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By A. Aitio

Sustainable development is one of the central themes of the work of the World Health Organization; chemical safety is one of its important components. For more than 25 years, WHO has had specialized units for assisting member countries in dealing with their problems in chemical safety. For one of the units involved, International Programme on Chemical Safety, a reorientation is in progress to make best use of existing resources, and to prioritise the work to optimally correspond to the needs of the member countries. The risk assessment work of IPCS, and specifically, the work on chromium and chromium compounds, are discussed.

Jan 1, 2004

By C. B. Alcock

The control of high temperature processes requires the ability to measure significant variables during operations. With increasing automatic computerized control there is need for sensors which can provide on-line chemical analyses of all phases present in a reactor without the necessity to withdraw samples from the high temperature reaction zone. Probes using electrochemical cells and conductivity measuring devices have provided the answers to some of these problems, notably the measurement of oxygen in liquid metals, and similar potential systems based on the same fundamental principles for the analysis of non-metallic and metallic elements appear feasible. In this discussion, the state-of-the-art in chemical sensors will be discussed in terms of the potential materials of construction, and, in some cases, the limitations of upper temperature at which some promising systems can, at present, be applied. It is concluded that a new phase of basic research could improve the outlook substantially by providing solutions for some problems in chemical sensors which are now well-defined.

Jan 1, 1990

By Omar A. Muhtadi, David A. Milligan

7.1 INTRODUCTION The circulating fluid (generally an aqueous cyanide solution) is the major active component of heap leaching. This solution extracts precious metal from the heap and is then processed to recover the precious metal. The solution continuously recycles through the heap to recover more precious metal. With each cycle through the heap, water and chemicals are lost. Make-up water and chemicals must be added to balance losses from evaporation, seepage, entrainment, and chemical reaction in the heap, as well as any other processing losses. Adding more water than needed can result in a build-up of water as inventory in the various ponds and can eventually require that water be discharged from the operation. This is an extremely undesirable condition, and can often be very expensive in both investment in water treating facilities and operating costs. Most heap leach facilities operate under a zero discharge permit; thus, a situation requiring water discharge can result in permit violation. Chemical solution control must be managed to maintain the optimum pH, dissolved oxygen content, and cyanide content, while preventing "scaling". Calcium-based precipitation is a common scaling problem in mill reclaim waters. A buildup of these deposits can result in severe reduction of water flow, loss of pump efficiency and eventual interruption in metal production. In addition, problems of plugged sprinkler heads, blinded leach pads and fouled carbon (in carbon recovery systems) can be and often are experienced when scale control is not maintained. The remainder of this chapter discusses chemical solution control and scaling prediction/prevention in the context of a "closed" system. Sizing of ponds to accommodate precipitation and runoff, collection systems, and other similar design considerations are not discussed here. These topics are deferred to later chapters, e.g. Chapter 10 considers design of collection systems while Chapter 12 discusses pond sizing. 7.2 CHEMICAL CONTROL Chemical composition of the circulating solution must be controlled by the operator if the heap leaching process is to be successful. The primary or essential chemical control parameters in any heap leaching operation are:

Jan 1, 1988

By May P. M

The role of chemical speciation in alkaline cyanide solutions is discussed by reference to recent experimental data from the authors' laboratories. It is shown that serious gaps exist in our present knowledge of the thermodynamics of cyanide complexes in solution. Nevertheless, using the available data and the JESS suite of computer programs it has been possible to develop a simplified chemical speciation model for alkaline cyanide solutions under conditions relevant to the gold extraction process. Some possible implications of the model for plant operations are Discussed.

Jan 1, 1991

By David C. Sanders, Rodney H. Sergent, Victor C. Storhok, Batric Pesic

In the past, considerable work has been done on the applica­bility of bromine chemistry in the extractive metallurgy of gold. While the research in this area spanned from the understanding of fundamental dissolution chemistry to the demonstration on a pilot plant scale, no work was done on the fate of discarded leach residues with respect to the stability of accompanied heavy met­als. Because the leach residues were the discharge products of halide/halogen systems, the general perception was that the con­tained heavy metals would be more susceptible to dissolution than in typical sulfate systems, thus causing increased environ­mental problems. A long-term study was performed to obtain the information on the stability of heavy metals contained in the leaching residues after bromination. The study involved the leach residues of three different ores, as well the precipitates prepared from the synthetic solutions (not presented here). The conclusion of this study is that the stability of solid residues produced by bromination leaching was same as the sta­bility of leach residues produced by leaching in the sulfate sys­tems. Also, contrary to the past expectations, the presence of bromide ions in the test solutions (up to 1 g/L NaBr) did not enhance the solubility of heavy metals (Cu, Zn, Pb, As) beyond the solubilities found in the sulfate systems.

Jan 1, 1998

By Z. Duan

A novel concept involving the deployment of chemical stabilization has the potential to eliminate the need of slurry impoundments and significantly reduce the release of trace elements from the high surface area fine coal waste. The process involves mixing the fine waste generated from the underflow of a thickener operation with chemical stabilization agents to tie up the water and to create a solid waste material that can be discharged directly. Portland cement, sodium silicate, F type flyash, C type flyash and hydraulic lime were evaluated as stabilizing agents. A detailed experimental study has been conducted to identify the conditions that provide the maximum compressive strength within a short curing time. Results to date show the ability to achieve compressive strengths adequate for equipment to maneuver on using a Portland cement concentration of around 10% by weight. Quick-setting concrete was not found to enhance stabilization time and compressive strength.

Jan 1, 2012

By Pritii Tam Wai Yin, Tony Leong, Neetu Bansal, James Vaughan, Amiel Boullemant

Mercury is a toxic element that is associated with many industrial activities including the Bayer process. Mercury is known to enter the Bayer process with the bauxite feed material and has the potential to accumulate as the process solution is recycled. This paper explores the speciation of mercury in Bayer process streams. The process parameters considered are the oxidising-reducing potential, basicity and temperature. The results of a refinery circuit survey are presented and compared with the thermodynamic predictions. Electrochemical measurements on relevant synthetic systems are also included.

Jan 1, 2014

By C. A. Anderson, C. A. Young, H-H. Huang, L. G. Twidwell

An equilibrium calculational computer program (STABCAL) can be used for titration simulation. The program can handle various forms of titrants: solid, aqueous, gaseous or another solution, and various type of reactions: reductive, oxidative and adsorption. Background chemistry, mathematical considerations, and program development will be illustrated. Also, simple titration applications such as how to determine the acidity of aqueous solutions and alkaline sulfide leaching of gold are presented. Processing of an acid mine water from the Berkeley Pit in Butte, Montana has been used for illustration purposes. The treatment studies included: cementation, sulfidization, and neutralization. The calculational results for the neutralization treatment using various alkaline reagents are compared to actual experimental data and potentially appropriate processes are discussed. Computational

Jan 1, 2005

By G. H. BUCHANAN

ALTHOUGH the nomenclature of the chemical tools of flotation is probably familiar to you, it will do no harm to review it; . In order to make the terms more real I have employed an illustration which likens flotation to an old-fashioned balloon ascension, such as we witnessed in boyhood at the county fair. The mineral to be floated is the aeronaut, conspicuous in his gilt-spangled tights, who is to be separated from you and me and the other small boys who are standing about, said boys being the g-a-n-g-u-e, or g-a-n-g, as we would have spelled it. The oil film surrounding the bubble is the counterpart of the silken fabric of the balloon, and bubble and balloon will rise for. the same reason, namely. that the fluid outside it is heavier than the fluid within. In flotation reagent nomenclature the material of which the bubble is made is called the "frother.",

Jan 1, 1930

By Carl-Henrik Knudsen, Rolf Tore Arnesen, Eigil R. Iversen

Recovery of iron and copper from acid mine drainage was studied in pilot scale at a continuous treatment plant at the mine site of the King's mine in Roeros, Norway. The average load on the plant was 1 m3/h. The process tested in this project is a three-step process consisting of: 1) Fe(OH)3 precipitation at pH 3.5, dewatering of iron sludge and transport to ferric chloride plant; 2) after filtration precipitation of residual metals at pH 9, concentration of metal sludge by flotation; 3) extraction of metals from the sludge with sulphuric acid followed by recovery of copper by electrolysis. The copper could be used for local production of different crafts, but this condition needs a further evaluation. The process economy at a full scale plant is evaluated.

Jan 1, 2000

By H. H. Power, Charles R. Houssiere

THE development of effective and dependable methods for drilling through the so-called "heaving-shale" horizons, particularly in the Gulf Coast area, is believed to comprise a major contribution to drilling technology, and to the task of finding and developing our undiscovered oil pools. Many mechanical remedies have been proposed and are in use in troublesome areas for combating heaving shale. However, in conducting a research program it was concluded that the physical and chemical properties of shales should be investigated, and the effect of added chemicals on such properties determined. As a preliminary step, the effect of chemicals on bentonitic suspensions was determined in accordance with recent contributions in the field of ceramics. The most plausible theoretical explanations for the behavior of the clay minerals involved are offered in the paper that follows. It is hoped that subsequent investigation of actual shale from troublesome wells will be aided by the initial work done on bentonitic suspensions of known composition. INTRODUCTION Formations variously designated as "heaving shale," "sloughing shale" and "caving shale" impede and may even preclude drilling of oil wells, particularly in certain parts of the Gulf Coast. In a previous paper1 it has been stated that the development of effective and dependable methods for drilling through these troublesome beds is believed to comprise a major contribution to drilling technology, and to the task of finding and developing our undiscovered oil pools. Since the attack on the heaving-shale problem by mechanical means was principally a matter of field investigation, it was concluded that a research program should be concerned with the physical and chemical properties of heaving shales, and the effect of added chemicals on such properties. It was realized that a study of shales required an advanced knowledge of the behavior of the individual clay minerals. A thorough review of the literature led the authors to the conclusion that very recent contributions2.3 in the field of ceramics furnished the most plausible theoretical explanations for the behavior of clay minerals. Accordingly, these fundamental ideas will be used in an attempt to explain the behavior of more complex systems whose composition and replaceable ions are known. In order to obtain comparable results it was deemed important to select an easily procurable clay of uniform characteristics. Accordingly, Wyoming bentonite, which is marketed under the name of "Volclay,"* was used for the preliminary investigations. The chemical analysis reported by the distribution is given as follows:

Jan 1, 1941

By P. Nicholls

PATENT records show that the attempt to improve the burning of fuel by mixture or pretreatment with chemicals dates back to the early years of the last century. By 1845 English and French patents had included the specific beneficiations of elimination or reduction of smoke, soot and clinker; reduction of the ashes; elimination of sulphur fumes; increase of the rate of burning; increase of the time a given charge of fuel would last; and, in most patents, a saving of fuel. The earlier patents specified additions up to 80 lb. or more per ton of fuel, but after 1860 the quantity was seldom more than 4 lb. There is no record of the extent to which these patents were commercialized, but after 1874 many American patents were assigned to companies specializing in treatment of coal, so it is probable that the products were marketed on a considerable scale at least as early as that date. From 1900 on, many proprietary products were marketed under the general name of "fuel savers," the principal sales being in small packages for the use of householders; savings of from 10 to 40 per cent of the coal were promised. Starting with 1927, the use of proprietary or other mixtures of chemicals was extended to power plants and to treatment of coals at the mines, the claims of saving of fuel being subordinated to those of general improvement and, in particular, to reduction of clinkering. Such expectations are attractive and a number of companies experi-mented with or adopted the practice. There were reports of improved operation, but, apparently, few were confident enough that these improvements were due to the salts to publish the results of tests or their records of operation. There are no data on the yearly tonnage of coal treated but indirect reports suggest that it has been relatively large. Since its establishment in 1910, the U. S. Bureau of Mines has con-tinually received inquiries about these products. At the request of. other governmental departments it made tests in 1910, 1916 and 1930, using certain proprietary products applied according to the instructions of the vendors; these tests were made with eastern coals in domestic and

Jan 1, 1937

Alkaline leaching with sodium carbonate solution adjusted to pH 9·5 to 10·0 preferentially dissolves thorium from a mixture of rare earth and thorium hydroxides. Rare earth sodium carbonates form in the alkaline leaching stage.These are converted to rare earth oxides for use as optical and ophthalmic polishing agents. Quadrivalent cerium is extracted under similar alkaline leaching conditions.INTRODUCTIONAustralia has made significant contributions to mineral chemistry and mineral dressing. As often happens with an industrially immature country, research investigations often outstrip the ability or desire of commerce to exploit them. It is wrong to think exclusively in terms of export of raw materials. Imagination assists in developing world trends. The chemical utilization of mineral sands has interested a group of investigators, chiefly at the Commonwealth Scientific and Industrial Research Organization (C.S.I.R.O.) and, more recently, in the mining industry itself. From an international point of view the highlight of this work was Newnham's (1960) process for the separation of hafnium from zirconium. Earlier work at C.S.I.R.O. investigated the chlorination of rutile, zircon, and monazite. Assuming that titanium tetrachloride would be available in large quantities in the post war years, extensive work was done by Kraitzer, McTaggart, and Winter (1948) on organic compounds of titanium. This work led to the development of heat resistant paints, plastic compositions, and improved organic protective coatings that predated overseas work by up to seven years. (Post, Shiihara and Schwartz, 1961; Anon, 1955). Contributions were made to the production of refractory hard metals (Kraitzer, 1949; Kraitzer and Newnham, 1956). Pilkington and Wylie (1947) and Urie (1947) investigated the production of rare earths from monazite by an acid process.

Jan 1, 1963

By Cyrus W. Field

Chemical, mineralogical, and petrographic data have been obtained for suites of plutonic rock samples from the Guichon Creek Batholith of British Columbia and the Mineral-Iron Mountain-Sturgill Peak- Cuddy Mountain-Peck Mountain areas of western Idaho. Intrusions at these two geographically separate localities represent composite plutons ranging from early gabbro through quartz diorite to late grano- diorite and more silicic-alkalic phases. They are early Mesozoic (200 m.y.) in age, and contain porphyry-type mineralization in close spatial and temporal association with late-stage intrusions of porphyry, aplite, pegmatite, and (or) breccia. Country rocks are eugeo-synclinal assemblages of metasedimentary and metavolcanic greenstones of Permian, Triassic, and Jurassic age. The petrochemical evolution of these intrusions, and the effects of subsequent hydrothermal alteration and metallization, are illustrated by standard ternary diagrams of the major oxide and mineralogical data. Samples plotted on an AFM diagram suggest a calc-alkaline magma trend. However, their distributions on NKC and Qz-Kf-Pf diagram show well-defined trondhjemitic (Na20-rich) and tonalitic (quartz-rich) variants to this trend, which are similar in part to those reported for mineralized island arc plutons of the northern Caribbean and southwest Pacific, but which contrast markedly to those for continental plutons of the Bingham District, Boulder Batholith, districts of southern Arizona, and elsewhere.

Jan 1, 1975

By Michael S. Moats, Jan D. Miller, Wlodzimierz W. Zmierczak

"For many, hydrogen in a pure hydrogen economy would be like natural gas in today’s energy economy. Unfortunately, hydrogen’s physical properties are unsuited to the energy market’s requirements in terms of packaging, storage, transfer, and delivery. In this paper, a hybrid energy economy that packages hydrogen chemically on carbon atoms from various sources including recycled carbon dioxide is introduced and discussed. For this new hybrid energy economy to become a sustainable reality, the ability to recycle carbon dioxide and use hydrogen to create an appropriate energy product, such as dimethyl ether (DME), is needed. DME is recognized as a potential next generation, “beyond-petroleum”, environmentally benign commodity for energy storage and distribution. It is expected that to maximize the sustainability of the proposed hybrid energy economy, “green” hydrogen will be utilized. The “green” hydrogen would be created by the electrolysis of water powered by renewable energy sources, such as solar, wind or geothermal heat.IntroductionWith the growing concerns surrounding trends in global warming and increasing concentrations of “greenhouse” gases, such as CO2 and CH4, efforts to mitigate the emission of these gases from industrial sources are growing. With respect to CO2, the demonstrations of various capture and sequestration methods are underway around the world.The sequestration of CO2 is mainly focused on storing the gas underground or deep in the ocean. The Intergovernmental Panel on Climate Change (IPCC) estimates that 2000 Gtonnes of CO2 can be stored underground in depleted oilfields, un-minable coal beds and other geologic features [1]. Additionally CO2 may be stored at the bottom of the ocean. The lure of storing carbon dioxide in depleted oilfields or un-mineable coal seams is that an economic benefit (enhanced oil or methane recovery) can offset the costs of gas capture, transportation and storage. Unfortunately, all of these storage methods have potential for the release of CO2 or CH4 back into atmosphere or creating environmental damage (mobilizing heavy metals, disrupting deep sea ecology)."

Jan 1, 2008

By Peter Brown

The present work involves the study of Chemical Vapor Deposition (CVD) of silicon carbide from the methyltrichlorosilane (MTS) - hydrogen system. A computer program, SOLGASMIX has been employed to calculate the equilibrium compositions of the gaseous and condensed phases in the MTS - H2 system. The results indicate the range of parameters such as temperature, pressure and species concentrations, required to deposit the single phase Sic under thermodynamic equilibrium conditions. A mathematical model for describing the transport phenomena and the rate of deposition of Sic onto a thin rod in a vertically-oriented hot-walled CVD reactor has been developed. Exper iments were conducted using the same operating conditions as those used in the model in order to validate the mathematical predictions. The predicted rates of deposition were found to be in good agreement with those obtained experimentally. The model can be used to study the effects of various operating parameters on the rate of Sic deposition on a fiber.

Jan 1, 1992

By Manolete Mena

WC-Co nanocomposite powder is among the first group of materials with a promising potential for nanocrystalline-materials application. A chemical vapor synthesis (CVS) process that has previously been used for preparing the aluminides of titanium and nickel, and other metallic and intermetallic powders has been applied to the preparation of WC-Co nanocomposite powder. This CVS system was designed so that a tungsten precursor (WCl6 powder) and a cobalt precursor (CoCl2 powder) were separately fed into each evaporator in a reactor by means of specially designed powder feeders. The reduction and carburization of the vaporized chlorides by methane-hydrogen mixtures produced nanosized WC and Co composite powder. The product is a very uniform mixture of the constituent powders, which is important to ensure a high quality of the bulk cemented tungsten carbide product after consolidation. In the present work, the effects of reaction temperature, CH4 to WCl6 ratio, CH4 to H2 ratio, residence time, and Co content on the powder composition and particle size were determined. The products were characterized using XRD, carbon analyzer, and TEM.

Jan 1, 2006

By Manolete Mena

WC-Co nanocomposite powder is among the first group of materials with a promising potential for nanocrystalline-materials application. A chemical vapor synthesis (CVS) process that has previously been used for preparing the aluminides of titanium and nickel, and other metallic and intermetallic powders has been applied to the preparation of WC-Co nanocomposite powder. This CVS system was designed so that a tungsten precursor (WCl6 powder) and a cobalt precursor (CoCl2 powder) were separately fed into each evaporator in a reactor by means of specially designed powder feeders. The reduction and carburization of the vaporized chlorides by methane-hydrogen mixtures produced nanosized WC and Co composite powder. The product is a very uniform mixture of the constituent powders, which is important to ensure a high quality of the bulk cemented tungsten carbide product after consolidation. In the present work, the effects of reaction temperature, CH4 to WCl6 ratio, CH4 to H2 ratio, residence time, and Co content on the powder composition and particle size were determined. The products were characterized using XRD, carbon analyzer, and TEM.

Jan 1, 2006

By Y. K. Rao

Relatively pure crystalline lead sulfate (PbSO4) can be produced by chemical vapor transport from an impure source such as the lead-acid battery paste or the roast-ore-leach-residue from a hy¬drometallurgical process-route. In a closed-reactor, transport of matter is induced by a tempera¬ture-gradient and the steady-state transfer rate can be calculated using the data on the standard free energies of formation for the species present and the pertinent binary diffusion coefficients. The present work focusses on chemical vapor transport in a tubular reactor (1.4-cm inner diameter x 10-cm long) with the source- and deposition-ends held at 850°C (T,) and 750°C (Td), respectively; PbC12(g) is the 'solvent' or 'transport agent' and NiSO4(s) placed in the source-zone -serves to maintain a sufficiently high S0,-potential such that the stability of the lead sulfate species is ensured. For the purposes of analysis, the gas-phase in the reactor is assumed to consist of eight species: H2O, PbC12, SO3, SO2. O2 HO, C12, and PbC14. The reaction between C12(g) and PbSO4(s) in the high-temperature source-zone produces PbCl2, SO2, and 02; four more reaction-equilibria in the same zone yield other species. In the low-temperature deposition-zone, reaction equilibrium involving PbC12, H2O, and SO, leads to the nucleation and growth of PbSO4 crystals; three other reaction-equilibria occur in this zone. By employing the virtual equilibrium state for the end-zones and coupling it to the Stefan-Maxwell diffusion equations for each of the gas species, the respective partial pressures for these, in the source- and deposition-zones, are computed at steady-state. From these data, the molar fluxes of PbCl2. PbCl4, and so forth, are determined. Allowing for the transport-enhancing effects of thermal convection, the net transport rate of lead (or PbSO4) is duly calculated for specified initial conditions. The predicted rates show very good agreement with measured rate data reported in the literature [ V. Plies, T. Kohlmann and R. Gruehn: Z. anorg. allg. Chem, 568, 62 (1989)

Jan 1, 1995

By M. Tangstad, J. D. Steenkamp

In April 2013 a 48 MVA submerged arc furnace producing silicomanganese was excavated in South Africa. Since the high shell temperatures recorded in the tap-hole area resulted in the furnace being switched out for relining, the tap-hole area was excavated systematically. A refractory wear profile of the tap-hole area with affected hearth and sidewall refractory was obtained in elevation. The carbon ramming paste in front of, above, andbelow the tap-hole was worn, as was the SiC with which the tap-hole was built. A clay mushroom formed but was detached from the refractories. Thermodynamic and mass-transfer calculations were conducted to quantify the potential for wear by chemical reaction between refractory and slag and refractory and metal in the tap-hole area. It was found that chemical reaction between refractory and slag or metal could offer only a partial explanation for the wear observed; erosion is expected to contribute significantly to wear.

Jan 1, 2015