of grain and dislocation structures evolution in samples, which have been uniaxially deformed to certain strains, are carried out. After statistical evaluation of results the grain elongation against strain is determined. A microstructure of a deep drawn cup is analyzed by means of SEM. A quantitative evaluation of grain elongation on the different cup zones and comparison of these data with prediction results based on tensile tests are carried out.

Jan 1, 2009

By F. J. J. van Loo, J. K. Kivilahti, M. Paulasto

"Activation mechanism and interfacial reactions in brazing of ShN4 with different AgCuTi filler alloys has been investigated thermodynamically and experimentally. During brazing the AgCuTi filler alloy is divided into two liquids Ll and L2, where the (Cu,Ti)-rich liquid L2 gathers at the ShN4 interface and reacts with it. The concentration of Ti in L2 is high, but due to the strong attractive interaction between Cu and Ti, the activity of Ti in L2 is considerably low. In reaction between ShN4 and Cu-containing brazes a Ti-Cu-Si-N compound is typically formed at the interface. In absence of Cu, in joints brazed with AgTi based filler alloys, extremely Ti-rich solution reacts with ShN4 and as reaction products TiN and TisSh[N] are formed. IntroductionAdvanced ceramics like silicon nitride are increasingly used as structural components in demanding applications as well as in electronics industry. Complex, multicomponent structures for engineering applications generally require interconnections and therefore joinability of ceramics largely determines the possibilities of metal-ceramic structures to enable demanding functions. Brazing with active filler metals, most of which are based on the Ag-Cu-Ti system, has been commonly employed for joining of ShN4 to other ceramics and metals. The interfacial microstructures formed when ShN4 is brazed with Ag-Cu-Ti braze alloys have been discussed in several recent studies [1-7]. However, some inconsistencies exist in the reported results. The formation of layers of TiN and titanium silicides, possibly TisSh, next to the ShN4 has been reported in several studies [1-5], while in another investigation, a layer of an orthorhombic TiSi- Cu-N phase was found beyond the TiN layer [6]. In few investigations the thermodynamics of the ShN4-Ti system has been considered, but no detailed thermodynamic analysis of the chemical interactions between the braze and ShN4 has been provided. In order to resolve which chemical reactions are possible under various joining conditions and thereby to be able to control the brazing of ShN4 the reactions in brazing has to be studied using both microstructural and thermodynamic analysis."

Jan 1, 1996

By E. A. Werner, W. Liebfahrt, J. Blaha

"The influence of the composition and the microstructure on the plane strain fracture toughness of five cold work tool steels all processed via the powder metallurgical route is investigated using 3-point bending specimens. The steels differ in composition and therefore possess different volume fractions of carbides. The amount, size and distribution of the carbides in the matrix are estimated by quantitative image analysis on a plane parallel to the fracture surface without discrimination of the carbide type, since the carbides are always much harder [1,2] than the matrix, irrespective of their composition. Due to the production of the steels via the powder metallurgical route almost all carbides are spherical in shape. The mechanical in-situ properties of the matrix are characterized by indentation tests performed with an ""UltraMicro"" -indenter in a scanning electron microscope.IntroductionCold work tool steels are used as tools in applications where excellent wear resistance and high hardness are required. Examples are cutting, woodworking, thread rolling, wire and deep drawing, cold extrusion and pressing of parts at process temperatures below 200°C. For such applications the steels must show an optimum combination of hardness, wear resistance and toughness while offering good machinability. Hardness and wear resistance are controlled by the amount of carbon and carbide forming elements such as molybdenum, tungsten, vanadium, chromium and niobium. These elements are present in the MC-, M6C and M7C3-carbides and are also responsible for the precepitation of secondary carbides during tempering. In this report attention is paid to the influence of the primary carbides only, while the very small ~~nm) secondary carbides will be treated as constituent of the homogeneous matrix. Increasing the amount of carbides (alloying elements) usually results in a decrease of the material's toughness which is caused by the presence of clusters and/or bands of carbides. To achieve an optimum combination of hardness, wear resistance and toughness many of the today's cold work tool steels are processed via the powder metallurgical (PM) route, which helps to prevent non-uniform element/carbide distribution because of the rapid solidification of the powders used. The resulting microstructure of the tool steel then consists of a tough matrix with uniformly distributed hard carbides· of globular shape. This shape of the carbides is also desirable instead of blocky carbides present in non-PM tool steels, since they improve the machinability of the steel. An additional advantage of PM-steels lies in the possibility to produce near net shaped tools thus lowering the costs of machining."

Jan 1, 2000

By Terence Makanyire, Animesh Jha

The dissolution and chemical properties of vanadium, zirconium, and niobium in rutile lattice are analyzed by comparing the octahedral site preference energies, with respect to Ti4+ ion in the solvent phase. The oxides are often present in rutile lattice and interfere in achieving the quality of pigment grade TiO2 due to favourable Gibbs energy for dissolution in the solvent rutile matrix. Binary mixtures of V2O5 { TiO2; Nb2O5 { TiO2 and ZrO2 { TiO2 with compositions of 80, 85, 90, 95 and 97 wt% TiO2 were made, pelletized and sintered at 1100 °C for 24 hours. The solidsolution mixtures were then cooled and leached in 2M NaOH for 3 hours at 60 °C. Phase and lattice parameter characterizations, and microstructural and compositional analyses were then carried out using X-ray diraction and SEM/EDX, respectively. The leachates were analysed by Atomic Absorption Spectroscopy (AAS), using which the solute dissolution model for oxides were investigated.

Jan 1, 2014

By Kuniaki Murase, Tetsuji Hirato, Koji Nitta, Yasuhiro Awakura

"The redox behavior of copper species in an ""ammonium imide"" room temperature molten salt was examined in order to clarify the applicability of the salt to the electroplating media of various metals. Trimethyl-n-hexylammonium bis(trifluoromethanesulfonyl)- amide (TMHA-Tf2N), having an electrochemical window of 5.6 V (50 °C), and corresponding copper(II) salt were synthesized. In TMHA-Tf2N media monovalent copper ion, Cu(I), was stable and Cu metal was oxidized, or corroded, in the presence of Cu(II) species. Cathodic electrodeposition of copper metal and anodic dissolution of it were, thus, one-electron reaction and their current efficiencies were almost 100%.IntroductionElectrodeposition of metals from aqueous solutions is an important soft process for manufacturing thin-film materials, surface finishing, and extractive metallurgy. However, the electrodeposition of base metals, such as zinc, chromium, and nickel, from aqueous media inevitably accompanies hydrogen evolution, which lowers the cathodic current efficiency of metal deposition. Since the electrodeposition of aluminium, titanium, and rare earths from aqueous media is actually impossible due to their largely negative redox potentials, nonaqueous media such as aprotic organic solvent and high-temperature molten salts have been employed for the electrodeposition of these metals. Room temperature molten salts (RTMS),1, 2) or room temperature ionic liquids, have also been developed as a promising electrolytes for the electrodeposition of base metals. In this field, chloroaluminates of alkylpyridinium or alkylimidazolium cation have been well investigated for aluminium3) or alluminium-alloy4-5) electroplating media. On the other hand, in order to avoid high hygroscopicity arising from the use of aluminium chloride, attempts have been made to combine the alkylimidazolium cations with fluorine-containing hydrophobic anions, e.g. BF4-,6) CF3SO3- (TfO-),7) (CF3SO2)2N- (Tf2N-),8) and H(HF)n-ions,9) and investigated for electrodeposition media.'°) Recently, a new series of RTMS consisting of tetraalkylammonium cations and Tf2N- anion, sometimes abbreviated as TFSI- anion, was found independently by MacFarlane et al.11, 12) and Matsumoto et al. 13) This type of RTMS, which is commonly named ""ammoniumimide"" salt, has a wide electrochemical window of ca. 5 V and, thus, the RTMS seems to be suited for practical application as a solvent for the electrodeposition process. In this paper, we report the electrochemical behavior of copper species in an ammoniumimide RTMS, trimethyl-n-hexylammonium bis(trifluoromethanesulfonyl)amide (TMHA-Tf2N)."

Jan 1, 2000

By Richard D. Hagni

Microscopic examination of selected, representative, unweathered samples of Birmingham, Alabama, Silurian, sedimentary iron ores has fully revealed the nature of the phosphorous-bearing mineral grains. The grains are composed of carbonate-fluorapatite (collophane), range in size from 1 um to 2.25 mm, and exhibit varied types of intergrowth with hematite. Modal analyses conducted under cathodolumi-nescence have provided quantitative data on the a3undance of each of 15 types of phosphorous-bearing mineral grains and made it possible to assess the potential phosphorous liberation from four types of iron ore. The results indicate that 27% of the total phosphorous contained in the iron ores in the western part of the Birmingham district can be expected to be liberated by fine grinding; 60% for ores in the eastern part of the district.

Jan 1, 1982

By A. Mezei

Samples of cobalt and bismuth concentrates produced from the NICO deposit in Northwest Territories were subjected to a comprehensive metallurgical testwork consisting of: pressure oxidation, ferric chloride leach and carbon in leach, to recover the cobalt, bismuth and gold, respectively. A specific testwork program was designed to allow for the optimization of process parameters under multiple restrictive criteria. The overall objective was to establish leaching sequences that could produce acceptable recoveries while generating environmentally disposable residues as well as solutions suitable for further processing. The recoveries for the leaching stage, under the optimum conditions, were 97% for cobalt and 95% for gold, in the case of the cobalt concentrate. The bismuth concentrate produced recoveries of 99% for bismuth, 99% for cobalt and 97% for gold, respectively

Jan 1, 1999

By Kenneth L. Driggs

The Environmental Protection Agency's Clean Air Act of .1970 provided the driving force for the current Magma Smelter configuration. The historical and technical perspectives of those process developments are reviewed. Innovations in procedures and equipment have allowed compliance with the requirements of the regulating authorities. The wet scrubbing of converter gasses and the monitoring of converter operations by a controlling foreman are two of the major contributors to these successes. The Clean Air Act Amendments of 1990 have posed many new concerns for all U.S. industry, including the few (seven) primary copper smelters remaining. Future concerns include tightening the sulfur dioxide ambient standard from the current three-hour averaging period to one hour"

Jan 1, 1992

By Willem P. C. Duyvesteyn

A novel hydrometallurgical process for Escondida copper concentrates has been developed by The Minerals Laboratory of BHP. The Escondida Process consists of concentrate leaching, solution purification, electrowinning and residue flotation. Part of the copper will be sold as high grade concentrate and part as high purity SX-EW copper. Contrary to previous efforts for the development of a hydrometallurgical process for copper concentrates, this patented process does not advocate the total dissolution of copper. It only aims for the copper that is readily soluble in a mildly oxidizing environment with an ammoniacal or acidic lixiviant. Both lixiviants were studied, but ammonia was preferred because of fast kinetics at ambient temperatures and pressures. By controlling the oxidation potential, the formation of sulfate ions and, consequently, of an ammonium sulfate byproduct, is precluded. These mild leaching conditions also prevent the dissolution of unwanted impurities and result in the production of ultra-high purity electrowon copper. Solution purification is carried out by solvent extraction with LIX-54. The very high loading capacity of this organic results in a compact SX circuit, consisting of two loading, one scrubbing, and one stripping stage. As the organic is selective for simple copper ions, the copper amine complex is broken down and free ammonia is regenerated and recycled for leaching. High purity copper cathodes are produced in a conventional sulfuric acid based electrowinning system. One scrubbing step is needed to separate the ammoniacal circuit from the acid circuit. Limiting copper dissolution to less than 50% also provides an opportunity to produce high grade concentrates by residue flotation. Copper recoveries in excess of 98% with precious metal values reporting to the final concentrate can readily be obtained. Complete breakdown of the copper mineral- pyrite middlings results in a final concentrate grade that can be even higher than the original feed material. The Escondida Process also provides an opportunity to accept lower grade copper concentrates producing improved copper recoveries in the mill and yet high quality concentrates for marketing. The Paul E. Queoeau International

Jan 1, 1993

By James C. Barker

Recent investigations of a 55-km long trend of intrusive complexes on southern Prince of Wales Island have identified significant resources of Nb, Y, REE. U, Zr, and a host of potential by-product metals. The northwesterly trend comprises multi-phased sodic alkaline and peralkaline diorite, monzonite, syenite, and riebeckite granite. There are at least three significant deposit types recognized, two of which, 1) pegmatite dikes/vein-dikes that zone laterally from the intrusions and 2) concentrically zoned pegmatites, contain most of the lithophile metals. A third, epigenetic replacement-type mineralization, contains much of the U resource. Other deposit types with minor or unknown resource potential include diatremes, carbonatite, and placers. This report summarizes the deposit evaluations, characterizes the mineralization, and estimates the resources. To date a total of 40.7 million tons of mineralized material is estimated as indicated or inferred. Most of the Y203 plus REO is at a grade exceeding 0.5% and half of the Nb20S exceeds 0.125%. Tonnage estimates would likely be substantially lncreased with additional exploration. Mineralogy is generally fine-grained and complex, and consists of more than a dozen principal REE-Y-Nb-U-Th-Zr phases, the sum of which may compose up to half of the rock. Approximately half of the REE-Y content comprises the heavy yttrium subgroup which is uncommon compared to deposits elsewhere. Although the Alaskan deposits are likely subeconomic at today's metal prices and consumption levels. recent technological advances suggest future demand may increase.

Jan 1, 1988