Scale-up of diluted sulfuric acid hydrolysis for producing sugarcane bagasse hemicellulosic hydrolysate (SBHH)

Sugarcane bagasse was pretreated with diluted sulfuric acid to obtain sugarcane bagasse hemicellulosic hydrolysate (SBHH). Experiments were conducted in laboratory and semi-pilot reactors to optimize the xylose recovery and to reduce the generation of sugar degradation products, as furfural and 5-hydroxy-methylfurfural (HMF). The hydrolysis scale-up procedure was based on the H-Factor, that combines temperature and residence time and employs the Arrhenius equation to model the sulfuric acid concentration (100 mg(acid)/g(dm)) and activation energy (109 kJ/mol). This procedure allowed the mathematical estimation of the results through simulation of the conditions prevailing in the reactors with different designs. The SBHH obtained from different reactors but under the same H-Factor of 5.45 +/- 0.15 reached similar xylose yield (approximately 74%) and low concentration of sugar degradation products, as furfural (0.082 g/L) and HMF (0.0071 g/L). Also, the highest lignin degradation products (phenolic compounds) were rho-coumarilic acid (0.15 g/L) followed by ferulic acid (0.12 g/L) and gallic acid (0.035 g/L). The highest concentration of ions referred to S (3433.6 mg/L), Fe (554.4 mg/L), K (103.9 mg/L), The H-Factor could be used without dramatically altering the xylose and HMF/furfural levels. Therefore, we could assume that H-Factor was directly useful in the scale-up of the hemicellulosic hydrolysate production. (C) 2009 Published by Elsevier Ltd.

Simultaneous saccharification and ethanol fermentation of oxalic acid pretreated corncob assessed with response surface methodology

Response surface methodology was used to evaluate optimal time, temperature and oxalic acid concentration for simultaneous saccharification and fermentation (SSF) of corncob particles by Pichia stipitis CBS 6054. Fifteen different conditions for pretreatment were examined in a 2(3) full factorial design with six axial points. Temperatures ranged from 132 to 180 degrees C, time from 10 to 90 min and oxalic acid loadings from 0.01 to 0.038 g/g solids. Separate maxima were found for enzymatic saccharification and hemicellulose fermentation, respectively, with the condition for maximum saccharification being significantly more severe. Ethanol production was affected by reaction temperature more than by oxalic acid and reaction time over the ranges examined. The effect of reaction temperature was significant at a 95% confidence level in its effect on ethanol production. Oxalic acid and reaction time were statistically significant at the 90% level. The highest ethanol concentration (20 g/l) was obtained after 48 h with an ethanol volumetric production rate of 0.42 g ethanol l(-1) h(-1). The ethanol yield after SSF with P. stipitis was significantly higher than predicted by sequential saccharification and fermentation of substrate pretreated under the same condition. This was attributed to the secretion of beta-glucosidase by P. stipitis. During SSF, free extracellular beta-glucosidase activity was 1.30 pNPG U/g with P. stipitis, while saccharification without the yeast was 0.66 pNPG U/g. Published by Elsevier Ltd.

Multipoint covalent immobilization of lipase on chitosan hybrid hydrogels: influence of the polyelectrolyte complex type and chemical modification on the catalytic properties of the biocatalysts

This work aimed at the production of stabilized derivatives of Thermomyces lanuginosus lipase (TLL) by multipoint covalent immobilization of the enzyme on chitosan-based matrices. The resulting biocatalysts were tested for synthesis of biodiesel by ethanolysis of palm oil. Different hydrogels were prepared: chitosan alone and in polyelectrolyte complexes (PEC) with kappa-carrageenan, gelatin, alginate, and polyvinyl alcohol (PVA). The obtained supports were chemically modified with 2,4,6-trinitrobenzene sulfonic acid (TNBS) to increase support hydrophobicity, followed by activation with different agents such as glycidol (GLY), epichlorohydrin (EPI), and glutaraldehyde (GLU). The chitosan-alginate hydrogel, chemically modified with TNBS, provided derivatives with higher apparent hydrolytic activity (HA(app)) and thermal stability, being up to 45-fold more stable than soluble lipase. The maximum load of immobilized enzyme was 17.5 mg g(-1) of gel for GLU, 7.76 mg g(-1) of gel for GLY, and 7.65 mg g(-1) of gel for EPI derivatives, the latter presenting the maximum apparent hydrolytic activity (364.8 IU g(-1) of gel). The three derivatives catalyzed conversion of palm oil to biodiesel, but chitosan-alginate-TNBS activated via GLY and EPI led to higher recovered activities of the enzyme. Thus, this is a more attractive option for both hydrolysis and transesterification of vegetable oils using immobilized TLL, although industrial application of this biocatalyst still demands further improvements in its half-life to make the enzymatic process economically attractive.

Effect of pH and oxalic acid on the reduction of Fe(3+) by a biomimetic chelator and on Fe(3+) desorption/adsorption onto wood: Implications for brown-rot decay

Fenton reaction is thought to play an important role in wood degradation by brown-rot fungi. In this context, the effect of oxalic acid and pH on iron reduction by a biomimetic fungal chelator and on the adsorption/desorption of iron to/from wood was investigated. The results presented in this work indicate that at pH 2.0 and 4.5 and in the presence of oxalic acid, the phenolate chelator 2,3-dihydroxybenzoic acid (2,3-DHBA) is capable of reducing ferric iron only when the iron is complexed with oxalate to form Fe mono-oxalate (Fe(C(2)O(4))(+)). Within the pH range tested in this work, this complex formation occurs when the oxalate:Fe(3+) molar ratio is less than 20 (pH 2.0) or less than 10 (pH 4.5). When aqueous ferric iron was passed through a column packed with milled red spruce (Picea rubens) wood equilibrated at pH 2.0 and 4.5. it was observed that ferric iron binds to wood at pH 4.5 but not at pH 2.0, and the bound iron could then be released by application of oxalic acid at pH 4.5. The release of bound iron was dependent on the amount of oxalic acid applied in the column. When the amount of oxalate was at least 20-fold greater than the amount of iron bound to the wood, all bound iron was released. When Fe-oxalate complexes were applied to the milled wood column equilibrated in the pH range of 2-4.5, iron from Fe-oxalate complexes was bound to the wood only when the pH was 3.6 or higher and the oxalate:Fe(3+) molar ratio was less than 10. When 2,3-DHBA was evaluated for its ability to release iron bound to the milled wood, it was found that 2,3-DHBA possessed a greater affinity for ferric iron than the wood as 2,3-DHBA was capable of releasing the ferric iron bound to the wood in the pH range 3.6-5.5. These results further the understanding of the mechanisms employed by brown-rot fungi in wood biodegradation processes. (C) 2009 Elsevier Ltd. All rights reserved.

Characterization of commercial cellulases and their use in the saccharification of a sugarcane bagasse sample pretreated with dilute sulfuric acid

This study aimed to correlate the efficiency of enzymatic hydrolysis of the cellulose contained in a sugarcane bagasse sample pretreated with dilute H(2)SO(4) with the levels of independent variables such as initial content of solids and loadings of enzymes and surfactant (Tween 20), for two cellulolytic commercial preparations. The preparations, designated cellulase I and cellulase II, were characterized regarding the activities of total cellulases, endoglucanase, cellobiohydrolase, cellobiase, beta-glucosidase, xylanase, and phenoloxidases (laccase, manganese and lignin peroxidases), as well as protein contents. Both extracts showed complete cellulolytic complexes and considerable activities of xylanases, without activities of phenoloxidases. For the enzymatic hydrolyses, two 2(3) central composite full factorial designs were employed to evaluate the effects caused by the initial content of solids (1.19-4.81%, w/w) and loadings of enzymes (1.9-38.1 FPU/g bagasse) and Tween 20 (0.0-0.1 g/g bagasse) on the cellulose digestibility. Within 24 h of enzymatic hydrolysis, all three independent variables influenced the conversion of cellulose by cellulase I. Using cellulase II, only enzyme and surfactant loadings showed significant effects on cellulose conversion. An additional experiment demonstrated the possibility of increasing the initial content of solids to values much higher than 4.81% (w/w) without compromising the efficiency of cellulose conversion, consequently improving the glucose concentration in the hydrolysate.

Phase fraction distribution measurement of oil-water flow using a capacitance wire-mesh sensor

In this paper, a novel wire-mesh sensor based on permittivity (capacitance) measurements is applied to generate images of the phase fraction distribution and investigate the flow of viscous oil and water in a horizontal pipe. Phase fraction values were calculated from the raw data delivered by the wire-mesh sensor using different mixture permittivity models. Furthermore, these data were validated against quick-closing valve measurements. Investigated flow patterns were dispersion of oil in water (Do/w) and dispersion of oil in water and water in oil (Do/w&w/o). The Maxwell-Garnett mixing model is better suited for Dw/o and the logarithmic model for Do/w&w/o flow pattern. Images of the time-averaged cross-sectional oil fraction distribution along with axial slice images were used to visualize and disclose some details of the flow.

Manufacture of ceramic membranes for application in demulsification process for cross-flow microfiltration

This paper describes the manufacture of tubular ceramic membranes and the study of their performance in the demulsification of soybean oil/water emulsions. The membranes were made by iso-static pressing method and micro and macro structurally characterized by SEM, porosimetry by mercury intrusion and determination of apparent density and porosity. The microfiltration tests were realized on an experimental workbench, and fluid dynamic parameters, such as transmembrane flux and pressure were used to evaluate the process relative to the oil phase concentration (analysed by TOC measurements) in the permeate. The results showed that the membrane with pores` average diameter of 1.36 mu m achieved higher transmembrane flux than the membrane with pores` average diameter of 0.8 mu m. The volume of open pores (responsible for the permeation) was predominant in the total porosity, which was higher than 50% for all tested membranes. Concerning demulsification, the monolayer membranes were efficacious, as the rejection coefficient was higher than 99%.

Evaluation of the performance of biodiesel from waste vegetable oil in a flame tube furnace

This work presents a theoretical and experimental study of the biodiesel (ethyl ester from a waste vegetable oil) performance in a flame tube furnace. The heat transfer rate was analysed in several sections along the furnace and the performance of the biodiesel was compared to that of diesel oil. The flow of heat from the burn of each fuel in the direction of the walls of the combustion chamber was evaluated under the same fuel injection pressure. The peak of the heat transfer occurred around 0.45 m far from the fuel injection nozzle in a 0.305 m inner diameter combustion chamber. The diesel oil showed a higher heat transfer rate in most parts exposed to the flame. In the region where the body of the flame is not present, the heat transfer of biodiesel becomes higher. (C) 2008 Elsevier Ltd. All rights reserved.

GIS applied to geotechnical and environmental risk management in a Brazilian oil pipeline

The paper presents the development of a decision support system for the management of geotechnical and environmental risks in oil pipelines using a geographical information system. The system covers a 48.5 km long section of the So Paulo to Brasilia (OSBRA) oil pipeline, which crosses three municipalities in the northeast region of the So Paulo state (Brazil) and represents an area of 205.8 km(2). The spatial database was created using geo-processing procedures, surface and intrusive investigations and geotechnical reports. The risk assessment was based mainly on qualitative models (relative numeric weights and multicriteria decision analysis) and considered pluvial erosion, slope movements, soil corrosion and third party activities. The maps were produced at a scale of 1:10,000.

Influence of carbon sources and C/N ratio on EPS production in anaerobic sequencing batch biofilm reactors for wastewater treatment

The objective of this work was to evaluate the influence of different carbon sources and the carbon/nitrogen ratio (C/N) on the production and main composition of insoluble extracellular polymers (EPS) produced in an anaerobic sequencing batch biofilm reactor (ASBBR) with immobilized biomass in polyurethane foam. The yield of EPS was 23.6 mg/g carbon, 13.3 mg/g carbon, 9.0 mg/g carbon and 1.4 mg/g carbon when the reactor was fed with glucose, soybean oil. fat acids, and meat extract, respectively. The yield of EPS decreased from 23.6 to 2.6 mg/g carbon as the C/N ratio was decreased from 13.6 to 3.4 gC/gN, using glucose as carbon source. EPS production was not observed under strict anaerobic conditions. The results suggest that the carbon source, microaerophilic conditions and high C/N ratio favor EPS production in the ASBBR used for wastewater treatment. Cellulose was the main exopolysaccharide observed in all experimental conditions. (C) 2009 Elsevier Ltd. All rights reserved.

Performance and molecular evaluation of an anaerobic system with suspended biomass for treating wastewater with high fat content after enzymatic hydrolysis

The effect of a lipase-rich fungal enzymatic preparation, produced by a Penicillium sp. during solid-state fermentation, was evaluated in an anaerobic digester treating dairy wastewater with 1200 mg of oil and grease/L The oil and grease hydrolysis step was carried out with 0.1% (w/v) of solid enzymatic preparation at 30 degrees C for 24 h, and resulted in a final free acid concentration eight times higher than the initial value. The digester operated in sequential batches of 48 h at 30 degrees C for 245 days, and had high chemical oxygen demand (COD) removal efficiencies (around 90%) when fed with pre-hydrolyzed wastewater. However, when the pre-hydrolysis step was removed, the anaerobic digester performed poorly (with an average COD removal of 32%), as the oil and grease accumulated in the biomass and effluent oil and grease concentration increased throughout the operational period. PCR-DGGE analysis of the Bacteria and Archaea domains revealed remarkable differences in the microbial profiles in trials conducted with and without the pre-hydrolysis step, indicating that differences observed in overall parameters were intrinsically related to the microbial diversity of the anaerobic sludge. (C) 2009 Elsevier Ltd. All rights reserved.

Influence of carbon source and inoculum type on anaerobic biomass adhesion on polyurethane foam in reactors fed with acid mine drainage

This paper analyzes the influence of carbon source and inoculum origin on the dynamics of biomass adhesion to an inert support in anaerobic reactors fed with acid mine drainage. Formic acid, lactic acid and ethanol were used as carbon sources. Two different inocula were evaluated: one taken from an UASB reactor and other from the sediment of a uranium mine. The values of average colonization rates and the maximum biomass concentration (C(max)) were inversely proportional to the number of carbon atoms in each substrate. The highest C(max) value (0.35 g TVS g(-1) foam) was observed with formic acid and anaerobic sludge as inoculum. Maximum colonization rates (v(max)) were strongly influenced by the type of inoculum when ethanol and lactic acid were used. For both carbon sources, the use of mine sediment as inoculum resulted in a v(max) of 0.013 g TVS g(-1) foam day(-1), whereas 0.024 g TVS g(-1) foam day(-1) was achieved with anaerobic sludge. (C) 2011 Elsevier Ltd. All rights reserved.

Citric acid as anti-hydration additive for magnesia containing refractory castables

Magnesia hydration is a key concern in refractory castable processing. The volumetric expansion that follows this reaction can result in cracks or even explosion during the first heating-up. Citric acid (CA) and other chelants can significantly reduce MgO hydration rate in aqueous suspensions by forming an insoluble magnesium citrate protective coating on the magnesia particles` surface. In the present work, the performance of CA as an anti-hydration additive in refractory castables was evaluated by hydration tests, mechanical strength and apparent volumetric expansion (AVE) measurements and thermogravimetry. The results attained have shown that CA effectiveness depends strongly on the amount added and by the interaction with other raw materials in the composition, in particular calcium aluminate cement. (C) 2011 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

A comparative study of GERIPA ethanol with other fuels

The GERIPA project aimed at generating renewable energy integrated with food production has led to a beneficial option for producing ethanol and electricity. Ethanol has economic, social and environmental potential. Considering just the first one, Brazil consumes 39 billion litres per year-L(D)/yr of diesel oil, 18% of it being imported. The Federal Government has a recovery programme for the soybean agribusiness aimed at soybean biodiesel (SBD) production in which a 10% addition to diesel has been proposed. This 10% involves producing 10.7 million L(SB)/d. Soybean bio-diesel production is not self-sustainable and such proposal could require an annual subsidy of up to US$1.33 billion. Soybean plantations would need about 10 to 12 times more land than is necessary for sugarcane plantations to produce the same equivalent thermal energy (ETE). Sixty-seven GERIPA projects (GP) producing 80,000 litres of ethanol per day (GP80) could be set up with the sum of US$1.33 billion; this would substitute current Brazilian biodiesel demand by 4.28%, adding the some value for each new subsidiary. Considering ETE, ethanol-GP cost would be 37% to 50% below that for a litre of SBD on account of its raw material (RM) and region. The diesel cycle`s thermal efficiency (eta(1)) yield is around 50% and that of the Otto cycle engine eta(1) is around 37%. The cost per km driven (CKD) by substituting SBD for ethanol-GP80 would thus indicate an 18% minimum and 59% maximum cost reduction for vehicle engines.

Slip ratio in dispersed viscous oil-water pipe flow

In this article, dispersed flow of viscous oil and water is investigated. The experimental work was performed in a 26.2-mm-i.d. 12-m-long horizontal glass pipe using water and oil (viscosity of 100 mPa s and density of 860 kg/m(3)) as test fluids. High-speed video recording and a new wire-mesh sensor based on capacitance (permittivity) measurements were used to characterize the flow. Furthermore, holdup data were obtained using quick-closing-valves technique (QCV). An interesting finding was the oil-water slip ratio greater than one for dispersed flow at high Reynolds number. Chordal phase fraction distribution diagrams and images of the holdup distribution over the pipe cross-section obtained via wire-mesh sensor indicated a significant amount of water near to the pipe wall for the three different dispersed flow patterns identified in this study: oil-in-water homogeneous dispersion (o/w H), oil-in-water non-homogeneous dispersion (o/w NH) and Dual continuous (Do/w & Dw/o). The phase slip might be explained by the existence of a water film surrounding the homogeneous mixture of oil-in-water in a hidrofilic-oilfobic pipe. (C) 2010 Elsevier Inc. All rights reserved.