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By Roy J. M. van Lier

In industrial aqueous solutions, germanium generally occurs in trace amounts amid high concentrations of other metals, such as zinc, copper and iron. Separation of germanium from these metals as well as its isolation from gallium and indium pose a real challenge to the hydrometallurgist. After a brief discussion of the aqueous chemistry of germanium, this paper reviews the flowsheet of the Apex Mine in Utah. The Apex property was the only mine in the world to be operated primarily for production of gallium and germanium, but apparently closed due to great operating difficulties. Several process variants proposed for the treatment of the Apex ore, including bioleaching methods, are addressed. Following a more general description of the behavior of germanium in hydrometallurgical zinc processing streams, available technology for its recovery from aqueous solutions is summarized. Precipitation, solvent extraction, ion exchange, electrowinning, ion flotation and liquid-membrane separation are all outlined in terms of the aqueous chemistry of germanium. Finally, the production of high purity germanium dioxide and metal is briefly discussed

Jan 1, 1995

By J. G. Eacott

This paper reviews the role of oxygen potential and the advances that have been made in the application of tonnage oxygen in copper smelting. Brief reference is made to reaction kinetics before attention is turned to the thermodynamic considerations in copper melting to illustrate the importance of oxygen and. oxygen potential in the component parts of the overall smelting process. The chemical potential diagram for the Cu-Fe-S-O-Si02 system is used to elucidate the difference b etween the conventional matte smelting process and the modern continuous processes. A progressive oxidation scale' is constructed to show the common elements which exist, and the matte grades produced, during the smelting of concentrates to blister copper in commercially available copper smelting processes and those under development. The common route in producing blister copper from molten mattes, regardless of process, is illustrated on the Cu-Fe-S equilibrium phase diagram. The essential features of oxygen enrichment, in terms of its effect on combustion conditions (i.e. oxidation of fuel and sulphide minerals) and the heat balance are outlined. The benefits of oxygen enrichment are listed. The influence of tonnage oxygen and its effect on productivity, fuel savings, gas volume and strength in various copper melting processes are examined as a state-of-the-art review. Reference is made to the economics of tonnage oxygen utilization.

Jan 1, 1983

By C. A. Young

The remediation of cyanide (CN-) and nitrate (NO)-) anions in mine and agricultural waters by various photolytic methods has been reviewed and investigated. Photolytic methods such as direct photolysis, homogenous photolysis, and heterogeneous photocatalysis are briefly described and compared. Results and discussions show that each method has certain advantages and disadvantages. For each method, Eh-pH diagrams prove useful for determining reaction mechanisms. Preliminary results obtained for cyanide oxidation and nitrate reduction show that homogeneous photolysis can be superior due to faster kinetics than the other methods. The photolytic methods were individually, not simultaneously, tested and compared. Differences in concentrations of products were obtained and attributed to differences in photoconversion efficiencies and other inherent characteristics of .the photolytic methods. Various reaction mechanisms are proposed in accordance with the literature as well as measurements obtained from solution analysis using ion selective electrodes and ion chromatography .

Jan 1, 1995

By Fumito Tanaka

The Mitsubishi process is the sole pyrometallurgical process for the continuous production of blister copper from copper concentrates and has been successfully operated around the world. The development of calcium ferrite slag (CaO-FeOx-Cu20), the so-called "C-slag", has enabled continuous converting from matte to blister copper in the commercial scale operations. Commercial interests in the slag led to many papers over the CaO-FeOx slag. However, CU2O- bearing slag has not been studied well due to experimental difficulties. The authors have quantified the thermodynamic properties ofthe CaO-FeOx-Cu2O system. The results have been utilized to analyze various issues related to the converting furnace, such as the magnetite precipitation from the slag or from blister copper and to develop better controlling criteria for the continuous converting operation.

Jan 1, 2003

By M. C. Furerstenau

Adsorption behavior of various surfactants on sulfide minerals is very much affected by the nature of the surface of the mineral. Since sulfides are naturally meta-stable, oxidation occurs when they are exposed to air, especially in aqueous environments. As a result. oxygen assumes a major role in sulfide flotation. Mechanisms of adsorption of various thiol collectors on sulfide minerals have been reviewed. The electrochemical behavior of various sulfide minerals has also been reviewed. Flotation behavior of galena, chalcocite, sphalerite, pyrite, chalcopyrite and pentlandite has been presented together with the. flotation of copper sulfide- nickel sulfide ore.

Jan 1, 1993

By R. H. Crist

Reactive components of algal cell walls include uronic and alginic acids: In addition, many marine species have half ester sulfate groups which function as fixed anions. Associated metals vary with the media, eg., Ca and Mg in fresh water (FV) and Na, Ca, Mg in seawater. . These metals readily exchange with aqueous phase protons or metal cations. A plot of the total amount of metal cations displaced by protons vs .. pH shows one inflection at pH 4 for FV algae and' in addition a second inflection at pH 2, 3 for marine algae. The first inflection is interpreted as. Indicating the cations associated with carboxyl groups ,and the ,second with half ester ?Sulfate groups. The exchange capacities of various aigal ,species vary widely. When FV algae is placed in a Pb2+ solution,- the amount of Pb2"' deposited on the algae is. Equivalent to the. Total Ca2?, Mg2, and H+ displaced? thereby confirming the ion exchange mechanism. Ion exchange equilibrium constants are reported for the displacement of ca2+ from Vaucheria. With Mg2+, sr2+, Cd2+, Pb2+_ and Na+ as well as the reverse reactions. Cd2+ can .be removed partially from algae by precipitating it as CdS or Cd(OH) 2 Pb2+ and Cu2+ are also partially removed as the hydroxides. Rates of reaction for various alkali hydroxides decrease with increasing .unhydrated cation radius. It is concluded that theory is useful in predicting viable applications for algae in pollution abatement.

Jan 1, 1991

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 Hongbo Yang, Tongbo Zhang, Ting Huang, Jingshe Li, Fangfang Song

"Liquid core length is a very important parameter of the process of continuous casting, which directly reflects the cooling status in secondary cooling zone and solidification rate of the slab. In this paper, the billet caster in some steel plant in China was chosen as the prototype of simulating. A numerical simulating model for calculating the liquid core length of continuous casting billet was built by ProCAST software, which was verified reasonable and accurate by pin-shooting technique. Based on the model, the relationships between casting speed, casting temperature and liquid core length of casting billet were found, which was very practically useful for the workers on sit to improve casting billet quality. IntroductionContinuous casting process developed very rapidly because of the high metal yield, energy saving, and low-cost 111• And the quality requirements of continuous casting billet for customers became higher and higher with the fast development of economic121• Internal defect usually is the major quality problem for continuous casting billet[3•61 , which is influenced by the solidification process of casting billet, especially the solidification process of liquid core17•81 • So it is very important to study on the relationship between casting parameters and the liquid core length which means the distance between the crystallizer meniscus and the casting billet solidification end-point. In practical production process, the workers usually control the quality of casting billet according to the liquid core length."

Jan 1, 2013

By Richard A. Leiby

The recycling of lead-acid batteries in the United States has become a challenge as to how to balance ever increasing environmental regulation and cost with efficient operations. East Penn's captive secondary lead smelter has developed into a recycling facility producing lead, polypropylene, sulfuric acid, ammonium bisulfite, and non-hazardous discard slag. The emphasis has been to design a facility to comply with environmental regulations, to eliminate wastes, and to produce products, while at the same time, continuing to supply the company's battery manufacturing raw material needs.

Jan 1, 1993

By R. W. Bartlett

The extensive central Idaho black sand placer deposits are a potential source of rare earth elements, particularly the heavy rare earth elements that are not prevalent in commercial bastnasite deposits. These placers derive from the Idaho batholith. The geology, occurrence, and extent of these deposits are reviewed and the diverse mineral assemblages and complex mineral chemical compositions of these sands are described. Niobium, yttrium and thorium are also present in significant concentrations. The results of prior mining practice, including concentration and separation of the heavy minerals are reviewed. Technical approaches to extraction of rare earths from Idaho black sand concentrates are discussed.

Jan 1, 1992

By M. M. Monte

A method for removing metallic mercury from contaminated tailing, using the flotation process, is described. In order to define some relevant parameters for the mercury flotation system, microflotation and electrophoretic mobility tests were carried out on (pure) metallic mercury in the presence of several surfactants. Based on the results obtained from fundamental studies a series of bench scale flotation experiments with mercury containing tailings from two wetland sites in Brasil were done. The results of microflotation tests with mercury showed that by using cetyl trimethyl ammonium bromide, an increase in mercury flotability is observed in the acid pH range, whereas in the presence of potassium oleate the highest mercury flotability was found in the alkaline pH region. The mercury flotability using potassium amyl xanthate was improved by the addition at sodium dithionate as an activator. The bench scale flotation tests with contaminated tailings from Poconé (brazilian wetland site) showed a recovery of 70% when sodium dithionate was used as activator and potassium amyl xanthate as collector. The resulting coefficient of separation is around 60%. However, the results of the flotation experiments with fine fractions from amalgamation tailings from Peixoto de Azevedo (brazilian wetland site) showed a low mercury recovery (32%).The results from this work suggest that since in the Poconé site tailings, the metallic mercury is not completely associated to the finer particles, the flotation process to recover the metallic mercury seems very promisor.

Jan 1, 1996

By Luben Savov

This paper presents recent research works on the removal of the tramp elements Cu, Sn, Zn and Pb from steel. The evaporation of Cu and Sn in iron-based melts treated at reduced pressure of the gas phase was studied in a vacuum induction melting furnace. The effect of chamber pressure, temperature and melt composition was investigated. Since the main source of contamination of steel with Sn and Zn is the recycling of tinplate and zinc coated steel, respectively, possibilities for the removal of meta1ic coatings in a scrap pre-treatment stage were studied, too. Tin was removed in the temperature range 400-5S0°C by treatment with reactive gases featuring high sulphur potential. Zinc can be removed by evaporation or by a combination of thermal and mechanical treatment. The paper discusses the thermodynamics of Pb in carbon-saturated iron melts, too.

Jan 1, 2001

By W. K. Collins

Engineered Scavenger Compounds (ESCs), developed by the U.S. Bureau of Mines, are a novel class of compounds that can selectively recover a desired element from a solid or molten alloy. Lithium titanate (Li2Ti3O7 or L'20-3T'02) is being used as an ESC to recover lithium (Li) from Aluminum-Lithium (Al-Li) alloys. X-ray diffraction measurements have shown that lithium titanate undergoes a phase change from an orthorhombic structure to a hexagonal structure. This change is due to the incorporation of Li in the matrix of the material and the effect of temperature. Although both are metastable, the hexagonal phase that forms during the scavenging of Li from Al-Li alloys appears to be the more stable phase. Recovering Li from the ESC by electrodeposition does not cause the structure to revert to the orthorhombic phase. Both the orthorhombic and the hexagonal structures of Li2Ti3O7 have similar scavenging capacities for Li. This paper proposes a new mechanism for the phase transformation.

Jan 1, 1993

By Walter E. Dean

Twenty six samples of carbonaceous gold ores and associated rocks from outcrop and mine localities in northcentral Nevada were analyzed for concentrations of major. minor, and trace elements, total sulfur, and organic carbon. Q-mode factor analysis was used to define six distinctive carbonate, organic, and detrital associations of elements, and to group samples based on these associations. The trace metals that have clearly enriched the organic-carbon-rich samples are V, Zn, Ni, Cu, Cr, and Mo, although few of the samples could be considered "metal-rich" when compared to other organic-carbon-rich black shales. Rock-Eval pyrolysis was used to evaluate thermal maturity and hydrocarbon yield of the samples. Unfortunately, most samples were too thermally altered to be suitable for routine organic geochemical characterization of organic matter. The 813C values of organic carbon in rocks from different deposits have a trimodal distribution, but there is no clear distinction between the three groups of deposits that can be related to age, thermal history, or depositional environment.

Jan 1, 1987

By David J. Howard, Christine Broadbridge, David C. Paine

"High pressure vapor/solid reactions offer an opportunity for novel synthesis and processing of thin film materials and structures for electronic, optical, and magnetic applications. In this paper we review the use of two high pressure techniques that operate from 25 to 1000 atm (2.5 to 100 MPa) to fabricate thin film oxide structures from Si1-xGex deposited on Si wafers. High pressure synthesis enables temperature-independent control of reaction rates in the oxidation of this multicomponent semiconductor system and hence offers the opportunity to form thennodynamically metastable Si1-xGex<h from the alloy. The thermodynamics of the Si-Ge-0 system are reviewed and a method is described that utilizes selective chemical reduction (via H2 gas) of Si1-xGcx<h to form Ge precipitates in an SiO2 matrix. IntroductionAlloys of Si1-xGex grown epitaxially on Si substrates by chemical vapor deposition (CYD) and molecular beam epitaxy (MBE) have been used to create high performance microelectronic devices1. These devices show improved performance over conventional Si technology because they exploit the Si/Si 1-xGex band-gap discontinuity and take advantage of higher hole mobilities in the Ge containing alloys. While a range of devices based on heteroepitaxial systems have been demonstrated, the Si1_xGex alloys are of particular interest because they are most closely compatable with standard Si device processing. One disadvantage of Si-based materials systems is that they are not typically useful emitters of light. This is important since the use of light (rather than electrons) for transmitting and processing signals into, out of, and within Si-based microelectronics would represent a major technological advance in microelectronics-based communication and computer technologies. Nevertheless, through the use of innovative processing techniques it may be possible to use the Si1_xGex/Si heteroepitaxial system in integrated microelectronic/light-wave technologies."

Jan 1, 1994

By W. D. Riley

Engineered Scavenger Compounds (ESCs), developed by the U. S. Bureau of Mines I are a novel class of compounds that can selectively recover a desired element from &apos;a solid or molten alloy. Lithium titanate (Li2Tip7 or Li20&apos; 3TiO.) is being used as an ESC to recover lithium (Li) from Aluminum-Lithium (AI-Li) alloys. X-ray diffraction measurements have shown that lithium titanate undergoes a phase change from an orthorhombic structure to a hexagonal structure. This change is due to the incorporation of Li in the matrix of the material and the effect of temperature. Although both of the structures are metastable, the hexagonal phase that forms during the scavenging of Li from AI-Li alloys appears to be the more stable phase. Recovering Li from the ESC by electtodeposition does not cause the structure to revert to the orthorhombic phase. Both the orthorhombic and the hexagonal structures of Li.Til07 have similar scavenging capacities for Li. This paper proposes a new mechanism for the phase transformation.

Jan 1, 1991

By C. O. Bounds

Management of emission control dust from electric? arc furnace (EAF) steelmaking as an RCRA-EPA listed hazardous waste places economic and environmental pressures on the steelmaking industry. Horsehead Resource Development Company, Inc. (HRD) serves the industry by recovering nonferrous metals from the dust in rotary kiln plants in Palmerton, PA and Chicago, IL, and has demonstrated the commercial viability of its patented coal-fired FLAME REACTOR Process. However, because of location and/or regulation, many steelmakers could be more economically served via on-site processing of its dust. Therefore, in 198-7, through a contract with the Gas Research Institute, HRD embarked on a program to develop a gas-fired reactor and test a prototype unit. The development program has successfully proven the environmental, technical and economic performance of the concept. Consistently high zinc, lead and cadmium recovery to an oxide concentrate as well as production of a nonhazardous, delistable slag have routinely been achieved. The gas-fired FLAME REACTOR field experiment results and the economic performance of on-site or smaller regional plants will be highlighted.

Jan 1, 1990

By Joseph Bloch

The hydriding of bulk metals and alloys is a gas-solid reaction in which a hydride product layer is initially nucleated adjacent to the gas-solid interface and continues to grow until a complete transformation of the parent (a) phase into the hydride phase. The combination of measurements of the overall hydriding kinetics of samples having defined shapes and dimensions, together with examinations of partially hydrided samples, enables the presentation of the reaction rate in terms of an appropriate reaction model. A common and important type of topochemical development of the hydride in bulk metals and alloys involves a hydride layer formed on the metallic surface. The continuity of the layer can affect the reaction rate. The rate of hydrogen absorption in a sample, in the presence of a hydride layer, is usually analyzed using a model combining several sequential steps in which the hydrogen is transferred from the gas phase into the reaction site. Coupling the flux equations across the layer under proper steady state conditions, results in a complex rate equation in which the steady state rate of hydrogen absorption (proportional to the hydride layer velocity) is expressed in terms of the pressure, temperature, the rate constants of the sequential steps and the critical concentrations of hydrogen in the hydride. Generally, the rate constants of the individual microscopic processes are comparable in magnitude, so that the overall rate is not controlled by any of the specific sequential steps. However, there are two limit cases related to the first stage, the adsorption, for which the general rate equation is much simpler, namely, the fast and the slow adsorption approximations. Using this limit cases, equations are derived for the steady state hydriding rate of a given system. These equations provide means to anticipate the pressure dependence of the steady state absorption rate under low pressures, close to Peq and under very high pressures. At the low pressure regime both the fast and slow absorption cases yield linear pressure dependence. For the very high pressure range, it is found that the rate become independent of the applied pressure. The rate is given then by a combination of the individual rate constants of the system and the critical hydrogen concentrations. The model is shown to apply in several real cases, such as ZrCo, LaNi5 and titanium.

Jan 1, 2002

By C. A. Young, J. D. Miller

Adsorption isotherms previously determined by in-situ Fourier transform infrared/internal reflection spectroscopy (FT-IR/IRS) for oleate adsorption at calcite and fluorite surfaces near pH 9 and at various temperatures are compared. Results indicate that, at both mineral surfaces, chemisorption occurs at equilibrium concentrations below approximately l x l0-5 M oleate while calcium dioleate surface precipitation occurs at higher equilibrium oleate concentrations. The extent of chemisorption at the calcite surface is 3 to 5 times less than that at the fluorite surface while the extent of calcium dioleate surface precipitation on calcite is nearly a magnitude larger than that on fluorite. However, for both minerals, surface precipitation decreases with increasing chemisorption. Contact angle measurements and flotation recoveries show the hydrophobicity of fluorite to be greater than that of calcite at each of the temperatures and oleate concentrations studied. Significant differences are noted only in the chemisorption region. Unlike calcite, the hydrophobicity of fluorite was sensitive to the presence of oxygen in the system. Multichannel Laser Raman Spectroscopy (MLRS) showed this behavior was caused by the double-bond reactivity of adjacent chemisorbed oleate molecules and subsequent formation of an epoxide/polyether complex at the fluorite surface. Such a reaction product could not be detected at the calcite surface. These differences in adsorption density, hydrophobicity, and polymerization behavior are discussed in terms of the intrinsic surface properties of the minerals.

Jan 1, 1999

By Batric Pesic

A hydrometallurgical process for recovery of Zn and Mn from Bunker Hill Water Treatment Plant sludge was developed. The process is unique because it treats an unusual combination of metals, Zn and Mn. Another non-standard feature of the process is that leaching takes place with ~S04 in the presence of a reductant (SO2). Zn and Mn are recovered simultaneously by electrowinning, Zn on a cathode and Mn on an anode, as MnO2 The major purpose of the process is to detoxify the sludge by removing toxic heavy metals. The recovered metal values could be marketed to offset the overall costs of water and sludge processing. This work is presented in two separate parts, 1. Leaching and Solution Purification, and II. Electrowinning. This paper covers only the first part of the hydrometallurgical process: Leaching and Solution Purification. Initially, the paper briefly discusses the history of the pollution problem at the Bunker Hill Superfund Site, the origin of heavy metals in the mine waters, and the development and use of the water treatment plant. The leaching of sludge was examined as a function of the following parameters: constant vs. initial pH, initial vs. delayed addition of SO2, temperature, and pulp density. It was found that leaching with H2SO4 at pH 2.0 for 15 minutes (at 60°C), followed by S02 addition for another 15 minutes, could completely dissolve Zn and Mn. Solution purifIcation was done in three stages. In the first stage iron was removed by adjustment of pH (to pH 5.0) and oxidation offerrous to ferric iron (with H2O2). In the second stage, Cu and Cd were removed by Zn dust cementation. Finally, Co and Ni were precipitated with the organic reagents 1-2 nitroso-naphthol and nitroso, respectively. Electrowinning of Zn and Mn is discussed separately in Part II of this paper.

Jan 1, 1996