No description available.

No description available.

A series of laboratory oxygen delignification were performed in this study at constant oxygen pressure and consistency to study the response of the pulp to the different process parameters, i.e. reaction temperature, reaction time, soda addition, and mechanical pretreatment, to the zero span tensile strength loss. The basic chemistry of the oxygen delignified pulps was under study including fiber charge, celluloses/hemicelluloses, and hexenuronic acid. The fiber structure such as curl, kink, fines, and fiber length were also discussed. NaOH charge can be reduced as much as 50 % by applying mechanical pretreatment to obtain the same level of selectivity at the oxygen delignification conditions described in this study.Mechanical pretreatment prior to oxygen delignification promoted a better selectivity for both Acacia mangium and MHW pulps. MHW kraft pulp did not show a significant extractive removal in all pretreatment methods during oxygen delignification. The ultrasonic pretreatment followed by filtering induced the best extractive removal among the other three methods.

Thesis (Ph. D.)--Institute of Paper Chemistry, 1978. / Includes bibliographical references (p. 146-151).

Thesis (M. S.)--Chemical Engineering, Georgia Institute of Technology, 2009. / Committee Chair: Muzzy, John; Committee Member: Frederick, Jim; Committee Member: Realff, Matthew. Part of the SMARTech Electronic Thesis and Dissertation Collection.

No description available.

No description available.

The objective of this study was to investigate the possibility of recycling enzymes during saccharification of cellulose for the production of ethanol from woodchips. To make enzyme recycling feasible and economical when woodchips are processed for ethanol, the lignin in the wood is to be removed before the enzymes are added. Since enzymes constitute a major part of the input costs, second only to the feedstock, the ability to reuse the enzymes could lead to a considerable decrease in the production cost of ethanol. Tulip poplar woodchips were selected as the feedstock. Different delignification methods with recovery of byproducts were investigated. Alkali extraction, using dilute NaOH for the removal of lignin after steam pretreatment, was used as the base case against which all other processes were compared. Recovery of furfural and methanol, produced during the pretreatment of the woodchips, for sale as byproducts was one modification to the alkali extraction process that was investigated. The conversion of xylose to furfural and the recovery of the furfural as a byproduct was the third case explored. Solvent extraction using a 50:50 ethanol-water mixture instead of extraction with NaOH was the fourth case examined. Process flow sheets were then developed to recycle the enzymes during the hydrolysis and fermentation of this prehyrolyzed and delignified wood. Two reactor setup schemes were examined for enzyme recycling. One scheme involved a single train of reactors, with the whole pretreated slurry flowing from one reactor to the next, whereas, in the other scheme, the slurry was split among parallel trains of reactors. The activity loss of the enzymes was modeled such that a part of the enzymes entering the reactor lost all their activity. The loss of activity in multiple steps, with enzymes losing only some of their activity, was also modeled. Here the enzymes entering the reactor constituted a mixture with different activities instead of all the enzymes having the same activity like in the previous single step model. Recovering methanol and furfural reduced the minimum ethanol selling price. High temperature ethanol water pretreatment and lignin extraction reduced the minimum ethanol selling price compared to the base case of steam pretreatment followed by alkali extraction. Enzyme recycling also reduces the minimum ethanol selling price. The magnitude of the price reduction depends on the recycling scheme selected and the rate of enzyme deactivation, which has not been measured.

The first part of this thesis describes my research towards the valorisation of lignin. Due to environmental and political pressures, there has been a drive to start the transition from a fossil fuel based economy to a renewable based one. This will require the development of novel routes to renewable chemicals, one source of which may be the biopolymer lignin. Through the synthesis of advanced lignin model compounds, the chemistry of real lignin is explored. This work culminates in the development of a novel method for the depolymerisation of real lignin to simple mixtures of aromatic chemicals that could be useful building blocks for the chemical industry. One of the key steps in this process is the oxidation of the β-O-4 linkages in lignin using catalytic amounts of DDQ and molecular oxygen as the terminal oxidant. The second part of this thesis details the first synthesis of melohenine B and O-ethyl-14-epimelohenine B, two medium sized ring containing natural products. The key step in the synthesis of these natural products was the photo-sensitised oxidative cleavage of an indolic substrate by molecular oxygen. Additionally, the use of residual dipolar coupling (RDC) analysis for the conformational analysis of these molecules in solution has been explored. Finally, the absolute configurational assignment of the natural products was established and their biological activities investigated.

A exploração de processos viáveis para a conversão da biomassa lignocelulósica em combustíveis limpos e produtos químicos de alto valor agregado, para complementar ou substituir produtos derivados de fontes não renováveis, é crucial para um desenvolvimento sustentável. A valorização e modificação dos componentes lignocelulósicos, torna-se imprescindível para viabilizar o sistema de biorrefinaria. A lignina, macromolécula aromática dominante na natureza, é um destes componentes que, devido a sua estrutura e composição, oferece rotas únicas para a produção de vários químicos de valor agregado. Este trabalho tem como objetivo avaliar o efeito de reações de oxidação em ligninas de bagaço e de palha de cana-de-açúcar, e de casca de café, na obtenção de compostos aromáticos de baixa massa molar, em especial a vanilina, e adicionalmente, verificar a aplicabilidade da lignina oxidada residual na obtenção de matrizes para liberação controlada de herbicida, buscando alternativas para agregar valor à lignina proveniente de resíduos agroindustriais e contribuir com a viabilização de biorrefinarias. Para isso, os materiais lignocelulósicos foram pré-tratados com ácido diluído e submetidos a deslignificação alcalina para obtenção da lignina. As frações obtidas durante cada etapa foram avaliadas quanto a composição química e Espectrometria no Infravermelho (FTIR), e as ligninas obtidas, foram ainda avaliadas por Espectrometria no Ultravioleta (UV) e por Ressonância Magnética Nuclear (1H RMN, 13C RMN e 2D RMN). As ligninas obtidas foram oxidadas em diferentes condições: oxidação enzimática utilizando lacase, em meio ácido e em meio alcalino com H2O2 e oxidação úmida em meio aquoso e alcalino utilizando H2O2. A fração líquida obtida foi analisada por Cromatografia Líquida de Alta Eficiência (CLAE) para identificar e quantificar os aldeídos aromáticos e outros compostos de degradação, enquanto a fração sólida, constituída pela lignina residual oxidada, foi avaliada por FTIR e UV. As ligninas oxidadas provenientes das condições que resultaram em um maior rendimento de vanilina, foram aplicadas na formulação de matrizes para liberação controlada de ametrina. Os resultados mostraram que a lignina de bagaço e de palha de cana não oxidadas são compostas principalmente por unidades siringil e guaiacil, respectivamente, e predominância de ligações ?-O-4, enquanto a lignina de casca de café foi composta principalmente por unidades hidroxil e predominância de ligações C-C, indicando uma estrutura mais condensada. Das oxidações avaliadas, a oxidação em meio alcalino (NaOH 10%) utilizando H2O2 9,1% gerou um maior rendimento de vanilina quando utilizada lignina de bagaço (8,13 mg/g lignina) e de casca de café (1,15 mg/g lignina), e H2O2 6,1% quando utilizada lignina de palha (6,48 mg/g lignina). A aplicação das ligninas oxidadas permitiu a obtenção de matrizes capazes de liberar o herbicida ametrina com diferentes cinéticas, dependendo das propriedades e das proporções das ligninas empregadas. / The exploration of feasible paths for the conversion of the lignocellulosic biomass into clean fuels and high value chemicals, to complement or replace products derived from non-renewable sources, is crucial for a sustainable development. The efficient utilization of the lignocellulosic components is of fundamental importance for the economic viability of biorefineries. Lignin, nature\'s dominant aromatic polymer, is a major component of the biomass that, due to its structuture and chemical composition, is a unique feedstock for producing high-value chemicals. The aim of this study is to seek for alternatives for adding value to lignin from agro-industrial waste in order to contribute to the vialbility of biorefineries. To achieve this, we evaluated the effect of oxidation reactions in sugarcane bagasse and straw lignin, and coffee husk, for obtaining aromatic compounds of low molecular weight, especially vanillin. In addition, the applicability of the residual oxidized lignin for obtaining matrices for the controlled release of herbicides was also examined in this work. For this purpose, the lignocellulosic materials were pretreated with dilute acid and subjected to alkaline delignification to achieve separation of the lignin. The fractions obtained at each stage were analyzed for chemical composition and with Infrared Spectroscopy (FTIR). The lignins were also analyzed using UV-vis Spectroscopy (UV) and Nuclear Magnetic Resonance (1H NMR, 13C NMR and HSQC). The lignins obtained were subjected to oxidation using different physiochemical conditions - enzymatic oxidation with laccase, oxidation in acidic and alkaline medium with H2O2 and wet oxidation in aqueous and alkaline medium using H2O2.The obtained liquid fraction was analyzed by High Performance Liquid Chromatography (HPLC) to identify and quantify the aromatic aldehydes and other compounds of lignin degradation, while the solid fraction, comprising the oxidized residual lignin, was analyzed by FTIR and UV. The oxidized lignins derived from the conditions that have resulted in a maximun yield of vanillin, were applied in the formulation of controlled release matrices of ametryne. Results for non oxidized lignin showed bagasse and straw lignin being composed mainly of syringyl and guaiacil units, respectively, linked predominantly by ?-O-4 bonds, while coffee husk lignin was mainly composed of hydroxyl units linked by C-C bonds predominantly, indicating a more condensed structure. Of all the oxidation reactions, the oxidation in alkaline medium (NaOH 10%) using H2O2 9.1% showed the highest yield of vanillin with bagasse lignin (8.13 mg/g lignin) and coffee husk lignin (1.15 mg/g lignin), and H2O2 6.1% with straw lignin (6.48 mg/g lignin). The application of oxidized lignins as matrices resulted in the release of the herbicide ametryne with different kinetics, depending on the proportions and properties of the lignins applied.