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By Jan G. H. du Preez, C. Viviers, B. J. A. M. van Brecht, H. E. Rohwer, Nicole M. Sumter

"At the basis of metal ion separation lies some particularly metal ion specific chemical property which lends itself towards exploitation. This could be in the form of an anionic complex or a neutral chelate complex. In the former a cationic centre with a particularly high affinity for the complex will have to be designed. In the latter case a stereospecific chelate ligand containing the correct symmetry and type of donor atoms will have to be designed. In both above cases the ""active centre"" can be entered in a from that it can function in different media of hydrophobicity, eg a precipitant, a resin or a solvent extractant. Recent results obtained in this laboratory will be used to illustrate how the above variables can be exploited to develop improved processes for the separation of base metal and platinum group metals.IntroductionThe separation of metal ions in hydrometallurgy can be performed broadly speaking with two major aims. Firstly the separation/removal of a certain group of metal ions, either as a means of preconcentration or as a removal from effluent as part of a purification process and, secondly the removal of a specific metal ion from an industrial stream in order to produce a specific metal in a pure form. This latter operation is by far the most difficult of the two and is becoming more so in the light of the fact that the world is moving in the direction of lower grade ores and increasing pollution. Such a process can be divided into three essential parts, firstly the molecular one in which an active centre is required to obtain specificity, secondly a matrix within which this active centre must function, i.e. as part of a resin or solvent extractant and thirdly the design of the total system to optimize the realization of the operation."

Jan 1, 1996

By E. S. Peterson

The selective separations of trace metals- and organics from water are processes of importance to industry. The application of a new metals capture technology coupled with polymer membrane technology has proven to be one avenue to accomplish such selective separations. The polymers used in these studies are polyphosphazenes. Polyphosphazene polymers consist of an alternating backbone of nitrogen and phosphorus atoms. The polymers have high thermal and chemical stabilities. Experiments at the Idaho National Engineering Laboratory demonstrate that polyphosphazene membranes coupled with Chromato Chem,"Chelation Chromatography" process are capable of removing both chlorinated hydrocarbons and metal ions from process streams. These results point to a wide range of potential industrial and environmental applications for such systems. Data will be presented which show the efficiency and selectivity of separations, postulated separation mechanisms, and the initial designs of industrial demonstration units which are currently under construction. Parts of this work have been performed under a Cooperative Research and Development Agreement (CRADA) between ChromatoChem, Inc. and Idaho National Engineering Laboratory (INEL). The work at INEL was been sponsored by the United States Department of Energy's Office of Industrial Technologies

Jan 1, 1995

By L. L. Sutter

Fly ash is a by-product produced from the combustion of most hels including municipal solid waste. Currently, most combustion residuals are disposed of in landfills at a continually increasing cost and with questionable impact on the environment. Due to the presence of heavy metal compounds, municipal waste combustor (MWC) fly ash has the potential to leach these metals (e.g., lead and cadmium) above regulatory limits. The heterogeneous nature of MWC fly ash makes detailed characterization difficult. This research focuses on the identification of lead compounds in MWC fly ash. Samples obtained from the Olmsted Waste-to-Energy Facility in Rochester, Minnesota were examined in this study. The fly ash was fractionated into six size ranges and prepared as geological thin sections for analysis. The worked discussed in this paper involves using an electron microprobe analyzer to determine phase composition in MWC fly ash. In addition, backscattered electron imaging, digital image processing, and mineral liberation analysis software were used to determine phase distributions and phase associations as a function of particle size. Several lead containing compounds in several forms are identified. The results of this study show that lead can be identified in small sectioned particles which would not be apparent using normal backscattered electron imaging.

Jan 1, 1994

By Dan Wang, Qian Xu, Guangshi Li, Xionggang Lu, Xingli Zou, Zhongfu Zhou, Hongwei Cheng, Changyuan Lu

The preoxidation of the ore has a profound significance to the concentration, separation and purification of nickel and copper from the lean complex ore. In this paper, the natural Ni-Cu sulfide mineral samples under the elevated temperature condition in air were investigated, as well as under isothermal condition at 600 oC in air. The mineralogical characterization was studied using XRF, ICP and the Rietveld method. The oxidation behavior and the element migration of the Ni-Cu sulfide ore were studied by XRD, SEM-EDS and TG. The XRD Rietveld method was successfully developed in the phase identification and quantification of this complex ore powder sample. The oxidative intermediates (Cu/Ni-ferrite) were detected by XRD, and the process of the element migration was obviously revealed by the line scans using SEM-EDS. It is the preoxidation of this mineral that provides guidance for the extraction of valuable metals from low-grade Ni-Cu sulfide ores in the future.

Jan 1, 2015

By Akira Yazawa

The continuous converting has attractive advantages, but further experimental studies on the slag are required, when the process is considered thermodynamically. The summarized experimental results, obtained with iron silicate slag and with ferrite slag and results relating to actual operation are described and discussed in this paper. At first, equilibrium relations at controlled oxygen potentials among three melts of silica-saturated iron silicate slag, white metal and copper are investigated. The results obtained for slag agreed with the thermo-dynamical predictions. Namely, to suppress a magnetite separation, the system should be at high temperature; in the case of the S02 gas of 10 kPa, for example, magnetite did not separate from the slag at 1300°C, but at 1250 and 1200°C the slag was saturated with magnetite even at lower SO2 pressure. Copper losses caused by dissolution of its oxide increased with increasing 5O2 pressure, and were slightly lower than those reported in previous papers without the matte phase. When the continuous converting slag does not contain any appreciable amount of silica - in contrast to the conventional smelting slag ferrite slag would form, but there was no published fundamental work on-ferrite slags. Hence, the melting behavior and activities of the system CaO-Cu2O-Fe2O3 have been investigated. The liquidus diagram in nitrogen atmosphere was, constructed using both thermal analysis and quenching method. The low liquidus temperature region without magnetite separation was found in the part of low content of Cu2O in the section Cu2O-CaO-Fe2O3 and Cu2O?Fe2O3¬CaO?Fe2O3. The activity of Cu2O in the system was also measured. Slags, composed-of CaO, Cu2O and Fe2O3, in platinum crucibles were equilibrated at 1250°C and controlled oxygen pressures. After quenching, the-composition of slag and platinum crucible were determined qualitatively. On the thermo-dynamic analysis of the results, iso-activity lines were drawn, and it was shown that the slag in the converting furnace of the Mitsubishi process exists in an adequate region of the composition triangle.

Jan 1, 1976

By L. Becze, S. J. Hock, G. P. Demopoulos

"Regeneration of HCl from chloride solutions is commercially practiced by high temperature (800-900 °C) pyrohydrolysis associated with high energy consumption and capital cost. As an alternative to pyrohydrolysis a novel low temperature ( <200 °C) non-autoclave hydrolytic process has been studied in this research work, which comprises two steps. In the first step, ferrous chloride is oxidized by oxygen at 1;150 °C, followed by hydrolytic decomposition of ferric chloride to coarse hematite particles and superazeotropic hydrochloric acid (8-9M) operated at approximately 180 °C. This paper provides a summary of the laboratory results related to both oxidation and hydrolysis and presents a newly designed conceptual process flowsheet.IntroductionRecovery of base, noble and rare metals from ores and secondary materials (slags, dusts, residues) by chloride-based hydrometallurgical processes holds a lot of promise if a low cost HCl process becomes available. This is particularly so due to the high activity of HCl or more accurately activity of hydrogen ion [1] in concentrated chloride media and the formation of chlorocomplexes allowing for effective leaching under atmospheric leaching conditions and simultaneous ease of metal separation. However, during leaching significant amount of iron, which is associated with most of ores and secondary materials, goes into the solution. Hence, the obtained leach solution has to be treated to convert iron chlorides into easily filterable iron oxide and simultaneously produce concentrated hydrochloric acid. Apparently the critical operation of these processes is the regeneration of the lixiviant (HCl). Currently in the industry, its regeneration is accomplished by high capital and intensive pyrohydrolysis which operates at 700- 900 °C. Aimed at lowering the operational cost of pyrohydrolysis a process called PORI [2] was developed and tested in pilot plant scale in the 1970s for the purpose of treatment of pickle liquors without, however, resulting in industrial application."

Jan 1, 2011

By G. A. Brooks

Reactive ball milling has been proposed as a new route for producing carbides from oxides through carbothermic reduction. It is claimed that through milling oxide and graphite powders to the nanoscale, amorphous materials with very high reactivity are formed, that allows for easy transformation of the starting material to another in a subsequent thermal process. Thermodynamic analysis of this proposed process suggests that unless particle sizes are reduced to below 10nm, then reduction in size alone cannot explain a change in the stability of oxides. Even with nanometer scale powders, the products formed need to have a lower total surface energy than the reactants before a chemical change will occur. A model developed by Bhattacharya and Arzt for predicting localized temperature changes based on milling conditions suggest that temperature rises less than 400 K will be achieved in laboratory conditions. The present calculations suggest that nanometer scale powders formed through high speed ball milling (> I 0 mls) may have undergone a process analogous to melting and quenching. Further work is required to fully distinguish these features.

Jan 1, 2003

By T. K. Mukcherjee

The importance of the processing of secondary resources such as solid industrial wastes and liquid effluents as well as byroducts for the recovery of the associated metal values hardly needs any elaboration. Such processing contributes in no small measure.towards the augmentation of the availability and the supply position of resources. As an added benefit, it leads to a reduction in environmental pollution caused by the undesirable waste materials. As some typical examples of secondary resources in the Indian scenario, mention&apos; can be made of spent catalysts, metal/alloy scrap, ash, consumed batteries, flue dust, slag, sludge and slime, pickling solutions, spent acids; plating rinse solutions, spent etchants, waste water from synthetic fibre manufacture and from tanneries etc. These wastes constitute a source of a variety of non ferrous metals. In the processing of secondary resources like these, the techniques of hydrometallurgy such as solvent extraction play a pivotal role. This paper outlines the efforts made to use solvent extraction to recover(1) base metals. such as copper, zinc, nickel and cobalt from a number of secondary resources like cake, and sludge(2) refractory metals like molybdenum and vanadium from sulphidic byproducts and spent catalyst and (3:) nuclear metal like uranium from phosphoric acid. In the case of base metals, process flowsheet involving the use of acidic extractants such as DEHPA and PC88A have been optimised. The problem of iron removal from the leach liquor, "which influences the metal recovery process significantly, has drawn a special emphasis. hi the case of refractory metals, basic extractants .like Alamine 336 has been pressed into service to produce kilogramme. quantities of pure salts of molybdenum and vanadium, Finally, the paper gives a brief account of plant experience in recovering uranium from phosphoric acid, using &apos;a solvent system comosed of DEHPA and TOPO.

Jan 1, 1996

By Takashi Fujii

In the OG (Osaka Gas) process which includes a fusion process of sewage disposal sludge in coke bed knowledge of molten and fluid properties of the sludge are most important to controll the process in good condition. Thus, the softening and melting temperatures and viscosity were measured by the sessile drop technique and a rotating viscometer. Obtained results are summarized as follows: Melting character of sludge slag is varied according to their composition, but closely related to CaO/SiO2 ratio in ordinary sludge and to CaO/(Cr2O3,+Al2O3+P2O5) ratio in Cr2O3 containing sludge. Fluid property of sludge slag has a correlation with optical basicity or Riboud parameter, However, the correlation is poorer than that of metallurgical slags. Especially, chromium oxide containing sludge shows high viscosity and behaves somewhat different manner from ordinary sludge.

Jan 1, 1992

By D. W. Collins

The uptake of gold from halide solutions by activated carbon has been investigated using various techniques. Halide systems typically exhibit combined adsorption-reduction type behavior. In an attempt to gain more information about the nature of these processes, samples of synthetic highly-oriented pyrolytic graphite (HOPG) were contacted with aqueous solutions of gold-iodide. HOPG represents a model structure for activated carbon comprising of basal- plane sites, edge sites, and various defect sites. Two basic instrumental methods were used to examine the uptake of gold by HOPG. The first was standard X-ray photoelectron spectroscopy (XPS). The other involved several scanning probe techniques. XPS clearly indicated a preferred uptake of gold at edge sites. However, iodine appeared to be distributed on both basal-plane and edge sites. At low iodine additions, tapping mode AFM showed that clusters were concentrated along steps and surface defects. At high iodine concentrations, the HOPG surface was uniformly covered by iodine.

Jan 1, 1998

By Sergey Komarov, Manuela Diaz, Sano. Masamichi

"Mixing time, bubble behavior and absorption rate of gas injected into a liquid bath through rotary L-shaped lances have been studied by cold models with an effort to improve refining characteristics of metallurgical processes. Two kinds of the rotary lances were tested, namely the single-hole lance and the multi-hole lance. The effects of gas flow rate, bath depth and rotation speed were examined.It is found that when gas is injected through the rotary lances, the mixing intensity and the gas absorption rate are larger than that for the gas injection through stationary lances. The effect of rotation speed decreases as the bath depth and the gas flow rate increase.The multi-hole lance produces much smaller bubbles, which lead to an increase in the volumetric mass transfer coefficient by 3-4 times as compared with the single-hole lance. However, the effect of rotation speed is smaller for the multi-hole lance. The obtained results are explained in terms of the bubble coalescence and fragmentation, the rate of which depends on the departure bubble size and the power supplied to the liquid bath.IntroductionIn recent years, there has been a growing interest in the development of gas injector for metallurgical processes. The majority of the previous work was focused on modification to the injector design to improve mixing and to increase the of chemical reaction rate. These two goals can not be necessarily achieved by the same way. Bottom nozzles and stationary immersed top lances, which have been widely applied to steelmaking processes, are effective for the bath mixing, but have a limit to decrease in the bubble size. This results from a vigorous coalescence occurring between the bubbles when they rise in the molten bath as a bubble swarm.One of the ways to ensure the small bubble size and the effective bath stirring is the gas purging through rotary injectors. A number of studies have been undertaken to improve the refining characteristics by using rotary injectors. All of them are related to aluminum refining. The SNIF equipment (The Spinning Nozzle Inert Flotation) has significantly improved the quality of aluminum products at National Luxemburg Aluminum [1]. Rotary injectors made in the form of a disc have been applied to the Alcoa 622 [2] and the GBF processes [3]. A study of the gas injection by a rotary impeller has been carried out by C. Leroy and G. Pignacelt [4]. All researchers note the significant improvement in removal of sodium, calcium, hydrogen and non-metallic inclusion."

Jan 1, 1996

Lead removal has been problematic in nickel production by electrowinning from chloride solutions, as developed by Falconbridge. The C12 leach liquor needs to be diluted by electrolyte to allow precipitation of the lead prior to electrowinning. This results in higher solution purification costs and an aversion to consider lead contaminated (secondary) feeds. In this paper, the electrowinning of nickel chloride is carried out in a membrane equipped electrolytic cell. When lead containing nickel solutions are fed into the anode compartment and the anolyte is separated from the catholyte with a cation exchange membrane, lead remains in the anolyte due to the presence of a negatively charged chloride complex. The positive nickel ions migrate preferentially through the membrane to the catholyte, allowing a lower lead nickel cathode to be produced. Lead concentration in the catholyte and the cathode product has been tested as a function of lead concentration in the anolyte. Results are presented and discussed.

Jan 1, 1998

By Ibrahim Yusufoglu, Cem Kahruman, Mert Zoraga

In this study, a strontium sulfate mineral (celestite) was converted to strontium oxalate in solutions containing ammonium oxalate as a reactant. The experiments were carried out under isothermal conditions. The effects of stirring speed, ammonium oxalate concentration, particle size and temperature on the conversion rate were investigated. During the conversion process, definite volumes of solutions were taken from the reactor after different reaction times for the determination of sulfate ions using ICPOES. Fractional conversions of strontium sulfate were determined at different times and fractional conversion vs time diagrams were generated. It was found that the conversion of strontium sulfate was increased by increasing the ammonium oxalate concentration and temperature in addition to decreasing the particle size. The effect of stirring speed was negligible on the reaction rate. It was observed that above 328 K, a protective layer of strontium oxalate was formed on the strontium sulfate particles. X-ray Powder Diffraction technique was used for characterization of solid substances.

Jan 1, 2014

By G. R. Adams, N. Y. Tang, N. Qiang

"Aluminum is the most important alloy addition to Zn baths for controlling the reaction kinetics between the steel substrate and molten Zn in continuous galvanizing operations. Due to the complexity of the Zn-Fe-Al ternary system, the measurement and control of effective bath Al remains a challenge for modem galvanizers. The successful development of Al sensors has made the real-time measurements of bath Al contents possible. To facilitate their application, a computer interface and a palm-size data logger have been developed by Cominco. Plant applications indicated that the sensor possessed sufficient accuracy for process monitoring and control. The working mechanism of the Al sensors and Cominco's development work is described, and the results of sensor applications are presented.IntroductionControl of bath Al content is critical in modem continuous galvanizing because it has a strong influence on coating structure and properties and the overall product quality. The control of effective bath Al content (Al in liquid solution) is particularly critical for galvannealing where a high bath Al content may lead to incomplete alloying during post annealing, and a low bath Al content may result in other operation problems, such as excessive bottom dross accumulation and difficulties in coating thickness control. The desirable accuracy of the Al control is within ±50 ppm of target levels. In principle, such an accuracy is achievable for modem chemical analysis facilities, such as atomic absorption photospectrometer (AAS) and induction-coupled plasma (ICP). However, a recent study carried out by the International Lead and Zinc Research Organization (ILZRO) indicated that such an accuracy is rarely achieved in the zinc and steel industries.(1)"

Jan 1, 1997

By Peter K. Liaw, Niann-i Yu, Wei Zhao

"For a plain-weave Nicalon ™ fiber fabric-reinforced silicon carbide (SiC) ceramic composite, little attentation has been paid to the effect of fabric stacking sequence on its mechanical behavior. In this paper, fiber-fabric stacking sequence effects on the elastic stress distributions, ceramic matrix-cracking stress, effective elastic moduli, and flexural strengths of laminated flexural test bars are quantified. A quantification model is established based on the combination of classical laminated plate theories and a fiber undulation model developed by Chou et al. A FORTRAN program is compiled to implement the modeling, which can be run in a SUN work station. The mechanical performance of a continuous fiber-reinforced ceramic-matrix composite (CFCC) with a [0/30/60] lay-up was analyzed and predicted. The variation in the fiber-fabric stacking sequence can vary the elastic stress distributions along the thickness direction of specimens, magnitude of ceramic matrix-cracking stress, effective elastic moduli of the laminate, and crack initiation sites as well as fracture modes. Moreover, all these factors contribute to scatter in flexural strengths of the CFCC.I. IntroductionWith enhanced fracture toughness and the ability of non-catastrophic (graceful) failure behavior, CFCCs are currently under evaluation for high-temperature structural applications in heat exchangers, combustors, hot-gas filters, boilers components, first walls and high-heat flux surfaces gas turbines, space vehicles and nuclear reactors.[1-8] Extensive applications of CFCCs by industry are still hampered by an insufficient understanding of the mechanical behavior, and sometimes, the lack of a well-developed and widely accepted design philosophy, in addition to the high-production costs."

Jan 1, 1998

By Marco Olper

Zinc bearing materials containing chlorides and fluorides of alkali metals, such as EAF dust, Waelz oxides, galvanizing ashes, zinc & brass foundry fumes and converter fumes are little attractive, both technically and economically for processing in ISF plant or in a conventional zinc sulphate electrolysis works. The Ezinexm Process allows for the recovery of high purity zinc in cathode form, from these materials, regenerating the leaching liquor. The process is based on a new electrochemical system which depolarizes the anode reaction with reduction of the cell voltage, compared with the traditional sulphate electrolysis method. The electrolyte, based on a chloroamrnino complex, allows for the recovery of other valued metals present in the zinc bearing materials such as lead, copper and silver, these being recovered as a metallic cement consequently improving the economics of the process.

Jan 1, 1994

By Roland Kammel

In combination with various physical and chemical methods also electrochemical techniques are most frequently used to improve the recovery of metals from aqueous dilute process streams or effluents e.g. in electroplating, metal finishing, mining and metallurgical plants. To insure cathodic metal recoveries with favorable current efficiency and high throughputs per unit of cell volume seve¬ral types of electrolysis cells have been developed comprising extended electrode surface areas and/or intensive electrolyte. agitation. The practical experiences with these units indicate especially for the electrolytic recovery of metals whose values are high, that the treatment cost permits profitable operations with relativly short payback periods for the units. Anodic reactions can be utilized for the removal of undesired anion contents or buildups of impurities. Appropriate combinations of these recovery methods are used to improve the versatility and the overall economy. Industrial applications reveal their potentional as addidtive techniques for existing processes to reduce the metal content of effluents to values that meet the guide lines of environmental legislation whereas integrated in-operation recovery methods are nowadays increasingly introduced to approach nearly close-loop operations.

Jan 1, 1992

By T. Shimizu

In Japan, the emission standard of selenium in effluent was set at a maximum of20 mgll in Feb. &apos;94 for the first time, and it is scheduled to be further decreased to a maximum of 0.1 mg/I from Feb. &apos;97 due to tightening of the Water Pollution Prevention Act. Selenium (IV) and (VI) are generally found in effluent from precious metals refineries. Although selenium (IV) can be easily eliminated by some reducing agents, selenium (VI) is more difficult to be reduced. Therefore, many smelters are having difficulty in complying with the new emission standard. At Mitsubishi Materials&apos; Naoshima smelter, the behavior and the elimination of selenium in effluent have been extensively investigated. As a result, it was found that two strategies were particularly effective. One of them is improving the overall operation of precious metals refinery, that is, feeding uniformly the effluent to the waste-water treatment plant, reducing the effluent volume by recycling and recovering more selenium (IV) in the effluent. The other is eliminating selenium (VI) in the effluent from the precious metals refinery. It was found that selenium (VI) can be effectively reduced by using hydrazine under high? sulphuric acid concentration and high temperature conditions. By using these measures, it is considered that Naoshima Smelter will be able to comply with the new emission standard.

Jan 1, 1996

By T. J. White

Xtaltite is the trade name for a generic technology which exploits the well known insolubility of some minerals, which naturally incorporate toxic waste elements, to consolidate and immobilise a range of inorganic waste products. It is a specific case of synthetic mineral immobilisation technology (SMITE) which is already used to immobilise high level nuclear wastes (HLW. Although HLW is highly toxic, it exists in relatively small volumes, occurs in central facilities and may be stabilised at low waste loading (< 10 wt%). In contrast, heavy metal wastes are of considerable volume, therefore Xtalitite waste forms must routinely accommodate high waste loadings (usually in excess of 30 wt% for a particular toxic oxide or combination of oxides) and be suitable for fabrication in remote locations using relatively simple technology. This paper details the methodology underlying Xtaltite, with particular emphasis given to the interplay between solid state chemistry, durability and economic considerations. Specific reference is made to the treatment of arsenious and mercurial wastes.

Jan 1, 1994

By G. A. Brooks

Reactive ball milling has been proposed as a new route for producing carbides from oxides through carbothcrmic reduction. It is claimed that through milling oxide and graphite powders to the nanoscale, amorphous materials with very high reactivity are formed, that allows for easy transformation of the starting material to another in a subsequent thermal process. Thermodynamic analysis of this proposed process suggests that unless particle sizes are reduced to below 10nm, then reduction in size alone cannot explain a change in the stability of oxides. Even with nanometer scale powders, the products formed need to have a lower total surface energy than the reactants before a chemical change will occur. A model developed by Bhattacharya and Arzt for predicting localized temperature changes based on milling conditions suggest that temperarure rises less than 400 K will be achieved in laboratory conditions. The present calculations suggest that nanometer scale powders formed through high speed ball milling (>10 mls) may have undergone a process analogous to melting and quenching. Further work is required to fully distinguish these features.

Jan 1, 2003