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By Donald Voit

"The reaction between zirconia/zircon, coke, and chlorine involves a slow reaction between the coke and the zirconia/zircon and a fast reaction with chlorine. Because of the fast chlorine reaction, the reaction rate for zirconia/zircon is nearly independent of chlorine concentration for most conditions. The reaction between zirconia/zircon and coke is particle size controlled and related to the degree of physical contact between the zirconia/zircon and the coke. Since particle-particle contact is critical, compaction of finely ground coke and zirconia/zircon produces the highest reaction rates. Uncompacted, coarse coke and zirconia/zircon has the slowest reaction behavior with static bed tests.SummaryZirconia reacts with chlorine in the presence of carbon to form zirconium tetrachloride, carbon monoxide, and carbon dioxide. A similar reaction occurs with zirconium silicate with the additional formation of silicon tetrachloride. The reaction rate depends primarily on temperature and the intimacy of contact between the zirconia and the coke. The reaction is multi-stepped with a slow reaction between coke and zirconia to form an intermediate that reacts rapidly with chlorine, causing the order of the reaction for chlorine to be near zero. Chlorination rates in the range of 1 µmole/hr/cm2 are seen for fluid bed reactors. Plug flow, and static bed reactors have reaction rates of the order of 1 mmole/hr/cm2, where the area is based on the zircon surface area in plug flow and fluid bed reactors and the boat cross sectional area in a static bed. Chlorination rates measured in zirconia/coke briquettes are higher with rates as high as 400 mmole/hr/cm2 reported. High chlorine diffusion resistance, not accounted for in the analysis of experimental results, has led to a lot of confusion in the literature interpretation of chlorination data.In general coke and zirconia/zircon particle size, coke and zirconia/zircon intimacy, coke to zirconia/zircon ratio, chlorine concentration, and temperature are important variables for chlorination. Decreasing the coke and zirconia/zircon particle size generally increase the reaction rate. The coke to zirconia/zircon ratio affects the reaction in a more complex way. Increasing the chlorine concentration generally increases the reaction rate, but the effect appears to be more related to the concentration dependency of diffusion than to its role in the kinetics. The reaction rate increases with temperature but the exact behavior is complicated by temperature effects on diffusion."

Jan 1, 2011

By Samantha Moodley, Rauf Hurman Eric, Cevat Kucukkaragoz, Aditya Kale

"Two titania slags, rutile and synthetic rutile were chlorinated with petroleum coke and CO in a small bubbling fluidized bed reactor. The study aims to identify differences in chlorination mechanism, compare conversion rates, blowover and the chlorination of impurities for the various titania feedstocks at different temperatures.Chlorination rates were highest at 1000ºC; rutile chlorination significantly increases as temperature increases from 800ºC to 1000ºC. At 1000ºC, synthetic rutile had the highest chlorination conversion rate; this was followed by Slag B which in turn was more reactive than Slag A and rutile. The mechanism for slag, synthetic rutile (SR) and rutile chlorination differs. Synthetic rutile feed is porous, providing a larger surface area for the chlorination reaction, hence the highest conversion rates was attained. Titania slag becomes porous with the initial chlorination of FeO and MnO whilst rutile remains solid. As the porosity of slag particles increases so does its tendency to be elutriated. Ti2O3 is oxidized within the early stages of chlorination during the chlorination of FeO and MnO. Ti2O3 not oxidized is then rapidly chlorinated.IntroductionTitanium dioxide (TiO2) is the most common compound of titanium, about 95 - 98% of extracted titanium minerals is processed into TiO2 white pigment [1]. Two processing routes exist for the production of TiO2 pigments, i.e., sulphate and chloride based processes. In the chloride process, titania feedstock is fed to a fluidized bed reactor together with reductant and chlorine gas. A temperature of 1000 - 1300ºC is maintained in the reaction zone and apart from silica, zirconia, uranium and thorium, virtually all the metal oxides in the feed are converted to their respective chlorides [2]. Chlorine is recovered and recycled back to the reactor."

Jan 1, 2012

By C. M. Wai

"Metal species in solid and liquid materials can be extracted by supercritical carbon dioxide containing a suitable ligand. This in situ che1ation-supercritical fluid extraction technique offers several advantages over conventional solvent extraction including minimization of organic liquid waste generation and exposure of personnel to organic vapors. One unique feature of this technique is that metal species can be removed from solid materials directly using supercritical carbon dioxide as a solvent. Several ligand systems including dithiocarbamates, B-diketones, organophosphorus reagents, and macrocyclic compounds have been tested for metal extraction in supercritical carbon dioxide. This novel extraction technique may have important applications for metal recovery and mineral processing.IntroductionSupercritical fluid extraction (SFE) offers several advantages over conventional solvent extraction including the minimization of organic liquid waste generation and exposure of personnel to organic vapors.[1] The high diffusivity, low viscosity, and T-P dependence of solvent strength are some attractive properties which make supercritical fluids excellent candidates for extraction and recovery of organic compounds from solid materials [2] Carbon dioxide is a gas of choice for SFE because of its moderate critical constants (Tc = 31 °·C and Pc = 73 atm), inertness, and availability in purified form. After extraction, the fluid phase is depressurized to separate organic solutes from CO2 gas and the gas can be recycled for repeated use. The SFE technology has been applied to industrial scale operations such as the preparation of decaffeinated coffee and hop extracts."

Jan 1, 1996

By Tianming Sun, Gabriella Tranell, Ragnhild E. Aune, Mark William Kennedy

Rare Earth Elements (REEs) are critical for the production of many advanced materials and products. Mining and primary production of REEs are generally associated with significant environmental impacts. By recovery of REEs from secondary sources, through recycling or as a byproduct, the adverse environmental impacts may be partly avoided. In the present study apatite concentrate originating from iron ore beneficiation done by LKAB in Kiruna, Sweden, is explored as a possible source for REEs. The composition and distribution of the REEs within the concentrates are studied using ICP-MS, XRD and SEM-EDS/EPMA, as well as the melting point and heat of fusion using DTA-TGA-MS. The behavior of the material during melting has also been studied through wetting and slag saturation experiments. The overall aim of the study is to evaluate the implications for future smelting experiments aimed at concentration and recovery of the REEs.

Jan 1, 2015

By H. H. Kellogg

The thermochemical properties of molten solutions in the binaries Cu-Bi, Cu-Sb and Bi-Sb, as well as the ternary Cu-Bi-Sb, have been correlated and described in mathematical form by use of the associated species concept combined with the three-suffix Margules equations to account for the non-idea 1 behavior of the solution species. Agreement of the correlations with experimental data is excellent (relative deviation of less than 2.5% in the values of the activity coefficients) in most cases. The correlations are applicable over the entire composition range of each system, and in the temperature range 700°-1250°C.

Jan 1, 1985

By R. J. Dippenaar, W. H. Van Niekerk

"An injectable lime-based desulphurization reagent for the treatment of liquid iron was developed. Firstly, selected lime based slags containing small quantities of CaF2 to increase fluidity, and Na20 to increase the basicity, have been evaluated on laboratory scale from a thermodynamic point of view. Subsequently, pilot plant and full scale industrial injection trials were conducted. It was found that lime-based slags, containing Na20 and CaF2, are able to desulphurize liquid iron efficiently. By the injection of a lime based reagent consisting of 60% lime, 25% soda ash and 15% fluorspar at a rate of 7 kg reagent/ton hot metal, the sulphur level in the metal (115kg) was reduced from 0,07% to 0,01 % within 5 minutes. The lime-based reagent developed in this study was successfully injected, both from a metallurgical and from a pneumatic point of view, on an industrial scale. The mathematical model utilised in this study, can be used successfully to predict the course and extent of desulphurization by lime-based slags. IntroductionMainly due to environmental difficulties encountered with pure soda ash, dry slag formation with CaC2 and high cost when Mg are used as desulphurizers, much incentive exists for the development of an inexpensive, environmentally friendlier desulphurization reagent. As a first step in the development of such a reagent, selected lime based slags containing small quantities of CaF2 to increase fluidity, and Na2O to increase the basicity, have been evaluated on laboratory scale from a thermodynamic point of view. This was followed by pilot plant injection experiments in which the kinetics of the relevant desulphurization reactions were evaluated. Finally, full scale industrial trials were conducted. All three phases of the investigation will be discussed with the major emphasis being placed on the kinetic study."

Jan 1, 1996

By Alicia E. Ares

316 L Stainless Steel samples were solidified directionally under conditions which produced the columnar to equiaxed transition. The position of the transition was located in each sample and the distance from the bottom of the ingot was measured. During solidification the distribution of temperatures were measured by means of thermocouples located strategically. From the measured temperatures the following parameters were derived; the local temperature gradient, the cooling rate and the velocities of the liquid and solidus fronts. Comparing the location of the transition and the values of these parameters it was found that the temperature gradient reaches negative values of as low as -13.44 "C/cm, and velocities of the fronts of around 0.1 cm/s. Also, a supercooling of 5.81°C were measured which was associated with the supercooling for the nucleation and growth of the equiaxed grains ahead of the columnar front. In addition the primary and secondary dendritic spacing was measured in both regions. The spacing was compared with the predictions from available models. The results are presented and discussed in the frame of the results obtained for other alloys

Jan 1, 2002

By Yutaka Shiraishi

Two methods were developed to measure the viscosity of the slag from the glassy to the liquid states in an ascending temperature process. The first method employs rotating parallel plates within which is placed a solid cylindrical sample in line with a sphere. The second method uses a tube which is pushed into a sample held in a rotating crucible. Both methods were tested using standard glasses, including boron trioxide and NBS standard glass #711. The main difference between these two methods is in sample preparation. Comparative measurements between two methods were performed using a sodium boro-disilicate glass containing 5%mol of alumina. The results showed good agreement in the mid-range of glassy viscosities, 105 to to7 Pa.s. In the liquid state, there were no significant differences between the two methods.

Jan 1, 2003

By Peter R. Sanford

Cyanides are present as a dilute constituent of streams from a variety of metallurgical and mineral-processing operations. In addition, a cyanide concentration in excess of approximately 100ppb is toxic to aquatic life, and consequently these operations require a waste-treatment process to reduce the already dilute cyanide species by several orders of magnitude. Furthermore, the waste streams may have flowrates in excess of a million gallons per day. The paper reports on research conducted with a laboratory?scale electrochemical porous (graphite felt) electrode (anode) flow-reactor, which was conducted in conjunction with a computer-aided simulation of a mathematical model describing the intrinsic rate-phenomena associate with the electrode processes. The laboratory-scale cell, of rectilinear geometry, was found to be capable of reducing a feed-stream anolyte (KCN-KOH and supporting electrolyte of a single salt ? K2SO4) with a cyanide concentration of 10ppm, to less than 100ppb, at current efficiencies in the neighborhood of 50%. The computer simulation of the cell performance based on the mathematical model (and constraints imposed for tractability) was found to provide only for qualitative agreement.

Jan 1, 1998

By Dian Adisty, Leiv Kolbeinsen, Eli Ringdalen

In Si and FeSi production, the main Si source is SiO2, in the form of quartz. Reactions with SiO2 generate SiO-gas that further reacts with SiC to Si. During heating, quartz will transform to other SiO2 modifications with cristobalite as the stable high temperature phase. Transformation to cristobalite has been investigated and shown to be a slow process where the rate varies between the investigated quartz types. The effect of quartz versus cristobalite as SiO2 source has been studied for reaction (1) 2SiO2 + SiC = 3SiO + CO, by heating of pellets with SiO2 + SiC in Ar-gas. The reaction was faster with cristobalite than with quartz. Initial experiments indicates that this is the case only in Ar and not in CO-atmosphere The higher specific surface area of cristobalite is believed to contribute to the higher rate. The industrial consequences of the observed difference between quartz types are discussed.

Jan 1, 2014

By Bao Xiancheng

Jinlong's copper flash smelting process started up in April 1997. In the early days of production, lots of equipment and process problems were encountered. But, through continuous improvements in equipment and operation, the designed productivity was reached two years later and the smelting operation has been greatly upgraded since then. After more than 4 yew of production, we have made great achievements, such as increasing the flash furnace availability, significant improvements in operation control, optimization of concentrate burner's structure and operation, and smooth operation of the whole smelter. This paper outlines Jinlong's operational achievements made after commissioning, and discusses problems that were encountered and their countermeasures. Operational experience is also summarized

Jan 1, 2002

By G. A. Irons, D. Colbert

Several electric arc furnace (EAF) shops have increased the zinc and lead grades of EAF dust by reinjecting it into their furnaces; however, the kinetics of this operation are poorly understood. To understand the kinetics, EAF dust was injected into 70 kg heats of iron or steel in an induction furnace. Supplemental additions of carbon and oxygen to overcome the heat load on the system were also investigated. In all cases, the dust was chemically transformed, and the zinc content increased from 16% Zn to 60 - 80% Zn. About 50% of the zinc in the EAF dust dissolved in the iron or steel. The zinc oxide in the dust is thought to be reduced by carbon and the zinc vapour subsequently dissolved in the iron. A kinetic model for the dissolution process is proposed, and the implications for EAF dust recycling are discussed.

Jan 1, 2000

By Tetsuya Uda

Our recent achievements of rare earth separation technique[1,2] and new process idea for rare earth magnet recycling[3] are reviewed, (1) Binary chloride mixtures of rare earths were separated by a new selective reduction-vacuum distillation process. According to our experimental results, apparent separation factors were 8.1 for the Pr-Nd chloride mixture and 570 for the Nd-Sm chloride mixture. These values are much higher than conventional solvent extraction methods. (2) A study of recycling process of magnet sludge was carried out. The rare earths in the neodymium magnet sludge were extracted by chlorination with FeCI2, An activated carbon was used as a de-oxidation reagent Metallic iron in the sludge was not chlorinated because the iron monochloride is not stable, The extracted rare earth chlorides were easily separated from Fe-alloy and the excess of FeCh by vacuum distillation, 96 % of neodymium and 94 % of dysprosium in the sludge were extraeted into chloride phase, By the vacuum distillation, a mixture of neodymium and dysprosium trichlorides of 99.2 % purity was recovered, On the other hand, the rare earth chlorides can be converted to the corresponding oxides by a pyrohydrolysis reaction accompanied by a formation of HCl gas, The HCI gas can chlorinate metallic iron to FeCh, Therefore, a new recycling process for rare earth magnet waste can be realized as a chlorine circulation type process. During the process, only carbon and water are consumed and there are no toxic pollutants, Moreover, the obtained rare earth oxide can be directly used as raw material in the conventional oxide electrolysis process,

Jan 1, 2003

By J. Pesl, U. Kemey, F. Sauert

"The CONTOP® smelting cyclone is a water-cooled, upright, high-intensity smelting reactor. The technology for the reactor was initially developed and brought into industrial-scale operation in the area of non-ferrous metallurgy. The two largest smelting cyclones were built with a capacity of 32 tons per hour of copper concentrate mix.The newest industrial CONTOP® plant treats up to five tons per hour of zinc-bearing residues including EAF dust. The highly concentrated zinc-lead oxide produced is sold to the zinc industry. The slag fulfills the leaching criteria and is used in waterway construction. The heat transferred to the cyclone cooling system and the off-gas boiler produces steam from which power is generated in a turbine.V AI has erected a new CONTOP® demonstration plant at MEFOS, Lulea, Sweden. A zinc volatilization rate of 90% was achieved during hot commissioning with Swedish EAF dust.Treatment costs in the range of 85 to 100 EUR per ton were estimated in a feasibility study on the treatment of 73,000 and 57 ,000 tons EAF dust for a group of steelmaking mills in Southern Europe."

Jan 1, 2000

By F. Shahbazian

attempt to systematize the knowledge on slag viscosities, the present work was carried out. The Among the physical properties of slags, viscosity is very important in understanding the mass out in the temperature range 1438-1762 Q The rotating cylinder method was used in the viscosity measurements. Crucibles and spindles made out of pure iron were employed. The transfer phenomena in metallurgical processes. The viscosities of fayalitic slags are of great interest in the non-ferrous metal industry, with special reference to copper production. In an slags were prefused before the measurements. In order to take into account the vaporization reactions involving CaF2, pre- and post measurement samples of the slags were chemically analysed and the compositions were ascertained. The results show that in the case of the CaO-SiO2 system, CaF2 additions tend to decrease the viscosity, in accordance with the expectations. In the case of the "FeO"-SiO2 system, at higher "FeO" / SiO2 ratios in the slags, a reverse trend was observed. The results are discussed on the basis of a viscosity model for silicate melts developed in the present laboratory as well as the structural considerations of silicates.

Jan 1, 2000

By Milorad Cirkovic

Kinetics of copper concentrate oxidation in roasting processes in a fluidized bed reactor has been studied at temperatures between 600°C and 720°C using particles of 0.038 to 2.5 mm in average size. The analysis of composition of samples has been done by chemical methods. Phase composition has been determined by Siemens X-ray equipment with Cu anticathode and Ni filters at a voltage of 40 kV and a current of 18 mA. The content of sulphur has decreased from 33.23 to 19.02 mass percent with the increase of temperature, but the content of Fe304 has increased from 0.15 to 17.14 mass percent. The new mechanism of copper concentrate oxidation in a fluidized bed reactor is proposed in this study. It has been shown from the mathematical model that the velocity of oxidation of copper concentrate between 600°C and 720°C is virtually controlled by the rate of diffusion of 02 through the layer of reaction product.

Jan 1, 1999

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 Th. Probst, M. Reuter, H. Orbon, U. Boin, J. Vonken, P. Vonk

Although secondary aluminum industry is well established in the world, the recycling process still requires further development to adequately control the process for a higher aluminum yield and a better product quality. In the present paper, recyclabilities of different aluminum scraps have been experimentally studied. Four types of commercial scraps were characterized and melted at 800 - 900 °C to recover 'aluminum metal with the protection salt flux of NaCl-KCl-Na3AlF6 under nitrogen atmosphere. According to the results, the difficulty of recycling aluminum scrap depends on the cleanness and the ratio of surface area to body volume. More non-metallic contaminates and higher ratio of surface area to body volume usually led to a lower metal yield. Usually cast ingots gave better results than rolling mill cuttings under similar conditions. Bottle caps can be recycled more easily than the margarine foil. The effect of temperature was not as significant as the composition of salt flux. The addition of cryolite was essential for a better metal recovery, especially for the scraps with higher surface area. Recycling

Jan 1, 2000

By Gui-fang ZHANG, Zhe SHI, Lei GAO

Secondary V-recycling slag, an industrial waste containing high gallium is being dumped continuously, which causes the loss of gallium. Thus, the alkali fusion process was employed to recover gallium from this slag. The effects factors on extraction of gallium such as roasting temperature, roasting time, alkali fusion agent concentration and CaO concentration were investigated in the paper. The experimental results indicated that excessive roasting temperature and roasting time is unfavorable to the recovery rate of gallium. The appropriate roasting temperature and duration are 1000 and 2 hours, respectively; The appropriate proportioning of Na2CO3: NaOH is 2:1 when the concentration of alkali fusion agent weighs 0.4 times the mass of the slag; In order to remove SiO2 from the leaching liquor, CaO should be used as an additive in the roasting process. The appropriate concentration of CaO should weigh 0.2 times the mass of the slag. Employing these optimal alkali fusion conditions in the roasting process, gallium recovery is above 90%

Jan 1, 2015

By T. C. -M. Cheng

Iron removal and disposal in zinc plants has imposed a major environmental challenge to the industry. Among the existing options of precipitating iron as jarosite, goethite, and hematite, the Hematite Process seems to be the best candidate for the future development of a waste-free technology, because of its potential of producing saleable iron oxide residues for feed in iron-steel making industry. Unfortunately, under the current practice of the Hematite Process, it is not possible to produce iron residues clean enough to meet the specifications of the said industry. In this paper, the practice of industrial hematite precipitation and the relevant technical literature are reviewed with the objective to identify the critical processing parameters which are responsible for the contamination of hematite, particularly with sulfur and zinc. The analysis is conducted from a crystallization theory standpoint with emphasis given to the role of supersaturation with respect to the cleanliness of hematite precipitates.

Jan 1, 1997