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By Renato G. Bautista

The chemistry of the separation of metals from each other and from the other undesirable components involve multiple simultaneous chemical reactions. In the case of leaching, the heterogeneous chemical reactions between the solid and the liquid phase may be limited to a few reactions. In the homogeneous liquid phase, the number of simultaneous chemical reactions could be double or triple that of the number of heterogeneous reactions:. The rate of dissolution becomes very dependent on the changing concentrations of the significant chemical species taking part in the multiple reactions in both the heterogenous and homogeneous phase. The rate expression developed for the process must take into account the mechanism of chemical reactions in order to best represent the actual process. This paper also examine the role of mass transfer with chemical reaction in the develpoment of the rate equations for dissolution, liquid-liquid extraction, membrane separation, precipitation, and electrodeposition.

Jan 1, 1996

By Sergey Shabala

Green leaf tissues convert solar energy into the energy of chemical bonds of sugar molecules during the process of photosynthesis. The efficiency of this conversion can be much higher than efficiency of any of the currently known silicon-based solar panels. Importantly, vast amounts of CO2 are assimilated during this process. The efficiency of photosynthesis is critically dependent on the availability of a large number of nutrients, among which metal cations such as K, Ca, Mg, Cu, Zn, Fe, Mn, and Ni play a key role. In this paper I summarize basic requirements and major functions for each of these essential nutrients in plant photosynthesis, both at the whole-plant and molecular level. I will talk about how these requirements may be affected by the global climate trends and discuss the prospects of creating artificial photosynthetic “bioreactors” for efficient energy conversion and CO2 assimilation.

Jan 1, 2009

By Chu Yong Cheng

Manganese is one of the main impurities in the recovery of base metals from their ores. This is especially true when laterite ores are processed using the pressure acid leach (PAL) process. The use of intermediate precipitation, solids/liquid separation and re-leach in the three Western Australian nickel laterite plants to separate nickel and cobalt from manganese and other impurities makes these processes complicated and costly in capital and operation. The research work carried out by the solvent extraction (SX) group at the A J Parker Cooperative Research Centre for Hydrometallurgy (CSIRO Minerals) has led to the development of direct solvent extraction processes to separate nickel and cobalt from manganese and other impurities. The simplicity of the process flowsheets and the expected savings in capital and operating costs are the major advantages of the new direct solvent extraction processes over the existing processes. By using a new synergistic organic system, Versatic 10 / dccyl-4-pyridinccarboxylatc ester, with a pilot plant leach solution from BHP¬Billiton (after iron precipitation), the metal values (Ni and Co) together with zinc and copper were separated from manganese and other major impurities (Mg, Ca and Cl) in the first SX circuit. The co-extracted manganese, magnesium and calcium were easily scrubbed out. The extraction and stripping kinetics of the metals with the new synergistic organic system were very fast and the synergistic system was found to be chemically stable. pH-extraction isotherms of metals with D2EHPA showed that the extraction order as a function of pH50 was Zn2+ > Ca2+ > Mn2+ > Cu2+ > Co2+> Ni2+> Mg2+. Semi-continuous test work with a cobalt pilot plant leach solution from Peko Rehabilitation Project Pty Ltd and a synthetic solution to simulate a concentrated laterite leach solution from BHP-Billiton showed that manganese, together with calcium, copper and zinc can be separated from nickel, cobalt and magnesium. This led to the development of another direct solvent extraction process to separate manganese and other impurities from nickel and cobalt and to recover nickel and cobalt from leach solutions. A project was initiated by HiTec Energy Ltd to recover manganese from waste laterite leach solutions using SX technology and to further purify it to produce high purity electrolytic manganese dioxide (EMD) for the high quality alkaline battery industry. Batch tests were conducted to select a suitable organic system for the extraction of manganese in terms of selectivity and extraction and stripping kinetics. A total of eight organic systems were tested using waste laterite processing solutions. A Versatie 10 / synergist system showed very promising results. By using the synergistic system, high manganese recovery would be obtained, fewer SX stages would be required and a higher A:O ratio could be used in extraction, resulting in a smaller organic inventory and lower capital costs. The risk of gypsum formation is also minimised with the synergistic system. Keywords: Solvent Extraction, Manganese, Laterite, Synergist

Jan 1, 2004

By Renato G. Bautista

"The chemistry of the separation of metals from each other and from the other undesirable components involve multiple simultaneous chemical reactions. In the case of leaching, the heterogeneous chemical reactions between the solid and the liquid phase may be limited to a few reactions. In the homogeneous liquid phase, the number of simultaneous chemical reactions could be double or triple that of the number of heterogeneous reactions. The rate of dissolution becomes very dependent on the changing concentrations of the significant chemical species taking part in the multiple reactions in both the heterogenous and homogeneous phase. The rate expression developed for the process must take into account the mechanism of chemical reactions in order to best represent the actual process. This paper also examine the role of mass transfer with chemical reaction in the develpoment of the rate equations for dissolution, liquid-liquid extraction, membrane separation, precipitation, and electrodeposition.IntroductionThe understanding and the elucidation of the mechanism of the rate phenomena for a specific chemical reaction system is of prime importance in the development of a successful chemical process. The development of successful emerging technologies for metals separation will depend on the accurate interpretation of the intrinsic chemical reaction kinetics and the rate of mass transfer of the desired metal species during its separation from the undesirable chemical species. This is the case whether the process application is for separation, concentration, and /or purification.The chemical processes that will be examined in this presentation will include leaching, solvent extraction, membrane separation, precipitation, and electrodeposition."

Jan 1, 1996

By James E. Hoffmann

Oxidative pressure leaching is gradually supplanting other techniques for the decopperizing of slimes. The reasons for this include: much more rapid reactions, more compact equipment, a reduced environmental burden, and perhaps most important, a much lower final copper concentration in the decopperized slimes. This paper will discuss the reactions occurring during decopperization, the acidity and temperatures encountered and the techniques employed for discharging non condensable gasses. A spreadsheet is provided which allows adjusting the operating conditions depending upon raw (undecopperized) slimes composition, solids concentration and lixiviant composition. A typical process equipment flowsheet is provided along with a process narrative.

Jan 1, 2000

By T. T. Nguyen, D. R. Gunasegaram, D. Celentano

"Heat transfer rates at the casting-mold interface are believed to be substantially reduced by the formation of an interfacial gap during the course of solidification of aluminum alloys in permanent molds. In the current work, the effect of force-cooling a permanent composite mold on (i) the initiation and growth characteristics of the gap and (ii) interfacial heat transfer rates are studied. Interesting comparisons are made with the case where no cooling is employed. Casting and mold displacements are measured using L VDTs, and the mold is force-cooled by air jets.IntroductionIn a gravity casting situation where an aluminum alloy solidifies in a permanent mold, a gap initiates and grows between the shrinking casting and the expanding mold (1). It is widely believed that the formation of this gap, customarily referred to as an 'air gap', results in a substantial reduction in the heat transfer coefficient at the casting-mold interface (2), and hence is an important factor in solidification studies.The nature of the air gap formation process is thermo-mechanical. The rate of heat loss from the casting first determines the rate of solidification, which, in turn, decides when the gap initiates. The reason for this is the requirement for the solidified casting surface 'skin' to gain sufficient thickness, and hence strength, to be self-supporting. Once the gap initiates, the gap width controls the rate of heat loss from the casting, which, again, determines the rate at which the gap expands."

Jan 1, 1997

By Harald Laux, Stein Tore Johansen

The plunging jet in tapping of steel from converters or electric arc furnaces entrains gas into the steel bath contained in a ladle. Gas entrainment rate and the effect of the gas on the flow pattern in the ladle are studied by means of Computational Fluid Dynamics CFD. The work focuses on the mathematical modeling. Two numerical methods, one for free-surface flows and one for dispersed multiphase flow are combined. A transport equation for the average bubble diameter that incorporates the effect of coalescence and breakup is presented. Results from computations for one ladle and tapping configuration are shown. Our findings indicate that the gas entrainment rate is affected by the material properties of the liquid in the sense that the material properties determine the shape of the jet. Moreover, bubble sizes in the range of two-orders of magnitude are predicted in the ladle. The dispersed diameter model seems to work well. It showed the expected response to material parameters and the turbulent field. However, the presented analysis is just a first step that was limited due to certain simplifications. In order to obtain better insight in the tapping process improvements of the analysis seem necessary.

Jan 1, 1999

By A. C. Mollison

In November of 1983 a fire inside the autoclave caused the curtailment of operation of the Kidd Creek pressure leaching facility. Subsequent repairs and recommissioning of the autoclave in 1984 allowed Kidd Creek to increase its production of zinc as originally planned. This paper describes the operation of this process from 1984 to 1988 and details major mechanical work carried out on the vessel in 1.988:

Jan 1, 1990

By G. A. Irons, D. Colbert

Several electric arc furnace (EAF) shops have increased the zinc and lead grades of EAF dust by reinjecting it into their furnaces; however, the kinetics of this operation are poorly understood. To understand the kinetics, EAF dust was injected into 70 kg heats of iron or steel in an induction furnace. Supplemental additions of carbon and oxygen to overcome the heat load on the system were also investigated. In all cases, the dust was chemically transformed, and the zinc content increased from 16% Zn to 60 - 80% Zn. About 50% of the zinc in the EAF dust dissolved in the iron or steel. The zinc oxide in the dust is thought to be reduced by carbon and the zinc vapour subsequently dissolved in the iron. A kinetic model for the dissolution process is proposed, and the implications for EAF dust recycling are discussed.

Jan 1, 2000

By Kumar M. Lyer

Residence time distribution (RTD) of light and heavy liquids in a pyrometallurgical channel reactor was mathematically modeled by representing the reactor as a combination of ideal reactors. Cold model studies simulated the counter-current flow of slag and matte (or metal) with high-strength bottom gas injection. The experimental variables include flow rates, heights, density and viscosity of the two liquids; gas flow rate; injector diameter; and distance between injectors. The experiments covered a wide range, of the appropriate dimensionless parameter, including conditions in ferrous and nonferrous extractive metallurgy. Dispersion modeling studies were also carried out to determine the degree of backmixing. Results indicate that the degree of backmixing in the channel reactor for various operating conditions corresponds to that for 3-20 perfectly mixed reactors in series.

Jan 1, 1993

By J. A. Bustnes

The present work deals with kinetic studies of the reduction of molybdenum- and tungsten oxides by hydrogen. The experimental method used was therrnogravimetry under isothermal as well as non-isothermal conditions. The non-isothermal kinetics in the case of the reduction of MOO, to Moo2 has been modeled considering surface reaction as rate- controlling. In the case of the reduction of W02 to W a model was developed on the basis of the movement of the reaction front. The activation energies calculated on the basis of the models were in good agreement with those derived from isothermal experiments.

Jan 1, 1994

By Ali S. Al-Watban

"In this paper, the room temperature friction and deformation properties of various polycrystalline diamonds; i.e. aggregates of diamond crystals with a ""binder"" phase of cobalt and a polycrystalline coating produced by a chemical vapour deposition processes (CVD) were studied when softer metallic and ceramic sliders were used. The experiments were conducted· at relatively low sliding speeds (10 mm/min), in a vacuum of 10-5 mbr after having cleaned the specimen surfaces by out-gassing them for about 30 min at 800 °C. As a result of increasing the number of traversals significant wear of the coated diamond by softer metallic sliders (aluminium and mild steel) was observed. With ceramic sliders, it is shown that the multiple traversals result in the formation of wear groove. With diamond silicon carbide, high friction and adhesion lead to significant metal transfer which then pre-empts cumulative deformation of the harder materials. With the diamond-cobalt composite, the friction is surprisingly low, there accumulation of wear debris on the tip of the slider but no permanent transfer of metal and the harder specimen is not damaged even after 5000 traversal.IntroductionPolycrystalline diamond is mainly produced as tool materials for the machining of hard metals and composites. Thus, the sliding friction and wear resistance are amongst the most important properties relevant to those applications.During cutting by PCD the wear mechanism is mostly influenced by the chemical affinity between the tool material and the workpiece. For example, diamond based materials are not recommended for machining ferrous materials because carbon is highly solubie in iron: This leads to the graphitisation of diamond particles and hence a high rate of diffusion wear is observed (Brookes and Lambert, 1982)."

Jan 1, 2000

By Richard S. Kunter

Artech Recovery Systems, Inc has developed a low pressure and temperature? leach process called the "Cashman Process" to extract metals from arsenical flue dusts and residues and fix the arsenic in an environmentally stable form as ferric arsenate (scorodite). The process was pilot tested at Hazen Research in an integrated plant including continuous recycle from August 1989 to October 1989 during which several tons of flue dust were processed. Based on this pilot program, the process was deemed technically feasible and produced commercially salable products. Residues from this pilot program were subjected to a long-term stability test jointly designed by PTI environmental services and the USEPA. The process, its versatility, and the nature of the products is discussed in some detail.

Jan 1, 1992

By Irshad A. Rana

In a modern copper smelter, the capital cost of a sulfuric acid plant constitutes the largest single cost item of the total investment. It is thus essential to properly size the acid plant in order to reduce its capital cost and enhance the economic viability of a new smelter project. Whereas the off-gas from a smelting furnace is continuous and generally uniform, the gas flow from the Peirce-Smith converters is intermittent with significant fluctuations. The converters off-gas volume is dependent upon a number of interrelating factors. The most significant factors are the matte feed grade, the system air infiltration, the converter's size and blowing rate, the maximum number of converters simultaneously blowing and the gas cooling system employed. The acid plant size, therefore, is heavily influenced by the converter off-gases. Several of these factors are discussed, and their impact in determining the acid plant size is explored.

Jan 1, 1993

By Matthew C. Binsfield

The simultaneous electro winning of zinc and manganese from waste water treatment plant sludge was studied as a part of the overall research program, which was conducted to develop the methods for removal of environmentally hazardous metals from the Bunker Hill Superfund Site. This paper discusses the electrolytic method for recovery of zinc and manganese from the solution produced by leaching of sludge with S02 + H2S04. After three stage purification of the leaching solution, zinc and manganese were electro won simultaneously in an undivided electrolytic cell. Zinc was deposited on an aluminum cathode, while manganese was simultaneously produced (as Mn02) on a lead silver anode. The electrowinning parameters studied were the effects of: temperature, current density, electrode material, spacing of electrodes, composition of electrolyte, and electrolyte additives. Anodic and cathodic efficiencies were 30 and 91%, respectively. In light of the process design parameters discussed in the paper, which are affecting the electrowinning, these efficiencies were found as acceptable with regard to the quality and marketability of the products.

Jan 1, 1996

By R. Cavanagh

Studies relating to the fixation of sulfur by reaction of 4 to 8 mm diameter cylinders of calcined limestone or dolomite with high strength sulfur dioxide in the temperature range 880°C to 1020°C were undertaken. Dolomites are far superior in sulfate capacity and reactivity than dense limestones even at high strength SO2. The sulfation reaction was first order with respect to SO2 concentration below 100 percent. Zero reaction rate at 100 percent SO2 concentration indicates that sulfate was the exclusive reaction product and that sulfite had no role in the reaction. At relatively low SO2 concentrations gaseous diffusion through the reaction product layer has a marked effect on the rate. As SO2 concentrations were increased up to 100 percent more complex rate controlling mechanisms unfold. By sectioning partially reacted dolomitic limestone pellets a moving interface was observed. Reaction ceased because of pore plugging for dense non-porous limestones at 30% conversion. With dolomitic material virtually complete sulfation of the calcium was observed. S.E.M. analysis showed that the average atom ratio Ca:S was 1.01, thus supporting the argument that little if any of the magnesium was sulfated.

Jan 1, 1996

By P. Blazy

A hydrometallurgical procedure for the recovery of metal from ore, particularly of copper from sulphide materials is described. In the course of this procedure, the raw material is first of all submitted to the action of an appropriate reducing system and then treated with a ferric salt solution which brings about the selective solubilisation of the elements to be recovered with respect to those constituting the pyritic phase. This procedure is investigated using two ore samples proceeding from massive sulphide deposits, presenting different chemical and mine- ralogical characteristics. The results of this investigation are compared with those obtained by a classical process employing a ferric salt solution. It appears that one solubilisation of copper takes place under particularly advantageous conditions when our procedure is used. The principal parameters affecting leaching of zinc, lead and copper are examined. The selectivity of this treatment is evaluated by following the change during the treatment in the pyritic phase.

Jan 1, 1976

By James O'Brien, Lyman Frost, Grant Hawkes, S. Elangovan, Manohar Sohal, J. S. Herring, Joseph Hartvigsen, Carl Stoots

"Pressing environmental and energy security concerns have brought much needed attention to economic production of hydrogen as the secondary energy carrier for non-electrical markets as well as to meet increasing demand for crude upgrading and desulfurization. While steam reforming of natural gas is currently the dominant method of hydrogen production, it is depleting a valuable fossil fuel while emitting green house gases. Thus, in the long run, efficient, environmentally friendly, and economic means of hydrogen production using nuclear and renewable energy needs to be developed. High temperature electrolysis using solid oxide electrolyte cells is an exceptionally efficient means of generation of high purity hydrogen. It is also capable of directly converting steam and CO2 into synthesis gas. This co-electrolysis process enables conversion of CO2 recovered from concentrated industrial sources into a feedstock for synthetic fuels production. Use of CO2 provides a means of storing hydrogen in a concentrated and convenient form – a hydrocarbon. This is also an effective storage medium for intermittent renewable energy sources such as wind and solar.Ceramatec, Inc and the Idaho National Laboratory are applying solid oxide fuel cell technology to the production of synthesis gas by high temperature co-electrolysis of steam and carbon dioxide. This technology utilizes solid oxide fuel cell stacks to electrochemically remove oxygen from steam and CO2, leaving a clean stream of hydrogen and carbon monoxide suitable for fuel synthesis. By varying the relative concentrations of carbon dioxide and steam, the hydrogen to carbon monoxide product ratio can be controlled as required by the desired type of synthetic fuel being produced from the syngas. The resultant synthesis gas has been used as the feedstock to produce synthetic methane and Fischer Tropsch liquid fuels.Alkaline and proton exchange membrane electrolysis cells typically operate below 100°C, while solid oxide electrolysis cells operates in the 750-850°C range. This higher temperature improves the efficiency significantly. Practically, it translates into a lower cell operating voltage, 1.1-1.4V for high temperature electrolysis vs. ~1.8V for water electrolysis. Hydrogen production is stoichiometric with current in all types of electrolyzers.Carbon dioxide is a valuable resource as a feedstock for energy storage as a hydrocarbon. There is a vast amount of renewable energy that cannot be effectively utilized as grid electricity, but which could be used to convert CO2 to hydrocarbons, offering a solution to the even more difficult (than supplying grid power) challenge of production of sustainable, domestic transportation fuels. Conventional electrolysis and chemical processes could be deployed to accomplish this conversion. However, high temperature co-electrolysis of CO2 and steam to produce synthesis gas using solid oxide fuel cell technology has the potential of improving the efficiency by nearly 50%. A domestic synfuel industry will enable a much larger reliance on intermittent renewable energy than can be accommodated by conventional electric demand profiles while increasing our energy security."

Jan 1, 2010

By Sarah Beutner Mavrogenes

The mineralogy of three slags from a domestic secondary copper refinery were studied by applied mineralogical techniques to determine the: 1) phases present, 2) phase chemistry, 3) phase abundance, 4) associations, 5) crystalline habit, 6) grain size, 7)microtextures, and 8) causes for certain metallurgical problems, such as metal losses to the slags. The slags were produced by skimming the bath prior to melt-down to allow heat from the flame to reach the bath. The first slag is highly viscous and all three slags contain a large amount of copper. The "first slag", which is skimmed prior to treatment of the bath with fluxes, contains metallic copper, cuprite, delafossite, magnetite, Mg-hercynite, common spinel-chromite solid solution, picrochromite-chromite solid solution, common spinel-picrochromite solid soiution, gahnite, cassiterite, silica-rich glass, and corundum. Its abundant solid refractory phases make the slag difficult to skim. The "soda-rich slag", skimmed after the treatment of the bath with sodium carbonate flux, contains cuprite, delafossite, magnetite, cassiterite, Na-Al-silicate, and Na-Al-Ca-silicate. It contains less metallic copper than the first slag and lacks the refractory minerals. The "phosphorus-rich slag", skimmed after treatment of the bath with a copper phosphide flUX, contains metallic copper, cuprite, delafossite, berlinite, cassiterite, silica, apatite, Cu-Fe-rich apatite, copper phosphate, Cu-Fe-phosphate, and a Pb-phosphate. In contrast to the above three copper-rich slags, recent charges have produced a silver-copper-rich slag. The "silver-rich slag", skimmed after the treatment of the bath with a copper phosphor ide-borax flux, contains, cassiterite, delafossite, cuprite, a Na-Al-silicate, magnetite, metallic copper, MgO, common spinel-chromite solid solution, and wollastonite. Silver ranging from 0.05 to 2.02% was found by atomic absorption and inductively coupled plasma spectrometry analyses in the metallic copper phase.

Jan 1, 1989

By B. Zilbergleyt

Current understanding of chemical equilibrium is based exclusively on the probabilistic considerations that are correct for isolated systems with only one chemical reaction to take place. For the systems with multiple chemical interactions, current paradigm of chemical thermodynamics promotes the idea of openness, artificially flavored with coefficients of thermodynamic activity. Recently introduced thermodynamics of chemical systems and the Method of Chemical Dynamics (MCD) offer explicit accounting for the multiple chemical interactions within the system. In the new theory, thermodynamic equilibrium of the j-subsystem obeys the logistic equation derived exclusively from the currently recognized concepts of thermodynamics. Having the only one new parameter -the subsystem's reduced chaotic temperature 'tj to describe external interactions, and reaction extent Ilj as independent variable, this equation covers the whole domain of the system's possible states from true thermodynamic equilibrium through the open equilibrium to bifurcations and chaos depending on the 'tj value. The MCD brings new opportunities to thermodynamic simulation of complex metallurgical and chemical systems, allowing for the analysis of their domains of states and the area limits, and for more accurate calculation of the equilibrium compositions. Its usage is exemplified in this paper by several applications. Keywords: chemical thermodynamics, open systems. complex systems, chemical dynamics.

Jan 1, 2003