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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 John L. H. Patterson

Handheld XRF has become the favorite way of measuring the content and identity of alloys in the field. This is because of the very portable nature of the instrumentation and its simple operation. However, these analyzers have been unable to determine the concentration of the light elements like Mg and Si due to the very low energy of the x-rays produced by these elements. In the past accessories such as vacuum and He flush have given some analyzers the ability to determine these light elements with modest detection limits. The introduction of the Silicon Drift Detector (SDD) into this class of instrumentation has added a new level of analysis capability to portable XRF instrumentation. X-ray fluorescence is achieved by exciting a sample with a beam of x-rays, which in recent portable equipment are generated by a small tube. This results in the emission of characteristic x-rays from the sample under test. By measuring the energy of each x-ray it is possible to determine what element generated it. By counting the number of x-rays at each energy it is possible to determine the concentration of each element. The detection limit for each element is dependent upon the number of x-rays which reach the detector. As the number of x-rays increases the detection limit will improve. One of the major factors in an x-ray reaching the detector is the energy of the x-ray. As the energy of an x-ray increases the probability of that x-ray reaching the detector increases. The energy of an x-ray is inversely proportional to the atomic number (AN) of the element generating the x-ray. For example, an iron x-ray (AN=26) is 6.40 keV while an aluminum x-ray (AN=13) is 1.49 keV. As the energy decreases, the detection of the x-ray becomes less and less probable because the x-ray may be absorbed by the windows which are part of the instrument and detector or the air in the path between the sample and detector. In SiPIN based portable XRF analyzers, the lowest element which is detected with acceptable detection limits is normally considered to be Ti (AN=22). The detection limits for 60 second measurements on typical SiPIN XRF analyzer are given in Table I. Thus, portable analyzers have not been useful for measurement of aluminum and titanium alloys as major components of these alloys are Mg (AN=12), Al (AN=13) and Si (AN=14).

Jan 1, 2009

By W. K. Choi

Stainless steel exposed to wet environments at ambient temperature is subject to the formation of a surface biofilm. Depending upon the prevailing environmental conditions (dissolved oxygen, pH, Eh, concentration of cationic/anionic species), the biofilm may stimulate corrosion through formation of differential aeration zones and concentration cells. Corrosion significantly impacts the United States economy, since on a yearly basis, corrosion induced losses are estimated to be over $200 billion. A large portion of this corrosion is imputable to bacterial activity, and basic information is needed for a better understanding and control of the biocorrosion phenomenon. The present study has investigated the influence of Thiobacillus ferrooxidans in the corrosion of American Iron and Steel Institute (AISI) 304, 316 and 416 stainless steel samples. The formation of biofilm and microstructural changes on the surface of stainless steel samples and their weldments were assessed by microscopic examination, and the changes in the mechanical properties by stress-strain measurements. The significance of the results will be discussed.

Jan 1, 1993

By Edward P. Hagarty

The Hazardous and Solid Waste Amendments (HSWA) of 1984 added Subtitle I to the Resource Conservation and Recovery Act (RCRA), authorizing the Environmental Protection Agency (EPA) to develop and implement a new regulatory program for Underground Storage Tanks (USTs) containing petroleum and other regulated substances. Technical standards required for release detection, prevention, and correction as necessary to protect human health and the environment were promulgated as described in 53 Federal Register 37082 (September 23, 1988). Virginia State Regulations (VR 680- 13-02) and U.S. Army Regulations require that a Corrective Action Plan and a Site Clearance Report be prepared to explain the details of remediation of any contaminated media. Construction of new buildings is proposed in two different areas at Fort Myer in Arlington, Virginia, where USTs containing gasoline, diesel and heating oil were located. Tightness testing performed on these USTs in September 1991 indicated that some of the tanks were leaking. Many of the tanks were removed for permanent closure. Initial Abatement (excavation of contaminated soil) was &ed out immediately. A detailed Site Characterization Study which included Hydropunch", field screening using immunoassay, and pilot test - dual phase (water and soil gas) extraction was conducted. Environmental media were analyzed for volatiles, semi-volatiles and metals. A detailed risk analysis (RA) was performed to determine risk-based clean up levels for benzene, toluene, ethylbenzene, xylenes (BTEX); polycyclic aromatic hydrocarbons (PAHs); and methyl-tertiary butyl ether (MTBE). The RA also discussed the presence of lead in the soil. Before constructing any buildings in these contaminated areas, remediation must be conducted in accordance with the State, Federal and other applicable regulations. The remedial alternatives evaluated included Vapor Enhanced Groundwater Extraction, Soil Vacuum Extraction, Soil Washing, Soil Steaming, Active and Passive Ventilation SolidificationlStabilization, Vapor Barrier Construction, and Excavation with Off-site Disposal. This paper discusses: (a) delineation of soil contamination @) risk analysis (c) evaluation of remedial alternatives and selection of the most appropriate technology and (d) consideration of various regulatory issues.

Jan 1, 1994

By M. L. Apel

A conceptual approach to the bioremediation of uranium mill tailings (UMT) is presented., This approach focuses on, biosorption to remediate the. effluent solution and bioleaching remediate the. solid fraction. Comparative biosorption studies were performed with synthetic single metal solutions using a commercially available biopolymer. The maximum rate of metal sorption by calcium alginate was found to be 5.43, 6,39, 6.48, and 9.74 mg dm-3 min-1 for U022*, Ba2+, Cd2+ and Zn2+, respectively. Activation energy (AEa) for barium uptake by calcium alginate beads was determined to be 11.5 kJ, indicating a diffusion controlled reaction mechanism. Thermodynamic values (AG+ AH+ and ASt) of the metal-alginate activated complex, as reported in the literature, were found to be in agreement with those calculated from this research. Results show that this biopolymer can be effectively applied in the removal of select metals prevalent in uranium mill tailing effluents and associated waste streams.

Jan 1, 1991

By F. Robert Hubbard

IMCO Recycling Inc. has developed a new, patented technology for the production of fertilizer, K-SOIL?, as a by-product of its aluminum recycling operations. This new technology can substitute for conventional technology which now results in a saltcake residue that is placed in 'landfills. Four years of research and development work by IMCO culminated in a U. S. patent issued April 5, 1994. As part of the technology development effort, IMCO engaged the services of a nationally renowned research organization and a prominent university. These two organizations have conducted in-depth agronomy studies In the laboratory, greenhouse, and the field. Results have shown K-SOIL? to be performance equivalent, on a nutrient content basis, to conventional potash fertilizer. The first field applications on commercial farms were made in the spring of 1994. K-SOIL? is a potassium-bearIng, granular solid which may find use in fertilizer blends, direct application, and other forms of fertilizer products. The overall benefit of this new technology is to create a useful by-product rather than generate a useless residue and, thereby, reduce or eliminate the amount of salt cake now placed in landfills. As such, It is a significant, step toward IMCO's ultimate goal of complete recycle.

Jan 1, 1995

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 Agnes Y. Lee

he U.S. Bureau of Mines developed a method to treat lead-contaminated soil and ebonite battery casing wastes to produce a nonhazardous material. The cleanup procedure involves wet screening to separate a minus 18-mesh soil fraction; removal of metal1ic lead, rocks, wood, etc. ; carbonation to change lead sulfate to acid-soluble lead carbonate; size reduction; acid leaching; and rinsing. The casing wastes undergo size reduction and washing to remove the lead sulfate sludge before carbonation. Similarly, the minus 18-mesh soil is carbonated, then acid leached and rinsed. In leaching, fluosilicic acid (H SiF,) and hydrogen peroxide (H20,) are used to dissolve lead compounds. An electrowinning method is employed to strip lead from the lead-rich leachate. The acid content in the leachate is replenished with fresh H,SiF, acid prior to recycling. Treated casing wastes and soils pass the Toxicity Characteristic Leaching Procedure (TCLP) test and can be reclassified as nonhazardous materia1s. Based on this process, a conceptual pilot plant has been designed which will be demonstrated on wastes from two Superfund sites.

Jan 1, 1993

By M. K. Mohan

Lead recovery from process solutions contributes not only to the conservation of resources but also clean environment. Zeolites are natural aluminosilicates, which finds applications as catalysts and in wastewater treatment. In the present investigation, studies were taken up on the processing of Pb from process solutions by zeolites. Effects of pH of the solution, time and type of zeolite viz. chabazite, mordenite, erionite and clinoptilolite on the removal of Pb from solutions was investigated. Rate of sorption was found to depend on the pH of the solution and about 99 pct. recovery was observed at pH 6. Optimal conditions were established for the maximum recovery of lead from process solutions. Possible sorption mechanisms were proposed. The calculated adsorption constants calculated from Langmuir and Freundlich equations showed that the adsorption of lead on chabazite was strong.

Jan 1, 1999

By Carlos M. Fontes Vieira, Ruben J. Sanchez Rodriguez, Carlos E. Gomes Ribeiro

"The worldwide demand for ornamental stones in building construction is motivating the use of their wastes, generated during fabrication, to produce compound stones. This work has as its objective to investigate the production of an ornamental compound marble (OCM) under vacuum and compression processing of a polyester matrix composite with addition of marble waste as load and as filler. Square OCM composite plates were subjected to compression and flexural mechanical tests. Samples were analyzed to obtain the density and water absorption. The OCM composites presented properties within the expected range of an artificial stone.IntroductionMarble is a limestone, composed mainly of calcite, more or less crystallized by metamorphism that ranges from granular to compact in texture. It has a density 2.7 g/cm3 and its porosity is approximately 0.4%. The UNI 8458 standard defined marble as: ""every crystalline rock constituted mainly by minerals with a Mohs hardness equal to 3-4"". In marble production around70 - 75% of whole extract material is lost in byproducts generation [1,2].In function of large volume of residues generated, the ornamental stones industry has attracted ever more the attention of environmentalists [3].Actually the marble can be pulverized to obtain calcium carbonate for industrial applications. It is also possible to obtain a thinner powder to produce concretes [l]. Some authors study the use of stone residues in concrete mortars and ceramic bricks, getting better properties to these materials [3,4].The marble residues can be also used in engineered stones, or ''agglomerated"" stones, production. The most common engineered stones in the market consist, like a polymer concretes, in polymer matrix composites incorporating petreous components. In the formulation of the engineered stones, the particulate or granular petreous components are the result of fragmentation or trituration processes to which natural stones were submitted to [ 5]."

Jan 1, 2014

By F. F. Aplan, G. Simkovich

"A review is given of the effects of solid state point imperfections upon a number of mineral benefication processes and a metal extraction process. It has been found in numerous flotation studies that small amounts of aliovalent impurities (dopants) in binary compounds may show major effects upon flotation behavior. Both semiconducting and ionic conducting compounds are affected. These effects are also seen in hydrometallurgical studies as well as in electrostatic operations. Additionally, de-copperization of lead melts appears to be strongly influenced by similar defects. It is hypothesized that the effects observed in these studies are present in actual operations and should be considered in designing processes. A few speculations concerning future efforts are advanced. IntroductionImperfections [point (e.g., vacancies, interstials, quasi-free electrons, electron holes, impurity ions), line (e.g., dislocations), two dimensional (e.g., grain boundaries) and three dimensional (e.g., 2nd phases) defects] are generally present in solid materials and these imperfections may, and often do, have important effects upon a variety of properties and processes. In general, one may, in most cases, attain elimination of three dimensional defects by a separation process of one type or another (e.g., gravity, electrostatic, magnetic, flotation, hydrometallurgical etc.,). Thus, this type of defect has rarely been investigated in a systematic fashion. Two dimensional defects are always present in non-single crystal materials but have also escaped systematic studies in processes primarily because the control of such defects is not easily attained. Line defects are non-equilibrium entities which are present in ill-defined quantities so that they present a variable that cannot be easily controlled although through careful systematic experiments one can attain some reproducible relations pertaining to this type of defect.Contrary to the lack of studies concerned with the effects of 1, 2 and 3 dimensional types of defects there has been some activity concerned with point defects and their effects upon a number of mineral/metallurgical processes, especially flotation processes. Thus, this article will present a review primarily of point defects in relation to their effects upon flotation although other processes and defects will also be mentioned."

Jan 1, 1988

By Abbas H. Mirza

Arsenic and selenium are found in low quantities together with other metals in several nonferrous metallurgical process streams such as scrubber blowdown solution, acid plant wastewater, gas cleaning plant water, etc. Normally, the other metals in these streams are present as cations and can be precipitated by conventional lime treatment and sulfide polishing. However, arsenic and selenium are invariably present as anions, AsO33-and AsO43 in the case of arsenic and SeO32 and SeO42 for selenium. Conventional lime treatment removes most of the arsenic, but it does not remove selenium. The present paper reviews the processes and technologies developed to date on the removal of arsenic and selenium from metallurgical process streams.

Jan 1, 1996

By M. H. Lin, S. Kou

"Czochralski pulling has been a very widely used process for growing single crystals for electronic and optical applications. Dopant segregation can significantly degrade the quality and yield of single crystals. We have used the floating-crucible technique for segregation control in Czochralski pulling, our floating crucibles being unique in that the melt passageway is very long. As such, dopant back diffusion is suppressed, even when the cross-section of the melt passageway has to be relatively large to help the melt go through or when the pulling rate is very low. Single crystals of model materials K-doped NaN03 and Pb-doped Sn have been grown with very uniform dopant concentrations. IntroductionSingle crystals of electronic and optical materials are often doped with a small amount of impurities to develop required physical properties, e.g., P and B in Si for n-type and p-type semiconductors, respectively, and Nd in YAG lasers. Dopant segregation can result in nonuniform physical properties, thus degrading the quality and yield of the resultant crystals.Figure 1 is an illustration of the conventional Czochralski process for crystal growth. Several techniques have been developed to control dopant segregation in Czochralski pulling, including the push-pull technique (1,2), the drop-pull technique (3-7) and the floating-crucible technique (8-13). The first two techniques require precise sensing devices and feedback control systems to keep the feeding rate equal to the pulling rate. The last technique is simple since the feeding rate is automatically equal to the pulling rate."

Jan 1, 1994

By S. Abe

An extensive study has been carried out to determine the true cause of floating slimes precipitation which sometimes occurs and badly affects the quality of copper cathodes. Soluhilities of floating slime compounds systematically measured for the ternary system As-Sb-Ri added solely or in combination with conventional copper electrolyte (63°C) and bench scale electrorefining experiments done by varying electrolyte composition, have shown conclusively that the level of Sb(V) ions plays a substantial role in the precipitation mechanism. It was, therefore, speculated that controlling the level of the less soluble S b ( V ) ions below a certain critical level should result in a complete elimination of the undesirable precipitation. This can be easily achieved, for instance, by the addition of a reducing agent such as SO2 gas and the simultaneous employment of a certain type of cheating agent that effectively removes excessive Sb and Bi from the contaminated electrolyte. Long-term pilot testing conducted in line with the above speculation has confirmed the SO2/chelating resin scheme to be industrially very attractive and feasible.

Jan 1, 1987

By Thomas E. Weyand

Prior to 1975, lead-based paints were commonly used in protecting steel structures. Because of the toxic effects of lead on human health and the environment, their use has been significantly reduced. However, problems with these paints persist when they are removed during normal maintenance by pneumatic blasting with mineral abrasives. Technologies are developed to contain the spent abrasive and paint during blasting operations. This paper reports on A study to identify beneficial reuses for the spent blasting material. Nine samples were gathered from different projects within Pennsylvania. The samples were thoroughly characterized with regard to composition, morphology, and EP and TCLP leach test performance. Potential reuse applications will be reviewed with regard to technical adequacy, economics, and environmental constraints.

Jan 1, 1992

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 Yasushi Sawada

An experimental investigation was carried out to study the rates of reduction of iron oxides dissolved in liquid Ca0-SO2-A203 slags by Fe-C droplets at temperatures ranging from 1325 OC to 1550 OC. The %FeO in the slag was varied from 5.5 to 18. Flash X-ray images were employed to observe the behavior of Fe-C droplets in the slags during the reactions and for determining the slag-gas-metal interfacial area. Effect of P205 in the slag and sulfur in the droplet was also investigated. The reduction rates were determined by measuring the volume of CO evolved as a function of time and the estimated slag-gas- metal interfacial area. The reduction rates have increased with increasing %FeO in the slag and the slag temperature. The experimentally established relationship between the reduction rates and FeO (wt%) in slag is given by

Jan 1, 1992

By Dirk Verhulst, V. I. Lakshmanan

Why Chloride Hydrometallurgy?The most available, cheapest and best known reagent for treating ores and other raw materials for the metallurgical industry is sulfuric acid. Hydrochloric acid is second in line. What often happens is that a process is developed on the basis of sulfuric acid, and that at some point the question arises: wouldn't hydrochloric acid do this better?Considering hydrochloric acid immediately opens a very interesting field of research. To summarize a few comments from another paper presented at this symposium [1]: chlorides are far more soluble than sulfates (with a few interesting exceptions); the hydrogen ion activity is greater in chloride than in comparable sulfate solutions; higher oxidative conditions are possible; regeneration is more straightforward; more diversity is possible and better conditions for the separation of species can be found for solvent extraction and ion exchange; sulfur in the ore can be separated as elemental S; higher metal concentrations in solution and more flexibility in the chosen oxidation state means significantly lower energy costs.Also, the volatility of many chlorides at higher temperature allows further separation without the need to go to a different system. Chlorides also form molten salts with a low melting point, providing another means of separation and purification in the same chloride medium.

Jan 1, 2011

By Kathryn C. Sole

A novel solvent-extraction process for the refining of gold was recently commercialised, with the commissioning in May 1997 of a 24 t a-' refinery at Harmony Gold Mine in Virginia, South Africa. The MinataurTM Process (Mintek Alternative Technology for Au Refining) uses solvent-extraction technology to produce gold of 99.99% purity from the cathode sludge arising from a conventional carbon-in-pulp / electrowinning circuit. Implementation of this process introduces significant cost benefits compared with the conventional dore smelting / toll-refining route previously followed. This paper outlines the process, presents selected operating results obtained during the first few months of operation, and provides some details of the associated techno-economic advantages.

Jan 1, 1998

By Yotamu Stephen Rainford Hara

"The aim of our work is to investigate a low energy and clean route for the recovery of copper and cobalt from complex sulphide mineral concentrates. The mineral concentrates were roasted in air, in the presence of CaO (MS + CaO + 202 =MO+ CaS04) at temperatures below 973K. The roasted products containing CuO, CoO and Fe203 were carbothermically reduced at 1073K within an hour to preferentially reduce copper and cobalt. The kinetics of reactions were studied using the thermogravimetric technique and by characterisation ofreaction products using the XRDSEM-EDX techniques. The effects of MS:CaO ratio, roasting temperatures and physical nature of the mineral concentrates were analysed. The method for capturing S02 by forming CaS04 was analysed for reuse in the process. The energy balance for the above process is compared with that of conventional continuous smelting/converting process.1.0 IntroductionCopper sulphide mineral concentrates from Zambia contains substantial amouot of cobalt. The cobalt metal content in the concentrates ranges between 0.7 and 2 % weight, which corresponds to 3 and 9 % weight copper, based on the spot price of copper ($7 386/tone) and cobalt ($31 000/tone). Although the traditional approach using a combination of roasting-leaching-electrowining steps can be applied to recover copper and cobalt from sulphide mineral concentrates [1-4], there are two major draw backs of the traditional process: (i) the S02 emitted during roasting is too lean for economical conversion for sulphuric acid manufacture, which causes serious environmental pollution. (ii) silver and gold which are normally present in the sulphide concentrates are lost out [5] because they are not leachable by H2S04 or HCl which are the common leachants. The above two problems have been overcome by adopting flash smelting in which a rich S02 gas above 20% is produced [1, 5] and successfully converted into sulphuric acid. The precious metals tend to partition to blister copper and recovered during refming. However, nearly all cobalt is lost into the slag phase uoder oxidising condition which prevails during flash smelting. It is important to note that the cobalt content in the slag can be up to 2.6 % weight [6]. The recovery of cobalt from the slag is a process which requires huge amouot of energy since the slag is smelted above 1873K [6]. With a view of minimising the amouot of energy and S02 emission during metal recovery, our investigation involves roasting the sulphide concentrates in the presence of lime and reducing the roasted samples with carbon."

Jan 1, 2013