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By Stephen W. Paff

The EPA has estimated that there are over 3,000 sites across the United States contaminated with lead. Techniques to remediate these sites include standard stabilization/disposal technologies, reclamation of lead using secondary lead smelters, soil washing, and biological removal technologies. In this paper, the current technologies used for lead remediation will be reviewed. Factors affecting the use of each technology, such as range of applicable concentrations, soil types, interferences from other contaminants, economics, and current technology status will be assessed. The paper will also focus on the results of a recent study completed by the Center for Hazardous Materials Research (CHMR), in conjunction with a major lead smelter, which demonstrates that secondary lead smelters may be used economically to reclaim lead from a wide range of lead-containing materials frequently found at Superfund sites. Such materials include battery case materials, lead dross, and debris containing between 3 and 70% lead. The results of development work completed by CHMR on the Acid Extraction Treatment System (AETS), which has been demonstrated to extract Lead from soils containing up to 30,000 mg/kg lead, will also be presented. The use of these technologies will be compared with other options for the remediation of sites.

Jan 1, 1994

By Devon A. Hannan

Thermodynamic modeling calculations were undertaken for the recovery of mercury from HgTe using a vacuum retort reactor. However, discrepancies were noted in the available thermodynamic data which introduced uncertainty in the model results. Consequently, a series of transpiration experiments were first undertaken on the thermal decomposition of HgTe into an inert carrier gas stream according to the following reaction: HgTe(s) Hg(g) + Te(s) From the measured weight loss of the HgTe samples, the Gibhs free energy change for the above volatilization reaction was determined as a function of temperature. The experimentally determined Gibbs free energy values were found to be approximately 30% larger (more posi-tive) than the values available in databases such as HSC Chemistry. By conducting a second-law analysis on the experimental data, the heat of formation of HgTe at 298.15 K and the en-tropyat 298.15 K were determined, which then formed the basis for a new database for the modeling calculations. The results of this study showed that HgTe was more stable at elevated temperatures than was generally indicated in the literature. The new database is given in a for-mat for direct insertion in HSC Chemistry. Using the new database, modeling calculations were conducted to examine the effects of the re-tort pressure and the molar ratio of purge gas to HgTe on the volatilization of mercury from HgTe. A diagram is presented that shows the minimum temperature for 100% volatilization of mercury from HgTe as a function of retort pressure for different molar ratios of purge gas (N2) to HgTe. For example, it was found that the minimum temperature for 100% volatilization could be decreased by 175 K, at a retort pressure of 0.05 bar, if the molar ratio ofN2 to HgTe is increased from 1.0: 1 to 100.0: I.

Jan 1, 2003

By Gaballah I.

Elimination of arsenic, mercury and zinc from synthetic solutions containing H;\A.sD4. HgCI2 and ZnCI2 using modified barks was investigated. The pH range was varied from ?1 to 10. The initial concentrations of individual element were 10,100 and 1000 ppm. More than 99 % of mercury and 65 % of zinc cations were removed by the modified bark .. In this case, the modified bark reacts as a cation exchanger leading to the release of ' two protons for every HgII or ZnII fixed by this material. About 30 % of arsenic was eliminated from the solution. This 'low efficiency could be attributed to? the presence of arsenic ,as. anion. Decontamination of a treated industrial effluent containing 4 ppm of ion? metals was performed on a pilot plant scale by the modified bll(k. More than 70'% of these ion metals were eliminated.

Jan 1, 1995

By Gabriel Riveros

Fire refining of copper consists of two stages copper oxidation and copper reduction. Very frequently the capacity of the anode furnace is determined by the rate of copper reduction. The analysis of factors affecting the rate of the oxygen reduction from a liquid copper with solid carbon or injected hydrocarbons pointed out the role of the mass transfer in a liquid copper in final stage of the reduction. Experimental results of copper reduction with graphite and injected natural gas in laboratory- scale crucibles showed two stages of the reduction process with a sharp change of the controlling mechanism. The estimated dynamic surface area of gas bubbles based on the measured bubble frequency and the gas flowrate allowed for the detennination of the reaction constant as a degree of the partial pre-combustion of the air/natural gas mix. The variation of the used reductant as a function of the oxygen concentration and temperature has been evaluated based on the detennined kinetic model. The intensification of copper reduction in fire refining has been discusses on the basis of obtained kinetic data and analysis of various factors detennining the time of reduction.

Jan 1, 2003

By David Tisdale, Phillip Mackey, Nagendra Tripathi, Matthew Kreuh, Pascal Coursol

Xstrata Nickel’s Sudbury smelter operation is based on fluid bed roasting of Ni-Cu sulphide concentrate, followed by electric furnace reductive smelting and Peirce-Smith converting to produce a Bessemer matte for electro refining, along with sulphuric acid produced from smelter gas. While the site dates back to the 1930s, the present smelter configuration has been operational since 1978, and currently has a nominal capacity of about 67,000 tpy of contained nickel and is investigating options to expand in future up to 85,000 tpy. As part of a review of plant capacity options, a new metallurgical model of the plant was developed in order to examine a number of processing alternatives. Based on the METSIM™ platform, the present model includes the ability to examine the impact of a number of plant parameters on potential plant performance including; for example, the following: percent of sulphur elimination in roasting, matte grade, degree of matte metallization, temperature, coke requirements, sulphuric acid production, CO2 emissions and overall energy requirements. The process model also includes a number of special features adopted; for example, approaches to effectively model the complex Ni-Cu-Co-Fe-S-O matte system. This paper provides a description of the model and gives an overview of the results. As well as presenting the results of the present study, the applicability of this modeling approach to pyrometallurgical systems in general is also briefly discussed in the paper.

Jan 1, 2009

By Christopher M. Moore

DK Recycling und Rohelsen GmbH converts 380 000 annual tonnes of iron containing waste materials Into pig Iron. Zinc Is the main reason that these materials are classified as waste. The materials are processed In the conventional way by making sinter which is then smelted in a blast furnace to foundry grade pig iron. The trick lies not in the unit operations which are quite standard but rather In the modifications made to the plant and operating procedures to cope with the much higher levels of tramp elements.

Jan 1, 1995

By E. Ilgar

"Deposition studies were conducted in acid copper electrolyte to determine the influence of chloride ions on cathode morphology. A statistically designed screening test was carried out in the absence and presence of 20 ppm CI- using a three factor, two level factorial design, in an electrolyte containing 36 gl'! Cu2+ and 150 gl-! H2S04, The independent variables evaluated were agitation; current density and temperature and their influence on surface roughness was determined. The copper deposited at current densities where activation was the primary control mechanism appeared similar in morphology whether stirring was used or not. The addition of 20 ppm CI- to the electrolyte gave rougher deposits under the same conditions. In the mixed control regions, considerably rougher, dendritic deposits were obtained when CI- was present. Agitation was effective in reducing the copper surface roughness both in the apparent activation and mixed control regions in the presence ofCI-. The results of this study showed that 20 ppm Cl- polarized the copper deposition at low overpotentials but caused depolarization at higher overpotentials.IntroductionChloride ion is inherently present in copper electrolyte, either as an additive or from other sources such as make up water. The behavior of the chloride ion is well documented in electrorefining operations, but its role in copper winning is less obvious. However in both cases there is evidence that cathode growth and solution chemistry are strongly influenced by its presence. The mechanism and electrochemical action of the Cl"" have been shown to be very complex, therefore a better understanding of its influence on electrocrystallization is essential for improved cathode deposit growth control. It was proposed that Cl"" polarizes the copper deposition reaction at low concentrations due to CuCI formation but depolarization occurs at higher concentrations due to the formation of a soluble CuCI2"" complex [1,2]. Franklin [3] reviewed the mechanism of additives in the electrodeposition process and proposed that the Cl"" complexed with copper, adsorbed on the cathode as an induced anion leading to an increase in the reduction rate. At cathodic overpotentials less than 100 mY, lppm NaCl had a polarizing effect, i.e. an increase in impedance of the charge transfer step. At higher Cl"" concentrations up to 100 ppm, depolarization occurred as evidenced by a decrease in impedance, which was attributed to soluble cuprous complexes [4]."

Jan 1, 1997

By Zhi-biao Yin

Copper smelter flue dusts often cannot be directly recycled to the smelting process and accumulate as hazardous wastes requiring environmentally acceptable disposal. Because of the limited amount of flue dust, a separate copper extraction process must be simple and require-a small plant investment. A flue dust process has been developed, consisting of the following steps: (1) roasting a pelletized mixture of hydrated lime and flue dust to fix arsenic and sulfur as insoluble calcium salts, (2) heap leaching the roasted pellets with a buffered ammonia/ammonium salt solution to extract copper as an ammine complex in a lined cell that is the final repository of the leached pellets, and (3) boiling ammonia from the lixiviant to precipitate copper. Condensed ammonia and the filtered solution are returned to leaching. Heap leaching in the final repository cell lowers the capital investment significantly compared with competing extraction processes. Chemistry with respect to arsenic, sulfur and copper is discussed.

Jan 1, 1992

By Norimasa Yamasaki, Masao Kurosaki

"The effects of plating conditions on the crystal orientation of electrodeposited zinc were investigated by varying elecyrolyte flow rate and current density. Precipitation of the Zn (00 • 2) basal plane is promoted at lower current density and higher flow velocity. Effect of the flow velocity on the mass transport was evaluated based on the polarization measurement in which Cu was used as the tracer. As a result, it has been clarified that the crystal orientation of electrodeposited zinc can be uniquely arranged by the overvoltage (iU0.5) that can be simply calculated by considering -the current density and boundary layer thickness. At the same time, the electrode potential during electrodeposition that can be calculated by using a model based on the competitive reactions of hydrogen reduction 'and zinc reduction exhibits an extremely good correlation with the crystal orientation of electrodeposited zinc.Introduction Electrogalvanized steel sheet has better surface properties than hot-dip galvanized steel sheet, and is used in home electric appliance and automobile applications. Factors such as crystal morphology, crystal orientation and surface roughness have a large influence on its appliance, formability and corrosion resistance [1-3].Electrolysis, condition, bath composition and alloying elements are reported as factors that affect the crystal orientation of the electrogalvanized coating. Factors that can be controlled on time in the production site are electrolysis condition that-is current density and plating solution flow velocity.Some studies[4-6] report that the crystal- orientation of the Zn(00 • 2) plane is increased by promoting, the mass transfer of zinc ions in the plating solution or decreasing the concentration overvoltage, but did not investigate in detail the plating solution flow conditions in the plating cell nor quantitatively determine the effects of both current density and plating solution flow conditions on the crystal orientation of ' electrodeposited zinc."

Jan 1, 2000

By Maija-Leena Metsiirinta

The behaviour of copper and lead in zinc roasting has been studied in laboratory scale roasting experiments as well as in large scale trials in an industrial fluidized bed, with the background of Outokumpu Kokkola Zinc smelter. Commercial zinc concentrates with a low and high ( up to 3 wt % ) copper content and with a low and high ( up to 3.5 wt % ) lead content were oxidized to various desulphurisation degrees in the fluidized bed to establish the reaction mechanisms and the paths for copper and lead oxidation in the roasting. Influences of the agglomerate size on the roasting kinetics and micro- scale phenomena were also determined. Optical microscopy was used on the calcine and the findings are presented as numerous photographs of the polished cross sections. SEM/EDS techniques were used for analyzing chemically the phases and particle morphologies present in the samples. Computational thermodynamics was applied to the complex phase equilibria occurring during roasting in the agglomerating calcine. A complete oxidation of zinc concentrate with a high copper and lead content requires a careful control of oxygen coefficient in the roasting in order to maintain a stable operation of the fluidized bed. Oxygen coefficient thus seems to have a significant impact on the hydrodynamic stability of the fluidized bed with fine raw materials.

Jan 1, 2003

By R. Hurman Eric

The electrode in a slag-resistance electric furnace is the central factor in the design and operation of the furnace by its role of conveying the smelting power, i.e. heat needed for the operation. The control parameters are the size and positioning in the slag bath which are defined by slag resistivity, furnace resistance, cell constant and power input sequence all of which are closely interrelated. The flow of heat generated by the electrode current determines the energy distributions and thus the furnace dimensions. Heat flow models concerning vertical, horizontal and combined two-dimensional flows are discussed. All these considerations are based on the experimentally determined slag properties such as its resistivity.

Jan 1, 1995

By Manfred K. Walther

"Tests were conducted on instrumented plates cast in the Abex Experimental Foundry to compare recorded solidification histories with results computed for corresponding models simulated with the C.A.S.T. program. The first plate was cast of low alloy steel and the second of carbon steel with a graphite chill at one end. Both were cast in molds of bonded silica sand. Temperature histories were recorded in the castings, molds and chill. Exceptionally good agreement was achieved between computed and experimental data. Other investigators will find the results useful as a benchmark against which they can compare the results of their own calculations.IntroductionSince the early 1970's our foundry engineers have used both two- and three-dimensional versions of the G.A.S.T. program to gain knowledge of the solidification process [1,2,3]. Study of the computed data gave insight as to how the rigging and risering of specific castings might be changed or adjusted to improve quality and yield. New schemes based on such analyses were then recommended for implementation on the foundry floor. The degree of success of the new practice was subsequently evaluated after the part had been poured, shaken out and examined. Similar conditions were noted in the sectioned castings whenever porosity and voids had been predicted by the computations. Appropriate modifications, when found successful in the model, were applied to the process. This led to a reduction, if not complete elimination, of the defects. Such results gave credence to the use of these programs as an aid in the production of better castings.Earlier investigations on simple shapes revealed excellent correlation between output derived with the G.A.S.T. program and exact solutions. Results also compared favorably with data calculated using other codes as reported in the literature [4] and summarized in the Appendix. However, since the computer program had not been verified by direct experiment, it was decided to run instrumented tests to check the theoretical predictions with actual measurements."

Jan 1, 1986

By Faustino G. Prado

In the, quest for an economical and environmentally friendly reclamation of metallurgical dusts generated during pyrometallurgical operations, our goal has been the separation and recovery of most of the components, as well as the complete recycle of all the reagents. Effluents have been avoided, within acceptable economic parameters. This presentation, which can be applied to a large spectrum of dusts and other residual-materials-, has focused on the dusts generated by the operation of Secondary Copper Smelters. Those dusts show a wide range of components, including zinc, lead-, copper, cadmium, tin, chlorine and-alkalies. Our present work deals with the use of ammonium salts in the separation and recovery of-the above mentioned elements in a marketable form. Most of the chemistry and techniques involved have teen already confirmed in commercial scale operations. Others have gone through pilot scale tests or bench scale tests. The recycle of reagents has also been- confirmed at the same operating levels. A preliminary evaluation indicates that the chosen route, in addition to a viable economy, offers a complete and safe reclamation within the most strict environmental regulations.

Jan 1, 1995

By Jie Ma, Shun-Li Zhao, Jian Zhao, Jie-Yu Zhang

"Microstructural morphology evolution of Ni-45wt.%Mo droplets during rapid solidification process was investigated using an advanced modified 3D cellular automaton-finite element(CAFE) model by CALCOSOFT software. The model was modified by User-defined functions (UDFs) and validated with experimental solidification microstructural morphology of Ni-45wt.%Mo droplets available in the literature. Then, the influences of convection heat transfer coefficient, superheat of the alloy droplets and droplets size were investigated during the rapid solidification process. The predictions show that microstructural morphology is obviously sensitive to convection heat transfer coefficient and droplet size. With the decrease of convection heat transfer coefficient, the grain density decreases. In addition, the decrease of the droplet size could obtain refined microstructure. However, decrease the superheat ofNi-45wt.%Mo droplets has little effect on microstructural morphology.IntroductionFor several decades, much attention has been paid to undercooled alloy droplets of rapid solidification process for which can obtain refined microstructure, decreased microsegregation and extended solubility of alloying elements [1-3]. Extensive prior work shows that solidification of droplets plays an essential role in advanced material properties [ 4]. Consequently, it is very important to investigate the microstructural morphology evolution, especially for dendrite growth during non-equilibrium solidification process, for dendrite growth reflected the kinetics of the crystal growth process."

Jan 1, 2013

By G. B. Harris

Jaguar Nickel Inc. is developing the Sechol Nickel-Cobalt Laterite Project in Guatemala, Central America. Recognizing the potential advantages offered by chloride brine chemistry, Jaguar, at the facilities of Process Research ORTECH Inc, Mississauga, has developed an Atmospheric Chloride Leaching Process using a mixed chloride lixiviant to recover the nickel and cobalt, whilst leaving the majority of the iron and magnesium in the leach residue. Subsequent solution purification and mixed nickel/cobalt hydroxide product recovery is by standard precipitation methods, using recycled caustic magnesia, with a final stage of pyrohydrolysis of a portion of the concentrated magnesium chloride brine for recycling both the caustic magnesia and chloride lixiviant. The flowsheet that has been developed also offers opportunities for by-product recovery and efficient, environmentally clean process effluent management. The paper discusses some of the early leaching results in the context of strong chloride brine chemistry, with emphasis on how the controlling of water activity, hydrogen ion activity and chloride concentration permits the selective leaching of nickel and cobalt from an iron-magnesium matrix. Keywords: nickel, cobalt, iron, magnesium, Sechol, Guatemala, chloride, pyrohydrolysis

Jan 1, 2004

By Fuming Wang, Lifu Hu, Changrong Li, Ruipeng Pang

The solidification structure of 430 ferritic stainless steel has been calculated in the solidification process by using 3D-CAFE model under the condition of water cooling. The calculated results consistent with those obtained from experiment. Under watercooling condition, the solidification structure consists of chilled layer, columnar grain zone, transition zone and equiaxed grain zone

Jan 1, 2015

By Zhao Guangwen, Wu Tan, Qiuzhan Tian, Duan Shuzhen

"A thorough study of lost currents in bipolar cells has been made for the development of the great potential of bipolar cells in energy saving. A proper equivalent circuit for bipolar cells has been found, and mathematic methods for computing lost currents at all kinds of polarization have been developed.At linear polarization, the lost currents can be computed by solving either a tridiagonal matrix or an ordinary differential equation of second order. This kind of values can be used to evaluate the minimal lost currents at given conditions. At other kinds of polarization, the lost currents can be computed by the same methods as above if the necessary experiments of measuring the cell voltages of every electrolytic compartment have been made. This kind of values can be used to design bipolar cells at practical conditions.Extensive experiments have been made to evaluate the effects of electrode polarization, emf of galvanic cell for the formation of electrolyzed substance, gaseous products, geometric dimensions of electrolytic cells, special resistance of electrolyte used, and the total and ordinal number of electrolytic compartments on lost currents. It is the first time to make such a systematic research by experiments in the world. Experiments showed that theoretic models were in good agreement with measured data. Experiments also showed that D.C. energy consumption of 0.45 kwh/kg of Pb for lead electrolysis from molten chlorides could be achieved in a cell with 7 bipolar electrodes.IntroductionIt is very promising to apply bipolar electrolytic cells to electrolysis of aluminum, magnesium, lead, zinc and perchlorinates for their great potential of energy saving for example, bipolar cells had been used in the production of magnesium and saved more than 30% of energy, being one of the three main techniques of energy saving in the production of titanium sponge (1)."

Jan 1, 1988

By T. Asahina, M. Nakamura, M. Mabuchi, I. Shigematsu, M. Nakanishi, G. Yamauchi

"Commercial stainless steels (SUS304L and SUS430) were subjected to equal channel angular extrusion (ECAE) at room temperature to a total strain of 2.3 to 9.2. For each type of stainless steel, it was shown that the sample processed by ECAE showed higher room temperature strength than the as-quenched sample. This is probably due to the heavily worked structure. On the other hand, both strength and elongation of the ECAE processed SUS430 were increased by annealing at 773K. It is likely that higher strength is attributed to both the heavily worked structure and fine substructures. It is also likely that higher elongation is attributed to the fine substructures. It is concluded that ECAE is available for improving the room temperature strength of commercial stainless steels.INTRODUCTIONEqual channel angular extrusion ( ECAE ) is a technique that provides the repetitive deformation and allows to high intensity of deformation. With this procedure, a sample is pressed through a channel that has an equal cross section but bent at an angle of ?> [1-2]. Shear strain is introduced when a sample passes through the bending point of the channel. Repetitive processing is feasible because the cross-sectional dimension of a sample has no change during processing. To date, many reports have described that ECAE is available for the fabrication of fine-grained materials [3-14]. On the other hand, an ECAE processed sample can achieve high intensity of deformation through repetitive deformation. According to the equation given by Segal [ 2 ], a strain of about 1 is introduced in each pass through die if the angle ? is 90 deg.It is well known that high tensile strength can be achieved in metallic materials through work hardening [15]. It is also known that metallic materials with fine grain size show high strength [16]. Hence, it is expected that ECAE is available for strengthening method in metallic materials. In the present paper, we will report the mechanical properties of stainless steels processed by ECAE. As samples, SUS304L austenite stainless steel and SUS430 ferritic stainless steel were chosen. Each alloy has a single-phase structure (fee or bee) and shows no phase transformation, so that transformation strengthening cannot be applied. Hence, a heavy cold work such as ECAE may be effective for strengthening of this stainless steel. Annealing was conducted for the ECAE processed SUS430 to vary its microstructure. Then, the effect of annealing on the strength of the ECAE processed SUS430 was also investigated."

Jan 1, 2000

By Stavros A. Argyropoulos, Henry H. Hu

"The assimilation of exothermic additions in liquid metals exhibit an array of unique coupled heat, mass and momentum transport phenomena. These phenomena are further complicated by the presence of a moving boundary.This paper describes a) A mathematical model which simulates the complex phenomena, and b) An extensive verification of the mathematical model. The SIMPLER algorithm was employed to solve numerically the pertinent partial differential equations. The computational results indicated that the exothermic heat of mixing led to a rapid increase in temperature around the moving boundary, which produced an enhanced convective flow in the liquid phase. The intensification of fluid flow around the moving boundary resulted in an acceleration of the melting process.Verification of the model was carried out in two contexts. The first was, in a low temperature physical model consisting of ice immersion in different sulfuric acid solutions. In this physical model, both temperature and velocity measurements were carried out. The model results were compared with experimental measurements and they were found to be in excellent agreement. The second context employed high temperatures, involving the assimilation of silicon in high carbon liquid iron. The model was also applied to predict fluid flow, heat and mass transfer for these high temperature experiments and a good agreement was obtained.In addition new dimensionless heat transfer correlations that quantify these complex phenomena will be presented."

Jan 1, 2001

By Donald L. Stewart, Ken Overfield, Edward M. Williams

"Recent increases in energy cost have lead to a renewed focus on energy efficiency during aluminum melting operations to reduce fuel usage. The goals of a batch melting operation are to melt the charge using the minimum required energy, to melt the metal to the required temperature within the required timeframe, and to avoid generating unwanted contaminants by overheating the charge.The heat transfer efficiency of a conventional hydrocarbon fired aluminum melting furnace varies over the course of the melt cycle, depending on the conditions in the furnace. The purpose of this work was to develop a method of determining the transient heat transfer efficiency throughout the furnace cycle and to take advantage of this knowledge to optimize the melting process through furnace controls and proper production operations. This furnace survey methodology has been developed and used to evaluate a number of furnaces.Description of a Typical Batch Melting Furnace CycleA typical batch melting furnace cycle will consist of three stages:1. Charging – Solid metal charged through an open roof, solid or molten charged through an open door, and/or molten poured through a furnace blister2. Melting – From the time the door or roof is closed and the burners are turned to high fire until the charge is all liquid and has reached a temperature suitable for alloying (typically ~1350 °F / 730 °C)3. Holding – From the end of the melting stage until transfer or casting is completeIn some cases, further charging can take place after the melting cycle has started. This can happen when the entire solid charge will not fit in the furnace in one load, or if additional molten metal is added while the charge is melting. The bulk of the energy used in the melter is consumed during the melting cycle. The thermodynamic minimum energy requirements for melting pure aluminum are:• Energy required to heat pure aluminum from room temperature to the melting point at 1220°F (660°C) is 288 BTU/lb (670 kJ/kg)• Energy required to change state of pure aluminum from solid to liquid (heat of fusion) is 171 BTU/lb (397 kJ/kg)• Energy required to heat molten from melting point at 1220°F (660°C) to 1350°F (730°C) is 36 BTU/lb (83 kJ/kg)• Total energy required to melt a solid charge from room temperature to 1350°F (730°C ) is 495 BTU/lb (1151 kJ/kg)"

Jan 1, 2009