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By E. Allaine

Carbochlorination kinetics of pure MoO3, Nb2O5, Ta2O5 and V2O5, by Cl2+CO+N2 gas mixtures was investigated between 380 and 1000 °C. Standard free energy of carhochlorination reactions and phase stability diagrams of these refractory metal compounds were calculated. The influence of total gas flow rate, temperature, reactants partial pressures on the reactivity of these oxides were investigated. The apparent activation energies were found to be about 83, 75, 110 and 100 kJ/mole below 650°C for MoO3, Nb2O5, Ta2O5 and V2O5, respectively. Above this temperature, the Arrhenius plots exhibit a rate anomaly attributed to thermal decomposition of COCl2 and/or structural changes of these refractory metal oxides. The apparent reaction order of carbochlorination of these oxides with respect to Cl2+CO was determined. For these refractory metal oxides, the reaction rate was maximum for a Cl2/CO ratio of about 1 in the chlorinating gas mixture. Results of carbochlorination of these oxides are compared and discussed.

Jan 1, 1995

By T. Ranki-Kilpinen

In the flash smelting technique, developed by Outokumpu Oyj, off-gases with dust load are directed into the heat recovery boiler (HRB). As the temperature decreases, metallic sulphates become thermodynamically stable. Sulphation of oxidic particles initiates. The release of heat causes an increase in particle temperatures, and soft sulphated particles can stick to the heat transfer surfaces. Dust accretion may form and cause operational problems. The objectives of the project are to study sulphation reaction mechanisms and kinetics of flue- dust particles under HRB conditions, and get more information for the flue-dust treatment possibilities. The sulphation behaviour of synthetic Cu2O particles (37-53 pm) was studied using a fluid-bed reactor of laboratory scale. The experimental parameters in the latest campaign were oxygen and sulphur dioxide contents of 2.5-10 vol-% 02 and 40-60 vol-% SO2 respectively and temperatures of 600-660°C. Samples were examined microscopically (SEM+EDS) and chemical analysis were conducted. The sulphation rate was found to have a maximum at the certain temperature, which was dependent on the gas SO2 content. Regardless of the level of SO2, a rise in oxygen content promoted sulphate formation.

Jan 1, 2002

By Sesha S. Srinivasan

Mechanochemical synthesis has been employed to prepare new light weight complex borohydrides, Zn(BH4)2. The thermal calorimetric and gravimetric analysis of these complex borohydrides shows the hydrogen decomposition temperature (Tdec) of about 100° C with theoretical capacity of ~8.0 wt%. This advanced materials based technology is considered to be suitable for attaining the US-DOE grand challenge technical targets. The powder x-ray diffraction analysis of the mechanically milled Zn(BH4)2 exhibits the presence of zinc borate and NaCl phase. The FTIR spectra of BH4-ion in NaBH4 has a characteristic band at 2290 cm-1,whereas in Zn(BH4)2, it occurs at ~2061 cm-1 (bridging B-H bonds) and ~2451 cm-1 (terminal B-H bonds) as well. The reversibility of hydrogen decomposition and recombination process is carried out by PCT measurements with multi-cycling procedure.

Jan 1, 2006

By Daniel Adolfsson, Ryan Robinson, Fenwei Su, Jelena Blagojevic

"Cold bonded briquetting of steel plant by-products has proven to be a viable recycling alternative concerning technology, economy and environment in both the traditional blast furnace route and the direct reduction process. A critical parameter in cold bonded briquettes is the type and amount of binder used during production. The binder material must meet certain quality requirements concerning low and high temperature strength, chemistry and economy. Currently, SSAB Tunnplåt uses ordinary Portland cement (OPC) as binder in their cold bonded briquettes. In order to improve binder quality and possibly decrease OPC dependency, a binder feasibility study has been conducted concerning an internal by-product, ladle slag, as a supplement and/or partial substitute for OPC. Several characterization techniques have been used to study the behaviour of ladle slag, these include: XRD, XRF, SEM, glass content analysis, calorimetric analysis, particle size distribution and thermochemical stability considerations concerning the CaO-Al2O3-SiO2 system.IntroductionRecently, a project was initiated at SSAB Tunnplåt AB, in Sweden, which aimed at reducing the amount of ordinary Portland cement (OPC) as hydraulic binder in cold bonded briquettes by partly replacing it with ladle slag. OPC is traditionally used within civil engineering, and widely accepted as a hydraulic binder in a number of different applications. OPC consists of four major crystalline phases, i.e. C3S, C2S, C3A and C4AF. Tricalcium aluminate as well as the ferrite phase in OPC reacts very quickly with water, for this reason gypsum is added to the clinker in order to retard these reactions. The fact that gypsum is present in the system limits the recycling of briquettes to the BOF, since the presence of gypsum during steelmaking results in a significant amount of sulphur emissions. The latter along with the expense that follows, makes it worthwhile to consider alternatives for OPC as binder in cold bonded briquettes."

Jan 1, 2008

By P. Chris Pistorius

"Use of coke in blast furnace ironmaking is the main origin of carbon dioxide emissions from integrated steelmaking. Use of pre-reduced iron feedstocks would reduce the coke rate and, if pre-reduction were carried out with natural gas, would decrease the overall carbon intensity of ironmaking. Blast furnace productivity would also increase, because the blast volume per unit of hot metal would decrease. This paper shows that these trends can be predicted quantitatively, by using a conceptually simple Rist-style blast furnace mass and energy balance, assuming furnace productivity to be limited by the tuyere gas flow rate. Such predictions would assist in optimizing the choice of the degree of reduction and relative amount of pre-reduced blast furnace feed.IntroductionSteelmaking is responsible for some 5% of world CO2 emissions, at a rate of approximately 1.9 tonnes of CO2 per tonne of cast steel [1]. In integrated steelmaking, the ultimate source of most of the CO2 emissions is coke, the indispensible (and expensive) fuel and reductant for blast furnaces. There are several research programs underway worldwide which seek to lower the carbon intensity of ironmaking; one of the largest is the European ULCOS program [2], in which the main proposed change to blast furnace ironmaking is to scrub CO2 from the furnace off-gas (for possible sequestration), recycling the remaining gas to the furnace. To limit the recycling nitrogen load, oxygen rather than air is used to combust coke.A conceptually simpler approach is to charge prereduced feed (direct-reduced iron) to the blast furnace. This approach has been used for some two decades at the AK Steel Middletown plant, where some 200 kg of direct-reduced iron (DRI) is charged per tonne of hot metal [3]. The Middletown blast furnace has exceptionally high productivity (rate of iron production relative to the furnace hearth area), simply because less coke is required per ton of hot metal if part of the feed is already metallic. Midrex [4] has provided some quantitative predictions of the implications of DRI use in the blast furnace, stating that for every 10% of Fe in the feedstock that is in metallic form, the fuel requirement decreases by 7% and the productivity increases by 8%."

Jan 1, 2012

By Sheng-hai Yang

The ultrafine, monodispersed, spherical cobalt powder has been fabricated by reducing cobalt hydroxide with glycol. It were investigated that the effect of NaOH concentration on the reaction rate and the effects of the concentration of cobalt hydroxide and surfactant on the morphology and particle size. The particles were characterized by the X-ray diffraction(XRD), scanning electron microscope(SEM), laser diffraction particle size analyzer and BET specific surface analyzer respectively. The XRD shows that the cobalt powders exist mostly in face centered cubic (fcc) structure, a little in simple hexagonal. The cobalt powders prepared at Co(OH)2150g/L, NaOH 40 g/L and surfactant 30g/L, its average particle size, specific surface area and cobalt content, were 0.88µm, 2.705m2/g. and more than 99.5% respectively.

Jan 1, 2006

By C. García

Several modifications to Zaldivar's original design have been made in order to reach the design cathode production. This paper describes the modifications to the crushing, leaching, solvent extraction and electrowinning operations, which in turn have increased the production by 14.8% over the design capacity in 1999. The principal modifications were to (1) incorporate a dry pre- screening plant between the secondary and tertiary crushers to increase the percentage of fines to the piles, (2) increase the retention time of the solutions inside of the piles, and (3) increase the efficiency of the tertiary crushers to reduce the particle size of the product material. The leaching ratio was increased from 2.8 to 5.6 m3/ton. The temperature of the pregnant leach solution (PLS) was increased, the amount of acid used was reduced, and a strain of native bacteria was adapted in highly contaminated solutions. The copper concentration in the PLS was increased by more than 50% and was stabilized at this level by commissioning a process of two-stage leaching. The current density in the tankhouse was increased from an average of 2 16 to 3 17 A/m

Jan 1, 1999

By Carla Lupi

In this work, nickel-cobalt electrodeposition under galvanostatic conditions was investigated. Ni-Co alloy was electrowon from an acid sulphate bath containing 40 g/L Ni and2-8 g/L Co.. The effect of electrolyte composition, current density, temperature, solution pH and presence of buffers such as H3BO3 and (NH4)2SO4 on Co content of the binary alloy has been investigated. In particular, current densities ranging from 180 to 400 A/m2 and temperatures ranging from 27 to 60°C were tested. The composition of Ni-Co alloys may be diversified through the selection of process parameters. The experiments show that the highest cobalt content of the alloy is reached by using a buffer free electrolyte without solution pH control. Though, in these conditions, the most homogeneous, fine and regular deposit morphology is obtained, energy requirements are the highest in tests lasting just two hours.

Jan 1, 2003

By Manolete Mena

WC-Co nanocomposite powder is among the first group of materials with a promising potential for nanocrystalline-materials application. A chemical vapor synthesis (CVS) process that has previously been used for preparing the aluminides of titanium and nickel, and other metallic and intermetallic powders has been applied to the preparation of WC-Co nanocomposite powder. This CVS system was designed so that a tungsten precursor (WCl6 powder) and a cobalt precursor (CoCl2 powder) were separately fed into each evaporator in a reactor by means of specially designed powder feeders. The reduction and carburization of the vaporized chlorides by methane-hydrogen mixtures produced nanosized WC and Co composite powder. The product is a very uniform mixture of the constituent powders, which is important to ensure a high quality of the bulk cemented tungsten carbide product after consolidation. In the present work, the effects of reaction temperature, CH4 to WCl6 ratio, CH4 to H2 ratio, residence time, and Co content on the powder composition and particle size were determined. The products were characterized using XRD, carbon analyzer, and TEM.

Jan 1, 2006

By Norihiro Murayama

The hydrothermal syntheses of zeolites from coal fly ash were carried out using NaOH and KOH as an alkali source. The cation exchange capacity (CEC) and the ion exchange selectivity were investigated for the zeolites synthesized by a hydrothermal treatment. The effective usage of the zeolite as a cation exchanger was considered from the viewpoint of engineering. Zeolite P, HS (hydroxysodalite) and K-CHA (potassium-chabazite) are mainly formed as zeolite species in NaOH or KOH solution at 393K. The zeolite P and K-CHA have a large exchange capacity as a cation exchanger. The cation exchange isotherms of various monovalent and divalent cations with various zeolites are investigated. The order of selectivity of the zeolites is as follows, NH4+> K+> Li+.For the divalent cation, the largest removal amount is obtained for Pb2+ in the low equilibrium concentrations below 0.2mmol/dm3, and almost perfect removal can be achieved for Pd2+. The order of selectivity of zeolites in low concentration is expressed in the following order; Pb2+> Co2+> Cd2+> Ca2+> Mg2+> Ni2+. Ii is considered the zeolites obtained from coal fly ash can be used as an excellent cation exchanger.

Jan 1, 2006

By Eun Duck Park

The gold catalyst supported on iron oxide was prepared from gold dissolved in aqua regia by a deposition-precipitation method and applied to CO oxidation in the absence and presence of hydrogen. Some characterization methods such as X-ray diffraction (XRD), nitrogen adsorption, transmission electron microscopy (TEM), temperature programmed reduction (TPR), temperature programmed oxidation (TPO), and the pulsed CO chemisorption with temperature programmed desorption (TPD) were conducted to explain different catalytic activities of Au/Fe2O3 catalyst pretreated at different conditions. The particle size of gold was about 10 nm for Au/Fe2O3 calcined in air at 373 and 573 K. For complete CO oxidation, the decreasing CO conversion with a reaction time was observed at low temperatures but its initial catalytic activity can be restored by a heat treatment at high temperatures. This catalyst was quite active for the selective CO oxidation in the presence of hydrogen especially at low temperatures. In the presence of hydrogen, the deactivation was significantly diminished.

Jan 1, 2006

By E. J. Peuraniemi

Recently commissioned Kennecott-Outokumpu flash converting was developed to replace the approved but environmentally outdated Peirce-Smith -converting to satisfy the globally tightening emission regulations. In the present study, dust formation and reaction mechanisms of two copper mattes with different experimental parameters were studied in lean suspension conditions. Both mattes had very high copper content of approximately 75 wt% and low iron content of 4.5 wt% and 1.2 wt% Fe. A laboratory scale, vertical laminar-flow furnace with a low feeding rate was used to simulate the phenomena taking place in the reaction shaft of a flash converter. Experimental conditions included temperature of 1300 °C with reaction gas oxygen contents of 20 vol%, 50 vol%, and 75 vol%. In the experiments, sieved particle fractions were fed to the furnace and sampled after short reaction time intervals by quenching them into a water film. Collected particles were analysed chemically for their main elements to define their removal rates. Also, optical and scanning electron microscopy with EDS-analyser were applied to determine phenomena occurring during reactions. Kinetics of oxidation as well as ignition of particles are discussed. Changes in particle morphology, size, and composition are reviewed to describe dust formation and reaction mechanisms.

Jan 1, 1999

By Kimio Itagaki

Thermodynamics and rate process fundamentals are two of the important principles involved in nonferrous production processes. The process configuration establishes whether thermodynamics or rate process behavior is most relevant in a particular application. In this paper, thermodynamic theory and rate process fundamentals are used to analyze the main characteristics of smelting and converting processes. The effect of increased oxygen potential .is examined with emphasis in view of the increased use of highly oxygen-enriched gas in modem smelting processes. Phase equilibrium and the distribution of minor elements between copper or nickel matte and FeOx-SO2- or FeOx-CaO-based slag are reviewed. The use of oxygen-rich gas has no serious effects on 'the recovery of valuable copper and silver in the matte phase, while the recovery of nickel and cobalt is adversely affected. The oxygen content in the gas also strongly affects the distribution behavior of arsenic, antimony and bismuth. Analysis of the rate processes occurring in the shaft of flash smelting, and converting furnaces by a 3-D computational fluid-dynamics model is also discussed. After being validated with experimental data collected in a large laboratory furnace, the computer model has been used to simulate the main features of an industrial flash converting operation. The results present quantitative features of the improved mixing of the particle-gas suspension and increased oxygen efficiency obtained with a distributor-cone burner compared with those with a single axial entry burner. The role of basic principles in the engineering analysis of high-intensity matte smelting processes is also discussed.

Jan 1, 2002

By A. M. Blount

In 1983, a final ruling of the U.S. Occupational Health and Safety Administration (OSHA) specified that chemicals containing >0.1 % of a carcinogenic substance or > 1 % of a substance hazardous to health must be labelled. Amphiboles of the fibrous or asbestos-type must be quantified at levels of 0. I % whereas the status of non-fibrous types is not finally determined at this time. Tremolite and actinolite can possibly be measured to 0.1 % by XRD, but anthophyllite cannot be so measured. Recently the International Agency for Cancer Research (IARC) has designated quartz as a suspected carcinogen, and its quantity must be measured to the 0.1 % level. Thus, it has become Increasingly important to be able to detect and quantify minerals in bulk samples down to low or "trace" levels. It has been found that minerals needing to be quantified can often be concentrated by microcentrifuge and counted by means of polarized-light microscopy. For example, amphiboles in talc samples can be separated by using a heavy liquid (thallium formate-malonate) of density 2.810. Talc floats, and amphiboles sink. After centrifuging, the denser particles are removed from the bottom with a Pasteur pipette and placed in a clean centrifuge tube. Distilled water is added to the tube containing the denser minerals and the tube centrifuged again. After several washings with distilled water, the sample is removed along with a drop of water to a clean glass slide. A drop of 1 .584 refractive index liquid and a cover glass are placed over the dried sample. The slide is scanned for particles greater than 5 um in length and having an aspect ratio greater than 1:3. These are checked for refractive index, sign of elongation and extinction angle to differentiate them from talc particles on edge and other minerals. Amphiboles have all indices greater than 1.584, and talc has all indices equal to or lower than this value. Alternately the heavies at the bottom of the centrifuge tube can be filtered through a nucleopore filter. After the filter has been washed with distilled water and dried, a 1.584 refractive index liquid renders the filter transparent in two of the four extinction positions so that a count of amphibole particles can be made directly on the filter. The refractive index-density method which is so useful for talc powders should be equally useful for other nonsoluble industrial minerals.

Jan 1, 1989

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

By C. Flores

The direct cementation of copper from a loaded D2EHPA 20 % vol. in kerosene using zinc, zinc-lead alloy and iron metallic powders was studied. Copper was loaded into the organic solvent from an aqueous copper sulfate solution. Results indicated that copper is reduced spontaneously with relatively fast reaction rates. The effects of several operating parameters such as water content in the organic system, initial copper concentration, reductant surface area, oxygen and nitrogen atmosphere, intensity of the agitation and temperature on the galvanic stripping of copper were studied. For a better understanding of the electrochemical reactions involved in the galvanic stripping, the dissolution of metallic copper in the organic solvent was also studied. Copper did not dissolve unless a small amount of water was present in the organic system. The results and possible reaction mechanisms are discussed.

Jan 1, 1999

By Florian Kongoli

The so-called "fayalite" slag, despite problems associated with it, is the most widely used slag in copper smelting processes. Thirty years ago, in order to overcomes some drawbacks of this slag a new "calcium ferrite" slag was proposed especially for continuous copper converting. Since both slags have strong and weak points depending on the field of their application about 8 years ago another new "ferrous calcium silicate" slag was proposed that is expected to solve the drawbacks of each slag. This new slag is defined as mainly consisting of FeOx, CaO and SiO2 as its main components but it can practically have several combinations of these constituents. In order to determine the best area of this slag for possible industrial application the quantification of phase relations is an important subject. In this paper the work carried out by the authors in quantifying through an original physical model the phase relations, liquidus surface, liquidus regions, behavior of solid phases and the effect of minor components is reviewed. Several special compositions of this slag have been identified and discussed for possible applications in the industrial practice.

Jan 1, 2006

By O. M. G. Newman

Research into potential applications of spouted bed electrowinning (SBE) in the zinc industry was conducted, in a collaboration between our two organizations. The main system investigated was zinc from acidic sulfate electrolytes. However, SBE can be extended to other electrolytes, or recovery of other elements. Electrolytic tests were carried out at the 0.01 to 0.1 m2 scale. Spouting behaviour has been studied at a larger scale, approaching a size suitable for an industrial unit cell. Much of our work was carried out using a micro-porous separator (Daramic®). However, we have also shown that ion exchange properties can have a controlling effect on the process chemistry, electrochemical efficiency, and plant flowsheet. In initial 0.1 m2 scale electrolytic tests, design and engineering issues for scale-up were identified. We review the major achievements, promising areas for application in the zinc industry, current status, and remaining barriers to development of SBE technology.

Jan 1, 2003

By N. Bazzanella

The hydrogen desorption kinetics of pure and Nb-doped magnesium hydride film samples was investigated by using a Sievert-type apparatus. The overall activation energy and the reaction order controlling desorption are (141±5) kJ mol-1H and n 4 for Mg hydride and (51±5) kJ mol-1H and n 1 for Nb-doped (5% at) Mg hydride indicating that, in the doped sample, hydrogen desorption is controlled by the H migration in transformed h-Mg layers. Structural analysis performed by X-Ray Diffraction (XRD) and Extended X-Ray Absorption Fine Structure spectroscopy (EXAFS) show that the catalytic effect of the Nb dopant is connected with the formation of NbH0.89 nanoclusters dispersed in the Mg hydride matrix. It is suggested that the catalysis process is also connected to the presence of Mg-Nb hydride interfaces where the transfer of H atoms preferentially occurs by connecting h-Mg grains and by the role of the MgH2-NbH0.89 interface as preferential site for the dissociation of the hydride phase.

Jan 1, 2006

By W. F. Drinkard

Many in the environmental movement have focused on this element. But, nothing they or anyone does will change the amount of arsenic in the world. This report is on actual commercial plants that we developed and operated to recover or stabilize arsenic values from metallurgical dusts from gold and copper pyro operations and arsenical gold bearing ores. When they were available gold and copper values were recovered. Our experience in arsenic extends over thirty years. My first corporation, Mineral Research & Development Corporation was the first in North America to manufacture the then new CCA (copper-chrome-arsenic) wood preservatives. This class of wood preservatives proved to be so effective that it made wood into an entirely new material of construction. It is not uncommon for wood properly treated with arsenical CCA preservatives to last for thirty; forty, and sixty years. Over a hundred years have been projected in some field tests. Hundreds of thousands of trees have been saved. Millions more trees would have been saved had environmentalists not decided that their arsenic phobia was more important than trees. There are several variations of CCA. The most popular is CCA-C. Its formula is: CrO3 . . . . . . . . . . . . . . . . . . . 47.5% CuO . . . . . . . . . . . . . . . . . . . 18.5% As2O5 . . . . . . . . . . . . . . . . . 34.0% Until recent restrictions were placed on the consumption of arsenical wood preservatives, annual consumption in North America was about 150,000,000 lbs./yr. About 64,500,000 of arsenic as the pentoxide was safely consumed this way. World CCA consumption has been about double the above figures or 300,000,000 lbs. as 100% CCA and 129,000,000 lbs/yr as As2O5. Close to 100% of all the arsenic used in wood preservatives is derived from gold or copper processing. The valence of arsenic required for CCA wood preservatives and many other markets is the same valence that is required for stabilization. The economic challenge is how to get there. We have built and operated eleven plants to oxidize arsenic trioxide to its pentavalent form. Most of these have been classic in that they used a common oxidants such as hydrogen peroxide or nitric acid to achieve this.

Jan 1, 2005