Este trabalho objetivou explorar o óleo de macaúba (Acrocomia aculeata) como matéria prima para produção de biodiesel, propondo uma via através da qual se possibilite a produção do biodiesel apesar da alta acidez do óleo. O processo proposto ocorreu em duas etapas de catálise homogênea, a primeira foi a reação de esterificação etílica dos ácidos graxos livres, catalisada por H2SO4; e a segunda é a transesterificação dos triglicerídeos remanescentes catalisada por álcali (KOH). A utilização das ondas ultrassônicas também foi investigada neste trabalho como potencializador do processo. Para determinação das melhores condições reacionais foi utilizado o delineamento experimental e para validação dos resultados utilizou-se análise de variância do modelo para as variáveis respostas índice de acidez na etapa de pré-tratamento e conversão de ésteres etílicos na etapa de transesterificação alcalina. Os resultados foram avaliados utilizando o software MINITAB 16. Na etapa de pré-tratamento os resultados demonstram que utilizando quantidades de H2SO4 de 2% (em massa), razão molar óleo:etanol de1:9 e temperatura de 50 ºC o índice de acidez foi reduzido de 19,25 mgKOH/g para 1,46 mgKOH/g em 2 h de reação. Com estes resultados foi possível a aplicação da reação de transesterificação alcalina. Na etapa etapa de transesterificação alcalina com agitação mecânica as melhores condições determinadas pelo delineamento experimental foram de 1,5% (massa) de KOH, razão molar de 1:6 e temperatura de 45 ºC em 30 min de reação as conversões alcançadas foram em torno de 100%. As reações processadas em banho ultrassônico e sonda ultrassônica apresentaram como principal vantagem a redução de tempo, sendo em que 10 min foram atingidas conversões próximas a 100%. As análises efetuadas nos ésteres etílicos de amêndoa de macaúba, obtidos a partir do processo em duas etapas, mostram que a viscosidade cinemática e densidade estão dentro dos parametros estabelecidos pela ANP. Os níveis de glicerina total e livre também estão dentro do estabelecido pelas normas e indica que a purificação dos produtos de reação foi adequada. / This study aimed to explore Macauba oil (Acrocomia aculeata) as an alternative raw material to the production of biodiesel, despite the high acid value of the oil. It was proposed a two-step process of homogeneous catalysis. The first step is the ethylic esterification of free fatty acids, catalyzed by H2SO4; the second is the transesterification catalyzed by alkali (KOH). The use of ultrassonic irradiation was also investigated in this work. Factorial design was used to determine the best reaction conditions and analysis of variance was used to evaluate the mathematical model for the variable responses, such as the acid level in the pre-treatment and conversion of ethyl esters in alkaline transesterification step. The results were evaluated using the software MINITAB 16. In the first step, the acid catalyzed reaction was carried out with 9:1 molar ratio ethanol-to-oil in the presence of 2% w/w H2SO4 at 50 ºC for 2 hours and the acid value of Macauba oil was reduced from 19 mgKOH/g to 1,46 mgKOH/g. With these results, it was possible the application of alkaline transesterification reaction. In the alkaline transesterification under mechanical stirring, the optimal experimental conditions were 1.5% (mass) of KOH molar ratio of 1:6 and temperature of 45 ºC in 30min. Conversions of approximately 100 %. were achieved in this process The reactions that were processed in ultrasonic bath and probe presented as the major advantage the reduction of the time, conversions of approximately 100% were achieved in 10 min. The analysis of the ethyl esters obtained from this two-step process show that the kinematic viscosity and density are within the parameters established by the ANP. The levels of total and free glycerol are also within the established standards and indicate that purification of products were adequate.

The continuous and aggressive dimensional miniaturization ofthe conventional complementary-metal-oxide semiconductor (CMOS)architecture has been the main impetus for the vast growth ofIC industry over the past decades. As the CMOS downscalingapproaches the fundamental limits, unconventional materials andnovel device architectures are required in order to guaranteethe ultimate scaling in device dimensions and maintain theperformance gain expected from the scaling. This thesisinvestigates both unconventional materials for the gate stackand the channel and a novel notched-gate device architecture,with the emphasis on the challenging issues in processintegration. High-κ gate dielectrics will become indispensable forCMOS technology beyond the 65-nm technology node in order toachieve a small equivalent oxide thickness (EOT) whilemaintaining a low gate leakage current. HfO2and Al2O3as well as their mixtures are investigated assubstitutes for the traditionally used SiO2in our MOS transistors. These high-κ filmsare deposited by means of atomic layer deposition (ALD) for anexcellent control of film composition, thickness, uniformityand conformality. Surface treatments prior to ALD are found tohave a crucial influence on the growth of the high-κdielectrics and the performance of the resultant transistors.Alternative gate materials such as TiN and poly-SiGe are alsostudied. The challenging issues encountered in processintegration of the TiN or poly-SiGe with the high-k are furtherelaborated. Transistors with TiN or poly-SiGe/high-k gate stackare successfully fabricated and characterized. Furthermore,proof-of-concept strained-SiGe surface-channel pMOSFETs withALD high-κ dielectrics are demonstrated. The pMOSFETs witha strained SiGe channel exhibit a higher hole mobility than theuniversal hole mobility in Si. A new procedure for extractionof carrier mobility in the presence of a high density ofinterface states found in MOSFETs with high-κ dielectricsis developed. A notched-gate architecture aiming at reducing the parasiticcapacitance of a MOSFET is studied. The notched gate is usuallyreferred to as a local thickness increase of the gatedielectric at the feet of the gate above the source/drainextensions. Two-dimensional simulations are carried out toinvestigate the influence of the notched gate on the static anddynamic characteristics of MOSFETs. MOSFETs with optimizednotch profile exhibit a substantial enhancement in the dynamiccharacteristics with a negligible effect on the staticcharacteristics. Notched-gate MOSFETs are also experimentallyimplemented with the integration of a high-κ gatedielectric and a poly-SiGe/TiN bi-layer gate electrode. Key words:CMOS technology, MOSFET, high-κ, gatedielectric, ALD, surface pre-treatment, metal gate, poly-SiGe,strained SiGe, surface-channel, buried-channel, notchedgate.

This thesis is focused on the novel wood chip refining process called AdvancedThermomechanical Pulp (ATMP) refining. ATMP consists of mechanical pretreatmentof chips in Impressafiner and Fiberizer prior to first stage refining atincreased intensity. Process chemicals (this study was concentrated on hydrogenperoxide and magnesium hydroxide) are introduced into the first stage refiner.It is known that the use of chemicals in TMP process and first stage refining atelevated intensity can reduce the energy demands of refining. The downside is thatthey also alter the character of the produced pulp. Reductions in fibre length andtear index are usually the consequences of refining at elevated intensity. Additionof chemicals usually leads to reduction of the light scattering coefficient. Usingstatistical methods it was shown that it is possible to maintain the TMP character ofthe pulp using the ATMP process. This is explained by a separation of thedefibration and the fibre development phases in refining. This separation allowsdefibration of chips to fibres and fibre bundles without addition of chemicals orincrease in refining intensity. Chemicals are applied in the fibre developmentphase only (first stage refiner). The energy demand in refining to reach tensileindex of 25 Nm/g was reduced by up to 1.1 MWh/odt (42 %) using the ATMPprocess on Loblolly pine. The energy demand in refining of White spruce, requiredto reach tensile index of 30 Nm/g, was reduced by 0.65 MWh/odt (37%).Characterizations of individual fibre properties, properties of sheets made fromlong fibre fractions and model fibre sheets with different fines fractions werecarried out. It was established that both the process equipment configuration (i.e.the mechanical pre‐treatment and the elevated refining intensity) and the additionof process chemicals in the ATMP process influence fibre properties such as external and internal fibrillation as well as the amount of split fibres. Improvementof these properties translated into improved properties of sheets, made from thelong fibre fractions of the studied pulps. The quality of the fines fraction alsoimproved. However, the mechanisms of improvement in the fines quality seem tobe different for fines, generated using improved process configuration andaddition of process chemicals. The first type of fines contributed to better bondingof model long fibre sheets through the densification of the structure. Fines whichhave been influenced by the addition of the process chemicals seemed in additionto improve bonding between long fibres by enhancing the specific bond strength.The improved fibre and fines properties also translated into better airpermeability and surface roughness of paper sheets, properties which areespecially important for supercalendered (SC) printing paper. The magnitude offibre roughening after moistening was mainly influenced by the processequipment configuration while the addition of process chemicals yielded lowestfinal surface roughness due to the lowest initial surface roughness. There was nodifference in how fines fractions from the studied processes influenced the fibreroughening. However, fines with better bonding yielded model fibre sheets withhigher PPS, probably due to their consolidation around fibre joints. Hence, thedecrease in PPS can probably be attributed to the improvements in the long fibrefraction properties while the improvement of fines quality contributed to thereduction of air permeability.The process chemicals, utilized in the ATMP process (Mg(OH)2 and H2O2) alsoproved to be an effective bleaching system. Comparable increases in brightnesscould be reached using the ATMP process and conventional tower bleaching.Maximum brightness of the pulp was reached after approximately 10 minutes ofhigh‐consistency storage after refining or 40 minutes of conventional bleaching.This study was conducted using a pilot scale refiner system operated as a batchprocess. Most of the experiments were performed using White spruce (Piceaglauca). In Paper I, Loblolly pine (Pinus taeda) was used. It is believed that theresults presented in this thesis are valid for other softwood raw materials as well,but this limitation should be considered.

The biological sludge formed in the pulp and paper wastewater treatment constitutes a costlyproblem to dispose off due to poor dewaterability. It is often incinerated or used as soilconditioner improvement. By using anaerobic digestion of the biological sludge, thedewaterability can be increased. Thanks to the formation of biogas, the sludge volume isdecreased and energy can be recovered as methane. By pre-treating the sludge, the biogasproduction can be increased, making the anaerobic digestion more economically feasible. Eleven samples of biological sludges from six Swedish pulp and paper mills, chosen torepresent different types and sizes of mills available in Sweden, were pre-treated with alkali(NaOH, pH12), heat (80˚C, 1 hr) and electroporation (2000 pulses, 10 kV/cm). Initialmethane production rate and methane potential of all sludges and pre-treatments weredetermined using batch experiment. A combination of two sludges (from the same mill) pretreatedwith alkali and heat was further investigated in a semi-continuous digester experiment. The batch experiments showed that alkali pre-treatment had the greatest positive effect onmethane production. Heat treatment performed second best, whereas electroporation had no orlittle effect. Overall, pre-treatments increased the initial methane production rate, but withinsignificant effects on the methane potential. Heat pre-treatment showed no difference inbiogas production compared to the control in the semi-continuous digester experiment. Alkalitreatment was shown to inhibit biogas production and cause high accumulation of acetate. Itcould not be concluded whether it was an effect from hydroxide or sodium ion addition.Further analysis of the NaOH impact on floc structure, toxicity and bioavailability issuggested to determine the suitability of alkali-treated sludge for anaerobic digestion. / Bioslam, som bildas vid vattenreningen på pappers- och massabruk, utgör en kostnad attomhänderta på grund av avvattningssvårigheter. Kvittblivning sker oftast genom förbränningeller användning som jordförbättringsmedel. Genom rötning kan slammet bli merlättavvattnat och tack vare att det bildas biogas minskar slamvolymen samtidigt som energikan utvinnas från metanet. Produktionen av biogas kan ökas genom att förbehandla slammetinnan rötning, vilket skulle innebära ekonomiska fördelar. Denna studie har undersökt effekten av förbehandling för elva bioslam från sex svenskapappers- och massabruk, valda att representera olika typer och storlekar på svenska bruk.Behandlingen gjordes med alkali (NaOH, pH12), värme (80˚C, 1 h) och elektroporering(2000 pulser, 10 kV/cm). Effekten av förbehandling på initial metanproduktionshastighet ochmetanpotential undersöktes med hjälp av satsvis utrötning (batch) av alla slam. Enkombination av två slam från samma burk utvärderades i ett semi-kontinuerligt rötningsförsökefter förbehandling med värme och alkali. Resultatet från utrötningsförsöket visade att den alkaliska förbehandlingen hade störst positivinverkan på metanproduktionen. Värmebehandlingen presterade näst bäst, medanelektroporeringen visade sig ha liten eller ingen effekt. Generellt sett ökade den initialametanproduktionshastigheten till följd av förbehandling, medan metanpotentialen förblevoförändrad. Värmebehandling gav ingen effekt på biogasproduktionen i det semikontinuerligarötningsförsöket jämfört med kontroll, medan alkalisk förbehandling inhiberadebiogasproduktionen och orsakade höga koncentrationer av ackumulerat acetat. Det kunde inteavgöras huruvida det var natrium- eller hydroxidjoner, som orsakade inhiberingen. För attkunna utvärdera möjligheten att röta slam, som förbehandlats med NaOH, rekommenderasvidare analys av dess påverkan på flockstruktur, toxicitet och biotillgänglighet.

Neuere Erzeugnisse zeichnen sich häufig durch eine Werkstoffvielfalt aus. Teilweise sind die Werkstoffe thermisch empfindlich. Aus allen diesen Gründen wird das weitgehend werkstoffunspezifische und wärmearme Verfahren Kleben für das Fügen von Bauteilstrukturen immer wichtiger. Es ist seit langem bekannt, dass die Festigkeit und vor allem die Alterungsbeständigkeit der Klebverbindungen neben der Art des gewählten Klebstoffes in ganz wesentlichem Umfang von den physikalischen, chemischen und morphologischen Eigenschaften der Fügeteiloberflächen abhängig ist. Die Eigenschaft der Klebverbindung wird nicht vorrangig durch die Haftung an der Fügeoberfläche, sondern durch den grenzflächennahen Polymerbereich, der so genannten Interphase oder Grenzschicht bestimmt. Ziel dieser Forschung ist daher die Untersuchung von Grenzflächenphänomenen des Verbundes Aluminium/ Epoxid-Klebstoff im µm-Bereich in Abhängigkeit von unterschiedlich vorbehandelten Aluminiumoberflächen unter Einschluss von Haftvermittlersauftrag durch thermoanalytische, spektroskopische, mikroskopische und elektrochemische Methoden, sowie die Korrelation der Ergebnisse mit den Festigkeiten und Langzeitbeständigkeiten der Klebverbindungen. Die in der Arbeit gewonnenen Erkenntnisse und erzielten Ergebnisse können in der Fügetechnik betriebswirtschaftlich sehr vorteilhaft zur Behandlung von Fügeteilen aus Aluminiumlegierungen angewendet werden.

<p>The continuous and aggressive dimensional miniaturization ofthe conventional complementary-metal-oxide semiconductor (CMOS)architecture has been the main impetus for the vast growth ofIC industry over the past decades. As the CMOS downscalingapproaches the fundamental limits, unconventional materials andnovel device architectures are required in order to guaranteethe ultimate scaling in device dimensions and maintain theperformance gain expected from the scaling. This thesisinvestigates both unconventional materials for the gate stackand the channel and a novel notched-gate device architecture,with the emphasis on the challenging issues in processintegration.</p><p>High-κ gate dielectrics will become indispensable forCMOS technology beyond the 65-nm technology node in order toachieve a small equivalent oxide thickness (EOT) whilemaintaining a low gate leakage current. HfO₂and Al₂O₃as well as their mixtures are investigated assubstitutes for the traditionally used SiO₂in our MOS transistors. These high-κ filmsare deposited by means of atomic layer deposition (ALD) for anexcellent control of film composition, thickness, uniformityand conformality. Surface treatments prior to ALD are found tohave a crucial influence on the growth of the high-κdielectrics and the performance of the resultant transistors.Alternative gate materials such as TiN and poly-SiGe are alsostudied. The challenging issues encountered in processintegration of the TiN or poly-SiGe with the high-k are furtherelaborated. Transistors with TiN or poly-SiGe/high-k gate stackare successfully fabricated and characterized. Furthermore,proof-of-concept strained-SiGe surface-channel pMOSFETs withALD high-κ dielectrics are demonstrated. The pMOSFETs witha strained SiGe channel exhibit a higher hole mobility than theuniversal hole mobility in Si. A new procedure for extractionof carrier mobility in the presence of a high density ofinterface states found in MOSFETs with high-κ dielectricsis developed.</p><p>A notched-gate architecture aiming at reducing the parasiticcapacitance of a MOSFET is studied. The notched gate is usuallyreferred to as a local thickness increase of the gatedielectric at the feet of the gate above the source/drainextensions. Two-dimensional simulations are carried out toinvestigate the influence of the notched gate on the static anddynamic characteristics of MOSFETs. MOSFETs with optimizednotch profile exhibit a substantial enhancement in the dynamiccharacteristics with a negligible effect on the staticcharacteristics. Notched-gate MOSFETs are also experimentallyimplemented with the integration of a high-κ gatedielectric and a poly-SiGe/TiN bi-layer gate electrode.</p><p><b>Key words:</b>CMOS technology, MOSFET, high-κ, gatedielectric, ALD, surface pre-treatment, metal gate, poly-SiGe,strained SiGe, surface-channel, buried-channel, notchedgate.</p>

A forma de tratamento e destinação final ainda mundialmente preponderante para os resíduos sólidos urbanos é o aterro sanitário, método que gera, além de uma massa sólida residual, parcialmente estabilizada, subprodutos finais líquidos e gasosos. O efluente líquido, conhecido como lixiviado, necessita tratamento específico, devido a sua elevada nocividade ao meio ambiente, em função, principalmente, de suas elevadas concentrações de nitrogênio amoniacal e de matéria orgânica, em elevado percentual, recalcitrante. O presente trabalho avaliou em escala de bancada o tratamento, via processo físico-químico, através de coagulação-floculação, de lixiviado bruto proveniente de aterro sanitário Central de Resíduos do Recreio (operado pela Companhia Riograndense de Valorização de Resíduos), desprovido de qualquer tratamento prévio, e de lixiviado pré-tratado biologicamente em reatores sequenciais em batelada (RSB). Para o processo de coagulação-floculação foram testados os coagulantes policloreto de alumínio (PAC), cloreto férrico, sulfato férrico e tanino. Sucessivas etapas foram planejadas para a determinação de dosagem e ajuste de pH ótimos, para cada coagulante empregado, e para a verificação da influência de tempos e gradientes de misturas, bem como foi testada a aplicação de polímeros auxiliares de floculação. As variáveis resposta utilizadas para o monitoramento e a avaliação de eficiências foram a cor verdadeira, turbidez (com e sem prévia filtração), DQO, volume de lodo gerado e pH. O uso de reator sequencial em batelada objetivou nitrificação/desnitrificação convencional das elevadas concentrações de nitrogênio amoniacal e eventual oxidação de matéria carbonácea. Verificou-se que os diferentes tempos e gradientes de mistura testados, assim como a utilização de polímeros auxiliares, não produziram impactos nos resultados. Os coagulantes inorgânicos apresentaram elevadas eficiências de remoção, com destaque para o cloreto férrico, o qual na dosagem de 1102 mgFe+3/L e ajuste inicial de pH em 6,2 removeu 98% da cor verdadeira e da turbidez filtrada, 63% da DQO, 40% da DBO5, e 88% de turbidez não filtrada do lixiviado bruto. Apesar da recalcitrância de considerável fração da matéria orgânica do lixiviado, o RSB2 removeu 40% da DQO e 60% da DBO5 originais. A coagulação-floculação do efluente do RSB2 necessitou inferiores dosagens dos coagulantes em relação ao processo com lixiviado bruto. O cloreto férrico, em dosagem ótima de 826 mgFe+3/L e ajuste de pH em 6,3, removeu 95% da cor, 77% da DQO, 82% da DBO5, 94% da turbidez filtrada e 92% da turbidez não filtrada. Concluiu-se por elevada viabilidade técnica do processo de coagulação-floculação para o lixiviado com e sem pré-tratamento, a partir da otimização das condições de contorno do processo. O pré-tratamento em RSB, quando utilizado controle de pH, demonstrou grande potencial para nitrificação/desnitrificação e oxidação de significante parcela da matéria carbonácea do lixiviado bruto. / The form of treatment and disposal still prevalent worldwide for solid waste is the landfill, a method that generates, in addition to a solid mass residual partially stabilized, liquid and gas end products. The effluent liquid, known as leachate, requires specific treatment, due to its high harmfulness to the environment, due mainly to its high concentrations of ammonia nitrogen and organic matter in high percentage, recalcitrant. This study evaluated the treatment on bench scale, via physico-chemical process, by coagulation-flocculation, of raw leachate from Central de Resíduos do Recreio landfill (operated by Companhia Riograndense de Valorização de Resíduos), devoid of any previous treatment, and biologically pretreated leachate reactors in sequential batch reactors (SBR). For the process of flocculation-coagulation were tested polyaluminum chloride (PAC), ferric chloride, ferric sulfate and tannin. Successive stages were designed for determining dosage and optimum pH adjustment for each coagulant employed and for verifying the influence of times and gradients mixtures, as well as tested in the application of polymers flocculation auxiliaries. The answers used for parametric monitoring and evaluation of efficiencies were the true color, turbidity (with and without prior filtration), COD, sludge volume and pH. The use of sequential batch reactor aimed conventional nitrification/denitrification of the high concentrations of ammonia nitrogen and eventual oxidation of carbonaceous matter. It was found that the different gradients and mixing times tested, as well as the use of auxiliary polymers, did not produce impact on the results. The inorganic coagulants showed high removal efficiencies, especially ferric chloride, which at a dose of 1102 mgFe+3/L and initial pH adjusted to 6.2, removed 98% of the true color and filtered turbidity, 63% of COD, 40% of BOD5 and 88% of unfiltered turbidity. Despite the considerable fraction of the recalcitrance of organic matter in the leachate, the SBR2 removed 40% of COD and 60% of BOD5 of the original. The coagulation-flocculation of the effluent from SBR2 required lower dosages of coagulants in relation to the similar process with raw leachate. Ferric chloride in optimum dosage of 826 mgFe+3/L and adjusting pH to 6.3, removed 95% of color, 77% of COD, 82% of BOD5, 94% of the filtered turbidity and 92% of unfiltered turbidity. It was concluded by high technical feasibility of the process of flocculation-coagulation for the leachate with and without pre-treatment, based on the optimization of the boundary conditions of the process. The pre-treatment with SBR, when pH control, demonstrated high potential for nitrification/denitrification and oxidation of a significant portion of the carbonaceous of the raw leachate.

68 f. / Submitted by Ana Hilda Fonseca (anahilda@ufba.br) on 2013-04-05T17:50:29Z No. of bitstreams: 1 Dissertacao - Wdson Costa Santos.PDF: 1066509 bytes, checksum: 0409b0432c52d5bd01e90ebcf214766a (MD5) / Approved for entry into archive by Ana Hilda Fonseca(anahilda@ufba.br) on 2013-06-06T14:53:28Z (GMT) No. of bitstreams: 1 Dissertacao - Wdson Costa Santos.PDF: 1066509 bytes, checksum: 0409b0432c52d5bd01e90ebcf214766a (MD5) / Made available in DSpace on 2013-06-06T14:53:28Z (GMT). No. of bitstreams: 1 Dissertacao - Wdson Costa Santos.PDF: 1066509 bytes, checksum: 0409b0432c52d5bd01e90ebcf214766a (MD5) Previous issue date: 2012 / CAPES / No presente trabalho foram investigados os efeitos sobre a recuperação de elementos causados por modificações em processos prévios a amostragem laboratorial e lixiviação dos analitos das polpas de abóbora e batata. Inicialmente, foi avaliado o efeito da inversão na ordem de operações do procedimento de tratamento preliminar das amostras brutas das polpas sobre as recuperações dos elementos. As amostras das polpas foram secas para posterior trituração (PA) ou as amostras foram trituradas antes de serem submetidas à secagem (PB). Os resultados obtidos empregando ambos os procedimentos foram comparados para 95% de confiança e eles mostraram diferenças significativas para alguns elementos determinados na amostra de batata. As concentrações de K, P e Mn, na polpa de batata, determinadas aplicando o primeiro procedimento de pré-tratamento (PA) foram 13,6±0,4 mg K g-1, 1,95±0,04 mg P g-1 e 5,7±0,2 μg Mn g-1, enquanto 12,2±0,3 mg K g-1, 1,62±0,03 mg P g-1 e 2,6±0,2 μg Mn g-1 foram determinadas quando a mesma amostra bruta foi submetida ao pré-tratamento PB para a obtenção da amostra teste. Em contraposição, no caso da amostra bruta de polpa de abóbora, os resultados para os elementos (K, P, Mn, Mg) foram maiores quando a polpa foi previamente esmagada antes da secagem. Em um estudo independente, a eficiência da extração de metais de amostras de polpas trituradas de abóbora ou batata para soluções diluídas de HNO3 foi avaliada variando o modo (agitação mecânica ou irradiação ultrassônica) e o período (de 10 a 30 min) de agitação, bem como a concentração da solução de HNO3 na solução de lixiviação (de 0,7 a 2,1 mol L-1). Os resultados foram também comparados com aqueles obtidos nas digestões assistidas por micro-ondas das amostras teste v em meio nítrico-peróxido. Foi observado que para ambas as amostras teste (abóbora e batata) e independentemente do modo ou período de agitação que a eficiência de extração de Ca, K, Mg e Mn foi diminuída para solução para 2,1 mol L-1 HNO3. Uma melhora no nível de recuperação de P foi obtida quando a lixiviação foi realizada com soluções diluídas de HNO3 (0,7 e 1,4 mol L-1) e sob irradiação ultrassônica. Esse efeito foi relacionado à presença de átomos de fósforo em moléculas estruturais de células de abóbora e batata, bem como à cominuição (ou fragmentação) das partículas submetidas a um campo ultrassônico intenso. Contudo, efeitos indesejados foram também observados para alguns elementos quando submetidos às lixiviações assistidas com ultrassom, como exemplificado pelo teor de cálcio determinado após a lixiviação da amostra teste de batata ter atingido valor 2,3 vezes maior que o valor obtido após a mineralização da amostra em micro-ondas. Muitos desses efeitos foram relacionados à erosão da superfície interna frascos irradiados. / Salvador

Made available in DSpace on 2016-06-02T19:56:43Z (GMT). No. of bitstreams: 1 3641.pdf: 2915031 bytes, checksum: 75a88eb9fcd13120c484443ffeae1a1a (MD5) Previous issue date: 2011-02-28 / Universidade Federal de Sao Carlos / The aim of this work was evaluated the sugarcane bagasse (SCB) pretreatment by aqueous ammonia, an alkaline method. Samples of SCB (in natura and steam exploded unwashed) were pretreated with ammonium hydroxide solution (NH4OH) at 1:5 solid-liquid ratio (by weight), in a bench scale. Preliminary assays were carried out employing NH4OH solution (28% w/w) at room temperature 24 ± 3 &#8304;C by 7, 15 and 30 days. In these experiments, it was observed that the pretreatment was selective in removing lignin and hemicellulose. New experiments were carried out using at 50&#8304;C and NH4OH 15% during 30, 60 and 90 minutes. In these pretreatments the same behavior was observed. In the next assays, it decided to fix the reaction time in 60 minutes and the temperature in 100&#8304;C. Samples of in nature and steam exploded SCB were pretreated at diffent NH4OH concentrations (4 to 15%). Enzymatic hydrolysis assays were carried out in Erlenmeyers flasks (50&#8304;C, pH 4.8 and 250 rpm) using 30 FPU/g bagasse (Accellerase 1500, Genencor) and 5 CBU/g bagasse (BG, Genencor). Experiments were carried out employing in natura SCB (pretreated conditions 4, 10 and 15% NH4OH solution, 60 min., 100&#8304;C) with 3% of solid loading. A glucose conversion of 64.2% was reached in the best condition (10% NH4OH solution). Experiments were carried out employing steam exploded SCB (5, 10 e 15% NH4OH solution, 60 min. and 100&#8304;C) with 5% of solid loading. A glucose conversion of 79.9% was reached in the best condition (15% NH4OH solution). Hydrolysis experiments using higher solid loading (5% for in natura and 10% for steam exploded) and 30 FPU/g cellulose (Accellerase 1500) were carried out. A glucose conversion of 69.6% for in natura and 82.2% for steam exploded SCB were obtained. Fermentation assays (250 rpm, 30&#8304;C) employing commercial and industrial Saccharomyces cerevisiae were conducted, in a rich and poor medium. A theoretical fermentation yield up to 78% was found for the poor medium and around 88% for the rich medium. The industrial S. cerevisiae shows a value of yield slightly superior to those of commercial strain. Samples of SCB (before and after pretreatment) were analyzed by scanning electron micrograph (SEM). / O objetivo deste trabalho foi avaliar a etapa de pré-tratamento do bagaço de cana de açúcar empregando amônia aquosa, um método alcalino. Amostras de bagaço (in natura e explodido a vapor não lavado) foram tratadas na proporção 1:5 (massa de bagaço seco por massa de solução de NH4OH), em escala de bancada. Ensaios preliminares foram realizados empregando solução 28% (m/m) de NH4OH, a temperatura ambiente 24 ± 3 &#8304;C por 7, 15 e 30 dias em recipiente fechado. Nestes experimentos verificou-se que o pré-tratamento foi seletivo na remoção de lignina e hemicelulose. Novos experimentos foram realizados fixando-se a temperatura em 50&#8304;C e a concentração de NH4OH em 15%. Avaliaram-se tempos de reação de 30, 60 e 90 min. Nestes prétratamentos o mesmo comportamento foi observado. Nos próximos ensaios o tempo de reação foi fixado em 60 min e a temperatura em 100&#8304;C. Amostras de bagaço foram pré-tratadas em soluções de NH4OH (4 a 15%). Experimentos de hidrólise enzimática foram realizados em frascos de Erlenmeyer (50&#8304;C, pH 4,8 e 250 rpm) empregando 30 FPU/g bagaço (Accellerase 1500, Genencor) e 5 CBU/g bagaço (BG, Genencor). Na hidrólise das amostras de bagaço in natura (pré-tratadas com soluções de NH4OH 4, 10 e 15%, 60 min, 100&#8304;C) com carga de sólidos de 3% a melhor conversão em glicose foi de 64,2% (amostra tratada NH4OH 10%). Na hidrólise da amostra de bagaço explodido (pré-tratadas com NH4OH 5, 10 e 15%, 60 min e 100&#8304;C) com carga de sólidos de 7% a melhor conversão em glicose foi de 79,9% (amostra tratada com NH4OH 15 %). Hidrólises com maior carga de sólidos, 5% (bagaço in natura) e 10% (bagaço explodido), utilizando 30 FPU/g celulose (Accellerase 1500, Genencor) foram realizadas. Nestes ensaios obteve-se conversão em glicose de 69,6% (bagaço in natura) e 82,2% (bagaço explodido). Experimentos de fermentação alcoólica (250 rpm, 30&#8304;C) foram realizados empregando levedura Saccharomyces cerevisiae (comercial e industrial) em meios de cultivo denominados rico e pobre . A eficiência na conversão da glicose em etanol nos experimentos foi acima de 78% (meio pobre ) e da ordem de 88% (meio rico ). A levedura industrial apresentou eficiência um pouco superior à comercial. As amostras de bagaço (antes e após o pré-tratamento) foram analisadas por microscopia eletrônica de varredura (MEV).

A forma de tratamento e destinação final ainda mundialmente preponderante para os resíduos sólidos urbanos é o aterro sanitário, método que gera, além de uma massa sólida residual, parcialmente estabilizada, subprodutos finais líquidos e gasosos. O efluente líquido, conhecido como lixiviado, necessita tratamento específico, devido a sua elevada nocividade ao meio ambiente, em função, principalmente, de suas elevadas concentrações de nitrogênio amoniacal e de matéria orgânica, em elevado percentual, recalcitrante. O presente trabalho avaliou em escala de bancada o tratamento, via processo físico-químico, através de coagulação-floculação, de lixiviado bruto proveniente de aterro sanitário Central de Resíduos do Recreio (operado pela Companhia Riograndense de Valorização de Resíduos), desprovido de qualquer tratamento prévio, e de lixiviado pré-tratado biologicamente em reatores sequenciais em batelada (RSB). Para o processo de coagulação-floculação foram testados os coagulantes policloreto de alumínio (PAC), cloreto férrico, sulfato férrico e tanino. Sucessivas etapas foram planejadas para a determinação de dosagem e ajuste de pH ótimos, para cada coagulante empregado, e para a verificação da influência de tempos e gradientes de misturas, bem como foi testada a aplicação de polímeros auxiliares de floculação. As variáveis resposta utilizadas para o monitoramento e a avaliação de eficiências foram a cor verdadeira, turbidez (com e sem prévia filtração), DQO, volume de lodo gerado e pH. O uso de reator sequencial em batelada objetivou nitrificação/desnitrificação convencional das elevadas concentrações de nitrogênio amoniacal e eventual oxidação de matéria carbonácea. Verificou-se que os diferentes tempos e gradientes de mistura testados, assim como a utilização de polímeros auxiliares, não produziram impactos nos resultados. Os coagulantes inorgânicos apresentaram elevadas eficiências de remoção, com destaque para o cloreto férrico, o qual na dosagem de 1102 mgFe+3/L e ajuste inicial de pH em 6,2 removeu 98% da cor verdadeira e da turbidez filtrada, 63% da DQO, 40% da DBO5, e 88% de turbidez não filtrada do lixiviado bruto. Apesar da recalcitrância de considerável fração da matéria orgânica do lixiviado, o RSB2 removeu 40% da DQO e 60% da DBO5 originais. A coagulação-floculação do efluente do RSB2 necessitou inferiores dosagens dos coagulantes em relação ao processo com lixiviado bruto. O cloreto férrico, em dosagem ótima de 826 mgFe+3/L e ajuste de pH em 6,3, removeu 95% da cor, 77% da DQO, 82% da DBO5, 94% da turbidez filtrada e 92% da turbidez não filtrada. Concluiu-se por elevada viabilidade técnica do processo de coagulação-floculação para o lixiviado com e sem pré-tratamento, a partir da otimização das condições de contorno do processo. O pré-tratamento em RSB, quando utilizado controle de pH, demonstrou grande potencial para nitrificação/desnitrificação e oxidação de significante parcela da matéria carbonácea do lixiviado bruto. / The form of treatment and disposal still prevalent worldwide for solid waste is the landfill, a method that generates, in addition to a solid mass residual partially stabilized, liquid and gas end products. The effluent liquid, known as leachate, requires specific treatment, due to its high harmfulness to the environment, due mainly to its high concentrations of ammonia nitrogen and organic matter in high percentage, recalcitrant. This study evaluated the treatment on bench scale, via physico-chemical process, by coagulation-flocculation, of raw leachate from Central de Resíduos do Recreio landfill (operated by Companhia Riograndense de Valorização de Resíduos), devoid of any previous treatment, and biologically pretreated leachate reactors in sequential batch reactors (SBR). For the process of flocculation-coagulation were tested polyaluminum chloride (PAC), ferric chloride, ferric sulfate and tannin. Successive stages were designed for determining dosage and optimum pH adjustment for each coagulant employed and for verifying the influence of times and gradients mixtures, as well as tested in the application of polymers flocculation auxiliaries. The answers used for parametric monitoring and evaluation of efficiencies were the true color, turbidity (with and without prior filtration), COD, sludge volume and pH. The use of sequential batch reactor aimed conventional nitrification/denitrification of the high concentrations of ammonia nitrogen and eventual oxidation of carbonaceous matter. It was found that the different gradients and mixing times tested, as well as the use of auxiliary polymers, did not produce impact on the results. The inorganic coagulants showed high removal efficiencies, especially ferric chloride, which at a dose of 1102 mgFe+3/L and initial pH adjusted to 6.2, removed 98% of the true color and filtered turbidity, 63% of COD, 40% of BOD5 and 88% of unfiltered turbidity. Despite the considerable fraction of the recalcitrance of organic matter in the leachate, the SBR2 removed 40% of COD and 60% of BOD5 of the original. The coagulation-flocculation of the effluent from SBR2 required lower dosages of coagulants in relation to the similar process with raw leachate. Ferric chloride in optimum dosage of 826 mgFe+3/L and adjusting pH to 6.3, removed 95% of color, 77% of COD, 82% of BOD5, 94% of the filtered turbidity and 92% of unfiltered turbidity. It was concluded by high technical feasibility of the process of flocculation-coagulation for the leachate with and without pre-treatment, based on the optimization of the boundary conditions of the process. The pre-treatment with SBR, when pH control, demonstrated high potential for nitrification/denitrification and oxidation of a significant portion of the carbonaceous of the raw leachate.