Optimization of ethanol production by yeasts from lignocellulosic feedstocks

Ethanol from lignocellulosic feedstocks is not currently competitive with corn-based ethanol in terms of yields and commercial feasibility. Through optimization of the pretreatment and fermentation steps this could change. The overall goal of this study was to evaluate, characterize, and optimize ethanol production from lignocellulosic feedstocks by the yeasts Saccharomyces cerevisiae (strain Ethanol Red, ER) and Pichia stipitis CBS 6054. Through a series of fermentations and growth studies, P. stipitis CBS 6054 and S. cerevisiae (ER) were evaluated on their ability to produce ethanol from both single substrate (xylose and glucose) and mixed substrate (five sugars present in hemicellulose) fermentations. The yeasts were also evaluated on their ability to produce ethanol from dilute acid pretreated hydrolysate and enzymatic hydrolysate. Hardwood (aspen), softwood (balsam), and herbaceous (switchgrass) hydrolysates were also tested to determine the effect of the source of the feedstock. P. stipitis produced ethanol from 66-98% of the theoretical yield throughout the fermentation studies completed over the course of this work. S. cerevisiae (ER) was determined to not be ideal for dilute acid pretreated lignocellulose because it was not able to utilize all the sugars found in hemicellulose. S. cerevisiae (ER) was instead used to optimize enzymatic pretreated lignocellulose that contained only glucose monomers. It was able to produce ethanol from enzymatically pretreated hydrolysate but the sugar level was so low (>3 g/L) that it would not be commercially feasible. Two lignocellulosic degradation products, furfural and acetic acid, were evaluated for whether or not they had an inhibitory effect on biomass production, substrate utilization, and ethanol production by P. stipitis and S. cerevisiae (ER). It was determined that inhibition is directly related to the concentration of the inhibitor and the organism. The final phase for this thesis focused on adapting P. stipitis CBS 6054 to toxic compounds present in dilute acid pretreated hydrolysate through directed evolution. Cultures were transferred to increasing concentrations of dilute acid pretreated hydrolysate in the fermentation media. The adapted strains’ fermentation capabilities were tested against the unadapted parent strain at each hydrolysate concentration. The fermentation capabilities of the adapted strain were significantly improved over the unadapted parentstrain. On media containing 60% hydrolysate the adapted strain yielded 0.30 g_ethanol/g_sugar ± 0.033 (g/g) and the unadapted parent strain yielded 0.11 g/g ±0.028. The culture has been successfully adapted to growth on media containing 65%, 70%, 75%, and 80% hydrolysate but with below optimal ethanol yields (0.14-0.19 g/g). Cell recycle could be a viable option for improving ethanol yields in these cases. A study was conducted to determine the optimal media for production of ethanol from xylose and mixed substrate fermentations by P. stipitis. Growth, substrate utilization, and ethanol production were the three factors used to evaluate the media. The three media tested were Yeast Peptone (YP), Yeast Nitrogen Base (YNB), and Corn Steep Liquor (CSL). The ethanol yields (g/g) for each medium are as follows: YP - 0.40-0.42, YNB -0.28-.030, and CSL - 0.44-.051. The results show that media containing CSL result in slightly higher ethanol yields then other fermentation media. P. stipitis was successfully adapted to dilute acid pretreated aspen hydrolysate in increasing concentrations in order to produce higher ethanol yields compared to the unadapted parent strain. S. cerevisiae (ER) produced ethanol from enzymatic pretreated cellulose containing low concentrations of glucose (1-3g/L). These results show that fermentations of lignocellulosic feedstocks can be optimized based on the substrate and organism for increased ethanol yields.

Kinetic characterization for pretreatment of timber varieties and switchgrass using diluted acid hydrolysis

In recent years, growing attention has been devoted to the use of lignocellulosic biomass as a feedstock to produce renewable carbohydrates as a source of energy products, including liquid alternatives to fossil fuels. The benefits of developing woody biomass to ethanol technology are to increase the long-term national energy security, reduce fossil energy consumption, lower greenhouse gas emissions, use renewable rather than depletable resources, and create local jobs. Currently, research is driven by the need to reduce the cost of biomass-ethanol production. One of the preferred methods is to thermochemically pretreat the biomass material and subsequently, enzymatically hydrolyze the pretreated material to fermentable sugars that can then be converted to ethanol using specialized microorganisms. The goals of pretreatment are to remove the hemicellulose fraction from other biomass components, reduce bioconversion time, enhance enzymatic conversion of the cellulose fraction, and, hopefully, obtain a higher ethanol yield. The primary goal of this research is to obtain kinetic detailed data for dilute acid hydrolysis for several timber species from the Upper Peninsula of Michigan and switchgrass. These results will be used to identify optimum reaction conditions to maximize production of fermentable sugars and minimize production of non-fermentable byproducts. The structural carbohydrate analysis of the biomass species used in this project was performed using the procedure proposed by National Renewable Energy Laboratory (NREL). Subsequently, dilute acid-catalyzed hydrolysis of biomass, including aspen, basswood, balsam, red maple, and switchgrass, was studied at various temperatures, acid concentrations, and particle sizes in a 1-L well-mixed batch reactor (Parr Instruments, ii Model 4571). 25 g of biomass and 500 mL of diluted acid solution were added into a 1-L glass liner, and then put into the reactor. During the experiment, 5 mL samples were taken starting at 100°C at 3 min intervals until reaching the targeted temperature (160, 175, or 190°C), followed by 4 samples after achieving the desired temperature. The collected samples were then cooled in an ice bath immediately to stop the reaction. The cooled samples were filtered using 0.2 μm MILLIPORE membrane filter to remove suspended solids. The filtered samples were then analyzed using High Performance Liquid Chromatography (HPLC) with a Bio-Rad Aminex HPX-87P column, and refractive index detection to measure monomeric and polymeric sugars plus degradation byproducts. A first order reaction model was assumed and the kinetic parameters such as activation energy and pre-exponential factor from Arrhenius equation were obtained from a match between the model and experimental data. The reaction temperature increases linearly after 40 minutes during experiments. Xylose and other sugars were formed from hemicellulose hydrolysis over this heat up period until a maximum concentration was reached at the time near when the targeted temperature was reached. However, negligible amount of xylose byproducts and small concentrations of other soluble sugars, such as mannose, arabinose, and galactose were detected during this initial heat up period. Very little cellulose hydrolysis yielding glucose was observed during the initial heat up period. On the other hand, later in the reaction during the constant temperature period xylose was degraded to furfural. Glucose production from cellulose was increased during this constant temperature period at later time points in the reaction. The kinetic coefficient governing the generation of xylose from hemicellulose and the generation of furfural from xylose presented a coherent dependence on both temperature and acid concentration. However, no effect was observed in the particle size. There were three types of biomass used in this project; hardwood (aspen, basswood, and red maple), softwood (balsam), and a herbaceous crop (switchgrass). The activation energies and the pre-exponential factors of the timber species and switchgrass were in a range of 49 - 180 kJ/mol and from 7.5x104 - 2.6x1020 min-1, respectively, for the xylose formation model. In addition, for xylose degradation, the activation energies and the preexponential factors ranged from 130 - 170 kJ/mol and from 6.8x1013 - 3.7x1017 min-1, respectively. The results compare favorably with the literature values given by Ranganathan et al, 1985. Overall, up to 92 % of the xylose was able to generate from the dilute acid hydrolysis in this project.

Concentration profiles in batch fermentation of hydrolyzed lignocellulose

Experimental data was obtained for profiling changes in concentrations of two inhibiting compounds in batch fermentation of a synthesized liquor resembling hydrolyzed lignocellulose, a furan (furfural) and a phenolic compound (vanillin), along with standard fermentation data, i.e. substrate, biomass and ethanol concentrations. The initial inhibitor concentrations and fermentation temperatures in the 18 experiments were varied according to a two-level complete center composite experimental design. Based upon these observed variations in the fermentative behavior, the fermentation kinetics were modeled, as published in the corresponding article, including microbial conversion rates of the inhibitive compounds into their less toxic derivatives.

Empleo de fermentaciones secuenciales con levaduras no-Saccharomyces y aplicación de bloqueadores metabólicos para reducir el grado alcohólico en vinos

La combinación secuencial de especies no-Saccharomyces y Saccharomyces durante la fermentación y la adición de bloqueadores metabólicos como el furfural, o-vainillina, glicolaldehído y p-benzoquinona pueden resultar unas técnicas de vinificación interesantes para reducir el grado alcohólico del vino. El grado alcohólico se determinó por HPLC-IR y los azúcares residuales mediante tests enzimáticos. Las cepas de levadura 7013 (Torulaspora delbrueckii) y 938 (Schizosaccharomyces pombe) destacaron por su capacidad para reducir significativamente el grado alcohólico (reducción media del 2.1 % v/v) dando lugar a un vino seco (azúcares menor que 1.5 gl-1) en fermentación secuencial con la 7VA (Saccharomyces cerevisiae). La o-vainillina permitió una disminución en el contenido de etanol del 0.54 % v/v a dosis de 50 mg l-1, mientras que el efecto bloqueador del glicolaldehído fue más efectivo a la dosis de 200 mg l-1 con una reducción del 0.95 % v/v. Finalmente con la p-benzoquinona se logró una reducción en el grado alcohólico de hasta 0.85 % v/v.

Utilización de bloqueadores metabólicos y optimización de las condiciones de aplicación para la reducción del grado alcohólico en vinos elaborados a partir de uva procedente de zonas cálidas

El presente trabajo de Tesis describe la posibilidad de modular la fermentación alcohólica utilizando bloqueadores metabólicos como furfural, o-vainillina, ácido cinámico, glicolaldehído, p-benzoquinona y cobre; para controlar la producción de etanol. El redireccionamiento de la ruta glicolítica en Saccharomyces cerevisiae favorece el descenso del grado alcohólico gracias al aumento de la producción de metabolitos secundarios de interés enológico. La primera parte de la Tesis presenta una revisión bibliográfica sobre estudios previos en los que se ha evaluado el efecto de los diferentes bloqueadores metabólicos en la producción de etanol durante la fermentación alcohólica. La segunda parte muestra los resultados experimentales de producción de etanol obtenidos con los bloqueadores metabólicos, observándose una amplia variabilidad en su efecto en función de la naturaleza química de cada bloqueador y de la naturaleza del medio fermentativo utilizado. Finalmente, la tercera parte del trabajo muestra el efecto de los bloqueadores metabólicos sobre los parámetros colorimétricos y la producción de metabolitos secundarios, observándose un importante efecto en la producción de glicerina y en algunos de los compuestos volátiles fermentativos. La principal aplicación de esta tecnología basada en la utilización de bloqueadores metabólicos sería la elaboración de vinos con una menor graduación alcohólica a partir de uva procedente de zonas cálidas. ABSTRACT This thesis describes the possibility of modulating the alcoholic fermentation using metabolic blockers such as furfural, o-vanillin, cinnamic acid, glycolaldehyde, p-benzoquinone and copper. The controlled production of ethanol by redirecting of the glycolytic pathway in Saccharomyces cerevisiae, is achieved through diverting some of the carbohydrates away from alcohol production into the formation of glycolytic intermediates of interest to the winemaking industry. The first part of this work shows a literature review on previous studies about the effect of different metabolic blockers in order to reduce the ethanol production during alcoholic fermentation. The second part deals about the experimental results of ethanol production obtained with the metabolic blockers, showing a wide variation in the inhibitory effect depending on the chemical nature of each blocker and the nature of the fermentation medium used. Finally, the third part discussed about the effect of the metabolic blockers on colorimetric parameters and production of secondary metabolites, showing a significant effect on the production of glycerol and in some of the volatile fermentative compounds. The main application of this technology based on the use of metabolic blockers could lie in the preparation of reduced-alcohol wines from grapes grown in hot climate regions.

Sequential pyrolysis of willow SRC at low and high heating rates:implications for selective pyrolysis

The main aim of the work is to investigate sequential pyrolysis of willow SRC using two different heating rates (25 and 1500 °C/min) between 320 and 520 °C. Thermogravimetric analysis (TGA) and pyrolysis - gas chromatography - mass spectroscopy (Py-GC-MS) have been used for this analysis. In addition, laboratory scale processing has been undertaken to compare product distribution from fast and slow pyrolysis at 500 °C. Fast pyrolysis was carried out using a 1 kg/h continuous bubbling fluidized bed reactor, and slow pyrolysis using a 100 g batch reactor. Findings from this study show that heating rate and pyrolysis temperatures have a significant influence on the chemical content of decomposition products. From the analytical sequential pyrolysis, an inverse relationship was seen between the total yield of furfural (at high heating rates) and 2-furanmethanol (at low heating rates). The total yield of 1,2-dihydroxybenzene (catechol) was found to be significant higher at low heating rates. The intermediates of catechol, 2-methoxy-4-(2-propenyl)phenol (eugenol); 2-methoxyphenol (guaiacol); 4-Hydroxy-3,5-dimethoxybenzaldehyde (syringaldehyde) and 4-hydroxy-3-methoxybenzaldehyde (vanillin), were found to be highest at high heating rates. It was also found that laboratory scale processing alters the pyrolysis bio-oil chemical composition, and the proportions of pyrolysis product yields. The GC-MS/FID analysis of fast and slow pyrolysis bio-oils reveals significant differences. © 2011 Elsevier Ltd. All rights reserved.

A comparative study of straw, perennial grasses and hardwoods in terms of fast pyrolysis products

The aim of this study is to characterise and compare fast pyrolysis product yields from straw, high yielding perennial grasses and hardwoods. Feedstocks selected for this study include: wheat straw (Triticum aestivum), switch grass (Panicum virgatum), miscanthus (Miscanthus x giganteus), willow short rotation coppice (Salix viminalis) and beech wood (Fagus sylvatica). The experimental work is divided into two sections: analytical (TGA and Py-GC-MS) and laboratory scale processing using a continuously fed bubbling fluidized bed reactor with a capacity of up to 1 kg/h. Pyrolysis-gas chromatography-mass spectrometry (Py-GC-MS) has been used to quantify pyrolysis products and simulate fast pyrolysis heating rates, in order to study potential key light and medium volatile decomposition products found in these feedstocks. Py-GC-MS quantification results show that the highest yields of furfural (0.57 wt.%), 2-furanmethanol (0.18 wt.%), levoglucosan (0.73 wt.%), 1,2-benzenediol (0.27 wt.%) and 2-methoxy-4-vinylphenol (0.38 wt.%) were found in switch grass, and that willow SRC produced the highest yield of phenol (0.33 wt.%). The bio-oil higher heating value was highest for switch grass (22.3 MJ/kg). Water content within the bio-oil is highest in the straw and perennial grasses and lowest in the hardwood willow SRC. The high bio-oil and char heating value and low water content found in willow SRC, makes this crop an attractive energy feedstock for fast pyrolysis processing, if the associated production costs and harvest yields can be maintained at current reported values. The bio-oil from switch grass has the highest potential for the production of high value chemicals. © 2013 Elsevier Ltd. All rights reserved.

Phosphorus catalysis in the pyrolysis behaviour of biomass

Phosphorus is a key plant nutrient and as such, is incorporated into growing biomass in small amounts. This paper examines the influence of phosphorus, present in either acid (HPO) or salt ((NH)PO) form, on the pyrolysis behaviour of both Miscanthus × giganteus, and its cell wall components, cellulose, hemicellulose (xylan) and lignin (Organosolv). Pyrolysis-gas chromatography-mass spectrometry (PY-GC-MS) is used to examine the pyrolysis products during thermal degradation, and thermogravimetric analysis (TGA) is used to examine the distribution of char and volatiles. Phosphorus salts are seen to catalyse the pyrolysis and modify the yields of products, resulting in a large increase in char yield for all samples, but particularly for cellulose and Miscanthus. The thermal degradation processes of cellulose, xylan and Miscanthus samples occur in one step and the main pyrolysis step is shifted to lower temperature in the presence of phosphorus. A small impact of phosphorus was observed in the case of lignin char yields and the types of pyrolysis decomposition products produced. Levoglucosan is a major component produced in fast pyrolysis of cellulose. Furfural and levoglucosenone become more dominant products upon P-impregnation pointing to new rearrangement and dehydration routes. The P-catalysed xylan decomposition route leads to a much simpler mixture of products, which are dominated by furfural, 3-methyl-2-cyclopenten-1-one and one other unconfirmed product, possibly 3,4-dihydro-2-methoxy-2H-pyran or 4-hydroxy-5,6-dihydro-(2H)-pyran-2-one. Phosphorus-catalysed lignin decomposition also leads to a modified mixture of tar components and desaspidinol as well as other higher molecular weight component become more dominant relative to the methoxyphenyl phenols, dimethoxy phenols and triethoxy benzene. Comparison of the results for Miscanthus lead to the conclusion that the understanding of the fast pyrolysis of biomass can, for the most part, be gained through the study of the individual cell wall components, provided consideration is given to the presence of catalytic components such as phosphorus.

Thermo-chemical behaviour and chemical product formation from Polar seaweeds during intermediate pyrolysis

Fundamental analytical pyrolysis studies of biomass from Polar seaweeds, which exhibit a different biomass composition than terrestrial and micro-algae biomass were performed via thermogravimetric analysis (TGA) and pyrolysis-gas chromatography/mass-spectrometry (Py-GC/MS). The main reason for this study is the adaptation of these species to very harsh environments making them an interesting source for thermo-chemical processing for bioenergy generation and production of biochemicals via intermediate pyrolysis. Several macroalgal species from the Arctic region Kongsfjorden, Spitsbergen/Norway (Prasiola crispa, Monostroma arcticum, Polysiphonia arctica, Devaleraea ramentacea, Odonthalia dentata, Phycodrys rubens, Sphacelaria plumosa) and from the Antarctic peninsula, Potter Cove King George Island (Gigartina skottsbergii, Plocamium cartilagineum, Myriogramme manginii, Hymencladiopsis crustigena, Kallymenia antarctica) were investigated under intermediate pyrolysis conditions. TGA of the Polar seaweeds revealed three stages of degradation representing dehydration, devolatilization and decomposition of carbonaceous solids. The maximum degradation temperatures Prasiola crispa were observed within the range of 220-320 C and are lower than typically obtained by terrestrial biomass, due to divergent polysaccharide compositions. Biochar residues accounted for 33-46% and ash contents of 27-45% were obtained. Identification of volatile products by Py-GC/MS revealed a complexity of generated chemical compounds and significant differences between the species. A widespread occurrence of aromatics (toluene, styrene, phenol and 4-methylphenol), acids (acetic acid, benzoic acid alkyl ester derivatives, 2-propenoic acid esters and octadecanoic acid octyl esters) in pyrolysates was detected. Ubiquitous furan-derived products included furfural and 5-methyl-2-furaldehyde. As a pyran-derived compound maltol was obtained by one red algal species (P. rubens) and the monosaccharide d-allose was detected in pyrolysates in one green algal (P. crispa). Further unique chemicals detected were dianhydromannitol from brown algae and isosorbide from green algae biomass. In contrast, the anhydrosugar levoglucosan and the triterpene squalene was detected in a large number of pyrolysates analysed. © 2013 Elsevier B.V. All rights reserved.

The thermal performance of the polysaccharides extracted from hardwood:cellulose and hemicellulose

The pyrolytic behaviour of individual component in biomass needs to be understood to gain insight into the mechanism of biomass pyrolysis. A comparative study on the pyrolysis of cellulose (hexose-based polysaccharides) and hemicallulose (pentose-based polysaccharides) is performed by two sets of experiments including TG analysis and Py-GC-MS/FTIR. The samples of these two polysaccharide components are thermally decomposed in TGA at the heating rate of 5 and 60 K/min to demonstrate the different characteristics of mass loss stage(s) between them. The yield of pyrolytic products is examined by a fluidized-bed fast pyrolysis unit. The experiment confirms that cellulose mainly contributes to bio-oil production (reaching the maximum of 72% at 580 °C), while hemicellulose works as an important precursor for the char production (∼25%). The compounds in the gaseous mixture (CO and CO2) and bio-oil (levoglucosan, furfural, aldehyde, acetone and acetic acid) are further characterized by GC-MS for cellulose and GC-FTIR for hemicellulose, and their formations are investigated thoroughly. © 2010 Elsevier Ltd. All rights reserved.

Avaliação do potencial da fibra e casca de coco maduro, casca de coco verde e cacto pré-tratados visando à produção de etanol

The present work investigated the potential of different residual lignocellulosic materials generated in rural and urban areas (coconut fibre mature, green coconut shell and mature coconut shell), and vegetable cultivated in inhospitable environments (cactus) aimed at the production of ethanol, being all materials abundant in the Northeast region of Brazil. These materials were submitted to pretreatments with alkaline hydrogen peroxide followed by sodium hydroxide (AHP-SHP), autohydrolysis (AP), hydrothermal catalyzed with sodium hydroxide (HCSHP) and alkali ethanol organosolv (AEOP). These materials pretreated were submitted to enzymatic hydrolysis and strategies of simultaneous saccharification and fermentation (SSF) and saccharification and fermentation semi-simultaneous (SSSF) by Saccharomyces cerevisiae, Zymomonas mobilis and Pichia stipitis. It was also evaluated the presence of inhibitory compounds (hydroxymethylfurfural, furfural, acetic acid, formic acid and levulinic acid) and seawater during the fermentative process. Materials pretreated with AHP-SHP have resulted in delignification of the materials in a range between 54 and 71%, containing between 51.80 and 54.91% of cellulose, between 17.65 and 28.36% of hemicellulose, between 7.99 and 10.12% of lignin. Enzymatic hydrolysis resulted in the conversions in glucose between 68 and 76%. Conversion yields in ethanol using SSF and SSSF for coconut fibre mature pretreated ranged from 0.40 and 0.43 g/g, 0.43 and 0.45 g/g, respectively. Materials pretreated by AP showed yields of solids between 42.92 and 92.74%, containing between 30.65 and 51.61% of cellulose, 21.34 and 41.28% of lignin. Enzymatic hydrolysis resulted in glucose conversions between 84.10 and 92.52%. Proceeds from conversion into ethanol using green coconut shell pretreated, in strategy SSF and SSSF, were between 0.43 and 0.45 g/g. Coconut fibre mature pretreated by HCSHP presented solids yields between 21.64 and 60.52%, with increased in cellulose between 28.40 and 131.20%, reduction of hemicellulose between 43.22 and 69.04% and reduction in lignin between 8.27 and 89.13%. Enzymatic hydrolysis resulted in the conversion in glucose of 90.72%. Ethanol yields using the SSF and SSSF were 0.43 and 0.46 g/g, respectively. Materials pretreated by AEOP showed solid reductions between 10.75 and 43.18%, cellulose increase up to 121.67%, hemicellulose reduction up to 77.09% and lignin reduced up to 78.22%. Enzymatic hydrolysis resulted in the conversion of glucose between 77.54 and 84.27%. Yields conversion into ethanol using the SSF and SSSF with cactus pretreated ranged from 0.41 and 0.44 g/g, 0.43 and 0.46 g/g, respectively. Fermentations carried out in bioreactors resulted in yields and ethanol production form 0.42 and 0.46 g/g and 7.62 and 12.42 g/L, respectively. The inhibitory compounds showed negative synergistic effects in fermentations performed by P. stipitis, Z. mobilis and S. cerevisiae. Formic acid and acetic acid showed most significant effects among the inhibitory compounds, followed by hydroxymethylfurfural, furfural and levulinic acid. Fermentations carried out in culture medium diluted with seawater showed promising results, especially for S. cerevisiae (0.50 g/g) and Z. mobilis (0.49 g/g). The different results obtained in this study indicate that lignocellulosic materials, pretreatments, fermentative processes strategies and the microorganisms studied deserve attention because they are promising and capable of being used in the context of biorefinery, aiming the ethanol production.

Caracterização de aguardente de cana-de-açúcar "grogue de Cabo Verde"

A aguardente de cana é uma bebida de grande importância económica para Cabo Verde, mais concretamente para as ilhas de Santiago, Brava, Nicolau e S. Antão, que apresentam boas condições climáticas para a produção de cana. O consumo tem vindo a crescer em todas as classes sociais e tem a pretensão de conquistar o mercado internacional. Mas isso gera dificuldades para os produtores de aguardente, que muitas vezes enfrentam barreiras para entrar no mercado externo, principalmente devido à qualidade do produto e à falta de padronização desta bebida. Este trabalho teve como objectivo obter uma identidade e qualidade padrão da aguardente de cana em Cabo Verde, portanto, fizeram-se 5 destilados na ESTM os quais foram avaliados sensorialmente quanto à padronização do produto e também quanto à qualidade através de comparação com duas aguardentes feitas por produtores cabo-verdianos. Para isso, foram preparados 40 litros de calda, dividida em 5 lotes de 7,5 litros no alambique, obtendo-se 5 destilados com 450, 470, 565, 300 e 430ml. Determinou-se o grau alcoólico, acidez total, teor furfural e teor de cobre dos destilados realizados na escola e em Cabo Verde. Os valores obtidos do grau alcoólico, acidez total e furfural encontramse dentro dos limites estabelecidos pela lei brasileira, com exceção para o furfural que apresentou um resultado positivo nas amostras dos destilados feitos em Cabo Verde, correspondente a 28,57%. Os valores de acidez total variaram entre 9,38 a 136,87 mg/100 ml (álcool anidrido). O cobre foi determinado através da técnica de espectroscopia de absorção atómica com câmara grafite. As amostras analisadas apresentaram valores de cobre que variaram de 0,406 a 7,380 mgL-1. Das amostras analisadas 71,43% estavam dentro do limite e 28,57 % apresentaram teores de cobre acima do permitido pela legislação. Relativamente à padronização das 5 amostras feitas na escola, demonstrou-se que a estrutura de dados apenas se evidenciou validada para os atributos oleosidade e aroma (p = 0.000 e p = 0.037, respetivamente). Comparando as amostras feitas na escola com as duas de Cabo Verde, mostrou-se que à cor franca (P <0,000) e aceitável (P <0,013), limpidez (P <0,000) brilhante e transparente (P <0,001), as variáveis independentes não exercem influências na variável dependente segundo o modelo proposto.

Produzione di alcol furfurilico da furfurale in fase gas con catalizzatori a base di CaO

The hydrogenation of biomass-derived molecules is a key reaction in upgrading these compounds into chemicals and fuels. The use of catalytic transfer hydrogenation, employing alcohols as hydrogen sources, offers an alternative approach to this process, avoiding the use of H2 under high pressure and precious metal catalysts. In this work, the gas-phase conversion of biomass-derived furfural into furfuryl alcohol and 2-methylfuran was studied, using methanol as the H-transfer agent and CaO-based catalysts. The results obtained with this catalyst were compared with those obtained by using MgO, which due to its basic properties and to its high surface area, at present appears to be among the best basic catalysts used for the conversion of biomass-derived molecules. Pure CaO, despite having a very low surface area, compared to MgO catalyst (5 m2/g vs. 172 m2/g), was shown to reduce furfural into its corresponding unsaturated alcohol at 350°C, thus allowing selective H-transfer from methanol to the substrate. These results highlight the potential application of the H-transfer reaction over CaO based catalysts as an efficient process for the selective reduction of biomass-derived molecules.

Melhoria de procedimentos internos no laboratório do Instituto dos Vinhos do Douro e do Porto, I.P.

Este relatório foi elaborado no âmbito do estágio curricular realizado na Direção de Serviços Técnicos e de Certificação do Instituto dos Vinhos do Douro e do Porto, I.P. Teve como principal objetivo apresentar propostas de alteração de procedimentos internos do laboratório do Instituto dos Vinhos do Douro e do Porto, I.P., no sentido de reduzir o tempo de resposta às solicitações, procurando uma melhor rentabilização tanto de equipamentos como de recursos humanos. Para atingir tal objetivo, foi elaborado o diagnóstico da situação, com base na informação recolhida na Direção de Serviços Técnicos e de Certificação, incluindo os dados fornecidos pelo software GLAB que dá apoio às operações realizadas no laboratório do Instituto dos Vinhos do Douro e do Porto. Além disso, foi efetuado o acompanhamento do circuito das amostras de produtos vínicos desde a sua receção, à análise nos setores do laboratório e posterior validação dos resultados. Dado que o estudo da entrada de amostras no setor Análise Mineral foi maioritariamente inconclusivo, apurou-se o custo por análise na determinação do chumbo e, ainda, foi realizada uma simulação determinar a despesa necessária para reduzir o número de amostras analisadas de cada vez que se liga o equipamento. Foi ainda comparado o custo da determinação do parâmetro furfural, análise que tanto pode ser realizada no setor Cromatografia Gasosa como no setor Cromatografia Líquida. Para isso, foram utlizados vários testes estatísticos. Com base na avaliação efetuada foram identificadas e propostas as seguintes oportunidades de melhoria: - Automação de uma das atividades realizadas no setor Físico-Química I, atividade esta necessária à preparação das análises; - Contrabalançar a sazonalidade verificada na receção de amostras dos clientes com as amostras provenientes da Direção de Serviços de Fiscalização e Controlo; - Inserção de algumas variáveis no software GLAB. É de realçar que a proposta referente à automação de uma das atividades realizadas no setor Físico-Química foi implementada pelo IVDP. Foram, também, identificadas propostas de futuras investigações.

Xylose from lignocellulosic waste in the production and industrial processing of pinneaple (Ananascomusus)

Lignocellulosicwaste from the pineapple production is a raw material useful for the xylose production by hydrolysis and it can be converted to xylitol. The objective of this work was to study the hydrolysis of pineapple peel with sulfuric acid at variable concentration (2-6%), reaction time (0-350 min) and temperature at 98 ˚C. The concentration of xylose, glucose and degradation products as acetic acid and furfural was determined. Optimal conditions found for hydrolysis were 6% H2SO4 at 98 ˚C for 83 min which yield was 26,9 g xylose/L, 2,61 g glucose/L, 7,71 g acetic acid/L and 0,29 g furfural/L.