Thermal processing of miscanthus, sugarcane bagasse, sugarcane trash and their acid hydrolysis residues

The research presented in this thesis was developed as part of DIBANET, an EC funded project aiming to develop an energetically self-sustainable process for the production of diesel miscible biofuels (i.e. ethyl levulinate) via acid hydrolysis of selected biomass feedstocks. Three thermal conversion technologies, pyrolysis, gasification and combustion, were evaluated in the present work with the aim of recovering the energy stored in the acid hydrolysis solid residue (AHR). Mainly consisting of lignin and humins, the AHR can contain up to 80% of the energy in the original feedstock. Pyrolysis of AHR proved unsatisfactory, so attention focussed on gasification and combustion with the aim of producing heat and/or power to supply the energy demanded by the ethyl levulinate production process. A thermal processing rig consisting on a Laminar Entrained Flow Reactor (LEFR) equipped with solid and liquid collection and online gas analysis systems was designed and built to explore pyrolysis, gasification and air-blown combustion of AHR. Maximum liquid yield for pyrolysis of AHR was 30wt% with volatile conversion of 80%. Gas yield for AHR gasification was 78wt%, with 8wt% tar yields and conversion of volatiles close to 100%. 90wt% of the AHR was transformed into gas by combustion, with volatile conversions above 90%. 5volO2%-95vol%N2 gasification resulted in a nitrogen diluted, low heating value gas (2MJ/m3). Steam and oxygen-blown gasification of AHR were additionally investigated in a batch gasifier at KTH in Sweden. Steam promoted the formation of hydrogen (25vol%) and methane (14vol%) improving the gas heating value to 10MJ/m3, below the typical for steam gasification due to equipment limitations. Arrhenius kinetic parameters were calculated using data collected with the LEFR to provide reaction rate information for process design and optimisation. Activation energy (EA) and pre-exponential factor (ko in s-1) for pyrolysis (EA=80kJ/mol, lnko=14), gasification (EA=69kJ/mol, lnko=13) and combustion (EA=42kJ/mol, lnko=8) were calculated after linearly fitting the data using the random pore model. Kinetic parameters for pyrolysis and combustion were also determined by dynamic thermogravimetric analysis (TGA), including studies of the original biomass feedstocks for comparison. Results obtained by differential and integral isoconversional methods for activation energy determination were compared. Activation energy calculated by the Vyazovkin method was 103-204kJ/mol for pyrolysis of untreated feedstocks and 185-387kJ/mol for AHRs. Combustion activation energy was 138-163kJ/mol for biomass and 119-158 for AHRs. The non-linear least squares method was used to determine reaction model and pre-exponential factor. Pyrolysis and combustion of biomass were best modelled by a combination of third order reaction and 3 dimensional diffusion models, while AHR decomposed following the third order reaction for pyrolysis and the 3 dimensional diffusion for combustion.

Shiitake (lentinula edodes) production on a sterilized bagasse substrate enriched with rice bran and sugarcane molasses

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

LIFE CYCLE ASSESSMENTS (LCAs) OF PYROLYSIS-BASED GASOLINE AND DIESEL FROM DIFFERENT REGIONAL FEEDSTOCKS: CORN STOVER, SWITCHGRASS, SUGAR CANE BAGASSE, WASTE WOOD, GUINEA GRASS, ALGAE, AND ALBIZIA

Renewable hydrocarbon biofuels are being investigated as possible alternatives to conventional liquid transportation fossil fuels like gasoline, kerosene (aviation fuel), and diesel. A diverse range of biomass feedstocks such as corn stover, sugarcane bagasse, switchgrass, waste wood, and algae, are being evaluated as candidates for pyrolysis and catalytic upgrading to produce drop-in hydrocarbon fuels. This research has developed preliminary life cycle assessments (LCA) for each feedstock-specific pathway and compared the greenhouse gas (GHG) emissions of the hydrocarbon biofuels to current fossil fuels. As a comprehensive study, this analysis attempts to account for all of the GHG emissions associated with each feedstock pathway through the entire life cycle. Emissions from all stages including feedstock production, land use change, pyrolysis, stabilizing the pyrolysis oil for transport and storage, and upgrading the stabilized pyrolysis oil to a hydrocarbon fuel are included. In addition to GHG emissions, the energy requirements and water use have been evaluated over the entire life cycle. The goal of this research is to help understand the relative advantages and disadvantages of the feedstocks and the resultant hydrocarbon biofuels based on three environmental indicators; GHG emissions, energy demand, and water utilization. Results indicate that liquid hydrocarbon biofuels produced through this pyrolysis-based pathway can achieve greenhouse gas emission savings of greater than 50% compared to petroleum fuels, thus potentially qualifying these biofuels under the US EPA RFS2 program. GHG emissions from biofuels ranged from 10.7-74.3 g/MJ from biofuels derived from sugarcane bagasse and wild algae at the extremes of this range, respectively. The cumulative energy demand (CED) shows that energy in every biofuel process is primarily from renewable biomass and the remaining energy demand is mostly from fossil fuels. The CED for biofuel range from 1.25-3.25 MJ/MJ from biofuels derived from sugarcane bagasse to wild algae respectively, while the other feedstock-derived biofuels are around 2 MJ/MJ. Water utilization is primarily from cooling water use during the pyrolysis stage if irrigation is not used during the feedstock production stage. Water use ranges from 1.7 - 17.2 gallons of water per kg of biofuel from sugarcane bagasse to open pond algae, respectively.

Evaluation of hexose and pentose in pre-cultivation of Candida guilliermondii on the key enzymes for xylitol production in sugarcane hemicellulosic hydrolysate

The evaluation of hexose and pentose in pre-cultivation of Candida guilliermondii FTI 20037 yeast on xylose reductase (XR) and xylitol dehydrogenase (XDH) enzymes activities was performed during fermentation in sugarcane bagasse hemicellulosic hydrolysate. The xylitol production was evaluated by using cells previously growth in 30.0 gl(-1) xylose, 30.0 gl(-1) glucose and in both sugars mixture (30.0 gl(-1) xylose and 2.0 gl(-1) glucose). The vacuum evaporated hydrolysate (80 gl(-1)) was detoxificated by ion exchange resin (A-860S; A500PS and C-150-Purolite(A (R))). The total phenolic compounds and acetic acid were 93.0 and 64.9%, respectively, removed by the resin hydrolysate treatment. All experiments were carried out in Erlenmeyer flasks at 200 rpm, 30A degrees C. The maximum XR (0.618 Umg (Prot) (-1) ) and XDH (0.783 Umg (Prot) (-1) ) enzymes activities was obtained using inoculum previously growth in both sugars mixture. The highest cell concentration (10.6 gl(-1)) was obtained with inoculum pre-cultivated in the glucose. However, the xylitol yield and xylitol volumetric productivity were favored using the xylose as carbon source. In this case, it was observed maximum xylose (81%) and acetic acid (100%) consumption. It is very important to point out that maximum enzymatic activities were obtained when the mixture of sugars was used as carbon source of inoculum, while the highest fermentative parameters were obtained when xylose was used.

PVA-Hydrogel Entrapped Candida Guilliermondii for Xylitol Production from Sugarcane Hemicellulose Hydrolysate

Viable cells of Candida guilliermondii were immobilized by inclusion into polyvinyl alcohol (PVA) hydrogel using the freezing-thawing method. Entrapment experiments were planned according to a 2(3) full factorial design, using the PVA concentration (80, 100, and 120 g L(-1)), the freezing temperature (-10, -15, and -20 degrees C), and the number of freezing-thawing cycles (one, three, and five) as the independent variables, integrated with three additional tests to estimate the errors. The effectiveness of the immobilization procedure was checked in Erlenmeyer flasks as the pellet capability to catalyze the xylose-to-xylitol bioconversion of a medium based on sugarcane bagasse hemicellulosic hydrolysate. To this purpose, the yield of xylitol on consumed xylose, xylitol volumetric productivity, and cell retention yield were selected as the response variables. Cell pellets were then used to perform the same bioconversion in a stirred tank reactor operated at 400 rpm, 30 degrees C, and 1.04 vvm air flowrate. At the end of fermentation, a maximum xylitol concentration of 28.7 g L(-1), a xylitol yield on consumed xylose of 0.49 g g(-1) and a xylitol volumetric productivity of 0.24 g L(-1) h(-1) were obtained.

Composite materials of thermoplastic starch and fibers from the ethanol-water fractionation of bagasse

The aim of this study was to evaluate the potential of the fibrous material obtained from ethanol-water fractionation of bagasse as reinforcement of thermoplastic starches in order to improve their mechanical properties. The composites were elaborated using matrices of corn and cassava starches plasticized with 30 wt%glycerin. The mixtures (0,5,10 and 15 wt% bagasse fiber) were elaborated in a rheometer at 150 degrees C. The mixtures obtained were pressed on a hot plate press at 155 degrees C. The test specimens were obtained according to ASTM D638. Tensile tests, moisture absorption tests for 24 days (20-23 degrees C and 53% RH, ASTM E104), and dynamic-mechanical analyses (DMA) in tensile mode were carried out. Images by scanning electron microscopy (SEM) and X-ray diffraction were obtained. Fibers (10 wt% bagasse fiber) increased tensile strength by 44% and 47% compared to corn and cassava starches, respectively. The reinforcement (15 wt% bagasse fiber) increased more than fourfold the elastic modulus on starch matrices. The storage modulus at 30 C (E(30 degrees C)`) increased as the bagasse fiber content increased, following the trend of tensile elastic modulus. The results indicate that these fibers have potential applications in the development of biodegradable composite materials. (c) 2011 Elsevier B.V. All rights reserved.

Supercritical steam cycles and biomass integrated gasification combined cycles for sugarcane mills

Back in 1970s and 1980s, cogeneration plants in sugarcane mills were primarily designed to consume all bagasse, and produce steam and electricity to the process. The plants used medium pressure steam boilers (21 bar and 300 degrees C) and backpressure steam turbines. Some plants needed also an additional fuel, as the boilers were very inefficient. In those times, sugarcane bagasse did not have an economic value, and it was considered a problem by most mills. During the 1990s and the beginning of the 2000s, sugarcane industry faced an open market perspective, thus, there was a great necessity to reduce costs in the production processes. In addition, the economic value of by-products (bagasse, molasses, etc.) increased, and there was a possibility of selling electricity to the grid. This new scenario led to a search for more advanced cogeneration systems, based mainly on higher steam parameters (40-80 bar and 400-500 degrees C). In the future, some authors suggest that biomass integrated gasification combined cycles are the best alternative to cogeneration plants in sugarcane mills. These systems might attain 35-40% efficiency for the power conversion. However, supercritical steam cycles might also attain these efficiency values, what makes them an alternative to gasification-based systems. This paper presents a comparative thermoeconomic study of these systems for sugarcane mills. The configurations studied are based on real systems that could be adapted to biomass use. Different steam consumptions in the process are considered, in order to better integrate these configurations in the mill. (C) 2009 Elsevier Ltd. All rights reserved.

Enzymatic hydrolysis of pretreated sugar cane bagasse using Penicillium funiculosum and Trichoderma harzianum cellulases

In this study, we investigated the enzymatic hydrolysis of pretreated sugarcane bagasse using eight different enzymatic blends obtained from concentrated crude enzyme extracts produced by Penicillium funiculosum and Trichoderma harzianum as well as from the extracts in combination with a commercial enzymatic cocktail. The influence of different levels of biomass delignification, degree of crystallinity of lignicellulose, composition of enzymatic activities and BSA on enzymatic hydrolysis yields (HYs) was evaluated. Our X-ray diffraction studies showed that crystallinity of lignocellulose is not a key determinant of its recalcitrance toward enzymatic hydrolysis. In fact, under the experimental conditions of our study, an increase in crystallinity of lignocellulosic samples resulted in increased glucose release by enzymatic hydrolysis. Furthermore, under the same conditions, the addition of BSA had no significant effect on enzymatic hydrolysis. The most efficient enzyme blends were obtained by mixing a commercial enzymatic cocktail with P. funiculosum or T. harzianum cellulase preparations (HYs above 97%) followed by the concentrated extract of P. funiculosum alone (HY= 88.5%). Increased hydrolytic efficiencies appeared to correlate with having an adequate level of both beta-glucosidase and xylanase activities in the blends. (C) 2011 Elsevier Ltd. All rights reserved.

PREPARATION and CHARACTERIZATION of CELLULOSE/HYDROUS NIOBIUM PHOSPHATE HYBRID

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Desempenho e composição corporal de novilhas alimentadas com dois níveis de concentrado e bagaço de cana submetidos a diferentes processos de hidrólise

O objetivo deste trabalho foi testar duas formas de hidrólise do bagaço de cana (com [17kgf/cm²]e sem [4kgf/cm²] rápida descompressão pós-hidrólise) e dois níveis de concentrado (25 e 45% MS) no desempenho e na composição corporal de novilhas em crescimento sob regime confinado durante 112 dias. Vinte e quatro novilhas Nelore e 12 Canchim foram distribuídas em delineamento de blocos casualizados em arranjo fatorial 2x2. Os resultados demonstraram que a omissão da explosão pós-hidrólise e o uso de níveis mais elevados de concentrado aumentaram o ganho de peso e o consumo de alimentos. Os resultados para ganho de peso e consumo de matéria seca, respectivamente, para tratamento sem vs com descompressão e 45 vs 25% de concentrado, foram 0,76 vs 0,67 e 0,76 vs 0,66 kg/d e 6,7 vs 5,8 e 6,8 vs 5,7 kg/dia. Entretanto, não houve diferença entre os tratamentos para conversão alimentar. Não foram observadas diferenças entre os tratamentos quanto à composição corporal determinada por meio do espaço de deutério ao final do período de confinamento, embora a taxa estimada de deposição de lipídios tenha sido maior para o tratamento sem explosão (216 vs 175 g/d) e o tratamento com 45% de concentrado (225 vs 166 g/d). Não foram observadas vantagens na descompressão rápida pós-hidrólise em alta pressão na eficiência de conversão de alimentos. Os resultados demonstram que animais alimentados com bagaço hidrolisado em níveis altos de ingestão (2,9% PV) e proporções baixas de concentrado apresentaram eficiência de utilização da dieta semelhante a dietas com níveis mais altos de concentrado.

Influence of the diet on in situ disappearance of dry matter, organic matter, and neutral detergent fiber of hydrolysed sugar cane bagasse

The effects of two diets based on hydrolysed sugarcane bagasse (HSB) and whole cottonseed (WCS), with or without oat hay, were analyzed for the in situ disappearance of dry matter (DM), organic matter (OM) and neutral detergent fiber (NDF) of HSB. Six mature castrated rams with a permanent T ruminai cannula were used in a complete randomized split plot design. The incubation times were 3, 6, 9, 12, 24, 48 and 72h. The diet with oat hay showed higher disappearance indexes for the NDF fraction. Furthermore, the maximum degradation of HSB constituents was reached around 48h of incubation. The diets were T1=64% hydrolyzed sugarcane + 36% whole cottonseed and T2=14% hydrolyzed sugarcane bagasse + 36% cottonseed + 50% oat hay.

Glass-ceramic material from the SiO 2-Al 2O 3-CaO system using sugar-cane bagasse ash (SCBA)

Brazil is the world's largest producer of alcohol and sugar from sugarcane. Currently, sugarcane bagasse is burned in boilers to produce steam and electrical energy, producing a huge volume of ash. The major component of the ash is SiO 2, and among the minor components there are some mineralizing agents or fluxing. Published works have shown the potential of transforming silicate-based residues into glass-ceramic products of great utility. This work reports the research results of SCBA use to produce glass-ceramics with wollastonite, rankinite and gehlenite as the major phases. These silicates have important applications as building industry materials, principally wollastonite, due to their special properties: high resistance to weathering, zero water absorption, and hardness among others. The glasses (frits) were prepared mixing ash, calcium carbonate and sodium or potassium carbonates as flux agents, in different concentrations. X-ray fluorescence was used to determine the chemical composition of the glasses and their crystallization was assessed by using thermal analysis (DTA/DSC/TGA) and X-ray diffraction. The crystallization kinetics was evaluated using the Kissinger method, giving activation energies ranging from 200 to 600 kJ/mol. © 2011 Ceramic Society of Japan.

Development and Biotechnological Application of a Novel Endoxylanase Family GH10 Identified from Sugarcane Soil Metagenome

Metagenomics has been widely employed for discovery of new enzymes and pathways to conversion of lignocellulosic biomass to fuels and chemicals. In this context, the present study reports the isolation, recombinant expression, biochemical and structural characterization of a novel endoxylanase family GH10 (SCXyl) identified from sugarcane soil metagenome. The recombinant SCXyl was highly active against xylan from beechwood and showed optimal enzyme activity at pH 6,0 and 45°C. The crystal structure was solved at 2.75 Å resolution, revealing the classical (β/α)8-barrel fold with a conserved active-site pocket and an inherent flexibility of the Trp281-Arg291 loop that can adopt distinct conformational states depending on substrate binding. The capillary electrophoresis analysis of degradation products evidenced that the enzyme displays unusual capacity to degrade small xylooligosaccharides, such as xylotriose, which is consistent to the hydrophobic contacts at the +1 subsite and low-binding energies of subsites that are distant from the site of hydrolysis. The main reaction products from xylan polymers and phosphoric acid-pretreated sugarcane bagasse (PASB) were xylooligosaccharides, but, after a longer incubation time, xylobiose and xylose were also formed. Moreover, the use of SCXyl as pre-treatment step of PASB, prior to the addition of commercial cellulolytic cocktail, significantly enhanced the saccharification process. All these characteristics demonstrate the advantageous application of this enzyme in several biotechnological processes in food and feed industry and also in the enzymatic pretreatment of biomass for feedstock and ethanol production. © 2013 Alvarez et al.

Sugarcane vinasse: Environmental implications of its use

The inadequate and indiscriminate disposal of sugarcane vinasse in soils and water bodies has received much attention since decades ago, due to environmental problems associated to this practice. Vinasse is the final by-product of the biomass distillation, mainly for the production of ethanol, from sugar crops (beet and sugarcane), starch crops (corn, wheat, rice, and cassava), or cellulosic material (harvesting crop residues, sugarcane bagasse, and wood). Because of the large quantities of vinasse produced, alternative treatments and uses have been developed, such as recycling of vinasse in fermentation, fertirrigation, concentration by evaporation, and yeast and energy production. This review was aimed at examining the available data on the subject as a contribution to update the information on sugarcane vinasse, from its characteristics and chemical composition to alternatives uses in Brazil: fertirrigation, concentration by evaporation, energy production; the effects on soil physical, chemical and biological properties; its influence on seed germination, its use as biostimulant and environmental contaminant. The low pH, electric conductivity, and chemical elements present in sugarcane vinasse may cause changes in the chemical and physical-chemical properties of soils, rivers, and lakes with frequent discharges over a long period of time, and also have adverse effects on agricultural soils and biota in general. Thus, new studies and green methods need to be developed aiming at sugarcane vinasse recycling and disposal. © 2013 Elsevier Ltd. All rights reserved.