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By E. T. White, Dean Ilievski

"Mathematical modelling of the precipitation process requires that the kinetics of crystal growth, nucleation and agglomeration be known. This paper reviews the current state of knowledge on these precipitation sub-processes (ie. growth, nucleation and agglomeration) and describes a number of experimental techniques for estimating their kinetics. The experimental methods used to generate the precipitation data and the data analysis techniques used to extract the kinetics information from the data are discussed separately. There is no universal ""best"" technique for determining the kinetics. However, studies on multi-crystal systems are more reliable for modelling purposes than are single crystal studies. The selection of a technique will depend on which sub-processes are present. A problem with all kinetics studies is that there is generally a large uncertainty in the estimated kinetic parameters. This stems from the scatter in the experimental data being further propagated by the mathematical techniques used to extract the kinetic parameters.IntroductionCrystallisation operations, including precipitation, are widely used in a number of hydrometallurgical processes to recover a desired component or to remove an undesired impurity. The goals of industrial precipitation processes are to maximise the recovery while maintaining product quality (generally product crystal size distribution, purity and morphology and product handling properties). Knowledge of the precipitation mechanisms and kinetics is invaluable for designing new precipitators or for improving existing units. The mechanistic and kinetic information is generally incorporated into mathematical precipitator models, which are then used for process design and optimisation."

Jan 1, 1996

Carbon injection into metallurgical slag is important in electric arc furnace (EAF) steelmaking for foamy slag practices and in nonferrous slag cleaning operations. The current publication presents kinetic data for coal injection into EAF slag to understand the interaction between injected carbon and metallurgical slag. Coal particles were injected into EAF slag and the kinetics were followed by gas and slag analysis. The results were analyzed, in terms of fundamental rate equations for each possible reaction step, as a function of temperature and slag composition.

Jan 1, 2003

By Gabriel Riveros

The stags from the Teniente Converter (TC) have high copper and magnetite contents. The reduction and copper impoverishment of these slags in an electric furnace was simulated in the laboratory, as part of a conceptual study for the Ventanas smelter of ENAMI. The effect of power input, electrode immersion, temperature of the slag, coke and solid revert additions on the rate of magnetite reduction and copper recovery was investigated. It was found that the addition of solid reverts, containing copper matte, enhanced the recovery of copper. Magnetite stratification and a corresponding gradient of the copper content occurred in the slag. Microscopic examination of slag samples showed the presence of copper in the form of matte and metallic copper inclusions. The results of the experimental work combined with an analysis of the phenomena that take place in an electric furnace led to a better understanding of the slag cleaning mechanism. The successful start-up of the slag cleaning electric furnace at the Ventanas smelter resulted in good copper recovery and confirmed the beneficial effect of solid reverts addition. Electrode consumption is lower than anticipated. No bottom build-up problems have been experienced. Keywords: copper, slag, magnetite.

Jan 1, 2001

By Xiang Ma, Halvor Dalaker, Kai Tang, Stefan Andersson

Silicon carbide (SiC) is one of the most important non-oxide ceramic materials for many industrial applications and is mainly synthesized by carbothermic reduction of silicon oxide by coke above 2200°C. Replacing natural gas (mostly methane, CH4) for coke in SiC synthesis could considerably reduce energy consumption and CO2-emissions owing to higher carbon activity of CH4 at lower temperature. The generally accepted reaction mechanism is that SiC is synthesized through gaseous intermediate silicon monoxide, SiO. In the present study, the reaction mechanism for the SiO and CH4 gaseous mixture has been examined using atomic scale modelling. Molecular dynamics (MD) using a reactive force field (ReaxFF) has been utilized to examine the initial stages of reactions involving a gas mixture of SiO and CH4 and surfaces of SiC. The MD results revealed some interesting SiC formation mechanisms. The reaction energies of the critical intermediate species were also estimated by density functional theory (DFT) calculations and the implications for the force field parameters used in ReaxFF was discussed.

Jan 1, 2015

By Isrun Bohlinger

Resources recovery of brasses for semifinished products often results in the formation of hard spots impairing the quality of following abrasive and/or surface finishing processes. A short survey is given on the recycling processes, followed by the actual knowlegde of genesis, composition, and possibilities of avoidance of hard spots. Informations on genesis and composition of hard spots are completed by data from recent experiments.

Jan 1, 1998

By Edgar E. Vidal

The deposition of ceramic materials onto substrates is of special interest in the development of surface related technologies. Research interest has been placed on using thermal plasma as the deposition method, specifically inductively coupled plasmas. Many different modifications to the same basic principle of deposition have been performed through out the materials research community. Such a technique may have many advantages over more conventional techniques, such as high deposition rates, high surface area coverage, clean energy source, no contamination from electrodes and operation near atmospheric pressures. Materials deposited vary from simple oxide systems like TiO2 to more complex structures like ternary oxides and nitrides. This paper reviews recent developments relative to the inductively coupled plasma deposition of thin films.

Jan 1, 2003

By Jean Goldschmidt

Recycling of fine oxidized particles of non-ferrous metals usually cannot be carried out by pyrometallurgical methods. 'Hydrometallurgy provides an alternative technology to reintroduce? the resulting products as secondary raw materials into the industrial cycle, thereby saving resources and energy while keeping the environment a little cleaner. The paper summarizes the methods employed by Hydrometal to achieve these objectives and? stigmatizes the latest counterproductive international regulations which create ever more obstacles to environmentally sound recycling.

Jan 1, 1995

By P. F. Kerr

This is not a conventional professional paper. It deals mostly with personal experiences. These concern a background in applied mineralogy. Your committee asked me to do this. I accepted with a California enthusiasm which has since diminished with the approach of a Chicago winter. Nevertheless, I wish to thank your committee and also to apologize in advance for omissions and inadequate statements, as such a paper must possess. My introduction to applied mineralogy took place in 1922 at Stanford University. Physicists had recently demonstrated that crystalline powders would reflect x-rays in a systematic manner. Professor A.F. Rogers sug¬gested that significant x-ray reflections might be obtained from powdered opaque minerals. With the aid of Professor D.L. Webster in the Physics Department, I constructed an x-ray diffraction outfit. It was a crude affair, but it worked. Starting with 1924, we secured recognizable patterns of a goodly number of ore minerals (1,2,3). Today x-ray diffraction outfits are common, and a card system of mineral identification is constantly used.

Jan 1, 1981

By Ramana G. Reddy

Thermodynamic modeling and experimental study on impurity capacities and their distribution between mattes or metal and slags in smelting, converting and refining of non-ferrous metals was discussed. A brief review on the recent developments in copper smelting and converting is presented. The analysis showed that, copper smelting capacity increased by a factor of 10 since 60's, smelting rate increased by a factor of more than 5 and process fuel equivalent decreased by a factor of 2. A thermodynamic model for prediction of impurities capacities in slags and their distribution in mattes and slags was developed. The impurities capacities (i.e. sulfur and arsenic) of slags were calculated a priori with no adjustable parameters using the Reddy-Blander model. The capacities predictions were made in a wide range of matte and slag compositions, Pso, and temperatures in conditions pertaining to copper and lead industrial slags. The calculated results for sulfide and arsenate capacities are in good agreement with the available experimental and industrial copper and lead industrial slags data. The sulfide and arsenate capacities in copper slags (fayalite, ferrite and olivine) and lead slags are reviewed. The application of RB model predicted ratios of 02 and S2 partial pressures in industrial copper smelting processes are discussed. Application of this model for the prediction of Sb, Bi and other impurity capacities and their distribution ratios in mattes or metal and slags, in industrial smelting and refining processes is discussed.

Jan 1, 2003

By Colin Dessemond

Since 1950, the traditional process has been dominating the production of lithium compounds from spodumene ores to sustain the lithium market because of its economic viability and the markets need for technical grade (99.5% purity) product. This traditional process includes thermal conversion, acid roasting and lithium leaching. However, this process has not been challenged and very few studies have tried to explain its limitation (95% lithium yield) or optimize the thermal treatment. Here, α to β spodumene conversion and lithium extraction were performed in a rotary kiln on a 2 mm to 2 cm spodumene concentrate instead of a micrometric one using a 1050 °C, 30 min conversion treatment and 250 °C, 30 min, 30% H2SO4 excess leaching treatment. X-Ray Diffraction analyses were performed on the converted material to determine the conversion rate by Rietveld analysis. It was observed after thermal treatment that the α-spodumene particles fractured and divided while the impurities remained compact. A sifting was performed after thermal treatment and it was determined that 65% of the initial mass became finer than 180 μm. X-Ray diffraction analyses and lithium content measurement were performed on both fractions and it was determined that the finer fraction had a very high lithium content of 3.24 wt%. Lithium extractions were performed on both fractions separately. While the coarser fraction’s lithium yield was only 61% the finer fraction’s lithium yield went up to 99% without any additional treatment. These observations may open more economical ways for the traditional process by potentially bypassing two third of costly steps such as grinding.

By Liang Li

Thermodynamic analysis and experiments were conducted in order to verify the feasibility of preparing crude titanium tetrachloride (TiCl4) via the carbochlorination of low-grade titanium slag in molten salt. Titanium slag, assaying 74.6 wt% TiO2 with high calcium and magnesium oxide impurities, was treated by an optimized carbochlorination process in NaCl molten salt. These impurities in the titanium slag were chloridized simultaneously, and chlorination products FeCl2, MnCl2, MgCl2, CaCl2 and CrCl3 were collected in the furnace slag. XRD and SEM/ EDS analysis of residue shown that SiO2 and Al2O3 in titanium slag were difficult to chlorinate completely. Theoretical calculations and industrial-scale experimental studies reveal the content of TiCl4 in the products was more than 98.8 wt% and thus proved the feasibility of utilizing low-grade titanium slag for TiCl4 preparation by molten salt chlorination technology.

By Robert S. Gärtner

The selective aluminum extraction by 3 different calixarenes (p-tert-butyl-calix[4]arene-tetra¬2-acetic-acid-ethyl-ester, p-tert-butyl-calix[4]arene-tetra-2-acetic-acid and p-tert-butyl-calix-[4]arene-di-2-acetic-acid-ethyl-ester) from an industrial pickling bath solution was studied. The pickling bath solution contained hydrofluoric and phosphoric acid as its main components. The aluminum removal was not successful and also no significant extraction of trace metals present was observed.

Jan 1, 1999

By E. G. Noble

The potential for using heterotrophic microorganisms to solubilize manganese from low-grade domestic ores is being assessed at the Reno Research. center, U.S. Bureau of Mines. More than 90 pct of the manganese has been extracted from a variety of oxide ores in shake-flask tests using molasses as a source of .. nutrients for the microorganisms. It has also been demonstrated that high recoveries of manganese can be obtained from a domestic wad ore using column bioleaching. 'l'he isolation and identification of organisms responsible for manganese extraction is discussed, as are the mechanisms responsible for manganese solubilization.

Jan 1, 1991

By Guy L. Fredrickson

A modified transpiration reactor was used to measure the composition of the equilibrium gas phase formed above compounds in the Hg-O-S system at high temperatures (600 to 900K). A thermodynamic database {(AGo°f AH°t. AS°t)} for-HgO, HgS, HgSO4, Hg2SO4, HgSO4?HgO, and HgSO4?2HgO was developed based on the experimental results. Prior to this study, only estimated data were available in the literature for the sulfates and oxysulfates at temperatures above 298K. A series of vapor pressure' stability diagrams were constructed from 473 to 973K with isobars of Hg(g), HgO(g), S2(g), and SO3(g). These diagrams were found to be significantly different than those available previously and do provide insight to the phase relations of importance during the thermal processing of Hg-containing wastes. The thermodynamic results were used to conduct a series of Gibbs energy minimization calculations for a thermal processor' afterburner system for the treatment of HgS-containing wastes. The retention of Hg in the discharge calcine was examined as a function of temperature and excess air. Hg was found to report to the calcine as HgSO4, Hg2SO4, or HgSO4 HgO depending on the process conditions, and Hg retention occurs at temperatures as high as 930K. The precipitation of Hg-containing phases from cooled afterburner discharge gas starts at approximately 900K and the cooling of the gas an additional 30K (to 870K) results in over 50% of the Hg being preCipitated as HgS04?HgO. It was also determined that for small amounts of Hg present in sulfide concentrates during roasting, the Hg will be retained as HgSO4 or HgSO4?HgO at temperatures as high as 870K.

Jan 1, 1996

By Jason M. Porter, Douglas L. Porter, David L. Olson, Travis W. Koenig, Van S. Blackwood, Brajendra Mishra, Robert D. Mariani

"Traditional alloy theory models have been applied relative to the three solid phases of uranium: alpha (orthorhombic), beta (tetragonal), and mainly gamma (body centered cubic)[l]. The Darken-Gurry and Miedema models, with modifications based on concepts of Waber, Gschneidner, and Brewer have been used to predict the behavior of four types of solutes: 1) Transition associated with alloying in and containment of the uranium fuel 2) Transuranic elements in the uranium 3) Rare earth fragmentation elements (lanthanides) 4) Transition metals and other fragmentation elements. Using these solute map criteria, elemental behavior have been predicted as highly soluble, marginally soluble, or immiscible (intermetallic phase formers) and have been used to compare solute effects during uranium phase transformations. The overlapping of these solute maps are convenient first approximation tools for predicting alloy behavior.IntroductionAn investigation is in progress to determine the role of various solute elements on size and shape of the 'Y phase field range for uranium to optimize the burning and material processing of nuclear fuel is in progress. Traditional alloy theory models based on correlations to elemental electronic and crystal properties are used to predict solubility and micro structural formation. The effectiveness of this model is based on microstructure property correlations. Darken and Gurry, and Miedema models, with modifications based on concepts of Waber, Gschneidner, and Brewer, models have been used to describe solute solubility with respect to uranium based the on correlation between elemental electronic structure and uranium phases. The alpha (orthorhombic), beta (tetragonal), and gamma (body centered cubic) phases have different solubilities for specific alloy additions as a function of temperature. Using the method of Waber, ellipse diagrams classified those solutes that should have broad solubility in the allotropes of uranium[2]. The predictive diagrams are made from four different correlations:"

Jan 1, 2012

By M. Misra

The bacterium?Mvcobacterium Phlei has a demonstrated potential to be used for the flocculation of a variety of finely divided minerals. The microorganism possesses both hydrophobic surface and high negatively electrostatic charge. It can adhere to many mineral surfaces ?if the charge and hydrophobic interaction? between the microorganism and the minerals are favorable to adhesion. Experimental results showed that the dolomitic phosphate slime from Florida and fine hematite can be :readily flocculated from dilute suspension.. In the case of dolomitic phosphate slime, a consolidated sediment containing 24'-25 weight% :solids can be obtained from .a dilute slurry .in a short time. Sediments obtained from hematite flocculation are rather massive and more .consolidated than phosphate slime. Mycobacterium Phlei has a specificity for selective flocculation of hydrophobic fine coal particles from pyrite and ash containing minerals. Because of mutual hydrophobic interaction of coal and Mycobacterium Phlei, it was noticed that coal particles appear to be strongly held in the aggregate by adhesion or bridging of bacteria. However, Mycobacterium Phlei is not a good flocculant for either associated pyrite or ash present in coal.

Jan 1, 1991

By Frame Ritzert, Dennis Keller, Vijay Vasudevan, David Arenas

"An investigation was conducted to describe topologically close packed (TCP) phase instability as' a function of composition in the advanced ·Ni-base superalloy Rene N6. TCP phases are detrimental to overfill high-temperature performance of Ni-base superalloys because of their brittle nature and because they deplete the Ni-rich matrix of potent solid solution strengthening elements. Thirty-four variations of polycrystalline .Rene N6 determined from a design-of-experiments approach were cast and homogenized at 13 l5°C for 80 hours followed by exposure at 1093°C for 400 hours to promote TCP formation. The alloys had the following composition ranges in atomic percent: cobalt 10.61 to 16.73, Mo 0.32 to 1.34%, W 1.85 to 2.52%, Re 1.80 to 2.11%, Ta 2.36 to 3.02%, Al 11.90 to 14.75%, and Cr 3.57 to 6.23%. Physical and chemical characteristics of all microstructures obtained were described using various analytical techniques. From these observations, a mathematical description of TCP occurrence (s and P phase) was generated for polycrystalline Rene N6.IntroductionNi-base superalloy single crystals represent the state-of-the-art for turbine engine airfoil application as they offer the best balance of properties to allow for the high operating temperatures required: for efficient engine operation.1 Current trends in alloy design take advantage of improved creep rupture strength with the addition .of higher levels of refractory elements. 2 In .particular, the addition of significantly higher levels of Re in third generation superalloys is key for both microstructural stability and creep rupture strength. 3 While the presence of the refractories is thought to provide strength benefits from solid solution hardening, a tendency for alloy instability in the form of topologically-close-packed (TCP) phases or secondary reaction· zone (SRZ) ·phenomena accompanies the high refractory content. 3 The formation of these phases in sufficient amount is detrimental to the overall high temperature performance of Ni-base superalloys because of their brittle nature and because they deplete the Ni-rich matrix of potent solid solution strengthening elements.4 The tendency for a particular composition to form TCP may not be immediately known since the precipitation of TCP phases in Ni-base superalloys is nucleation controlled, thereby requiring long times at elevated temperatures to precipitate. 5 They preferentially nucleate along the octahedral planes of the Ni-base superalloys, usually in areas of refractory metal enrichment at grain boundaries or inside dendrites.5-6 In Rene N6, two closely related TCP phases, a and P, have been observed.2"

Jan 1, 1998

By Corby G. Anderson

For over a century, the Sunshine Mine in Idaho has been a major producer of silver. An estimated 335,000,000 troy ounces of silver has been mined. This has established the Sunshine Mine as the largest single source of silver in the world. Because the dominant silver containing mineral is tetrahedrite, a copper and antimony sulfide, normal metallurgical treatments to recover the precious metal are not practical. Thus, over the course of the company's history, novel, hydrometallurgical technologies have been developed on-site to handle complex, precious metal containing materials. Recently, the use of Sunshine technology has been extended to the recycle of secondary materials. As well, the use of Sunshine technology by other organizations for treatment of both primary and secondary feedstocks containing precious and base metals is an area of growing interest. This paper will provide an overview of Sunshine hydrometallurgical technologies including the applicability of Sunshine technology to the recycling of precious and base metals.

Jan 1, 1995

By J. A. Eisele

There is currently much interest in how extraction of gold and silver from ores with acidic thiourea solution compares with extraction using alkaline cyanide solution. Agitation leaching tests were performed by the Bureau of Mines on 14 precious metal ores using sodium cyanide (?NaCN) and thiourea [(NH2)2CS) as extractants. The objective was to compare the results of the two extractants. NaCN was used at a concentration of 2 g/L with and without H202 as an oxidant. (NH2)2CS was used at concentrations of 2 and 20 gjL, and the solution potential was controlled at 390 to 420 mV standard hydrogen electrode (Eh) with Fe2(S04)3. With both reagents a.t 2 g/L extractant levels, NaCN extracted more gold and silver than (NH2liCS from all of the ores. At 20 g/L (NH2)2CS compared with 2 g/L NaCN, (NH2)2CS extracted more gold than NaCN from two ores, the same amount from one ore, and more silver from one ore. NaCN extracted more gold than (NH2 )2CS from 10 ores and more silver from 4 ores.

Jan 1, 1989

By Yasuyuki Murayama

MF is the semi-blast furnace which has been developed at Mitsui Miike Smelter in the 1960's to treat vertical retort residue. The MF has also been tested for treatment of various recycling materials and wastes. Now various secondaries and wastes (steel dust, zinc leaching residue, Cu-Ag sludge, spent catalyst and spent rubber, etc.) are mainly treated. Powder materials are briquetted with reductant before being fed to the furnace. Products are crude zinc oxide, matte, non-hazardous slag and steam. Zinc and lead are recovered in oxide dust, and copper and silver are recovered in the matte. The MF furnace can be widely applied to many kinds of materials which contain such non-ferrous metal-valuables. In addition, the improvement in operation and technology has effectively made the unit capacity much larger. The MF furnace now has many advantages for these treatment processes.

Jan 1, 1992