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By Mitsuru Tanahashi

In order to develop an effective process for the production of from metallurgical-grade one (MG-Si), the oxidation removal of boron from molten MG-Si was investigated at a solar-grade silicon (SOG-Si) 1773K by the following two CaO-saturated CaO-CaF2 flux treatment processes. I) Boron removal by flux addition onto the molten M6-8 followed by oxygen gas injection into the melt (Two-stage connecting process). II) Boron removal by simultaneous injection of flux powders and oxygen gas into the molten MG-Si (Simultaneous injection process). These processes can establish the special condition of both high basicity of the flux and the high oxygen partial pressure at the boron removal reaction sites. Through these processes, especially by the simultaneous injection Process using a flux powder injection equipment, the boron content in MG-Si can be efficiently reduced. The obtained results clarified that both processes should be conducted for a time period as short as possible by using as much flux as possible. By repeating the simultaneous injection process for 60 s three times under the optimum operating conditions determined in the present study, the boron content in MG-Si can be reduced from 14 to 4.7 mass ppm.

Jan 1, 2003

The reported values of the standard reduction potentials of the Au(NH3)2+/Au(0) and Au(S2O3)23-/Au(0) couples are reviewed to emphasise the experimental difficulties associated with the measurement of reliable values for these quantities. The standard reduction potential for Ag(I)/Ag(0) in ammonia and thiosulphate solutions measured at ionic strength 0.1 and 25oCis used to predict the following relevant stability constants () for gold complexes based on the linear free energy correlations: Au(NH3)2+2 = 1013, Au(S2O3)23-2 = 1024 and Au(NH3)43+4 = 1033. The equilibrium constant ( 10-11) for the reaction Au(S2O3)23- + 2NH3 = Au(NH3)2+ + 2S2O32- based on these stability constants is in reasonable agreement with the measured value (10-9) based on potentiometric and spectroscopic data when excess ammonia was added to a solution of Na3Au(S2O3)2. This also indicates that the stability constant of Au(NH3)2+ is 9 to11 orders of magnitude less than that of Au(S2O3)23-. Relevant species distribution and Eh-pH diagrams based on the revised data are presented.

Jan 1, 2003

By A. V. Tarasov

In order to improve the efficiency of hydrometallurgical processing of pyrrhotite concentrates, an integrated set of research has been carried out to investigate the use of sulfur dioxide in individual unit operations and as a leaching agent in the autoclave process as a substitute for oxygen. Treating iron-containing raw materials for production of nonferrous metals are based on the selective reaction of SO2 with iron sulfides and oxides. Iron is dissolved as sulfate, which can be treated in a separate circuit to produce iron-containing pigments or it can be disposed of after neutralization. Nonferrous and precious metals contained in pyrrhotite concentrate do not react with sulfur dioxide and remain virtually completely in the solid phase, i.e. high-grade sulfide concentrate to be treated by hydro- or pyrometallurgical methods. Elemental sulfur formed in the process of leaching is separated from the pulp in granulated form as a result of the use of special surfactants. The process of sulfide concentrate leaching with the use of sulfur dioxide is conducted at temperatures above the sulfur melting point (119°C) with distributed feeding of surfactant and under a partial pressure of sulfur dioxide of up to 0.3 to 0.5 MPa.

Jan 1, 2006

By A. H. Rosenberger, M. A. Tschopp, M. A. Groeber, K. N. Solanki, A. L. Oppedai, J. D. Miller

"Characterizing the spacing of primary dendrite arms in directionally-solidified microstructures is an important step for developing process-structure-property relationships by enabling the quantification of (i) the influence of processing on microstructure and (ii) the influence of microstructure on properties. The research objective herein is to evaluate the capability of various conventional approaches, as well as new or modified approaches, for spatial point pattern analysis with application to characterizing experimental dendritic microstructures. Both computer-generated and experimental dendritic microstructures are used for this analysis along with numerous techniques based on the nearest neighbor spacing, Voronoi tessellation, Delaunay triangulation, or graph theory. Comparison of new metrics with traditional primary dendrite arm spacing metrics will also be discussed for both local and global measures. The current methods investigated will supply information of local spacing and coordination number while addressing edge effects, parameter sensitivity, and correlation with interdendritic features, thus providing insight into how processing affects properties.IntroductionDeveloping an enhanced understanding of mechanical behavior in materials relies upon sufficiently characterizing microstructure details at the relevant length scales that contribute to this behavior. Moreover, to truly enhance the predictive capability of processing-structureproperty models that aim to improve material performance requires a quantitative description of the relevant microstructure features and, thereby, the material itself"

Jan 1, 2013

By Alain Jardy, Valerio De Felice, Jean-Pierre Bellot, Ismael Lis Alves Daoud, Stephane Hans

"Gas-stirring ladle treatment of liquid metal has been pointed out for a long time as the processing stage mainly responsible for the inclusion population of specialty steels. A steel ladle is a complex three-phase reactor, where strongly dispersed inclusions are transported by the turbulent liquid metal / bubbles flow. We have coupled a population balance model with CFD in order to simulate the mechanisms of transport, aggregation, flotation and surface entrapment of inclusions. The simulation results, when applied to an industrial gas-stirring ladle operation, show the efficiency of this modelling approach and allow us to compare the respective roles of these mechanisms on the inclusion removal rate.IntroductionThe reduction of the weight of high performance materials together with the improvement of mechanical properties and the increase of the recycling of used metal are new challenges which emphasize the importance of metal cleanliness. Ladle treatment of specialty steels has long been described as the secondary metallurgical process mainly responsible for the non-metallic inclusion derived from the deoxidation process. The treatment is accomplished by blowing argon through one or more porous plugs for the purposes of desulphurization, minor composition adjustments, and inclusion removal. Gas injection is applied on routine basis to achieve both the stirring of the liquid bath (thermal and chemical homogenization) and the entrapment of the inclusions by the bubbles (flotation). Furthermore, the turbulence produced in bubble swarms enhances the probability of inclusion collisions and makes aggregation the first mechanism for particle removal. The physical processes involved in gas stirred ladles are numerous and complex owing to the three dimensional and multiphase (metal-gas and inclusions) nature of the reactor. Despite these difficulties, the population balance equations can be implemented in CFD code11'21 and combined CFD-PBM (computational fluid dynamics - population balance method) models are investigated for steel ladle processes13'41 and produce very promising results in terms of inclusion removal efficiency."

Jan 1, 2012

By Eduardo Juncal, Jorge Alberto Soares Tenorio, Jose Roberto de Oliveira, Denise Crocce Romano Espinosal

"Steel industry has been expanding every year, consequently there has been an increase in waste generation in this area. Thus, companies in this sector are finding it difficult to give a correct destination of waste. For example, only in a basic oxygen furnace (BOF) converter are generated about l8kg of dust per ton of steel. The aim of this work was the characterization of dust generated in the BOF converter. The characterization was performed by chemical analysis (titration for iron and its oxides and Inductively Coupled Plasma Atomic Emission Spectroscopy for other elements), scanning electron microscopy, size analysis using Mastersizer 2000 equipment and X-ray diffraction. It was observed that dust is composed mainly iron in form of magnetite, metallic iron and wustite with approximately 99% of the particle size below 100 µm.IntroductionToday, steel is a important metal for the world. It can be produced for two routes, blast furnace/ basic oxygen furnace (BOF) converter and electric arc furnace (EAF) [1].First route, the iron is produced from the reduction of iron ore and coke for fuel injection and! or natural gas for a production of pig iron in blast furnace. The pig iron is sent until BOF converter to perform the blowing of oxygen to obtain the steel. In the second route, the steel is produced using scraps or direct reduced iron (DR!) using electric arc.During steel production are generated a lot of wastes like slag, sludges, scraps and dust [2]. Only in the first six months of201O, world steel production totaled 706 million tons [3]. According to Watson and Wang [4], some 10 to 20 kg of dust is generated per tonne of liquid steel produced. Thus, the reuse of these wastes can be a great to companies, because it reduces the amount of raw material to be extracted and reducing disposal costs [5,6]."

Jan 1, 2012

By M. E. Coleman, G. Money

"Clyde Materials Handling is an established customer-driven solutions provider, which utilizes its knowledge, expertise and technologies to transform the production processes of its customers, who operate in the ferrous and non-ferrous metals industries.With over 30 years experience in the process improvement industry, Clyde Materials Handling has helped their global customer base transform the way in which they operate their processes, which has enabled them to generate sustainable economic benefit and maintain their positions as leaders in their respective markets.Clyde Materials Handling has supported operators within the metals market by developing and deploying pneumatic conveying and pneumatic injection technologies. These environmentally supportive and sustainable solutions have been used to transport raw materials within operating facilities, from storage to silo, as well as injecting these materials directly into the heart of production processes.Clyde Materials Handling has worked closely with their customers, such as Codelco in Chile, where their pneumatic solutions have been used to inject a consistent, pulseless and accurate flow of copper concentrate into a bath smelter, which has helped to fuel the operational capacity, availability and productivity.This paper will discuss and highlight the ways in which pneumatic injection technologies, created by Clyde Materials Handling, and applied in partnership with their customers, have helped to improve the operational performance of the production processes of operators across the non-ferrous metals markets with specific reference to applications in the Peirce Smith Converter.Clyde Materials Handling has applications injecting Electronic Scraps, Dusts, Reverts, and other additives to the Peirce Smith Converter. They also have experience of modified PS Units used for Slag Cleaning. There experience with the Codelco Teniente Converter is also directly related to this area of operation."

Jan 1, 2009

By A. Navarra

Within conventional copper and nickel-copper sulfide smelters, ladles of molten matte are fed into converters. These converters blast oxygen-enriched air into the matte, thereby eliminating iron and sulfur. The converting reactions are exothermic and, indeed, the converter heat balance is often a limiting consideration on the smelter throughput. If a portion of the matte were fed in solidified (granulated) form, this would support higher oxygen enrichment, and lower volumes of converter offgas, allowing higher throughput. This approach is not applied in conventional smelters, partly because of the copious amounts of water that must be evaporated in typical granulators, as in the Kennecott-Outotec process. The current paper recalls a waterless matte granulator that had been pioneered in the 1990’s, and is applicable to conventional smelters. A mathematical formulation is presented that can be used in the context of simulation-based optimization, to estimate the size and impact of waterless matte granulation.

By N. G. Azeredo

This work dealt with the evaluation of engineering structural clay brick samples that were sintered at estimated temperatures of 700 and 800°C. They were collected in a red-brick plant in Campos dos Goytacazes, RJ, Brazil. From a lot, a sample already sintered in its kiln at 700°C were collected and also a sample from the same lot only dried by the air, which were then sintered at 800°C controlled temperature. The samples were subjected to Brazilian Standard tests (ABNT NBR 15270:2005) to determine their geometric, physical and mechanical properties. In order to be classified as structural clay brick it is required minimum 3.0 MPa for the characteristic compressive strength (fbk) to be suitable for up to five floors structural building applications. We also used the Weibull Probability Plot and Weibull Maximum Likelihood Estimation to evaluate distribution parameters in order to compare the results of compressive strength obtained in the tests.

Jan 1, 2015

By Dorothée Proffit

Characterization of solids containing cyanides is carried out according to recommendations and standard guidelines. Most of these procedures are based on the analysis of leachates collected either on site or after leaching in the laboratory of samples. Unfortunately, these sole results are often insufficient to identify the source of the pollution. To provide 'a more complete characterization of polluted solids, optical and electron microscopy, XRD, Mossbauer spectroscopy, and transmission infrared spectroscopy were combined to analyze leachates and raw or ground samples. This combination of techniques allows the determination of the kind of cyanoferrate complexes are present in the solid state, different from insoluble Prussian Blue, since they do not have the same extraction' behavior. The use of all these techniques to characterize solid samples combined ,to the usual analysis of solutions gives a better understanding of ' the cyanide behavior.

Jan 1, 1998

By Christian Bernhard, Mario Hartl, Susanne K. Michelic

"One aspect of an efficient process and product optimization of the liquid steelmaking process is the understanding of reactions and interactions between the components steel, slag and nonmetallic inclusions. The present paper focuses on a fundamental study of this topic by combining the powerful methods of thermodynamic modeling with systematic experiments on a laboratory scale and subsequent SEM/EDS analyses. The modeling aspect is addressed by the commercial software FactSage 6.1; laboratory experiments are performed for a low-alloyed, Ca-treated carbon steel combined with varying slag compositions. The consequent SEM/EDS analyses provide a detailed insight into the inclusion landscape which offers a strong tool for characterizing the modification of inclusions. In the present study the combination of these methods is mainly applied to oxides, due to their crucial influence on the final product quality, thus giving important indications for further optimizing the secondary metallurgy processes.IntroductionIn recent years, the range of application for steels has been enlarged continuously; also resulting in extreme surrounding conditions combined with considerable stresses for the material. This trend is directly linked with higher demands on the properties of steels. In order to optimize the final product quality, the cleanness of steels is an important criterion. For this reason, the broad topic ""Steel Cleanness"" has become one of the main research points at the Chair of Metallurgy. Next to the continuous optimization of methods for the characterization of cleanness, the primary aim is to combine thermodynamic modeling and laboratory experiments in order to describe the changes in inclusion landscape under different conditions.The steel cleanness can particularly be influenced in the processes of secondary metallurgy. In different processes the reactions and interactions between the components steel, slag and nonmetallic inclusions (NMI) are essential for the final inclusion landscape. Consequently, the understanding of the occurring reactions is a fundamental aspect for further development and process optimization. In secondary metallurgy especially oxide-slag systems consisting of the components Ca0-Ah03-Mg0-Si02, which significantly influence the modification of NMI, are of importance. Several works dealing with the interactions of oxide non-metallic inclusions with different slag systems have been published in the last years [1-4]. In order to observe the dissolution of oxides in different slag compositions a Laser Scanning Electron Microscope is frequently used. A very detailed study on the ternary system Ah03-Ca0-Mg0 and its subsystems was also done by De Aza et al. [5, 6]."

Jan 1, 2011

By Mônica Suede Santos Silva

This work describes characterization of the performance of the tundish of a six strand continuous casting unit of the Companhia Siderúrgica Belgo Mineira, João Monlevade, Brazil using physical modeling. Permanent and transient conditions, due to ladle metal composition changes are considered. Pulse and step tracer addition techniques are employed to assess the control variables. For transient conditions the degree of inter-mixing and the minimum residence time are determined with a view to optimize the process especially during the grade changes of steel.

Jan 1, 2003

By P. C. A. Maia, J Alexandre, F. A. J. Saboya, A. R. G. Azevedo, G. C. Xavier

"This work shows the characterization of clay and the granite waste by-product from the sawing process of the granitic blocks, used as raw material for brick ceramic. Besides, shows the degradation of the ceramic material obtained with different by-product contents in the waste after lab test degradation, is investigated. The clay is obtained from mine use areas of ceramic industry in Campos-RI and the waste is originating from of the area of Cachoeiro-ES, an important center of decorative stone in Brazil. The mixes were made by the addition of 0% up to 10% of the waste in the raw material. After drying and firing up to 900°C, obtained prismatic pieces were considered intact. Physico-mechanical properties were obtained from wet and drying tests in laboratory considering 50 and 150 cycles. The results showed that the use of powder byproduct has a considerably influence on the weathering and strength of the material.IntroductionThe ornamental rocks and coating defines the most promising areas of business in the mineral sector [l]. In this context, the Espirito Santo appears as the main Brazilian state in production and export of ornamental rocks, representing 47% of national production [2] which in tum is one of the economic sectors most representative of this State, due of its transport logistics and port vocation that facilitates the export of such products.It is estimated that the state of Espirito Santo there are approximately 1,200 companies dedicated to the activities of ornamental rock by providing 20,000 direct jobs [ 1]. These mobilize support activities, such as companies that provide machinery, equipment and supplies for industries, including service providers for maintenance.However, the production of rocks produces about 15,000 tons of granite waste/month [3] only in the municipality of Cachoeiro ltapemirim-ES. This is justified by the presence of more than 500 extraction industries, cutting and processing of stone, with about 900 looms, waste generators.According to [4], there is great potential for the use of granite waste in red ceramics introduced for the manufacture of bricks, blocks structural ceramics. and other ceramic products, especially when evaluated on exposure to weathering."

Jan 1, 2014

By Gustavo Díaz, Miguel A. García, Carlos Frías

"Under the auspices of the Commission of the European Union, a consortium composed of six European organi~ations has conducted a project to scale up the PLACID electrowinning cell to industrial size within the Placid process development. This paper is concerning the results and achievement of the industrial cell prototype after more than 1,000 hours operating time and about 10,000 Kg electrolytic lead production. In general, results have been very satisfactory, demonstrating the ability ofthe PLACID electrowinning cell to produce top quality electrolytic lead (> 99.99 %) with high current efficiency and low energy consumption.IntroductionThis paper is concerning the development of an industrial size PLACID electrowinning cell within the PLACID process development. This project began on January 1993 and was finished on April 1996.Lead metal production and manufacturing industries produce large amounts of dusts and also lead bearing slags. Spent lead-acid battery recycling also produces lead oxides from the battery pastes rather similar to those mentioned above. Those lead secondary materials are hazardous and difficult to handle by usual procedures.Existing processes to treat-lead oxides may inflict considerable damage on the environment, incur high operating costs and have limitations to produce top quality lead.The main aim of this project has been to develop a novel hydrometallurgical process able to deal with different lead bearing materials, mainly lead oxide secondaries: lead-acid battery pastes, lead fumes, furnace slags, oxide residues, etc., producing ""four nines"" pure lead in an efficient manner with a benign influence on the environment; it is called the PLACID process."

Jan 1, 1997

By G. Diáz

The PLACID process applied to the recycling of spent lead-acid batteries is being developed by an European Consortium within the Brite-Euram II programme. The status of the project entitled "Lead Recovery from Lead Oxide Secondaries" is described in this paper. The main laboratory and batch experimental results and the preliminary feasibility study are summarised. The description of the demonstration pilot plant and continuous campaigns programme for 1995 are also included. An interesting global approach is proposed, integrating the Placid process in the existing spent battery recycling pyrometallurgical facilities. This yields important improvements in the overall process. Grids would be easily treated by the conventional pyrometallurgical route, obtaining lead alloys,, while battery pastes, slags and fumes would be fed to the Placid process, obtaining pure electrolytic lead (>99.99 %), ideal for battery paste manufacturing. The implementation of the Placid process into the existing battery recycling pyrometallurgical facilities is analyzed from technical, environmental and economical viewpoints. Greater overall lead recovery, lower operating costs, reduced waste production, environmentally safer residues and much better lead product quality are the key advantages. The authors draw the following final conclusion : Integration of the Placid process with conventional pyrometallurgical treatment is a feasible and very attractive alternative route for spent lead-acid battery recycling.

Jan 1, 1995

By S. Ferlay

"The main purpose of the ZIMA VAL project (Label EUREKA EU1367 and LIFE ENV/F/000278) is to demonstrate industrial scale recovery and recycling of the main components of used dry batteries (zinc, manganese dioxide, mercury, and stainless steel) into high added value products. The originality of the ZIMA VAL process resides in:1- the use of hydrometallurgy2- alkaline treatment implementation (highly selective) for zinc and mercury3- electrochemical recovery of high quality products.4- the recycling of all the battery components (zinc, mercury, manganese dioxide, stainless steel) ·5- low operating and investment costs.The process consists of physical classification, mechanical dismantling, hydrometallurgy and electrochemistry. The purpose of the demonstration plant in FALAISE (Calvados - France) is to define the technical and technological parameters of an industrial unit for the treatment of 2400 tonnes per year of used batteries."

Jan 1, 2000

By K. H. Bech, S. T. Johansen

"The mass transfer at fluid-fluid interfaces due to turbulent agitation is investigated theoretically. In particular a theory is derived for interface stresses due to interface energy and surface renewal. This theory indicates that surface renewal may take place if the geometry is sufficiently large and if surface tension is sufficiently low.By using a model for a typical turbulent structure we compute the interface mass transfer for a stressless interface and a fully interface. Results for the general situation is not presently available. The computed results are used to derive analytical expressions for the mass transfer based on turbulent kinetic energy and free stream turbulent length scales.One important application of the theory is the mass transfer at the electrolyte side of the bath-metal interface in the Hall-Heroult process. For this process we show that mass transfer should be expected to be of the rigid surface type."

Jan 1, 1999

By Jingbo Liu, Zhimin Wang, Wenchao Li

"IntroductionThe advantages of non-stoichiometric perovskite material are highlighted in many papers[l]and many of this family of materials are well-suited to integration into microsensor devices. Among them, barium titanate is the most promising due to it's piezoelectric, pyroelectric, dielectric properties. Through modification, BaTiO3-based materials can be utilized in many kinds fields, such as surface wave probe; pholoconducting devices, field-effect transistor, permanent memory permanent storage, and ultrasonic transducerl2-3l. In this Paper, a series of BaTiO3-based polycrystals were synthesized by sol-gel processing which appears to be a very promising method for the manufacture of ceramic, because it offers significant advantages such as high purity, chemical homogeneity, controlled particle sizes of ceramics, and lower processing temperatures [4]. In a sol-gel process, alkoxides of the constituent elements show different reactivity toward water so that the preparation of multi-component homogenous system is difficult. In the experiment, inorganic salt was substituted for some of the alkoxides. Acetic acid which is employed for the solvent and catalyst, acts as donor ligand to titanium alkoxide and controls, the hydrolysis polycondensation reaction. Taking these aspects into consideration, we select the system Ba(OAc)2, , La(OAc)3, Ti(O11Bu)4 and acetic acid which is used as both solvent and homogeneous catalyst for the first time.ExperimentalA series of La3+-doped BaTiO3-based nano-crystals were prepared with sol-gel technology using various parameters. The precursor solution was prepared in the presence of barium acetate, lathanium acetate, and titanium tetrabutoxide monomer in butyl alcohol. According to the flow chart (fig. I.), Ba(OAc)2, La(OAch dissolved in the glacial acetic acid (0. lmol/40ml) in a three-neck flask were mixed with a solution of titanium tetrabutoxide monomer in butyl-alcohol(l 7ml/20ml) at room temperature and under constantly, vigorous stirring conditions. In most cases, the resultant solution was golden yellow and stable in the air. To this precursor solution, containing Ba, La, Ti in the desired ratio, water was added incrementally for hydrolysis under continuous stirring until sol was formed. After aging for more than 2 hours, sol was transformed to gel at room temperature. If heated during aging, the gel was formed in a shorter time. The wet gel was allowed to dry at 50°C for more than 10 hours. The dried gel was transparent or light yellow. In order to obtain BaTiO3-based nano-crystals, the amorphous dry gel was calcined at 600°C, 700°C, 800°C, 900°C, 1000°C respectively[5]. The ceramic humidity sensor was formed through the cold-pressed, aged, capsulated routes. The dried gels were crushed in an agate mortar and then pressed into discs of ? 1.5 X l.5mm (l.5mm diameter and l.5mm thickness), then held at about 16.5 MPa pressure for 3 min [6]. The disc was sintered at 1350°C and 1400°C for I hour respectively. During the processing, an Ag-Pt electrode was inserted in the sensor [7]. (See the flow chart.)"

Jan 1, 2000

By R. M. G. S. Berezowsky

Treatment of Hudson Bay Mining and Smelting Co. Ltd. (HBM&S) zinc concentrate in the Sherritt zinc pressure leach process produces a residue containing elemental sulphur, residual sulphides, precipitated iron species, si1ver and gold. Flotation of the residue recovers most of the elemental sulphur and residual sulphides to the concentrate, leaving iron oxides and bask sulphates in the tailings. The tailings also contain most of the sflver and some gold. Direct cyantde leaching of the oxide tailings (220 g/t Ag, 1.4 g/t Au) was capable of leaching most of the gold, but only a minor portion of the silver. This paper reports testwork, conducted by Sherritt on behalf of HBM&S, to define a process for a high recovery of the precious metals from the oxide tailings. A si1ver enhancement treatment, consisting basically of digestion of the residue with lime at 90°C to render the silver amenable to enhanced recovery by subsequent cyanidation, was selected as the most promising approach. Batch silver enhancement and cyanidation tests showed that treatment of the oxide residue with 80 kg/t CaO at 90°C for 1 to 2 h increased the silver extractability in subsequent cyanidation from <20% to 96%. A 96 h continuous miniplant test (1 kg/h solids feed rate), of a circuit including a silver enhancement treatment step followed by conventional cyanidation and carbon in pulp silver and gold recovery, confirmed metal recoveries to the carbon of 90% Au and 96% Ag. Reagent consumption rates were 1ess than 100 ?kg/t CaO and 5 kg/t NaCN.

Jan 1, 1990

By Ana P. Paiva, Marc F. Comella, Sandra S. Reis, Joao N. Reis, M. Soledade Santos

"In this work, the influence of the malonamide structure, acidity of the aqueous phase and diluent on the equilibrium interfacial tension (IT) of N,N'-dimethyl-N,N'-diphenylmalonamide (DMDPHMA) and N,N'-dimethyl-N,N'-dicyclohexylmalonamide (DMDCHMA) in 1,2- dichloroethane (1,2-DCE), and DMDCHMA in toluene, with aqueous HCl, were investigated. IT isotherms were determined using the Du N ouy ring method. Densities of the organic phases were determined, and used to screen solute-diluent interactions. Formation of third phases was never observed; furthermore, ITs increase with the phase separation period, constant values being obtained for separation periods larger than 1000 seconds. Each malonamide interfacial efficiency at the oil/water interface is interpreted in terms of malonamide basicity, diluent polarity and malonamide - hydrochloric acid- diluent interfacial interactions.IntroductionFor several years now, N,N'-tetrasubstituted malonamide derivatives have been extensively investigated as liquid-liquid extraction agents since they were first proposed as the organic components of the DIAMEX process, with the aim of advantageously replacing tributylphosphate in PUREX [1]. Therefore, a significant part of research studies with malonamides appearing in the literature deal with the extraction of major and minor actinides in real or simulated spent nuclear fuels in nitric acid solutions [2]. Under typical experimental process conditions, the tendency shown by some N,N'-tetrasubstituted malonamide derivatives to aggregate in the organic phase, leading in a few cases to the formation of undesirable third phases, has been remarked and consequently thoroughly investigated [3, 4]. The increasing use of chloride streams as hydrometallurgical aqueous feeds is becoming a reality, and this fact is obviously deeply founded on an extensive research carried out to recover value-adding metals from these media. Following this trend, a number of N,N'-tetrasubstituted malonamides have already been screened for the recovery of iron(III) [5, 6] and platinum-group metals [7] from hydrochloric acid solutions. The results obtained are quite promising either in terms of total metal ion recoveries or selectivity patterns achieved. The formation of a third phase when iron(III) was extracted by the tested N,N'-tetrasubstituted malonamide derivatives has never been observed under the adopted experimental conditions, and the extraction data collected would need to be reinterpreted accordingly if any aggregation phenomena involving the considered extraction systems were to take place."

Jan 1, 2011