A injeção de carvão pulverizado (PCI — pulverized coal injection) nos altos-fornos (AFs) é uma tecnologia utilizada pelas usinas siderúrgicas para aumentar a produtividade e diminuir o consumo de coque no AF. Nas últimas décadas as taxas de injeção de carvão pulverizado aumentaram na maior parte dos AFs. O principal problema associado à utilização de altas taxas de PCI é a geração de char (carvão incombusto) na zona de combustão. Este material percorre um caminho ascendente junto ao fluxo gasoso, podendo acumular-se e assim prejudicar a permeabilidade do AF. A presença, nas amostras sólidas recolhidas do gás de saída do AF, de altos teores de char pode ser o resultado da injeção de um carvão pulverizado com uma combustibilidade inadequada e de uma operação instável do AF. Portanto, conhecer a proporção de char que sai do AF contribuirá na seleção do tipo de carvão utilizado e na otimização da prática de PCI. Análises químicas das amostras de pó do AF revelam, sem distinguir, a presença de materiais carbonosos. A microscopia ótica foi utilizada para estudar estas amostras sólidas, mas apresenta certas limitações. A difração de raios-X (DRX) é uma técnica padrão para caracterizar a estrutura cristalina dos materiais. Ela também pode ser utilizada para quantificar as dimensões dos cristalitos (Lc, La, etc.) dos materiais carbonosos. Uma vez que a estrutura do coque é mais ordenada que a do char, seria possível quantificar a proporção destes materiais nas amostras de pó do AF através da DRX combinada a análises químicas. O objetivo principal deste trabalho foi identificar e quantificar os componentes carbonosos (char e finos de coque) presentes no pó de balão (PB) do AF, por DRX e análise elementar de carbono. O efeito da temperatura sobre a grafitização do coque também foi avaliado, a fim de identificar a possível origem dos finos de coque gerados no AF. Três amostras de PB coletadas de um AF, uma em operação a coque e duas a PCI, foram selecionadas. Os pós foram fracionados e analisados quimicamente. Após, as frações destas amostras foram moídas, desmineralizadas e analisadas por DRX e análise elementar de carbono. Amostras de char produzidas em laboratório e respectivos carvões foram utilizados como padrões para a quantificação. Amostras de coque foram tratadas termicamente a diferentes temperaturas, sendo posteriormente analisadas por DRX. Este estudo mostrou que a DRX pode ser usada como técnica padrão para identificar as estruturas do char e do coque podendo ser utilizada para quantificar a proporção destes materiais carbonosos no pó de balão do AF. Além disto, observou-se que quanto maior a temperatura de tratamento térmico mais ordenada fica a estrutura cristalina do coque. / In a Blast Furnace (BF), Pulverized coal injection (PCI) is the most popular injection technology used worldwide to reduce coke consumption and to increase the productivity. In the last decades the PCI injection rates raised in the most of BFs. One of the problems during the PCI operation in BF is the unburnt char formation. Higher char levels in the BF stack could impact burden permeability. The off gas BF solid samples contain char, coke fines, metallic oxides, etc. The quantification of the carbonaceous materials content in these samples could be used to improve the PCI performance in operating BF. Chemical analysis in the BF dust samples reveal without differentiates some carbonaceous material. The optical microscopy was used to study these solid samples but with some restrictions. XRD (X-ray diffraction) is a standard means of characterizing the structure of materials. This technique has been utilized to determine the crystallite sizes (Lc, La, etc.), in carbonaceous materials. Since the coke structure is more ordered than the char structure, it would be possible to quantify the proportion of these materials in the off-gas BF samples by chemical analysis in combination with XRD. The aim of this work is to identify and quantify carbonaceous components (coal, char and coke fines) in the flue dust BF samples through the use of the XRD technique and ultimate analysis. Besides, the effect of temperature on coke graphitization will be studied aiming to identify the possible origin of coke fines in the BF dust. Four dusts collected in the off-gas BF, two at all coke and two at PCI operations, were selected for this investigation. The dusts were fractioned and chemically analyzed. After the fractions were grounded, demineralized and analyzed by ultimate analysis and XRD. Besides, were investigated the atomic structure of raw coals and its laboratory char, and raw coke and its laboratory heattreated samples. This study has shown that the XRD technique could be used as a standard procedure to identify the char and coke structures and could be used to quantify the fines proportions of these carbonaceous materials in the BF flue dust. It was concluded that the bigger the annealing temperature the more ordered becomes the atomic coke structure.

Nas etapas de processamento do couro, de limpeza da pele, de recortes e ajuste da espessura do couro, diferentes tipos de resíduos sólidos são gerados. Dentre esses resíduos, os pelos provenientes da etapa de depilação são descartados. Além disso, nas etapas finais do acabamento molhado do couro, em especial no tingimento, são adicionados corantes e outros produtos químicos com o objetivo de dar ao couro características superficiais, como cor e textura, gerando, consequentemente, efluentes de difícil tratamento devido ao potencial recalcitrante dos produtos químicos. O objetivo deste trabalho é apresentar uma alternativa ao uso do pelo proveniente da etapa de depilação, possibilitando assim uma extensão no ciclo de vida deste resíduo como um adsorvente alternativo para remoção de corantes empregados na indústria do couro. O pelo (CHW) foi caracterizado através de microscopia eletrônica de varredura (MEV), espectroscopia de raios X dispersiva de energia (EDS), espectroscopia de infravermelho (FTIR), bem como sua área superficial específica e distribuição de tamanho de poro por análises de BET/BJH. A capacidade de remoção dos corantes Azul Ácido 161 (AB-161) e Preto Ácido 210 (AB-210) em soluções aquosas foi estudada emfaixas de pH de 1,0 a 10,0 e também a dosagem ótima de adsorvente. Nas isotermas de adsorção,o modelo de Liu foi o que melhor apresentou resultados para os dois corantes estudados em todas as temperaturas analisadas (30, 40 e 50ºC) No estudo cinético, o modelo de ordem-geral apresentou o melhor ajuste dos dados, com menor tempo de contato para remoção do corante AB-161 de 600 min com o pelo (CHW) e 90 min com o carvão ativado comercial (CAC), nos valores de pH 3,0 e pH 4,0, respectivamente. Para o corante AB-210 o menor tempo de contato para atingir o equilíbrio foi de 120 min e 90 min para CHW e o CAC, nos valores ótimos de pH de 2,0 e 4,0, respectivamente. O carvão produzido (AC-CHW) a partir do pelo residual foi ativado com H3PO4, caracterizado e testado em efluentes reais para remoção dos corantes Laranja Ácido 142 (AO-142) e Marrom Ácido 414 (AB-414). O carvão produzido apresentou um elevado diâmetro de poro (140,70 A), o que favoreceu a adsorção de moléculas maiores e mais complexas, como as presentes nos efluentes reais. Através do MEV e do FTIR observou-se a presença dos compostos estudados no AC-CHW após aadsorção, onde os resultados indicaram que os grupos funcionais de -CH=CH- participaram ativamente do processo de remoção. O pHzero obtido do AC-CHWfoi de 3,65, o que favoreceu a remoção desses compostos já que o efluente real apresenta um pH inferior a 4,0. Os percentuais de remoção obtidos de área sob as curvas de adsorção indicam uma remoção de 51,94% e 49,73% dos efluentes contendo AB-414 e AO-142, respectivamente. / In the stages of leather processing, skin cleansing, trimming and leather thickness adjustment, different types of solid waste are generated. Among these residues, hairs from the depilation stage are discarded. In addition, in the final stages of the wet finishing of leather, in particular in dyeing, dyes and other chemical products are added with the aim of giving the leather surface characteristics, such as color and texture, thus generating effluents that are difficult to treat due to the potential recalcitrant of chemicals. The objective of this work is to present an alternative to the use of hair from the depilation stage, thus allowing an extension in the life cycle of this residue as an alternative adsorbent for the removal of dyes used in the leather industry. The hair (CHW) was characterized by scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), infrared spectroscopy (FTIR), as well as its specific surface area and pore size distribution by analysis of BET/BJH. The ability to remove Acid Blue 161 (AB-161) and Acid Black 210 (AB-210) dyes in aqueous solutions was studied in pH ranges from 1 to 10 and also the optimum dosage of adsorbent. In the adsorption isotherms, Liu model presented the best results for the two dyes studied at all temperatures (30, 40 and 50ºC). In the kinetic study, the general-order model presented the best fit of the data, with a lowest contact time to remove the AB-161 dye of 600 min with the hair (CHW) and 90 min with the commercial activated charcoal (CAC) at pH 3.0 and pH 4.0, respectively For the dye AB-210, the lowest contact time to reach equilibrium was 120 min and 90 min for CHW and CAC, at the optimum pH values of 2.0 and 4.0, respectively. The charcoal produced (AC-CHW) from the residual was activated with H3PO4, characterized and tested in actual effluents to remove the Acid Orange 142 (AO-142) and Acid Brown 414 (AB-414) dyes. The carbon produced had a high pore diameter (140,70 A), which favored the adsorption of larger and more complex molecules, such as those present in the actual effluents. The presence of the compounds studied in the AC-CHW after adsorption was observed through the SEM and the FTIR, where the results indicated that the functional groups of -CH = CH- actively participated in the removal process. The obtained pHzero of AC-CHW was 3.65, which favored the removal of these compounds since the actual effluent had a pH lower than 4.0. The percentages of removal obtained from area under the adsorption curves indicate a 51.94% and 49.73% removal of the effluents containing AB-414 and AO-142, respectively.

A injeção de carvão pulverizado (PCI — pulverized coal injection) nos altos-fornos (AFs) é uma tecnologia utilizada pelas usinas siderúrgicas para aumentar a produtividade e diminuir o consumo de coque no AF. Nas últimas décadas as taxas de injeção de carvão pulverizado aumentaram na maior parte dos AFs. O principal problema associado à utilização de altas taxas de PCI é a geração de char (carvão incombusto) na zona de combustão. Este material percorre um caminho ascendente junto ao fluxo gasoso, podendo acumular-se e assim prejudicar a permeabilidade do AF. A presença, nas amostras sólidas recolhidas do gás de saída do AF, de altos teores de char pode ser o resultado da injeção de um carvão pulverizado com uma combustibilidade inadequada e de uma operação instável do AF. Portanto, conhecer a proporção de char que sai do AF contribuirá na seleção do tipo de carvão utilizado e na otimização da prática de PCI. Análises químicas das amostras de pó do AF revelam, sem distinguir, a presença de materiais carbonosos. A microscopia ótica foi utilizada para estudar estas amostras sólidas, mas apresenta certas limitações. A difração de raios-X (DRX) é uma técnica padrão para caracterizar a estrutura cristalina dos materiais. Ela também pode ser utilizada para quantificar as dimensões dos cristalitos (Lc, La, etc.) dos materiais carbonosos. Uma vez que a estrutura do coque é mais ordenada que a do char, seria possível quantificar a proporção destes materiais nas amostras de pó do AF através da DRX combinada a análises químicas. O objetivo principal deste trabalho foi identificar e quantificar os componentes carbonosos (char e finos de coque) presentes no pó de balão (PB) do AF, por DRX e análise elementar de carbono. O efeito da temperatura sobre a grafitização do coque também foi avaliado, a fim de identificar a possível origem dos finos de coque gerados no AF. Três amostras de PB coletadas de um AF, uma em operação a coque e duas a PCI, foram selecionadas. Os pós foram fracionados e analisados quimicamente. Após, as frações destas amostras foram moídas, desmineralizadas e analisadas por DRX e análise elementar de carbono. Amostras de char produzidas em laboratório e respectivos carvões foram utilizados como padrões para a quantificação. Amostras de coque foram tratadas termicamente a diferentes temperaturas, sendo posteriormente analisadas por DRX. Este estudo mostrou que a DRX pode ser usada como técnica padrão para identificar as estruturas do char e do coque podendo ser utilizada para quantificar a proporção destes materiais carbonosos no pó de balão do AF. Além disto, observou-se que quanto maior a temperatura de tratamento térmico mais ordenada fica a estrutura cristalina do coque. / In a Blast Furnace (BF), Pulverized coal injection (PCI) is the most popular injection technology used worldwide to reduce coke consumption and to increase the productivity. In the last decades the PCI injection rates raised in the most of BFs. One of the problems during the PCI operation in BF is the unburnt char formation. Higher char levels in the BF stack could impact burden permeability. The off gas BF solid samples contain char, coke fines, metallic oxides, etc. The quantification of the carbonaceous materials content in these samples could be used to improve the PCI performance in operating BF. Chemical analysis in the BF dust samples reveal without differentiates some carbonaceous material. The optical microscopy was used to study these solid samples but with some restrictions. XRD (X-ray diffraction) is a standard means of characterizing the structure of materials. This technique has been utilized to determine the crystallite sizes (Lc, La, etc.), in carbonaceous materials. Since the coke structure is more ordered than the char structure, it would be possible to quantify the proportion of these materials in the off-gas BF samples by chemical analysis in combination with XRD. The aim of this work is to identify and quantify carbonaceous components (coal, char and coke fines) in the flue dust BF samples through the use of the XRD technique and ultimate analysis. Besides, the effect of temperature on coke graphitization will be studied aiming to identify the possible origin of coke fines in the BF dust. Four dusts collected in the off-gas BF, two at all coke and two at PCI operations, were selected for this investigation. The dusts were fractioned and chemically analyzed. After the fractions were grounded, demineralized and analyzed by ultimate analysis and XRD. Besides, were investigated the atomic structure of raw coals and its laboratory char, and raw coke and its laboratory heattreated samples. This study has shown that the XRD technique could be used as a standard procedure to identify the char and coke structures and could be used to quantify the fines proportions of these carbonaceous materials in the BF flue dust. It was concluded that the bigger the annealing temperature the more ordered becomes the atomic coke structure.

Les essais de gazéification effectués dans le cadre de cette étude ont été réalisés à l’aide d’une installation instrumentée et équipée d’un réacteur à lit fixe en utilisant du dioxyde de carbone d’une part, et de la vapeur d’eau d’autre part, comme réactifs. Dans cette étude, nous avons considéré le procédé de gazéification étagée. Par ailleurs, l’étude concernant la disponibilité de la ressource, effectuée sur dix ans, nous a permis de sélectionner deux résidus agricoles, en tenant compte de leur disponibilité dans le temps, l’absence de conflit nutritionnel ainsi que de leurs caractéristiques physicochimiques... A l’issue de cette étude, deux résidus agricoles ont été sélectionnés : les balles de riz et les rafles de maïs. L’étude de la pyrolyse de ces deux biomasses a été effectuée dans un four à moufle à une température de 450 °C pour un temps de séjour de 45 minutes. Un modèle mathématique basé sur la méthode de Newton a été proposé pour estimer le rendement en cokes des balles de riz et des rafles de maïs en fonction de la température, pour un temps de séjour fixé. Nous avons également procédé à une caractérisation physicochimique de ces deux résidus agricoles ainsi que de leurs cokes de pyrolyse. Plusieurs essais de pyrolyse ont également été réalisés en ATG afin de déterminer l’ordre réel des réactions de décomposition, par pyrolyse, de ces deux biomasses, en fonction de la température. Pour les essais de gazéification, ils ont été réalisés sur le coke de pyrolyse des deux biomasses retenues, à l’aide d’une installation équipée d’un réacteur à lit fixe d’une part, ainsi que par analyse thermogravimétrique d’autre part. Plusieurs modèles cinétiques (VRM, SCM et RPM) ont été utilisés pour modéliser la cinétique de gazéification des balles de riz et des rafles de maïs avec du dioxyde de carbone et de la vapeur d’eau. Il ressort que le modèle RPM est le plus adapté des trois modèles étudiés pour simuler au mieux la gazéification du charbon de balles de riz et de rafles de maïs dans les conditions opératoires étudiées dans la présente étude. Ainsi, les énergies d’activation obtenues sont respectivement de 165,8 kJ/mol et de 152,9 kJ/mol avec le dioxyde de carbone et la vapeur d’eau pour les balles de riz pendant que le facteur exponentiel varie de 2595.4 s-1 à 3473.4 s-1 avec des valeurs respectives du paramètre structural Ψ=3,8 pour la réaction de Boudouard et Ψ= 2.16 pour la vapogazéification. Cependant, les énergies d’activation obtenues pour les rafles de maïs sont respectivement de 114,4 kJ/mol et de 105,5 kJ/mol avec le dioxyde de carbone et la vapeur d’eau pendant que le facteur exponentiel varie de 13,9 s-1 à 18,3 s-1avec des valeurs respectives du paramètre structural Ψ=12,3 pour la réaction de Boudouard et Ψ= 8,68 pour la vapogazéification. / The gasification tests in this study were carried out using an instrumented installation equipped with a fixed bed reactor using carbon dioxide and water steam, as reagents. In this study, we considered the stepped gasification process. In addition, the ten-year resource availability study allowed us to select two agricultural residues, taking into account their availability over time, the absence of nutritional conflict and their physicochemical characteristics… At the end of this study, two agricultural residues were selected: rice husks and corn cobs. The pyrolysis of these two biomasses was carried out in a muffle furnace at a temperature of 450 °C for a residence time of 45 minutes. A mathematical model based on the Newton method has been proposed to estimate the coke yield of rice husk and corn cobs as a function of temperature, for a fixed residence time. We also carried out a physicochemical characterization of these two agricultural residues as well as their pyrolysis cokes. Several pyrolysis tests have also been carried out in ATG in order to determine the real order of the decomposition reactions by pyrolysis, of these two biomasses, as a function of temperature. For the gasification tests, they were carried out on the pyrolysis coke of the two retained biomasses, using an installation equipped with a fixed-bed reactor on the one hand, and by thermogravimetric analysis of another hand. Several kinetic models (VRM, SCM and RPM) were used to model the gasification reaction kinetics of rice husk and corn cobs with carbon dioxide and water steam. It appears that the RPM model is the most suitable of the three models studied to best simulate the gasification reaction of char from rice husk and corn cobs under the operating conditions studied in this study. Thus, the activation energies obtained are respectively 165.8 kJ/mol and 152.9 kJ/mol with carbon dioxide and water steam for rice husk while the exponential factor varies from 2595.4 s-1 to 3473.4 s-1 with respective values of the structural parameter Ψ = 3.8 for the Boudouard reaction and Ψ = 2.16 for the water steam gasification. However, the activation energies obtained for corn cobs are 114.4 kJ/mol and 105.5kJ/mol respectively with carbon dioxide and water steam while the exponential factor varies from 13.9 s-1 to 18.3 s-1 with respective values of the structural parameter Ψ = 12.3 for the Boudouard reaction and Ψ = 8.68 for the water steam gasification.

Previous studies suggest that global warming threatens populations of Arctic char (Salvelinus alpinus L.) and that interspecific competition from brown trout (Salmo trutta L.) can have negative effects when the species occur in sympatry. The aim of this study was to investigate if populations of Arctic char have declined in the last decades in lakes where they in the past have coexisted with brown trout. I examined this by revisiting five lakes previously sampled in the mountain region of Västerbotten (Sweden) during the 1960´s. This study repeated earlier sampling methods and examined the population size, biomasses and individual size and weight of all fish. Results showed increased abundances of brown trout and a trend towards declining Arctic char populations in the five lakes. Both Arctic char and brown trout currently had higher mean lengths than previous sampling years. This study also examined the diet and growth rate of both species. The diet analysis showed that the species to some extent overlapped in diet, while they also showed clear differences, where Arctic charr e.g. consumed more pelagic zooplankton. The growth rate was higher for Arctic char and differed between lakes. The shift towards more brown trout dominated lakes could depend on both that the two species are differently affected by a warmer climate, and that fishing habits have changed since the 1960´s. A warmer climate likely changed the species interaction in favor of trout and could lead to more competition and predation on Arctic char.

This dissertation investigates the effects of autocorrelation on the performances of various sampling plans for control charts in detecting special causes that may produce sustained or transient shifts in the process mean and/or variance. Observations from the process are modeled as a first-order autoregressive process plus a random error. Combinations of two Shewhart control charts and combinations of two exponentially weighted moving average (EWMA) control charts based on both the original observations and on the process residuals are considered. Three types of sampling plans are investigated: samples of n = 1, samples of n > 1 observations taken together at one sampling point, or samples of n > 1 observations taken at different times. In comparing these sampling plans it is assumed that the sampling rate in terms of the number of observations per unit time is fixed, so taking samples of n = 1 allows more frequent plotting. The best overall performance of sampling plans for control charts in detecting both sustained and transient shifts in the process is obtained by taking samples of n = 1 and using an EWMA chart combination with a observations chart for mean and a residuals chart for variance. The Shewhart chart combination with the best overall performance, though inferior to the EWMA chart combination, is based on samples of n > 1 taken at different times and with a observations chart for mean and a residuals chart for variance. / Ph. D.

Работа посвящена изучению проблематики интерпретации и перевода поэзии французского поэта и участника Сопротивления Рене Шара. Материал исследования составили шесть его стихотворений из поэтического сборника «Fureur et mystère». В первой части работы рассматривается поэтика Рене Шара. Сначала приводится краткая биография поэта для понимания основных тем его творчества. Затем на примере отдельных стихотворений рассматриваются четыре поэтические формы, доминирующие в творчестве поэта: стихотворение в прозе, верлибр, фрагмент и песня. Во второй части работы рассматриваются две классификации поэтических переводов, необходимые для дальнейшего исследования, а также шесть принципов перевода, выделенных переводчиком и теоретиком перевода С. Ф. Гончаренко. Затем анализируются некоторые опубликованные переводы стихотворений Рене Шара, выполненные М. Н. Ваксмахером, С. Ф. Гончаренко, В. М. Козовым, М. П. Кудиновым и А. В. Марковым. Производится попытка оценить, насколько эти переводы адекватны оригиналу. Переводные тексты отбирались по следующим критериям: максимальная герметичность, сложный ритм, нерегулярная рифма и интертекстуальность. В третьей части работы приводится анализ шести стихотворений Рене Шар и их перевод. К переведенным стихотворениям составлен комментарий, отображающий возможные пути интерпретации данных текстов и, соответственно, обоснование избираемой стратегии перевода. Представлен алгоритм работы над текстом, учитывающий особенности поэтики Рене Шара: сначала предпринимается попытка дешифровки текстов с учетом биографии поэта и историко-культурного контекста создания стихотворений, затем рассматриваются особенности передачи ритма, рифмы, фоники, лексики и синтаксиса оригинала на русский язык. Результаты исследования могут быть использованы при дальнейшей работе над переводами стихотворений Рене Шара. / The current thesis deals with the problems of interpretation and translation of poetic works of the French poet and the participant of the Resistance, René Char. The study focuses on six of his poems from the poetic collection “Fureur et mystère”. The first part of the work is devoted to the poetics of René Char’s verse. It opens with a short biography, providing some insight into where the main themes of his work may proceed from. Consequently, by example of selected poems, four poetic forms that dominate the poet’s work are considered: a poem in prose, a vers libre, a poetic fragment, and a song. In the second part of the paper, two theories of poetic translations are considered, which are necessary for further research, as well as six translation principles, formulated by the translator and translation theorist S.F. Goncharenko. Further, some published translations from the René Char’s oeuvre, performed by M.N. Vaksmakher, S.F Goncharenko, V.M. Kozov, M.P. Kudinov and A.V. Markov are analyzed. An attempt is made to assess whether these translations are adequate to the original. The translated texts were selected according to the following criteria: maximum “hermiticity”, complex rhythm, irregular rhyme and intertextuality. The third part of the work provides analysis of the six pre-selected poems by René Char and their translation. The translations are complemented by a commentary that reflects the possible ways of interpreting these texts and, accordingly, the rationale for the chosen translation strategy. The algorithm of text interpretation, taking into account the features of René Char’s poetics, is introduced: first, an attempt for deciphering the texts, with account for the poet’s biography and the historical and cultural context of poems in made, then the features of rhythm, rhyme, phonics, lexicon, and syntax of the original are translated into Russian. The results of the research can be used in further work on the translation of poems by René Char.

The effect of HZSM-5 catalyst and NaOH pretreatment on the product distribution and bio oil properties from pyrolysis of cellulose, hemicellulose and lignin model compounds was investigated at 450 °C. NaOH pretreated and untreated cellulose was pyrolyzed on sand and the HZSM-5 catalysts; VPISU001 HZSM-5, BASF HZSM-5, and Sud-Chemie HZSM-5. The pyrolysis of cellulose on BASF and Sud-Chemie HZSM-5 catalysts increased the yields of the organic liquid fraction, total liquid and char while decreasing the gas yields. However the catalyst decreased the organic and char yields while increasing the water yields but there was no change in gas yields. The NaOH treatment caused a decrease in the organic and total oil yields relative to the control but the char yield increased. The change in gas yields was not significant. The characterization of the oils using FTIR and ¹³C−nmr showed that, the VPISU001 HZSM-5 with and without NaOH pretreatment caused elimination of the levoglucosan fraction while increasing the aromatic fraction. The NaOH pretreated cellulose pyrolyzed on sand reduced the levoglucosan groups while increasing the aromatic fraction of the bio oil. In the hemicellulose studies, birchwood xylan and NaOH treated xylan samples were pyrolyzed on sand and VPISU001 HZSM-5 catalyst. The organic liquid yields were very low and ranged from 3.3 wt% to 7.2 wt%, the water yields ranged from 17.8-25.7 wt%, the char yield were 17.8-25 wt% and gas yield were 40.9-49.6 wt%. The HZSM-5 catalysts increased the water and gas yields and produced the lowest char yield. NaOH pretreatment produced the lowest water yield while the char yield was the highest. The combined effect of NaOH pretreatment and HZSM-5 produced the lowest organic yield and highest char yield. The FTIR and ¹³C-nmr analyses of the organic liquids showed that the HZSM-5 catalyst promoted the formation of aromatic products, while the NaOH pretreatment promoted the formation of aliphatic hydrocarbons. The combined effect of NaOH pretreatment and HZSM-5 catalyst seem to promote the formation of anhydrosugars. The main gases evolved were CO, CO₂ and low molecular weight hydrocarbons. The HZSM-5 catalyst promoted CO formation while NaOH pretreatment promoted CO₂. The HZSM-5 catalyst produced the highest yield of low molecular weight hydrocarbon gases. The lignin and model compounds studies involved using low molecular weight kraft lignin, guaiacol, and syringol which were pyrolyzed on sand and VPISU001 HZSM-5 catalyst at 450 °C. The kraft lignin pyrolysis produced low liquid and gas yields and high char yields. The HZSM-5 catalysts increased the water yield and decreased the organic liquid yield. NaOH pretreatment increased the char yield and decreased the liquid products. NaOH and the HZSM-5 catalyst together decreased the char and increased the gas yields. The ¹³C-nmr and FTIR analysis showed that NaOH pretreatment promoted the formation of mainly guaiacol while the HZSM-5 catalyst formed different aromatic components. NaOH pretreatment promoted the formation of more CO₂ than CO whilst HZSM-5 catalyst promoted the formation of more CO than CO₂. Methane formation was enhanced by NaOH pretreatment. Other hydrocarbon gases were however enhanced by the HZSM-5 catalysts. Pyrolysis of the model compounds on the HSZM-5 catalyst showed an increase in pyrolytic water. The HZSM-5 catalyst promoted demethylation in syringol pyrolysis as compared to guaiacol. / Master of Science

The effects of adding a biodegradable litter amendment (AmmoSoak), developed from steam exploded corncobs, to poultry litter prior to pyrolysis on the product yields and qualities were investigated. Mixtures of litter and AmmoSoak were pyrolyzed in a bench-scale fluidized bed reactor. The objective of the second phase was to start-up a pilot-scale fluidized bed reactor unit. The poultry litter had a lower higher heating value (HHV), higher moisture, ash, nitrogen, sulfur, and chlorine contents than AmmoSoak. Analysis of the poultry litter indicated a mixture of volatiles, hemicelluloses, cellulose, lignin, ash, and proteins. AmmoSoak had a simpler composition than the litter; mainly hemicelluloses, cellulose, and lignin. Bench-scale studies indicated that adding AmmoSoak affected the yields and characteristics of the products. Addition of Ammosoak increased the bio-oil and syngas yields and decreased char yields. Adding AmmoSoak to the feed decreased the pH, water contents, initial viscosity, and the rate at which the viscosity increased with time, while densities and HHVs increased. The addition of Ammosoak to poultry litter also increased the carbon and oxygen contents of the boi-oils while nitrogen, hydrogen, sulfur, chlorine and ash contents decreased. A pilot-scale fluidized bed reactor was designed, constructed, installed and investigated for the pyrolysis of poultry litter. Fluidization and thermal equilibrium of the reactor were successfully demonstrated. The reactor was heated by combustion of propane. To ensure complete combustion, the combustion water was collected and compared to the stoichiometric yield. Complete combustion was achieved. Bio-oil yields on the pilot scale were lower than those obtained on the bench-scale pyrolysis unit. The water soluble fractions of the bio-oils were rich in oxygen. Water insoluble fractions were rich in carbon and ash. / Master of Science

<p>U doktorskoj disertaciji vr&scaron;eno je istraživanje mogućnosti konverzije energije<br />različitih vrsta drvne biomase procesom pirolize. Ispitivanu drvnu biomasu<br />predstavljale su strugotina hrasta, bukve, tre&scaron;nje, oraha, jele, lipe, kao i<br />me&scaron;avina navedenih vrsta. Dobijeni eksperimentalni rezultati ukazuju da<br />prinos gasa, tečne i čvrste faze tokom odvijanja procesa pirolize zavise od<br />reakcionog vremena, temperature i brzine zagrevanja.</p> / <p>Doctoral dissertation investigates possibilities for energy conversion of<br />different woody biomass types through pyrolysis process. Investigated woody<br />biomass included oak, beech, cherry, walnut, fir, lime wood chips and their<br />mixture. Obtained experimental results imply that gas, liquid and solid phase<br />yields during pyrolysis process depend on reaction time, temperature and<br />heating rate.</p>