Estudos exploratórios sobre propriedades térmicas do compósito cimento-polpa celulósica(CPC)

The search for a more aware use of available raw materials has led to a need to create more sustainable products. The use of natural fibers to reinforce cement, for instance, has been widely studied in the past decades because of the possibility that they can improve material properties such as thermal resistance and to compression, besides conferring a decrease in their total weight. This present study aimed at to conduct preliminary studies on the thermal resistance of the composite cement - Cellulose Pulp, using waste from the pulp and paper industry. Through experiments, it was found that the composite manufactured using the ratio 30 % Portland cement and 70 % pulp, showed satisfactory results regarding its thermal resistance, so it could be considered as a potential thermal insulation material, for use in constructions

Catalytic liquid- and gas-phase oxidations for the synthesis of intermediates and specialty chemicals: some examples of industrial relevance

Nowadays, it is clear that the target of creating a sustainable future for the next generations requires to re-think the industrial application of chemistry. It is also evident that more sustainable chemical processes may be economically convenient, in comparison with the conventional ones, because fewer by-products means lower costs for raw materials, for separation and for disposal treatments; but also it implies an increase of productivity and, as a consequence, smaller reactors can be used. In addition, an indirect gain could derive from the better public image of the company, marketing sustainable products or processes. In this context, oxidation reactions play a major role, being the tool for the production of huge quantities of chemical intermediates and specialties. Potentially, the impact of these productions on the environment could have been much worse than it is, if a continuous efforts hadn’t been spent to improve the technologies employed. Substantial technological innovations have driven the development of new catalytic systems, the improvement of reactions and process technologies, contributing to move the chemical industry in the direction of a more sustainable and ecological approach. The roadmap for the application of these concepts includes new synthetic strategies, alternative reactants, catalysts heterogenisation and innovative reactor configurations and process design. Actually, in order to implement all these ideas into real projects, the development of more efficient reactions is one primary target. Yield, selectivity and space-time yield are the right metrics for evaluating the reaction efficiency. In the case of catalytic selective oxidation, the control of selectivity has always been the principal issue, because the formation of total oxidation products (carbon oxides) is thermodynamically more favoured than the formation of the desired, partially oxidized compound. As a matter of fact, only in few oxidation reactions a total, or close to total, conversion is achieved, and usually the selectivity is limited by the formation of by-products or co-products, that often implies unfavourable process economics; moreover, sometimes the cost of the oxidant further penalizes the process. During my PhD work, I have investigated four reactions that are emblematic of the new approaches used in the chemical industry. In the Part A of my thesis, a new process aimed at a more sustainable production of menadione (vitamin K3) is described. The “greener” approach includes the use of hydrogen peroxide in place of chromate (from a stoichiometric oxidation to a catalytic oxidation), also avoiding the production of dangerous waste. Moreover, I have studied the possibility of using an heterogeneous catalytic system, able to efficiently activate hydrogen peroxide. Indeed, the overall process would be carried out in two different steps: the first is the methylation of 1-naphthol with methanol to yield 2-methyl-1-naphthol, the second one is the oxidation of the latter compound to menadione. The catalyst for this latter step, the reaction object of my investigation, consists of Nb2O5-SiO2 prepared with the sol-gel technique. The catalytic tests were first carried out under conditions that simulate the in-situ generation of hydrogen peroxide, that means using a low concentration of the oxidant. Then, experiments were carried out using higher hydrogen peroxide concentration. The study of the reaction mechanism was fundamental to get indications about the best operative conditions, and improve the selectivity to menadione. In the Part B, I explored the direct oxidation of benzene to phenol with hydrogen peroxide. The industrial process for phenol is the oxidation of cumene with oxygen, that also co-produces acetone. This can be considered a case of how economics could drive the sustainability issue; in fact, the new process allowing to obtain directly phenol, besides avoiding the co-production of acetone (a burden for phenol, because the market requirements for the two products are quite different), might be economically convenient with respect to the conventional process, if a high selectivity to phenol were obtained. Titanium silicalite-1 (TS-1) is the catalyst chosen for this reaction. Comparing the reactivity results obtained with some TS-1 samples having different chemical-physical properties, and analyzing in detail the effect of the more important reaction parameters, we could formulate some hypothesis concerning the reaction network and mechanism. Part C of my thesis deals with the hydroxylation of phenol to hydroquinone and catechol. This reaction is already industrially applied but, for economical reason, an improvement of the selectivity to the para di-hydroxilated compound and a decrease of the selectivity to the ortho isomer would be desirable. Also in this case, the catalyst used was the TS-1. The aim of my research was to find out a method to control the selectivity ratio between the two isomers, and finally to make the industrial process more flexible, in order to adapt the process performance in function of fluctuations of the market requirements. The reaction was carried out in both a batch stirred reactor and in a re-circulating fixed-bed reactor. In the first system, the effect of various reaction parameters on catalytic behaviour was investigated: type of solvent or co-solvent, and particle size. With the second reactor type, I investigated the possibility to use a continuous system, and the catalyst shaped in extrudates (instead of powder), in order to avoid the catalyst filtration step. Finally, part D deals with the study of a new process for the valorisation of glycerol, by means of transformation into valuable chemicals. This molecule is nowadays produced in big amount, being a co-product in biodiesel synthesis; therefore, it is considered a raw material from renewable resources (a bio-platform molecule). Initially, we tested the oxidation of glycerol in the liquid-phase, with hydrogen peroxide and TS-1. However, results achieved were not satisfactory. Then we investigated the gas-phase transformation of glycerol into acrylic acid, with the intermediate formation of acrolein; the latter can be obtained by dehydration of glycerol, and then can be oxidized into acrylic acid. Actually, the oxidation step from acrolein to acrylic acid is already optimized at an industrial level; therefore, we decided to investigate in depth the first step of the process. I studied the reactivity of heterogeneous acid catalysts based on sulphated zirconia. Tests were carried out both in aerobic and anaerobic conditions, in order to investigate the effect of oxygen on the catalyst deactivation rate (one main problem usually met in glycerol dehydration). Finally, I studied the reactivity of bifunctional systems, made of Keggin-type polyoxometalates, either alone or supported over sulphated zirconia, in this way combining the acid functionality (necessary for the dehydrative step) with the redox one (necessary for the oxidative step). In conclusion, during my PhD work I investigated reactions that apply the “green chemistry” rules and strategies; in particular, I studied new greener approaches for the synthesis of chemicals (Part A and Part B), the optimisation of reaction parameters to make the oxidation process more flexible (Part C), and the use of a bioplatform molecule for the synthesis of a chemical intermediate (Part D).

Eine ökologische Landeskunde der Rhön

Die Ökologische Landeskunde der Rhön – mit einem Schwerpunkt auf dem hessischen Teil – behandelt als moderne Landeskunde neben der Geostruktur und der humangeographischen Struktur im Besonderen die ökologische Struktur, denn nur durch diese Pointierung können Räume in ihrer Gesamtheit und Komplexität beschrieben werden. Das gilt im Besonderen für ökologisch bedeutsame Schutzräume wie die Rhön. Der Mittelgebirgsraum Rhön ist eine über Jahrhunderte gewachsene Kulturlandschaft mit einem weitgehend intakten, aber fragilen Ökosystem, das eine einzigartige und schützenswerte floristische und faunistische Ausstattung aufweist. Durch die weitreichenden mittelalterlichen Rodungen und die anschließende extensive Weidenutzung haben sich unter dem Eingriff des Menschen besonders auf den Höhenlagen im Laufe der Zeit artenreiche und ökologisch bedeutsame Ökosystemtypen, wie Borst- und Kalkmagerrasen, entwickelt. Um das naturräumliche und touristische Potential des Untersuchungsraums langfristig erhalten zu können, haben ökologische und nachhaltige Entwicklungen in den einzelnen Wirtschaftssektoren eine überragende Funktion. Im primären, sekundären und tertiären Sektor zeigen sich deutliche Entwicklungen hin zu ökologischen Erzeugnissen und Dienstleistungen. Der Ökolandbau gewinnt in der Rhön zunehmend an Bedeutung, Betriebe spezialisieren sich immer mehr auf Bio-zertifizierte und regionale Produkte und werben verstärkt mit ökologischen und rhöntypischen Begrifflichkeiten. Vor allem der für die Rhön wirtschaftlich bedeutende Tourismussektor, der im Spannungsfeld zwischen Ökonomie und Ökologie steht, entwickelt sich ebenfalls in Richtung nachhaltiger und umweltfreundlicher Formen. Am Beispiel des Milseburgradwegs konnte anhand einer Besucherbefragung auf Basis standardisierter Fragestellungen mit vornehmlich geschlossenen Fragen gezeigt werden, wie wichtig den Nutzern eine intakte Natur ist und wie Ökotourismus, Wirtschaftlichkeit und Naturschutz koexistieren können. Die Prämierung der Rhön zum Biosphärenreservat Rhön durch die UNESCO im Jahre 1991 erwies sich als Glücksfall und konnte dem strukturschwachen ländlichen Raum wichtige ökologische und wirtschaftliche Impulse geben, vor allem in Richtung ökologischer und nachhaltiger Erzeugnisse und Dienstleistungen. Die Auszeichnung kann dabei als Synthese zwischen Geostruktur und humangeographischer Struktur angesehen werden und ist Würdigung, Mahnung und Pflicht zugleich. Zusätzlich verdeutlicht sie auf eindringliche Weise die Fragilität und Schutzwürdigkeit des Ökosystems. Gegenwärtig zeichnen sich im Untersuchungsraum einige Entwicklungen ab, die die ökologische Raumstruktur gefährden und zusätzlich zur Aberkennung des Titels Biosphärenreservat führen könnten, weshalb sie kritisch gesehen werden müssen. Hier stechen der Bau der geplanten Bundesstraße B 87n von Fulda nach Meiningen oder das Kernzonendefizit hervor. Die Arbeit ist deshalb ein Plädoyer für den unbedingten Erhalt des identitätsstiftenden Titels Biosphärenreservat sowie für eine aktive Umweltbildung, denn eine erfolgreiche Zukunft und Identifikation der Bewohner mit ihrem Heimatraum ist unmittelbar an das Prädikat gekoppelt. Ökologische Landeskunden verstehen sich als aktive Elemente in der Umweltbildung und richten sich an die Menschen, die immer mehr zum prägenden Faktor von Räumen und ihren Ökosystemen werden. In der Rhön können sie sogar als Ausgangspunkt für die Herausbildung aufgefasst werden. Trotz der begrenzten Aussagekraft der Arbeit und der Komplexität des Untersuchungsraums zeigen sich vielfältige, ökologisch relevante Entwicklungen, die jedoch durch weitere sozialwissenschaftliche und wirtschaftswissenschaftliche Arbeiten erweitert, vertieft und stetig abgeglichen werden müssen.

Squash Bug, Squash Vine Borer, and Striped Cucumber Beetle on Butternut Squash and Muskmelon

Alternative agricultural schemes are gaining attention as the demand for organic and sustainable products continues to grow. Pest insects pose a sizeable challenge to agricultural production because their activities reduce crop fitness and productivity. Effective management of pest-insects is, therefore, crucial for successful management, and increasingly entails a multi-dimensional approach.

Strategic sourcing in the UK bioenergy industry

Successful supply chain management requires the management of a complex, multi-stakeholder, multi-criteria system. Stakeholder inclusion in the supply chain design and decision making processes is an area of growing interest for companies looking to design sustainable supply chains or produce sustainable products. This paper demonstrates the use of the integrated quality function deployment and analytic hierarchy process (QFD-AHP) method for the inclusion of a wide group of stakeholder requirements into the supplier selection process. The method provides a weighted ranked list of evaluating criteria which can be used to assess potential suppliers in the UK renewable bioenergy industry. The bioenergy industry is suitable as there are many stakeholders placing various requirements upon potential biomass suppliers. The paper uses a mixture of literature review and semi-structured industry interviews to answer three research questions: which stakeholder groups are important when selecting biomass suppliers for the UK? What requirements are made by these stakeholders on the supply of biomass fuels and feedstocks? Which evaluating criteria are most important? © 2013 Elsevier B.V.

Konsumenters uppfattning och kännedom om hållbar produktion och konsumtion : Teknologiska produkter och mobiltelefoner

Sambandet mellan konsumtion och klimatförändringar blir mer tydligt och jordens naturresurser som utarmas kan enligt forskning helt tillskrivas mänskligt beteende. För att lösa denna kris behöver delvis konsumentbeteendet förändras och konsumenter behöver välja mer hållbara produkter. Den överkonsumtion som finns idag är ett stort hot mot en hållbar utveckling och svenska konsumenter är en grupp som är snabba att konsumera det nyaste på marknaden. Konsumtionen av teknologiska produkter som exempelvis mobiltelefoner, datorer och tv-apparater har ökat kraftigt under de senaste tjugo åren då dessa produkter har blivit en del av konsumentens vardag. Nya modeller av mobiltelefoner kommer ständigt ut på marknaden och mobiltelefonen är en av de teknologiska produkterna där konsumtionen har ökat kraftigt. Syftet med denna uppsats var att undersöka konsumenters uppfattning och kännedom om hållbar produktion och konsumtion av teknologiska produkter. Mobiltelefonen är den teknologiska produkt som valdes som studieobjekt. Vi valde att genomföra en kvalitativ metod med semistrukturerade intervjuer för att uppfylla syftet. Intervjuerna genomfördes med tio studenter vid olika utbildningsprogram vid Högskolan Dalarna. Resultatet visade att konsumenters generella uppfattning och kännedom om hållbar produktion och konsumtion av teknologiska produkter var låg. Det fanns en viss kännedom om hållbarhetsfrågor hos våra respondenter men ingen hade tidigare reflekterat över detta i samband med produktion och konsumtionen av teknologiska produkter. Uppfattningen hos respondenterna är i stor utsträckning att produktion och konsumtion har påverkan på den hållbara utvecklingen.

Green supply chain management practices and firm performance: evidence from Finland

In order to address the increasing stakeholder requirements for environmentally sustainable products and processes, firms often need the participation of their supply chain partners. Green supply chain management has emerged as a set of managerial practices that integrate environmental issues into supply chain management. If implemented successfully, green supply chain management can be a way to achieve competitive advantage while enhancing the environmental sustainability of the firm. The overall purpose of this dissertation is to contribute to the discussion on green supply chain management practices from the perspective of their drivers and performance implications. The theoretical background arises from the literature on competitive strategy, firm performance and green supply chain management. The research questions are addressed by analysing firm-level data from manufacturing, trading and logistics firms operating in Finland. The empirical data comes from two consecutive Finland State of Logistics surveys in 2012 and 2014, combined with financial reporting data from external databases. The data is analysed with multiple statistical methods. First, the thesis contributes to the discussion of the drivers of GSCM practices. To enhance the understanding of the relationship between competitive strategy and GSCM practices, a conceptual tool to describe generic competitive strategy approaches was developed. The findings suggest that firms pursuing marketing differentiation are more likely to be able to compete by having only small environmental effects and by adopting a more advanced form of external green supply chain management, such as a combination of strong environmental collaboration and the increased environmental monitoring of suppliers. Furthermore, customer requirements for environmental sustainability are found to be an important driver in the implementation of internal GSCM practices. Firms can respond to this customer pressure by passing environmental requirements on to their suppliers, either through environmental collaboration or environmental monitoring. Second, this thesis adds value to the existing literature on the effects of green supply chain management practices on firm performance. The thesis provides support for the idea that there is a positive relationship between GSCM practices and firm performance and enhances the understanding of how different types of GSCM practices are related to 1) financial, 2) operational and 3) environmental performance in manufacturing and logistics. The empirical results suggest that while internal GSCM practices have the strongest effect on environmentalperformance, environmental collaboration with customers seems to be the most effective way to improve financial performance. In terms of operational performance, the findings were more mixed, suggesting that the operational performance of firms is more likely to be affected by firm characteristics than by the choices they make regarding their environmental collaboration. This thesis is also one of the first attempts to empirically analyse the relationship between GSCM practices and performance among logistics service providers. The findings also have managerial relevance. Management, especially in manufacturing and logistics industries, may benefit by gaining knowledge about which types of GSCM practice could provide the largest benefits in terms of different performance dimensions. This thesis also has implications for policy-makers and regulators regarding how to promote environmentally friendly activities among 1) manufacturing; 2) trading; and 3) logistics firms.

Crystal engineering of co-crystals and host-guest systems for environmentally friendly applications: sunscreens stabilization, pollutant sequestering and herbicide reformulation.

Solid state engineered materials have proven to be useful and suitable tools in the quest of new materials. In this thesis different crystalline compounds were synthesized to provide more sustainable products for different applications, as in cosmetics or in agrochemistry, to propose pollutants removal strategy or to obtain materials for electrocatalysis. Therefore, the research projects presented here can be divided into three main topics: (i) sustainable preparation of solid materials of widely used active ingredients aimed at the reduction of their occurrence in the natural environment. The systems studied in this section are cyclodextrins host-guest compounds, obtained via mechanochemical and slurry synthesis. The first chemicals studied are sunscreens inclusion complexes, that proved to have enhanced photostability and desired photoprotection. The same synthetic methods were applied to obtain inclusion complexes of bentazon, a herbicide often found to leach in groundwaters. The resulting products showed to have desired water solubility properties. The same herbicide was also adsorbed on amorphous calcium phosphate nanoparticles, to obtain a biocompatible formulation of this agrochemical. This herbicide could benefit by the adsorption on nanoparticles for what concerns its kinetic release in different media as well as its photostability. (ii) Sustainable synthesis of co-crystals based on polycyclic aromatic hydrocarbons, for the proposal of a sequestering method with a resulting material with enhanced properties. The co-crystallization via mechanochemical means proved that these pollutants can be sequestered via simple solvent-free synthesis and the obtained materials present better photochemical properties when compared to the starting co-formers. (iii) Crystallization from mild solvents of nanosized materials useful for the application in electrocatalysis. The study of compounds based on nickel and cobalt metal ions resulted in the obtainment of 2D and 1D coordination polymers. Moreover, solid solutions were obtained. These crystals showed layered structures and, according to preliminary results, they can be exfoliated.

Desarrollo sustentable de Productos y Servicios de Camélidos orientados al mercado en la región andina (DECAM). Sustainable Development Products and Services Marketed oriented in Andean Region

Este proyecto cuenta con el financiamiento del sistema INCO de la Unión Europea e incluye 5 contrapartes europeas, y Bolivia y Perú como contrapartes americanos. Consta de cuatro paquetes: producto, mercado, difusión y coordinación. En el primer paquete se desarrollan fundamentalmente los aspectos relacionados con la carne fresca y los productos cárnicos tanto tradicionales como nuevos a desarrollar. Se realizan faenas protocolizadas y espontáneas comparando animales con distintos tratamientos nutricionales de edades entre 19-21 meses. Se realizan análisis de calidad de carne y paneles de degustación. Los productos tradicionales como el charqui se evalúan en su forma tradicional y se implementan sistemas mejorados como desecadores solares. Los chacinados no son tradicionales en el altiplano por eso se realizan en La Pampa con la idea de transferir la tecnología desarrollada. La evaluación de calidad de la carne incluye técnicas de evaluación del animal en pié como la conservación morfológica y la ecografía para predecir calidad de res en el animal vivo. Estas observaciones se corroboran a la faena donde se realiza toda la batería de evaluaciones de calidad de la res.

Green furniture: sustainable design guidelines for the Irish furniture and wood products industry.

This thesis presents the research and development of sustainable design guidelines for the furniture and wood products industry, suitable for sustainably enhancing design, manufacturing and associated activities. This sustainable guideline is based on secondary research conducted on subject areas such as ‘eco’ design, ‘green’ branding and ‘green’ consumerism, as well as an examination of existing certifications and sustainable tools techniques and methodologies, national and international drivers for sustainable development and an overview of sustainability in the Irish furniture manufacturing context. The guideline was further developed through primary research. This consisted of a focus group attended by leading Irish designers, manufacturers and academics in the area of furniture and wood products. This group explored the question of ‘green branding’ saturation in the market and the viability of investing in sustainability just yet. Participants stated that they felt the market for ‘green’ products is evolving very slowly and that there is no metric or legal framework present to audit whether or not companies are producing products that really embody sustainability. All the participants believed that developing and introducing a new certification process to incorporate a sustainable design process was a viable and necessary solution to protecting Irish furniture and wood manufacturers going forward. For the purposes of the case study, the author investigated a ‘sustainable’ design process for Team woodcraft, Ltd., through the design and development of a ‘sustainable’ children’s furniture range. The case study followed a typical design and development process; detailing customer design specifications, concept development and refinement and cumulating in final prototype, as well as associated engineering drawings. Based on this primary and secondary research, seven fundamental core principles for this sustainable guideline have been identified by the author. The author then used these core principles to expand into guidelines for the basis of proposed new Irish sustainable design guidelines for the furniture and wood products industry, the concept of which the author has named ‘Green Dot’. The author suggests that the ‘Green Dot’ brand or logo could be used to market an umbrella network of Irish furniture designers and manufactures who implement the recommended sustainable techniques.

Quality and safety requirements for sustainable phage therapy products.

The worldwide antibiotic crisis has led to a renewed interest in phage therapy. Since time immemorial phages control bacterial populations on Earth. Potent lytic phages against bacterial pathogens can be isolated from the environment or selected from a collection in a matter of days. In addition, phages have the capacity to rapidly overcome bacterial resistances, which will inevitably emerge. To maximally exploit these advantage phages have over conventional drugs such as antibiotics, it is important that sustainable phage products are not submitted to the conventional long medicinal product development and licensing pathway. There is a need for an adapted framework, including realistic production and quality and safety requirements, that allowsa timely supplying of phage therapy products for 'personalized therapy' or for public health or medical emergencies. This paper enumerates all phage therapy product related quality and safety risks known to the authors, as well as the tests that can be performed to minimize these risks, only to the extent needed to protect the patients and to allow and advance responsible phage therapy and research.

Biofuels and high value added products from the yeast Rhodosporidium toruloides NCYC 921: Strategies towards a true cost-effective and environmentally sustainable integrated multiproduct driven biorefinery [Poster]

Single-cell oils (SCO) have been considered a promising source of 3rd generation biofuels mainly in the final form of biodiesel. However, its high production costs have been a barrier towards the commercialization of this commodity. The fast growing yeast Rhodosporidium toruloides NCYC 921 has been widely reported as a potential SCO producing yeast. In addition to its well-known high lipid content (that can be converted into biodiesel), is rich in high value added products such as carotenoids with commercial interest. The process design and integration may contribute to reduce the overall cost of biofuels and carotenoid production and is a mandatory step towards their commercialization. The present work addresses the biomass disruption, extraction, fractionation and recovery of products with special emphasis on high added valued carotenoids (beta-carotene, torulene, torularhodin) and fatty acids directed to biodiesel. The chemical structure of torularhodin with a terminal carboxylic group imposes an additional extra challenge in what concern its separation from fatty acids. The proposed feedstock is fresh biomass pellet obtained directly by centrifugation from a 5L fed-batch fermentation culture broth. The use of a wet instead of lyophilised biomass feedstock is a way to decrease processing energy costs and reduce downstream processing time. These results will contribute for a detailed process design. Gathered data will be of crucial importance for a further study on Life-Cycle Assessment (LCA).

Refrigeration needs for sustainable preservation of horticultural products

Fresh horticultural products are highly perishable and need refrigeration for further preservation. Refrigeration needs energy consumption with consequent economical cost and damage for the environment. The objective of the present work was to use efficiently the refrigeration according to the product needs and time for consumption. Salicornia ramosissima and Sarcocornia perennis fresh branch tips, which are used for fresh salads, were stored at 1, 4 and 9 °C for up to 21 days. In both species, fresh tips were of good consumer acceptability for up to 14 days at 9°C. At 1 and 4 °C fresh tips could be stored in good conditions up to 21 days. For efficient use of energy in refrigeration of fresh salicornia and sarcocornia we conclude that if it is to put those products in the market earlier we can use the higher temperature for storage saving energy. Only for further storage we shall use the lower temperatures.

Refrigeration needs for sustainable preservation of horticultural products

Fresh horticultural products are highly perishable and need refrigeration for further preservation. Refrigeration needs energy consumption with consequent economical cost and damage for the environment. The objective of the present work was to use efficiently the refrigeration according to the product needs and time for consumption. Salicornia ramosissima and Sarcocornia perennis fresh branch tips, which are used for fresh salads, were stored at 1, 4 and 9 °C for up to 21 days. In both species, fresh tips were of good consumer acceptability for up to 14 days at 9°C. At 1 and 4 °C fresh tips could be stored in good conditions up to 21 days. For efficient use of energy in refrigeration of fresh salicornia and sarcocornia we conclude that if it is to put those products in the market earlier we can use the higher temperature for storage saving energy. Only for further storage we shall use the lower temperatures.