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By R. H. Crist

Reactive components of algal cell walls include uronic and alginic acids: In addition, many marine species have half ester sulfate groups which function as fixed anions. Associated metals vary with the media, eg., Ca and Mg in fresh water (FV) and Na, Ca, Mg in seawater. . These metals readily exchange with aqueous phase protons or metal cations. A plot of the total amount of metal cations displaced by protons vs .. pH shows one inflection at pH 4 for FV algae and' in addition a second inflection at pH 2, 3 for marine algae. The first inflection is interpreted as. Indicating the cations associated with carboxyl groups ,and the ,second with half ester ?Sulfate groups. The exchange capacities of various aigal ,species vary widely. When FV algae is placed in a Pb2+ solution,- the amount of Pb2"' deposited on the algae is. Equivalent to the. Total Ca2?, Mg2, and H+ displaced? thereby confirming the ion exchange mechanism. Ion exchange equilibrium constants are reported for the displacement of ca2+ from Vaucheria. With Mg2+, sr2+, Cd2+, Pb2+_ and Na+ as well as the reverse reactions. Cd2+ can .be removed partially from algae by precipitating it as CdS or Cd(OH) 2 Pb2+ and Cu2+ are also partially removed as the hydroxides. Rates of reaction for various alkali hydroxides decrease with increasing .unhydrated cation radius. It is concluded that theory is useful in predicting viable applications for algae in pollution abatement.

Jan 1, 1991

By Andrew Case

The Port Nickel facility in Braithwaite, Louisiana, is known for pioneering hydrometallurgical processes for the 'separation and recovery of nickel, cobalt and copper. Ten years ago, in 1985, a new CRI-MET process for the recovery of molybdenum, vanadium, nickel, cobalt and alumina from spent catalysts was developed and implemented. Spent- catalysts from the petroleum industry consietute the majority of feed. These are not only a valuable-source of metals, but due to EPA regulations are frequently classified as hazardous under RCRA. Molybdenum and vanadium are selectively leached in an oxidative hydrothermal step. Alumina is then extracted in a caustic digestive leach. The unique technology produces four primary commercial products l molybdenum trioxide, vanadium oxide, aluminum trihydrate and nickel-cobalt concentrate. This paper discusses the process, modifications. during ten years of operation, and the relationship of these modifications to the future of the catalyst recycling business.

Jan 1, 1995

By Xun An

Slag from an electric slag cleaning furnace was injected with methane and air mixtures to facilitate the recovery of copper and cobalt. The effects of methane-to-air ratio, gas flow rate and temperature on the reduction and metal separation were investigated. The results showed that over 90 percent copper and up to 60 percent cobalt could be recovered from the slag with a gas utilisation of around 70 percent, as calculated by thermodynamic simulation. Methane-to- air ratio was a major factor affecting the rate of reduction under the present experimental conditions. Further, injection of gaseous reductants greatly enhanced the coalescence and settling of entrained metal droplets. A reduction mechanism is proposed and the factors influencing the coalescence of copper droplets are discussed.

Jan 1, 1998

By A. Treverrow, G. A. Brooks, H. K. Worner

"The work by H.K Worner and co-workers at CRA in the 1960s, and early 1970s, established that molten metals could be refined continuously utilising counter current flow of metal and slag. Womer also demonstrated that counter current refining could produce highly refined metal products. These developments coincided with the advent of high intensity metallurgical reactors in both the ferrous and non-ferrous industries (e.g. BOS, Q-BOP and later Sirosmelt) that utilised high levels of gas injection to produce rapid stirring and very fast reaction. These new generation of high intensity metallurgical reactors allowed high tonnage rates through relatively small volume vessels.Whilst, it is well known that the counter current flow of reacting phases offers the potential of efficient mass transfer and high purity products, the application of counter current reactors to molten metal/slag systems has been criticized on the basis that they suffer from either low intensity or, alternately, from poor refining due to excessive dispersion. These criticisms relate to the balance between intensity and the refining capacity of a reactor. That is, whilst high levels of mixing transversely to the direction of flow promotes high mass transfer, longitudinal mixing (dispersion) is detrimental to refining. Of course, mixing in one direction invariably leads to mixing in other directions, thus creating a playoff between high mass transfer and excessive dispersion.This balance between intensity and refining has been the subject of recent studies overseas, and at"" the University of Wollongong, using cold modelling techniques to evaluate the effect of mixing on dispersion in a counter current refining launder. These studies have shown that for a given geometry and mixing regime, dispersion decreases with increasing flow of liquid phases. This means that whilst high mass transfer cannot be achieved in a refining launder without sacrificing the degree of refinement, there is no impediment to achieving high productivity through such a system, in fact, high through puts may favour good refining. Thus, it may be possible to match a high productivity smelting operation with a equally productive counter current refining stage."

Jan 1, 1996

By A. Kar

A mathematical model is presented for pure titaqium deposition from titanium tetrabromide on a stainless-steel (SS 304) substrate. Five three-dimensional, transient, and nonlinear partial differential equations are used to account for the diffusion of various species inside the deposition chamber and the thermal decomposition of titanium tetrabromide, titanium dibromide, and titanium monobromide at the surface of the substrate in order to determine the thickness of the titanium film deposited on the substrate. The effects of various process parameters on the deposition and shape of titanium films are examined, and under certain conditions, the deposited titanium films are found to have volcanic profiles.

Jan 1, 1992

By N. Kanari

One of the criteria to define the market value of chromite concentrate is its chromium to iron ratio. Changing this ratio for a definite chromite mineral is impossible by physical processing. This study investigated the possibility of increasing this ratio through the carbochlorination and the oxychlorination of chromite concentrates. Experiments are carried out up to 1000 °C. The characteristics of samples and reaction products are determined by SEM, XRD and chemical analysis. The carbochlorination of a chromite concentrate at about 600 °C leads to the . selective partial elimination of iron allowing a higher Cr/Fe ratio of the treated concentrate. Selective extraction of iron could also be achieved at about 950 °C by oxychlorination. In this case, a part of chromium contained in the concentrate is recovered as chromium oxychloride. The obtained residue had high content of Cr, Mg and A1 oxides. Such material has probably better chemical and thermal properties that may. be useful for foundary and refractory applications. Two flow-sheets for the beneficiation of the chromite concentrates using carho- and oxychlorination are suggested.

Jan 1, 1997

By Barry Welch, Kai Grjotheim

"The capital intensive nature of the present process for aluminium smelting, the low productivity per unit reactor, and pressure to reduce the electdcal energy demand have motivated the search for an alternative process. Optional routes include carbo-thennal reduction of alumina (using an alloy phase immediate), chlorination followed by electrolysis of aluminium chloride, and electrolytic decomposition of alumina using inert electrodes. Materials performance and reactor design constraints have been a major limitation for alternatives. However parallel research has led to considerable advances in the process efficiencies and scale of both the Bayer process and the Hall-Heroult cells.Future development of alternatives is dependent on breakthroughs in Materials Science such as the development of stable conducting anodes and stable wettable cathode materials. However if successful it is probable that some spin-offs will be retrofitted to existing cells. Therefore the basic Hall-Heroult technology will continue as the dominant process for at least the next half century.IntroductionThe present Bayer/Hall-Heroult process for production of aluminium is just over 100 years old. Frequently, during the century of its technological development questions have been raised as to whether it is the ideal route for metal production. The questioning was particularly intense in the period between the mid-1950s and the mid-1060s when the limitations of the Hall-Heroult electrolytic stage were evident. Then the cells were only 30 to 35 % efficient with respect to the utilisation of the hydro-electricity (requiring 16 18 kWh/kg, thus making it strongly dependent on cheap electrical energy), while the size of cells being installed were 80 to 130 kA. Hence the process was capital intensive, the productivity per reactor volume low, and the process was labour intensive (requiring about 15 man hours per tonne of aluminium). In addition, the use of pitches for Soderberg anodes and the fluoride electrolyte were creating problems through emission. At that time material science had paid little attention to the manufacture and use of carbonaceous materials or the development of alternatives that were corrosion resistant to cryolite or liquid aluminium. Hence cell lives were short - typically 600 to 1000 days - thus adding to operating costs. Thus the grass over the fence, as foreseen in 1960s vintage crystal balls appeared much greener for alternative processes."

Jan 1, 1988

By S. Seetharaman

A mathematical model has been developed to evaluate the viscosities of melts at high temperatures. The viscous flow in liquid is described by the equation, {n = Aexp(AG*/RT)} based on the absolute reaction rate theory. The Gibbs energy of activation,{ AG* } is considered to be a function of the temperature as well as the composition of the melt. The model has been applied successfully to various metallic and slag systems from unary to quaternary. On the basis of this model, a relationship has been suggested to relate the Gibbs activation energy of viscosity to the Gibbs energy of mixing in binary metallic melts. The viscosities predicted from available thermodynamic data in the case of a number of binary metallic systems using this correlation show satisfactory agreement with the reported experimental values.

Jan 1, 1994

By James P. Bennett

EAF slag chemistry and its control have been recognized as important in producing quality steel at a low price for a number of decades_ EAF steel producers make lime and dolomite additions to furnaces, controlling the CIS ratios and sulfur pickup from the steel. Existing phase diagram data at 1600°C for CaO, MgO, FeO, SiO2, and Al2O3 was used to write a computer model optimizing slag chemistry for slag foaming and reduced refractory wear. The model, its development, and its use in an industrial steelmaking environment will be discussed along with how the model can improve energy efficiency. The importance of EAF mass balance to account for critical materials like Si in scrap and refractory wear using the model will also be emphasized_

Jan 1, 2003

By A. V. Reddy, C. Beckermann

"The DC continuous casting of a grain refined AI-4.5%Cu round ingot with realistic boundary conditions is numerically simulated. Of particular interest are the effects of the transport of free solid in the form of equiaxed grains on the macro segregation patterns and the final grain size distribution. The study uses a previously developed two-phase model that incorporates descriptions of heat transfer, solute redistribution, melt convection, and solid transport on the system scale with microscopic models of solutal undercooling, microsegregation and grain impingement. The numerical results indicate that grain transport inhibits the formation of inverse segregation in the ingot shell and promotes negative centerline segregation. This is explained by the reduction in the solid coherency next to the mold and the advection of solute-lean grains towards the centerline. Comparisons with the experiments of Finn et al. [5] illustrate the need for considerable improvements in the model. IntroductionMacrosegregation continues to be one of the concerns in DC continuous casting of aluminum ingots. The variation in composition over the ingot cross section results in the need to adjust alloy composition in order to meet mechanical property specifications in finished products. The extent of macrosegregation is greatly affected by the casting conditions, such as casting speed, superheat, cooling rate, mold size, alloy composition, and grain refining practices. Thus, it is of great interest to develop a comprehensive mathematical model to simulate the casting process, enabling the selection of conditions that minimize macrosegregation while maintaining a high productivity."

Jan 1, 1994

By James P. Bennett

EAF slag chemistry and its control have been recognized as important in producing quality steel at a low price for a number of decades. EAF steel producers make lime and dolomite additions to furnaces, controlling the CIS ratios and sulfur pickup from the steel. Existing phase diagram data at 1600°C for CaO, MgO, FeO, SiO2, and Al2O3 was used to write a computer model optimizing slag chemistry for slag foaming and reduced refractory wear. The model, its development, and its use in an industrial steelmaking environment will be discussed along with how the model can improve energy efficiency. The importance of EAF mass balance to account for critical materials like Si in scrap and refractory wear using the model will also be emphasized.

Jan 1, 2003

By J. W. Lyman

Nickel-metal hydride (Ni-MH) battery electrodes have been developed as a substitute for cadmium-containing negative electrodes. Use of Ni-MH electrodes offers enhanced electrochemical properties in many instances as well as reduced environmental toxicity. Rechargeable batteries using Ni-MH electrodes are also strong candidates for electric vehicles. During the production and secondary reclamation of these battery types, recycling procedures will be needed to prevent environmental impact caused by these wastes as well as to recover the value inherent in the scrap. The U.S. Bureau of Mines (USBM) is investigating hydrometallurgical technology that separates and recovers purified metallic components from Ni-MH battery scrap of two types, AB, and AB,. An investigation of acid dissolution and metal recovery techniques has determined several processing alternatives that may be used to promote the successful recycling of much of the battery fabrication scrap and eventual secondary scrap. Although recovery techniques have been identified in principal, their applicability to mixed battery waste stream and economic attractiveness remain to be demonstrated.

Jan 1, 1995

By V. P. Keran

The lead and copper smelting processes employed by Mount Isa Mines Limited, Mount Isa, Australia, are used to illustrate an operating viewpoint of some problems and solutions encountered in existing commercial sulphide smelters. The smelting processes discussed; include updraught sintering, blast furnace and reverberatory smelting, and converting. Selected examples are given of methods implemented, and options available, to improve the productivity and efficiency of conventional smelting processes.

Jan 1, 1983

By James C. Barker

Recent investigations of a 55-km long trend of intrusive complexes on southern Prince of Wales Island have identified significant resources of Nb, Y, REE. U, Zr, and a host of potential by-product metals. The northwesterly trend comprises multi-phased sodic alkaline and peralkaline diorite, monzonite, syenite, and riebeckite granite. There are at least three significant deposit types recognized, two of which, 1) pegmatite dikes/vein-dikes that zone laterally from the intrusions and 2) concentrically zoned pegmatites, contain most of the lithophile metals. A third, epigenetic replacement-type mineralization, contains much of the U resource. Other deposit types with minor or unknown resource potential include diatremes, carbonatite, and placers. This report summarizes the deposit evaluations, characterizes the mineralization, and estimates the resources. To date a total of 40.7 million tons of mineralized material is estimated as indicated or inferred. Most of the Y203 plus REO is at a grade exceeding 0.5% and half of the Nb20S exceeds 0.125%. Tonnage estimates would likely be substantially lncreased with additional exploration. Mineralogy is generally fine-grained and complex, and consists of more than a dozen principal REE-Y-Nb-U-Th-Zr phases, the sum of which may compose up to half of the rock. Approximately half of the REE-Y content comprises the heavy yttrium subgroup which is uncommon compared to deposits elsewhere. Although the Alaskan deposits are likely subeconomic at today's metal prices and consumption levels. recent technological advances suggest future demand may increase.

Jan 1, 1988

By J. E. Clemson

The Black Pine sediment-hosted, disseminated gold deposit is located in Cassia County, Idaho. Gold mineralization occurs in flat-lying zones 50 to 100 feet thick. Total geological ore reserves are 5.6 million tons grading 0.049 oz/t. Ore types include: non-carbonaceous, oxidized ore; carbonaceous, sulfide ore; and carbonaceous, partly oxidized ore. In the oxidized ores, native gold grains commonly occur in porous hematite pseudomorphs that have replaced disseminated framboidal and euhedral pyrite, and this gold should be readily leached by cyanide solutions. Approximately 4 % of the native gold observed in the oxidized ores is locked within gangue and may be refractory to cyanide solutions. Native gold has not been observed in the unoxidized samples, all of which are characterized by primary sulfides. It is suspected that the bulk of the gold mineralization in the sulfide ore occurs as submicroscopic particles within pyrite and will be refractory to cyanidation. It is believed that much or all of the gold observed in the oxidized samples was originally in pyrite but was released and re-precipitated during oxidation. The degree of oxidation of the pyrite and the presence/absence of preg-robbing carbonaceous material is used as a guide in delimiting zones of mineralization amenable to heap leaching.

Jan 1, 1988

By F. F. Aplan, G. Simkovich

"A review is given of the effects of solid state point imperfections upon a number of mineral benefication processes and a metal extraction process. It has been found in numerous flotation studies that small amounts of aliovalent impurities (dopants) in binary compounds may show major effects upon flotation behavior. Both semiconducting and ionic conducting compounds are affected. These effects are also seen in hydrometallurgical studies as well as in electrostatic operations. Additionally, de-copperization of lead melts appears to be strongly influenced by similar defects. It is hypothesized that the effects observed in these studies are present in actual operations and should be considered in designing processes. A few speculations concerning future efforts are advanced. IntroductionImperfections [point (e.g., vacancies, interstials, quasi-free electrons, electron holes, impurity ions), line (e.g., dislocations), two dimensional (e.g., grain boundaries) and three dimensional (e.g., 2nd phases) defects] are generally present in solid materials and these imperfections may, and often do, have important effects upon a variety of properties and processes. In general, one may, in most cases, attain elimination of three dimensional defects by a separation process of one type or another (e.g., gravity, electrostatic, magnetic, flotation, hydrometallurgical etc.,). Thus, this type of defect has rarely been investigated in a systematic fashion. Two dimensional defects are always present in non-single crystal materials but have also escaped systematic studies in processes primarily because the control of such defects is not easily attained. Line defects are non-equilibrium entities which are present in ill-defined quantities so that they present a variable that cannot be easily controlled although through careful systematic experiments one can attain some reproducible relations pertaining to this type of defect.Contrary to the lack of studies concerned with the effects of 1, 2 and 3 dimensional types of defects there has been some activity concerned with point defects and their effects upon a number of mineral/metallurgical processes, especially flotation processes. Thus, this article will present a review primarily of point defects in relation to their effects upon flotation although other processes and defects will also be mentioned."

Jan 1, 1988

By Jerold L. Johnson

Remediation of small-arms firing ranges is being investigated by the Naval Civil Engineering Laboratory and the U.S. Bureau of Mines. Scheduled closures of military installations, as well as the management of active ranges, require the development of methodologies for heavy metals removal to prevent their entering the surrounding environment. The impact berms contain high concentrations of metals, and the soil and vegetation surrounding the berms were found to have slightly elevated levels. The heavy metals characterized are in the form of whole bullets, a wide size distribution of free fragments, smeared lead on the surface of the soil grains, and very finely attached particles. Gravity beneficiation can remove liberated metal contamination effectively. Weak acetic acid leaching shows promise in lowering the final metal contamination to allow the ,soil to pass the Environmental Protection Agency's (EPA) Toxicity Characteristic Leaching Procedure (TCLP) criteria.

Jan 1, 1993

By William R. Opie

Considerable effort by extractive metallurgical research organizations has been devoted recently to developing pollution-free processes for treating copper sulfide concentrates. A number of hydrometallurgical processes are in various stages of development and have been subjected to economic evaluation. Although the hydrometallurgical approaches eliminate SO2 emission problems, they create objectionable effluents and residues, make precious metals recovery complex, and are not very efficient for treating chalcopyrite. Furthermore, they are consumers of considerably more energy than pyrometallurgical processes which produce blister copper that can be electrorefined to commercial grade cathodes. This paper discusses a pyrometallurgical process under development by AMAX Base Metals Research & Development, Inc. (1) The original objectives set for the process development were: 1. Sulfur control of at least 95% with elimination of fugitive emissions. 2. Copper and precious metal recoveries as good as or better than conventional processes. 3. Low capital cost. 4. Competitive operating costs 5. Use of known proven technology where applicable.

Jan 1, 1976

By D. Papazoglou

This work was undertaken to investigate the thermodynamic and kinetic feasibility of using hot sulfur dioxide bearing gases from smelting processes to selectively sulfate the nickel in nickel laterite ores for subsequent extraction in water. The environmental benefits ofthis approach, as opposed to releasing the gas to the atmosphere, and the economic benefit of directly utilizing the S02 rather than converting it to sulfuric acid are strong drivers for such a process. A thermodynamic analysis indicated that selective sulfation of the nickel could be feasible under appropriate conditions and these were explored through a series of laboratory scale experiments. Laterite samples were reacted at temperatures between 500 and 800°C with an equilibrated mixture of sulfur dioxide, oxygen and nitrogen in a fixed bed reactor. Tests were conducted on saprolitic ore from Bulong, Western Australia, limonitic ore from New Caledonia and garnieritic ore from Indonesia. Nickel extractions were highest from the limonite and relatively low from the other ores. The maximum selective extraction of nickel from the limonite in a single stage sulfation was 73%. Sulfation of other elements present in the laterites was also examined. A two-stage process was also identified which involved sulfation using a strong sulfation potential followed by weaker sulfation potential to attempt to convert ferric sulfate formed in the first stage to ferric oxide. This increased the extraction for the limonite ore to around 84% Ni, 95% Co and 2% Fe. Direct sulfation of laterite could be feasible in locations where sulfide smelting or roasting operations are relatively close to laterite deposits.

Jan 1, 2003

By Suresh Sundarraj

A diffusion mass transport model for predicting the microsegregation in a solidifying and coarsening dendritic mushy region of a binary alloy is presented. Two versions of this model are tested; one based on expressing the solute concentration in terms of mole fraction and the other on expressing the solute concentration in terms of mass fraction. On comparing previous model data sets and conditions, used in the analysis of Aluminum-Copper systems, a number of inconsistencies emerge. These inconsistencies are resolved on identifying a single set of data and conditions which take account of compositional density changes, "non-linear" thermodynamics and dynamic coarsening. An additional investigation is carried out to study the effect of assumed cooling mechanisms.

Jan 1, 1992