Estudo da valorização de um resíduo de ácidos gordos livres

Com o desenvolvimento económico a gestão de recursos é um desafio que a sociedade moderna enfrenta. Um desenvolvimento sustentável, que procure satisfazer as necessidades da geração actual e futuras, é fundamental. É pois necessário encontrar novas fontes de energia e reduzir/valorizar resíduos. O objectivo deste trabalho prende-se com a valorização de um resíduo de ácidos gordos livres como fonte alternativa de energia. Estes ácidos gordos são obtidos na purificação primária da glicerina proveniente da produção de biodiesel por via alcalina, cedida pela empresa SOCIPOLE SA. Inicialmente separaram-se os ácidos gordos livres e ésteres presentes na glicerina, e caracterizou-se o produto obtido. Efectuaram-se dois ensaios, obtendo-se 42,9% e 53,8% em massa de ácidos gordos livres e 41,7% e 34,0% de ésteres no 1º e 2º ensaio respectivamente. Além dos ésteres e ácidos gordos livres, no 1º produto existem 15,4% de matéria não esterificável e no 2º 12,2%. Na primeira parte do trabalho, estudou-se a possibilidade de utilização directa deste produto como combustível. Determinou-se o PCI, obtendo-se 29,8 e 29,4 MJ/kg para o 1º e 2º ensaio respectivamente. Estes valores são superiores aos que se encontram no despacho 17313/2008 de 26 de Junho de 2008, para biogasolina e biodiesel (27,2 MJ/kg), significando que os ácidos gordos livres separados têm forte potencial para serem usados como combustível. Efectuou-se também um estudo de corrosão de aço do corpo e tubos de uma caldeira através de ensaios de polarização, usando um Potenciostato/Galvanostato, e por variação da massa de amostras mergulhadas nos ácidos gordos livres a 105ºC e à temperatura ambiente. Nas condições estudadas, os ácidos gordos não promoveram corrosão nas amostras. Por fim, fez-se a combustão de uma amostra dos ácidos gordos livres num bico de Meeker e verificou-se a formação de depósitos equivalentes a 1,93% da massa inicial. Na segunda parte estudou-se a possibilidade de produzir biodiesel por esterificação, dos ácidos gordos livres. Fez-se um estudo prévio para verificar qual a melhor razão molar de amostra/metanol a utilizar, optando-se por 1:6. Após cinco etapas de esterificação, obteve-se um produto final com 85,6% de ésteres. Não foram então atingidos os 96,5% exigidos pela norma europeia EN 14214, devido à presença de matéria não esterificável na matéria-prima, que não foi possível separar totalmente do produto durante o processo (esterificação, lavagem e secagem). Pela análise de todos os parâmetros, o produto obtido não pode ser considerado biodiesel, não sendo possível ser comercializado como tal. A análise dos resultados aponta para a opção da valorização do resíduo de ácidos gordos na queima directa em geradores e caldeiras que deverá no entanto, ser precedida de um estudo mais detalhado que inclua a análise da constituição da matéria não esterificável, para garantir uma combustão segura.

Oxidative Leaching of metals from electronic waste with solutions based on quaternary ammonium salts

The treatment of electric and electronic waste (WEEE) is a problem which receives ever more attention. An inadequate treatment results in harmful products ending up in the environment. This project intends to investigate the possibilities of an alternative route for recycling of metals from printed circuit boards (PCBs) obtained from rejected computers. The process is based on aqueous solutions composed of an etchant, either 0.2 M CuCl2.2H2O or 0.2 M FeCl3.6H2O, and a quaternary ammonium salt (quat) such as choline chloride or chlormequat. These solutions are reminiscent of deep eutectic solvents (DES) based on quats. DES are quite similar to ionic liquids (ILs) and are used as well as alternative solvents with a great diversity of physical properties, making them attractive for replacement of hazardous, volatile solvents (e.g. VOCs). A remarkable difference between genuine DES and ILs with the solutions used in this project is the addition of rather large quantities of water. It is shown the presence of water has a lot of advantages on the leaching of metals, while the properties typical for DES still remain. The oxidizing capacities of Cu(II) stem from the existence of a stable Cu(I) component in quat based DES and thus the leaching stems from the activity of the Cu(II)/Cu(I) redox couple. The advantage of Fe(III) in combination with DES is the fact that the Fe(III)/Fe(II) redox couple becomes reversible, which is not true in pure water. This opens perspectives for regeneration of the etching solution. In this project the leaching of copper was studied as a function of gradual increasing water content from 0 - 100w% with the same concentration of copper chloride or iron(III) chloride at room temperature and 80ºC. The solutions were also tested on real PCBs. At room temperature a maximum leaching effect for copper was obtained with 30w% choline chloride with 0.2 M CuCl2.2H2O. The leaching effect is still stronger at 80°C, b ut of course these solutions are more energy consuming. For aluminium, tin, zinc and lead, the leaching was faster at 80ºC. Iron and nickel dissolved easily at room temperature. The solutions were not able to dissolve gold, silver, rhodium and platinum.

Expatriates’ influence on knowledge sharing: an empirical study with International portuguese companies

Despite the abundant literature in knowledge management, few empirical studies have explored knowledge management in connection with international assignees. This phenomenon has a special relevance in the Portuguese context, since (a) there are no empirical studies concerning this issue that involves international Portuguese companies; (b) the national business reality is incipient as far as internationalisation is concerned, and; (c) the organisational and national culture presents characteristics that are distinctive from the most highly studied contexts (e.g., Asia, USA, Scandinavian countries, Spain, France, The Netherlands, Germany, England and Russia). We examine the role of expatriates in transfer and knowledge sharing within the Portuguese companies with operations abroad. We focus specifically on expatriates’ role on knowledge sharing connected to international Portuguese companies and our findings take into account organizational representatives’ and expatriates’ perspectives. Using a comparative case study approach, we examine how three main dimensions influence the role of expatriates in knowledge sharing among headquarters and their subsidiaries (types of international assignment, reasons for using expatriation and international assignment characteristics). Data were collected using semi‐structured interviews to 30 Portuguese repatriates and 14 organizational representatives from seven Portuguese companies. The findings suggest that the reasons that lead Portuguese companies to expatriating employees are connected to: (1) business expansion needs; (2) control of international operations and; (3) transfer and knowledge sharing. Our study also shows that Portuguese companies use international assignments in order to positively respond to the increasingly decaying domestic market in the economic areas in which they operate. Evidence also reveals that expatriation is seen as a strategy to fulfill main organizational objectives through their expatriates (e.g., business internationalization, improvement of the coordination and control level of the units/subsidiaries abroad, replication of aspects of the home base, development and incorporation of new organizational techniques and processes). We also conclude that Portuguese companies have developed an International Human Resources Management strategy, based on an ethnocentric approach, typically associated with companies in early stages of internationalization, i.e., the authority and decision making are centered in the home base. Expatriates have a central role in transmitting culture and technical knowledge from company’s headquarters to the company’s branches. Based on the findings, the article will discuss in detail the main theoretical and managerial implications. Suggestions for further research will also be presented.