The need for effective disposal of huge volumes of industrial waste is becoming more challenging due to expected imposition of stringent pollution control regulations in the near future. Thermochemical conversion, particularly gasification of organics in the waste is considered the best route from the perspective of volume reduction and prevalent eco-friendly concept of waste-to-energy transformation. It is considered imperative to have adequate understanding of basic combustion features as a part of the thermochemical conversion process, leading to gasification. The aim of this thesis is to understand the fundamental combustion processes associated with one of the top listed hazardous wastes from distilleries (Biochemical Oxygen Demand (BOD) ~ 40,000 - 50,000 mg/L), commonly known as vinasse, stillage or spent wash, through experiments and modeling efforts. Specially designed experiments on distillery effluent combustion and gasification are conducted in laboratory scale reactors. As an essential starting point of the studies on ignition and combustion of distillery effluent containing solids consisting of 62 ± 2 % organics and 38 ± 2 % inorganics (primarily sugarcane derivatives), the roles of solids concentration, drop size and ambient temperature were investigated through experiments on (1) liquid droplets of 65 % and 77 % solids (remaining water) and (2) spheres of dried effluent (100 % solids) of size 0.5 mm to 20 mm diameter combusted at ambient temperatures of 773 to 1273 K. The investigation reveals that the droplets burn with two distinct regimes of combustion, flaming and char glowing. The ignition delay ‘t1’ of the droplets increased with size as is in the case of non-volatile droplets, while that of bone-dry spheres was found to be independent of size. The ‘t1’ decreased with increase in solids concentration. The ignition delay has showed an Arrhenius dependence on temperature. The initial ignition of the droplets and the dry spheres led to either homogeneous (flaming) or heterogeneous (flameless) combustion, depending on the ambient temperature in the case of sphere and on solid concentration and the ambient temperature, in the case of liquid droplets. The weight loss during the flaming combustion was found to be 50 - 80 % while during the char glowing it was 10-20 % depending on the ambient temperature. The flaming time tc is observed as tc~ d2c , as in the case of liquid fuel droplets and wood spheres. The char glowing time tc' is observed as tc ~ d2c as in the case of wood char, though the inert content of effluent char is as large as 50 % compared to 2 - 3 % in wood char. In the case of initial flameless combustion, the char combustion rate is observed to be lower. The heterogeneous char combustion in quiescent air in controlled temperature conditions has been studied and modeled using one-dimensional, spherico-symmetric conservation equations and the model predicts most of the features of char combustion satisfactorily. The measured surface and core temperatures during char glowing typically are in the range of 200 to 400 K and are higher than the controlled temperature of the furnace. Based on the results of single droplet combustion studies, combustion experiments were conducted in a laboratory scale vertical reactor (throughput ranging from 4 to 10 g/s) with the primary aim of obtaining sustained combustion. Spray of effluents with 50 % and 60 % solids (calorific value 6.8 - 8.2 MJ/kg), achieved by an air blast atomizer, was injected into a hot oxidizing environment to determine the parameters (ambient temperature and air-fuel ratio) at which auto-ignition could occur and subsequently studies were continued to investigate pre-ignition, ignition and combustion processes. Effluent with lower solids concentration was considered first from the point of view of the less expensive evaporator required in the field conditions for concentration and a spin-off in terms of better atomization consequently. Three classes of experiments were conducted: 1) Effluent injection from the wall with no auxiliary heat input, 2) Effluent injection with auxiliary heat input and 3) effluent injection within kerosene enveloping flame. Though individual particles in the spray periphery were found to combust, sustained spray combustion was not achieved in any of the three sets of experiments even with fine atomization. While conducting the third class of experiments in an inclined metallic reactor, sustained combustion of the pool resulting of accumulated spray seemed to result in large conversion of carbon. This led to the adoption of a new concept for effluent combustion in which the residence time is controlled by varying reactor inclination and the regenerative heat transfer from the product gases supplies heat for endothermic pre-ignition process occurring on the bed. Combustion and gasification experiments were conducted in an inclined plate reactor with rectangular cross section (80 mm x 160 mm) and 3000 mm long. A support flame was found necessary in the injection zone in addition to the regenerative heat transfer. Effluent with 60% solids was injected as film on the reactor bed. This film disintegrated into fine particles due to induced aerodynamic stretching and shear stripping. Combustion of individual particles provided exothermic heat profile and resulted into high carbon conversion. However, effluent clogging in the cold injection zone hindered system from attaining steady state. Effluent injected directly on the hot zone caused it to remain mobile due to the spheroidal evaporation and thus assuaging this problem. Improved mass distribution was achieved by displacing nozzle laterally in a cycle, actuated by a mechanism. Consistent injection led to sustained effluent combustion with resulting carbon conversion in excess of 98 %. The typical gas fractions obtained during gasification condition (air ratio = 0.3) were CO2 = 14.0 %, CO = 7.0 %, H2 = 12.9 %, CH4 - 1 % H2S = 0.6 - 0.8 % and about 2 % of saturated moisture. This composition varied due to variation in temperature (± 30 K) and is attributed to combined effect of local flow variations, shifting zones of endothermic processes due to flowing of evaporating effluent over a large area. In order to minimize this problem, experiments were conducted by injecting effluent at higher solids (73 % solids is found injectable). The effluent was found to combust close to the injection location-due to the reduced ignition delay and lower endothermic evaporation load helped raising the local temperature. This caused the pyrolysis to occur in this hottest zone of the reactor with higher heating rates resulting in larger yield of devolatilized products and improved char conversion. Effluent combustion was found to sustain temperature in the reactor under sub-stoichiometric conditions without support of auxiliary heat input and achieved high carbon conversion. These results inspired the use of higher concentration effluent, which is also known in the case of wood to have improved gasification efficiency due to reduction in moisture fraction. In addition, the recent studies on the sulfur emission in the case of black liquor combustion in recovery boilers have revealed that with increase in solids concentration, release of sulfur in gas phase is reduces. The required concentration can be carried out using low-grade waste heat from the reactor itself. It was found through experiments that, even though spray ignition occurred at this concentration, the confined reactor space prevented the spray from attaining sustained combustion. This led to the conduct of experiments in a new vertical reactor with adequate thermal inertia, essential to prevent variations in local temperature to reach a steady state gasification and required space to accommodate the spray. The results of the experiments conducted in the vertical reactor in which effluents with 73 % solids, heated close to the boiling point and injected as fine spray in a top-down firing mode are consolidated and reported in the thesis in detail. Single particle combustion with enveloping faint flame was seen unlike stable flame found in coal water slurry spray combustion. Sustained gasification of gas-entrained particles occurred at reactor temperature in the range of 950 K - 1000 K and sub-stoichiometric air ratio 03 - 0.35 without the support of auxiliary fuel. The typical gas fractions obtained during gasification condition (air ratio = 0.3) were CO2 = 10.0 -11.5 %, CO - 10.0 - 12.0 %, H2 - 6.7 - 8.0 %, CH4 = 1.75 % H2S = 0.2 - 0.4 % and about 2 % of saturated moisture. The carbon conversion obtained was in the range of 95 - 96 %. These experiments have provided the conditions for gasification. The extraction of potassium salts (mostly sulfates, carbonate and chloride) from the ash, using a simple water leaching process, was found to recover these chemicals to as high an extent as 70 - 75 % of total ash. In summary it is concluded that increasing the solid concentrations to as high levels as acceptable to the system (~ 75 %) and introducing as a fine spray of heated material (~ 363 K) into furnace with air at sub-stoichiometric conditions in a counter current combustion reactor will provide the frame work for the design of a gasification system for vinasse and similar effluent material. The thesis consists of seven chapters. Chapter 1 introduces the problem and motivation of the work presented in the thesis. Literature review is presented in Chapter 2. The Chapter 3 deals with the single particle combustion studies. The results of effluent spray combustion experiments conducted in a laboratory scale vertical reactor are presented in Chapter 4. The results of combustion and gasification experiments conducted in another variant of a reactor, namely, inclined flat plate rectangular reactor is consolidated in Chapter 5. The results of gas-entrained spray gasification experiment of higher concentration effluent injected as spray in the vertical reactor are presented in Chapter 6. The general conclusions and scope for the future work are presented in the concluding chapter 7.

L'objectif de cette thèse est d'étudier la valorisation de la liqueur noire non soufrée par deux procédés hydrothermaux : la gazéification en eau supercritique et la liquéfaction hydrothermale. Ceux-ci seront comparés au procédé actuel de valorisation (évaporation puis combustion dans chaudière Tomlinson) selon 3 critères : le rendement énergétique, la récupération du sodium et la production de molécules aromatiques biosourcées.Lors de la gazéification, il a été montré que la formation de gaz est compétitive à celle de char. Une chauffe rapide et des températures élevées vont favoriser le rendement gaz et donc le rendement énergétique. Cependant les rendements énergétiques sont plus faibles que le procédé actuel car la conversion des composés aromatiques provenant de la lignine est faible dans la gamme de température étudiée. Lors d'un procédé en continu, à plus haute température (700°C) avec une chauffe rapide, le rendement énergétique peut être le double au procédé actuel (simulé à l'équilibre thermodynamique). La préhydrolyse du bois et l'utilisation de bois de résineux vont défavoriser la conversion de la liqueur noire en gaz.La liquéfaction quant-à-elle permet la formation composés phénoliques et d'un biocrude dont la combustion permettant de meilleur rendements énergétique que le procédé actuel. En effet, la lignine de la liqueur noire est hydrolysée en fragments réactifs, pouvant être soit dégradés soit se recombiner pour former le biocrude. Cette dernière est favorisée par la présence des carbohydrates. L'utilisation de bois de feuillus et la préhydrolyse vont améliorer le rendement énergétique.La récupération du sodium est satisfaisante pour les deux procédés, validant la faisabilité de la substitution de la chaudière par ces procédés hydrothermaux. / This thesis aims to study sulfur free black liquor valorization through two hydrothermal processes: supercritical water gasification and hydrothermal liquefaction. These processes will be compared to the industrial process (evaporation and Tomlinson boiler) with 3 mains criteria: energetic yield, sodium recovery and phenolic molecules production.In supercritical conditions, gas formation is competitive with char formation. Fast heating and high temperature permit to increase gas yield, thus energetic yield. However, conversion of phenolic compounds from lignin is low below 500°C, leading to a lower energetic yield than reference. In a continuous process, at high temperatures (700°C) and fast heating, energetic yield should be 2 times higher than industrial process (simulation at thermodynamic equilibrium). Wood prehydrolysis and softwood lead to a lower conversion of black liquor.Hydrothermal liquefaction produces a biocrude which can be burnt and phenolic platform compounds. Indeed, lignin is depolymerized into reactive fragments which can be degraded into platform phenolic molecules. Moreover, the recombination of these fragments, leading to biocrude formation, is favored by the carbohydrates derivatives in black liquor. Wood prehydrolysis and hardwood lead to better energetic and phenolic molecules yields.Sodium recovery is satisfactory for both processes. Substitution of Tomlinson recovery by a hydrothermal process is then possible.

Submitted by ELZIMAR TADEU DE FREITAS FERREIRA null (elzimar@feg.unesp.br) on 2016-08-17T20:29:45Z No. of bitstreams: 1 Tese de doutorado de Elzimar Tadeu de Freitas Ferreira.pdf: 3358273 bytes, checksum: 0b61e834c1870d60b5531502a4c3e8b9 (MD5) / Approved for entry into archive by Ana Paula Grisoto (grisotoana@reitoria.unesp.br) on 2016-08-19T18:18:10Z (GMT) No. of bitstreams: 1 ferreira_etf_dr_guara.pdf: 3358273 bytes, checksum: 0b61e834c1870d60b5531502a4c3e8b9 (MD5) / Made available in DSpace on 2016-08-19T18:18:10Z (GMT). No. of bitstreams: 1 ferreira_etf_dr_guara.pdf: 3358273 bytes, checksum: 0b61e834c1870d60b5531502a4c3e8b9 (MD5) Previous issue date: 2016-07-08 / Agência Nacional de Energia Elétrica (ANEEL) / Atualmente, a grande preocupação relacionada ao meio ambiente e redução do uso de combustíveis fósseis levou a comunidade acadêmica/científica a se concentrar em novas tecnologias de conversão de energia que possam garantir sua produção nos níveis necessários ao atendimento das necessidades humanas, mas considerando também os meios para minimizar os impactos ambientais. Propõe-se estabelecer o estado da arte da estrutura de geração termelétrica, conceituando a estrutura tecnológica de ciclos térmicos no mundo, caracterizada em centrais termelétricas distribuída e centralizada. São precedidos estudos termodinâmicos em centrais termelétricas de diferentes configurações, nas escalas industrial, municipal e nacional. Para fins de avaliação do desempenho de uma central térmica, é apresentado o desenvolvimento de uma modelagem térmica, utilizando ciclos combinados com gaseificação integrada (IGCC) e suas variações, usando balanço de massa, balanço de energia e balanço de exergia. Na geração distribuída em nível industrial, foi realizada uma análise no setor de papel e celulose, mostra-se que seu subproduto, o licor negro, um passivo ambiental, será mais bem aproveitado se passar por um processo de gaseificação e antes da queima em ciclo combinado em um sistema de cogeração. Na geração distribuída em escala municipal, o estudo de uma configuração de planta piloto foi elaborado para operar em empreendimento vinculado a alguma forma às cidades. Para o projeto de uma instalação piloto, dentre as opções de tecnologias envolvidas, as mais recomendadas seriam o ciclo IGCC (gaseificação do resíduo sólido urbano) e diferentes concepções de ciclos híbridos (incineração de resíduo sólido urbano, integrada a conjuntos a gás acionados com biogás de aterro ou gás natural). Na geração centralizada em escala nacional, empregaram-se centrais de grande porte que são usualmente encontradas na literatura. Nesta parte do estudo verificou-se a utilidade de um ciclo IGCC, com tecnologia avançada de co-gaseificação de resíduo sólido urbano e carvão aplicada a um gaseificador entrained-flow, sistema ASU (Air Separation Unit), com injeção de oxigênio e captura de CO2 pré-combustão, como alternativa eficiente de geração de energia frente às tecnologias convencionais, como a incineração e o aterro sanitário para o tratamento de materiais residuais. / Currently, the major concern related to the environment and reduction of fossil fuels has led the academic/scientific community to focus on new energy conversion technologies that can guarantee production levels necessary to meet human needs, but also that consider the means to minimize environmental impacts. In this work, it is proposed to establish the state of the art of thermoelectric generation structure, conceptualizing the technological structure of thermal cycles in the world, in the context of distributed and centralized thermal power plants, as well as their technological characteristics. Thermodynamic studies are performed in thermal power plants of different configurations, considering scales in industrial, municipal and national levels. For the purpose of evaluating the performance of a thermal power plant, it is presented the development of a thermal modeling for combined cycles with an integrated gasification (IGCC) and their variations, using mass, energy and exergy system balances. In distributed generation at the industrial level, an analysis in the paper and pulp sector was held. It is shown that its by-product, the black liquor, an environmental liability, would be better used if sent through a process of gasification before being burned in a combined cycle cogeneration system. In distributed generation at the municipal level, the study of a pilot plant configuration is designed to operate in an enterprise linked to some form to the cities. For the design of a pilot plant, from the options of technologies involved, the most recommended would be the IGCC cycle (gasification of municipal solid waste) and different conceptions of hybrid cycles (municipal solid waste incineration, integrated to gas cycles powered with landfill biogas or natural gas). For the centralized generation at the national level, it was employed large-scale plants that are usually found in the literature. In this part of the study it is demonstrated the utility of an IGCC cycle, with advanced technology co-gasification of municipal solid waste and coal applied to an entrained-flow gasifier, ASU system (Air Separation Unit), with oxygen injection and capture of CO2 in a pre combustion mode as an efficient alternative compared to power generation with conventional technologies such as incineration and the use of a landfill for the treatment of waste materials. / ANEEL: PD-0553-0022/2012

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.

Carbon fiber is a lightweight, versatile material with many current and potential applications. To be able to expand the market for carbon fiber composites in other areas than special applications the production costs must be reduced. One way of accomplishing this could be to use a less expensive raw material where lignin is a good example as it can be provided at lower cost, is renewable and abundantly available compared to commercially used raw materials today. So far, the mechanical properties of lignin-based carbon fibers are inferior relative to commercial carbon fibers. For lignin-based carbon fibers to enter the commercial market more research is necessary to gain knowledge of the conversion of lignin to carbon fiber. The LightFibre project investigates the possibilities to produce carbon fibers based on a mixture of softwood kraft lignin and cellulose. The kraft lignin is isolated from black liquor in the kraft/sulfate process with the LignoBoost process. This master thesis project was conducted within in the LightFibre project and evaluated whether metal ions generally present in kraft lignin had an influence on the final carbon fiber quality in terms of mechanical properties and morphology. The mechanical properties were determined with tensile testing, the morphology by scanning electron microscopy (SEM) and the relative abundance of studied elements with electron dispersive spectroscopy (EDS). The influence of the chosen metal ions was tested by impregnation of dry-jet wet spun prefibers based on 70 wt.% softwood kraft lignin and 30 wt.% dissolving pulp cellulose. The fibers were impregnated in room temperature with solutions containing Na2SO4, K2SO4, MgSO4, FeSO4 and Al2(SO4)3 salts where the cations were the focus in these trials. The concentrations used for impregnation were 0.2 and 1M of the cations. The obtained mechanical properties of the carbon fibers of the samples impregnated with different metal ions did not deviate significantly from the reference which had a tensile strength of 870 MPa and tensile modulus of 68 GPa. The analysis of morphology with SEM showed no defects or damage of any of the fibers. Therefore, it was concluded that the impregnated metal ions: K+, Na+, Al3+, Mg2+ and Fe2+ at the obtained levels in the fibers cause no effects on the fibers during the stabilization and carbonization that affects the mechanical performance of final carbon fiber.  The amount of potassium in one of the samples was estimated to 0.1 wt.%. From the results of this study it may be suggested that the general recommendation of <0.1 wt.% ash in lignin can be exceeded, for dry-jet wet-spun kraft lignin/cellulose-based carbon fibers.

<p>Ved består huvudsakligen av tre typer av polymerer, cellulosa, hemicellulosa och lignin. Lignin bildas i naturen genom enzymatiskt initierad oxidativ koppling av tre olika typer av fenylpropan-enheter. Dessa bygger genom olika kol-kol- och kol-syre-bindningar upp en amorf tredimensionell polymer. När kemisk massa tillverkas bryts lignin ner och löses ut i kokluten. Luten innehåller de förbrukade kokkemikalierna och bränns generellt i en sodapanna för att regenerera kemikalierna och producera ånga. Sodapannan är emellertid dyr. Därför har den blivit produktionsbegränsande på många massabruk. Att avlägsna en del av ligninet från avluten vore därför önskvärt och att finna ekonomiskt intressanta produkter baserade på lignin från svartlut är därför ett viktigt forskningsområde .</p><p>Ett lämpligt område för ligninprodukter vore som tillsatts i oblekt massa. Oblekt massa används till stor del för tillverkning av kraftliner, topp- och bottenskikten på wellpapp. När lådor av wellpapp lagras i containrar som färdas över haven, förändras den relativa luftfuktigheten. Detta gör att lådorna kollapsar lättare än om de skulle ha lagrats vid konstant luftfuktighet, även en hög sådan. Detta är på grund av det så kallade mekanosorptiva- eller accelererade krypfenomenet. Genom tillsatts av våtstyrkemedel till kraftliner eller behandla den med hydrofoba ämnen, finns indikatoner på att mekanosorptiva effekten skulle kunna minska.</p><p>För att försöka minska den effekten har ett lågmolekylärt kraftlignin, som utvunnits med hjälp av tvärsflödesfiltrering av svartlut och svavelsyrafällning, använts. Genom derivatisering av detta lignin med linolja erhölls ett hydrofobt ligninderivat som uppvisar strukturella likheter med biopolymeren suberin. När detta suberinlika ligninderivat tillsätts till massa verkar det mekanosorptiva krypet minska. När lågmolekylärt lignin används tillsammans med ligninradikalinitiatorerna lackas eller mangan(III) i kraftlinermassa erhålls dessutom en våtstyrka på ca 5% av torrstyrkan. Efter aminering av detta lignin gav en tillsatts till kraftlinermassan en våtstyrka på upp till 10% av torrstyrkan. Det finns indikationer på att det mekanosorptiva krypet samtidigt minskar när dessa behandlingar görs som ger upphov till ökad våtstyrka.</p> / <p>Wood consists mainly of three types of polymers; cellulose, hemi cellulose and lignin. Lignin is formed in nature through enzymatic initiated oxidative coupling of three different kinds of phenyl propane units. These form by various carbon-carbon and carbon-oxygen bonds, an amorphous three-dimensional polymer. As chemical pulp is produced, lignin is degraded and dissolved into pulping liquors. These liquors contain the spent cooking chemicals and are generally burnt in a recovery boiler to regenerate cooking chemicals and produce steam. However, the recovery boiler is expensive. Hence, it has become the bottleneck for production in many pulp mills. Removal of some lignin from the spent cooking liquor would, for that reason, be desired and valuable products based on lignin from cooking liquors are searched for.</p><p>One suitable area for lignin products would be as additive in unbleached pulp. A major product from unbleached pulp is kraftliner, the top and bottom layers of corrugated board. When boxes of corrugated board are stored in containers travelling overseas the relative humidity is varying. This makes the boxes collapse more easily than if they were stored at constant humidity, even a high one. This is due to the so called mechano-sorptive or accelerated creep phenomenon. By addition of wet strength additive to kraftliner or treating it with hydrophobic compounds there are indications on that the mechano-sorptive effect would decrease.</p><p>Trying to decrease this effect, low molecular weight kraft lignin has been used. It was obtained by cross-flow filtration of black liquor and precipitation by sulphuric acid. By derivatisation of this lignin by linseed oil, a hydrophobic lignin derivative was obtained, similar in structure to units in the biopolymer suberin. As this suberin-like lignin-derivative was added to pulp the mechano-sorptive creep seemed to be lowered. Furthermore, when the low molecular weight lignin was used together with the lignin radical initiators laccase or manganese(III) in kraftliner pulp, a wet strength of about 5% of dry strength was obtained. An amination treatment of this lignin and addition to kraftliner pulp resulted in a wet strength of up to 10% of dry strength. There are indications of that the mechano-sorptive creep also decreases as these treatments, resulting in increased wet strength, are made.</p>

Made available in DSpace on 2017-07-10T18:08:03Z (GMT). No. of bitstreams: 1 Cristiano Luiz Diel.pdf: 3361169 bytes, checksum: 272490d70ac95c5008fc77d50f4431d0 (MD5) Previous issue date: 2013-02-22 / Klabin Fabricadora de Papel e Celulose S/A / The pulp and paper industries are major consumers of energy. The plant of black liquor evaporation consumes significant portion of this energy. Any effort to improve their energy efficiency is beneficial to the industry. The computer simulation is a powerful tool to aid the understanding of industrial processes and may help identify mechanisms involved in the prediction of responses to changes in operating conditions and optimization of process control. The objective of this work is the development of a mathematical model phenomenological representing the evaporation plant of Klabin Papéis Monte Alegre (KPMA) and the use of it to study and improve operational conditions of the plant. To achieve this goal, firstly it was developed a simplified model based on the work of other authors. The model was built in Maple ® platform. The model was built from mass and energy balances and phase equilibrium equations. Correlations were used to estimate properties, e. g. boiling point raise, enthalpies of the liquor, steam and condensate. The model reproduced well the results of the authors, with the largest percentual error equal to 5.5% and most of the parameters with percentual errors less than 1%. The model was adapted to represent the first effect of evaporation plant of KPMA. Historical operating data were used to compare the model results. Good results were found for temperature and solid content of the liquor. Good results were found for mass flows in some effects, but the model could not effectively predict the mass flow of all effects and the variables related to the flash tanks. The differences are attributed mainly to considerations of steady state and saturated vapor with no entrainment of particles in the liquor and the use of literature correlations to predict the properties of the liquor that do not correspond to the liquor used. / As indústrias de papel e celulose são grandes consumidoras de energia. A planta de evaporação de licor negro consome parte significativa dessa energia. Qualquer esforço no sentido de melhorar sua eficiência energética é benéfico para a indústria. A simulação computacional é uma ferramenta poderosa no auxílio da compreensão de processos industriais, podendo auxiliar na identificação de mecanismos envolvidos no processo, na predição de respostas a mudanças de condições de operação e na otimização do controle de processos. Assim, o objetivo do presente trabalho é o desenvolvimento de um modelo matemático fenomenológico representando a planta de evaporação da Klabin Papéis Monte Alegre (KPMA) e a utilização do mesmo para estudo e melhoria das condições operacionais da planta. Para atingir a este objetivo, primeiramente foi desenvolvido um modelo simplificado baseado no trabalho de outros autores. O modelo foi construído em plataforma Maple®. O modelo foi construído a partir de balanços de massa e energia e equações de equilíbrio de fases. Foram utilizadas correlações para estimar propriedades, e.g. elevação do ponto de ebulição, entalpias do licor, vapor e condensado. O modelo reproduziu bem os resultados dos autores, sendo o maior desvio percentual igual a 5,5% e a grande maioria dos parâmetros com desvio percentuais inferiores a 1%. O modelo foi adaptado para representar o primeiro efeito da planta de evaporação da KPMA. Dados históricos de operação foram utilizados para comparação dos resultados do modelo. Foram encontrados bons resultados para os teores de sólidos e temperaturas do licor, bem como para as vazões para alguns dos evaporadores. O modelo não pôde predizer com eficácia as vazões de todos os evaporadores e das variáveis referentes aos tanques de expansão de licor. As diferenças encontradas são atribuídas principalmente às considerações de regime estacionário e de vapor saturado com ausência de arraste de partículas no licor, bem como da utilização de correlações da literatura para predizer as propriedades do licor que não correspondem ao licor utilizado na evaporação.

La liqueur noire, sous-produit de l’industrie papetière, est convertie par un processus hydrothermal. Elle a été choisie pour son contenu élevé en eau (80 wt%), matière organique (14 wt%) et minéraux (6 wt%) qui font d'elle une biomasse à haute valeur ajoutée bien qu'encore peu exploitée. L'étude en batch, balayant une large gamme de température (350°C-600°C), permet d'identifier deux flux sortant : une proportion d'hydrogène élevée dans la phase gazeuse (600°C), ainsi qu'une phase solide, appelée coke, générée quelques soient les conditions opératoires utilisées. La génération de solide modifie la composition du milieu réactionnel en procédé batch et peut poser problème en cas de transposition en réacteur continu. Il est donc important de comprendre sa formation pour pallier ces verrous. L'analyse du résidu montre qu'à 350°C, pour des temps de réaction courts (<2h), de microparticules carbonées se forment. Leur taille est influencée par les vitesses de montée et descente en température. Pour des températures plus hautes, le solide ne présente pas d'intérêt morphologique et sa proportion massique augmente avec la température. Ainsi, une production d'hydrogène significative s'accompagnera d'un dépôt solide dans le réacteur. Une étude catalytique a donc été menée en vue d'augmenter la quantité d'hydrogène et de diminuer la formation de coke tout en travaillant à plus basse température. Cette étude, menée à 350°C et 450°C, montre que les réactions d'hydrogénation et d'oxydation mises en jeu par le catalyseur conduisent aux résultats escomptés. La conversion de molécules modèles de la liqueur noire, menée dans les mêmes conditions d'expériences, a permis d'appréhender les mécanismes majeurs mises en jeu lors de la conversion hydrothermale. Les microparticules à 350°C peuvent être valorisées. Cependant, le changement de taille et de morphologie au cours du temps interroge sur la possibilité de passer en réacteur continu. La formation de solide peut être évitée à partir de 450°C en présence de catalyseur, favorisant en parallèle la production d'hydrogène. De ce fait, ce travail de thèse aborde les verrous scientifiques, techniques et technologiques liés à la conversion hydrothermale de la liqueur noire et notamment de la formation du solide, en présence ou non de catalyseur. / Black liquor, a by-product of paper industry, is converted by hydrothermal process. It was chosen for its high water content (80 wt%), organic material (14 wt%) and minerals (6 wt%) that make it a high-value biomass while still untapped. The study in batch, screening a wide temperature range (350°C-600°C), used to identify two outgoing flows: a high proportion of hydrogen in the gas phase (600°C) and a solid phase, called coke, generated regardless the operating conditions used. The generation of solid changes the composition of the reaction medium in batch process and can be problematic in case of transposition in continuous reactor. Thus it is important to understand its formation to overcome these obstacles. Analysis of the residue shows that at 350°C, for short reaction times (< 2h), carbonaceous micro-particles are formed. Their size is influenced by the temperature rates of rise and fall. For higher temperatures, the solid is of no morphological interest and its weight proportion increased with temperature. Thus, a significant production of hydrogen will be associated with a solid deposit in the reactor. A catalytic study was conducted to increase the amount of hydrogen and reduce the formation of coke while working at lower temperature. This study, conducted at 350°C and 450°C, shows that hydrogenation and oxidation reactions involved with the catalyst, lead to the expected results. Converting models molecules of black liquor, conducted with the same experimental conditions, helped to understand the major mechanisms involved during the hydrothermal conversion. The micro-particles at 350°C can be valorized. However, the change in size and morphology over time wondered about the possibility of implement in continuous reactor. The solid formation can be prevented from 450°C in the presence of catalyst, favoring in parallel hydrogen production. Therefore, this thesis deals with scientific, technical and technological locks related to hydrothermal conversion of black liquor and especially the solid formation, with or without catalyst.

This paper discusses the potential of gasoline, ethanol and methanol ternary blend as an alternative passenger car fuel in Sweden. Sweden has set various targets aimed to reduce its GHG emissions and to increase the share of renewables in the transportation sector. Nevertheless, the majority of the energy consumed in the road transportation sector still comes from fossil fuels. In order to replace the energy supply of fossil fuels by more renewable fuels, the potential of alternative renewable fuels needs to be explored. Therefore, the potential of a domestically produced ternary blend of Gasoline‐Ethanol‐ Methanol (GEM) fuel blend is analysed in this report. In order to test whether it has the potential to become a successful alternative fuel, an analysis is performed on the: methanol and ethanol production potential from domestic second‐generation feedstocks, the selection of the most suitable production pathways of the biofuels, the potential for a Swedish GEM fuel distribution infrastructure, the economic competitiveness of GEM fuel, and lastly on the environmental impact of the shift from cars running on neat gasoline to GEM fuel. In order to perform the analysis, two scenarios are developed for projecting the share of the GEM cars(cars running on GEM fuel blends) in the Swedish passenger car fleet, considering a time horizon from 2017 to 2030. In Scenario 1, a high share of passenger cars running on GEM fuel is obtained with 22 percent by 2030. In Scenario 2, a low share of cars running on GEM fuel is obtained with 17 percent by 2030. In both scenarios, the passenger cars running on GEM fuel take over the share of cars running on gasoline. The scenarios serve to project the energy demand for GEM fuels. By 2030, the projected energy demand for GEM fuels is 9.7 and 7.5 TWh for Scenario 1 and Scenario 2, respectively. From the biofuel potential studies, it can be concluded that the production potential of the alcohol fuels, derived from currently untapped domestic secondary resources, exceeds the projected energy demand of 9.7 and 7.5 TWh in 2030. According to this thesis, the production potential of 2nd generation ethanol and methanol are 36 and 61.1 TWh, respectively, by 2030. Moreover, the study shows that the majority of the existing fuel distribution network of E85 and gasoline, which is forecasted to have a significant overcapacity in the same time‐span as the scenarios, can be utilized in a GEM fuel distribution network. As a consequence, no major investments are required to develop a Swedish GEM fuel distribution network. Regarding the selection of the biofuel production pathways, this study indicates the most suitable way of producing methanol is by black‐liquor gasification. Regarding second‐generation ethanol, this thesis indicates that the fermentation forestry residues is the most beneficial production pathway. The biofuel production pathways are selected based on the energy yield ratios, the biofuel production cost and biomass feedstock cost. Moreover, this study demonstrates that under the current Swedish policies, GEM fuels blends are economic competitive with gasoline and E85. In order to test the economic competitiveness, a pay‐off curve was developed based on the pump price of gasoline and fuel economy of GEM fuel blends. This study shows the pump prices of GEM fuel blends pay‐off in comparison to gasoline. This analysis indicates that the pump prices of GEM fuel blends lays between 0.87 and 0.92 euro per liter. Regarding the environmental impact, this study indicates that the amount of GHG emissions avoided varies between 10.1 and 13.3 million metric tons CO2eq in Scenario 1. In Scenario 2, the amount of GHG emissions that can be avoided varies between 8.6 and 11.3 million metric tons CO2eq. Moreover, this study indicates that high methanol containing GEM fuel blend are more favourable in terms of biomass utilization, and high ethanol containing GEM fuel blends are more favourable in terms of economy and GHG savings.

Ved består huvudsakligen av tre typer av polymerer, cellulosa, hemicellulosa och lignin. Lignin bildas i naturen genom enzymatiskt initierad oxidativ koppling av tre olika typer av fenylpropan-enheter. Dessa bygger genom olika kol-kol- och kol-syre-bindningar upp en amorf tredimensionell polymer. När kemisk massa tillverkas bryts lignin ner och löses ut i kokluten. Luten innehåller de förbrukade kokkemikalierna och bränns generellt i en sodapanna för att regenerera kemikalierna och producera ånga. Sodapannan är emellertid dyr. Därför har den blivit produktionsbegränsande på många massabruk. Att avlägsna en del av ligninet från avluten vore därför önskvärt och att finna ekonomiskt intressanta produkter baserade på lignin från svartlut är därför ett viktigt forskningsområde . Ett lämpligt område för ligninprodukter vore som tillsatts i oblekt massa. Oblekt massa används till stor del för tillverkning av kraftliner, topp- och bottenskikten på wellpapp. När lådor av wellpapp lagras i containrar som färdas över haven, förändras den relativa luftfuktigheten. Detta gör att lådorna kollapsar lättare än om de skulle ha lagrats vid konstant luftfuktighet, även en hög sådan. Detta är på grund av det så kallade mekanosorptiva- eller accelererade krypfenomenet. Genom tillsatts av våtstyrkemedel till kraftliner eller behandla den med hydrofoba ämnen, finns indikatoner på att mekanosorptiva effekten skulle kunna minska. För att försöka minska den effekten har ett lågmolekylärt kraftlignin, som utvunnits med hjälp av tvärsflödesfiltrering av svartlut och svavelsyrafällning, använts. Genom derivatisering av detta lignin med linolja erhölls ett hydrofobt ligninderivat som uppvisar strukturella likheter med biopolymeren suberin. När detta suberinlika ligninderivat tillsätts till massa verkar det mekanosorptiva krypet minska. När lågmolekylärt lignin används tillsammans med ligninradikalinitiatorerna lackas eller mangan(III) i kraftlinermassa erhålls dessutom en våtstyrka på ca 5% av torrstyrkan. Efter aminering av detta lignin gav en tillsatts till kraftlinermassan en våtstyrka på upp till 10% av torrstyrkan. Det finns indikationer på att det mekanosorptiva krypet samtidigt minskar när dessa behandlingar görs som ger upphov till ökad våtstyrka. / Wood consists mainly of three types of polymers; cellulose, hemi cellulose and lignin. Lignin is formed in nature through enzymatic initiated oxidative coupling of three different kinds of phenyl propane units. These form by various carbon-carbon and carbon-oxygen bonds, an amorphous three-dimensional polymer. As chemical pulp is produced, lignin is degraded and dissolved into pulping liquors. These liquors contain the spent cooking chemicals and are generally burnt in a recovery boiler to regenerate cooking chemicals and produce steam. However, the recovery boiler is expensive. Hence, it has become the bottleneck for production in many pulp mills. Removal of some lignin from the spent cooking liquor would, for that reason, be desired and valuable products based on lignin from cooking liquors are searched for. One suitable area for lignin products would be as additive in unbleached pulp. A major product from unbleached pulp is kraftliner, the top and bottom layers of corrugated board. When boxes of corrugated board are stored in containers travelling overseas the relative humidity is varying. This makes the boxes collapse more easily than if they were stored at constant humidity, even a high one. This is due to the so called mechano-sorptive or accelerated creep phenomenon. By addition of wet strength additive to kraftliner or treating it with hydrophobic compounds there are indications on that the mechano-sorptive effect would decrease. Trying to decrease this effect, low molecular weight kraft lignin has been used. It was obtained by cross-flow filtration of black liquor and precipitation by sulphuric acid. By derivatisation of this lignin by linseed oil, a hydrophobic lignin derivative was obtained, similar in structure to units in the biopolymer suberin. As this suberin-like lignin-derivative was added to pulp the mechano-sorptive creep seemed to be lowered. Furthermore, when the low molecular weight lignin was used together with the lignin radical initiators laccase or manganese(III) in kraftliner pulp, a wet strength of about 5% of dry strength was obtained. An amination treatment of this lignin and addition to kraftliner pulp resulted in a wet strength of up to 10% of dry strength. There are indications of that the mechano-sorptive creep also decreases as these treatments, resulting in increased wet strength, are made. / QC 20101103