Yes / Rhodium nanoparticles or rhodium organometallic complexes are mainly used in catalysis for reduction or hydroformylation reactions. In this work instead, we explored the capabilities of Rh nanoparticles as an oxidation catalyst, applied to the oxidation of benzyl alcohol to benzaldehyde under very mild conditions (100 °C, and atmospheric pressure) as a model reaction. Here we report the preparation of novel Rh/C catalysts by using an impregnation protocol, with particular emphasis on the pre-treatment of the carbon supports by using HNO3 and HCl, as well as the characterization of these materials by using an array of methods involving TEM, XPS and XRPD. Our preparation method led to a wide Rh particle size distribution ranging from 20 to 100 nm, and we estimate an upper limit diameter of Rh nanoparticles for their activity towards benzyl alcohol oxidation to be ca. 30 nm. Furthermore, a HNO3 pre-treatment of the activated carbon support was able to induce a smaller and narrower particle size distribution of Rh nanoparticles, whereas a HCl pre-treatment had no effect or sintered the Rh nanoparticles. We rationalise these results by HNO3 as an acid able to create new nucleation sites for Rh on the carbon surface, with the final effect of smaller nanoparticles, whereas for HCl the effect of sintering was most likely due to site blocking of the nucleation sites over the carbon surface. The roles of acid centres on the carbon surfaces for the oxidation reaction was also investigated, and the larger their amounts the larger the amounts of by-products. However, by treatment with HNO3 we were able to convert neutral or basic carbons into supports capable to enhance the catalytic activity of Rh, and yet minimised detrimental effects on the selectivity of the oxidation to benzaldehyde.

The increasing concern about water quality and energy demand promotes the development of innovative and low-cost processes to improve the nutrient uptake and energy efficiency of existing wastewater treatments (WWT). In this context, the inclusion of a microalgae system (MAS) in the flowsheet of a WWT plant represents a sustainable alternative to conventional technologies, as it combines a low-cost nutrient uptake system with the production of biomass suitable for biofuel production. However, at present, the energy required to cultivate and process the algae cells is often too high to justify their use. The adoption of a low energy harvesting system and an efficient energy conversion process are the sine qua non requirements to guarantee the sustainability of the process. In this thesis, current and innovative harvesting technologies for large scale applications have been reviewed to identify the optimal working conditions of each system and their link to the main characteristics of the algae suspension. In particular, the performance of the Ballasted Dissolved Air Flotation (BDAF) system was investigated using different algae and compared to the conventional Dissolved Air Flotation (DAF). BDAF was demonstrably a very viable harvesting method where the use of floating microspheres as ballasting agents allowed significant coagulant savings, reduced the level of energy dissipation within the flotation chamber, and lowered the overall carbon emissions and the process costs. Cont/d.

Orientador: Fernanda Elizabeth Xidieh Murr / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia de Alimentos / Made available in DSpace on 2018-08-08T04:46:19Z (GMT). No. of bitstreams: 1 Antonio_GraziellaColato_D.pdf: 42506769 bytes, checksum: 5f92bccd2127615161debdd246e72ec7 (MD5) Previous issue date: 2006 / Doutorado / Doutor em Engenharia de Alimentos

This thesis resumes both theoretical and practical knowledge with surface protection by wet painting which the student achieved during her studies and within her practice which she got in the painting shop of cabs for building, handling and agricultural machines. In her thesis the student has found out that one of current trends focuses on the method which is ecologically friendly and preserves paint lifetime. To achieve that, ED-coat painting is used first and then followed by the painting of waterborne paint. Within the scope of her thesis objective she has also optimised the process of surface protection respective technological pre-treatments and parameters which are carried out during ED-coat and e-coat painting, such as optimal thickness of coating, temperatures or technological time outs.

A cana-de-açúcar é uma das matérias primas para a produção de açúcar e álcool. Durante o processo de produção, é gerado como subproduto (ou resíduo) o bagaço, que possui várias aplicações, entre elas a geração de energia, fertilizantes, produção de combustíveis e ração animal. O bagaço da cana-de-açúcar é composto principalmente por materiais lignocelulósicos, possuindo como constituintes principais a celulose, a hemicelulose e a lignina. A lignina é um dos materiais mais recalcitrantes na natureza e, conseqüentemente, dificulta o acesso de enzimas aos carboidratos fermentáveis, reduzindo a eficiência da degradação da celulose e da fermentação. Uma das vias de degradação da lignina ocorre através da ação de enzimas produzidas por fungos de degradação branca, marrom e macia. Essas enzimas são capazes de degradar e expor a celulose e a hemicelulose, que, por sua vez são prontamente utilizadas por outros microrganismos. Para que isso ocorra, esses fungos promovem um processo de oxidação de compostos fenólicos e não fenólicos da molécula de lignina por meio de enzimas ligninolíticas extracelulares entre elas a lacase e a manganês peroxidase (MnP), em baixa velocidade, porém com grande eficiência. O presente trabalho tem como objetivo avaliar diferentes tratamentos químicos alcalinos (NaOH e Ca(OH)2) e biológicos (Penicillium sp. e Aspergillus niger) por microscopia óptica, eletrônica de transmissão e de varredura com o intuito de promover uma alteração física na estrutura da fibra do bagaço de cana-de-açúcar. Os resultados foram avaliados pelas técnicas de microscopia demonstrando que a ação dos tratamentos químicos, principalmente do NaOH + Ca(OH)2, provocou uma eficiente desestruturação das fibras em comparação aos outros tratamentos. Em relação às atividades enzimáticas, o pré-tratamento do bagaço com NaOH +. Ca(OH)2 associado ao A. niger mostrou ser mais eficiente para a produção de lacase. Já para a atividade enzimática de MnP, o tratamento controle (bagaço autoclavado) foi o que apresentou maior eficiência. Para Penicillim sp., a atividade enzimática da lacase não aprsesentou diferença significativa entre os pré-tratamentos bagaço autoclavado e NaOH + Ca(OH)2, no entanto, quando comparados aos pré-tratamentos com NaOH e Ca(OH)2 foram os mais eficientes para a produção dessa enzima. Para a enzima MnP, o pré-tratamento associado às duas bases foi mais eficiente. / Sugarcane is one of the raw materials used for sugar and alcohol production. During the production process, bagasse is generated as a subproduct (or residue), which has a large range of application, as electric power generation, fertilizers, combustible production and animal feeding. Sugarcane bagasse is mainly composed by lignocellulosic material, containing as main component cellulose, hemicelluloses and lignin. Lignin is one of the most recalcitrant naturally found molecules, and, consequently, hardens the access of enzymes to fermentable carbohydrates, decreasing the efficiency of cellulose degradation and fermentation. One of the lignin degradation pathways occurs throughout the action of enzymes produced by white-rot, brown and soft-rot fungi. These enzymes are able to degrade lignin, exposing cellulose and hemicelluloses, which get available for other microorganisms. In order to perform this process, these fungi promote an oxidation process of phenolic and non-phenolic compounds of the lignin molecule, by the lignolytic extracellular enzymes. Among them are the enzymes laccase and manganese peroxidase (MnP), which have a slow rate activity, however of high efficiency. The present work has as objective to evaluate different alkaline chemical (NaOH and Ca(OH)2) and biological (Penicillium sp. and Aspergillus niger) treatments by optic microscopy, scanning electron microscopy and transmission electronic microscopy to promote alteration on the physical structure of the sugarcane bagasse fiber. The results were evaluated by the microscopy technique, showing that the activity of the chemical treatments, in special of NaOH + Ca(OH)2 promoted an efficient loss of structure of fibers in comparison to the other treatments. In respect to the enzymatic activity, the bagasse pre-treated with NaOH + Ca(OH)2, in association with A. Niger showed to be more efficient for laccase production. Meanwhile, for the MnP enzymatic activity, the control treatment (only autoclaved bagasse) was that presented the highest efficiency. For Penicillium sp., the laccase enzymatic activity did not present any significant difference among the pre-treatments autoclaved bagasse (control) and NaOH + Ca(OH)2. However, when compared to the pretreatments with NaOH and Ca(OH)2, they were more efficient for the production of the referred enzyme. For MnP, the pre-treatments associated to both alkalis had an increased efficiency.

A cana-de-açúcar é uma das matérias primas para a produção de açúcar e álcool. Durante o processo de produção, é gerado como subproduto (ou resíduo) o bagaço, que possui várias aplicações, entre elas a geração de energia, fertilizantes, produção de combustíveis e ração animal. O bagaço da cana-de-açúcar é composto principalmente por materiais lignocelulósicos, possuindo como constituintes principais a celulose, a hemicelulose e a lignina. A lignina é um dos materiais mais recalcitrantes na natureza e, conseqüentemente, dificulta o acesso de enzimas aos carboidratos fermentáveis, reduzindo a eficiência da degradação da celulose e da fermentação. Uma das vias de degradação da lignina ocorre através da ação de enzimas produzidas por fungos de degradação branca, marrom e macia. Essas enzimas são capazes de degradar e expor a celulose e a hemicelulose, que, por sua vez são prontamente utilizadas por outros microrganismos. Para que isso ocorra, esses fungos promovem um processo de oxidação de compostos fenólicos e não fenólicos da molécula de lignina por meio de enzimas ligninolíticas extracelulares entre elas a lacase e a manganês peroxidase (MnP), em baixa velocidade, porém com grande eficiência. O presente trabalho tem como objetivo avaliar diferentes tratamentos químicos alcalinos (NaOH e Ca(OH)2) e biológicos (Penicillium sp. e Aspergillus niger) por microscopia óptica, eletrônica de transmissão e de varredura com o intuito de promover uma alteração física na estrutura da fibra do bagaço de cana-de-açúcar. Os resultados foram avaliados pelas técnicas de microscopia demonstrando que a ação dos tratamentos químicos, principalmente do NaOH + Ca(OH)2, provocou uma eficiente desestruturação das fibras em comparação aos outros tratamentos. Em relação às atividades enzimáticas, o pré-tratamento do bagaço com NaOH +. Ca(OH)2 associado ao A. niger mostrou ser mais eficiente para a produção de lacase. Já para a atividade enzimática de MnP, o tratamento controle (bagaço autoclavado) foi o que apresentou maior eficiência. Para Penicillim sp., a atividade enzimática da lacase não aprsesentou diferença significativa entre os pré-tratamentos bagaço autoclavado e NaOH + Ca(OH)2, no entanto, quando comparados aos pré-tratamentos com NaOH e Ca(OH)2 foram os mais eficientes para a produção dessa enzima. Para a enzima MnP, o pré-tratamento associado às duas bases foi mais eficiente. / Sugarcane is one of the raw materials used for sugar and alcohol production. During the production process, bagasse is generated as a subproduct (or residue), which has a large range of application, as electric power generation, fertilizers, combustible production and animal feeding. Sugarcane bagasse is mainly composed by lignocellulosic material, containing as main component cellulose, hemicelluloses and lignin. Lignin is one of the most recalcitrant naturally found molecules, and, consequently, hardens the access of enzymes to fermentable carbohydrates, decreasing the efficiency of cellulose degradation and fermentation. One of the lignin degradation pathways occurs throughout the action of enzymes produced by white-rot, brown and soft-rot fungi. These enzymes are able to degrade lignin, exposing cellulose and hemicelluloses, which get available for other microorganisms. In order to perform this process, these fungi promote an oxidation process of phenolic and non-phenolic compounds of the lignin molecule, by the lignolytic extracellular enzymes. Among them are the enzymes laccase and manganese peroxidase (MnP), which have a slow rate activity, however of high efficiency. The present work has as objective to evaluate different alkaline chemical (NaOH and Ca(OH)2) and biological (Penicillium sp. and Aspergillus niger) treatments by optic microscopy, scanning electron microscopy and transmission electronic microscopy to promote alteration on the physical structure of the sugarcane bagasse fiber. The results were evaluated by the microscopy technique, showing that the activity of the chemical treatments, in special of NaOH + Ca(OH)2 promoted an efficient loss of structure of fibers in comparison to the other treatments. In respect to the enzymatic activity, the bagasse pre-treated with NaOH + Ca(OH)2, in association with A. Niger showed to be more efficient for laccase production. Meanwhile, for the MnP enzymatic activity, the control treatment (only autoclaved bagasse) was that presented the highest efficiency. For Penicillium sp., the laccase enzymatic activity did not present any significant difference among the pre-treatments autoclaved bagasse (control) and NaOH + Ca(OH)2. However, when compared to the pretreatments with NaOH and Ca(OH)2, they were more efficient for the production of the referred enzyme. For MnP, the pre-treatments associated to both alkalis had an increased efficiency.

Made available in DSpace on 2014-07-29T15:07:53Z (GMT). No. of bitstreams: 1 Dissertacao-Raphael Rocha de Oliveira.pdf: 769424 bytes, checksum: 06c1655cb89d85d3f14e0f0ed376e67e (MD5) Previous issue date: 2010-02-26 / This work was carried out to develop a method for the determination of CMP in UHT milk using near-infrared spectroscopy. UHT milk from eight different brands were used for the construction of calibration models. In each of these brands were obtained eight treatments based on the addition of reconstituted whey powder to milk, to 0 (sample with no added whey), 1%, 2%, 3%, 4%, 6% 8% and 10%, giving a total of 64 treatments. The spectra were obtained by NIRS in three replicates, giving a total of 192 spectra. The HPLC results showed a rate of CMP in the samples obtained in the market, ranging between 33.64 and 398.78 mg/L. These results indicate fraud by the addition of whey or low quality of raw milk used. Altogether, 48 models were obtained, showing that the development of a calibration model suitable for the detection of CMP in UHT milk should be used with the PLS method, the method of selecting maximum distance and the pretreatment 2nd derivative and standard normal variate. The near-infrared regions most closely correlated with the vibrational motion of the amino acids present in the CMP were: 1100-1310, 1400-1430, 1490-1550, 1640-1680, 1780-1970, 2020- 2100 and 2310-2350 nm. When these regions were grouped with the selected chemometric tools, have been found the best results from R2 (0,8946) and PRESS (1323569,25), using 6 factors, and eliminating only 1.56% of the spectra (outliers). The results of the samples used for validation, indicates that the addition of whey, or the use of materials of poor quality for the production of UHT milk can be a routine. The results also showed that the calibration model was fine adjusted, as the ratio SEC/SEV was within the range of similarity (0.74). Moreover, the calibration model showed the ability to distinguish, because it recognized the 48 spectra of validation, but did not recognized spectra of four brands of skim milk UHT. However, there is a need for a calibration set wider so that be representative of the entire population / O presente trabalho foi realizado com o objetivo de desenvolver um método para a determinação de CMP em leite UAT através da aplicação da espectroscopia de infravermelho próximo. Leites UAT de oito marcas diferentes foram utilizados para a construção dos modelos de calibração. Em cada uma dessas marcas foram obtidos oito tratamentos, com base na adição de soro em pó reconstituído ao leite, em 0 (amostra sem adição de soro), 1%, 2%, 3%, 4%, 6%, 8% e 10%, formando um total de 64 tratamentos. Os espectros foram obtidos por NIRS em três replicatas, formando um total de 192 espectros. Os resultados da CLAE mostraram um índice de CMP nas amostras obtidas no mercado, variando entre 33,64 e 398,78 mg/L. Esses resultados indicam fraude por adição de soro de queijo ou baixa qualidade do leite cru utilizado como matéria-prima. Ao todo, 48 modelos foram obtidos, mostrando que para o desenvolvimento de um modelo de calibração adequado para a determinação de CMP em leite UAT deve-se utilizar juntamente com o método de regressão PLS, o método de seleção de espectros máxima distância e os pré-tratamentos 2ª derivada e variável normal padronizada. As regiões do infravermelho próximo mais correlacionadas com os movimentos vibracionais dos aminoácidos presentes no CMP foram: 1100-1310; 1400-1430; 1490-1550; 1640-1680; 1780-1970; 2020-2100 e 2310-2350 nm. Quando foram agrupadas essas regiões, utilizando as ferramentas quimiométricas selecionadas, foram encontrados os melhores resultados de R2 (0,8946) e de PRESS (1323569,25), utilizando seis fatores e eliminando apenas 1,56% dos espectros (outliers). Os resultados das amostras utilizadas na etapa de validação, indicam que a adição de soro de queijo, ou a utilização de matérias-primas de baixa qualidade inicial para a fabricação de leite UAT, pode ser rotineira. Os resultados também mostraram que o modelo de calibração foi bem ajustado, já que a razão SEC/SEV apresentou-se dentro do intervalo de similaridade (0,74). Além disso, o modelo de calibração apresentou capacidade de distinção, pois reconheceu os 48 espectros da validação, mas não reconheceu espectros de quatro marcas de leite UAT desnatado. A espectroscopia de infravermelho próximo pode ser uma alternativa para a determinação de CMP em leite UAT, desde que haja um conjunto de calibração com amostras representativas da população a ser predita no futuro

The formation of conversion coatings based on Ce, trivalent Cr and Ti/Zr is triggered by the local pH increase at cathodic IM sites of the aluminium alloy microstructure. The pH gradient is created over the cathodic intermetallic (IM) sites of the microstructure and its intensity is influenced by their activity which depends on their chemical composition, their size, and spatial distribution. Furthermore, the pre-treatment applied also affects the surface reactivity. The role of each of the microstructural features on the increased pH gradient and the subsequent triggering of local conversion coating deposition remains to be understood. To address the knowledge gap, model cast Al-Si-Fe and Al-Si-Cu-Fe alloys have been designed. Cerium based conversion coating treatment with standard parameters is applied to investigate the microstructure’s influence. Furthermore, four different surface pre-treatments’ effect on the topographical and electrochemical properties have been investigated by localized techniques and have been correlated with deposition experiment observations to prove surface reactivity. In this study, it was found that the four surface pre-treatments – polishing, NaOH, NaOH-HNO3, NaOH-H2SO4 activate the surface of alloys containing Fe-rich IM and Cu-rich IM differently. The surface pre-treatment NaOH-HNO3 was found most detrimental to the surface reactivity as the pre-treatment resulted in passivation of the IM and a drastic reduction in its volta potential. The best pre-treatment for the alloy Al-Si-Fe was found to be one with NaOH etching. In the case of Al-Si-Cu-Fe alloy, pre-treatments where a pickling step (with either H2SO4 or HNO3) was applied followed a NaOH etching step, the surface of the IM was activated more than other pre-treatments due to selective Al dealloying and Cu-redeposition. The extent of Cu-redeposition was observed to be the most when surfaces were pickled with HNO3 solution and with the NaOH- HNO3 pre-treatment, fastest deposition kinetics were observed. In the cast Al-Si-Cu-Fe alloy, the localized deposits were preferentially observed to form on only strong cathodic Cu-rich IM. The size (surface area) of the Cu-rich IM correlated linearly with the lateral deposition area as well as z-direction spread. It was found that the pH gradient resulting from the oxygen reduction reaction near an IM is very local and does not affect pH gradients of a neighbouring Cu-rich IM. The size did not have a profound impact on the extent of deposition occurring on a Cu-rich IM, but it was found that big Cu-rich IM activated faster for deposition reaction than small Cu-rich IM. When the progression of deposition on both coarse and fine microstructure cast Al-Si-Cu-Fe was quantitatively monitored at increasing conversion coating times 0.5h, 1h and 2h, it was observed that big Cu-rich IM in the coarse alloy triggered deposition faster than small Cu-rich IM. Deposition mechanism on Fe-rich IM was found to be composition specific. In the cast of big Fe-rich β-Al5FeSi IM, localized deposition initiated at the border on the IM and is explained based on Si content in the composition of the IM, which has very high resistivity. In another Fe-rich IM, although of a much smaller size, which had lower Si content and was richer in Fe, a localized deposition was observed on the entire IM. / Bildning av omvandlingsbeläggningar baserade på Ce, trivalent Cr och Ti/Zr initieras av lokalt förhöjd pH vid katodiska intermetalliska platser I aluminiumlegeringens mikrostruktur. Utbredningen av den starka pH-gradientens uppkomst över katodiska intermetalliska (IM) platser av mikrostrukturen påverkas av dess aktivitet som i sin tur beror på dess kemiska sammansättning, storlek, och rumslig fördelning. Ytans reaktivitet påverkas dessutom av dess förbehandling. Rollen av mikrostrukturens egenskaper på den förhöjda pH-gradienten och efterföljande initiering av lokal omvandlingsbeläggning återstår att förstå. För att komplettera detta kunskapsgap har Al-Si-Fe och Al-Si-Cu-Fe modellgjutlegeringar utformats. Cerium-baserade behandlingar för omvandlingsbeläggning med standardparametrar tillämpas för undersökning av mikrostrukturens påverkan. Effekten av fyra olika ytförbehandlingar på topografiska och elektrokemiska egenskaper har dessutom undersökts med lokaliserade metoder och har korrelerats med observationer vid depositionsexperient för att bevisa ytreaktivitet. I denna studie har det visats att de fyra ytförbehandlingarna – polering, NaOH, NaOH-HNO3, NaOH-H2SO4 – aktiverar ytan hos legeringar innehållande Fe-rika intermetaller och Cu-rika intermetaller på olika vis. Ytförbehandlingen med NaOH-HNO3 visades vara skadligast för ytans reaktivitet eftersom förbehandlingen resulterade i passivering av IM och en drastisk sänkning av dess volta-potential. Den bästa förbehandlingen för Al-Si-Fe-legeringen visades vara med NaOH-etsning. I Al-Si-Cu-Fe-legeringens fall, var förbehandling där ett betningssteg (antingen med H2SO4 eller HNO3) tillämpades följt av etsning med NaOH, aktiverades ytan av IM mer än med andra förbehandlingar på grund av selektiv korrosion av Al och Cu-återdeposition. Utbredningen av Cu-återdeposition observerades vara störst när ytor var betade med HNO3-lösning och depositionens kinetik var som hastigast vid förbehandling med NaOH-HNO3. I den gjutna Al-Si-Cu-Fe-legeringen observerades lokaliserade depositionerna att bildas endast på starkt katodiska Cu-rika IM. Storleken (ytarea) på de Cu-rika IM korrelerade linjärt med den laterala depositionsytan samt med spridning i z-riktning. Det visade sig att pH-gradienten som uppkom via syrereduktionsreaktionen nära IM är väldigt lokal och påverkar ej pH-gradienter vid närliggande Cu-rik IM. Storleken hade ingen anmärkningsvärd verkan på utbredningen av deposition på Cu-rik IM, men stora Cu-rika IM visade sig aktiveras snabbare för depositionsreaktion än små Cu-rika IM. När depositionens framfart över grov och fin mikrostruktur i gjuten Al-Si-Cu-Fe följdes kvantitativt vid ökande omvandlingsbeläggningstid 0,5h; 1h och 2h, så observerades att stora Cu-rika IM i den grova legeringen påbörjade depositionen snabbare än små Cu-rika IM. Depositionsmekanismen på Fe-rika IM visades vara specifik för sammansättning. I gjutgodset med stora Fe-rika β-Al5FeSi IM visades lokaliserad deposition initieras vid gränsen av IM vilket förklaras baserat på Si-halt i IM sammansättning, som har väldigt hög resistivitet. I en annan Fe-rik IM, dock av mycket mindre storlek, som hade lägre Si-halt och rikare med Fe, en lokaliserad deposition var observerad över hela IM.