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By James A. Voigt

"The efficient separation of metal species from aqueous streams by precipitation techniques requires a fundamental understanding of the various processes that occur during precipitation. These processes include particle nucleation, particle growth by solute deposition, agglomerate formation, and agglomerate break-up. The application of the population balance approach has been used to develop a kinetic model that accounts for these competing kinetic processes. The usefulness of the model is illustrated through its application to the precipitation of yttrium hydroxynitrate, YHN. The kinetic parameters calculated from the model equations and system specific solution chemistry are used to describe several aspects of the effect of pH on the precipitation of the YHN. Implications with respect to the simultaneous precipitation of more than one cation type are also discussed through use of example systems. The effects of solution chemistry, precipitator design, and solvent choice are considered.IntroductionThe application of precipitation technologies to the separation of metals from solution is widely used. Regardless of its application, be it in such diverse areas as the preparation of metal oxide powders for use in commercial products or as a unit operation in the removal of trace metals during wastewater clean up, the fundamental processes involved are the same. These processes include: nucleation from solution, either homogeneous or heterogeneous; growth from solution with chemical reaction either in solution or at the precipitate/solution interface; growth by particle agglomeration; and particle break-up by collisional or shear forces. The effectiveness of the operation and the properties of the precipitate formed, or ""quality"" of the product, are determined by the competing kinetics of the different processes. The kinetics of the processes, in tum, are determined by system-specific solution chemistries and the conditions used to carry out the precipitation operation. For example, generally, when system conditions are such that the supersaturation driving force for precipitation is very high, growth species normally do not have the time to organize themselves with a high degree of crystallographic order and the precipitate is amorphous. In this case nucleation rates are invariably extremely high and the primary mechanism for growth is the agglomeration of nuclei. Conversely, when the supersaturation levels for the same system are reduced, the kinetics of the nucleation and growth processes also are greatly reduced, and a crystalline precipitate can be formed, since the growth species have time to order on particle surfaces."

Jan 1, 1996

Several processes are now available for the recovery of free and WAD cyanide from gold plant solutions and pulps. In the past, the incentive for evaluating cyanide recovery in gold plant flowsheets has been economic. In many cases, it has been possible to demonstrate (at least in the laboratory and on paper), an improvement in process economics by; (i) reducing the costs of tailings detoxification, (ii) recycling cyanide at lower cost than the purchase/delivery price of new cyanide, and (iii) generating additional revenue via by¬product sales. Despite these convincing arguments, few cyanide recovery plants have been built at operating gold mines. Also, there is arguably an even more compelling reason for mining companies to consider cyanide recycling. With the growing storm of negative public opinion that the use of cyanide in the mining industry is attracting - following several highly publicized spills over the last couple of years - the time has come for the gold industry to demonstrate environmental diligence and stewardship in the use of this commodity that is so vital for their industry. There is no doubt that the widespread implementation of cyanide recycling will reduce the impact of the cyanidation process on the environment, both by reducing the risk of spills (with less cyanide being transported from manufacturing plants to gold mines), and by reducing the loading of toxic and non-toxic metals and ions in the tailings. In this paper, the various processes that are available for cyanide recovery are discussed, along with the process chemistry. Results of several laboratory and pilot plant trials that have been conducted over the last few years are also presented.

Jan 1, 1998

By S. G. Kumar

The performance of nickel based high temperature materials is directly related to their microstructure, which is controlled by the various processing steps. Nickel base alloys are melted and refined by a variety of processes that include Vacuum Induction Melting (VIM), Vacuum Arc Remelting (VAR) and Electroslag Remelting (ESR). The limitation of VIM is that the metallrefractory reactions lead to the disintegration of the crucible and hence contamination of the product due to macrosegregation. This macrosegregation is alleviated to some extent by controlling the solidification in VAR. The main attraction of ESR is its ability to produce a clean product by controlling the deleterious inclusions. In recent years Electron Beam Melting (EBM) is emerging as an alternative to the VIM, VAR and ESR. This paper reviews the current status of these processes and outlines the scope for further improvements in the processing technology.

Jan 1, 1993

By . Menad Gaballah I

Three samples of solid wastes generated by the non ferrous metallurgy were characterized. These residues contain up to 42 % of valuable metal compounds ( Cu, Pb and Zn ) and 23 %of toxic compounds t As, Hg, Cd and Se ). These sample were subjected to thermal treatments between 200 DC and 800 °C in controlled oxidizing. reducing and chlorinating atmospheres. Up to 99 % of As, Cd, Hg and Se were eliminated from these industrial wastes. Cu, Pb, and Zn compounds were concentrated in the treatments' residues of these samples. A Global Decontamination Factor' GDF ' was defined to measure the efficiency of the elimination of toxic elements and the recovery of valuable elements for a specific sample submitted to a given treatment. It seems that the thermal treatment in a reducing atmosphere was the most efficient in decontaminating these solids and the concentration of valuable elements. a.

Jan 1, 1995

By P. Heald-Wetlaufer

Doubly polished sections (i.e., sections polished on both sides) allow insights into complex paragenetic relationships, the interpretation of which is essential to understanding ore-forming processes. Alternate viewing of these optically superior sections in transmitted and. reflected light facilitates the recognition and definition of growth zones in ore and gangue minerals and the interpretation of postdepositional changes, such as hydrothermal leaching and replacement. Many such observations would escape detection by conventional petrographic methods. Our procedure for preparing doubly polished sections has evolved during the past 20 years and incorporates many standard procedures. Studies from such diverse districts as Creede, Colorado, Hokuroku, Japan, and the Upper Mississippi Valley zinc-lead district, southwestern Wisconsin, demonstrate the value of observations from doubly polished sections in constructing genetic models. The advent of doubly polished sections represents a major advance in the study of ore deposits and they should be a standard tool in every ore petrology laboratory.

Jan 1, 1982

By Gus Van Weert

Solvent extraction of iron from zinc refinery liquors has been investigated before, mainly on the MEHPA / HC1 stripping combination. Leakage of chloride into the zinc electrolyte and the costs of handling the ferric chloride eluate have prevented this option from being adopted. This work explores the stripping of the ferric loaded organic phase with nitric acid to take advantage of the possibility of regenerating up to 6N nitric acid, and clean spheroidal hematite production by autoclave treatment of ferric nitrate solution. The work was carried out with DEHPA (di 2-ethyl-hexyl phosphoric acid) in kerosine. Degradation testing proved the DEHPA to be very stable, when exposed to nitric acid solutions up to 6N and temperatures up to 70" C over a period of five days. Ferric iron was removed completely froma synthetic hot acid leach liquor, irrespective of the DEHPA concentration. Stripping the ferric turned out to be the problematic step. Although the stripping efficiency was considerable better at 50 than at 20° C, it decreased with increasing DEHPA/Fe ration in the organic phase. Eluates of no more than 5-10 g/l ferric nitrate were produced. surprisingly, nitric acid was found to be a less efficient stripping agent than sulphuric at equivalent normality and its efficacy levelled off above 4N. It was concluded that DEHPA does not appear to be the S.X. reagent to take advantage of the low cost autoclave decomposition of ferric nitrate opportunity in zinc hydrometallurgy and that another S.X. reagent, also resistant to nitric acid, but based on weaker compound formation is needed.

Jan 1, 1998

By Dirk Verhulst

The Altair Hydrochloride Pigment Process is a new ?third route?, besides the established high-temperature chloride process and the older sulfate process, to manufacture TiO2 pigment from ilmenite ore. It has been tested at a scale of 5 t/day feed. The ore concentrate is digested in high-acid, high total chloride solution (+/- 39% Cl). Titanium and iron both go into solution. Iron is separated as FeCl2 crystals after reduction and cooling. Titanium is transferred by solvent extraction into a purified, high-Ti stream. It is spray-hydrolyzed to produce a TiO2 hydrate and further calcined with additives into high-quality pigment. HCl solutions generated by pyrohydrolysis and spray hydrolysis are treated by pressure-swing distillation to regenerate HCl gas for re-injection into the digestion reactor. All chloride streams are recycled. Recent work has concentrated on optimization, particularly in 3 areas: - Solvent extraction: a new organic mixture, including a new diluent, makes it possible to work at room temperature, to avoid TiO2 hydrolysis problems and to improve phase disengagement and impurity separation. - Pigment finishing: a systematic study of the parameters involved, followed by long runs in the best conditions confirm pigment quality. - Flow sheet optimization: innovative modifications of the conditions of spray hydrolysis and pyrohydrolysis, combined with re-routing of streams achieve significant energy savings. A 100 t/year pilot plant including these features as well as other process improvements is under construction.

Jan 1, 2006

By Jean-François Boulanger

The production of rare earth elements from ore usually consists of three steps; the separation of a concentrate of REE bearing minerals; the cracking of the REE minerals to liberate the REE into an aqueous solution and separation of REE into individual elements. This paper describes the results of laboratory tests conducted on a carbonate-rich REE ore containing bastnaesite and monazite. The tests cover the whole processing sequence of beneficiation, preparation of the REE solution using a caustic leach followed by acid leach to break monazite and bastnaesite and liberate REE into an aqueous solution and the partial separation of the REE using solvent extraction. Details on the product quality and process performances (recovery and impurities removal) are given for each studied step. The paper also discusses the economic advantage of separating the REE rather than producing a mixed REO product to be sold to a refinery for REE separation. A mini-pilot plant version of the process is currently planned.

By J. E. Dutrizac

Fracture-exposed surfaces of sphalerite samples having five different solid solution iron contents ranging from 0.0 wt% to 14.8 wt% Fe were leached for 15 to 120 s at 100°C in 0.3 M Fe(S04)1.5 -0.3 M H2S04 media. The reacted samples were examined using X-ray photoelectron spectroscopy (XPS) which provides chemical state information on the first few nanometers of the solid surface. Surface compositions show that the leaching rate increases with increasing solid solution iron content of the sphalerite. Detailed evaluation of high resolution S2p spectra show that the leaching progresses via the formation of polysulphide species. Disulphide species were not detected in any of the experiments. Examination of the Zn2p and Fe2p spectra indicate little change in the chemical states of these elements over the duration of the experiments. Longer leaching times resulted in the generation of elemental sulphur. The ratios of elemental sulphur to dissolved ferrous ions and zinc suggest that less than 5% of the sulphide is oxidized to sulphate. Morphological studies showed that the elemental sulphur commonly formed at a few isolated sites, such as the grain boundaries. Furthermore, euhedral sulphur crystals were often identified. These observations suggest that at least part of the elemental sulphur forms via dissolved sulphide species which are oxidized in solution by ferric sulphate.

Jan 1, 2003

By James C. Barker

Near Rainbow Mountain in the east-central Alaska Range an ultramafic complex forms a sill-like intrusion composed of dismembered bodies exposed along the south side of the Denali Fault and Broxson Gulch Thrust. The complex comprises dunite and peridotite with lesser gabbro, which together exhibit poorly defined, steeply-dipping compositional layering. The complex hosts four types of copper-nickel occurrences which have characteristic platinum-group elements (PGE), gold, and cobalt distributions. Three of the occurrence-types are considered to have formed as a result of primary mineral segregations which developed during intrusion of the complex. The fourth type of copper-nickel occurrence formed as a result of post-magmatic hydrothermal fluids at intrusive contacts. Scanning electron microscope examination indicates that PGE occur as micron-size telluride and arsenide minerals.

Jan 1, 1987

By M. Moinpour, E. Liao, C. Y. Aw, D. J. Brown, P. W. Cheung

"Currently, silicon-based insulated-gate field-effect devices are being widely developed as the basic structural elements in a new generation of chemical microsensors. In this paper, we discuss some of the process considerations related to the fabrication of the Chemically Sensitive Field-Effect Transistor (CHEMFET). This ion-sensitive CHEMFET (or ISFET as it is often called) can be used for pH measurements (i.e., as a pH sensor) when the gate insulator of the electrolyte/insulator interface is made of Si3N4 obtained by the LPCVD method. Effects of processing parameters such as the Si3N4 deposition rate, gas composition, total flow rate, annealing treatment, etc. on Si/Si02, Si/Si3N4 and Si/Si02/Si3N4 structures are discussed in relation to the CHEMFET fabrication. Their effects on the electrical characteristics and chemical response of the sensor are also examined. Capacitance-Voltage (C-V) measurements and ESCA analysis have been used to interpret the results. The Si3N4/Si02 double dialectric layer provides improved ion blocking for the gate insulator in electrolyte solutions with enhanced pH sensitivity over time. The stability and performance of the fabricated CHEMFET sensors were tested by measuring the pH sensitivity in various storage conditions. The SEM analysis was used to evaluate the hydration effect at the ISFET's gate insulator with respect to different storage conditions.IntroductionThere has been a continuous interest in the development and fabrication of various chemical microsensors for chemical and biomedical applications over the last fifteen years. The application of semiconductor (particularly silicon) technology to the area of sensor fabrication has led to an emergence of a new generation of miniaturized, microelectronic, solid-state chemical sensors. There are numerous clinical situations where continuous monitoring of body electrolytes concentrations such as Na+, K+, Ca+2 , etc. and blood gases (pH, Po2 , and PC02) would be essential for the effective diagnosis and management of patients under critical conditions. Solid- state microsensors can be used for direct and continuous in vivo measurement of the above parameters in most instances."

Jan 1, 1988

By Batric Pesic

Gold dissolution with bromine was studied by using the rotating disc technique. Geobram TM 3400 was used as a source of bromine. The parameters studied were: rotating speed, Geobrom 3400 concentration, pH, temperature, sulfuric and hydrochloric acid concentration, and the concentration of various cations (copper, iron, zinc, aluminum, manganese, potassium and sodium) and anions (chloride, bromide, sulfate, nitrate, and iodide) According to the Levich plot and activation energy, gold dissolution was controlled by a chemical reaction rate. Copper, iron, and manganese in their highest oxidation states, aluminum, zinc, sodium and potassium did not have any effect on gold dissolution rate. The presence of manganous ion dramatically decreased the gold dissolution rate. Kinetic performance of bromine, in the form of Geobram TM 3400, was compared with performance of cyanide and thiourea.

Jan 1, 1990

By Stephen W. Paff

The EPA has estimated that there are over 3,000 sites across the United States contaminated with lead. Techniques to remediate these sites include standard stabilization/disposal technologies, reclamation of lead using secondary lead smelters, soil washing, and biological removal technologies. In this paper, the current technologies used for lead remediation will be reviewed. Factors affecting the use of each technology, such as range of applicable concentrations, soil types, interferences from other contaminants, economics, and current technology status will be assessed. The paper will also focus on the results of a recent study completed by the Center for Hazardous Materials Research (CHMR), in conjunction with a major lead smelter, which demonstrates that secondary lead smelters may be used economically to reclaim lead from a wide range of lead-containing materials frequently found at Superfund sites. Such materials include battery case materials, lead dross, and debris containing between 3 and 70% lead. The results of development work completed by CHMR on the Acid Extraction Treatment System (AETS), which has been demonstrated to extract Lead from soils containing up to 30,000 mg/kg lead, will also be presented. The use of these technologies will be compared with other options for the remediation of sites.

Jan 1, 1994

By Tian Sugui

By means of the measurement of the enduring property and microstructure observation, an investigation has been made into the influences of the element Re and TCP phase on the enduring property of the single crystal nickel base superalloys. Results show that the needle-like TCP phase is precipitated along the <110> orientation on {111} planes in Re-containing/free superalloys during the long term aging, the TCP phase is identified as µ phase, and the precipitated µ phase in 4.5%Re alloy is gradually spheroidized during aging. Thereinto, the needle-like µ phase may obviously decrease the enduring lifetimes of the alloys due to the consumption of the refractory elements and the effect of the stress concentration. But the stress concentration is not easily generated in the regions near the spherical-like µ phase, which is a main reason of reducing the enduring lifetime of 4.5%Re alloy to a small extent.

Jan 1, 2010

By E. I. Gedgagov, A. V. Tarasov, V. M. Paretsky, A. D. Besser

"Hydrometallurgical technology and equipment have been developed in the Gintsvetmet Institute (Moscow, Russia) for processing of rhenium-containing alloys waste to produce commercial- grade metal products with recovery of all valuable components. The technology is based on waste treatment with hydrofluoric acid with subsequent decomposition with nitric acid at pH = 1 to 1.5 to ensure maximum degree of rhenium conversion to the liquid phase of pulp. Some experimental lots of ammonium rhenate and ammonium molybdate were produced at a pilot plant. The following main techno-economic performance values have been achieved when processing grinding residues (balance-based tests were conducted with a lot of SP-2 alloy waste) to produce ammonium rhenate of high purity, as well as tantalum-niobium, nickel-cobalt and tungsten-molybdenum concentrates: rhenium recovery of 92.3% into a commercial product from grinding waste; production cost of 170-210 US Dollars per 1 kg of rhenium in commercial-grade ammonium perrhenate taking into account its recovery; tantalum and niobium recovery of 75- 77% into bulk concentrate; nickel and cobalt recovery of 88-89% into a mixed concentrate; tungsten and molybdenum recovery of 88% to 91% into concentrate. Introduction During the recent years the use of rhenium has been increasing at a fast pace worldwide [1]. The growing prices for this refractory metal are an essential factor encouraging collection and processing of rhenium-containing wastes. Double-component waste, such as molybdenum- rhenium or tungsten-rhenium alloys can be readily decomposed and the process of rhenium recovery does not cause, therefore, any difficulties. The main separation of metals takes place at the stage of waste digestion with acid, because molybdenum and especially tungsten remain in precipitate in the form of hydrated oxides and rhenium reports in the liquid phase, from which it can be easily extracted by solid ion-exchange or solvent extraction techniques. However, most of rhenium is contained in super-alloy waste [2]. Such waste has different contents of valuable components, such as tantalum, niobium, molybdenum, tungsten, cobalt, nickel, chromium and other metals. The basis of all such super-alloy waste is nickel. Refractory metals in the super- alloy composition are in the form of metallized target-oriented eutectics, and due to this reason hydrometallurgical decomposition of such alloys is a difficult technological task."

Jan 1, 2008

By N. L. Piret

In copper smelting minimization of solid waste generation is receiving increased attention with more stringent environmental legislation and lower disposal space availability. Copper smelting slags generally being valorizable, solid waste generation is attributed to the presence in the feed of unvalorizable impurities which do not report to the slag and to the unavoidable formation of contaminated dilute acid solutions which need neutralization. As to unvalorizable impurities, solid waste minimization is achieved by rejecting them in the highest possible concentration. Dilute acid is mainly due to the formation of SO3 in the smelter gases and to the discard of decopperized bleed-off electrolyte. Its generation is substantially lowered by preventing SO3 formation, by converting the dilute acid to a valorizable product, e.g., by thermal decomposition for H2S04 recovery or by precipitation as chemical gypsum, and by suitable treatment of the bleed-off electrolyte for impurity removal. Industrial processes are evaluated and alternatives are discussed.

Jan 1, 1994

By J. Murdoch Mackenzie

Two commercial nickel solvent extraction plants treating laterite leach solutions and using LIX®84-I have been operated in Australia. These circuits employ similar extraction chemistry but differ in their leaching and stripping operations. An alternative process involving elements of both can be conceived. The preparation of the feed solution to solvent extraction plays an important role in nickel extraction using LIX®84-I and the special features of manganese removal and cobalt oxidation in the preparation of the PLS are discussed. This paper compares these three circuit configurations with special reference to the extraction and reductive stripping of cobalt, the transfer of zinc and copper to the strip aqueous, ammonia transfer and sulfur transfer. The potential degradation of the organic and remediation using re-oximation is discussed. Keywords: Nickel, Solvent Extraction, Oxime

Jan 1, 2004

By Daojin Cao

Aiming at many controversial reports on Raman spectral pattern of heptamolybdate ion in aqueous solution appearing in the literature and the absence of its standard pattern, the comparative investigations on Raman spectral pattern of saturated solution of ammonium heptamolybdate tetra hydrate were done. The results showed that the main vibrant frequencies of Raman spectral pattern of the saturated solution were in good agreement with those introduced in the literature, and that the intensity ratio (4.4) of the strongest peak to the second strongest peak recorded in Raman spectrum of the saturated solution had three obvious characteristics: it was greater than each of the results (ranging from 3.7 to 1.3) reported in the literature, much closer to that (4.7) of crystal and well conformed to the change rule of Raman spectra occurring in the process of the first-step polymerization of acidified molybdate solution. It was found that Raman spectrum of heptamolybdate ion in aqueous solution was determined by not only the main vibrant frequencies but also the intensity ratio, which is also the crucial result in this study. The comparative investigations indicate that the pattern of Raman spectrum of the saturated solution is the standard pattern of Raman spectrum of heptamolybdate ion in aqueous solution essentially. The affirmed standard pattern is reliable and can be used to the identification of heptamolybdate ion in aqueous solution, applied in the research of the equilibrium of acidified molybdate solution and the exploration of the best technologic condition for the production of high quality heptamolybdates.

Jan 1, 2006

By T. S. Krishnan

Among the established permanent magnets, SmCo5 magnet occupies the foremost position as it offers a unique combination of high energy product, coercivity and curie temperature. The SmCo5 magnets are thus extensively used for high field applications. These are also best suited for use in environments where high demagnetising field and high temperature are operative. Also, for applications where high performance and miniaturisation are the over-riding considerations, the choice again falls on SmCo 5 magnets. The main deterrent to the widespread use of SmCo5 magnet is its high cost. Both samarium and cobalt metals are high priced, and the magnets prepared from their directly melted alloy are thus naturally very expensive. An alternate process involving calcium reduction of their oxide intermediates has, therefore, been studied and the alloy prepared by this process has been evaluated and found satisfactory for magnet production. The process essentially involves compaction of the charge mix containing samarium oxide, cobalt oxide (or metal) and calcium metal and&apos; reduction of the charge compact at 1000-1300°C in hydrogen atmosphere, followed by water and acid leaching, drying and classification. The calcium reduction process offers three distinct advantages over the conventional melting processes: (i) The oxide intermediates are relatively cheaper and do not pose any handling problems. (ii) The operation temperatures are comparatively lower and hence precise composition control is possible as samarium losses due to volatilisation

Jan 1, 1989

By Pertti Pekkala

Outokumpu has 25 years of experience in the SX area. The development of the solvent extraction plants responds to an ever increasing demand for lower operational costs wd for adaptability to process disturbances with minimized risks. In this paper the features of the VSF ("Vertical Smooth Flow") SX technology are described, such as the separated pumping and mixing, the homogenous gentle mixing, the droplet coalescence and the ultra pure settling. A major advantage of the mixing technology is the high stage efficiency of above 99 per cent. The connection between this and some features of the settler front section is clarified. The present design of VSF plants is based on experience of existing operations at, for example, Zaldivar, Radomiro, Morenci, Kokkola and Harjavalta. These production plants cover a unit capacity range of 60 to 3,600 m3/h expressed as a total flow. It is evident that there are no restrictive factors to increase the total flow up to 5,000-6,000 m3/h by introducing the VSF technology. The copper SX technology has a long history reflecting many individual features of the separate copper SX plants. Still it is necessary to verify all actual running parameters by pilot tests taking into account impurities, chemicals used etc. The design of SX plants is not only about the delivery of equipment but also a process concept, and it is best tailor-made and adapted to specific local requirements.

Jan 1, 1999