Orientador: Jose Vicente Hallak d'Angelo / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Quimica / Made available in DSpace on 2018-08-09T15:39:11Z (GMT). No. of bitstreams: 1 Santos_PauloRenatodos_M.pdf: 964248 bytes, checksum: 21cab8449ad59d56ad3ec7f876ee846d (MD5) Previous issue date: 2007 / Resumo: O setor de papel e celulose gera a maior parte da energia consumida em seus processos pela queima de dois combustíveis: biomassa e licor negro, sendo este último o mais utilizado entre eles. O setor vem ao longo dos anos utilizando sistemas de cogeração, que geram energia elétrica para o processo a partir da queima desses combustíveis. Nos últimos anos o setor vem tendo um aumento crescente em sua produção e com isso vem sendo gerada uma grande quantidade de licor negro, formando gargalos na unidade de recuperação (evaporação e caldeira de recuperação). Problemas como corrosão, incrustação e perigo de explosões na planta vêm se tornando realidade nesses anos. Outro fator é o tempo de vida útil das caldeiras de recuperação que vem se esgotando em várias indústrias brasileiras. Diante desse contexto, sobre crescente consumo de energia elétrica, aumento de produção de papel e celulose e maior quantidade de resíduos gerados, a gaseificação de licor negro se torna uma proposta interessante como processo alternativo. Foi analisado um sistema de cogeração de energia a partir da gaseificação do licor negro, como forma de avaliar a viabilidade técnica de se utilizar esse processo em substituição ao processo tradicional utilizado para geração de vapor de processo e energia elétrica. Para isso foi realizada uma simulação do sistema de cogeração em um simulador comercial (HYSYS© 2.2 daHyprotech), avaliando a influência da composição dos gases obtidos no gaseificador sobre as perdas exergéticas no sistema de cogeração. São apresentados os modelos para o sistema de gaseificação através de balanços de massa, energia e exergia, verificando e quantificando as irreversibilidades do ciclo. Os resultados obtidos demonstraram que a composição dos gases gerados no gaseificador tem grande influência sobre o processo, principalmente com relação à presença de água, hidrogênio e monóxido de carbono. Isso pôde ser verificado pelas perdas exergéticas analisadas, sendo o combustor o detentor das maiores perdas do processo. A gaseificação de licor negro é uma tecnologia ainda incipiente e relativamente nova e sua plena utilização nos processos industriais ainda requer estudos mais detalhados. Porém ela vem se tornando cada vez mais atraente e estudos no sentido de avaliar melhor sua viabilidade pode ser importante para que, num futuro próximo, essa tecnologia seja definitivamente implementada / Abstract: The pulp and paper industries generate most part of energy for self consumption burning two different fuels: biomass and black liquor, which is more used than the first one. This industrial sector has been used cogeneration systems, to produce electric energy from the combustion of these fuels. In the last years an increase in the production of the industries has caused an increase in the amount of black liquor available for burning, generating a bottlenecking effect in the recovery unit (evaporators and recovery boiler). Operational problems due to corrosion, fouling and explosions risks have aroused because of this great production of black liquor. Another important factor parallel to this is the lifetime of recovery boilers which is near to its end in many brazilian pulp and paper industries. In this scenario of increasing in electric energy consumption and pulp and paper production, generating more industrial residues, the black liquor gasification process has become an interesting alternative to use the excess of black liquor produced in the industries to produce more energy or as a substitute for the traditional recovery boilers. In this work an energy cogeneration system from gasification of black liquor was studied in order to evaluate the technical viability of using this process to replace the traditional one used to produce process vapor and electric energy. To do this a simulation of the cogeneration system was performed in a commercial simulator (HYSYS© 2.2 from Hyprotech), analyzing the influence of the composition of the gas stream from the gasificator over the exergetic losses in the cogeneration system. Mass, energy and exergy balances are presented for the system studied, verifying the irreversibilities of the cycle. The results obtained have shown that the composition of the gases produced in the gasificator has a great influence over the exergy balance of the process, mainly related with the presence of water, hydrogen and carbon monoxide. This was verified buy an exergetic analysis, that has shown that the greatest losses occur in the combustion chamber of the gases. Black liquor gasification process is an incipient and relatively new technology and its full usage in industrial scale still requires more detailed researches. Despite of this, it is becoming more and more attractive and any study that contributes to evaluate its viability may be important to help in the consolidation of this technology / Mestrado / Sistemas de Processos Quimicos e Informatica / Mestre em Engenharia Química

The last couple of decades have seen entrained-flow gasification of black liquor (BL) undergo an incremental process of technical development as an alternative to combustion in a recovery boiler. The ability of the technology to combine chemical recovery with the production of clean syngas renders it a promising candidate for the transformation of chemical pulp mills into integrated forest biorefineries. However, techno-economic assessments have shown that blending BL with the more easily transportable pyrolysis oil (PO) can not only increase the system efficiency for methanol production but remove a significant roadblock to development by partially decoupling production capacity from limitations on black liquor availability. The verification and study of catalytic co-gasification in an industrially-relative scale can yield both scientifically interesting and practically useful results, yet it is a costly and time-consuming enterprise. The expense and time involved can be significantly reduced by performing thermodynamic equilibrium calculations using a model that has been validated with relevant experimental data. The main objective of this thesis was to study, understand, quantify and compare the gasification behaviour and process performance of black liquor and pyrolysis oil blends in pilot-scale. A secondary objective of this work was to demonstrate and assess the usefulness and accuracy of unconstrained thermodynamic equilibrium modelling as a tool for studying and predicting the characteristics of alkali-impregnated biomass entrained-flow gasification. The co-gasification of BL/PO blends was studied at the 3 MWth LTU Green Fuels pilot plant in a series of experimental studies between June 2015 and April 2016. The results of the studies showed that the blending of black liquor with the more energy rich pyrolysis oil increased the energetic efficiency of the BLG process without adversely affecting carbon conversion. The effect of blend ratio and reactor temperature on the gasification performance of PO and BL blends with up to 20 wt% PO was studied in order to assess the impact of alkali-dilution in fuel on the conversion characteristics. In addition to unblended BL, three blends with PO/BL ratios of 10/90, 15/85 and 20/80 wt% were gasified at a constant load of 2.75 MWth. The decrease in fuel inorganic content with increasing PO fraction resulted in more dilute green liquor (GL) and a greater portion of the feedstock carbon ended up in syngas as CO. As a consequence, the cold gas efficiency increased by about 5%-units. Carbon conversion was in the range 98.8-99.5% and did not vary systematically with either fuel composition or temperature. The validation of thermodynamic equilibrium simulation of black liquor and pyrolysis co-gasifications with experimental data revealed the need to be mindful of errors and uncertainities in fuel composition that can influence predictions of equilibrium temperature. However, provided due care is to taken to ensure the use of accurate fuel composition data, unconstrained TEMs can serve as a robust and useful tool for simulating catalytic entrained-flow gasification of biomass-based feedstocks. / LTU Biosyngas (Catalytic Gasification)

Biomass is the only renewable carbon source that can compete with fossil energy sources in terms of production of materials, chemicals and fuels. Biomass can be transformed into charcoal, liquid and gas through pyrolysis, i.e. pure thermal decomposition. By changing the pyrolysis conditions either solid, liquid or gaseous fractions can become the main product and pyrolysis is thus a very versatile process. Pyrolysis is also the first step in combustion and gasification, two important thermal processes in our society. The importance of biomass pyrolysis has led to extensive research in this area but due to the complexity of the process there is still no general understanding of how to describe biomass pyrolysis, which is essential in order to optimize thermal processes. The research presented in this thesis thus aims at finding a simple yet accurate way to model the decomposition rate of biomass during pyrolysis. Thermogravimetric analysis, a well known method that is simple to use, was chosen to collect the experimental data used for kinetic evaluation. The reaction kinetics were derived using two different model-free, isoconversional methods, i.e. the non-linear form of the Friedman method and the incremental, integral method ofVyazovkin. By using these two methods and experimental data, complete reactionrate expressions could be derived for commercial cellulose, Norway spruce and seven different samples originating from kraft cooking, the most common process to produce pulp for the paper industry. The derivation of model-free rate expressions have never been performed before for these materials and since the rate expressions are model-free, no assumptions or knowledge about the pyrolysis reactions were required. This is a great advantage compared to the commonly used model-fitting methods that rely on information about these aspects. All therate expressions were successful in predicting mass-loss rates at extrapolated pyrolysis conditions. This is a clear indication of the soundness of the methodologypresented in this thesis. / Biomassa är den enda förnybara kolkällan som kan konkurrera med fossila energikällor när det gäller produktion av material, kemikalier och bränslen. Biomassakan omvandlas till biokol, bioolja och gas med hjälp av pyrolys, dvs termisk nedbrytning. Genom att variera de processförhållanden som råder under pyrolysen kan man få antingen fast, flytande eller gasfasiga ämnen som huvudprodukt, något som gör pyrolys väldigt flexibelt. Utöver detta är pyrolys även betydelsefull vid förbränning och förgasning, två viktiga processer i dagens samhälle. Vikten av biomassapyrolys har resulterat i omfattande forskning inom området men pga biomassas komplexa natur råder det ännu ingen enighet gällande hur biomassapyrolys bör modelleras. Detta försvårar utveckling och optimering av termiska processer matade med biomassa. Forskningen som presenteras i denna avhandling fokuserar således på att finna en enkel men noggrann metod för att beskriva hastigheten med vilken biomassa bryts ned under pyrolys. Termogravimetrisk analys, en vanligt förekommande metod som är enkel att använda, valdes för att samla in experimentell data som kan användas för att undersöka hastigheten för termisk nedbrytning, dvs kinetiken. Två olika metoder som på engelska går under benämningen “model-free” och “isoconversional” har använts, nämligen den icke-linjära formen av Friedmans metod och den stegvisa, integrala metoden som utvecklats av Vyazovkin. Genom att använda dessa två metoder och experimentell data kunde kompletta reaktionshastighetsuttryck tas fram för kommersiell cellulosa, gran och sju olika material framställda genom sulfatprocessen, den idag vanligast förekommande pappersmassaprocessen. Pyrolyskinetiken för dessa material har aldrig tidigare analyserats med dessa två metoder och fördelarna med metoderna gjorde det möjligt att bestämma hastighetsuttryck utan någon kunskap om de pågående reaktionerna. Detta är en viktig fördel jämfört med andra metoder som är beroende av sådan information. Alla framtagna reaktionshatighetsuttryck kunde användas för att framgångsrikt förutsäga minskningen av massa vid extrapolerade pyrolysförhållanden. Detta är en tydlig indikation på att metoden använd i denna avhandling fungerar väl. / <p>QC 20160524</p>

Este estudo teve como objetivo avaliar o desempenho de 2 reatores anaeróbios de fluxo ascendente e manta de lodo (UASB), em escala de bancada, tratando licor negro diluído, durante 635 dias de operação contínua. Durante a Fase I os reatores foram alimentados com licor negro diluído, enriquecido com nutrientes essenciais, simulando os efluentes de uma indústria de pasta celulósica não branqueada. Durante a Fase II, um dos reatores foi alimentado com o mesmo substrato mais uma mistura de cinco compostos organoclorados, simulando os efluentes de uma indústria de pasta celulósica branqueada. O aumento da taxa de carregamento orgânico, na Fase I, de 0,40 kg DQO/dia m3 para 0,70 kg DQO/dia m3 não provocou diminuição da eficiência de remoção de DQO. Por outro lado, o aumento da taxa de carregamento hidráulico de 0,50 m3/dia m3 para 1,00 m3/dia m3 provocou diminuição de aproximadamente 10% na eficiência média de remoção de DQO no reator 1 e em torno de 12% no reator 2. A adição de 15,00 mg/L dos compostos organoclorados, não influenciou significativamente o desempenho do reator. A eficiência média de remoção de DQO na Fase II foi de 82% no reator de controle e de 79% no reator de tratamento. As eficiências médias de remoção dos compostos organoclorados foram de: 99,9% para o 2-clorofenol, 97,5% para o 2,4- diclorofenol, 95,8% para o 2,6-diclorofenol, 98,9% para o 2,4,6-triclorofenol e 92,8% para o tetraclorocatecol. / This research was conducted to assess the performance of two bench scale upflow anaerobic sludge blanket (UASB) reactors used for the treatment of diluted black liquor, over 635 days of continuous operation. During Phase I of the study both reactors were fed with the diluted black liquor enriched with essential nutrients. This substrate simulated the wastewater from unbleached cellulose pulp plant. Progressing in the research, during Phase II, one of the reactors was fed with the same substrate plus a mixture of five chlorinated organic compounds to simulate the wastewater from a bleached pulp plant. The increase in the organic loading rate, during Phase I, from 0.40 kg COD/m3.day to 0.70 kg COD/m3.day did not result in a decrease in the COD removal efficiency. On the other hand, the increase in the hydraulic loading rate from 0.50 m3/day.m3 to 1.00 m3/day.m3 resulted in a decrease of approximately 12 percent points in the average COD removal efficiency in the reactor 1 and approximately 12 percent points in the reactor 2. The addition of 15 mg/L of chlorinated organic compounds did not have a significant influence in the reactor performance in this research. The removal efficiency of COD during the second phase reached 82% in the control reactor and 79% in the treatment reactor. The average removal efficiencies for the chlorinated organic compounds were: 99.9% for 2-chlorophenol; 97.5% for the 2,4-dichlorophenol; 95.8% for the 2,6- dichlorophenol; 98.9% for the 2,4,6-trichlorophenol and 92.9% for the tetrachlorocatechol.

A importância da energia elétrica gerada pelo setor de celulose e papel têm crescido no mercado brasileiro, pois com a crise hídrica que tem causado transtornos financeiros aos diversos setores da economia, muitas empresas têm optado por ter a geração de energia como um novo plano de negócio. Desta forma, para que esta produção cresça são necessários investimentos nessa área. Por isso, é essencial conhecer o processo, bem como os parâmetros envolvidos na produção de energia. Com a finalidade de ampliar os conhecimentos da área de energia dentro do setor de celulose e papel, este trabalho teve como objetivo identificar a relação dos parâmetros das caldeiras de recuperação e biomassa, bem como de seus combustíveis, afim de determinar sua influência na produção de vapor. Para isso, foram utilizados os valores dos parâmetros das caldeiras de recuperação e biomassa, entre eles: consumo de combustível, vazões de ar, temperaturas da água de alimentação e do vapor gerado, como também os valores das características químicas e físicas do licor negro, incluindo poder calorífico superior, teor de sólidos totais, teor de orgânicos e inorgânicos, e da biomassa, densidade aparente, poder calorífico superior, umidade e teor de cinzas. Os parâmetros e as características dos combustíveis foram disponibilizados por uma empresa do setor de celulose e papel do Brasil. Para análise e discussão dos dados foram feitos cálculos de eficiência energética, análise de diagramas de dispersão, correlação de Pearson, elaboração de modelos matemáticos para estimativa de produção de vapor e a determinação dos valores ideais dos parâmetros dos combustíveis, para produção máxima de vapor. A partir das análises de eficiência energética, a caldeira de recuperação manteve uma média de 86%, enquanto que a caldeira de biomassa obteve uma média de 51%. Analisando as relações entre todos os parâmetros, nas caldeiras as variáveis com maior influência na operação foram as vazões de ar, vazão da água de alimentação, o consumo de combustível, temperatura da água de alimentação, temperatura dos gases de saída e a pressão do vapor, enquanto que nos combustíveis a maior influência foi do poder calorífico superior. Dentre os modelos matemáticos analisados para a predição da produção de vapor, apenas o modelo utilizando parâmetros da caldeira de recuperação foi estatisticamente significativo. Através da análise das características dos combustíveis, relacionando-as com o objetivo de obter a máxima produção de vapor, os valores ideais calculados destas características químicas e físicas do licor negro e da biomassa se mantiveram de acordo com a literatura. / The importance of the electric energy generated by the pulp and paper sector has grown in the Brazilian market, because the water crisis has caused financial distress to the various sectors of the economy, and then many companies have chosen to have the power generation as a new business plan. In this way, for this production to grow, investments in this area are necessary. Therefore, it is essential to know the process as well as the parameters involved in energy production. With the purpose of increasing the knowledge of the energy area within the pulp and paper sector, this work aimed to identify the relation of the parameters of recovery and biomass boilers, as well as their fuels, in order to determine their influence in the production of steam. In order to do this, the values of the parameters of the recovery and biomass boilers were used, among them: fuel consumption, air flows, feed water and steam temperatures, as well as the values of the chemical and physical characteristics of the black liquor, including higher calorific value, total solids content, organic and inorganic content, and of biomass, apparent density, higher calorific value, moisture and ash content. The parameters and characteristics of fuels were made available by a Brazilian pulp and paper company. In order to analyze and discuss the data were made energy efficiency calculations, dispersion diagrams analysis, Pearson correlation, mathematical models for estimation of steam production and determination of the ideal values of the fuel characteristics for maximum steam production. From the energy efficiency analyzes, the recovery boiler maintained an average of 86%, while the biomass boiler obtained an average of 51%. Analyzing the relationships among all parameters, the variables with the greatest influence on the operation were air flow, feed water flow, fuel consumption, feed water temperature, outlet gas temperature and steam pressure, while in fuels the greatest influence was the higher calorific value. Among the mathematical models analyzed for the prediction of steam production, only the model using parameters of the recovery boiler was statistically significant. Analyzing the characteristics of the fuels in order to obtain the maximum steam production, the estimated ideal values of these chemical and physical characteristics of black liquor and biomass were kept in agreement with the literature.

Le stéarate de butyle, un matériau de changement de phase biosourcé (MCP), a été encapsulés dans des matrices polymères (pullulane, lignine, hémicelluloses) par la technique des émulsions concentrées. Les matrices polymères ont été réticulées avec du trimetaphosphate de sodium (STMP) dans des conditions alcalines afin d’obtenir un réseau poreux interconnecté rigide. L’influence du processus de séchage sur les matériaux composites obtenus a été étudiée, indiquant la lyophilisation comme la technique la plus efficace. Des études de calorimétrie à balayage différentiel (DSC) ont permis de déterminer que l’encapsulation de stéarate de butyle dans des matrices polymères ne modifiait pas ses propriétés thermiques de changement de phase. Des essais de compression mécanique et de résistance à la déformation ont permis d'évaluer le potentiel des monolithes en tant que panneaux de stockage de chaleur installés directement dans des bâtiments et des serres.Les produits de réticulation par le STMP ont été identifiés et caractérisés par RMN solide du31P. Il a ainsi été possible de synthétiser des monolithes ayant différents taux de réticulation afin d’optimiser la formulation d'encapsulation de MCP. Les matrices polymères vidée de tous leurs contenus liquides ont été étudiées par microscopie électronique à balayage afin d’étudier leur structure poreuse (distribution de taille des pores). Cette nouvelle approche d’encapsulation en une étape apparaît comme efficace et devrait permettre un développement important des applications énergétiques. / Emulsion-templated polymer based (pullulan, lining and hemicelluloses) monoliths encapsulating butyl stearate as bio-based phase change material (PCM) were synthesized. Polymer-bases were crosslinked with sodium trimetaphosphate (STMP) under alkaline aqueous conditions leading to an interconnected porous network. The influence of the drying process on the obtained composite materials morphology was studied indicating freeze-drying as the most effective technique. Differential Scanning Calorimetry (DSC) studies allow to assess that encapsulation of butyl stearate onto matrices do not alter its phase change thermal properties. Mechanical compression and strain resistance tests allowed to evaluate monoliths potential as heat storage panels installed directly in buildings and greenhouses, STMP crosslinking products were identified by solid-NMR characterization, this allowed to synthetize monoliths at different crosslinking yields to find a formulation that improves PCM encapsulation. Polymer matrices were studied by scanning electron microscopy to identify the pore size distribution obtained in STMP crosslinked materials. This new one-step encapsulating approach appears as efficient and cost-effective and is expected to find a broad development in energy storage applications

Made available in DSpace on 2017-07-10T19:24:09Z (GMT). No. of bitstreams: 1 Isamara_ Godoi.pdf: 2059512 bytes, checksum: c7f04b4bfb9d29047a6d89e02a8418e1 (MD5) Previous issue date: 2016-02-15 / Researches concerning the use of biomass lignocellulosic composition for second-generation ethanol production have received special attention as a possible contribution to energy sustainability. Although such activity has mainly used waste from the agricultural industry, it also generates other impactful solid and liquid wastes to the environment because they contain high concentrations of acids, alkaline and toxic elements. Thus, this trial aimed registering chemical characterization and recovering wastes generated in order to obtain a second-generation ethanol, particularly the precipitate produced during detoxification process by overliming hydrolyzed hemicellulose from sugarcane bagasse and liquid waste produced during cellulignin delignification phase in the pre-treatment to make the process of enzymatic saccharification of cellulose easier. Initially, the solid residue was submitted to physical and chemical analyses such as granulometric, analysis of metal compounds, content of inhibitory compounds to microbial activity such as acetic acid, furfural, hydroxymethylfurfural and phenols, sugars and moisture content. Waste potential determination as corrective of soil acidity was carried out by analyzing the attributes of corrective quality in soil (PN, PRNT), Ca and Mg and granulometry). Solid residue was also evaluated for its influence on bacterial communities by traditional microbiological techniques, bioassays with worms and lettuce seed germination. Liquid waste was characterized based on its metal contents present and inhibitory compounds. The lignin present in such liquor was precipitated with sulfuric acid and, after its characterization by infrared spectroscopy, was used as a biosorbent on lead ions adsorption in aqueous solution. The results have suggested that the waste generated during second-generation ethanol obtainment have some potential to become by-products to be applied in agricultural and environmental area. Lastly, the present trial has contributed to the production of bioethanol to be implemented in industry according to lignocellulosic biorefinery concept from an integrated model for a full biomass use in a sustainable management and correct disposal of the generated waste. / Pesquisas sobre o aproveitamento de biomassas de composição lignocelulósica para produção de etanol de segunda geração têm recebido atenção especial como possível contribuição para a sustentabilidade energética. Embora tal atividade utilize principalmente resíduos da agroindústria, gera outros resíduos sólidos e líquidos impactantes para o meio ambiente por conterem alta concentração de elementos ácidos, alcalinos e tóxicos. Por conseguinte, este trabalho visou à caracterização química e ao aproveitamento dos resíduos gerados na obtenção de etanol de segunda geração, em particular o precipitado formado no processo de destoxificação por overliming do hidrolisado hemicelulósico de bagaço de cana-de-açúcar e o resíduo líquido gerado na etapa de deslignificação da celulignina durante o pré-tratamento para facilitar o processo de sacarificação enzimática da celulose. Inicialmente o resíduo sólido foi submetido a análises físico-químicas, granulométrica, análise de metais, ao teor de compostos inibidores para a atividade microbiana, tais como ácido acético, furfural, hidroximetilfurfural e fenóis, açúcares e teor de umidade. A determinação do potencial do resíduo como corretivo da acidez do solo foi realizada através da análise dos atributos da qualidade dos corretivos do solo (PN, PRNT, teores de Ca e Mg e granulometria). O resíduo sólido foi também avaliado quanto à sua influência nas comunidades bacterianas através de técnicas microbiológicas tradicionais, bioensaios com minhocas e testes de germinação de sementes de alface. O resíduo líquido foi caracterizado quanto aos teores de metais presentes e compostos inibidores. A lignina presente no licor foi precipitada com ácido sulfúrico e, após caracterização por espectrometria de infravermelho, utilizada como biossorvente na adsorção de íons chumbo em solução aquosa. Os resultados indicam que os resíduos gerados na obtenção de etanol de segunda geração possuem potencial para se tornarem subprodutos com aplicação na área agrícola e ambiental. Desta forma, o presente trabalho vem a contribuir para a implementação industrial da produção de bioetanol dentro do conceito de biorrefinaria lignocelulósica, a partir de um modelo integrado para completo aproveitamento da biomassa, de forma sustentável e com adequada destinação dos resíduos gerados.

Made available in DSpace on 2017-05-12T14:47:26Z (GMT). No. of bitstreams: 1 Isamara_ Godoi.pdf: 2059512 bytes, checksum: c7f04b4bfb9d29047a6d89e02a8418e1 (MD5) Previous issue date: 2016-02-15 / Researches concerning the use of biomass lignocellulosic composition for second-generation ethanol production have received special attention as a possible contribution to energy sustainability. Although such activity has mainly used waste from the agricultural industry, it also generates other impactful solid and liquid wastes to the environment because they contain high concentrations of acids, alkaline and toxic elements. Thus, this trial aimed registering chemical characterization and recovering wastes generated in order to obtain a second-generation ethanol, particularly the precipitate produced during detoxification process by overliming hydrolyzed hemicellulose from sugarcane bagasse and liquid waste produced during cellulignin delignification phase in the pre-treatment to make the process of enzymatic saccharification of cellulose easier. Initially, the solid residue was submitted to physical and chemical analyses such as granulometric, analysis of metal compounds, content of inhibitory compounds to microbial activity such as acetic acid, furfural, hydroxymethylfurfural and phenols, sugars and moisture content. Waste potential determination as corrective of soil acidity was carried out by analyzing the attributes of corrective quality in soil (PN, PRNT), Ca and Mg and granulometry). Solid residue was also evaluated for its influence on bacterial communities by traditional microbiological techniques, bioassays with worms and lettuce seed germination. Liquid waste was characterized based on its metal contents present and inhibitory compounds. The lignin present in such liquor was precipitated with sulfuric acid and, after its characterization by infrared spectroscopy, was used as a biosorbent on lead ions adsorption in aqueous solution. The results have suggested that the waste generated during second-generation ethanol obtainment have some potential to become by-products to be applied in agricultural and environmental area. Lastly, the present trial has contributed to the production of bioethanol to be implemented in industry according to lignocellulosic biorefinery concept from an integrated model for a full biomass use in a sustainable management and correct disposal of the generated waste. / Pesquisas sobre o aproveitamento de biomassas de composição lignocelulósica para produção de etanol de segunda geração têm recebido atenção especial como possível contribuição para a sustentabilidade energética. Embora tal atividade utilize principalmente resíduos da agroindústria, gera outros resíduos sólidos e líquidos impactantes para o meio ambiente por conterem alta concentração de elementos ácidos, alcalinos e tóxicos. Por conseguinte, este trabalho visou à caracterização química e ao aproveitamento dos resíduos gerados na obtenção de etanol de segunda geração, em particular o precipitado formado no processo de destoxificação por overliming do hidrolisado hemicelulósico de bagaço de cana-de-açúcar e o resíduo líquido gerado na etapa de deslignificação da celulignina durante o pré-tratamento para facilitar o processo de sacarificação enzimática da celulose. Inicialmente o resíduo sólido foi submetido a análises físico-químicas, granulométrica, análise de metais, ao teor de compostos inibidores para a atividade microbiana, tais como ácido acético, furfural, hidroximetilfurfural e fenóis, açúcares e teor de umidade. A determinação do potencial do resíduo como corretivo da acidez do solo foi realizada através da análise dos atributos da qualidade dos corretivos do solo (PN, PRNT, teores de Ca e Mg e granulometria). O resíduo sólido foi também avaliado quanto à sua influência nas comunidades bacterianas através de técnicas microbiológicas tradicionais, bioensaios com minhocas e testes de germinação de sementes de alface. O resíduo líquido foi caracterizado quanto aos teores de metais presentes e compostos inibidores. A lignina presente no licor foi precipitada com ácido sulfúrico e, após caracterização por espectrometria de infravermelho, utilizada como biossorvente na adsorção de íons chumbo em solução aquosa. Os resultados indicam que os resíduos gerados na obtenção de etanol de segunda geração possuem potencial para se tornarem subprodutos com aplicação na área agrícola e ambiental. Desta forma, o presente trabalho vem a contribuir para a implementação industrial da produção de bioetanol dentro do conceito de biorrefinaria lignocelulósica, a partir de um modelo integrado para completo aproveitamento da biomassa, de forma sustentável e com adequada destinação dos resíduos gerados.

<p>Black liquors are presently combusted in recovery boilers where the inorganic cooking chemicals are recovered and the energy in the organic material is converted to steam and electricity. A new technology, developed by Chemrec AB, is black liquor gasification (BLG). BLG has more to offer compared to the recovery boiler process, in terms of on-site generation of electric power, liquid fuel and process chemicals. A prerequisite for both optimization of existing processes and the commercialization of BLG is better understanding of the physical and chemical processes involved including interactions with the refractory lining. The chemistry in the BLG process is very complex and to minimize extensive and expensive time-consuming studies otherwise required accurate and reliable model descriptions are needed for a full understanding of most chemical and physical processes as well as for up-scaling of the new BLG processes. However, by using these calculated model results in practice, the errors in the state of the art thermochemical data have to be considered. An extensive literature review was therefore performed to update the data needed for unary, binary and higher order systems. The results from the review reviled that there is a significant range of uncertainty for several condensed phases and a few gas species. This resulted in experimental re-determinations of the binary phase diagrams sodium carbonate-sodium sulfide (Na2CO3-Na2S) and sodium sulfate-sodium sulfide (Na2SO4-Na2S) using High Temperature Microscopy (HTM), High Temperature X-ray Diffraction (HT-XRD) and Differential Thermal Analysis (DTA). For the Na2CO3-Na2S system, measurements were carried out in dry inert atmosphere at temperatures from 25 to 1200 °C. To examine the influence of pure CO2 atmosphere on the melting behavior, HTM experiments in the same temperature interval were made. The results include re-determination of liquidus curves, in the Na2CO3 rich area, melting points of the pure components as well as determination of the extent of the solid solution, Na2CO3(ss), area. The thermal stability of Na2SO3 was studied and the binary phase diagram Na2SO4-Na2S was re-determined. The results indicate that Na2SO3 can exist for a short time up to 750 °C, before it melts. It was also proved that a solid/solid transformation, not reported earlier, occurs at 675 ± 10 °C. At around 700 °C, Na2SO3 gradually breaks down within a few hours, to finally form the solid phases Na2SO4 and Na2S. From HTM measurements a metastable phase diagram including Na2SO3, as well as an equilibrium phase diagram have been constructed for the binary system Na2SO4-Na2S. Improved data on Na2S was experimentally obtained by using solid-state EMF measurements. The equilibrium constant for Na2S(s) was determined to be log Kf(Na2S(s)) (± 0.05) = 216.28 – 4750(T/K)–1 – 28.28878 ln (T/K). Gibbs energy of formation for Na2S(s) was obtained as ΔfG°(Na2S(s))/(kJ mol–1) (± 1.0) = 90.9 – 4.1407(T/K) + 0.5415849(T/K) ln (T/K). The standard enthalpy of formation of Na2S(s) was evaluated to be ΔfH°(Na2S(s), 298.15 K)/(kJ mol–1) (± 1.0) = – 369.0. The standard entropy was evaluated to be S°(Na2S(s), 298.15 K)/(J mol–1 K–1) (± 2.0) = 97.0. Analyses of used refractory material from the Chemrec gasifier were also performed in order to elucidate the stability of the refractory lining. Scanning electron microscopy (SEM) analysis revealed that the chemical attack was limited to 250-300 μm, of the surface directly exposed to the gasification atmosphere and the smelt. From XRD analysis it was found that the phases in this surface layer of the refractory were dominated by sodiumaluminosilicates, mainly Na1.55Al1.55Si0.45O4.</p>

Black liquors are presently combusted in recovery boilers where the inorganic cooking chemicals are recovered and the energy in the organic material is converted to steam and electricity. A new technology, developed by Chemrec AB, is black liquor gasification (BLG). BLG has more to offer compared to the recovery boiler process, in terms of on-site generation of electric power, liquid fuel and process chemicals. A prerequisite for both optimization of existing processes and the commercialization of BLG is better understanding of the physical and chemical processes involved including interactions with the refractory lining. The chemistry in the BLG process is very complex and to minimize extensive and expensive time-consuming studies otherwise required accurate and reliable model descriptions are needed for a full understanding of most chemical and physical processes as well as for up-scaling of the new BLG processes. However, by using these calculated model results in practice, the errors in the state of the art thermochemical data have to be considered. An extensive literature review was therefore performed to update the data needed for unary, binary and higher order systems. The results from the review reviled that there is a significant range of uncertainty for several condensed phases and a few gas species. This resulted in experimental re-determinations of the binary phase diagrams sodium carbonate-sodium sulfide (Na2CO3-Na2S) and sodium sulfate-sodium sulfide (Na2SO4-Na2S) using High Temperature Microscopy (HTM), High Temperature X-ray Diffraction (HT-XRD) and Differential Thermal Analysis (DTA). For the Na2CO3-Na2S system, measurements were carried out in dry inert atmosphere at temperatures from 25 to 1200 °C. To examine the influence of pure CO2 atmosphere on the melting behavior, HTM experiments in the same temperature interval were made. The results include re-determination of liquidus curves, in the Na2CO3 rich area, melting points of the pure components as well as determination of the extent of the solid solution, Na2CO3(ss), area. The thermal stability of Na2SO3 was studied and the binary phase diagram Na2SO4-Na2S was re-determined. The results indicate that Na2SO3 can exist for a short time up to 750 °C, before it melts. It was also proved that a solid/solid transformation, not reported earlier, occurs at 675 ± 10 °C. At around 700 °C, Na2SO3 gradually breaks down within a few hours, to finally form the solid phases Na2SO4 and Na2S. From HTM measurements a metastable phase diagram including Na2SO3, as well as an equilibrium phase diagram have been constructed for the binary system Na2SO4-Na2S. Improved data on Na2S was experimentally obtained by using solid-state EMF measurements. The equilibrium constant for Na2S(s) was determined to be log Kf(Na2S(s)) (± 0.05) = 216.28 – 4750(T/K)–1 – 28.28878 ln (T/K). Gibbs energy of formation for Na2S(s) was obtained as ΔfG°(Na2S(s))/(kJ mol–1) (± 1.0) = 90.9 – 4.1407(T/K) + 0.5415849(T/K) ln (T/K). The standard enthalpy of formation of Na2S(s) was evaluated to be ΔfH°(Na2S(s), 298.15 K)/(kJ mol–1) (± 1.0) = – 369.0. The standard entropy was evaluated to be S°(Na2S(s), 298.15 K)/(J mol–1 K–1) (± 2.0) = 97.0. Analyses of used refractory material from the Chemrec gasifier were also performed in order to elucidate the stability of the refractory lining. Scanning electron microscopy (SEM) analysis revealed that the chemical attack was limited to 250-300 μm, of the surface directly exposed to the gasification atmosphere and the smelt. From XRD analysis it was found that the phases in this surface layer of the refractory were dominated by sodiumaluminosilicates, mainly Na1.55Al1.55Si0.45O4.