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By Nitin Bhavsar, Kaushik Vakil, Lakshmikanth Reddy, Sanjay Sarkar, Tathavadkar. Vilas, Bhavin Desai, Raghavendra Adiga

Gold and platinum group metals (PGM) do not dissolve in sulfate electrolyte from anode during electro-refining of primary copper. The PGM form solid ‘slimes’ which accumulates at bottom of the electrolytic cell. Typically, 8 to 10 ppm silver is present in copper cathodes, which is equivalent to almost 2% of silver loss during electro-refining. The silver can be cemented with cathode copper as soon as it is dissolved into the electrolyte from anode or during entrapment of slime particles in cathode. Over a period of time, the concentrates grade has deteriorated and change in type & amount of impurities in concentrate has resulted in higher silver loss during refining process. Therefore, an in-depth investigation was carried out in both fire- and electro-refining processes to understand the root causes of higher silver loss in copper cathodes. The detailed characterization and the plant data analysis were carried out. The results of study revealed that higher silver loss in 3rd crop cathodes as compared to 1st and 2nd crop cathodes from same anode. In anode silver was present in two forms, dissolved in copper (solid solution) and in slime phases such as Cu2-xAgxSeTe. SEM-EDX study of anode cross section confirmed higher silver and oxygen content in central region (core) of anode as compared that in both air and mold sides. This is due to non-uniform cooling of anode which was confirmed by the solidification modeling. Higher concentration of oxygen & silver at core of anode rised Ag+ concentration in electrolyte and slime particles during 3rd crop. The results of study were used to optimize the anode cooling process and also electrolyte chemistry to reduce the silver loss. The details of study carried out are discussed in this paper using the results of modeling, characterization and experimental studies. INTRODUCTION In the electrolytic refining of copper, fire refined copper anodes are used as raw material. Anodes contains copper of the range 99.5 to 99.6%, rest being the impurities. Hence, the purpose of the refining is (1) to remove the impurities so that final cathode conforms to the LME specifications and also (2) to recover the precious metal from the anode copper. When anode is dissolved, most of the impurities reports to the anode slime settled at the bottom of the cell, and rest dissolves in the electrolyte. Dissolved impurities remains in electrolyte and are removed during electrolyte recycling. However, sometime dissolved impurities and slime particles get entrapped in cathode due to disturbances in operational conditions. Metals dissolving in the electrolyte are the elements such as Ni, Co, Fe, Zn. The electrode potential of As, Sb and Bi being close to that of copper, these elements partly dissolve in the electrolyte. Noble metals like Ag, Au, Pt and Pd are generally insoluble and are thus expected to report to the anode slime. A small amount of the sliver content from the anode is dissolved in the electrolyte. Because the dissolved silver electroplates on the cathode at a smaller applied potential than copper, the cathode typically contains up to 8 ppm of silver. This is referred to as ‘silver loss’ in cathode (Cooper, 1987). Fortunately, silver is a rather benign impurity in copper due to its electrical conductivity being higher than copper. However, higher silver loss in cathode is loss of revenue for Copper smelter due to significant difference in their LME price.

Jan 1, 2019

By E. A. Roux

As the first mine-to-metal zinc operation utilising atmospheric leaching, solvent extraction and electrowinning, Skorpion Zinc faces unique challenges and opportunities. One of these challenges is found in the solvent extraction circuit, in which di-ethylhexyl phosphoric acid (D2EHPA) is used as the organic extractant. Although D2EHPA is an excellent extractant for zinc, it suffers from the co-extraction of ferric iron, which is produced during leaching and by the corrosion of the grinding media. This situation is partially mitigated by iron precipitation in the neutralisation step prior to solvent extraction. Unfortunately, some ferric iron still reports to the solvent extraction process. This leads to a slow build up of iron in the organic phase. Chemical stripping is used to maintain the Fe concentration at an acceptable level. In this paper, the efficiency of the iron removal process is discussed.

Jan 1, 2006

By 000-900-009-492

The flotation has been and is still the most widely used mineral concentration method. Because of its complexity, the flotation process required the development of robust control strategies which was facilitated by the introduction of on-line sensing instruments such as x-ray fluorescence (XRF) on stream analyzer (OSA), gamma density gauges and electromagnetic flowmeters. The interest in developing control strategies has persisted because the benefits to be gained in terms of improved metallurgical performance are substantial. As the flotation control becomes more and more difficult due to the emergence of low grade and complex ore cases, other control strategies have to be introduced. Froth based control is one of the emerging useful control strategy This paper will focus on the state of the art in the on-line froth characterization as obtained by numerical image analysis. The technology of machine vision provides a novel solution to several of the problems encountered in conventional flotation systems for monitoring and control, and constitutes a powerful tool for the investigation and interpretation of the effect of various flotation parameters as driven for the froth phases. Copyright @2001CIM

May 1, 2001

By Mahmood Alemrajabi, Ake Rasmuson, Kerstin Forsberg, Kivanc Korkmaz

"In the present study, the recovery of rare earth elements (REE) in the nitrophosphate process of fertilizer production is investigated. The apatite has been recovered from iron ore tailings by flotation. After digestion of apatite in concentrated nitric acid, Ca(NO3)2.4H2O is first separated by cooling crystallization and then the REEs are recovered by precipitation. Optimum conditions in these steps have been determined in a previous study. The precipitate mainly consists of CaHPO4.2H2O and REE phosphates.In the present study, selective dissolution and re-precipitation have been studied in order to obtain a precipitate that is more concentrated in REEs. The precipitate was selectively dissolved in nitric and phosphoric acid at different acidities (pH 6 to 0) with the liquid /solid ratio of 100 mL/g. It is shown that most of the CaHPO4.2H2O and other calcium containing compounds will be dissolved at pH 2 while the REE phosphates are not dissolved above a pH of approximately 2. Thus, by partial dissolution of the REE precipitate at pH 2.5 most of the solid calcium phosphates will be dissolved and the remaining solid phase, which is more concentrated in REEs, can be filtered off as a fairly concentrated REE solid mass and the liquor can be recycled back to recover more P nutrients. Alternatively, the REE enriched precipitate was dissolved completely in nitric acid and re-precipitated again by addition of ammonium hydroxide to pH 1.2. A chemical equilibrium software, MEDUSA (Puigdomenech, 2013) has been used to evaluate the experimental results and to estimate the optimum conditions for selectively dissolving the precipitate."

Jan 1, 2016

By Roger J. Berdusco

Kaiser Resources Ltd. owns and operates a 5-million-tonper- year open-pit and hydraulic coal mine near Sparwood in southeastern British Columbia. Since 1969, Kaiser has maintained a field-scale reclamation program dedicated to the reclamation of disturbances associated with past and present mining and exploration activities . Since that time, over 1400 acres have been treated using modified forestry and agricultural techniques with encouraging results.

Jan 1, 1978

By K. D. Peaslee

Slag splashing is an important development that has dramatically improved BOF vessel campaign life and reduced operating costs. This paper highlights research from physical modeling work using a 1/8-scale room temperature model BOF and slag characterization studies from several plants in North America and China. In the model studies, gas flow rate during blow and viscosity of the liquid were found to be two of the most important factors to changing the overall rate of liquid splashed onto the vessel sidewalls. When the flow rate was increased or viscosity decreased, the lower regions of the walls were splashed at a much greater rate. It was also shown that by changing the lance height, more liquid was deposited in the upper regions of the vessel at the expense of lower regions. Reducing the number of nozzles was found to be the most effective method of selectively coating a particular vertical section of the wall. Studies of BOF's using slag splashing in North America and China showed a difference in the melting characteristics of the final slag. Generally, slag splashing is successful when the melting point of the slag is 220-270°C below the tap temperature to maintain a balance between fluidity and refractoriness.

Jan 1, 2004

By G. Titichoca

Modification of the blasting process considers that any increase in the energy consumption generates greater benefits if done in the later stages (associated with a larger decrease in energy consumption). Therefore, although the blasting cost is doubled, generating a greater proportion of fines in addition to a weaker ore (because with greater loads and appropriate distribution of explosives a greater number of internal cracks is generated), the reduction of the unit cost that occurs in the grinding stages (SAG and ball mills) generates a positive balance in the overall size reduction process. Codelco Chile, Division Andina, has developed an extensive experimental plan to evaluate the concept of blasting modification applying greater energy. This was implemented in two stages, each including a specific mine sector: La Union and Don Luis. This paper reviews the experience of implementing such blasting modifications at the La Union mine and its impact on the design concepts and the operation of the SAG mill plant

Jan 1, 2007

By R. Khettabi

The mechanical, thermal and bioproperties of titanium alloys allow their wide use in different industries. Compared to aluminum alloys, titanium alloys are very tough, making them that much more difficult to machine than aluminum alloys. Most studies conducted on these types of materials have mainly covered and made comparisons in terms of cutting speed, cutting force and mechanical properties. Recently however, their sustainability and environment parameters have begun to attract significant interest, and it has been found that machining processes generate particles that can be harmful for health and the environment. In this paper, particle emission is investigated during the turning of the titanium Ti6A14V and 6061-T6 aluminum alloys.

Jan 1, 2011

By L. R. Bottomer, G. M. Leary

"The Copper Canyon property is located in the Galore Creek area of northwestern British Columbia. Porphyry copper-gold mineralization on the property is notable for its high gold content and close spatial relationship with a distinctive suite of high level syenitic and monzonitic intrusions, and pseudoleucite-bearing volcanic country rocks. The style of alteration and mineralization is similar in many respects to the nearby Galore Creek deposits.The current geological resource of 32.4 million tonnes grading 0.75% Cu, 1.17 g/ t Au and 17.1 g/t Ag is insufficient to support a mining operation, but definition of additional reserves combined with improved transportation infrastructure in the region may change this in the future. The climate, topography and proximity to an active glacier indicate that the most likely production scenario is an underground bulk mining operation, with the ore being milled offsite.IntroductionThe property is located at 57°07' North latitude, 131 °21' West longitude, on NTS sheet 104G/ 3W, approximately 160 km northwest of Stewart and 90 km south of Telegraph Creek (Fig. 1). The Galore Creek camp and airstrip are located 6 km to the west. Current access to the property is via helicopter either from Galore Creek, or from the Bronson Creek airstrip 32 km to the south-southeast.The deposit occurs within the Boundary Ranges of the Coast Mountains, on the north side of the east fork of Galore Creek, which flows northerly into the Scud River and thence westerly to the Stikine River.Topography is rugged. In the deposit area, elevations range from 1130 m to 1750 m. Valley glaciers and permanent snow and ice fields are characteristic of the region at these elevations, and at its southern limit, mineralization is truncated by the East Fork Glacier.The property is entirely above the treeline, and except for areas of moraine cover and talus slopes, outcrop is abundant."

Jan 1, 1995

By Y. Y. Yemelyanov, S. S. Gudkov, A. V. Boldyrev, A. V. Bogorodskiy, S. V. Balikov

"A series of tests to optimize pressure oxidation- carbon-in-leach process (POX-CIL) of goldbearing flotation concentrate with the addition of sodium chloride and activated carbon were carried out. Flotation concentrate which was generated during primary ores concentration from a large Russian deposit was used for these tests. The tests were performed with different concentrations of sodium chloride. It was found that the required sodium chloride concentration for gold leaching was 5 g/L. The tests performed with different additions of activated carbon showed that the amount of activated carbon should be at least 6% of the concentrate mass. The rate of sulfides oxidation was 67.7–99.8 %. The highest gold recovery was 98.6 %.INTRODUCTIONThe majority of gold-bearing ores are recommended to classify as amenable to cyanidation and refractory. Processes at elevated pressures and temperatures have become increasingly important in base metals hydrometallurgy (Lodeischikov, 1999, 2007; Naboichenko, Shneerson, Kalashnikova, & Chugaev, 2009; Thomas, 2005).Current pressure autoclaves – cyanidation flow sheets are capital intensive due to numerous circuits and the use of environmentally-unfriendly sodium cyanide. The use of halide-based lixiviants during pressure oxidation of precious metals can be a promising technique for refractory sulfide goldbearing mineral raw material hydrometallurgical processing (Fleming, 2002, 2007, Kotlyar, Meretukov, & Strizhko, 2005).In this paper, we presented the results of the research on finding the optimum process parameters of pressure oxidation using an adsorbent for a refractory gold-bearing concentrate. A proposed flow sheet involves (Bogorodsky, Yelelianov, & Balikov, 2012):1. Gold-bearing sulfides oxidation followed by precious metals dissolution and the formation of gold and silver chloride complex;2. Reaction of the precious metals chloride complex with a carbon-based adsorbent;3. Precipitation of precious metals onto the adsorbent by EW and smelting of cathode precipitates into Dore bullions.This process allows POX of gold-bearing sulfides, precious metals dissolution and their precipitation on the adsorbent to be executed in one single vessel. This study found that the most suitable lixiviant was sodium chloride. Fleming (2002) suggested that in the presence of a halide-based reagent (e.g. chlorine- ion reaction), the dissolution of gold during POX is achieved according to reaction 1:"

Jan 1, 2016

By Sylvie Lévesque, Cory Hennessey, Daniel Amariei

"In the iron ore industry, fine particles recovery is an important concern in terms of process performance and production costs. Continuous efforts are thus devoted to increase the efficiency in handling these fines.The Reflux Classifier (RC) is a relatively new technology that is mainly used in the coal and industrial minerals industries. The operating principle of this system is based on three mechanisms: hindered settling, autogenous dense medium and lamella settling. A preliminary evaluation of the Reflux Classifier technology for the beneficiation of iron ore fines was formerly done at the pilot scale using a RCTM300 unit. The good results obtained, using iron ore fines from screened spiral stream, made this technology very attractive for the iron industry. However, the high capacity of the RCTM300 unit (1–3 t/h), makes it unsuitable for R&D purposes. Thus, a smaller unit, the RCTM100, was assessed to validate the performances obtained with the RCTM300.This paper summarizes the performances obtained with the RCTM100. The challenges of the scale-down related to the adaptability of this technology to the iron ore industry are also presented. The results are compared to the RCTM300 performances, as well as benchmarked against sink-float tests. The metallurgical results on feed and products issued after the test work with the RCTM100 unit are supported by mineralogical characterization using a Mineral Liberation Analyzer.INTRODUCTIONFine particles recovery by physical separation means is a historical concern (Holland-Batt, 1992; Peukert and Wadenpohl, 2001; Srivastavaa et al., 2001; Majumder et al., 2003). Attempts to improve fine particle recovery at the laboratory, pilot and industrial scales adopting different strategies with traditional equipment or assessing new promising devices such as the MGS (multi-gravity separator), the Kelsey jig, the Yang jig, etc. (Kim, 2002; Goudreau, 2008; Kerr, 2012) have yielded variable success."

Jan 1, 2016

Lonmin RoM ball mills are treating two types of feed ore produced by conventional mining and mechanised mining methods. It was reported that reduction in mill throughput was observed when treating the mechanised mining ore. Detailed grinding surveys were conducted for troubleshooting. Ore samples were collected for breakage characterisation using a JKRBT based on different particle density components. XRD analysis was conducted to investigate the association of minerals with density components. The plant surveys and the breakage characterisation tests all suggested that the two mining methods did not significantly affect either the ore breakage properties or the RoM mill performance. Instead, the mill discharge open area exerted a remarkable influence on mill throughput. The RoM ball mill operated at Lonmin K4 Concentrator has been proven to be a versatile mill that performed stably with variations in feed size distribution and feed ore changes by different mining techniques. The reasons are elucidated by the multi-component breakage characterisation and the plant surveys data.

Jan 1, 2012

By Rolf Andreas Lauten, Yanhong Wang, Yongjun Peng

"In mineral flotation, bentonite as a kind of clay mineral imposes deleterious effects on the flotation of valuable minerals, possibly through its ability to increase the pulp viscosity. A higher viscosity lowers the amount of froth and affects the bubble-particle collision frequency. A previous study found that adding gypsum to a bentonite-ore mixture lowered the viscosity, possibly by inhibiting the formation of interconnected network structures. In this study, sulfate as an anion with different types of cations, Na+, K+, Mg2+ and Ca2+ were used to reduce bentonite viscosity and to improve flotation performance. It was found that at the same concentration, MgSO4 was the most effective salt in reducing bentonite suspension viscosity, while CaSO4 was not as effective likely due to the lower solubility of CaSO4. Na2SO4 and K2SO4 reduced bentonite suspension viscosity at high concentration. Flotation kinetics of ore blended with bentonite was increased with increasing the electrolytes concentration, which generally correlated with the reduction of bentonite viscosity. Meanwhile, significant discrepancies were found between flotation results and rheological measurements in the presence of monovalent ions. It is indicated that the morphology of bentonite aggregates in electrolytes solution is likely to influence the hydrodynamics in the froth zone.INTRODUCTIONClay is present in many ore bodies as a gangue mineral. Presence of clay presents several challenges in the processing of valuable minerals. They are soft compared to valuable minerals, which means that during grinding of the ore, clay particles are likely to obtain a smaller particle size than the valuable mineral. Often clay particles may be within the colloidal size domain (<20 µm). The smaller size increases the probability of entrainment in the concentrate. Another challenge is their anisotropic charge distribution, where depending upon the pH, edges (E) and faces (F) carry charges of opposite sign. This facilitates formation of aggregation structures that may impede percolation of bubbles through a froth, but also increase the viscosity more than expected from the mere change in volume fraction. In addition to lowering the froth mobility, a high slurry viscosity will have implications for the gas dispersion in the flotation column as it affects the dispersion of the suspended particles, and it modifies the bubble-particle collision rate and attachment efficiency (Bakker, Meyer, & Deglon, 2009; Shabalala, Harris, Leal Filho, & Deglon, 2011). A pragmatic approach to this problem is to blend high clay ore with ore of lower clay content, reducing the overall clay concentration. Alternatively, one may lower the solids content of the flotation slurry to counteract the viscosity-building properties of clay. While feasible, this approach has the disadvantage of increasing required flotation volume, and it also affects the properties of the froth. Thus, there are currently limited options in lowering the impact of clays and their tendencies to increase viscosity in flotation slurries."

Jan 1, 2016

By G. Mousavian, R. Bagheri, N. Dalili

Polypropylene (PP) and its composites have an increasing use in automobile and domestic industries. Since the published results on strain rate effect on yield behavior do not match, and there is a high attention paid for effect of nanometeric fillers on deformation behavior of composites, in this research the strain rate effect on yield behavior of PP and the effect of nanometeric fillers on deformation behavior of PP have been studied. Microscopic observations and tensile tests in different strain rates on neat PP samples and on samples filled with 5, 10 and 15 %wt have been used. A dramatic change in behavior for the modulus and post-yield slope curves when the strain rate is between 0.0433-0.05 s-1 has been observed. Microscopic observations on PP indicate a change in deformation mechanism from shear yield to crazing at the same strain rate that the change in behavior of curves occurs. It has been observed that in PP nanocomposites with higher amount of calcium carbonate, fracture in early stages of deformation occurs in lower strain rates. In other words for a fixed stain rate there is a critical filler percentage such that if the filler percentage is higher then early-stage fracture will occur. Similarly for a fixed filler percentage there is a critical strain rate and in higher strain rates early fracture will occur. The critical stain rate will decrease as the filler percentage increases and vice versa.

Jan 1, 2006

By F. Roemer, D. Goldmann, T. Elwert

Tantalum is an important minor metal for the production of high performance capacitors. Approximately 60% of the annual tantalum production is used in this application. Despite its high price of 298 US$/kg (average price 2010–2014), at the moment, no recycling from end-of-life products takes place. In the established recycling processes of waste electrical and electronic equipment (WEEE), tantalum is lost in the slags of copper smelting, where it is highly diluted. An economic recovery is not possible at that point. Although tantalum must therefore be extracted from the WEEE stream before it enters smelting, no industrial recycling processes exist. The main reasons are its low concentration in the WEEE stream, lack of information about tantalum bearing devices, technical difficulties of extraction, and conflicts of interests regarding the recycling of other valuable metals in WEEE. In this paper, the results of a cooperation research project are presented. The aforementioned challenges are addressed and a novel tantalum recycling process is developed. Small pilot scale experiments show that a mechanical processing route can produce marketable tantalum-concentrates of 30% tantalum with yields between 60 and 70%. This is reached through a manual pre-sorting of potentially tantalum bearing products followed by a combination of an optimized comminution, sieving, air classifying, eddy-current (EC), and two stage magnetic separation. Key to the implementation of this process was a detailed survey of the tantalum concentrations in different products carried out by the industrial partner.

Jan 1, 2016

By M. M. C. Lima, L. C. S. Solimani, M. A. Quintela

Galvanized steel scrap is recycled to B OF converters where zinc escapes from the bath and is captured by the gas control system, appearing in BOF sludge. As BOF sludge contain high iron content, it could be recycled, but due to its zinc content, it is disposed in landfills. In this study techniques were evaluated for zinc layer removal from scrap by sulfuric acid leaching. The effects of coating weight, temperature, time and sulfuric acid concentration were evaluated for three different galvanized scrap. The results showed that the behavior of each galvanized scrap was different. Nevertheless zinc removal efficiency was more than 80% with low dissolved iron in the leached solution.

Jan 1, 2011

By R. M. de Carvalho

Empirical and phenomenological models of SAG and AG mills have dominated the scene for the last few decades, being used nearly every time a mill is scale-up or an attempt is made to improve its performance. However, in spite of their success, these models fail to describe the details of both the grinding environment and the breakage mechanisms. The result is a generally good track record, with a few ? but very important ? instances when these models fall short in their predictions, which can be very costly. Further, nearly all of these models require detailed calibration to industrial and pilot plant data, being costly in their application, although still with limited predictive capabilities. Recognizing these challenges, a new model framework has been proposed which overcomes the limitations of currently used models by coupling the microscale population balance model, the discrete element model and functions that describe internal classification at the mill grate. This model framework has already been applied to describe breakage in ball mills, with showing very promising results. However, in the case of SAG and AG mills a much greater level of complexity is involved in the model, given the interaction between the mechanical environment that is formed totally or, in part, by the ore itself, and the breakage response in the mill. The paper describes the model framework, demonstrating how it can address appropriately effects such as mill speed, mill filling and size distribution, on the response from the mill. Some of the advantages of the model are related to its intrinsic multi-component and dynamic nature, which allows simulating appropriately mixtures of ores of different competences in a transient manner.

Jan 1, 2012

By E. Asselin

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

Jan 1, 2005

By A. Mitura

The paper presents the initial investigation of possible energetic applications of chosen wastes from groups: 06, 03, 05 and 01, including coal slimes being secondary product of hard coal processing. These categories of wastes are catalogued according to the polish law, where 06 ? wastes from production, preparation, purchasing and application of products of non-organic chemistry; 03 ? wastes from wood processing and from plates and furniture, celluloid mass, paper and card board production; 13 ? oil wastes and wastes from liquid fuels; 01 ? wastes produced by searching, extracting, physical and chemical processing of ores and other mineral raw materials. The change of combustion heat value was evaluated in produced energetic mixtures containing these types of wastes together with the change of their individual components. All combinations of ingredients were taken into consideration giving 256 various mixtures, from which 36 were selected to investigation. This allowed the performance of statistical factor analysis. For such prepared materials the application of regressive method was proposed in purpose of calculating combustion heat value and then the comparison of empirically determined and theoretically calculated heat values was performed. The change of regressive coefficients can be determined by the nature of Hess law (eq. 1) what was investigated and the attempt of its explication and validation was done.

Aug 1, 2013

By József L. Margitfalvi

Different Au/MgO catalysts modified with Mn, and Fe were prepared by precipitation-deposition. The catalysts were characterized by XRD, FTIR, Temperature Programmed Reduction (TPR) and CO chemisorption and were tested in CO oxidation in the temperature range of 243-523 K. The catalytic tests using both Temperature Programmed Oxidation (TPO) technique and time on stream (TOS) experiments revealed the high activity of catalysts prepared. In TPO experiments the modification by Mn significantly increased the activity above 300 K, however in the subambient temperature range the activity decreased considerably. Catalysts modified by iron did not show any decrease in the activity below 300 K, while the activity at high temperature increased significantly. Catalysts modified by Mn, Fe showed higher activity, selectivity and stability in preferential CO oxidation, carried out in the presence of hydrogen than the unmodified Au/MgO catalysts. Results of in situ FTIR spectroscopy on both the base Au/MgO and the iron modified catalyst unambiguously revealed the formation of ionic gold in the presence of CO/O2 mixture. The formation of this species was strongly hindered in catalyst modified by manganese. Results obtained strongly support the need for the formation of "metal ion - metal nanocluster" ensemble sites. These sites are involved in the activation of the CO molecule prior to its reaction with atomic oxygen. It is suggested that at subambient temperature these ensemble sites contain mainly ionic forms of gold, while at higher temperature iron or manganese ions are involved in CO activation.

Oct 1, 2003