Síntese, caracterização e aplicação de LaSBA-15 e como catalisador para obtenção de biodiesel de soja via rota etílica

Biodiesel is an alternative fuel, renewable, biodegradable and nontoxic. The transesterification of vegetable oils or animal fat with alcohol is most common form of production of this fuel. The procedure for production of biodiesel occurs most commonly through the transesterification reaction in which catalysts are used to accelerate and increase their income and may be basic, acid or enzyme. The use of homogeneous catalysis requires specific conditions and purification steps of the reaction products (alkyl ester and glycerol) and removal of the catalyst at the end of the reaction. As an alternative to improve the yield of the transesterification reaction, minimize the cost of production is that many studies are being conducted with the application of heterogeneous catalysis. The use of nano-structured materials as catalysts in the production of biodiesel is a biofuel alternative for a similar to mineral diesel. Although slower, can esterify transesterified triglycerides and free fatty acids and suffer little influence of water, which may be present in the raw material. This study aimed at the synthesis, characterization and application of nano-structured materials as catalysts in the transesterification reaction of soybean oil to produce biodiesel by ethylic route. The type material containing SBA-15 mesoporous lanthanum embedded within rightly Si / La = 50 was used catalyst. Solid samples were characterized by X-ray diffraction, thermogravimetric analysis, infrared spectroscopy, nitrogen adsorption and desorption. For the transesterification process, we used a molar ratio of 20:1 alcohol and oil with 0.250 g of catalyst at 60°C and times of 6 hours of reaction. It was determined the content of ethyl esters by H-NMR analysis and gas chromatography. It was found that the variable of conversion obtained was 80%, showing a good catalytic activity LaSBA-15 in the transesterification of vegetable oils via ethylic route

AN EXPERIMENTAL INVESTIGATION INTO THE EFFECTS OF BIODIESEL BLENDS ON PARTICULATE MATTER OXIDATION IN A CATALYZED PARTICULATE FILTER DURING ACTIVE REGENERATION

Active regeneration experiments were carried out on a production 2007 Cummins 8.9L ISL engine and associated DOC and CPF aftertreatment system. The effects of SME biodiesel blends were investigated in this study in order to determine the PM oxidation kinetics associated with active regeneration, and to determine the effect of biodiesel on them. The experimental data from this study will also be used to calibrate the MTU-1D CPF model. Accurately predicting the PM mass retained in the CPF and the oxidation characteristics will provide the basis for computation in the ECU that will minimize the fuel penalty associated with active regeneration. An active regeneration test procedure was developed based on previous experimentation at MTU. During each experiment, the PM mass in the CPF is determined by weighing the filter at various phases. In addition, DOC and CPF pressure drop, particle size distribution, gaseous emissions, temperature, and PM concentration data are collected and recorded throughout each experiment. The experiments covered a range of CPF inlet temperatures using ULSD, B10, and B20 blends of biodiesel. The majority of the tests were performed at CPF PM loading of 2.2 g/L with in-cylinder dosing, although 4.1 g/L and a post-turbo dosing injector were also used. The PM oxidation characteristics at different test conditions were studied in order to determine the effects of biodiesel on PM oxidation during active regeneration. A PM reaction rate calculation method was developed to determine the global activation energy and the corresponding pre-exponential factor for all test fuels. The changing sum of the total flow resistance of the wall, cake, and channels was also determined as part of the data analysis process in order to check on the integrity of the data and to correct input data to be consistent with the expected trends of the resistance based on the engine conditions used in the test procedure. It was determined that increasing the percent biodiesel content in the test fuel tends to increase the PM reaction rate and the regeneration efficiency of fuel dosing, i.e., at a constant CPF inlet temperature, B20 test fuel resulted in the highest PM reaction rate and regeneration efficiency of fuel dosing. Increasing the CPF inlet temperature also increases PM reaction rate and regeneration efficiency of fuel dosing. Performing active regeneration with B20 as opposed to ULSD allows for a lower CPF temperature to be used to reach the same level of regeneration efficiency, or it allows for a shorter regeneration time at a constant CPF temperature, resulting in decreased fuel consumption for the engine during active regeneration in either scenario.

Biodiesel production from waste cooking oil over sulfonated catalysts

Biodiesel production from waste cooking oil with methanol was carried out in the presence of poly(vinyl alcohol) with sulfonic acid groups (PVA-SO3H) and polystyrene with sulfonic acid groups (PS-SO3H), at 60°C. The PVA-SO3H catalyst showed higher catalytic activity than the PS-SO3H one. In order to optimize the reaction conditions, different parameters were studied. An increase of waste cooking oil conversion into fatty acid methyl esters with the amount of PVA-SO3H was observed. When the transesterification and esterification of WCO was carried out with ethanol over PVA-SO3H, at 60°C, a decrease of biodiesel production was also observed. The WCO conversion into fatty acid ethyl ester increased when the temperature was increased from 60 to 80°C. When different amounts of free fatty acids were added to the reaction mixture, a slight increase on the conversion was observed. The PVASO3H catalyst was reused and recycled with negligible loss in the activity.

Composites Chitosan/SBA-15 with sulfonic acid as heterogeneous catalysts for biodiesel production

Free fatty acids (palmitic, stearic and oleic acid) were converted into biodiesel with methanol over composites catalysts consisting in SBA-15 with sulfonic acid groups (SBA-15-SO3H) immobilized in Chitosan (CH), at 60ºC. It was observed that the catalytic activity increased with the amount of SBA-15-SO3H dispersed in CH. It was also observed that the catalytic activity decreased in the series: palmitic acid > stearic acid > oleic. The catalytic stability of [SBA-15-SO3H]3/CH composites was studied. A good stability was observed.

Investigation of innovative combustion systems for reduced fuel consumption and increased specific power production

This work resumes a wide variety of research activities carried out with the main objective of increasing the efficiency and reducing the fuel consumption of Gasoline Direct Injection engines, especially under high loads. For this purpose, two main innovative technologies have been studied, Water Injection and Low-Pressure Exhaust Gas Recirculation, which help to reduce the temperature of the gases inside the combustion chamber and thus mitigate knock, being this one of the main limiting factors for the efficiency of modern downsized engines that operate at high specific power. A prototypal Port Water Injection system was developed and extensive experimental work has been carried out, initially to identify the benefits and limitations of this technology. This led to the subsequent development and testing of a combustion controller, which has been implemented on a Rapid Control Prototyping environment, capable of managing water injection to achieve knock mitigation and a more efficient combustion phase. Regarding Low-Pressure Exhaust Gas Recirculation, a commercial engine that was already equipped with this technology was used to carry out experimental work in a similar fashion to that of water injection. Another prototypal water injection system has been mounted to this second engine, to be able to test both technologies, at first separately to compare them on equal conditions, and secondly together in the search of a possible synergy. Additionally, based on experimental data from several engines that have been tested during this study, including both GDI and GCI engines, a real-time model (or virtual sensor) for the estimation of the maximum in-cylinder pressure has been developed and validated. This parameter is of vital importance to determine the speed at which damage occurs on the engine components, and therefore to extract the maximum performance without inducing permanent damages.

Microbial Lipid Production: Screening With Yeasts Grown On Brazilian Molasses.

Rhodotorula glutinis CCT 2182, Rhodosporidium toruloides CCT 0783, Rhodotorula minuta CCT 1751 and Lipomyces starkeyi DSM 70296 were evaluated for the conversion of sugars from Brazilian molasses into single-cell oil (SCO) feedstock for biodiesel. Pulsed fed-batch fermentations were performed in 1.65 l working volume bioreactors. The maximum specific growth rate (µmax), lipid productivity (Pr) and cellular lipid content were, respectively, 0.23 h(-1), 0.41 g l(-1) h(-1), and 41% for Rsp. toruloides; 0.20 h(-1), 0.27 g l(-1) h(-1), and 36% for Rta. glutinis; 0.115 h(-1), 0.135 g l(-1) h(-1), and 27 % for Rta. minuta; and 0.11 h(-1), 0.13 g l(-1) h(-1), and 32% for L. starkeyi. Based on their microbial lipid productivity, content, and profile, Rsp. toruloides and Rta. glutinis are promising candidates for biodiesel production from Brazilian molasses. All the oils from the yeasts were similar to the composition of plant oils (rapeseed and soybean) and could be used as raw material for biofuels, as well as in food and nutraceutical products.

Enzymatic Biodiesel Synthesis From Yeast Oil Using Immobilized Recombinant Rhizopus Oryzae Lipase.

The recombinant Rhizopus oryzae lipase (1-3 positional selective), immobilized on Relizyme OD403, has been applied to the production of biodiesel using single cell oil from Candida sp. LEB-M3 growing on glycerol from biodiesel process. The composition of microbial oil is quite similar in terms of saponifiable lipids than olive oil, although with a higher amount of saturated fatty acids. The reaction was carried out in a solvent system, and n-hexane showed the best performance in terms of yield and easy recovery. The strategy selected for acyl acceptor addition was a stepwise methanol addition using crude and neutralized single cell oil, olive oil and oleic acid as substrates. A FAMEs yield of 40.6% was obtained with microbial oils lower than olive oil 54.3%. Finally in terms of stability, only a lost about 30% after 6 reutilizations were achieved.

Biomass Refinery as a Renewable Complement to the Petroleum Refinery

Biomass Refinery is a sequential of eleven thermochemical processes and one biological process with two initial basic treatments: prehydrolysis for lignocellulosics and low temperature conversion for biomass with medium-to-high content of lipids and proteins. The other ten processes are: effluent treatment plant, furfural plant, biodiesel plant, cellulignin dryer, calcination, fluidized bed boiler, authotermal reforming of cellulignin for syngas production, combined cycle of two-stroke low-speed engine or syngas turbine with fluidized bed boiler heat recovery, GTL technologies and ethanol from cellulose, prehydrolysate and syngas. Any kind of biomass such as wood, agricultural residues, municipal solid waste, seeds, cakes, sludges, excrements and used tires can be processed at the Biomass Refinery. Twelve basic products are generated such as cellulignin, animal feed, electric energy, fuels (ethanol, crude oil, biodiesel, char), petrochemical substitutes, some materials (ash, gypsum, fertilizers, silica, carbon black) and hydrogen. The technology is clean with recovery of energy and reuse of water, acid and effluents. Based on a holistic integration of various disciplines Biomass Refinery maximizes the simultaneous production of food, electric energy, liquid fuels and chemical products and some materials, achieving a competitive position with conventional and fossil fuel technologies, as well as payment capacity for biomass production. Biomass Refinery has a technical economical capability to complement the depletion of the conventional petroleum sources and to capture its GHGs resulting a biomass + petroleum ""green"" combination.

Net greenhouse gas fluxes in Brazilian ethanol production systems

Biofuels are both a promising solution to global warming mitigation and a potential contributor to the problem. Several life cycle assessments of bioethanol have been conducted to address these questions. We performed a synthesis of the available data on Brazilian ethanol production focusing on greenhouse gas (GHG) emissions and carbon (C) sinks in the agricultural and industrial phases. Emissions of carbon dioxide (CO(2)) from fossil fuels, methane (CH(4)) and nitrous oxide (N(2)O) from sources commonly included in C footprints, such as fossil fuel usage, biomass burning, nitrogen fertilizer application, liming and litter decomposition were accounted for. In addition, black carbon (BC) emissions from burning biomass and soil C sequestration were included in the balance. Most of the annual emissions per hectare are in the agricultural phase, both in the burned system (2209 out of a total of 2398 kg C(eq)), and in the unburned system (559 out of 748 kg C(eq)). Although nitrogen fertilizer emissions are large, 111 kg C(eq) ha-1 yr-1, the largest single source of emissions is biomass burning in the manual harvest system, with a large amount of both GHG (196 kg C(eq) ha-1 yr-1). and BC (1536 kg C(eq) ha-1 yr-1). Besides avoiding emissions from biomass burning, harvesting sugarcane mechanically without burning tends to increase soil C stocks, providing a C sink of 1500 kg C ha-1 yr-1 in the 30 cm layer. The data show a C output: input ratio of 1.4 for ethanol produced under the conventionally burned and manual harvest compared with 6.5 for the mechanized harvest without burning, signifying the importance of conservation agricultural systems in bioethanol feedstock production.

Identification of the biodiesel source using an electronic nose

Biodiesel is an important new alternative fuel. The feedstock used and the process employed determines whether it fulfills the required specifications. In this work, an identification method is proposed using an electronic nose (e-nose). Four samples of biodiesel from different sources and one of petrodiesel were analyzed and well-recognized by the e-nose. Both pure biodiesel and B20 blends were studied. Furthermore, an innovative semiquantitative method is proposed on the basis of the smellprints correlated by a feed-forward artificial neural network. The results have demonstrated that the e-nose can be used to identify the biodiesel source and as a preliminary quantitative assay in place of expensive equipment.

Performance of different immobilized lipases in palm oil biodiesel synthesis

Performance of different immobilized lipases in palm oil biodiesel synthesis. Optimized conditions for palm oil and ethanol enzymatic biodiesel synthesis were determined with different immobilized lipases SiO(2)-PVA-immobilized lipase from Pseudomonas fluorescens and acrylic resin-immobilized lipase, Novozym (R) 435, from Candida antartica, in solvent-free medium. A full factorial design assessed the influence of temperature (42 - 58 degrees C) and ethanol: palm oil (6:1 - 18:1) molar ratio on the transesterification yield. Main effects were adjusted by multiple regression analysis to linear models and the maximum transesterification yield was obtained at 42 degrees C and 18:1 ethanol: palm oil molar ratio. Mathematical models featuring total yield for each immobilized lipase were suitable to describe the experimental results.

The Influence of Initial Xylose Concentration, Agitation, and Aeration on Ethanol Production by Pichia stipitis from Rice Straw Hemicellulosic Hydrolysate

Rice straw hemicellulosic hydrolysate was used as fermentation medium for ethanol production by Pichia stipitis NRRL Y-7124. Shaking bath experiments were initially performed aiming to establish the best initial xylose concentration to be used in this bioconversion process. In the sequence, assays were carried out under different agitation (100 to 200 rpm) and aeration ((V) under bar (flask)/V(medium) ratio varying from 2.5 to 5.0) conditions, and the influence of these variables on the fermentative parameters values (ethanol yield factor, Y(P/S); cell yield factor, Y(X/S); and ethanol volumetric productivity, Q(P)) was investigated through a 2(2) full-factorial design. Initial xylose concentration of about 50 g/l was the most suitable for the development of this process, since the yeast was able to convert substrate in product with high efficiency. The factorial design assays showed a strong influence of both process variables in all the evaluated responses. The agitation and aeration increase caused a deviation in the yeast metabolism from ethanol to biomass production. The best results (Y(P/S) = 0.37 g/g and Q(P) = 0.39 g/l. h) were found when the lowest aeration (2.5 V(flask)/V(medium) ratio) and highest agitation (200 rpm) levels were employed. Under this condition, a process efficiency of 72.5% was achieved. These results demonstrated that the establishment of adequate conditions of aeration is of great relevance to improve the ethanol production from xylose by Pichia stipitis, using rice straw hemicellulosic hydrolysate as fermentation medium.

An integrated approach to produce biodiesel and monoglycerides by enzymatic interestification of babassu oil (Orbinya sp)

Two screenings of commercial lipases were performed to find a lipase with superior performance for the integrated production of biodiesel and monoglycerides. The first screening was carried out under alcoholysis conditions using ethanol as acyl acceptor to convert triglycerides to their corresponding ethyl esters (biodiesel). The second screening was performed under glycerolysis conditions to yield monoglycerides (MG). All lipases were immobilized on silica-PVA composite by covalent immobilization. The assays were performed using babassu oil and alcohols (ethanol or glycerol) in solvent free systems. For both substrates, lipase from Burkholderia cepacia (lipase PS) was found to be the most suitable enzyme to attain satisfactory yields. To further improve the process, the Response Surface Methodology (RSM) was used to determine the optima operating conditions for each biotransformation. For biodiesel production, the highest transesterification yield (>98%) was achieved within 48 h reaction at 39 degrees C using an oil-to-ethanol molar ratio of 1:7. For MG production, optima conditions corresponded to oil-to-glycerol molar ratio of 1: 15 at 55 degrees C, yielding 25 wt.% MG in 6 h reaction. These results show the potential of B. cepacia lipase to catalyze both reactions and the feasibility to consider an integrated approach for biodiesel and MG production. (C) 2009 Elsevier Ltd. All rights reserved.

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.

Atmospheric impacts of the life cycle emissions of fuel ethanol in Brazil: based on chemical exergy

An assessment is made of the atmospheric emissions from the life cycle of fuel ethanol coupled with the cogeneration of electricity from sugarcane in Brazil. The total exergy loss from the most quantitative relevant atmospheric emission substances produced by the life cycle of fuel ethanol is 3.26E+05 kJ/t of C(2)H(5)OH, Compared with the chemical exergy of 1 t of ethanol (calculated as 34.56E + 06 kJ). the exergy loss from the life cycle`s atmospheric emission represents 1.11% of the product`s exergy. The activity that most contributes to atmospheric emission chemical exergy losses is the harvesting of sugarcane through the methane emitted in burning. Suggestions for improved environmental quality and greater efficiency of the life cycle of fuel ethanol with cogenerated energy are: harvesting the sugarcane without burning, renewable fuels should be used in tractors, trucks and buses instead of fossil fuel and the transportation of products and input should be logistically optimized. (C) 2009 Elsevier Ltd. All rights reserved.