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By M. J. Adam

The Bureau of Mines is investigating the feasibility of partitioning complex sulfide minerals to simpler sulfide phases by sulfidation reactions. Such partitioning can afford opportunity to improve selective extraction of mineral constituents of value. This report describes research involving sulfidation partitioning of byproduct chalcopyrite concentrates from Missouri lead ore processing, and a Utah chalcopyrite concentrate from Cu ore processing. Small chalcopyrite samples were sulfidized with elemental S in glass capsules sealed after evacuating and backfilling with He, by heating for 1 to 24 h at specific temperatures in the range of 250? to 500? C, extending from below to above the boiling point of S (-4450 C).

Jan 1, 1987

By Emilia Visileanu, Eftalea Carpus

"The strategy of developing the Romanian textile industry sub-sectors envisages the achieving of certain superior production indices, from a physical and value point of view, in 2010, a quantitative increase of textile wastes by 14% in 2010 as compared to 2000, implicitly. The percentage of the turned-to-profit wastes will have an increasing tendency, from 53.6% in 2000 to 74.7% in 2010. The article synthetically presents the innovative elements of the technology of processing the industry textile wastes.1. Introduction“People will need to re-adopt this sense of rarity that has been forgotten over the last two centuries. Humans need to collect, sort, recover, going back to the old ideal of alchemists: complete the material cycle, turn waste into resource, reduce all forms of predatory behaviour as much as possible”Irrespective of the historical period, geographical positioning, economic power or employed technologies, wastes resulted and will result in a bigger or smaller quantity as long as life and activity on Earth go on. The negative effects of these over the environment factors and implicitly over population health are well known all over the world and not approaching this matter enough may have catastrophic consequences over life. Having in view these aspects, finding solutions for diminishing the general waste quantity and limiting the negative effects of those products is important, by effecting the reusing of the recyclable ones in the production processes as secondary raw materials, and by ecologically treating and storing those than cannot be reused.2. Experiments and researchesThe textile industry affects the environment by the high water, energy and chemical consumption, as well as by the high quantity of wastes that are the result of using an impressive number of chemical substances and technological processes.The development strategy of the Romanian textile industry sub-sectors foresees, for 2010, the achieving of certain higher production indices as compared to 2000, both in terms of materials (as merchandise) and in terms of value, which implicitly leads to a quantitative increase of wastes.The flexible, economic and ecologic technologies which include systems of waste preliminary preparing (cutting, opening) and conventional or non-conventional system of processing the recovered fibres lay at the basis of substantiating the activity of implementing the notion of zero wastes."

Jan 1, 2008

Cuspidine (3CaO?2SiO2?CaF2) is one of the most important compounds crystallized in mold flux films during casting in the continuous casting process of steel. The primary crystallization field of cuspidine has been experimentally developed in the CaO-SiOrCaF2-SiF4 system. The cuspidine-NaF binary and cuspidine-CaF2-NaF ternary systems have been also experimentally determined to study effects of addition of NaF on the primary field of cuspidine. In order to discuss its thermodynamic stability the standard Gibbs energy of formation of cuspidine has been determined by an electromotive force method using CaF2 as solid electrolyte and a transpiration method as follows: The chemical potential diagram and constituent activities for the CaO-Si02-CaF2 system have been evaluated based on the obtained thermodynamic data.

Jan 1, 2003

Cospidie (3CaO*2SiO2*CaFe2) is one of the most important compounds crystallized in mold flux films during casting in the continuous casting process of steel, The primary crystallization field of cuspidine has been experimentally developed in the CaO-SiO2-CaF2-SiF4 system. The cuspidine-NaF binary and cuspidine-CaF2-NaF ternary systems have been also experimentally determined to study effects of addition of NaF on the primary field of cuspidine. In order to discuss its thermodynamic stability the standard Gibbs energy of formation of cuspidine has been deterimed by an electromotive force methods using CaF2 as solid electrolyte and a transpiration method as follows: ^fG° (cuspidine) /kjmol-1 = 5198 + 0.825T (+12) (1313<T/K<1329): EMF method ^fG° (cuspidine) /kjmol-1 = 5178 + 0.813T (+8) (1221<T/K<1469): Transpiration method The chemical potential diagram and constituent activities for the CaO-SiO2-CaF2 System have been evaluated based on the obtained thermodynamic data.

Jan 1, 2003

By Sven Eck, Andreas Ludwig, Menghuai Wu

"Phase separation is a frequently occurring phenomenon during solidification accompanied by melt convection, sedimentation or, in the case of two unmixable liquids, a Marangoni driven motion. In order to describe these phase separation phenomena a two-phase volume-averaging model was employed for globular equiaxed solidification of binary alloys and decomposition and solidification of hypermonotectic alloys. The model considers nucleation and growth of equiaxed grains or second phase droplets, motion and sedimentation of grains or droplets, feeding flow and solute transport by diffusion and convection. It allows the prediction of macro segregations and the distributions of grain size or droplet size. Evaluations were made by comparing the numerical predictions with experimental results. For example it is shown that the numerically predicted grain size distribution in a plate casting (Al-4wt%Cu) agrees reasonably well with the experimental analyses.IntroductionModeling of metallurgical processes is a rapidly expanding field and the research activities in the last decades cover a wide range of areas including melt pre-treatment, solidification and subsequent manufacturing routes. Among those activities solidification stands in the central position, because the primary structure of the materials, and even many defects such as porosity, (macro or micro) segregation and inclusions form during solidification. Those primarily formed structures or defects once existing are difficult to be removed or modified by the subsequent material processing.Solidification is a multi-disciplinary field involving thermodynamics, fluid dynamics and solid mechanics, heat and mass transfer, and other disciplinesr1 -31• One of the most challenging problems in solidification modeling is the complex interactions between physical phenomena occurring on different length scales ranging from atomic rearrangement over single crystal-melt interactions to heat extraction, momentum and species transport at the system level. Modeling an industry process on atomic scale is umealistic, even on grain scale (e.g. phase field method) it would need another 40 years to be able to model the exact grain morphology in a casting space envelope of 10x10x10 cm3 [ 4]. Therefore, the realistic models for industry process are based on the solution of the macro transport equations (mass, momentum, enthalpy and species) on system scale. The microscopic phenomena such as thermodynamics, nucleation law, crystal growth kinetics and interactions at the liquid-solid interface are considered with simplified models, which are coupled with the macroscopic transport equations."

Jan 1, 2004

By M. J. Adam

As part of its research programs, the Bureau of Mines is investigating the partitioning of complex sulfide minerals to simpler sulfide phases by sulfidation reactions. Partitioning in this manner can afford opportunity to improve selective extraction of mineral constituents of value. This report describes research involving the sulfidation partitioning of the mineral pentlandite, which is an important source of Ni in primary production. For the laboratory studies, the pentlandite was synthesized in nominally equiatomic proportions of Ni and Fe. Elemental Ni, Fe, and S powders were blended, compacted, and sealed under reduced He pressure in vitreous silica tubes. The tubes were heated under controlled conditions at SOD? C for 24 h. The product was verified by X-ray diffraction and chemical analysis to consist essentially of (Ni,Fe)9S8. Small samples of the (Ni,Fe) S were encapsulated with sulfur in silica tubes at reduced He pressures and heated for 1 to 24 h at specific temperatures between 400? and 600? C, both below and above the boiling point of sulfur (_445° Cl. Reaction rate increased with temperature. Within this temperature range, partitioning to individual Ni and Fe disu1fides proceeded to essential completion according to the reaction

Jan 1, 1988

By T. B. Braun

Cathode contamination is the principal factor affecting the quality of electrorefined copper. It is commonly accepted that annealability is unfavorably affected by the following elements, in decreasing order of adverse effect: tellurium, selenium, bismuth, antimony, and arsenic. Silver in cathodes has importance as it represents a nonrecoverable loss of silver to the refinery. Mechanisms for the contamination of cathodes by these elements are examined and the effect of operating variables on contamination, including anode composition, electrolyte composition, electrolyte temperature, addition agent practice, and electrolyte discard rate, are discussed.

Jan 1, 1976

By O. Forsén

A new cell construction was designed for the study of the electrochemical behaviour of additives in conditions that simulate real copper, electrorefining. The behaviour of gelatine and thiourea was studied by applying different electrochemical methods, i.e. polarization resistance and voltametric measurements. In this study, individual galvanostatic electrolysis experiments were carried out for 120 hours. The organic additives were introduced to the electrolyte at certain intervals and their concentration was varied in the range &om zero to four ppm. An optical microscope was applied for the examination of copper cathode deposit microstructures. The results show that gelatine has a polarizing effect on the deposition potential of copper whereas even small amounts of thiourea depolarize the electrodeposition of copper. The maximum inhibitor efficiency of gelatine was obtained at a gelatine concentration of slightly lower than two ppm. When both gelatine and thiourea were present in the electrolyte, the depolarizing effect of thiourea exceeded completely the polarizing effect of gelatine. If chloride ions were added to gelatine and thiourea containing electrolyte, the electrochemical behaviour of the system was altered drastically. Chloride ions resulted in the prevailing of polarization effect caused by gelatine while the depolarizing effect of thiourea disappeared in this system. The polarizing effect of gelatine increased until chloride ion concentration of 30 ppm was reached. Also, the above electrochemical phenomena could be detected in the optical examination of copper deposit microstructure.

Jan 1, 1995

By Chu Yong Cheng

The solvent extraction (SX) processes of the three pressure acid leach (PAL) nickel plants in Western Australia have been reviewed. The use of intermediate precipitation, solids/liquid separation and re-leach in the three W A nickel plants make these processes complicated and costly in capital and ?operation. The research work carried out by the SX group at the AJ Parker Cooperative Research Centre for Hydrometallurgy I CSIRO Minerals has led to the development of direct solvent extraction (DSX) processes to recover and purify nickel and cobalt from leach solutions. The simplicity of the process flowsheets and the expected savings in capital and operating costs are the major advantages of the new DSX processes over the reviewed processes. By using a new synergistic organic system in semi-continuous tests with a pilot plant leach solution (after iron precipitation) from BHP-BiIliton Stainless Steel Materials, the metal values (Ni and Co) together with zinc and copper were separated from the major impurities (Mn, Mg and Ca, together with Cl) in the first SX circuit. The co-extracted manganese, magnesium and&apos; calcium were easily scrubbed out. After stripping, the metal values (Ni and Co) together with zinc and copper were concentrated, resulting in a much smaller second SX circuit and equipment in the down stream processes. The extraction and stripping kinetics of the metals with the new synergistic organic solution were very fast. The extraction and stripping almost reached steady state within 0.5 minutes. Semi-continuous test work with a synthetic leach solution, a cobalt pilot plant leach solution from Peko Rehabilitation Project Pty Ltd and a synthetic solution to simulate a concentrated laterite leach solution from BHP-Billiton Stainless Steel Materials showed that manganese, calcium, copper and zinc can be effectively and efficiently separated from nickel, cobalt and magnesium by extraction, scrubbing and stripping. This led to the development of another DSX process using D2EHPA to recover nickel and cobalt from leach solutions.

Jan 1, 2003

By M. C. Esposito

Seven pyrite samples purified from coal sources and one ore source pyrite (for comparative purposes) have been characterized by chemical and mineralogical analyses, inherent floatability, apparent specific gravity, surface area, semiconductor type, optical anisotropy, dissolution and oxidation rate. The data clearly demonstrate that pyrites from various coal sources differ not only from ore pyrite but from each other as well.

Jan 1, 1987

By D. L. Jones

The leaching of natural chalcopyrite was studied in both ferric sulfate and ferric chloride solutions. The chemistry of the two reactions is quite different, with substantial sulfur oxidation occurring only in sulfate solutions. Ferric chloride is a more effective reagent, for the leaching rate is greatly increased with finer particles and higher (Fe+++), and unaffected by high (Fe++); none of these advantages are found with ferric sulfate. In addition, the morphology of leaching appears to be different, with ferric sulfate leaching preferentially along fissures or grain boundaries. The kinetics were found to be linear over an extended period, rather than parabolic as reported elsewhere. An explanation of the observed phenanena is proposed using the electrochemical theory of leaching, and experimental measurement of the mixed potential of the mineral during leaching.

Jan 1, 1976

By A. Van den Steen

In the early fifties Professor Breckpot of the Louvain University in Belgium in collaboration with the Research Laboratory of Metallurgie Hoboken, discovered the possibility to separate nickel from cobalt sulfate solutions by a nickel sulfide depolarized cementation. This reaction, completed later with a zinc precipitation, was developed into purification processes for the Shituru and Luilu Gécamines cobalt plants in Zaíre. Due to increasing demand for higher quality products and the necessity of lowering the production costs, more laboratory and pilot plant investigations concerning the key parameters for the nickel and zinc sulfides precipitation were under- taken. Especially the relative stabilities of cobalt, nickel and zinc sulfides, precipitated with elemental sulfur or sodium hydrosulfide, were examined in relatlon with the pH and with the redox potential. These investigations have led to better plant practice and new development possibilities. The valorisation of the precipitated sulfides has also been considered.

Jan 1, 1988

By Kazuteru Tozcwa

The oxidation of several sulfide minerals in aqueous ammoniacal solution is discussed thermodynamically. The region in which Cu(NH3)2 4+ is stable has been estimated as a function of pH and concentration of total ammonia, {[NH3) + [NH4)}. In ammonia leaching when copper in sulfides is assumed to be extracted in the form of Cu(NH3)2 which will be rapidly converted to cupric ammine, thermodynamic data predict that such minerals are oxidized readily in the following order, CuS, Cu2S, CuFeS2, ZnS, NiS, Ag2S. This agrees with investigations on ammonia leaching of sulfide minerals, reported previously. The leaching of copper sulfide concentrate has been examined experimentally. Copper in a copper sulfide concentrate, in which the main constituents were chalcopyrite and pyrite, was effective¬ly extracted. The copper extraction was affected by factors such as (1) agitation intensity, (2) oxygen partial pressure, (3) NH3/Cu molar ratio, (4) leaching temperature and (5) addition of ammonium sulfate. From the results obtained in this work, it is concluded that mass transfer of oxygen plays the most important role in ammonia leaching of copper sulfide minerals.

Jan 1, 1976

By James D. Navratil

Neutral bifunctional organophosphorus solvent extractants (such as carbamoylmethylphosphonates and carbamoylmethylphosphine oxides) strongly extract lanthanides and actinides and do not extract more than 40 other elements from mineral acids. Because of their excellent properties they have been found useful for F-element recovery and purification processes. A brief overview of the lanthanide and actinide extraction chemistry of these reagents will be given.

Jan 1, 1990

By A. A. Bustos

A model was developed to simulate the blow-by-blow operation of the converting process. From the weights, compositions and temperatures of all converter feeds the model calculates the composition and tonnage of both converter matte and slag as well as bath temperature at the end of each blow. The development of the model and its application to the converter aisle operation are described. There is good agreement between model predictions and observed results. At the present time the model is being used to investigate different converting schemes and their effect on pay metal recoveries, slag chemistry and temperature of the bath. Future work involves the use of the simulation model as a process control tool for the converting operation.

Jan 1, 1988

By G. Haesebroek

In L969 Metallurgie Hoboken-Overpelt started an industrial plant for the separation of iron and zinc from a concentrated CoCL2 solution. Iron and zinc are extracted in column contactors by a solvent containing 12 vol % of tertiary amines in xylene. The extracted metals are stripped from the pregnant organic phase by precipitation with a NaOH solution at pH LL. In this paper an overview is given of the industrial process. In order to overcome some drawbacks of this process (low flash point of the diluent, reagent consumption, batchwise stripping) an alternative solvent extraction process has been examined. In this alternative process, iron and zinc are extracted with an or¬ganic phase containing 50 vol % of TBP in Escaid 110. The pregnant solvent is stripped with water in conventional mixer settlers. Despite the ability of this process to overcome most of the inconveniences due to the use of tertiary amines, it suffers from the poor stability of TBP in concentrated chloride solutions, resulting in unavoidable and inacceptable precipitation phenomena in the stripping section.

Jan 1, 1988

By Brent W. Madsen

The acid-ferric sulfate leaching of low-grade sulfide copper mine waste provides more than 10 percent of the U.S. supply of new copper, but recoveries and leaching rates are very low. In Federal Bureau of Mines research to improve the leaching process, experiments on 5- to 10-ton lots of mine-run ore were more revealing than bench-scale tests on fine ore. This report discusses the results obtained by leaching run-of-mine and minus 6-inch plus 112-inch samples of low-grade chalcocite-bearing mine waste. The samples were leached for 461 days and 61.6 and 37.7 percent of the copper was extracted from the minus 6-inch plus -112-inch and run-of- mine samples, respectively. A mixed kinetics model was applied successfully to the leaching of the sample with the fines removed where bulk solution transport was not rate controlling. The model, when applied to the run-of- mine ore, gave somewhat higher predicted copper extractions than experimentally determined. Subsequently, oxygen was introduced into the run-of- mine ore, leaching continued for an additional 312 days, and an additional 53.0 percent of the copper was extracted. Before the leaching experiment was dismantled and the residue sampled, the ore was treated with sulfur dioxide and its permeability was improved markedly. The results of each of these procedures are interpreted in relation to the attendant condition of the test.

Jan 1, 1976

By Akira Yazawa

The continuous converting has attractive advantages, but further experimental studies on the slag are required, when the process is considered thermodynamically. The summarized experimental results, obtained with iron silicate slag and with ferrite slag and results relating to actual operation are described and discussed in this paper. At first, equilibrium relations at controlled oxygen potentials among three melts of silica-saturated iron silicate slag, white metal and copper are investigated. The results obtained for slag agreed with the thermo-dynamical predictions. Namely, to suppress a magnetite separation, the system should be at high temperature; in the case of the S02 gas of 10 kPa, for example, magnetite did not separate from the slag at 1300°C, but at 1250 and 1200°C the slag was saturated with magnetite even at lower SO2 pressure. Copper losses caused by dissolution of its oxide increased with increasing 5O2 pressure, and were slightly lower than those reported in previous papers without the matte phase. When the continuous converting slag does not contain any appreciable amount of silica - in contrast to the conventional smelting slag ferrite slag would form, but there was no published fundamental work on-ferrite slags. Hence, the melting behavior and activities of the system CaO-Cu2O-Fe2O3 have been investigated. The liquidus diagram in nitrogen atmosphere was, constructed using both thermal analysis and quenching method. The low liquidus temperature region without magnetite separation was found in the part of low content of Cu2O in the section Cu2O-CaO-Fe2O3 and Cu2O?Fe2O3¬CaO?Fe2O3. The activity of Cu2O in the system was also measured. Slags, composed-of CaO, Cu2O and Fe2O3, in platinum crucibles were equilibrated at 1250°C and controlled oxygen pressures. After quenching, the-composition of slag and platinum crucible were determined qualitatively. On the thermo-dynamic analysis of the results, iso-activity lines were drawn, and it was shown that the slag in the converting furnace of the Mitsubishi process exists in an adequate region of the composition triangle.

Jan 1, 1976

By J. H. Huang

In this investigation, the selective precipitation of cobalt and molybdenum from Co-Mo aqueous solutions was studied in order to recover efficiently valuable elements from industrial effluents generated from a novel electrodeposition of nanocrystalline Co-based alloys process and reduce the effluent impact on environment. It was found that the behavior of cobalt in aqueous solutions was substantially affected by the presence of molybdenum. When adding 11.6 to 46.6g/L molybdenum to a 50g/L cobalt solution, the co-precipitation of molybdenum and cobalt started to occur at pH value of 3-4. However, without the presence of molybdenum, cobalt could only be precipitated out of the solution at about pH 6. Most of the molybdenum was found in the solid phase when the solution pH reached 5. After further increasing pH to greater than 7, the molybdenum dissolved back into the solution. Cobalt kept precipitating as the pH increased. When the pH was greater than 7, most of the cobalt was present in the solid phase. The chemical and physical characteristics of the precipitated materials were investigated by SEM, XRD, AAS and EDX. It was revealed that the precipitate was initially present as cobalt molybdate oxide hydrate and subsequently transformed as sodium cobalt molybdenum oxide. With further increasing the solution pH, the precipitate was transformed into cobalt hydroxide. Further investigation implied that most of molybdenum was chemically tied to the precipitate produced at the low pH, yet at the same time, physically entrapped at the high pH. The paper also presents the influence of reaction temperature and time on the precipitation process and kinetics.

Jan 1, 2003

By R. L. Miller

Oil -bearing metal sulfide sludges produced in treatment of an industrial wastewater, which includes plating wastes, have yielded to treatment by electrooxidation and hydrogen peroxide processes. The oxidation can be controlled to be mild enough to avoid decomposition of the organic phase while oxidizing the sulfides to sulfates. The pH is controlled to near neutral conditions where iron, aluminum and chromium(II1) precipitate as hydrous oxides. Other metals, such as lead and barium, may be present as sulfate precipitates with limited solubility, while metals such as nickel and cadmium would be present as complexed ions in a sulfate solution. The oxidations were found to proceed smoothly, without vigorous reaction; heat liberation was minimal.

Jan 1, 1992