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By Zhuo Sheng

We have designed a high-temperature Raman micro-furnace and cell that is suited for the electrochemical process study of the NO3 − in molten NaNO3– KNO3 (fraction of NaNO3 50 wt%) salt. During the cycle voltammetry and constant potential electrolysis process, the Raman laser beam was focused near the electrode; subsequently, the Raman spectra are obtained and the reduction process of NO3 − is analyzed. In the CV cathodic scan process, the new peak attributed to the ν1 mode of NO2 − emerges, and the peaks assigned to superoxide ions (O2 −) and peroxide ions (O2 2−) are not found. In the constant electrolysis process, the peaks at 1130 and 800 cm−1 appear when the potentials are between −2.0 V and −3.2 V (vs. Pt). The results show that when the NO3 − is reduced in molten the NaNO3–KNO3 mixtures, the reduction product O2− cannot stably exist, and O2− will react with NO3 − to form of superoxide ions (O2 −) and peroxide ions (O2 2−).

By Jozef Zmik, Sergey Dobatkin, Martin Fujda, George Raab, Libor Kraus

"The present work, likewise, deals with grain refinement of medium carbon steel AISI 1045 having different initial microstructure resulting from thermal and/or thermomechanical treatment (TM) applied prior severe plastic deformation. In case of TM treated steel, structure refinement was conducted in two steps. Preliminary structure refinement has been achieved due to multistep open die forging process which provided total strain Eef ~ 3. Uniform and fine recrystallized ferrite structure with grain size of the order of 2-5 µm and with nest-like pearlite colonies was obtained. The further grain refinement of steel samples having different initial structure was accomplished during warm Equal Channel Angular Pressing (ECAP) at 400°C. The microstructure development was analyzed in dependence of effective strain introduced ( Eef ~ 2.5 - 4). Employment of this processing route resulted in extensive deformation of ferrite grains where mixture of subgrains and ultrafine grain was found regardless the preliminary treatment of steel. As straining increases the dynamic polygonization and recrystallization became active to form mixture of polygonized subgrains and submicrocrystalline grains having high angle boundaries. The intensive straining and moderate ECAP temperature caused the partial cementite lamellae fragmentation and spheroidization as straining increased. The lamellae cementite spheroidization was more extensive in TM treated steel samples. The deformation behavior of for both steel structural state confirm the strength increase; however the work hardening behavior was modified with respect to initial structure of steel prior SPD processing.IntroductionIn the last years, ultrafine grained materials have attracted considerable research interest because they tend to possess high strength without sacrificing toughness and ductility. Microstructural refinement of steel is usually achieved by alloying and/or by thermomechanical treatment process, which modifies phase transformation. Recently, advancement of severe plastic deformation (SPD) techniques provides another efficient access for grain refinement of metals and alloys. The fabrication of bulk materials with ultrafine grain sizes has attracted a great deal of attention over the past two decades because of the materials' enhanced properties [ 1, 2]. In last decade a worldwide effort in manufacturing process to obtain ultrafine grain structures in steels is persisting."

Jan 1, 2011

By José Brant, Douglas Torres, Rogério Navarro, Rodrigo Souza, Eduardo Brocchi

The steelmaking process requires the input of ferro-alloys to implement the adjustment of some elements composition in the final product. In the particular case of stainless steel production, the high carbon FeCr alloy stands out as one important precursor. However in the production of this material a certain quantity of fine powder with remarkable chromium and carbon content is also generated, which, in turn, could be processed through alkaline roasting in order to selectively recovery this element in a subsequent aqueous route. In the present work, this process is investigated, using excess of NaOH as oxidizing agent, and H2O2 for precipitating chromium as Cr(OH)3, which is next calcinated to Cr2O3. According to the results, the global achieved recovery has shown to be around 98%, suggesting that the proposed route can be seen as a potential process for chromium oxide production from the mentioned fine powder.

Jan 1, 2015

By Tracey Brommer, Britt Elin Gihleengen, Elsa Olivetti, Randolph Kirchain

"Increased demand resulting from the economic and environmental advantages of recycling secondary materials has constrained secondary material supply. As a result of constrained supply, the conventional strategy to maximize recycled content in an individual aluminum alloy must be expanded to maximizing total recycled content in a given production period. This work compares the performance over a two week period of an actual remelter for two strategies; a sequential charge-by-charge optimization framework and an integrated approach that explicitly incorporates the production schedule. Optimizing across the entire two week production is found to increase recycled content and minimize primary and alloying material additions. It is expected that as the scrap material market continues to be constrained by high demand, longer term batch planning strategies that can optimize material allocation will deliver improved performance.IntroductionIntensifying economic and environmental pressure to incorporate secondary aluminum into products is pushing remelters to explore additional strategies and tools to increase recycled content. Aluminum remelters are exploring alternative sources of secondary materials because of constrained secondary material supply and relatively high primary and secondary material cost [1]. Computational models, such as blending models are a tool that could help industrial remelters mitigate supply and cost challenges and thereby increase recycled content. In particular, computational tools can help manage the incorporation of new raw materials of variable quality. Blending models find many industrial applications and have been explored for over sixty years originating with the classic nut-mix problem dating back to 1950’s [2]. Blending models optimize the raw material input to make a desired product subject to a series of constraints such as product specifications and material availability. Deterministic and linear blending model formulations are presently implemented in some industrial aluminum remelters [3]. The primary reluctance of aluminum remelters against computational model implementation is the incapability of their blending models to reflect the intricacy of industrial remelting conditions [4]. For example, to reduce calculation time, industrial aluminum blending models usually optimize a batch plan for a single alloy and are not formulated to optimize several products simultaneously. Since such a model does not include knowledge of subsequent charges in the optimized batch plan, the resulting batch plans tend to deplete the “cleanest” secondary materials leaving the more uncertain and compositionally challenging materials for later charges. As a result, a remelter may override the calculated batch plan or leave certain scrap materials out of the material input to conserve these materials for alternative products scheduled for later production. This work explores an alternative aluminum charge planning tool that can optimize across an extended production schedule and compares it to a heuristic sequential optimization strategy reflecting an industrial remelter."

Jan 1, 2012

By James A. Voigt

The efficient separation of metal species from aqueous streams by precipitation techniques requires 'a fundamental understanding of the various processes that occur during precipitation. These processes include particle nucleation, particle growth by solute deposition, agglomerate formation, and agglomerate break-up. The application of the population balance approach has been used to develop a kinetic model that accounts for these competing kinetic processes. The usefulness of the model is illustrated through its application to the precipitation of yttrium hydroxynitrate, YHN. The kinetic parameters calculated from the model equations and system-specific solution chemistry are used to describe several aspects of the effect of pH on the precipitation of the YHN. Implications with respect to the simultaneous precipitation of more than one cation type are also discussed through use of example systems: The effects of solution chemistry, precipitator design, and solvent choice are considered.

Jan 1, 1996

By Ronald Klepper

In hydrometallurgy, pure gases like oxygen and hydrogen are used for oxidation and reduction. The gases are expensive and therefore should be used efficiently. Non reacted gas can be recycled into the liquid. Historically vortex gassing has been used; Le. a mixing impeller close to the liquid surface entrains gas from the headspace into the liquid through a gas vortex. Novel and more efficient methods are surface gassing with up pumping impellers and self- inducing gassing impellers. These alternative impeller systems are well established and common in the chemical industry, but have not been used until recently in hydrometallurgy. Gassing impellers act as internal compressors and increase the interfacial surface for a much higher mass transfer compared to alternate methods mentioned. In the paper results from lab and pilot tests and data from operated plants will be presented. The reactions with gases normally take place under moderate to high pressure, therefore a safe enclosure with mechanical seals and the safety "philosophy" is important. Experienced life and replacement cycles will be reported.

Jan 1, 2000

By R. Nilsson

In the present work the sulphide capacities of Ca0-Mn0-Si0, ternary slags have been measured in the temperature range 1798 - 1873 K by equilibrating the slag with a gas-mixture containing CO, CO,, SO, and Ar. The results are compared with the data reported in literature. A theoretical model has been developed in the present work where the sulphide capacity is expressed as a function of the slag composition and temperature. The model enables the estimation of sulphide capacities of complex slags with a knowledge of the capacities of simpler systems.

Jan 1, 1994

By W. Petruk

A study was performed to determine whether mineral textures affect are breakage during grinding, and to establish a correlation between are breakage and mineral liberation. A base metal are from the Brunswick No. 12 deposit in New Brunswick, Canada was ground for different periods of time in a laboratory ball mill, and both the unbroken are and the ground products were studied by image analysis. Similar size distributions were obtained for material from the 15-minute grind in a laboratory ball mill (K. 0 67 pm), for the grinding circuit discharge from a commercial mill (K. 0 = 59-72 pm), and for pyrite grains in unbroken are (K,. = 74 pm). This similarity indicates that the 1S-minute grind separated weakly adhering pyrite grains along grain boundaries, and represents the limit of easy breakage for the are. At this grind (15 minutes) large discrete are mineral grains and weakly adhering interstitial fillings aIrong pyrite were liberated. On the other hand, the 15-minute grind neither separated rooderately bonded pyrite grains nor released rooderate1y bonded interstitial minerals from pyritei a 45-minute grind (K.. 31 pm) in a laboratory ball mill was required. For Brunswick No. 12 are, a 45-minute grind in a laboratory ball mill (Keo = 31 pm) is equivalent to regrinding in a commercial mill (K ?? Fl:$ 30 pm). Grinding beyond 45 minutes in the laboratory ball mill broke the are by fracturing pyrite across grain boundaries and by Chipping grain edges. Such intense grinding (longer than 45 minutes) did not markedly increase sphalerite liberation. In contrast, the intense grinding increased galena liberation because a significant proportion of the galena occurs as minute inclusions in pyrite. These findings show that ore breakage and coincident liberation depend upon size distributions, intergrowths, and mode of occurrence of the minerals in an ore.

Jan 1, 1988

By A. M. T. S. Bandara

The solubility of rare earth (RE) salts in aqueous solutions depends on many factors including the type of cations and anions in solution, their concentrations, temperature and the type of solid precipitated. Experiments were conducted using anhydrous La2(SO4)3 and Ce2(SO4)3⋅8H2O as solids and lanthanum(III) perchlorate prepared by dissolving La2O3 in HClO4 solutions as RE-sources. Solutions of H2SO4, H3PO4 and their mixtures in the presence or absence of Na+, Ca2+, Fe(III) or Al(III) as perchlorates served as test solutions. Saturated solutions and precipitated solids were assayed and characterized using standard techniques to show that the La(III) and Ce(III) ions precipitate as hydrated sulphates, phosphates or double salts with sodium, depending upon the solution composition. The change in solubility of RE-salts with solution composition and temperature is the result of the composite effect of changes in solubility products (pKSP) of salts, pKa of acids and other equilibrium constants for ion-association.

Equilibrium calculational software programs can be effectively utilized to illustrate the importance of activity or concentration, solubility, temperature, solution pH, solution potential, and ligand complexation to students studying hydrometallurgy. The calculational program STABCAL will be demonstrated. illustrative examples for the creation of diagrams such as EH-pH, activity or concentration-pH and activity or concentration-EH will be presented to demonstrate the fundamentals of real hydrometallurgical systems. Speciation, titration and mixing will be used to simulate or predict operational processes. Applications will include treatment of Acid Mine Drainage (Berkeley Pitlake water and sediments), mass balance potential/pH diagrams, leaching and selective separation of metals from electroplating sludge, metal adsorption at femhydrite surfaces, and flowsheet development for treating mercury sulfide K106 sludge.

Jan 1, 2002

By Stephen K. Pave1

Over 1,100 tons per day of Fluid Catalytic Cracking Unit (FCCU) catalyst is used worldwide. During the cracking reaction, catalyst is contaminated by deposited metals including nickel, vanadium, potassium, copper, iron, sodium, etc. To compensate for contaminants, a portion of the circulating catalyst inventory is withdrawn for disposal and fresh catalyst is added. The DEMETR process takes spent FCCU catalyst and removes a portion of the metal contaminants, enabling the refiner to recycle demetallized catalyst, thus reducing the solid waste from the refinery. Through August, 1993, the operation of one unit for one refiner has resulted in the recycling of over 7,500 tons of spent catalyst.

Jan 1, 1994

By William Petruk

Many gold operations lose gold during processing because some ore characteristics which affect recoveries have not been determined, and consequently the plant could not be designed to account for them. The ore characteristics can be determined with mineralogical techniques by analyzing the plant feed, final tailings and mill products. The plant feed and/or final tailings are commonly analyzed first as a separate project. Mill products are analyzed only if the process employs a minerals separation circuit to produce a concentrate (e.g. secondary flotation circuit to concentrate gold-bearing arsenopyrite), and if assays and materials balances indicate a recovery problem in the minerals separation circuit. Many ores have been evaluated at CANMET on a confidential cost-recovery basis by custom-designing a work plan which was dependent upon the problem and on the characteristics of the ore. The reasons for gold losses have been identified in most cases, and suggestions for modifying flowsheets have been proposed. The methods used in performing the analyses are described in this paper, and non-confidential results from in-house projects are provided as examples of the benefits of such analyses. The analytical methodology involves a combination of the following procedures: -producing heavy mineral concentrates and identifying the gold minerals in the concentrates; -determining quantities of invisible gold in gold-bearing sulphides, sulpharsenides, etc. by SIMS; -determining quantities and liberation characteristics of all gold minerals and gold-bearing minerals in the sample; -finding and identifying gold minerals in silicates; -extensive grinding and cyanidation to determine the ultimate amount of cyanidable gold; -determining impact of clay minerals and graphite; -performing a mineral balance for the gold in each sample; -performing a materials balance to determine the distribution of the gold minerals, gold-bearing minerals, and other minerals throughout the flowsheet, and; -interpreting the results.

Jan 1, 1995

By John J. Mazza

Treatability studies were performed to determine the effectiveness of two commercially available treatment methods (solvent extraction and thermal desorption) for the removal of PCBs and PAHs from contaminated dredged riverbed sediments. The solvent extraction method evaluated was the B.E.S.T. process which extracts the contaminants with triethylamine. The thermal desorption method utilized was the ATP process which desorbs the contaminants at elevated temperature in an anaerobic atmosphere. A description of both methods and. an evaluation of the treatability study results is provided. Each treatment method was used to treat two separate samples (high and low concentration) from the site. Overall, both methods proved to be very effective with solvent extraction achieving 98% removal of both PCBs and PAHs and thermal desorption achieving better than 99% removal of both the PCBs and PAHs from the high concentration sample. Both solvent extraction and thermal desorption achieved greater than 99% removals of PCBs and PAHs from the low concentration sample. Vendor cost estimates for full scale treatment were roughly equivalent. The primary differences between the two methods lies in the realm of permitting, operational requirements, and emission concerns.

Jan 1, 1994

By P. R. Taylor

Laboratory experiments have been performed to evaluate the kinetics of roasting pyrite and arsenopyrite in air at elevated temperatures, in the presence of lime. The effects of temperature, time, air flow rate, particle size, lime type, and mineral/lime weight ratio on the rates of oxidation, lime sulfation, and lime arsenation were studied. The reaction products were identified using chemical analysis, x-ray diffraction, SEM analysis, and optical microscopy. The results are discussed in terms of the utilization of lime to capture sulfur and arsenic during the roasting of refractory precious metal concentrates. More than 99.9% of the arsenic and 98% of the sulfur are contained when roasting pyrite and arsenopyrite with hydrated lime under typical roasting conditions.

Jan 1, 1991

By James J. Komadina, Robert R. Beebe

"Heap leaching of gold ores has enjoyed wide acceptance in the arid and semi-arid regions of the western U.S., Australia and South America. There are areas, however, where cold weather or excessive precipitation can limit the usefulness of heap leaching. Even in Nevada difficulties can be encountered which call for special operating procedures.The paper discusses the general climatological limitations and some of the techniques used to extend heap leaching into colder conditions. A case history of the Cripple Creek and Victor Gold Mining Company operation in Colorado examines 'valley-fill"" technology as an ideal cold-climate solution, where topographical conditions permit.AcknowledgementsThe authors gratefully acknowledge the management of Independence Mining Company for their permission to present this paper. The contributions of Golder Associates; Pikes Peak Mining Company Environmental Affairs Department staff, and the Colorado Department of Mines and Geology were all invaluable in successfully concluding this project.BackgroundWhen heap leaching of oxidized gold ores was introduced in the rnid-1970s it was aimed at large tonnages of low-grade material which could not, in general, be developed via conventional milling. Normally, the reasons for this were economic rather than technical: capital and operating costs for milling were simply too high. At first, grade was almost the only criterion, but deposits too small to justify milling were also potential targets for heap leaching.Renewed interest in gold was centered in the western United States and Australia, where exploration for milling-grade deposits had never really died. When heap leaching came along, it was in these areas that the first developments took place. Coincidentally, these same areas were favorable for heap leaching: climates were temperate for most of the year and competing land uses were limited. Even so, in the western United States in particular, winter temperatures were low enough to complicate operations. Precipitation was less a problem, although heavy snowfalls could periodically interfere as well."

Jan 1, 1997

By L. L. Tavlarides, N. V. Deorkar

"Recovery/Recycling of metal ions from industrial process waste streams is a preferred alternative to disposal by conventional techniques. This paper presents methods for preparation of inorganic chemically active adsorbents to be used in fixed bed adsorbers. Methods for immobilization of chelating agents on the inorganic supports are discussed. The prepared adsorbents are characterized to determine coverage density of functional groups, effect of pH on metal ion removal efficiency, regeneration efficiency and uptake capacity. Results from the laboratory scale and bench scale experiments are presented here.IntroductionRemoval of heavy metal ions from processing wastes in various industries is an important problem. Waste streams in electroplating, electronic, catalyst preparation and hydrometallurgical industries contain metal ions such as copper, nickel, chromium, lead, tin, cadmium, silver, gold and platinum. One major concern for the non-ferrous metal industry is secondary recovery of precious metals and cyanide from cyanide leachate from smelter residue and hydrometallurgical waste streams.Recovery methods recently considered include evaporation, electrolyte metal recovery, reverse osmosis (1), adsorption, ion exchange (2,3), membrane separation (4,5) and Solvent extraction. These processes have met with various levels of limited success. The use of liquid ion exchange molecules to selectively extract metal ions for on-site treatment of these waste streams is currently receiving substantial interest (6,7). This interest seems from an awareness of the advances made in the development of commercial extractants for metal ion separation in hydrometallurgical industries (8). However, separation by solvent extraction processes is generally considered to be economical in the range of aqueous metal ion concentrations from 0.01 to 1.0 mol/lit (9). In order to exploit the selectivity of chelating agents, the idea of immobilizing chelating agent into a solid matrix has attracted growing attention in recent years. Many supports such as inorganic oxides, organic polymers, cellulose powder and polyurethane foam can be used for immobilization of chelating agents. Over the last decade, considerable efforts have been directed toward attachment/introduction of chelating agents into a polymer matrix (10,11). Inorganic supports as compared to polymer supports provide high mechanical strength, chemical and thermal stability, and high reaction rates due to open pore structure. On the contrary, organic resins shrink and swell, thus affecting mass transfer (12). Many of the disadvantages of polymer supports can be excluded by the use of inorganic supports. Innovative use of immobilization techniques can produce inorganic chemically active adsorbents with comparable capacity, stability and reaction rates. Consequently, the objective of our program is the development of inorganic chemically active adsorbents to be used in a fixed-bed unit operation as an alternative heavy metal ion recovery process. Methods of preparation of inorganic chemically active adsorbents, (ICAAs) characterization and applications are discussed in this paper. A brief summary of the results from laboratory scale studies and bench scale studies is presented."

Jan 1, 1996

By Guilian Gao

TbFeCo is a common choice for many rare-earth transition metal films currently used as the magneto-optic layer for magneto-optical: recording devices. Since the environmental stability of RE-TM alloys is typically poor compared with traditional metal oxide particle media, such devices rely on multiple functional overlayers (metallic and/or dielectric) and organic coatings for durability. This paper presents an electrochemical evaluation of the degree of protection of several candidates for the reflective layer, Al, AlCr and AIPt and for the dielectric layer, SiN, AISIN and AIN. Cyclic voltammetry In 0.2M K2SO4 solutions at room temperature revealed that AIPt film offers superior corrosion protection compared to Al and AICr films. Of the three dielectric layers examined, SIN seems to be the most corrosion resistant. Examination by optical and scanning electron microscope confirm the findings of electrochemical experiments. The corrosion resistance of single layers of Al, AICr and AIPt has also been examined and factors affecting their performance are discussed.

Jan 1, 1992

By Vianey Garcia-Osorio

One of the problems in the carbothermic aluminum process is the substantial loss of aluminum compounds as vapors due to the high temperatures in the process. In order to solve this problem a Vapor Recovery Unit (VRU) is proposed. In this unit operation the aluminum vapor undergoes a series of heterogeneous non-catalytic reactions forming solid, liquid and gas products. In this work a model for the simulation of this unit was developed which includes heat and material balances as well as heterogeneous non-catalytic reactions. The model leads to a system of differential equations; its solution was implemented in Matlab giving as a result a stage-by- stage solid-fluid reaction model.

Jan 1, 2001

By C. L. Lin

Multiphase, irregularly-shaped randomly-oriented PARGEN particles were grown to determine the breakage/liberation characteristics of such locked particles. The simulated locked particles were randomly broken to establish the liberation characteristics of the broken fragments. The progeny size distributions are consistent with Gilvarry's volume and surface flaw model for single particle breakage. The extent of liberation of both continuous and dispersed phases can be described from the conservation of interfacial area. In this regard the data can be normalized and liberation described for a wide range of dispersed phase grades and dispersion densities.

Jan 1, 1988

By Xiangwen Wang

Electrochemical measurements associated with the electrowinning of lead metal from concentrated brine (NaCI) - lead chloride (PbCI,) electrolytes at temperatures in the range 328 to 353°K (55 - 80°C) were conducted. The electrodeposition of lead metal onto a lead rotating-disk electrode may be described by the electrodic reaction: {PbCl 4 2 + 2e- = Pb° + 4Cl-} The deposition-overpotential requirements are low (approximately 41mV per decade of current density - Am+), with a corresponding high exchange current (approximately 0.018 A.cm2). The diffusion coefficient of the electroactive PbC142- species in a 3.5 NaCl electrolyte at 353°K was insensitive to the total PbCI, concentration (0.01 to 0.1M), and its value was found to be (1.21*0.1)~10-5 cm2Is with a temperature-sensitivity coefficient (E,/R) of approximately 1.98x103K-1 (328OK(T<353OK).

Jan 1, 1993