Thesis (doctoral)--Rijksuniversiteit te Groningen.

In sliding bearing wear is a very common problem and can be affected by several factors. The wear in a bearing can lead to total failure of the component and lower the lifetime. In a sliding bearing used in a machine in the pulp and paper industry large wear has been detected, but no clear evidence of what the wear depends on. The environment in the machine is strong alkaline (pH 14), a solution of white liquor and lime mud. The penetration of this solution into the bearing might lead to increased wear. A wear study and test were done to see if a better material choice could reduce the wear. In this project an investigation of the wear for seven different bearing materials was done. Two cobalt-based alloy Stellite 6 and Stellite 12, two different precipitation hardened martensitic stainless steel with different number of alloying elements, 17-4PH and Endotec 04. The different metals were welded on the pin with a minimum of 3mm. The other material was three different PEEK polymer composites. PEEK HPV reinforced with carbon fiber, PTFE and graphite. PEEK CA30 with carbon fibers and PEEK GF30 with glass fiber. The method used for the wear test was grinding machine that was reconstructed to a pin-on-disc tribology test. The tests were executed in room temperature with sliding speed of 150rpm and duration of 20 minutes. The metals were tested with the solution of white liquor mixed with lime mud, at two different loading conditions of 300N and 550N. The polymer composites were tested at the load of 300N but with different solution present, white liquor mixed with lime mud and with water. All the pins were sliding against a disc of austenitic stainless steel. Equipment used to investigate the wear mechanisms was a scanning electron microscope. The wear rate was measured by weighing of the pin before and after each test. How the material was affecting the roughness of the austenitic steel countersurface was done with the profilometer. The results of this work showed that both Stellite 6 and Stellite 12 was almost wear resistance in the condition similar to the bearing. Endotec 04 also showed low wear and 17-4PH had the highest of the metals. The dominant wear mechanism seemed to be different severity of adhesive wear. The polymer composite showed all higher wear than the metals, the reason to the high wear rate was harder to decide. It might be a combination between adhesive wear, pulverization of fibers, adsorption of calcium carbonate and matrix/fiber interfacial removal. The alkaline liquid was also believed to increase the wear of the polymer and adhere to some of the metals. The metals seemed to increase the roughness of the countersurface, but the polymers seemed to have more of a polishing effect.

O biodiesel substituto renovável do diesel convencional é quimicamente definido como ésteres monoalquílicos de ácidos graxos derivados de óleos vegetais e gorduras animais. O processo mais empregado para a sua produção é a transesterificação em meio alcalino. Este processo consiste em uma reação química na qual óleos vegetais e/ou gorduras animais reagem com um álcool de cadeia curta utilizando catalisador alcalino (usualmente hidróxido de potássio e metilato de sódio) resultando na mistura de ésteres monoalquílicos (biodiesel) e glicerina. O presente trabalho teve como objetivo avaliar o desempenho dos catalisadores alcalinos: metilato de sódio e hidróxido de potássio na produção de biodiesel pela rota metílica utilizando óleo de soja como fonte de triglicerídeo. A avaliação foi dividida em 3 partes: 1- Técnica: Qualidade do biodiesel, da glicerina gerada e a eficiência da conversão de óleo de soja em biodiesel. 2- Econômica: Custo de produção global do biodiesel. 3- Ambiental: Geração de resíduo quantitativa e qualitativa. A metodologia consistiu em realizar 3 bateladas com cada catalisador em um reator de vidro tipo batelada de 2.000 mL com circulação externa de água. Foi utilizado o mesmo óleo de soja refinado, metanol, procedimento experimental e metodologia analítica. Os resultados demonstraram que o catalisador metilato de sódio apresentou eficiência 4,8% superior ao hidróxido de potássio na conversão de óleo de soja em biodiesel, o custo de produção global teve redução de 3,2% (R$ 0,080/Kg de biodiesel produzido) e a geração de resíduo em volume foi reduzida em 9,8%. Ambos catalisadores apresentaram resultados dentro da especificação da resolução ANP no42. Estes resultados demonstram a grande vantagem do metilato de sódio frente ao hidróxido de sódio e exalta a importância da escolha do catalisador que oferece o melhor desempenho que é fundamental para a viabilidade técnica, financeira e ambiental do Programa Nacional de Produção de Biodiesel (PNPB). / Biodiesel is a renewable alternative to petroleum diesel fuel and is chemically defined as mono-alkyl esters of fatty acid derived of vegetable oils and animal fat. The most commonly used process in its production is alkaline transesterification. This process consists in a chemical reaction in which vegetable oil and/or animal fats react with a short chain alcohol, using an alkaline catalyst (usually potassium hydroxide and sodium methylate), resulting in a mixture of mono- alkyl esters (biodiesel) and glycerin. The objective of the present research is to evaluate the performance of alkaline catalysts: sodium methylate and potassium hydroxide in the production of biodiesel by the methylic route, using soybean as a triglyceride source. The evaluation was divided in 3 parts: 1 - Technical: biodiesel quality, generated glycerin quality and the soybean oil to biodiesel conversion efficiency. 2 - Economical: Biodiesel\'s global production cost. 3 - Environmental: Quantitative and qualitative waste generation. The methodology consisted in carrying through 3 (three) batches with each catalyst in a 2.000 mL batch type glass reactor with external water circulation. The same refined soybean, methanol, experimental procedure and analytical methodology were used. The results demonstrated that the sodium methylate catalyst presented an efficiency 4,8% higher than potassium hydroxide in the conversion of soybean into biodiesel, that the global production cost had a 3,2% reduction (R$ 0.08/Kg of produced biodiesel) and that waste generation in volume was reduced in 9,8%. Both catalysts presented results, within the specification of ANP no42 Ordinance. These results demonstrate the great advantage of sodium methylate in comparison to potassium hydroxide and exalts the importance of chossing the catalyst that offers the best performance that is necessary for the technical, financial and environmental viability of the National Biodiesel Production Program.

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Orientadores: José Vicente Hallak d'Angelo, Marcelo Cardoso / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Química / Made available in DSpace on 2018-08-16T11:11:44Z (GMT). No. of bitstreams: 1 Emunds_RonaldLaauser_M.pdf: 1808008 bytes, checksum: cc469195b9e12b310096a07506d0138c (MD5) Previous issue date: 2010 / Resumo: Elementos não processáveis são definidos como sendo elementos cujos compostos não participam ativamente das diversas etapas do processo, porém seu acúmulo traz como conseqüência inúmeros distúrbios operacionais, tendo em vista a formação de compostos indesejáveis. O aumento das pressões ambientais sobre a indústria de um modo geral, fez com que a mesma iniciasse esforços no sentido de promover a diminuição das emissões de seus efluentes hídricos e gasosos, bem como a diminuição da captação de água, o que acarretou em acúmulo de elementos não processáveis. Este trabalho tem como objetivo estabelecer um balanço dos principais elementos não processáveis de uma fábrica de celulose avaliando o impacto dos resultados no processo. Análises para determinação da concentração dos elementos foram realizadas, além da validação do balanço elaborado mediante a comparação do mesmo com dados operacionais de processo. Verifica-se que a madeira utilizada na fabricação de celulose é a maior fonte destes elementos ao processo / Abstract: Non process elements are defined as the elements bonded to chemical compounds that do not actively participate on pulp production process steps, but the increasing concentration of these elements can cause many operational problems due to the formation of undesirable chemical compounds. The environmental stress from the society has forced industries to make efforts in order to close their process, minimizing effluent discharge and water consumption, causing the non process elements concentration to build up. The main objective of this work is to make a non process elements mass balance on a pulp Mill evaluating the extension of the non process elements concentration build up on the process. Chemical analysis were done to determine the non process elements concentrations in different points of the process done and mass balance data were confirmed with data taken from the process. The results have shown that wood is the main source of non process elements / Mestrado / Sistemas de Processos Quimicos e Informatica / Mestre em Engenharia Química

Orientador: Glaucia Maria Pastore / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia de Alimentos / Made available in DSpace on 2018-08-06T21:40:30Z (GMT). No. of bitstreams: 1 Prazeres_JanainaNicanuziados_D.pdf: 4737437 bytes, checksum: ec3f9eaf0835996e8527fb6b9970354f (MD5) Previous issue date: 2006 / Resumo: Recentemente, a aplicação industrial de lipases microbianas tem sido estendida a muitas áreas, como por exemplo, na modificação de triglicerídeos, síntese de vários compostos de ésteres e detergentes. As lipases podem ser aplicadas na limpeza de maquinários industriais ou em detergentes como sabões em pó na remoção de manchas de lipídeos em tecidos. A linhagem de fungo Fusarium oxysporum 152B foi selecionada entre 216 linhagens de microrganismos isolados de amostras de frutas e solo do Nordeste do Brasil, como maior produtora de lipase alcalina extracelular em meio de cultura. Os efeitos da composição do meio, pH e temperatura foram investigados para a produção de lipase alcalina de Fusarium oxysporum. A máxima quantidade de atividade lipolítica produzida foi 7,12 U.mL-1 em meio contendo óleo de oliva, peptona e extrato de levedura como fontes de carbono e nitrogênio, em pH 10,0 e 30 °C. Um desenho experimental 22 com configuração estrela, totalizando 11 experimentos, foi desenvolvido para estudar os efeitos do pH e temperatura de incubação e o máximo de atividade encontrada foi de 33 U.mL-1 em pH 6,0 e a 30 °C. Um segundo desenho experimental 22 foi desenvolvido para estudar duas variáveis, composição do meio e a concentração de óleo de oliva. Máxima atividade enzimática foi produzida em meio de cultura suplementado com óleo de oliva (2% m/v). A atividade enzimática da lipase de Fusarium oxysporum foi avaliada na presença de diferentes detergentes comerciais e surfactantes, através de ensaios com pnitrofenilpalmitato (pNPP). A enzima foi compatível com vários surfactantes iônicos e não-iônicos como também com detergentes comerciais. Atividade lipolítica foi fortemente inibida por SDS, mas não por Triton X-100 e Triton X-114. A enzima mostrou-se estável em pH alcalino e manteve 93% da atividade durante 1 h de incubação a 60°C. A maior atividade lipolítica foi medida com triglicerídeos de ácidos graxos de cadeia média e longa (C8-C18). Esta enzima mostrou ampla especificidade hidrolítica para várias gorduras e óleos. Todas estas propriedades e sua resistência a vários surfactantes e detergentes comerciais fazem desta lípase um aditivo em potencial para formulação de detergentes. Esta lipase alcalina extracelular foi purificada cerca de 20 vezes através de cromatografia em colunas de DEAE-Sepharose e Sephacyl-200. A preparação de lipase purificada apresentou três isoenzimas em gel IEF-PAGE, com pontos isoelétricos 7,15, 6,84 e 4,55. As massas moleculares das lipases Lip 1 e Lip 2 foram verificadas em gel SDS-PAGE, 30 e 29 kDa, respectivamente. Comparandose as seqüências de aminoácidos, confirmou-se que as lipases Lip 1 e Lip 2 são isoenzimas que apresentam alta similaridade com a lipase de F. heterosporum. A lipase purificada apresentou atividade ótima em pH 8,0 e 40°C, utilizando o substrato p-nitrofenilpalmitato. A lipase purificada mostrou-se termoestável, perdendo cerca de 50% de atividade durante 1h de incubação a 40°C em pH 8,0. Um método de separação e purificação foi estudado para a obtenção da lipase do meio de cultura. Os experimentos foram desenvolvidos com o surfactante nãoiônico Triton X-114. Dois parâmetros foram estudados, pH e taxa de fluxo de nitrogênio. A máxima recuperação desta lipase foi verificada em pH 8,5 e fluxo de 60 mL N2 min-1. Após otimização, uma taxa de enriquecimento de 8,77 e um fator de purificação de 5,86 foram atingidos para esta enzima com uma recuperação de 93,56%. O fracionamento com espuma foi aplicado com sucesso para a concentração da lipase do meio de cultivo / Abstract: Recently, industrial application of the microbial lipases has been extended in many areas, exemplified by their use in modification of triglycerides, synthesis of various ester compounds and additives in detergents. Lipases are potentially suitable for lipid stain removal applications in washing industrial machine and household detergents. One strain Fusarium oxysporum 152B was isolated from fruit and soil samples from Northeast of Brazil, which produced the largest amount of extracellular alkaline lipase in the culture media. The effects of medium composition, pH and incubation temperature conditions were investigated to alkaline lipase production. The maximum amount of lipolytic activity produced was 7.12 U.mL-1 in medium containing olive oil, peptone and yeast extract, as carbon and nitrogen sources, at pH 10.0 and 30 °C. A 22 factorial design with star configuration, totaling 11 experiments, was carried out to study the effect of pH and incubation temperature conditions and the maximum lipase activity was found of pH 6.0 and 30 °C conditions (33 U.mL-1). A second experimental design, 22 factorial was developed to study two variables, medium composition and olive oil concentration. Maximum enzyme activity was produced in culture medium supplemented with olive oil (2% w/v). Enzymatic activities of lipase from Fusarium oxysporum were compared through spectrophotometric p-nitrophenylpalmitate (pNPP) assay at different commercial detergents and surfactants. The enzyme was compatible with various ionic and nonionic surfactants as well as commercial detergents. Lipase activity was strongly inhibited by SDS, but not by Triton X-100 and Triton X-114. The enzyme was stable at alkaline pH and remained 93% of activity during 1 h incubation at 60°C. The highest lipase activity was measured with triglycerides of middle and long chain fatty acids (C8-C18). This enzyme showed a broad specificity/hydrolytic activity towards various fats and oils. All these properties and its resistance towards various surfactants and detergents make this lipase a potential additive for detergent formulation. The extracellular alkaline lipase from Fusarium oxysporum was purified 20-fold, using DEAE-Sepharose and Sephacyl-200 chromatography. The purified lipase presented three isoenzymes in IEF-PAGE, with the following isoelectric points 7.15, 6.84 and 4.55. The molecular mass were determined to Lip 1 and Lip 2 in SDSPAGE as 30 and 29 kDa, respectively. Comparing the amino acids sequences, Lip 1 and Lip 2 were confirmed to be isoenzymes and high similarity with the lipase from F. heterosporum. The purified lipase showed optimum activity in pH 8.0 and 40°C, using p-nitrophenylpalmitate as substrate. The purified lipase showed to be termostable, losing around 50% of activity under 1h incubation at 40°C in pH 8.0. A separation method was performed to recover alkaline lipase from F. oxysporum cultures. Experiments were carried out with non-ionic surfactant Triton X-114. Two parameters were studied, pH and nitrogen flow rate. The maximal recovery of this lipase was verified at pH 8.5 and 60 mL N2 min-1 conditions. After optimization, an enrichment ratio of 8.77 and a purification factor of 5.86 were achieved for this enzyme along with 93.56 % recovery. Foam fractionation showed to be an efficient method for lipase recovery from culture broths / Doutorado / Doutor em Ciência de Alimentos

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RESUMO As fosfatases alcalinas sao enzimas que participam da atividade catalitica na hidrolise de ésteres fosfóricos. Nesta Dissertação, investigou-se a sua adsorção em monocamadas de Langmuir e também em filmes do tipo Langmuir-Blodgett (LB) de fosfolipídios em diferentes temperaturas. Esses sistemas são considerados como modelos para membranas biológicas. O efeito de um dissacarídeo (trealose), bem como as impurezas contidas na amostra do açúcar, foi testado na subfase que suporta a monocamada,. Constatou-se que a trealose nao purificada altera a isoterma superficial de monocamadas do sal de sódio do acido dimiristoilglicerofosfatidico, DMPA, e atua como um bom agente de ligação entre camadas sucessivas do fosfolipídio para a obtenção de filmes LB. Já para trealose purificada nao se observaram esses efeitos. A caracterização das impurezas foi realizada por espectroscopia na região do infravermelho e por absorção atômica, detectando-se a presença de moléculas anfifílicas e de íons metálicos (Na+, K+, Ca2+, Mg2+), respectivamente. Dois tipos de fosfatases alcalinas foram usadas: uma purificada de placa óssea de ratos por extração com tensoativo nâo-iônico, chamada de DSAP e outra purificada de conídia de Neurospora crassa, denominada CNCAP. As interações com o fosfolipídio foram estudas por meio das mudanças nas curvas -A e a adsorção em filmes LB de DMPA/Zn2+ e DMPA/trealose, por meio da técnica de microbalança a cristal de quartzo (QCM). A presença das enzimas nos filmes foi também comprovada pela detecção de suas atividades catalíticas na hidrolise do PNPP (p-nitrofenilfosfato). Para a DSAP, a melhor atividade foi obtida quando a imobilização da proteína ocorreu a baixa temperatura (10º C). / ABSTRACT Alkaline phosphatases (AP) are unspecific enzymes that hydrolyze phosphate esthers. In this Dissertation we have studied the adsorption of two forms of AP in phospholipid Langmuir monolayers and Langmuir-Blodgett films, considered as biomembrane models, at different temperatures. Further, the effect of the presence of a disaccharide, trehalose, as well as some impurities present in its commercial form, in the subphase of the monolayers was tested. We concluded that the use of trehalose without further purification alters the surface pressure-area (Pi-A) curves of the monolayers. In addition, it acts as a good linking agent between successive layers in the Langmuir-Blodgett films of the sodium salt of 1,2-dimirystoyl-sn-glicero-3-phosphate acid, DMPA. In the presence of purified trehalose instead, these effects were not observed. No difference was noticed in the Pi-A curves of DMPA for trehalose concentrations between 10-3 mmol L-1 to 0.1 mmol L-1. The characterization of the impurities by atomic absorption and infrared spectroscopy reveal the presence of amphiphilic compounds as well as electrolytes such as: sodium, magnesium, calcium and potassium Two forms of AP were used: one purified from rat osseous plates using detergent solubilization, named DSAP, and the other from Neurospora crassa conidia, CNCAP. Enzyme interaction with phospholipids was followed by changes in Pi-A curves, and their adsorption on DMPA/Zn2+ or DMPA/trehalose LB films using the quartz crystal microbalance technique, QCM. Their presence within the films was also monitored by catalytic activity assays, using PNPP (p-nitrophenylphosphate) as hydrolysis substrate. For DSAP, the highest enzymatic activity was observed when the immobilization was carried out at low temperature (10o C).

Cette étude a été menée afin d’identifier les paramètres qui permettent de contrôler la réaction de géopolymérisation et les propriétés d’usage des matériaux finaux. Différentes sources aluminosilicates et solutions alcalines ont donc été sélectionnées afin d’évaluer leur réactivité. Ensuite, une étude de faisabilité des matériaux consolidés a été initiée pour identifier les zones d’existence des matériaux géopolymères dans le diagramme ternaire Si/Al/M/O. L’évolution des échantillons au cours de la formation a été suivie par analyses thermiques (ATD-ATG), pour quantifier l’énergie nécessaire à la formation des oligomères, et par spectroscopies infrarouge et résonance magnétique nucléaire afin de déterminer la nature des réseaux formés et le taux de la réaction. Une forte corrélation a été mise en évidence entre la réactivité des précurseurs, la structure locale et poreuse et les propriétés mécaniques. Ces données ont été exploitées pour valoriser d’une part une argile tunisienne de faible réactivité et d’autre part pour recycler un déchet géopolymère dans des nouvelles formulations. / This study was undertaken to identify the parameters that control the geopolymerization reaction and the working properties of the final materials. To do this, various aluminosilicate sources and alkaline solutions have been studied to exacerbate their reactivity. Then a feasibility study of the consolidated materials was conducted to identify the geopolymer existence domain in Si-Al-M / O ternary diagram. The evolution of samples during formation was monitored by thermal analysis (DTA-TGA), to quantify the required energy for oligomer formation, and infrared and nuclear magnetic resonance spectroscopies to determine the nature of formed networks and the reaction rate. A strong correlation was evidenced between the precursors reactivity, the local and porous structure and the mechanical properties. The obtained results have been exploited to use poorly reactive Tunisian clay as alternative aluminosilicate source and also to reuse geopolymer waste in new formulations.

In 2015, 96.7 million tonnes of textile fibres were produced world-wide. Our high consumption of textiles leads to an increased amount of textile waste. In Sweden, the majority of used clothing and textiles are incinerated due to the lack of recycling techniques. A large amount of post-consumer textile waste is made from blended materials. One of the most common blends, used in as near as all workwear and service textiles, is cotton/polyester. To enable chemical recycling of such textiles, cotton and polyester must first be separated. The aim of this thesis was to separate the materials by depolymerizing the polyester using alkaline hydrolysis. The focus of the work was on how such a process should be performed without a catalyst, in order to result in both a high yield and a high purity of the cotton residue. In order to recycle the residue as a raw material for manufacturing of man-made cellulosic fibres, the cellulose chains in the cotton must also be maintained as unaffected as possible. The polyester in new sheets was completely depolymerized after 390 min at a temperature of 90ºC using a 10% sodium hydroxide concentration and a 1% material-to-liquor concentration. The separation using these conditions gave high yields (above 96%) of the cotton residue regardless of the material fineness used in the process. Furthermore, the separation performed on old sheets show that a pure cotton residue could be produced using higher material concentrations. It was shown that the cotton residue from old sheets, laundered around 50 times, had an intrinsic viscosity comparable to dissolving pulps used for viscose fibre spinning. This study concludes that alkaline hydrolysis without the use of a catalyst could be used to separate cotton and polyester in blended textiles. Furthermore, the findings show that cotton percentage in old sheets only decreased slightly after 50 launderings. Characterization of the materials using ATR FTIR spectroscopy indicate that an integrated textile recycling of hospital bed sheets could be performed since the sheets only contain cotton and polyester in all parts of the sheets.