Papers by Author: Carlos A. Nogueira

Abstract: In electronic appliances, printed circuit boards (PCB) represent an important component, containing high grade of valuable metals, besides organic resins and some ceramic materials. Copper is the major metal in PBC’s composition (normally higher than 20% w/w) but many other secondary and minor metal elements, including precious metals, are found in PCB’s. Recycling of PCB´s involves firstly the shredding operation, which is crucial in order to liberate particles from different materials, allowing its further processing by other mechanical, physical and chemical technologies. An efficient shredding operation is difficult to achieve due to the high heterogeneity of these wastes involving materials with different mechanical properties and complex assemblies. This paper presents results from laboratorial studies of shredding of PCB’s and the evaluation of size reduction efficiency as well as the chemical characterization of the obtained shredded fractions. Results showed that an efficient size reduction (characteristic average diameter d50=1.0mm) is obtained using two shredding stages of PCB’s, the first one with a grab shredder and the second one with a cutting mill. Chemical analysis of shredded PCB’s indicated that copper is the principal metal present (28%) followed by Sn, Zn, Pb and Al (3-5%) and many other minor elements. The fine fractions were rich in plastic materials while the metals were essentially present in the intermediate fractions (0.3-1.5 mm). These results can lead to guidelines regarding further design of the physical separation steps in the recycling processes.

Abstract: Laboratorial studies were carried out to characterise the influence of different cutting systems (grab shredder and cutting mill) on the physical processing efficiency of spent Zn-MnO2 batteries. The grab shredder operate based on an indented cutting rotor which applies shear and abrasion stresses with a moderate rotation speed, while the cutting mill operation is based on shear and impact stresses at higher rotation speed. After shredding with the grab shredder, two fractions of material were obtained (above and below the 6 mm discharge grid), which allows a previous separation of the scrap. With the cutting mill, all the grinded material passed the bottom grid (with the same 6mm opening). Results obtained showed that alkaline batteries were more efficiently shredded than saline batteries, mainly with the grab shredder. Average diameters (d50) for saline and alkaline batteries fragmented with the grab shredder were 2.29 and 1.47 mm respectively, while with the cutting mill were 3.09 and 1.54 mm respectively. Chemical analyses were carried out for different size fractions allowing identifying metals distribution through size categories. In general chemical composition was not substantially different using both shredding systems. Zinc distribution was almost constant with the grain size while manganese distribution decreased with particle size. More than 94% of the iron scrap from the battery cases presents a particle size higher than 1.4 mm using both cutting systems. Due to this result, it is possible to separate the scrap retained in the coarse fraction by sieving with the identified mesh. Maximum selectivity points, corresponding to the maximum separation of zinc plus manganese from iron, were also determined. Higher zinc and manganese recoveries were obtained with the grab shredder, despite iron contamination (20-25%) can be considered significant.

Abstract: The hydrometallurgical processing of metal bearing residues is one of the established routes envisaging metals recovery. In these processes, the leaching operation plays a central role as allows the solubilization of metals for further separation and recovery as pure products. This route can be applied to spent domestic batteries recycling, which studies on sulphuric acid leaching of spent alkaline batteries are reported in this paper. Material samples used in the trials were prepared concerning the real proportion of the most common sizes and shapes of batteries found in the usual stream of this type of wastes. The research involved the evaluation of some factors which affect leaching yields namely temperature, reaction time and stirring speed, through a two-level factorial design methodology and analysis of variance. In this study, other factors related with leachant concentration and stoichiometry were maintained constant. Zinc leaching yields were generally high and even near 100% when the high levels of the variables were used, meaning that zinc oxides present in the electrodes are very reactive to acid leachant. The variables had all positive effects being temperature the most significant factor (confidence level 99%) while the other factors were less significant (98.8% for time and 95% for stirring speed). Concerning manganese, leaching yields obtained were more dependent from the factors, being also positive and varying from 11% (for low levels of factors combination) to 89% (for high levels of factors combination). Temperature and time were highly significant (confidence levels above 99.9%) while stirring speed was less significant (97%). Contamination of leach liquors with iron was also evaluated since it is an impurity which requires special attention during the process development. For the higher levels of the factors (t = 1 h, T=80°C and ω=400 rpm) the final solution contained 10 g/L Zn, 15 g/L Mn and 3.2 g/L Fe. The removal of the iron from the solution is a necessary step prior to the separation and recovery of zinc and manganese.

Abstract: Sludges generated in leather tanning processing are very complex wastes with potential deleterious effect on the environment and its management constitutes a high cost for the companies. In this work, sludges from a Portuguese tanning company were characterized and leached with acid solutions in order to evaluate the metals removal yields. The sludges contain, as main metals, 15% Ca, 5% Fe and 2.2 % Cr, in a dry basis. Other minor elements namely Al, Ti, Zn, Pb and Cu were also detected. The leaching experiments were carried out with two types of acids – hydrochloric and sulfuric – and the effects of the reaction time, temperature and leachant concentration were evaluated. The reaction conditions strongly affected the chromium leaching yields, being temperature and acid concentration highly significant (confidence level above 99.9%). About 90% of Cr was leached using the higher levels of the factors (4h, 80°C and 2M H+, with both acids). Concerning the other major metals, iron leaching was very efficient (yields usually above 90%) whatever the conditions tested while calcium behaviour was quite different, depending on the type of acid used for the same H+ concentration: H2SO4 leaching efficiency was generally lower than HCl, probably due to the formation of less soluble calcium sulfate. The maximum calcium removal achieved was near 75%. The leaching process developed can be useful not only as a decontamination step of the tanning sludges, but also as a process for metals recovery to be potentially applied in an integrated recycling system, where several metal wastes from different sources could be processed.

Abstract: This study focus on the synthesis of Ca-deficient apatites (CDA) by using the wet chemical precipitation method in demineralised water solutions at pH=7 and synthesis temperature of 90 °C. Upon calcination at 1000°C, the resulting HAP powders decomposed leading to the formation of small amounts of β-TCP. Surprisingly, under some conditions, minor amounts of α- TCP were also formed at 1000°C together with β-TCP. The appearance of α-TCP is favoured by the absence of mineral ions in the precipitation medium, which in turn depends on the purity of the water used. Factors affecting the formation of both β-TCP and α-TCP are discussed.

Abstract: When preparing β-tricalcium phosphate (β-TCP), it is difficult to industrialise traditional methods because of the problem of particle aggregation. In this paper, β-TCP was prepared by calcining calcium-deficient hydroxyapatite (CDHA) powders obtained by the wet precipitation method at pH=6 and 40 °C, together with additions of poly (ethylene glycol) (PEG), in order to prevent powder agglomeration. The effect of the Ca/PEG mass ratio on the particle size distribution and the morphology of the resulting powders was evaluated. For comparison purposes, one powder without PEG addition was also synthesized. All synthesized powders were characterized by means of X-ray diffraction analysis, particle size analysis and scanning electron microscopy prior and after calcination in static air at 1000 °C for 15 h. Single-phase β-TCP powders have been obtained by calcining CDHA powders in the temperature range of 850°C-1150°C. It was also found that increasing the PEG content in solution decreased the particle size distribution of the agglomerated particles and the β→α-TCP transition temperature. A plausible explanation consistent with these experimental findings is proposed.

Abstract: Domestic-type batteries sample was tested aiming at its characterization and the evaluation of the feasibility of physical separation of its main components. The sample was essentially constituted by saline and alkaline types (Zn-MnO2 based systems, >90% w/w) and cylindrical shape (> 90% w/w). The mass balance of alkaline battery samples indicated as main battery components the steel case materials (25 %), the electrodes (71%) and the connector and separator/insulating materials (4 %), while the corresponding values to the saline type are 16%, 72% and 12% respectively. Despite electrochemical principles are similar, internal constitution of saline and alkaline batteries is different. Differences in electrolytes are also relevant (KOH in alkaline type and chloride salts in saline type) affecting therefore the mass balances in the chemical treatment. Fragmentation of batteries was done aiming at to evaluate the efficiency of the liberation of different components, namely scrap and electrodes. Results obtained are very promising considering the good efficiency reached on the physical separation treatment and consequently the chemical step will be necessarily improved.

Abstract: A conventional method of chemical precipitation was used to produce hydroxyapatite (HAp) powders, with a molar ratio of Ca/P=1.67, for biomedical applications. The aim of this work was to study the effect of four control factors, namely pH, reaction temperature, reagent concentration and flow rate addition, at three levels, on the Ca/P ratio of the synthesized powders, using the Taguchi design of experiments method. Nine powders were synthesized using Ca(NO3)2ּ4H2O and (NH4)2HPO4 as starting reagents. The Ca/P molar ratio of each powder was determined by ICP-AES. Data obtained were used in the Taguchi’s design of experiments to optimize the Ca/P molar ratio. Results showed that the pH of the reaction is the main control parameter (74% contribution) affecting the Ca/P molar ratio of the powders. Therefore, attention should be paid to the control of the pH during the synthesis, in order to obtain HAp powders in a reproducible fashion. High pH values (9.5) and reaction temperature at 70 °C favoured the synthesis of HAp powders with a Ca/P ratio close to the target value of 1.67.