Made available in DSpace on 2016-06-02T19:10:01Z (GMT). No. of bitstreams: 1 2601.pdf: 5587826 bytes, checksum: 717a8aef3900d3dc9c6e48239028afeb (MD5) Previous issue date: 2008-04-04 / The evolution of the world-wide production of steel in rates superior to 7% per year in the last five years, strongly driven by China, which got off 222,4 millions in 2003 for 489,0 million tons in 20071, leads to a strong increase in the demand of iron ore. Therefore, fine ore price of Carajás for Asia went out from 28,14 in 2003 for 73,20 US$ cents for unity of iron in 2007. An increase of 160%. These facts, when related to the layer exhaustion and the growing environmental pressures on Iron and Steel Plants of the whole world, have been taking to a series of studies to the use of the residues bearers from iron produced in these factories. Up to that time, there has not been consolidated any technology which is technically and economically viable for the recycling of these residues so far. The present work is about the usage of the blast furnace mud, the mill scale and the iron oxide produced in the pickling lines of Companhia Siderúrgica Nacional (CSN) in self reduction pellets shape. It starts the productions in scale laboratorial and industrial after the chemical and physical characterizations from these raw materials. As soon as the most appropriated formulation was defined, the production in experimental scale began. These tests were carried out in the residues palletizing pilot plant, developed by CSN. There were also tests of self reduction and of meltreduction. In the first one, the formation of a metal drop inside a hallow sphere was obtained, and in the second one a metal profit of 99,1%. In sequence, the alternatives were valued for internal recycling of these pellets. The use of the heat contained in the empty hot-metal torpedo-cars for self-reduction showed the most economical route. This technology of recycling was introduced industrially in CSN. Thus, in the present work of doctorate, it was developed an unpublished route for industrial recycling for iron and steel residues, which was technically and economically feasible. / O crescimento da produção mundial de aço bruto em taxas superiores a 7% ao ano nos últimos cinco anos, fortemente impulsionado pela China, que saltou de 222,4 milhões em 2003 para 489,0 milhões de toneladas em 20071, gerou um forte aumento na demanda de minério de ferro. Com isso, o preço do minério fino de Carajás para a Ásia saiu de 28,14 em 2003 para 73,20 US$ cents por unidade de ferro em 2007. Um aumento de 160%. Estes fatos, associados à exaustão das jazidas e as crescentes pressões ambientais sobre as Siderúrgicas de todo o mundo, têm levado a uma série de estudos para o aproveitamento dos resíduos portadores de ferro gerados nestas Usinas. Até então, não se consolidou nenhuma tecnologia viável técnica e economicamente para esta reciclagem. O presente trabalho trata da utilização da lama de alto-forno, da carepa de laminação e do óxido de ferro gerado nas linhas de decapagem da Companhia Siderúrgica Nacional CSN na forma de pelotas auto-redutoras. Após as caracterizações químicas e físicas destas matérias-primas, partiu-se para as produções em escala laboratorial e industrial. Definida laboratorialmente a formulação mais adequada, partiu-se para a produção experimental. Esta foi realizada na planta piloto de pelotização de resíduos, desenvolvida pela CSN. Foram realizados ensaios de auto-redução e de fusão-redução. No primeiro, o resultado foi a formação de uma gota metálica dentro de uma esfera oca e no segundo, um rendimento metálico de 99,1%. Em seqüência, foram avaliadas as alternativas para reciclagem interna destas pelotas. A utilização do calor contido nos carrostorpedo vazios para a auto-redução se mostrou como a rota mais econômica. Esta tecnologia de reciclagem já se encontra implantada industrialmente na CSN. Portanto, no presente trabalho de doutoramento, desenvolveu-se uma rota inédita de reciclagem industrial dos resíduos siderúrgicos portadores de ferro, viável técnica e economicamente.

A proposta deste trabalho é de criar receita e renda para comunidades de baixa renda e, de certa forma chamar a atenção da sociedade para esta necessidade, ou seja, a de gerar mecanismos de melhoria da renda familiar. Através dos Postos de Troca, as pessoas residentes em comunidades atendidas pelo Programa Comunidade Eficiente, administrado pela Light junto a ANEEL, poderão trocar seus recicláveis por descontos em suas contas de energia elétrica. Os resíduos sólidos recicláveis possíveis por uma família de comunidade de baixa renda têm potencialidade em torno de 11,69 kg /mês, tendo sido estimada uma receita mensal por família de R$1,30. Este valor representa 40% da tarifa mínima cobrada pela Light, que é muito usual para esta classe de clientes. A viabilidade de implantação dos Postos de troca pode ser possível desde que haja um prazo mínimo para retorno do investimento de pelo menos 24 meses. / The proposal of this project is to create financial revenue for low-income communities and somehow look at this reality of the particular society and this need, or in another words, to generate income improvement mechanisms. Through the Recycling Exchange Stations, people residing in communities served by Efficient Community Program, administered by Light next to a ANEEL will be able to change its recycle waste for discounting in its bills of electric energy. The solid residues recyclable possible for a family of low income community has potentiality around 11,69 kg /month, having been estimate a monthly financial revenue for family of R$1,30. This value represents 40% of the minimum tariff charged by the Light, which is very usual for this class of customers. The viability of implantation of the Recycling Exchange Stations can be possible since that it has a minimum stated period for return of the investment of at least 24 months.

Made available in DSpace on 2015-09-25T12:18:45Z (GMT). No. of bitstreams: 1 IsraelNunesHenrique.pdf: 1394330 bytes, checksum: 72328b064472d745a8632e5b12e4b28c (MD5) Previous issue date: 2006-02-20 / The treated domestic sewer when available for the agricultural activities provides economy of water of good quality and chemical fertilizers and it motivates to the agricultural activities. In the semi-arid area of Brazil the reuse of water can be an alternative for the coexistence with the shortage of the hydric resources. In this context, the rural workers of the Municipal district of Lagoa Seca, PB, that produce vegetables during all year as source of revenue happening of the family agriculture. Several researches were already accomplished with the purpose of developing technologies of treatment of sewers that produces effluents with smaller risks of transmission of diseases, but guaranteeing appropriate concentrations of nutrients to the irrigated cultures. The present study had as objective to evaluate the sanitary aspects and nutricionais of the effluents of treated sewers in a system formed by a reactor UASB followed by polishing pond. The use of those effluents was also verified in the fertigation of bell pepper (Capsicum annuum L.). Compared with treatments of the soil using mineral and organic manuring, the planting of the bell pepper obeyed the statistical planning of blocks random, with 5 treatments and 4 repetitions. During the experimental period weekly analyses of the effluents were accomplished and of the culture of bell pepper. The pos-treatment of the sewer in the polishing pond produced effluent with sanitary quality inside of the values recommended by the World Organization of Health (OMS, 1989) for irrigation of vegetables consumed raw. The bell pepper irrigated with effluent of the reactor UASB didn't present significant difference of productivity (at the level of 5% of probability for the test Tukey), when compared to the application of mineral and organic manuring. / O esgoto doméstico tratado quando disponibilizado para as atividades agrícolas proporciona economia de água de boa qualidade e fertilizantes químicos e incentiva às atividades agrícolas. Na região semi-árida do Brasil o reúso de água poderá ser uma alternativa para a convivência com a escassez dos recursos hídricos. Neste contexto, estão inseridos os trabalhadores rurais do Município de Lagoa Seca, PB, que produzem hortaliças durante todo ano como fonte de renda advindo da agricultura familiar. Diversas pesquisas já foram realizadas com a finalidade de desenvolver tecnologias de tratamento de esgotos que produza efluentes com menores riscos de transmissão de doenças, mas garantindo concentrações adequadas de nutrientes às culturas irrigadas. O presente estudo teve como objetivo avaliar os aspectos sanitários e nutricionais dos efluentes de esgotos tratados em um sistema formado por um reator UASB seguido de lagoa de polimento. Também foi verificada a utilização desses efluentes na fertirrigação de pimentão (Capsicum annuum L.). Comparada com tratamentos do solo utilizando adubação mineral e orgânica, o plantio do pimentão obedeceu ao delineamento estatístico de blocos ao acaso, com 5 tratamentos e 4 repetições. Durante o período experimental foram realizadas análises semanais dos efluentes e da cultura de pimentão. O pós-tratamento do esgoto na lagoa de polimento produziu efluente com qualidade sanitária dentro dos valores recomendados pela Organização Mundial de Saúde (OMS, 1989) para irrigação de vegetais consumidos crus. O pimentão irrigado com efluente do reator UASB não apresentou diferença significativa de produtividade (ao nível de 5% de probabilidade pelo teste Tukey), quando comparado à aplicação de adubação mineral e orgânica.

Submitted by Georgia Vaz (georgia.vaz@mackenzie.br) on 2016-07-07T21:20:26Z No. of bitstreams: 2 license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) Kátia Lucia da Silva Gonçalves Cunha.pdf: 8068781 bytes, checksum: ed19238146c2f43be9d3c93dc70712b7 (MD5) / Made available in DSpace on 2016-07-07T21:20:26Z (GMT). No. of bitstreams: 2 license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) Kátia Lucia da Silva Gonçalves Cunha.pdf: 8068781 bytes, checksum: ed19238146c2f43be9d3c93dc70712b7 (MD5) Previous issue date: 2016-02-19 / The growing concern for the environment, driven by the increasing difficulty in depositing waste in landfills, has encouraged the search for alternatives to the waste through recycling. The need to reclaim waste is not new, however, still is given little importance to proper environment dispose of diapers. In Brazil, several materials that could be recycled, are still designated to dumps generating, as well as, an environmental problem, an economic problem. After the implementation of the National Policy on Solid Waste, waste come to be considered good value, when is possible to be reused. Disposable diapers residues in most countries, has the final destination in landfills or incinerators and represent a large portion of the waste. Disposable diapers have a wide variety of natural and synthetic polymeric materials of high quality, which is desirable to reuse the same. The technologies currently known to recycle diapers are not satisfactory, due to the process of implementation issue that, generate large amounts of pollutants and organic waste, high spending of energy, in addition the difficulty in promote an efficient sterilization. This work aimed to research new technologies for the recycling of disposable diapers using radiation as a method for sterilization, also observe the effects of radiation on the mechanical, thermal, rheological and morphological properties of the obtained blends and composites. To develop this work and research of new technologies, was performed the characterization of the components of the disposable diaper, it was obtained and applied artificial solution urine, after were sterilized by gamma radiation, mechanical recycling, development of polymer blends and composites and obtaining and characterization of tests samples. The tests aimed to characterize the components of the disposable diapers and blends and composites obtained. Thermal, morphological, chemical, rheological and mechanical tests were performed. The results showed that irradiation acted differently and in isolation in each component of the disposable diaper in the presence of artificial urine solution, caused significant changes in superabsorbent polymers, improving the mechanical recycling process and enabling cost reduction in same. The recycling of disposable diapers can keep some properties and changing others. It was observed that the absence of the superabsorbent polymer influences to improve, not only the stages of recycling, as well as, in thermal and mechanical properties. It highlights the importance of recycling these materials, now worthless, however, of great environmental impact because of the advantages to providing low weight products, also obtaining economic and environmental advantages. / O crescimento da preocupação com o meio ambiente, impulsionado pela crescente dificuldade em depositar os resíduos em aterros, tem incentivado a busca de alternativas para o resíduo através de reciclagem. A necessidade de se reaproveitar resíduos não é nova, contudo, ainda é dada pouca importância para a disposição ambientalmente correta das fraldas descartáveis. No Brasil, muitos materiais que poderiam ser reciclados continuam sendo destinados a aterros sanitários gerando, além de um problema ambiental, um problema econômico. Após a implantação da Política Nacional de Resíduos Sólidos, os resíduos passaram a ser considerados bens de valor, quando possível seu reaproveitamento. Os resíduos de fraldas descartáveis, na maioria dos países, têm o destino final em aterros ou incineradores e representam uma grande parcela do refugo. As fraldas descartáveis possuem uma vasta variedade de materiais poliméricos naturais e sintéticos de alta qualidade, o que torna desejável o reaproveitamento dos mesmos. As tecnologias conhecidas atualmente para a reciclagem de fraldas não são satisfatórias devido ao problema de implementação do processo que geram grandes quantidades de poluentes e resíduos orgânicos, alto gasto energético, além da dificuldade em promover uma esterilização eficiente. Este trabalho teve como principal objetivo a pesquisa de novas tecnologias para a reciclagem de fraldas descartáveis pós-consumo, utilizando a radiação gama como método para a esterilização, também observar os efeitos da radioesterilização nas propriedades mecânicas, térmicas, reológicas e morfológicas das blendas e compósitos obtidos. Para o desenvolvimento deste trabalho e pesquisa de novas tecnologias, realizou-se a caracterização dos componentes da fralda descartável, obtenção e aplicação de solução de urina artificial, esterilização, reciclagem mecânica, desenvolvimento de blendas e compósitos e obtenção e caracterização de corpos de provas. Os ensaios visaram a caracterização dos componentes da fralda descartável e das blendas e compósitos obtidos. Foram realizados ensaios térmicos, morfológicos, químicos, reológicos e mecânicos. Os resultados mostraram que a irradiação, agiu de forma diferente e isolada em cada componente da fralda descartável, na presença de solução de urina artificial, provocou modificação do polímero superabsorvente, viabilizando o processo de reciclagem mecânica e possibilitando a redução de custos no mesmo. A reciclagem de fraldas descartáveis é possível mantendo algumas propriedades e alterando outras. A ausência do polímero superabsorvente, influenciou para a melhoria, não só das etapas de reciclagem, como também em propriedades térmicas e mecânicas. Destaca-se a importância de reaproveitamento destes materiais, atualmente sem valor, porém, de grande impacto ambiental, devido as vantagens em proporcionar produtos de baixo peso, obtendo também vantagens econômicas e ambientais.

Orientador: José Roberto Nunhez / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Química / Made available in DSpace on 2018-08-19T14:59:08Z (GMT). No. of bitstreams: 1 Merendino_EdyMaicon_M.pdf: 4244405 bytes, checksum: c56623b83b7e229872966885f5e9eca5 (MD5) Previous issue date: 2011 / Resumo: As embalagens cartonadas assépticas para alimentos são comuns em nosso dia-a-dia. Tais embalagens são compostas por três materiais: papel, polietileno de baixa densidade e alumínio. Seu processo de reciclagem se dá em duas etapas sucessivas: a reciclagem do papel e a posterior reciclagem do composto de polietileno e alumínio. Durante a primeira etapa de reciclagem, um percentual das fibras de papel não é retirado do composto de polietileno e alumínio o que pode comprometer a qualidade de produtos feitos a partir da reciclagem deste composto. Para a extração do papel residual foi desenvolvido de maneira empírica um equipamento centrífugo em escala industrial. Visando o estudo do funcionamento deste equipamento fez-se a simulação deste usando o método dos elementos discretos (DEM). O primeiro passo foi a determinação de parâmetros físicos e de interação através de experimentos práticos e respectivas simulações computacionais para a calibração de um modelo, o qual foi conseguido de maneira satisfatória. Uma vez tendo o modelo calibrado, foram realizadas simulações com diferentes geometrias para o rotor e parte estática deste equipamento buscando levantar hipóteses para o entendimento do funcionamento do equipamento. Os resultados para diferentes especificações foram comparados e discutidos / Abstract: Milk and beverages carton packages are very common in our lives. These packages are made of three different materials: paper, low density polyethylene and aluminium. The recycling process of these packages takes place in two successive stages: the recycling of paper and the subsequent recycling of polyethylene and aluminium composite. During the first stage of recycling a percentage of the paper is not removed from the composite of polyethylene and aluminium which can compromise the quality of products made from recycling of this composite. An industrial-scale centrifuge equipment was developed empirically for extraction of residual paper. In order to study the operation of this equipment, it was made its simulation using the discrete element method (DEM). The first step was set-up of physical and interaction parameters through practical experiments and computer simulations to calibrate a model, which was achieved satisfactorily. Once the model was calibrated, simulations were performed with different geometries for rotor and static body of this equipment seeking hypotheses in order to understand equipment operation. The results for different specifications were compared and discussed / Mestrado / Processos em Tecnologia Química / Mestre em Engenharia Química

There has been considerable interest in finding and explaining the basic elements that can drive product quality up. In the literature this is largely done by modelling the effects of investing in learning and process improvement, and of cost reduction. In the first essay, demand is modelled as a function of price and quality. With this demand function, the firm should produce output of higher quality, the increase in quality being dependent on consumers’ sensitivity to quality and to price, and the effect of technological improvement on product price and quality are very different from those when the demand is a function of price alone. Some twenty states in the U.S. have passed recycling laws which mandate consumption of old newspaper by the newsprint industry. To study the effect of regulation, a model is used in which two firms compete under the regulatory constraint—one firm producing the recycled product, the other the virgin product. Assuming the regulatory constraint is binding, and the demand for the recycled product is derived solely from the legislation, interesting results such as the two firms share equal profits, and consumers pay higher average price in competitive equilibrium than the cartel price, are obtained in the second essay. The two firm model is generalized to include n firms which compete under the same kind of regulatory constraint in the third essay. Results similar to the two firm case are obtained. When the recycled product and the virgin product are partially substitutable, regulation that mandates consumption of the recycled product results in infinitely many equilibria. A dominating equilibrium exists if the demand parameters satisfy a certain condition, otherwise it is not clear how to select an equilibrium. On the other hand, a suitable tax on the virgin product, or its producer, serves to induce compliance with the recycling policy and equilibrium selection. The equilibrium prices and profits of the two firms under the schemes of production tax, excessive consumption tax and progressive profit tax are examined and compared in the fourth essay. It is interesting to find that the tax rate for excessive consumption is comparatively low and, in equilibrium, this tax scheme collects no tax payment. / Business, Sauder School of / Graduate

Made available in DSpace on 2017-06-01T18:20:38Z (GMT). No. of bitstreams: 1 dissertacao_paula_macedo.pdf: 713310 bytes, checksum: 941c18a8ca32e16587bf1e5a6169267d (MD5) Previous issue date: 2012-12-10 / The coconut fibers (Cocos nucifera) when intended in landfills under anaerobic conditions, cause the emission of methane, one of the most important greenhouse gas. In this work, is proposed the use of coconut fiber mixed in different ratios with alternative waste in order to mitigate the impacts caused by waste, enabling the production of new products. As an alternative, it was proposed to do the relationship coconut / residue equal to 100/0, 75/25 50/50 25/75 and 0/100 by collecting the waste orange, banana, and cashew acerola (pulp and peel) in the appropriate places. For immediate analysis were determined the ash content (600 ° C) and humidity (105 ° C)ASTM D-1762/64, the levels of volatile material (ash in a muffle furnace at 950 ° C) and fixed carbon, ASTM D-1762/64, and calorific power, according to ABNT-NBR 8633/84, the various treatments. The data were submitted to statistical analyzes where it was possible to draw graphs that demonstrate the relationship among the measurements performed, indicating the mixture of coconut fiber with cherry and banana the most promising. / As fibras-de-coco (Cocos nucifera) quando destinadas em aterros sob condições anaeróbias, provocam a emissão de metano, um dos mais importantes gases de efeito estufa. Neste trabalho, são propostos usos das fibras-de-coco misturadas em diferentes relações com resíduos alternativos, com o objetivo de mitigar os impactos provocados pelos resíduos, possibilitando a produção de carvão ativado. Como alternativa, fez-se a proposição de se utilizar a relação coco/resíduo igual a 100/0, 75/25, 50/50, 25/75 e 0/100, coletando-se os resíduos de laranja, banana, caju e acerola (bagaço e cascas) nos locais apropriados. Para análise imediata foram determinados os teores de cinzas (a 600 ºC) e umidade (a 105 ºC) segundo a norma ASTM D-1762/64, os teores de material volátil (a cinza em mufla a 950 ºC) e de carbono fixo, segundo a norma ASTM D-1762/64, e o poder calorífico, segundo a norma ABNT-NBR 8633/84, dos diversos tratamentos. Os dados obtidos foram submetidos à análise estatística onde foi possível elaborar gráficos que demonstrassem a relação entre as determinações realizadas, indicando a mistura da fibra-de-coco com acerola e com banana a mais promissora.

More sustainable private consumption is necessary to achieve the common goal of sustainable development. This dissertation deals with the underlying socio-psychological determinants of sustainable consumer behavior in different domains, based on which promotion measures are recommended to companies and policymakers. Among others, I discuss consumers’ perceptions of their responsibilities for sustainability in contrast to their expectations on governments’ and companies’ contributions. Furthermore, I shed light on a main barrier of sustainable consumption that most consumers support sustainability but their behaviors are, to a decisive extent, driven by other motives such as customer-oriented services or offered incentives, which primarily benefit consumers themselves instead of the sustainability agenda. To tackle this barrier, I develop several promotion measures based on activating psychological concepts such as empowerment and self-determination in a single or multi-country setting. Results of this dissertation serve to more effectively understand consumers’ concerns with sustainable consumption and to add new perspectives to improve tactics to promote sustainable behaviors.

Master´s thesis deals with the study properties of polymer modified mortars using recycled glass and is divided into two parts, theoretical and practical. In the theoretical part has been expert search which deals with polymer modified mortars using recycled glass. On the basis of this information has been formulate practical part, which focused on the study properties of mortars depending on the time period and environment.

Die eingereichte Dissertation mit dem Thema „Heterogen katalysierte Hydrodehalogenierung von Borhalogeniden im Rahmen eines in sich geschlossenen BNHx-Recyclingkonzepts“ beinhaltet drei für das BNHx-Recycling zentrale Reaktionsschritte: Supersäureaufschluss, Hydrodehalogenierung und den Basenaustausch. Mit Hilfe dieser drei Schritte ist es möglich, die Zersetzungsrückstände von BH3NH3(Polyaminoboran, Borazin und Polyborazylen) wieder in BH3NH3 zu überführen, ohne teure Reduktionsmittel wie LiAlH4 oder Hydrazin verwenden zu müssen. Das Verfahren ermöglichte in einem Durchlauf die Gewinnung von 60 % der eingesetzten Menge an BH3NH3 ohne eine Erzeugung von Abfallprodukten. Mit Hilfe der Chloralkalielelektrolyse kann das Verfahren an Wind- bzw. Solarkraftwerke gekoppelt und über diese alle benötigten Ausgangsstoffe hergestellt werden. Die katalytische Erzeugung von B-H-Spezies auf der Grundlage der Aktivierung von molekularem Wasserstoff ist als Schwerpunkt dieser Arbeit zu sehen. Die mechanistischen Studien lieferten ein genaueres Verständnis über fundamentale Zusammenhänge zwischen dem Lösungsmittel Et3N und der Wasserstoffbereitstellung über die N-CH2-Gruppierung sowie der Wirkungsweise des Katalysators.:1 Einleitung und Motivation 8 2 Literaturteil 15 2.1 Borazan (AB) Zersetzung 15 2.2 Regenerierung der Zersetzungsprodukte 17 2.3 Gemeinsamkeiten und Unterschiede der Recyclingverfahren 20 2.3.1 Supersäure-Aufschluss zur Herstellung von BCl3 und BBr3 aus BNHx-Abfall 22 2.3.2 Bekannte Verfahren zur Herstellung von BCl3 23 2.3.3 Bekannte Verfahren zur Herstellung von BBr3 24 2.3.4 Basenaustausch zwischen Trialkylamin-Boranen und NH3 24 2.4 Hydrodehalogenierung 26 2.4.1 Gasphasen-Verfahren ohne Verwendung von Aminen als Hilfsbase 28 2.4.2 Flüssigphasen-Verfahren mit Aminen als Hilfsbase 31 2.4.3 Mechanistische Betrachtung 34 2.4.4 Hydrodehalogenierung von Borhalogeniden mit homogenen Katalysatoren 37 2.5 Amorphe Nickelboride als heterogene Katalysatoren 38 2.5.1 Synthese des amorphen Nickelborids 40 2.5.2 Angewandte Synthese- und Charakterisierungsmöglichkeiten zur Darstellung und Charakterisierung von amorphen Nickelboriden 41 2.5.3 Bekannte Hydrodehalogenierungen mit Nickelborid-Katalysatoren 47 2.5.4 Bekannte Nickelboride als Wasserstoffspeichermaterial 47 2.5.5 Nickelboranat (Ni(BH4)2) – Das wasserstoffreichste Nickelborid? 48 2.6 Heterogene Katalyse am Beispiel der Hydrodehalogenierung von Amin-BX3-Addukten (X=Cl, Br, I) in flüssiger Phase (Et3N) 51 2.6.1 Stofftransport innerhalb eines Drei-Phasen-Slurry-Reaktors 51 2.7 Methoden zur Bestimmung einer Katalysatorvergiftung (TPR) und zur Bestimmung der katalytischen Aktivität (TDS) des amorphen Nickelborids 55 2.7.1 Temperaturprogrammierte Reduktion (TPR) 55 2.7.2 Temperaturprogrammierte Desorption (TDS) 58 3 Ergebnisteil und Diskussion 59 3.1 Charakterisierung von amorphen Nickelboriden der allgemeinen Zusammensetzung NixByHz 59 3.1.1 Bestimmung der katalytischen Produktivität und der Aktivität am Beispiel der Hydrodehalogenierung von Et3NBCl3 59 3.1.2 Bestimmung des Ni/B-Verhältnisses mittels ICP-OES 61 3.1.3 Photoelektronenspektroskopie (XPS) -Bestimmung der Elementzusammensetzung an der Katalysatoroberfläche 62 3.1.4 TPR-Nachweis für das Vorhandensein oxidierter Metall-Spezies im Material 70 3.1.5 DSC-Untersuchung der Phasenumwandlung 73 3.1.6 TPD-Untersuchung der Wasserstoffabgabe 75 3.1.7 Wiederbeladung des Materials mit Wasserstoff (Zyklenstabilität) 81 3.1.8 PXRD-Röntgenpulverdiffraktometrie 84 3.1.9 IR-Spektroskopische Untersuchung zur Aufklärung der Bindungssituation des Wasserstoffs in amorphen Nickelboriden 90 3.1.10 TEM- und REM-Aufnahmen zur Bestimmung der Morphologie von amorphem Nickelborid 94 3.1.11 Bestimmung der BET-Oberfläche durch N2-Physisorption (T=-196 °C) 97 3.1.12 Zusammenfassung der Ergebnisse der Katalysatoraufklärung 100 3.2 BNHx-Abfall Recycling und die Wiedergewinnung von BH3NH3 102 3.3 Die Herstellung von BX3 (X= Cl, Br) aus BNHx –Abfall 102 3.3.1 Supersäure-Aufschluss von Polyaminoboran (BH2NH2)x mit AlCl3/HCl/CS2 und AlBr3/HBr/CS2 103 3.3.2 Supersäure- Aufschluss von Borazin AlCl3/HCl/CS2 106 3.3.3 Supersäure-Aufschluss von stark vernetztem Polyborazylen (PB) mit den Systemen AlCl3/HCl/CS2 und AlBr3/HBr/CS2 108 3.3.4 Zusammenfassung der Ergebnisse der vorgestellten Aufschlussverfahren 112 3.3.5 Mechanistische Betrachtungen zum Supersäure-Aufschluss des BNHx-Abfalls 113 3.4 Reaktionstechnische Untersuchungen zur Hydrode-halogenierung von Borhaliden des Typs BX3 (Cl, Br, I) 116 3.4.1 Stofftransportphänomene innerhalb der heterogen katalysierten Hydrodehalogenierung 117 3.4.2 Diffusion der Reaktanten in der flüssigen Phase zum Katalysator 119 3.4.3 Wechselwirkungseinflüsse der Addukte Et3NBCl3, Et3NBHCl2, Et3NBH2Cl und Et3NBH3 auf den Katalysator 122 3.4.4 Zusammenfassung der Ergebnisse aus den Stofftransport-Untersuchungen 123 3.5 Katalytische Hydrodehalogenierung von Et3NBCl3 123 3.5.1 Verfolgung der Reaktion über die Probenentnahme der Flüssigphase und Konzentrationsbestimmung mittels 11B NMR-Spektroskopie 124 3.5.2 Bestimmung der Geschwindigkeitskonstanten durch die Verwendung der Methode der Anfangsgeschwindigkeit 133 3.5.3 Katalytische Hydrodehalogenierung anderer Et3NBX3 (X=Br,I) Addukte 134 3.5.4 Nebenreaktionen – Eine Frage von Temperatur und Druck 138 3.6 Reaktionsmechanismus-Aufklärung am Beispiel der Hydrodehalogenierung von Et3NBCl3 145 3.6.1 Die Rolle des tertiären Amins 146 3.6.2 Die Rolle des Katalysators 154 3.6.3 Markierungsexperimente mit schwerem Wasserstoff (D2) 158 3.6.4 Einfluss von Radikalstartern auf die Reaktionsgeschwindigkeit der HDC 162 3.7 Disproportionierung von Et3NBH2Cl durch BCl3-Überschuss 165 3.8 Basenaustausch- Synthese von BH3NH3 aus Et3NBH3 und NH3 167 4 Thermodynamische Bewertung beider Recycling-Verfahren (Cl und Br) auf der Basis der Standard-Reaktionsenthalpien 170 5 Zusammenfassung der Ergebnisse 176 5.1 Amorphe Nickelboride 176 5.2 Supersäureaufschluss 178 5.3 Hydrodehalogenierung 178 5.4 Basenaustausch 180 5.5 Durchführung eines vollständigen Zyklus: Von der Dehydrierung bis zur Synthese von BH3NH3 180 5.6 Bewertung des Recyclingprozesses- Kopplung des Verfahrens mit einer Chloralkalielektrolyse 181 6 Ausblick 184 7 Anhang 185 7.1 Experimenteller Teil 186 7.1.1 Herstellung des BNHx-Abfalls (spent fuel) 186 7.1.2 Supersäure-Aufschluss des BNHx-Abfalls mit dem System AlCl3/HCl/CS2 187 7.1.3 Supersäure-Aufschluss des BNHx-Abfalls mit dem System AlBr3/HBr/CS2 189 7.1.4 Bestimmung der Donor-Akzeptor-WW in Bortrihalid- Trialkylaminkomplexen 190 7.2 Synthese des amorphen Nickelboridkatalysators 198 7.2.1 Probenvorbereitung und Analyseparameter für die einzelnen Analysemethoden 200 7.3 Synthese von wasserstoffreichem Nickelborid unter wasserfreien Bedingungen 203 7.4 Hydrodehalogenierung 204 7.4.1 Experimente für den Katalysatorvergleich in Kapitel 3.1.1 205 7.4.2 Hydrodehalogenierungsexperimente aus Kapitel 3.5 205 7.4.3 Experimente mit Probenentnahme aus Kapitel 3.4 206 7.4.4 Hydrodehalogenierung mit anderen Borhalogenid-Addukten (Et3NBBr3, Et3NBI3) aus Kapitel 3.5.3 206 7.4.5 Hydrodechlorierungsexperimente mit Me2EtN und Me3N 206 7.4.6 Markierungsexperimente mit schwerem Wasserstoff siehe Kapitel 3.6.3 207 7.4.7 Testexperiment Imminiumsalzbildung 207 7.4.8 Nebenreaktionen der Hydrodehalgenierung durch thermische Zersetzung der Addukte 208 7.5 Disproportionierung 209 7.6 Basenaustausch zwischen Et3NBH3 und NH3 210 7.7 Durchführung eines vollständigen Recycling-Zyklus 211 7.7.1 Die Dehydrierung von BH3NH3 (Herstellung von Polyborazylen) 211 7.7.2 Supersäureaufschluss des Polyborazylens 211 7.7.3 Hydrodechlorierung von BCl3 213 7.7.4 Basenaustausch-Experiment 214 8 Kalorimetrie –Bestimmung thermodynamischer Stoffdaten 215 9 NMR-Daten ausgewählter Zersetzungsprodukte von Et3NBX3-Addukten 216 10 Verzeichnisse 217 10.1 Abkürzungsverzeichnis 217 10.2 Tabellenverzeichnis 219 10.3 Abbildungsverzeichnis 221 11 Liste verwendeter Chemikalien 227 12 Versicherung 228 13 Literaturverzeichnis 229