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By Rui-Qing Li, John G. Peacey, Peter J. Hancock

"Noranda has been investigating a pyrometallurgical process for the direct recovery of zinc from zinc concentrate and zinc and iron containing residues. The process consists of injecting dry zinc concentrate and secondary zinc materials into a molten iron oxysulphide bath, volatilizing metallic zinc into furnace off gas essentially free of sulphur or S02, fixing sulphur contained in the feed materials as iron oxysulphide matte which is disposed, and recovering metallic zinc in an ISP type lead splash condenser. Combustion of petroleum coke with air or oxygen enriched air inside the oxygen containing matte supplies part of the heat, and the products of combustion dilute the zinc-laden gas to a desired level.This paper describes the process concept, thermodynamic background, experimental tests, mass and heat balance calculation for a conceptual flowsheet, environmental stability of the residue and advantages and disadvantages of the process. Experimental tests have successfully proved the process concept and thermodynamic predictions. Direct smelting of zinc concentrate and residues inside an iron oxysulfide bath has a great potential to become a cost effective and flexible zinc smelting process.1. INTRODUCTIONZinc is mainly produced by a roast-leach-electrowinning process route, which accounts for about 80% of the world primary zinc production. This process produces high quality zinc with very high zinc recovery (>95%) but suffers from several major drawbacks such as using high cost electricity as reductant, producing environmentally problematic iron containing leach residue (jarosite or goethite) and the difficulty in treating secondary zinc feed materials containing high impurity levels, such as electric arc furnace dusts from the steel industry, and other complex sources. Also in some areas, markets for sulphuric acid are distant resulting in negative realizations on acid sales.The Imperial Smelting Furnace (ISF) process is the major pyrometallurgical process to treat zinc-lead concentrate. The advantage of this process over the electrolytic zinc process is its flexibility in treating high-lead, bulk concentrates with high recoveries of lead, copper and precious metals. However, this is a two-stage process involving sintering of Zn-Pb concentrates followed by blast furnace reduction. The process requires large amounts of high-quality coke which is a major operation cost, and the sintering process which results in serious environmental problems."

Jan 1, 1996

By Fathi Habashi

The recovery of uranium from wet process phosphoric acid was applied on industrial scale in the 1940's by using octylpyrophosphoric acid as an extractant. Later, more efficient reagents were used, e.g., di(2-ethylhexyl) phosphoric acid and actylphenyl phosphoric acid. In the 1970's the rare earths in Kola phosphate were recovered in Finland and recently (1997) in Norway using HNO, as a leaching agent and di(2-ethylhexyl) phosphoric acid as solvent. It was demonstrated later on laboratory scale that both uranium and rare earths could be extracted from the rock by tributyl phosphate but at different pH values provided that the rock is leached with nitric or hydrochloric acids instead of the commonly used sulfuric. This new concept opens the way to the possibility of treating phosphate rock by in-situ, dump, or vat leaching for the recovery of phosphate values as well as uranium and the rare earths. Another solvent extraction process is used industrially for the purification of phosphoric acid using butyl and amyl alcohols.

Jan 1, 1998

By Houyuan Liu

A new process was developed to recover nickel and cobalt by leaching laterite ore at atmospheric pressure and.95"-105" C. The nickel-containing goethite in limonite was first leached with sulphuric acid to liberate over 90% of nickel, cobalt and iron. The dissolved iron was then precipitated as Ni-free goethite by the additioil of saprolite. The acid released during iron precipitation as goethite was simultaneously used as lixiviant to leach saprolite to recover more nickel. With this process the limonite and saprolite were essentially converted into goethite-, gypsum- and silica- containing tailings. Twenty bench scale tests and two campaigns of pilot plant operation were carried out at BHP Billiton's Newcastle Technology Centre (NTC) from January to August 2002. The overall nickel and cobalt extractions were 81 to 90% and 91 to 100% respectively. The average plant availability was 99%. The advantages of this process over existing processes include high plant availability, high consistency, robustness and simplicity of the operation.

Jan 1, 2004

By Upali Siriwardane, Tushar V. Kudale, Naidu V. Seetala

"Cellulose acetate (CA) membranes with 25% triethyl citrate (TEC) as plasticizer were prepared with varying thickness for CO2 gas separation from water-gas-shift (WGS) reaction products. The AFM analysis of the CA membrane showed that the uniform coating had fewer and smaller pores as the film thickness increased, and corroborated by gas permeability studies. The CO2 permeability has decreased faster than CO permeability with the CA/TEC membrane thickness, and findings support that the CA membrane could be used to entrap CO2. Several CA/TEC membranes were also staked to increase the separation efficiency. Positron Annihilation Lifetime Spectroscopy (PALS) was used to estimate the nano-porosity (pore size and concentration) changes of CA/TEC films. PALS results show a decrease in pore size with increasing CA-TEC concentration in acetone, while the pore concentration increases. The PALS results are correlated with the CO2/CO permeability variations as the CA-TEC concentration change.IntroductionHydrogen is one of the main energy sources available for the future advancement of clean fuel technologies especially for fuel cells. Generation of hydrogen and CO2 from Water Gas Shift (WGS) reaction mixtures of CO and H2O is of interest to many researchers since it allows a large scale production of hydrogen [1, 2]. Once hydrogen is produced using the WGS reaction, the output products contain mixture of CO, CO2, H2, and water vapor. Metallic membranes have been used as hydrogen separation membranes [3-6]. As H2 is separated from the mixture using the metal membranes, we need to separate CO2, and find ways of sequestration of CO2 to avoid environmental problems by greenhouse gasses. Polymeric Membranes have been used for CO2 separation [7]. Plasticizer can control the micro-structural properties such as pore size and concentration of polymer membranes [8], which influence the size/molecular weight dependent diffusion rates of the gas molecules. We have used cellulose acetate with triethyl citrate as plasticizer to separate CO2 from the WGS reaction products. Positron annihilation lifetime spectroscopy (PALS) is very sensitive and able to identify different kinds of defects and their agglomerates such as vacancies, vacancy loops, and voids [9, 10]. PALS has been successful in determining the free volume in polymers that influence the properties of the polymers [11, 12]. Microscopic properties of the free volume obtained from PALS have been correlated to macroscopic properties [13, 14]. We used PALS to study the nanoporosity (pore size and concentration) and fractional free volume changes of CA/TEC films, and used to understand the variations observed in the CO2/CO permeability as the CA-TEC concentration in the membranes change."

Jan 1, 2014

By Roderick Guthrie

Gas injection into liquid steel baths is widely practiced, ever since the early days of Bessemer’s pneumatic steelmaking process. What has not been fully appreciated is the critical role of bubble sizes for delivering higher quality commercial steels than is presently possible. This was first proposed by Prof P. Hayes and his research group. Using a full-scale water model of a typical 4-strand Ladle-Tundish-Mold system, we demonstrate the potential advantages of modifying a typical ladle shroud, to generate microbubbles within the water flowing into the tundish. This is possible by taking advantage of high shear rates and turbulence kinetic energy available in that region. These microbubbles enhanced the removal of “micro-inclusions” (hollow glass microspheres) in the 5–50 micron size range, to the upper surface of the tundish. There, they were absorbed into an overlaying “slag” phase. Accompanying CFD studies confirmed that no microbubbles in the size range generated (500–900 μm), pass through the submerged entry nozzles into the moulds.

By Jong-Jip Kim, J. G. Byrne, W. Kim, In-Ok Shim, John E. Flinn

"Two rapid solidification processes for 304 stainless steel were studied: centrifugal atomization (CA) in a helium atmosphere and atomization by exposing argon-containing melt to vacuum (VGA). Positron annihilation and x-ray line broadening measurements of explosively consolidated monoliths were used to clarify microhardness measurements as a function of annealing temperature. Interesting differences in positron response between CA and VGA materials are ascribed to more carbide formation in the CA material than in the VGA material in the 600 0C range. In addition, hot isostatic pressing of the CA material was examined as to the relations between mechanical behavior, pore shape, and relative density. A variable stress concentration factor is introduced into the theory to allow for changing pore shape as relative density increases.IntroductionThere are many potential advantages of rapid solidification processing (RSP), such as a high degree of matrix supersaturation, finely dispersed microstructures, improved chemical homogeneity, and retention of metastable phases, which have been studied extensively. To consolidate rapidly solidified material which is in powder form into useful shapes often requires subjecting the material to elevated temperature for extended periods of time under mechanical forces, as in hot isostatic pressing or hot extrusion. In such cases, some of the characteristics of the rapid-cooling step can be strongly affected. An alternative is dynamic consolidation (1), for example by explosive forming, where the time frame at least is extremely short.In the present work, effects of the consolidation processes of hot isostatic pressing (HIP) and explosive forming in a die are examined. The particular material is 304 stainless steel. The characteristics of both RS and VGA 304 stainless-steel powders were described by Wright, Flinn, and Korth (2) earlier."

Jan 1, 1988

By Anja Pfennig, Thomas Böllinghaus, Marcus Wolf

During CCS components are exposed to a corrosive environment and mechanical stress which results in corrosion fatigue and is inevitably followed by the lifetime reduction of these components. The lifetime reduction of the cyclically loaded high alloyed stainless injectionpipe steel AISI 420C (X46Cr13, 1.4034) constantly exposed to highly corrosive CO2- saturated hot thermal water is demonstrated in in-situ-laboratory experiments (T = 60 °C, brine: Stuttgart Aquifer, flow rate: 30 l/h, CO2) in an environment similar to the on-shore CCS-site in the Northern German Bassin. In-situ tension-compression experiments were established simultaneously along with electrochemical measurements using a newly designed corrosion chamber in a resonant testing machine at a frequency as low as 30 – 40 Hz. In addition technical CO2 was introduced into the closed system at a rate close to 9 L/h. S-N plots, micrographic analysis and surface analysis of the fracture surface are demonstrated. X46Cr13 (surface roughness Rz = 4) reached the maximum number of cycles (12.5 x 106) at stress amplitude of 173 MPa producing a low scatter range of 1:3.5. Hydroxide and siderite layers were found on pits and crack surfaces. No typical fatigue limit exists. Pit corrosion prior to crack initiation may be identified as failure cause.

Jan 1, 2016

By O. Barbosa F.

The thermochemistry of the systems SCN-H2O, Au-SCN-H2O and Ag-SCN-H2O is discussed. Potential-pH diagrams at 25°C are drawn for each system considering several sets of concentrations of the species involved. The information provided by the potential-pH diagrams is.complemented by distribution curves for each series of gold and silver complexes with thiocyanate. The analysis includes comparisons between the thiocyanate systems and the analogous cyanide systems, pointing out analogies and differences between the leaching of gold and silver with thiocyanate and with cyanide. The possibility of using soluble oxidizing agents such as ferric ions, hydrogen peroxide and Caro's acid is evaluated. The thermodynamic data used in the calculations and the chemical reactions represented in the Pourbaix diagrams are all reported in three Appendices. The overall results indicate the thermodynamic conditions for gold and silver leaching by thiocyanate.

Jan 1, 1989

By ZHANG Ting

In view of the high consumption and contamination of traditional vanadium extraction technology, a new process of leaching the converter vanadium slag without roasting with titanium dioxide waste was proposed. Extraction mechanism of P204 in the leaching solution had been researched and single factor experiments show that after a prereduction of Fe, and under conditions: ambient temperature，leaching solution original pH=2.5, phase ratio (A/O)=1:3, shaking time 8min, the extraction rate of V is more than 98.62% meanwhile the separation rate between V and Fe is up to 135.3 in the 20%P204-10%TBP-Sulfonated kerosene extraction system.

Jan 1, 2015

By K. M. Parida

The kinetics of dissolution of manganese dioxide in dilute sulphuric acid solution have been investigated using iron pyrites as a reductant. The dissolution rate of manganese is independent of the speed stirring but depends upon temperature, particle size, specific surface area of manganese ore, acid concentration, Fe(II) concentration and amount of pyrite. The activation energy is 43.6 KJ/mol and the linear relationship between the rate of dissolution and lido indicates that the reaction is chemically-controlled. The redox reactions of MnO2 with iron pyrites and Fe(II) are the rate-controlling reactions.

Jan 1, 1990

By M. D. Stephens

A new, one-step process for extracting titanium from titaniferrous materials has been demonstrated. In the process, depleted uranium tetrafluoride (DUF 4), a solid, is mixed with ilmenite (FeTi03) and heated to 900°C. Titanium is extracted in the vapor phase as titanium tetrafluoride (TiF4) and the DUF4 is converted to uranium-iron oxide. The process has been found to selectively fluorinate the titanium in ilmenite and is capable of producing high purity TiF 4 with very low iron content. TiF 4 can be collected by condensation or through reaction with a fluoride salt such as NH4F, KF, or NaF. The TiF4 produced from the process can be used to make titanium metal, titanium oxide, or fluorotitanate compounds. Since the fluorination process is highly selective for titanium, it avoids many of the separations and waste issues common to other titanium extraction processes.

Jan 1, 2001

By A. M. T. S. Bandara

The solubility of rare earth (RE) salts in aqueous solutions depends on many factors including the type of cations and anions in solution, their concentrations, temperature and the type of solid precipitated. Experiments were conducted using anhydrous La2(SO4)3 and Ce2(SO4)3⋅8H2O as solids and lanthanum(III) perchlorate prepared by dissolving La2O3 in HClO4 solutions as RE-sources. Solutions of H2SO4, H3PO4 and their mixtures in the presence or absence of Na+, Ca2+, Fe(III) or Al(III) as perchlorates served as test solutions. Saturated solutions and precipitated solids were assayed and characterized using standard techniques to show that the La(III) and Ce(III) ions precipitate as hydrated sulphates, phosphates or double salts with sodium, depending upon the solution composition. The change in solubility of RE-salts with solution composition and temperature is the result of the composite effect of changes in solubility products (pKSP) of salts, pKa of acids and other equilibrium constants for ion-association.

By B. Mishra

The major waste product of the alkaline extraction of alumina from bauxite [Bayer Process] is known as red-mud. Approximately, a ton of red-mud is produced for every two tons of bauxite that is mined. The red-mud produced from Jamaican bauxite is rich in hematite, alumina and titanium oxide. It has been shown that over 90 wt. pct. alumina can be recovered from red-mud by soda-ash sintering and caustic leaching. Hematite can be carbothermically reduced with a degree of metallization of over 94 pct. At this stage, the product could be charged through the tuyeres in an iron blast furnace or smelted to produce pig iron. The mineralogical characteristics of the reduced product are not amenable to magnetic separation for iron recovery. The problems associated with the use of reduced red-mud as an alternative to direct-reduced iron [DRI] has also been discussed. Special attention has been paid to lower the alkali content of the reduced material. If smelted, the concentration of titanium oxide in the slag will be significantly high justifying its recovery by an acid-leach process. This paper describes the successful efforts of iron and alumina recovery.

Jan 1, 2000

By T. R. A. Davey

The technologies of lead, zinc and tin extraction have made varying degrees of progress over the past twenty years. Producers of all metals have faced increasing demands for reduction of pollution and environmental degradation, and the level of public concern is rising rather than abating. New processing techniques must therefore be not only economically feasible, but politically acceptable, even when the demands of "conservationists" and ?environmentalists? are unreasonable. A new generation of processing techniques has come into being, which do not rely on an expensive sintering stage, nor use metallurgical coke, which is difficult to make without serious pollution. They utilise intense reactors, conveying materials from one stage to the next preferably within an enclosed space, obviating fume emissions, and avoiding heat losses as far as possible. The acceptability of the new techniques? is increased if lowgrade or complex materials can be treated, along with a variety of returns and wastes. In addition, a good selling and servicing organisation seems to be as important as good process technology in determining the spread of the new processes. In the field of pyrometallurgical refining the need is for more general application of several recently developed techniques rather than a search for alternatives to the existing process technologies. However, there is a need for fundamental work investigating the phenomenon of oxygen anode overvoltage in the electrolytic zinc process, in order to make progress in the further reduction of energy consumption. There is also scope for further development and application of vacuum distillation to up-grade thermally produced zinc. This paper presents a personal view of processes which should be developed to overcome existing problems, as we approach the turn of the century,

Jan 1, 1990

By Yasuhiro Konishi, Norizoh Saitoh

"We have developed new recycling technologies, based upon an eco-friendly biotechnology, in order to extract precious and rare metals sourced from post-consumer products. Recently we have been focusing on the metal ion-reducing bacteria, Shewanella algae and Shewanella oneidensis, which are able to reduce and deposit the precious metal ions (gold (III), platinum (IV), palladium (II), and rhodium (Ill)) into metal nanoparticles at room temperature within 120 min. When targeting the leachates from printed circuit boards, the Shewanella bacteria were able to allow selective reduction and deposition of gold (III) ions under acidic conditions in the presence of heavy metal ions, proposing a new bio-recovery system for gold. We also found that the Shewanella bacteria can separate and concentrate soluble rare metal ions (dysprosium (III), indium (Ill), and gallium (Ill)) from dilute solutions. Using this biomass adsorbent, the effectiveness of system for the novel recovery of indium from the leachate of used LCD (liquid crystal display) panels has been demonstrated.IntroductionMany high-tech manufacturing industries are highly dependent upon the use of critical raw materials that are the rare metals (e.g. rare earth elements/indium) and precious metals (e.g. gold/platinum group metals). There are now serious global concerns over the short term and long term availability of critical raw materials for high-tech manufacturing. This highlights the paramount importance of sustainable component reuse and material recycling technologies for recovery of critical raw materials. We believe that the most important domestic source of precious metals is through more recycling, and this will require more research and further development for the recycling of precious and rare metals. In general, chemical/thermal recycling is deemed to be the most appropriate means to extract the precious and rare metals from postconsumer products. However, there are issues related to the heavy use of toxic and hazardous chemicals, and the release of toxic emissions.Biological recovery methods provide an attractive alternative strategy and use microorganisms to separate and concentrate soluble precious and rare metals from dilute solutions into microbial cells via biosorption [1-3] and biomineralization [ 4, 5]. Biological systems generally operate at ambient temperature and near-neutral pH. Consequently, microbial recovery of metals would be an environmentally friendly method for recycling precious and rare metals from end-of-use products."

Jan 1, 2014

By Patrick R. Taylor

Ilmenite concentrate and methane are fed to a non-transferred arc thermal plasma reactor to produce a powder that is primarily TiC and Fe. This material has promising characteristics for powder metallurgy applications. Free energy minimization plots were used to predict the feasibility of the reaction. An estimate of the optimum molar ratio between the ilmenite concentrate and methane was made based on the mineral composition. Argon-helium mixtures were used as plasma gases. The effects of power input level, carrier gas flow rate, powder feeding rate, and methane-ilmenite molar ratio were studied and the behavior of the system characterized. Two different powder injection angles were tried. A mathematical model to describe the temperature profiles in the reactor was formulated and solved. The product has been characterized by x-ray diffraction and atomic absorption. A conversion of 97 % of Ti to TiC was achieved. It was found that minor amounts of titanium oxides, iron carbide and free carbon are also present. TEM and SEM were used to study the morphology.

Jan 1, 1996

By M. Opler

Presently, only a few large copper refineries are able to produce Grade A cathodes from copper scrap. Today's technology needs large plants for smelting, converting or refining the main impurities and casting the anodes for electrolytic refining. A new ECUPREX® PROCESS, by-passes all pyrometallurgical operations and produces directly copper cathodes starting from copper scrap with high lead and tin contamination. Copper scrap from chopped cables, copper cements and electronic scrap are suitable feed for ECUPREX® PROCESS. This process uses a non-conventional electrolyte and produces a surprisingly high quality, smooth cathode assaying only few ppms of total metallic impurities. Bench-scale work followed by a successful mini-pilot plant run, has led to the construction of an operating pilot plant equipped with a 1,000 Ampere cell. The results of the operations of this pilot plant are presented and described in this paper.

Jan 1, 1995

By Hidekazu Nakagawa

We investigated the anodic dissolution behavior of titanium in TMHA-Tf2N molten salt, which has a wide electrochemical window of about 5 V, in order to develop an electrodeposition method for titanium. By etching a titanium electrode in HF?HNO3?H3PO4 solution, the titanium electrode became electrochemically active, and a redox reaction was observed at around -0.15 V vs. I-/I3- in (TMHA-Tf2N)?HTf2N solution. We identified the redox reaction consists of the reduction of the proton and the oxidation of hydrogen. The diffusion coefficient of the proton in TMHA-Tf2N was calculated to be 6.9 10-8 cm2 s-1 at 50 °C from the cathodic peak current in the cyclic voltammogram. Anodic decomposition of the molten salt was not observed up to 6.0 V vs. I-/I3- on titanium electrode, while it was observed at around 2.0 V vs. I-/I3- on platinum and glassy carbon electrodes. Cathodic decomposition of the molten salt was observed at around -3.0 V on the titanium electrode, as well as on the platinum and glassy carbon electrode.

Jan 1, 2006

By Li Fangi

This paper describes the characteristics and regularities of a process to recover rare earth minerals from Baotou Ore with H-205 collector. H-205 is a kind of hydroxamic acid with amide as a polar group and poly-cycle aromatic hydrocarbon as a non-polar group, having strong ability to capture RE minerals (bastnasite, monazite). When adding a certain dosage of water glass and some other modifying agents, and maintaining pH value between 8.5 and 9.5, RE minerals can be effectively separated from calcium and barium minerals, such as fluorite and barite, etc. Under normal flotation temperature and concentration, when using H-205 to float RE minerals, it needs a bit longer conditioning time (a few minutes longer than that for the conventional collectors). It is also shown that the reagent has the property of resistance to hard water. The laboratory scale and pilot scale tests of the process have been carried out on bulk froth containing RE minerals and fluorite taken from Ore Dressing Plant of Baotou Iron and Steel Company, in both cases, high grade RE concentrates were obtained and the recovery increased remarkably. Therefore, the process has a great practical value.

Jan 1, 1989

By L. W. Beckstead

In a conventional zinc refinery plant, zinc concentrates were roasted at 950°C. The calcine was ground and leached in a series of leaching vessels using sulfuric acid. The pH in the first leaching vessel was maintained at 2.5, while the pH of the solution exiting the last vessel was about 5.4. The leached residue typically contained (in percent) 0.1 Ag, 0.2 As, 0.7 Cd, 2 Cu, 15 Fe, 10 Pb, and 15 Zn, and it was classified as hazardous material according to the EP-toxicity test. In order to make the residue non-hazardous, and to recover most of the metal values from the residue, a brine leach process was developed. The process consisted of leaching the zinc leach residue in CaCI, brine solution at pH 2 for 1 hour at 90°C. Silver extraction was about 95 percent, while lead, copper, cadmium, zinc, and iron extractions were about 80, 50, 50, 30, and less than 0.5 percent, respectively. More extreme conditions of acidity could have been used in the leaching stage to increase zinc dissolution, but iron dissolution would have significantly increased which would have complicated subsequent recovery steps. The leached and washed residue passed the EP-toxicity leach test and could be disposed as non-hazardous. Silver, copper, and lead in the leach solution were recovered by zinc cementation, while zinc and cadmium were recovered by sulfide precipitation. The resulting solution can be recycled in the process after magnesium precipitation.

Jan 1, 1993