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By David C. Lynch

FeCl3 particulate of 10 to 100 um in diameter was reacted with radicals produced in an oxygen plasma at pressures between 1 to 20 Torr. The particulate, in a fluidized bed, was positioned above the plasma to avoid over heating the oxide product which is known to lead to crust and clinker formation[ 1 ]. Reaction between the iron chloride and the gas phase occurred at temperatures between 66 and 226 °C. Oxygen radicals react with the surface material to a depth of approximately 2.5 4m. Surface material, analyzed with a x-ray technique, indicates that the maximum amount of FeCl3 reacted on a weight basis was found to be approximately 67%. More typically, 40 to 50 wt% of the chloride was reacted within 30 minutes to 1 hour.

Jan 1, 1996

By Hongqiang Wang, Qingliang Wang, Eming Hu, Zhiwu Lei, Fang Hu, Rui Zhang, Wei Hou

Pyrite, a mineral associated with uranium ore, is closely related to uranium leaching. In this study, Ozone micro-nano bubbles (OMNBs), as an environmentally friendly advanced oxidation technology, were used for the first time to oxidize pyrite under experimental conditions to improve the leaching rate of uranium. A laboratory-scale agitation leaching experiment of pyrite was carried out with a pH of 1.0–3.0, gas flow of 1–3 L/min, ozone generation rate of 0.55–2.22 mg/s, and pyrite concentration of 0.1–5.0 g/L for 1 h. By adding three different co-oxidant: Mn(II), Mn(IV), and Fe(III), it was found that only Mn(IV) increased the oxidation rate of pyrite by 21.7%. The results of the scanning electron microscope (SEM) and X-ray photoelectron spectroscopy (XPS) show that the formation of Fe(III)-O film on the surface of the ore suppresses the oxidation rate of pyrite to a certain extent. Pyrite can be rapidly oxidized up to 57.6% by OMNBs, which is beneficial to uranium leaching. This method is expected to be used for in situ acid leaching of uranium with OMNBs injected into the ground.

Jan 3, 2022

The merging of flash smelting with spray converting in one single furnace is proposed as a continuous copper making process. The proposed process is expected to produce blister copper, clean slag and gas with high sulfur dioxide concentration. Some high grade matte is an intermediate product recycled within the proposed furnace, spray-atomized and converted. The thermodynamic equilibria of the simultaneous oxidations which take place during copper smelting and converting are discussed in order to establish the gradient of oxygen potential along the furnace required for smooth operation. The proposed process is a dynamic system designed to reach equilibrium only close to the slag skimming end of the furnace. The process feasibility is based on the predesigned significant difference between the rates of converting reactions in a finely dispersed system and the rates of deconverting reactions between immiscible liquid phases of restricted interface area. The converting of small stationary droplets of matte, in a silica saturated system, was studied in the laboratory for extremely short oxidation times (10 to 120 seconds). These experiments led to some interesting observations on reaction mechanisms and kinetic trends. The droplet size and the matte grade affected very strongly the oxidation rate and the proportion of the different products obtained.

Jan 1, 1976

By H. Soto, J. Jara, F. Nava

"A combination of oxidation and precipitation was used to eliminate cyanide from gold milling effluents. Preliminary laboratory work developed with both synthetic cyanide solutions and with industrial effluents indicated that ozone can easily destroy free cyanide and weakly complexed cyanide (i.e. copper and zinc cyanide). In this case the reaction is quite fast and seems to be controlled by the mass transfer of ozone to the solution. Experimental results indicate that free cyanide and weak-acid dissociable cyanide in mill effluents can be reduced to less than 1 ppm. However, the iron-cyanide complexes proved to be quite resilient to destruction with ozone and they remained in the solution even after most of the free and weakly complexed cyanide was destroyed with ozone. These results were confirmed in a pilot trial developed at the Sphinx plant in northern Quebec.To deal with the problem presented by the presence of the iron complexes two different approaches were studied: use of a combination ozone-ultraviolet light oxidation, and the precipitation of iron-ferrocyanide complexes in the residual solution after ozonation. This last method proved quite promising since reduced the total cyanide levels of industrial solutions assaying as much as 250 ppm to less than 1 ppm of total cyanide. Control of the · pH of the solution was the key to obtain the precipitation of the iron complexes. The use of iron to precipitate cyanide complexes has the advantage of being less expensive and less toxic than copper (used by the Inco process)."

Jan 1, 1992

By H. Soto, J. Jara, F. Nava, J. B. Hiskey, B. J. Scheiner

Laboratory tests showed that ozone can destroy free cyanide and weakly complexed cyanide (copper and zinc cyanides). The iron cyanide complexes were resilient to ozonation but they were effectively eliminated by precipitation with Fe (II) ions under controlled pH conditions. Tests carried out with effluents from a number of gold mills confirmed the results obtained previously in the laboratory. The industrial samples contained cyanide in the form of free cyanide and also complex copper, zinc and iron cyanides. Solutions that contained up to 184 mg/L total cyanide, after the ozone treatment analyzed only 2-3 mg/L dissociable cyanide and 50-90 mg/L CN(t) (accounted for by iron complexes). After precipitation with ferrous ions total cyanide was reduced below 1.5 mg/L. For most solutions ozone consumption ranges from 3 to 6 g per g of cyanide destroyed. However, certain impurities (such as SCN and S203 ), present in some effluents, increase ozone consumption and make it more difficult to reduce copper concentration to satisfactory levels.

Jan 1, 1993

By G. Wren

As base metal sulphide resources become increasingly challenging to process, producers seek alternative options to treat concentrates. This study considers the mineral, elemental, and leaching character of a West Australian nickel sulphide deposit (Cosmos Nickel Project). After a brief review of the published work bench top leach tests were conducted to examine the factors which impact the kinetics of nickel sulphide leaching such as particle size, temperature, acid strength and type, concentration of copper sulphate and sodium chloride, and oxygen partial pressure. The effect of sodium chloride was considered due to the common occurrence of hyper saline water at West Australian nickel sulphide mine sites. Ultrafine grinding to an 80% passing size of 10 µm resulted in high nickel leaching efficiency. Moreover, higher concentrations of acid, copper(II) and sodium chloride also gave higher nickel and cobalt leaching efficiencies but arsenic precipitated as FeAsO4. Under the most suitable conditions the extractions of nickel, cobalt and arsenic at 90oC after 6 hours were >95%, 90% and <5%, respectively. The comparison with results from high pressure operations indicates the possibility of using a hydrometallurgical flowsheet based on fine grinding and atmospheric pressure leaching and warrants further investigations.

Jan 1, 2014

By H Y. Niu

The coal left in the goaf is easily submerged by groundwater damage. During the mining process of the underlying coal seam, it is necessary to drain the water in the overlying goaf. The coal sample is prone to spontaneous combustion after being soaked in water and air-dried. To explore the effect of micro-functional group transformation of water-immersed coal samples on the spontaneous combustion characteristics of coal samples during the low-temperature oxidation process. Using the experimental method of infrared spectroscopy, the migration law of special functional groups under different oxygen concentrations of water-soaked coal samples was analysed. By means of thermal analysis, the endothermic and exothermic properties of the functional groups in the water-soaked coal samples were studied. The results show that: the higher the oxygen concentration, the more oxygen-containing functional groups in the water-soaked coal sample, compared with the 18 per cent oxygen concentration, the 14 per cent oxygen concentration has a small increase, and the chain length is shortened. The temperature increase together with the oxygen concentration content determines the functional group content, the pyrolysis process produces some functional groups. The lower the oxygen concentration, endothermic rate decreases and endothermic temperature increases, the higher the ignition temperature of coal oxy-combustion, the lower the total heat release, the higher the burnout temperature, and the faster the oxygen-absorbing weight gain and the conversion of functional groups. Below 14 per cent oxygen concentration, the oxidative combustion process will be greatly reduced. The results provide a theoretical basis for preventing long-term water-soaked coal body oxidative spontaneous combustion in shallow buried coal seams.

Oct 12, 2022

By Patrick G. Hatcher

Studies of sedimentary humic acids by nuclear magnetic resonance (NMR), stable isotopes, and elemental analysis show they are derived by oxidative degradation of complex plant macromolecules that are insoluble in aqueous or organic solvents. The mechanism by which humic acids originate is fundamental to our understanding of the role of organic matter in ore deposition, because these substances can complex and mobilize a number of metal ions. The organic matter associated with uranium ores of the San Juan Basin, New Mexico and Carlin-type disseminated gold deposits of Nevada has certain organic geochemical characteristics that suggest an origin from humic acids.

Jan 1, 2013

By E. Maziar Sauber

In order to prepare a more desirable feedstock for a rare earth elements separation refinery, cerium, a penalty element in the refinery feedstock, should be removed from the mixed rare earth elements oxide or carbonate feedstock. In this study, cerium (III) to cerium (IV) oxidation by calcium hypochlorite and subsequent precipitation was used to remove cerium from a mixed rare earth elements chloride solution. A factorial design of experiments was used to determine the effect of process variables such as temperature, pH, and oxidizer addition on the oxidation of cerium (III) using synthetic solutions. Under certain test conditions, all of the cerium was successfully removed from the chloride solution, and some REE accompanied cerium and reported to the precipitate. This proposed technology can allow for low cost removal of cerium from mixed rare earth elements chlorides.

By J. J. Egan

ADVANCES in the production of quality steel have emphasized the need for greater knowledge of the amount and distribution of oxygen in the steel. Control of inclusion content and quality is largely dependent on such knowledge. While many analytical methods have been de-vised for the accomplishment of this end, few are without serious limita-tions in accuracy, convenience, or skill required in application. Usually at least two methods are necessary to determine total oxygen and constituent oxides. Because of the great importance of this problem and the specific interest in the application of such methods of analysis, the various procedures were carefully reviewed at the Union Carbide and Carbon Research Laboratories, with the view of developing a method free from the limitations mentioned above. Intensive experimentation finally led to an improved iodine extraction analysis described by Cunningham and Price. I After this had been thoroughly checked from the standpoint of the analytical chemist, it was rechecked from that of the metallurgist. This involved preparation of a number of small heats of varying composition with determination of total oxygen in the molten metal by the alumina method2 and an analysis of the solidified material without the aluminum addition by means of iodine extraction; the oxides of iron, manganese, silicon and aluminum also being determined by the iodine analysis. The report of this work constitutes the subject of this paper.

Jan 1, 1933

By J. W. Hickman

INTRODUCTION MOST of the electron diffraction studies of oxide films which form on metals and alloys have been carried out by oxidizing the specimens in an auxiliary furnace, cooling down to room temperature and then inserting the sample in the camera and taking a diffraction photograph. Prior to the investigations at the Westinghouse Research Laboratories, no systematic study of the oxidation of any metal or alloy had been made over a wide temperature range with photographs taken at elevated temperatures except the investigation of iron by Jackson and Quarrell.1 In order to interpret the electron diffraction patterns of the oxides which may form on alloys, it seemed advisable to make a comprehensive study of the oxidation of the purest metals available in the bulk form. Thus far studies have been completed on iron,2 cobalt,2 nickel,2 chromium ,2 Copper2, tungsten,3 molybdenum,3 beryllium ,4 uranium,4 thorium4 titanium5 and zirconium5 while investigations are in progress on tantalum and columbium, The next step in the study is concerned with the investigation of the oxides which form on binary alloys. Some of the alloys consist of a single, phase while others contain more than one phase. The identification of the oxides on the surface of a binary alloy may be more difficult than on the metals since oxides containing both metals as well as those of each metal separately may form. Furthermore, it is possible that solid solutions of the various oxides may occur. In these cases the electron diffraction method may not be able to identify the oxidation products unequivocally, Examples of solid solutions which may present difficulties are MoO2 and W02, Fe3O4 and FeO-Cr2O3 since the diffraction patterns are so similar. Since electron diffraction can determine only the structure of the oxide, the chemical composition must be inferred from the diffraction data based upon X ray diffraction investigations of specimens of known composition. It is possible in some cases to decide whether a given solid phase reaction can occur on the surface of an alloy by a study of available thermodynamic data. Table I lists the equations for the formation of most of the oxides from the elements together with values of log10 KR for the several temperatures. [OF°R = -RT In KR 0 and-~75T = logi°KR] [?F°R] and KR are the free energy and equilibrium constant of the reaction. Calculations may be made using the values given in Table I to determine whether a given solid phase reaction is possible thermodynamically. For example, a solid phase reaction should occur between aluminum and chromium&apos; oxide to form

Jan 1, 1948

L. E. WEMPLE, St. Louis, Mo. (written discussion *).-Mr. Stone refers to cadmium as one of the worst impurities in ores used for the production of zinc oxide for pigment purposes, because it is very volatile and its dark brown oxide and bright yellow sulphide both have strong coloring powers so that small fractions of 1 percent. injure the whiteness of the oxide. Numerous tests have recently been made by the American Zinc, Lead and Smelting Co. to determine what effect the percentage of cadmium, as ordinarily present in zinc ores, has upon the color of oxide made from such ores by the usual grate-furnace process. It has been found that while the cadmium is readily volatile and may be detected in the oxide product by chemical analysis, the oxide product is not discolored, but is of a clear white color. Analysis of the 12 leading brands of zinc oxide, French process, lead-free, and leaded grades now on the market for pigment purposes, show them to contain from 0.02 to 0.35 per cent. cadmium, figured as metal. If these proportions of cadmium were present as oxide or sulphide, the percentages would run from approximately 0.022 to 0.40 per cent. in the first case and 0.025 to 0.45 per cent in the latter case. All these grades of oxide are widely used for pigment purposes and are of a clear white color, except the leaded grades, the whiteness of which may be diminished by the lead sulphate. Tests made with admixtures of as low as 0.02 per cent. of cadmium oxide or sulphide to zinc oxide of the greatest hiding power (lead-free

Jan 1, 1918

By C. K. C. K. Gupta

The rare earths in elemental form are required for a variety of scientific and technological purposes. They are not easily obtained in this form, due to the great chemical stability of the rare-earth compounds and the strong tendency of elemental metals to react with everything they come in to contact with, especially at high temperatures. Beginning in the 1950s, when sufficient quantities of separated rare earths became available, as the result of intense research and development, three processing routes were developed to accomplish the preparation of all 16 naturally occurring rare-earth elements. They are chemical reduction of the halide intermediates, the oxides and electrochemical reduction of chlorides and oxide-fluoride mixtures. Not all the processes are effective with all the rare earths. In spite of the celebrated similarity of trivalent rare earths, the physical properties of individual rare-earth elements are sufficiently different that a variety of techniques are required for their preparation. The development of reduction processes for the rare-earth metals are covered in this paper, with focus on the oxide reduction routes. The strong reliance of effective reduction processes on the fundamental science of reduction reactions is highlighted.

By Raymond Ward

IN the past few years several papers have appeared dealing with different aspects of the oxidation of dilute alloys, especially with respect to the formation of internal oxides or subscales. Subscale has been defined1 as that layer or zone of oxide particles precipitated in a matrix of metallic metal in which the oxide particles are dispersed uniformly and occur by diffusion of the oxygen inward from the metal surface. Alloys composed of a solvent metal more noble than the alloying elements are subject to subscaling or internal oxidation. In these alloys the solute must be present in such quantities that if the alloy is exposed to an oxidizing atmosphere at elevated temperatures, the rate of diffusion of the oxygen into the metal will be greater than the rate of diffusion of the solute outward. There is a composition range of the iron-silicon system that falls into this classification. Knowledge of the nature and rates of oxidation of iron-silicon alloys is of great commercial importance, but very little information of this nature is available. Darken2 recently has made calculations to show the limits of concentration of silicon for which subscales are produced in iron-silicon alloys; however, the main thesis of his paper was to analyze and to explain the already existing data. The purpose of this paper is to present the effect of com position, temperature, time, and atmosphere on the type of scale-metal layer obtained and to give some qualitative indication of the effect of these variables on the rates of oxidation. Since this paper is a study of silicon steels that are available commercially, extremely low-silicon and high-silicon alloys are not included. EXPERIMENTAL PROCEDURE The alloys used in the experiment were taken from heats of silicon steel that ranged in analysis from 0.70 to 5.8 per cent silicon. This composition range takes in most of the commercial silicon steels. In Table I are listed the compositions of alloys used. Other than iron and silicon, the alloys normally contained approximately the following impurities: carbon, 0.03 per cent; manganese, 0.07; phosphorus, 0.008; sulphur, 0.02; copper, 0.07; tin, 0.01, and from nil to a trace of chromium, nickel and copper. All of the alloys used were melted in open-hearth furnaces, except where otherwise noted, and were hot-rolled to 0.100-in. plate. Samples approximately 1/2 in. square were then cut from these materials. So that the surface conditions of the samples used for oxidation would be standardized, each sample was ground through 000 emery paper immediately before oxidation. Two different techniques were employed in carrying out the oxidizing treatments. One consisted simply of heating the samples with free access to air. In this treatment the samples were set on edge on a refrac-

Jan 1, 1945

By K. G. Tshilombo

It should be possible to use an oxygen probe to follow iron removal during converting, if local equilibrium is established between iron in the matte and the iron oxides in the fayalitic slag. The oxygen activity is expected to increase strongly as the iron content of the matte decreases (and the iron activity in the matte drops) while the iron oxide activity in the slag remains constant. To test this idea, oxygen activities were measured in synthetic mattes (made up of mixtures of Cu2S, FeS and Ni3S2) when in contact with silica saturated SiO2-FeO slags, and silica and (initially) magnetite saturated SiO2-FeO-Fe3O4slags. The measurements were performed on laboratory scale at 1250°C, using an oxygen probe consisting of an MgO-stabilized zirconia electrolyte and Fe/FeO reference, and containing the sample in a silica crucible. Electrical contact to the matte was by means of a platinum wire. The measured oxygen activity was sensitive to the iron content of the matte, and insensitive to the composition of the gas atmosphere over the melt. The measured oxygen activity was generally close to that predicted by Fact Sage calculations. This indicates that such oxygen activity measurements could be useful to monitor iron removal during converting of nickel-copper-iron mattes.

Jan 1, 2007

By Daniel B. Brimhall

The research presented here was initiated to investigate the role of atmospheric oxygen in the leaching of copper waste dumps. The problem of increasing the recovery rate of copper from these dumps is or great importance considering there are by conservative estimate in excess of fifteen billion pounds of copper located in dumps in the western United States. At this time, there is an increased interest in recovering copper from these dumps on a large scale. Large tonnages of low-grade material are being placed on the waste dumps of most copper mining operations in the western United States each day. The size of these dumps ranges from 5.5 million tons at Mineral Park, Arizona, to 4 billion tons at Kennecott&apos;s Utah operation (1). Leach solutions are recycled and contain ferrous and ferric sulfates. Large quantities of dissolved aluminum, magnesium and calcium salts may also be present. To this solution make up water is added to maintain the solution inventory and sulfuric acid is added for pH adjustment. Iron is introduced into the leach solution by the dissolution of the iron-containing sulfide and oxidized minerals present in the ore deposit. In addition to the iron from dump leaching, iron is also introduced during the precipitation process when the pregnant solution is passed over metallic scrap iron if cementation is used to reduce the copper in solution.

Jan 1, 1972

By E. Asselin

Electrochemical polarization experiments were conducted on alloy 625 in ammonia solution between 25 and 225°C and the results were compared with those of an oxygen solubility model. Results confirm that corrosion is under oxygen control, Normalized corrosion rates are determined based on the rate of oxygen diffusion to the corroding surface, and the corrosion rate at 200°C (-9.7 µA.cm-2) is roughly 24 times higher than the corrosion rate at 25°C (0.4 nA,cm-2), An oxygen-solubility model for Supercritical Water Oxidation (SCWO) conditions was generated using the Redlich¬Kwong-Soave (RKS) equation of state, Results of the model confirm many of the experimental observations from SCWO reactors which suggest that corrosion is at a maximum at temperatures just short of the critical point, The RKS/oxygen diffusion model predicts that the corrosion rate at 365° C is ?85 times higher than the corrosion rate at 25&apos; C. Given that a normalized corrosion rate is obtained, this type of model could be useful for selection of SCWO reactor materials.

Jan 1, 2005

By N. S. Dalal, B. Jafarl, M. M. Suryan, V. Vallyathan

"The biologic events leading to coal workers' pneumoconiosis (C'WP) are not yet fully understood. There is no good correlation between toxicity studies or animal models with human epidemiologic and pathologic data. Several studies have shown that the severity and prevalence of the CWP in miners correlate strongly with the rank and type of the coal mined. However this has not been found to be the case with laboratory animal models or in vitro studies. In 1980 Russian scientists Artemov and Resnik suggested that the discrepancy may be related to the excessive amount of short-lived free radicals present in freshly generated coal mine dust. Because of their short life, such free radicals would be absent in the ""stale"" coal dust used in most animal experiments. To test this hypothesis we have undertaken a systematic study of the generation, reactivity with oxygen and biological significance of free radicals in coal dust.Electron spin resonance (ESR) was used as a technique for the direct detection of radical production and kinetics of decay. ESR signals from the newly generated radicals decreased with time on exposure to oxygen or when stored in biological buffers at a rapid rate. In vitro biological tests were carried out which suggest that the reaction between the newly generated radicals and oxygen plays a significant role in the sample's cytotoxicity.Materials and MethodsESR measurements were made at X-band (~9.7 GHz) using a computer-controlled Bruker ER200D ESR spectrometer. 11te two coals studied in detail were obtained from the Pennsylvania State University Coal Depository. These were, a bituminous sample, PSOC-1172 (72% carbon) and an anthracite sample, PSOC 867 (95% carbon). Coal particles of several millimeter (mm) dimensions were evacuated to a pressure of ~10-3 mm Hg typically overnight. Without exposure to air, these particles were ground in an agate mortar with an agate pestle for about 30 minutes and then sieved through a 20 \1111 mesh filter before ESR measurements or cytotoxicity studies. As an index of cytotoxicity, hemolysis was measured according to the method of Harrington, with minor modifications. Sheep erythrocytes (2%) were incubated with test samples at 37°C for one hour, and the hemoglobin released was quantitatively estimated photometrically. Additionally, release of alveolar macrophage enzyme lactate dehydrogenase (LOH) was estimated after incubation of the macrophages with the coal particles at different time intervals after the grinding. Enzyme activity was assayed according to the method of Wrobleski and LaDue and expressed as percent of enzyme released in 2 hours per million cells with 1 mg of coal."

Jan 1, 1989

By G. S. Victorovich

Technical progress in primary smelting has changed the face of the copper industry in the years since the Second World War. Much of this change has resulted from a wide acceptance of flash smelting technology. In addition, research has been directed toward devising converting processes to replace conventional Peirce-Smith converting technology. One major thrust has involved a revival of the old " ", idea of oxygen flash converting of comminuted mattes. This paper reviews the 60-year history of flash converting. Particular attention is paid to Inco&apos;s investigations into the processing of white metal containing significant amounts of nickel and, in some cases, iron. Thermodynamic analysis and laboratory experimental results are presented which throw light on the behaviour of nickel and other salient features of flash converting. The possible role of oxygen flash converting in the copper pyrometallurgy of the future is briefly discussed vis-a-vis direct production of copper.

Jan 1, 1993

R. MOLDENKE, Watchung, N. J. (written discussion*).-It is some-what difficult to discuss the paper of Mr. Stork, when the description of the cupola melting occurrences indicates that his practice is open to question. The evident burning of much of the steel charged,. coupled with the remarkably low silicon content of the mixture as shown by the resulting product, throws the entire melting practice into that of making cupola malleable. If anything is wanted here, it is a. high bed to melt upon, and yet Mr. Stork in the very beginning of his paper speaks of the evils of oxidation due to a "high" bed, etc. The experienced foundry-mall would judge at the outset that Mr. Stork has kept his bed in the cupola too low, and naturally got a lot of oxidation from the blast. The oxidation of steel when used in large quantities in cupola mixtures is a well-known phenomenon, and is readily understood. One has but to. put a file into the forge fire and watch it burn when heated high enough. The melting point of steel being higher than cast iron, heavy pieces may dig way into the bed before being completely melted away, the last por-tions being directly exposed to free oxygen from the blast. Another situation not to be forgotten is the oxidizing effect of carbon dioxide at high temperatures. A serious oxidation of the steel is quite conceivable if in the zone of maximum carbon dioxide and minimum carbon monoxide-free oxygen being entirely absent. Hence the well understood practice of never melting a mixture with much steel unless the bed is kept exceed-ingly high; or again the above-mentioned malleable practice. Mr. Stork mentions the impossibility of deoxidizing a heat. after the steel contained has been oxidized. This is true to a great extent with the ordinary deoxidizers, such as silicon and manganese, but can be brought about by vanadium, titanium, magnesium, etc. Proper melting, however, makes this unnecessary.

Jan 10, 1919