Minimização de odores em contentores de resíduos sólidos

Mestrado em Engenharia Química

Implementação e validação de um método de avaliação do perfil de ácidos gordos e do teor de gordura em alimentos por cromatografia gasosa

Nos dias de hoje é necessário criar hábitos de vida mais saudáveis que contribuam para o bem-estar da população. Adoptar medidas e práticas de modo regular e disciplinado, pode diminuir o risco do aparecimento de determinadas doenças, como a obesidade, as doenças cardiovasculares, a hipertensão, a diabetes, alguns tipos de cancro e tantas outras. É também importante salientar que, uma alimentação cuidada dá saúde e aumenta a esperança média de vida. Em Portugal, nos últimos anos, os costumes alimentares da população têm vindo a alterar-se significativamente. As refeições caseiras confeccionadas com produtos frescos dão lugar à designada “cultura do fast food”. Em contrapartida, os consumidores são cada vez mais exigentes, estando em permanente alerta no que se refere ao estado dos alimentos. A rotulagem de um produto, para além da função publicitária, tem vindo a ser objecto de legislação específica de forma a fornecer informação simples e clara, correspondente à composição, qualidade, quantidade, validade ou outras características do produto. Estas informações devem ser acessíveis a qualquer tipo de público, com mais ou menos formação e de qualquer estrato social. A qualidade e segurança dos produtos deve basear-se na garantia de que todos os ingredientes, materiais de embalagem e processos produtivos são adequados à produção de produtos seguros, saudáveis e saborosos. A Silliker Portugal, S.A. é uma empresa independente de prestação de serviços para o sector agro-alimentar, líder mundial na prestação de serviços para a melhoria da qualidade e segurança alimentar. A Silliker dedica-se a ajudar as empresas a encontrar soluções para os desafios actuais do sector, oferecendo uma ampla gama de serviços, onde se inclui o serviço de análises microbiológicas, químicas e sensorial; consultadoria em segurança alimentar e desenvolvimento; auditorias; rotulagem e legislação. A actualização permanente de procedimentos na procura de uma melhoria contínua é um dos objectivos da empresa. Para responder a um dos desafios colocados à Silliker, surgiu este trabalho, que consistiu no desenvolvimento de um novo método para determinação de ácidos gordos e da gordura total em diferentes tipos de alimentos e comparação dos resultados, com os obtidos com o método analítico até então adoptado. Se a gordura é um elemento de grande importância na alimentação, devido às suas propriedades nutricionais e organoléticas, recentemente, os investigadores têm focado a sua atenção nos mais diversos ácidos gordos (saturados, monoinsaturados e polinsaturados), em particular nos ácidos gordos essenciais e nos isómeros do ácido linoleico conjugado (CLA), uma mistura de isómeros posicionais e geométricos do ácido linoleico com actividade biológica importante. A técnica usada nas determinações foi a cromatografia gasosa com ionização de chama, GC-FID, tendo as amostras sido previamente tratadas e extraídas de acordo com o tipo de matriz. A metodologia analítica desenvolvida permitiu a correcta avaliação do perfil em ácidos gordos, tendo-se para isso usado uma mistura de 37 ésteres metílicos, em que o ácido gordo C13:0 foi usado como padrão interno. A identificação baseou-se nos tempos de retenção de cada ácido gordo da mistura e para a quantificação usaram-se os factores de resposta. A validação do método implementado foi baseada nos resultados obtidos no estudo de três matrizes relativas a materiais certificados pela BIPEA (Bureau Interprofessionnel des Etudes Analytiques), para o que foram efectuadas doze réplicas de cada matriz. Para cada réplica efectuada foi calculado o teor de matéria gorda, sendo posteriormente o resultado comparado com o emitido pela entidade certificada. Após análise de cada constituinte foi também possível calcular o teor em ácidos gordos saturados, monoinsaturados e polinsaturados. A determinação do perfil em ácidos gordos dos materiais certificados foi aceitável atendendo aos valores obtidos, os quais se encontravam no intervalo de valores admissíveis indicados nos relatórios. A quantificação da matéria gorda no que se refere à matriz de “Paté à Tartinier” apresentou um z-score de 4,3, o que de acordo com as exigências internas da Silliker, não é válido. Para as outras duas matrizes (“Mélange Nutritif” e “Plat cuisiné à base de viande”) os valores de z-score foram, respectivamente, 0,7 e -1,0, o que permite concluir a validade do método. Para que o método possa vir a ser adoptado como método alternativo é necessário um estudo mais alargado relativamente a amostras com diferentes composições. O método foi aplicado na análise de amostras de fiambre, leite gordo, queijo, ovo com ómega 3, amendoim e óleo de girassol, e os resultados foram comparados com os obtidos pelo método até então adoptado.

Re-use assessment of thermoset composite wastes as aggregate and filler replacement for concrete-polymer composite materials: a case study regarding GFRP pultrusion wastes

Glass fibre-reinforced plastics (GFRP), nowadays commonly used in the construction, transportation and automobile sectors, have been considered inherently difficult to recycle due to both the cross-linked nature of thermoset resins, which cannot be remoulded, and the complex composition of the composite itself, which includes glass fibres, polymer matrix and different types of inorganic fillers. Hence, to date, most of the thermoset based GFRP waste is being incinerated or landfilled leading to negative environmental impacts and additional costs to producers and suppliers. With an increasing awareness of environmental matters and the subsequent desire to save resources, recycling would convert an expensive waste disposal into a profitable reusable material. In this study, the effect of the incorporation of mechanically recycled GFRP pultrusion wastes on flexural and compressive behaviour of polyester polymer mortars (PM) was assessed. For this purpose, different contents of GFRP recyclates (0%, 4%, 8% and 12%, w/w), with distinct size grades (coarse fibrous mixture and fine powdered mixture), were incorporated into polyester PM as sand aggregates and filler replacements. The effect of the incorporation of a silane coupling agent was also assessed. Experimental results revealed that GFRP waste filled polymer mortars show improved mechanical behaviour over unmodified polyester based mortars, thus indicating the feasibility of GFRP waste reuse as raw material in concrete-polymer composites.

New recycling approaches for thermoset polymeric composite wastes – an experimental study on polyester based concrete materials filled with fibre reinforced plastic recyclates

In this study, a new waste management solution for thermoset glass fibre reinforced polymer (GFRP) based products was assessed. Mechanical recycling approach, with reduction of GFRP waste to powdered and fibrous materials was applied, and the prospective added-value of obtained recyclates was experimentally investigated as raw material for polyester based mortars. Different GFRP waste admixed mortar formulations were analyzed varying the content, between 4% up to 12% in weight, of GFRP powder and fibre mix waste. The effect of incorporation of a silane coupling agent was also assessed. Design of experiments and data treatment was accomplished through implementation of full factorial design and analysis of variance ANOVA. Added value of potential recycling solution was assessed by means of flexural and compressive loading capacity of GFRP waste admixed mortars with regard to unmodified polymer mortars. The key findings of this study showed a viable technological option for improving the quality of polyester based mortars and highlight a potential cost-effective waste management solution for thermoset composite materials in the production of sustainable concrete-polymer based products.

Hybrid thermoset polymeric composites – an Innovation towards sustainability

In this study, a new waste management solution for thermoset glass fibre reinforced polymer (GFRP) based products was assessed. Mechanical recycling approach, with reduction of GFRP waste to powdered and fibrous materials was applied, and the prospective added-value of obtained recyclates was experimentally investigated as raw material for polyester based mortars. Different GFRP waste admixed mortar formulations were analyzed varying the content, between 4% up to 12% in weight, of GFRP powder and fibre mix waste. The effect of incorporation of a silane coupling agent was also assessed. Design of experiments and data treatment was accomplished through implementation of full factorial design and analysis of variance ANOVA. Added value of potential recycling solution was assessed by means of flexural and compressive loading capacity of GFRP waste admixed mortars with regard to unmodified polymer mortars. The key findings of this study showed a viable technological option for improving the quality of polyester based mortars and highlight a potential cost-effective waste management solution for thermoset composite materials in the production of sustainable concrete-polymer based products.

A case study on the improvement of eco-efficiency ratios: application to a composite processing industry

The World Business Council for Sustainable Development (WBCSD) defines Eco-Efficiency as follows: ‘Eco- Efficiency is achieved by the delivery of competitively priced-goods and services that satisfy human needs and bring quality of life, while progressively reducing ecological impacts and resource intensity throughout the life-cycle to a level at least in line with the earth’s estimated carrying capacity’. Eco-Efficiency is under this point of view a key concept for sustainable development, bringing together economic and ecological progress. Measuring the Eco-Efficiency of a company, factory or business, is a complex process that involves the measurement and control of several and relevant parameters or indicators, globally applied to all companies in general, or specific according to the nature and specificities of the business itself. In this study, an attempt was made in order to measure and evaluate the eco-efficiency of a pultruded composite processing company. For this purpose the recommendations of WBCSD [1] and the directives of ISO 14301 standard [2] were followed and applied. The analysis was restricted to the main business branch of the company: the production and sale of standard GFRP pultrusion profiles. The main general indicators of eco-efficiency, as well as the specific indicators, were defined and determined according to ISO 14031 recommendations. With basis on indicators’ figures, the value profile, the environmental profile, and the pertinent eco-efficiency’s ratios were established and analyzed. In order to evaluate potential improvements on company eco-performance, new indicators values and ecoefficiency ratios were estimated taking into account the implementation of new proceedings and procedures, both in upstream and downstream of the production process, namely: a) Adoption of new heating system for pultrusion die in the manufacturing process, more effective and with minor heat losses; b) Implementation of new software for stock management (raw materials and final products) that minimize production failures and delivery delays to final consumer; c) Recycling approach, with partial waste reuse of scrap material derived from manufacturing, cutting and assembly processes of GFRP profiles. In particular, the last approach seems to significantly improve the eco-efficient performance of the company. Currently, by-products and wastes generated in the manufacturing process of GFRP profiles are landfilled, with supplementary added costs to this company traduced by transport of scrap, landfill taxes and required test analysis to waste materials. However, mechanical recycling of GFRP waste materials, with reduction to powdered and fibrous particulates, constitutes a recycling process that can be easily attained on heavy-duty cutting mills. The posterior reuse of obtained recyclates, either into a close-looping process, as filler replacement of resin matrix of GFRP profiles, or as reinforcement of other composite materials produced by the company, will drive to both costs reduction in raw materials and landfill process, and minimization of waste landfill. These features lead to significant improvements on the sequent assessed eco-efficiency ratios of the present case study, yielding to a more sustainable product and manufacturing process of pultruded GFRP profiles.

Recycling of pultrusion production waste into innovative concrete-polymer composite solutions

In this study, the added value resultant from the incorporation of pultrusion production waste into polymer based concretes was assessed. For this purpose, different types of thermoset composite scrap material, proceeding from GFRP pultrusion manufacturing process, were mechanical shredded and milled into a fibrous-powdered material. Resultant GFRP recyclates, with two different size gradings, were added to polyester based mortars as fine aggregate and filler replacements, at various load contents between 4% up to 12% in weight of total mass. Flexural and compressive loading capacities were evaluated and found better than those of unmodified polymer mortars. Obtained results highlight the high potential of recycled GFRP pultrusion waste materials as efficient and sustainable admixtures for concrete and mortar-polymer composites, constituting an emergent waste management solution.

Experimental study on polyester based concretes filled with glass fibre reinforced plastic recyclates – a contribution to composite materials sustainability

The development and applications of thermoset polymeric composites, namely fibre reinforced plastics (FRP), have shifted in the last decades more and more into the mass market [1]. Despite of all advantages associated to FRP based products, the increasing production and consume also lead to an increasing amount of FRP wastes, either end-of-lifecycle products, or scrap and by-products generated by the manufacturing process itself. Whereas thermoplastic FRPs can be easily recycled, by remelting and remoulding, recyclability of thermosetting FRPs constitutes a more difficult task due to cross-linked nature of resin matrix. To date, most of the thermoset based FRP waste is being incinerated or landfilled, leading to negative environmental impacts and supplementary added costs to FRP producers and suppliers. This actual framework is putting increasing pressure on the industry to address the options available for FRP waste management, being an important driver for applied research undertaken cost efficient recycling methods. [1-2]. In spite of this, research on recycling solutions for thermoset composites is still at an elementary stage. Thermal and/or chemical recycling processes, with partial fibre recovering, have been investigated mostly for carbon fibre reinforced plastics (CFRP) due to inherent value of carbon fibre reinforcement; whereas for glass fibre reinforced plastics (GFRP), mechanical recycling, by means of milling and grinding processes, has been considered a more viable recycling method [1-2]. Though, at the moment, few solutions in the reuse of mechanically-recycled GFRP composites into valueadded products are being explored. Aiming filling this gap, in this study, a new waste management solution for thermoset GFRP based products was assessed. The mechanical recycling approach, with reduction of GFRP waste to powdered and fibrous materials was applied, and the potential added value of obtained recyclates was experimentally investigated as raw material for polyester based mortars. The use of a cementless concrete as host material for GFRP recyclates, instead of a conventional Portland cement based concrete, presents an important asset in avoiding the eventual incompatibility problems arisen from alkalis silica reaction between glass fibres and cementious binder matrix. Additionally, due to hermetic nature of resin binder, polymer based concretes present greater ability for incorporating recycled waste products [3]. Under this scope, different GFRP waste admixed polymer mortar (PM) formulations were analyzed varying the size grading and content of GFRP powder and fibre mix waste. Added value of potential recycling solution was assessed by means of flexural and compressive loading capacities of modified mortars with regard to waste-free polymer mortars.

GFRP waste reinforced polymer mortars: a new waste management solution for GFRP scrap material

To date, glass fibre reinforced polymer (GFRP) waste recycling is very limited and restricted by thermoset nature of binder matrix and lack of economically viable enduse applications for the recyclates. In this study, efforts were made in order to recycle grinded GFRP waste proceeding from pultrusion production scrap, into new and sustainable composite materials. For this purpose, GFRP waste recyclates, a mix of powdered and fibrous materials, were incorporated into polyester based mortars as fine aggregate and filler replacements, at different load contents (between 4% up to 12% of total mass) and particle size distributions. Potential recycling solution was assessed by mechanical behaviour of resultant GFRP waste modified polymer mortars. Test results revealed that GFRP waste filled polymer mortars present improved flexural and compressive behaviour over unmodified polyester based mortars, thus indicating the feasibility of GFRP waste reuse in concrete-polymer composites.

Desenvolvimento de uma cola biodegradável

Este documento especifica o trabalho realizado no estágio, que decorreu na Colquímica, sediada em Valongo. Este trabalho teve como objetivo colaborar no desenvolvimento de uma cola com características biodegradáveis. O estágio foi orientado pela Engenheira Cristina Frutuoso, no que diz respeito à orientação por parte da Colquímica, e pelo Professor Dr. Gilberto Pinto e Alfredo Crispim, ISEP. O trabalho foi dividido em duas instâncias, sendo a primeira direcionada para a formulação de uma cola com características biodegradáveis e a segunda para a realização do teste de Sturm, um teste de biodegradabilidade capaz de quantificar a quantidade de CO2 produzido pelo processo de biodegradação. Inicialmente foram desenvolvidas e estudadas dez formulações através das variações de resinas e óleo plastificante e estudado o seu comportamento reológico relacionado à variação de viscosidade em função da temperatura. Com base nos resultados obtidos verificou-se que a melhor formulação seria a A8. Estudaram-se as propriedades mecânicas da formulação escolhida e decidiu-se que esta estaria apta a ser usada no fecho de caixas de cartão de produtos ultra congelados assim como no fecho de caixas de cartão de detergentes em pó com peso até 3 Kg. Depois de escolhida a formulação deu-se início ao teste de Sturm, teste meramente orientativo. Durante dezassete dias avaliou-se a quantidade de CO2 produzida durante o processo de biodegradação. Após avaliação dos resultados verificou-se que a taxa de biodegradação para a amostra foi de 0,055 g de CO2. Com a finalidade de confirmar os resultados obtidos no teste de Sturm foi efetuada uma réplica do ensaio, a qual se encontra a decorrer sendo os resultados facultados, posteriormente, à empresa.

Re-Use Assessment of Thermoset Composite Wastes as Aggregate and Filler Replacement for Concrete-Polymer Composite Materials: A case study regarding GFRP pultrusion wastes

Glass fibre-reinforced plastics (GFRP), nowadays commonly used in the construction, transportation and automobile sectors, have been considered inherently difficult to recycle due to both the cross-linked nature of thermoset resins, which cannot be remoulded, and the complex composition of the composite itself, which includes glass fibres, polymer matrix and different types of inorganic fillers. Hence, to date, most of the thermoset based GFRP waste is being incinerated or landfilled leading to negative environmental impacts and additional costs to producers and suppliers. With an increasing awareness of environmental matters and the subsequent desire to save resources, recycling would convert an expensive waste disposal into a profitable reusable material. In this study, the effect of the incorporation of mechanically recycled GFRP pultrusion wastes on flexural and compressive behaviour of polyester polymer mortars (PM) was assessed. For this purpose, different contents of GFRP recyclates (0%, 4%, 8% and 12%, w/w), with distinct size grades (coarse fibrous mixture and fine powdered mixture), were incorporated into polyester PM as sand aggregates and filler replacements. The effect of the incorporation of a silane coupling agent was also assessed. Experimental results revealed that GFRP waste filled polymer mortars show improved mechanical behaviour over unmodified polyester based mortars, thus indicating the feasibility of GFRP waste reuse as raw material in concrete-polymer composites.