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Thesis (MEng)--Stellenbosch University, 2014. / ENGLISH ABSTRACT: Concerns surrounding the world’s current dependence on quickly depleting fossil fuels and their negative environmental impacts have brought about much research into renewable and sustainable energy sources. With population and economic growth not only is this dependence increasing but there is an increasing production of waste by society in general. With space becoming a premium commodity and environmental protection a necessity, landfilling of the majority of the world’s waste is no longer feasible. Thus, research is being carried out into waste-to-energy (WTE) processes and refuse derived fuels (RDF). This study focuses on thermochemical conversion, specifically pyrolysis of solid wastes as a means of energy product recovery. Before a specific waste stream can be used in WTE or RDF contexts its composition and degradation behaviour needs to be investigated. For this reason, a full physical characterisation of the municipal solid waste (MSW) from the Stellenbosch municipality was carried out. It was found that the composition of waste differs between areas within the municipality but the composition of the waste in general compares well with international data. It was found that six main components present in the recyclables stream; namely high and low density polyethylene (HD/LDPE), poly(ethylene terephthalate) (PET), glossy paper, office paper and newspaper would be suitable for thermochemical conversion. The thermal properties and pyrolytic degradation of these six components were investigated by multi heating rate thermogravimetric analysis (TGA) from which kinetic parameters (activation energy, pre-exponential factor and kinetic rate constants) were calculated by a differential isoconversional method. The volatiles released during degradation were identified by way of online mass spectrometry (TGA-MS) yielding six individual kinetic schemes. In order to gauge to what extent milligram pyrolytic experimentation (TGA-MS) can be used to predict larger scale pyrolytic behaviour, runs were performed on one plastic (HDPE) and one paper (glossy paper) sample on a gram scale pyrolytic plant under both slow and vacuum conditions. It was found that, especially for high thermal conductivity samples, yields on gram scale experimentation can be accurately predicted on a milligram scale. Further, the compositions of slow pyrolysis oils from glossy paper, obtained by gas chromatography–mass spectrometry (GC-MS), were compared to TGA-MS results as well as off gases captured from TGA runs by thermal desorption (TGA/TD-GC-MS). It was found that TGA-MS and TGA/TD-GC-MS can be used to predict the main functional groups in pyrolysis oil produced on a gram scale. Thus small scale experimentation can be used to determine the suitability of different waste components for pyrolytic conversion. / AFRIKAANSE OPSOMMING: Kommer oor die wêreld se huidige afhanklikheid van fossielbrandstowwe en die negatiewe uitwerking op die omgewing het baie navorsing oor hernubare en volhoubare energie bronne meegebring. Bevolking en ekonomiese groei veroorsaak 'n toename in hierdie afhanklikheid en in die produksie van afval deur die samelewing. Daar is baie min onbenutte grond oop en die beskerming van die omgewing het noodsaaklik geword. Dus is storting van die meeste van die wêreld se afval nie meer ‘n aanvaarbare opsie nie. As gevolg daarvan word daar tans navorsing in afval-tot-energie (ATE) prosesse en afval afgeleide brandstowwe (AAB) gedoen. Hierdie studie fokus op die termochemiese omskakeling van afval, spesifiek pirolise, as 'n methode vir energie-produk hernuwing. Voordat 'n spesifieke afvalstroom gebruik kan word as 'n AAB moet die samestelling en afbrekings gedrag eers ondersoek word. Daarom is 'n volledige fisiese karakterisering van die munisipale afval (MA) van Stellenbosch munisipaliteit uitgevoer. Resultate het getoon dat daar ‘n verskil in die samestelling van afval tussen die gebiede binne die munisipaliteit is. Afgesien daarvan vergelyk die samestelling van die afval in die algemeen goed met internasionale data. Daar is gevind dat daar ses belangrike komponente teenwoordig is in die herwinbare stroom wat geskik sou wees vir termochemiese omskakeling, naamlik; hoë en lae digtheid poliëtileen (HD/LDPE), poli(etileen tereftelaat) (PET), glans, kantoor en koerant papier. Die termiese eienskappe en termiese afbreking van hierdie ses komponente is ondersoek deur middel van multi-verhittimgs tempo termogravimetriese analise (TGA) waaruit kinetiese parameters (aktiveringsenergie, pre-eksponensiële faktor en kinetiese snelheidskonstantes) deur 'n differensiële omskakelings metode bereken is. Die vlugtige komponente wat tydens die afbreking vrygestel is, is geïdentifiseer deur aanlyn-massaspektrometrie (TGA-MS) wat ses individuele kinetiese skemas verskaf. Om vas te stel tot watter mate milligram pirolitiese eksperimente (TGA-MS) gebruik kan word om op ‘n groter skaal die pirolitiese gedrag te kan voorspel, is eksperimentele lopies op een plastiek- (HDPE) en een papier (glans papier) monster op 'n laboratorium skaal pirolise opstelling onder stadige- en vakuum omstandighede uitgevoer. Daar is gevind dat, veral met hoë hitte geleiding komponente, die opbrengs op gram skaal eksperimente akkuraat voorspel kan word op ‘n milligram skaal. Verder was die samestelling van die stadige pirolise olies uit glans papier, wat verkry word deur gaschromatografie-massaspektrometrie (GC-MS), vergelyk met TGA-MS resultate sowel as af-gasse gevang van TGA lopies deur termiese desorpsie (TGA/TD-GC –MS). Daar is gevind dat TGA-MS en TGA/TD-GC-MS gebruik kan word om die belangrikste funksionele groepe in pirolise olie, wat op 'n gram skaal geproduseer word, te voorspel. Dus kan milligram eksperimente gebruik word om die geskiktheid van afval komponente vir pirolitiese omskakeling te bepaal.

Le furfural, identifié comme l'un des 30 principaux produits chimiques biologiques, est une molécule importante en terme de chimie verte et développement durable. L'objectif de ce travail de doctorat est de réaliser la synthèse et la conversion du furfural en flux continu et par lots. Ici, nous avons développé des méthodes plus éco-efficiente pour la synthèse du furfural, et valorisé le furfural en produits à haute valeur ajoutée, tels que le 2-furonitrile, l'alcool furfurylique, etc... Plusieurs questions clés ont été identifiées afin de concevoir des processus plus écologiques que les processus actuels. En détail, des expériences de synthèse du furfural ont été réalisées dans l'eau pure ou dans un mélange eau-solvants organiques lorsque des co-solvants (verts ou écologiques) sont nécessaires. L'irradiation par micro-ondes a été choisie comme méthode de chauffage pour accélérer le processus de déshydratation, et un réacteur à flux continu à micro-ondes a également été utilisé pour améliorer la productivité du furfural. En partant du furfural pour produire des produits chimiques à haute valeur ajoutée, des réacteurs à flux efficace, tels que Pheonix, H-cube Pro ainsi que des micro-ondes à flux continu avec micro-réacteur, ont également été identifiés comme des alternatives intéressantes pour améliorer la productivité des composés cibles. En conséquence, certains résultats prometteurs ont été obtenus du point de vue de l'industrie. / Furfural, which has been identified as one of top 30 bio-based chemicals, is an important green platform molecule, The aim of this PhD work is to realize the synthesis and conversion of furfural in batch and continuous flow. Here, we developed sorne greener methods for furfural synthesis, and valorized furfural into high value-added products, such as 2-furonitrile, furfuryl alcohol etc. Several keys issues were identified in order to design processes greener than the current ones. ln detail, experiments for furfural synthesis were performed in water or in water and organic solvent when co-solvents (green or eco-friendly) are necessary. Microwave irradiation has been chosen as the heating method to accelerate the dehydration process, and microwave continuous flow reactor was also applied to improve furfural productivity. When starting from furfural to produce high value-added chemicals, efficient flow reactors, suc as Pheonix, H-cube Pro as well as microwave continuous flow With micro-reactor, were also identified as interesting alternatives to improve the productivities of target compounds. As a result, some promising results were obtained in the viewpoint of industry.

Na atualidade, a geração de eletricidade e a produção de etanol de segunda geração a partir de materiais lignocelulósicos se apresentam como uma alternativa de desenvolvimento tecnológico no setor sucroenergético. Não obstante, a introdução de novos processos produtivos representa um verdadeiro desafio devido à complexidade e diversidade das rotas tecnológicas alternativas que podem ser avaliadas. Além disso, existem fatores econômicos e ambientais, que devem ser considerados durante o desenvolvimento e consolidação destas novas configurações. Nesse sentido, o presente trabalho tem como objetivo desenvolver uma metodologia para realizar a hierarquização exergética e exergo-ambiental de processos para obtenção de etanol e eletricidade a partir da cana-de-açúcar em distintas configurações de biorrefinarias. Para este fim, dados técnicos de operação foram adotados nas rotas tecnológicas envolvidas, bem como os aspectos ambientais da utilização destes sistemas. Os modelos propostos avaliaram as rotas Convencional (Caso 1), Bioquímica (Caso 2) e Termoquímica (Caso 3), utilizando programas de simulação e ferramentas matemáticas para simular estes processos. Ainda, a integração dos processos e diferentes usos para o bagaço excedente foram estudados, junto com diversos métodos de pré-tratamento visando à otimização e hierarquização destas rotas. O resultado final indicou configurações ótimas que permitiram a hierarquização em termos do índice exergético de renovabilidade dos processos de produção das rotas analisadas. Desse modo a rota convencional otimizada apresentou a máxima eficiência exergética dos processos e, por tanto, o menor custo exergético unitário médio das plataformas avaliadas. Ao passo que a rota bioquímica foi o sistema que promoveu um incremento de 28,58 % e 82,87 % na produção de etanol, quando comparado com o Caso 1 e o Caso 3, respectivamente. Além disso, a rota termoquímica apresentou a configuração com a maior taxa de geração de eletricidade excedente (214,98 kWh/TC). Em relação aos resultados do impacto ambiental das rotas tecnológicas, encontrou-se que a configuração mais sustentável foi a plataforma bioquímica, apresentando as menores taxas de emissões globais de CO2 (131,45 gCO2/MJ produtos). / Currently, electricity generation and second-generation bioethanol production from lignocellulosic materials represent technological alternatives in the sugar-energy sector. Nevertheless, the introduction of new production processes represents a real challenge due to the complexity and diversity of the technological routes that can be evaluated. In addition, there are economic and environmental factors that must be considered during the development and consolidation of these new configurations. Accordingly, this project aims to develop a methodology to perform the exergy and exergo-environmental analysis, evaluation and ranking of processes in order to obtain ethanol and electricity from sugarcane in different biorefinery configurations. Hence, operating technical data of each technological route were adopted as well as the environmental aspects of using these systems. The proposed models assessed the Conventional (Case 1), Biochemical (Case 2) and Thermochemical (Case 3) routes using simulation programs and mathematical tools to simulate the ethanol production and electricity generation. Furthermore, the process integration and different uses for the excess bagasse were studied with various pretreatment methods aiming the optimizing and ranking of routes. The results indicated optimal settings that allowed the ranking in terms of the environmental exergy indicator \"renewability\" of the production processes for analyzed routes. In this way, the optimized conventional route presented the maximum exergy efficiency of the processes, therefore the lowest exergetic cost average of the evaluated platforms. While the biochemical route was the system that promoted an increase of 28.58 % and 82.87% in the ethanol production, when compared to Case 1 and Case 3, respectively. In addition, the thermochemical route presented the configuration with the highest power generation rate exceeding (214.98 kWh/TC). Concerning, the environmental impact results, it was found that the most sustainable configuration was the biochemical platform, which presented the lowest overall CO2 emissions rates (131.45 gCO2/MJ products).

Na atualidade, a geração de eletricidade e a produção de etanol de segunda geração a partir de materiais lignocelulósicos se apresentam como uma alternativa de desenvolvimento tecnológico no setor sucroenergético. Não obstante, a introdução de novos processos produtivos representa um verdadeiro desafio devido à complexidade e diversidade das rotas tecnológicas alternativas que podem ser avaliadas. Além disso, existem fatores econômicos e ambientais, que devem ser considerados durante o desenvolvimento e consolidação destas novas configurações. Nesse sentido, o presente trabalho tem como objetivo desenvolver uma metodologia para realizar a hierarquização exergética e exergo-ambiental de processos para obtenção de etanol e eletricidade a partir da cana-de-açúcar em distintas configurações de biorrefinarias. Para este fim, dados técnicos de operação foram adotados nas rotas tecnológicas envolvidas, bem como os aspectos ambientais da utilização destes sistemas. Os modelos propostos avaliaram as rotas Convencional (Caso 1), Bioquímica (Caso 2) e Termoquímica (Caso 3), utilizando programas de simulação e ferramentas matemáticas para simular estes processos. Ainda, a integração dos processos e diferentes usos para o bagaço excedente foram estudados, junto com diversos métodos de pré-tratamento visando à otimização e hierarquização destas rotas. O resultado final indicou configurações ótimas que permitiram a hierarquização em termos do índice exergético de renovabilidade dos processos de produção das rotas analisadas. Desse modo a rota convencional otimizada apresentou a máxima eficiência exergética dos processos e, por tanto, o menor custo exergético unitário médio das plataformas avaliadas. Ao passo que a rota bioquímica foi o sistema que promoveu um incremento de 28,58 % e 82,87 % na produção de etanol, quando comparado com o Caso 1 e o Caso 3, respectivamente. Além disso, a rota termoquímica apresentou a configuração com a maior taxa de geração de eletricidade excedente (214,98 kWh/TC). Em relação aos resultados do impacto ambiental das rotas tecnológicas, encontrou-se que a configuração mais sustentável foi a plataforma bioquímica, apresentando as menores taxas de emissões globais de CO2 (131,45 gCO2/MJ produtos). / Currently, electricity generation and second-generation bioethanol production from lignocellulosic materials represent technological alternatives in the sugar-energy sector. Nevertheless, the introduction of new production processes represents a real challenge due to the complexity and diversity of the technological routes that can be evaluated. In addition, there are economic and environmental factors that must be considered during the development and consolidation of these new configurations. Accordingly, this project aims to develop a methodology to perform the exergy and exergo-environmental analysis, evaluation and ranking of processes in order to obtain ethanol and electricity from sugarcane in different biorefinery configurations. Hence, operating technical data of each technological route were adopted as well as the environmental aspects of using these systems. The proposed models assessed the Conventional (Case 1), Biochemical (Case 2) and Thermochemical (Case 3) routes using simulation programs and mathematical tools to simulate the ethanol production and electricity generation. Furthermore, the process integration and different uses for the excess bagasse were studied with various pretreatment methods aiming the optimizing and ranking of routes. The results indicated optimal settings that allowed the ranking in terms of the environmental exergy indicator \"renewability\" of the production processes for analyzed routes. In this way, the optimized conventional route presented the maximum exergy efficiency of the processes, therefore the lowest exergetic cost average of the evaluated platforms. While the biochemical route was the system that promoted an increase of 28.58 % and 82.87% in the ethanol production, when compared to Case 1 and Case 3, respectively. In addition, the thermochemical route presented the configuration with the highest power generation rate exceeding (214.98 kWh/TC). Concerning, the environmental impact results, it was found that the most sustainable configuration was the biochemical platform, which presented the lowest overall CO2 emissions rates (131.45 gCO2/MJ products).

The fast pyrolysis plant at RISE – ETC, Piteå produces carbon rich chars in bulk from various sources of biomass as feedstock. These in-house manufactured carbon rich chars were upgraded via pyrolysis as well as chemical activation using KOH to enhance their potential as an electrode material for supercapacitors. Commercial activated charcoal (Merck) was also studied and used as a yardstick for comparing performance of our materials. Investigations using EDX show enrichment in carbon content and very low amounts of impurities in the materials prepared from wood char after specific treatments for upgrading. Two-electrode coin cell apparatus with an aqueous electrolyte was used to determine the electrochemical performance of these materials. Wood char after KOH activation shows a high specific capacitance of ~105 Fg-1 at 2 Ag-1 in galvanostatic charge discharge measurements which outperformed activated charcoal used in this study (~68 Fg-1 at 2 Ag-1). This material was tested in a wide range of conditions (current density ranging from 0.1 Ag-1 to 10 Ag-1) and showed specific capacitance from ~90 Fg-1 (for 10 Ag-1) up to ~118 Fg-1 (for 0.1 Ag-1). Fatigue testing for >20000 cycles showed a remarkably high retention (>96%) of capacitance. Currently, most commercial supercapacitors use activated carbon materials prepared from coconut shells as the active electrode material which are not native to Sweden. In this study, we upgrade wood chars produced at RISE – ETC from biomass sources obtained locally (Sweden and Scandinavia) and demonstrate their applicability as supercapacitor electrode materials. / Den snabba pyrolysanläggningen vid RISE - ETC, Piteå, producerar kolrika kol i bulk från olika källor till biomassa som råvara. Dessa interna tillverkade kolrika karaktärer uppgraderades via pyrolys samt kemisk aktivering med hjälp av KOH för att förbättra deras potential som ett elektrodmaterial för superkondensatorer. Kommersiellt aktivt kol (Merck) studerades och användes som en måttstock för att jämföra våra materials prestanda. Undersökningar med EDX visar berikning av kolinnehåll och mycket låga mängder föroreningar i material som framställts av träkol efter specifika behandlingar för uppgradering. Tvåelektrodmyntcellapparater med en vattenhaltig elektrolyt användes för att bestämma den elektrokemiska prestandan hos dessa material. Träkol efter KOH-aktivering visar en hög specifik kapacitans på ~ 105 Fg-1 vid 2 Ag-1 i galvanostatiska laddningsurladdningsmätningar som överträffade aktivt kol som användes i denna studie (~ 68 Fg-1 vid 2 Ag-1). Detta material testades under ett stort antal betingelser (strömtäthet från 0,1 Ag-1 till 10 Ag-1) och visade specifik kapacitans från ~ 90 Fg-1 (för 10 Ag-1) upp till ~ 118 Fg-1 (för 0,1 Ag-1). Trötthetstestning för > 20000 cykler visade en anmärkningsvärt hög retention (> 96%) av kapacitansen. För närvarande använder de flesta kommersiella superkondensatorer aktivt kolmaterial framställt av kokosnötskal som det aktiva elektrodmaterialet som inte är hemma i Sverige. I den här studien uppgraderar vi träkolor som produceras vid RISE - ETC från biomassakällor erhållna lokalt (Sverige och Skandinavien) och visar deras användbarhet som superkapacitorelektrodmaterial.

La première partie de ce projet à consisté à isoler la lignine à partir de liqueurs industrielles et à la purifier pour s’affranchir des sucres, des minéraux et autres constituants. Pour cela, un protocole efficace en trois étapes a été proposé pour obtenir des échantillons de lignine avec une pureté satisfaisante (95%) et pour récupérer 68% de la lignine initialement présente dans la liqueur alcaline de départ. La lignine alcaline purifiée a ensuite été caractérisée d’un point de vue moléculaire et par analyses thermiques. L’élucidation de la structure de la lignine alcaline a permis d’appréhender sa fonctionnalisation par oxydation. Les analyses par chromatographie d’exclusion stérique de la lignine après oxydation ont montré une diminution de la masse molaire confirmant ainsi le clivage. Trois fractions différentes ont été isolées après l’oxydation de la lignine selon le solvant d’extraction ; d’une part des oligomères (plus ou moins fonctionnalisés) et d’autre part des molécules aromatiques (dont15% de vanilline). Ce travail de thèse aura abouti à la synthèse de composés aromatiques à haute valeur ajoutée (vanilline) et d’oligomères de lignine fonctionnalisés par des fonctions acide carboxylique. Les applications envisageables de ces « polyacides » issus de lignine sont nombreuses pour la formation de nouveaux polymères bio-sourcés tels que des polyesters, polyamides ou encore polyuréthanes. / A valorization of alkaline lignin from an industrial pulping liquor has been proposed for this project. Before considering any chemical modification or potential applications, the lignin structure has been elucidated. An efficient three-steps protocol for extraction and purification of lignin from industrial liquor has been established. This protocol leads to high purity sample of lignin (95%) and allows the recovery (68%) of the lignin initially present in the alkaline liquor. Alkaline lignin has been characterized utilizing analytical methods and thermogravimetric analysis. This precise structure elucidation was critical for proceeding to chemical modification of alkaline lignin. Chemical modification of alkaline lignin has been done by oxidation in alkaline media. Three major oxidized products have been isolated depending on the extraction solvent: oligomers bearing carboxylic groups and aromatic molecules. This thesis work led to the synthesis of value-added bio-sourced chemicals and functionalized oligomers. The polyacids from lignin obtained should be studied to form new biobased polymers such as polyesters, polyamids or polyurethanes.

Lignocellulosic bioethanol is currently being explored as a substitution to fossil fuels. Many lignocellulosic materials are being examined but the importance is to find those with attractive agro-energy features. Producing lignocellulosic ethanol is challenging because lignocellulosic biomass is resistant to chemical and biological degradation. To reduce biomass recalcitrance, a pretreatment stage is required. Pretreatment is considered to be the most intensive operating/operating cost component of cellulosic ethanol production. Therefore, research is heavily focused on understanding the effect of pretreatment technologies on the fundamental characteristics of lignocellulosic biomass. The first study in the thesis investigates Buddleja davidii as a potential biomass source for bioethanol production. The work focuses on the determination of ash, extractives, lignin, hemicellulose, and cellulose content in this plant, as well as detailed elucidation of the chemical structures of both lignin and cellulose by NMR spectroscopy. The study showed that B. davidii has several unique agro-energy features as well as some undesired characteristics. The second study presents research on the ethanol organosolv pretreatment (EOP) of B. davidii and its ability to produce enzymatically hydrolysable substrates. It was concluded that the removal of hemicellulose, delignification, reduction in the degree of polymerization (DP) of cellulose, and the conversion of crystalline cellulose dimorphs (Iα/Iβ) to the easily degradable para-crystalline and amorphous celluloses were the characteristics accounted for efficient enzymatic deconstruction of B. davidii after EOP. The third study provides a detailed elucidation of the chemical structure of ethanol organosolv lignin (EOL) of B. davidii by NMR spectroscopy. Such research was needed to understand the pretreatment mechanism in the context of delignification and alteration of the lignin structure. Future applications of the resulted EOL will be valuable for industrially viable bioethanol production process. EOP mainly cleaved β-O-4' interlinkages via homolysis, decreased the DP of lignin, and increased the degree of condensation of lignin. EOL had low oxygen content, molecular weight, and aliphatic OH as well as high phenolic OH, which are qualities that make it suitable for different co-product applications. The last study provides information on the anatomical characteristics of pretreated B. davidii biomass after EOP. The importance of this research was to further understand the alterations that occur to the cellular structure of the biomass which can then be correlated with its enzymatic digestibility. The results concluded that the physical distribution of lignin within the biomass matrix and the partial removal of middle lamella lignin were key factors influencing enzymatic hydrolysis.