Avaliação da produção de biodiesel de microalga Isochrysis galbana via transesterificação in situ

Microalgae are microscopic photosynthetic organisms that grow rapidly and in different environmental conditions due to their simple cellular structure. The cultivation of microalgae is a biological system capable of storing solar energy through the production of organic compounds via photosynthesis, and these species presents growth faster than land plants, enabling higher biomass yield. Thus, it is understood that the cultivation of these photosynthetic mechanisms is part of a relevant proposal, since, when compared to other oil producing raw materials, they have a significantly higher productivity, thus being a raw material able to complete the current demand by biodiesel . The overall aim of the thesis was to obtain biofuel via transesterification process of bio oil from the microalgae Isochrysis galbana. The specific objective was to estimate the use of a photobioreactor at the laboratory level, for the experiments of microalgae growth; evaluating the characteristics of biodiesel from microalgae produced by in situ transesterification process; studying a new route for disinfection of microalgae cultivation, through the use of the chemical agent sodium hypochlorite. The introduction of this new method allowed obtaining the kinetics of the photobioreactor for cultivation, besides getting the biomass needed for processing and analysis of experiments in obtaining biodiesel. The research showed acceptable results for the characteristics observed in the bio oil obtained, which fell within the standards of ANP Resolution No. 14, dated 11.5.2012 - 18.5.2012. Furthermore, it was demonstrated that the photobioreactor designed meet expectations about study culture growth and has contributed largely to the development of the chosen species of microalgae. Thus, it can be seen that the microalgae Isochrysis galbana showed a species with potential for biodiesel production

Equilíbrio líquido-líquido para o sistema biodiesel de óleo de semente de melão (Cucumis melo l.) + metanol + glicerina

Rio Grande do Norte, northeast state from Brazil, it is the greatest producer and exporter of yellow melon, well known as Spanish melon. Despite the consumption of this fruit to be mainly its pulp, melon seeds are an important source of lipids considered an industrial residue it has been discharge product. The use of oilseeds in order to produce biodiesel establishes an important raw material and the increase of its production promotes the national development of the agriculture. In this background, the aim of this work has been to use oil from seeds of yellow melon to produce biodiesel and to accomplish a study of the phase equilibrium of the system evolving biodiesel, methanol and glycerin. The biodiesel was obtained by oil transesterification through methylic route with molar ratio 1:9.7 (oil:alcohol) and with a mass of NaOH of 0.5% from the oil mass; the reaction time was 73 minutes at 55 °C. A yield of 84.94% in biodiesel was achieved. The equilibria data present a well-characterized behavior with a great region of two phases. The tie lines indicate that methanol has a best solubility in the phase that is rich in glycerin. Consistency of the experimental data was made based on Othmer-Tobias and Hand correlations which values above 0.99 were found to correlation coefficients, this fact confers a good thermodynamic consistency to the experimental data. NRTL and UNIQUAC models were employed to predict liquid-liquid equilibrium of this system. It was observed a better concordance of the results when NRTL was applied (standard deviation 1.25%) although the UNIQUAC model has presented a quite satisfactory result either (standard deviation 2.70%). The NRTL and UNIQUAC models were also used to evaluate the effect of temperature in the range of 328 K to 358 K, in which a little change in solubility with respect to the data obtained at 298 K was observed, thus being considered negligible the effect of temperature

Hydrogen production utilizing glycerol from renewable feedstocks-The case of Brazil

Various reports concerning catalytic reaction of glycerol for hydrogen production is available. However, economic analyses of this activity are not found yet. The objective of this work is to evaluate the process of hydrogen production via steam reforming of glycerol obtained through transesterification process of bio-oils. The thermochemical process of steam reforming process was determined due to high efficiency, feasibility and lower cost of design, development, operation and maintenance. These bio-oils come from feedstocks largely encountered in Brazil such as soybean, palm, castor bean, peanut and cotton seed as also come from residues such as defective coffee, tallow beef, wastewater (scum) and others. Various findings were obtained such as potential of production of glycerol utilizing residues (considering available amounts in the Brazilian states) and some vegetable feedstocks (considering production of harvested feedstock per hectare). Subsequently, production of hydrogen via steam reforming of generated glycerol, and foreseen electricity production via fuel cells were also determined. An additional estimation was paid for production of H-BIO, an innovative fuel developed by PETROBRAS (Petroleo Brasileiro S.A.), where hydrogen and bio-fuel are utilized and generates propane as co-product. About this work, it was concluded that high amounts of hydrogen and electricity could be produced considering an enormous potential from each cited feedstock being an attractive alternative as distributed electricity source and as an additional source for some activities, inclusively those that produce their own feedstocks such as abattoirs (beef tallow), and wastewater treatment plants. (C) 2010 Elsevier Ltd. All rights reserved.

Avaliação do comportamento termoanalítico e oxidativo do biodiesel de mamona

In this work biodiesel was gotten through the transesterification reaction using the oil of castor as source of triglycerides and using the methylic route for obtaining of esters. For the characterization of biodiesel and its mixtures with mineral diesel oil, physical chemical parameters and several analytical techniques had been used, as well as: gas chromatography (GC), nuclear magnetic resonance of proton (1H NMR), infrared spectroscopy (IR) and thermal analysis. The chromatography confirmed the complete reaction of esters in biodiesel presenting a 97,08% conversion. The 1H - NMR presented singlet in 3,6 ppm corresponding to the hydrogen of the group ester RCOO CH3. The infrared presented a strong band in 1741 cm-1 referring to stretching C=O of ester and an average band in 1175 cm-1 referring C O deformation. With the data of thermal analysis it was possible to observe the thermal and oxidative stability of the samples changing the atmospheres of synthetic air and nitrogen, where stages of the thermal decomposition had been verified and had been attributed to the volatilization and/or decomposition of the triacylglycerides. The thermal degradation of the samples was carried through 150 and 210°C during 1, 12, 24 and 48 hours and was observed change in the thermogravimetric profile, therefore an increase in the number of stages of the thermal decomposition also occurred indicating characteristic intermediate composites of polymerization, being this confirmed through the rheological study that presented brusque increase of viscosity. The kinetic study showed that the activation energy has the following order: biodiesel > mineral diesel oil > mixtures biodiesel/diesel

Hidróxidos duplos lamelares aplicados à obtenção de biodiesel

In this paper, the Layered Double Hydroxides (LDH s) type hydrotalcite were synthesized, characterized and tested as basic heterogeneous catalysts for the production of biodiesel by transesterification of sunflower oil with methanol. The synthesis of materials Layered Double Hydroxides (LDH s) by co-precipitation method from nitrates of magnesium and aluminum, and sodium carbonate. The materials were submitted to the variation in chemical composition, which is the amount of Mg2+ ions replaced by Al3+. This variation affects the characteristic physico-chemical and reaction the solid. The molar ratio varied in the range of 1:1 and 3:1 magnesium / aluminum, and their values between 0.2 and 0.33. This study aims to evaluate the influence of variation of molar ratio of mixed oxides derived from LDH s and the influence of impregnation of a material with catalytic activity, the KI, the rate of conversion of sunflower oil into methyl esters (biodiesel) through transesterification by heterogeneous catalysis. .The catalysts were calcined at 550 ° C and characterized by X-ray diffraction (XRD), scanning electron microscopy and energy dispersive spectroscopy of X-ray (SEM / EDS), thermogravimetric analysis (TG) and test basicity. The transesterification reaction was performed for reflux is a mixture of sunflower oil and methanol with a molar ratio of 15:1, a reaction time of 4h and a catalyst concentration of 2% by weight. The physical-chemical characterization of sunflower oil and biodiesel obtained by the route methyl submitted according NBR, EN, ASTM. Subsequently, it was with the chromatographic and thermogravimetric characterizations of oils. The results of chromatographic analysis showed that the catalysts were effective in converting vegetable oil into biodiesel, in particular the type hydrotalcite KI-HDL-R1, with a conversion of 99.2%, indicating the strong influence of the chemical composition of the material, in special due to presence of potassium in the structure of the catalyst

Obtenção de biodiesel através da transesterificação do óleo de farelo de arroz utilizando KI/Al2O3

This study proposes to find a biodiesel through transesterification of rice bran oil with KI/Al2O3 checking the influence of two types of alumina (Amorphous and Crystalline) for conversion into methyl esters. The catalyst was synthesized by the wet impregnation method. Adding 30 mL of 35% KI(aq.) in 10 g of alumina, under stirring at 80 °C for 3 hours. The reaction conditions used in this study were optimized, with a molar ratio methanol:oil of 15:1, 8 h of reaction time and reflux temperature. The catalyst amount was varied in the range of 1 to 5 % wt. The solid catalysts materials were analyzed by: x-ray diffraction (XRD), thermogravimetry (TG), N2 adsorption/desorption, scanning electron microscopy (SEM) and basicity, for the identification of its structure and composition, verifying the presence of basic sites. The results showed that Al2O3(A) presents an amorphous structure, high surface area and a better catalytic activity, in relation to the catalyst synthesized with Al2O3(C) support that proved to have a more crystalline structure, having as well, a lesser surface area, enabling difficulties for the incorporation of active sites. The obtained biodiesel with 5% wt. KI/Al2O3(A) presented physicochemical properties within the standards specified by the Resolution No 7/2008 ANP and obtained the best reaction yield with 95.2%, according to quantitative measurement from the TG, which showed 96.2% conversion into methyl esters. It was furthermore found that with the increasing amount of the quantity of the catalyst in the reaction, there was also an increase in the ester content obtained. The specific mass and the kinematic viscosity were reduced with the increase of the amount of quantity of the catalyst, indicating an increase in the conversion of triglycerides

Eficiência do processo de obtenção do biodiesel de girassol usando o catalisador KNO3/Al2O3

It is known that the head office world energetics is leaning in the fossil fuels. However, the world panorama is changing quickly, for linked reasons to three of the humanity's great concerns in that century beginning: environment, global economy and energy. The biodiesel production is based on the transesterificação of vegetable oils or animal fats, using catalysts homogeneous or heterogeneous. The process of heterogeneous transesterificação presents lower conversions in comparison with the homogeneous, however, it doesn't present corrosion problems and it reduces to the occurrence of parallel reactions as saponification. In this sense, this work has for purpose the synthesis of a heterogeneous catalyst, KNO3/Al2O3, that soon afterwards was used in the reaction of transesterificação of the oil of the Helianthus annuus L. (sunflower). The solid materials (it supports and catalyst) they were analyzed by diffraction of ray-X (XRD) and electronic microscope of sweeping (MEV). After the analysis of Al2O3, a structure monophase amorphous tetragonal was verified, with characteristic patterns of that material, what could not be visualized in the difratograma of the catalyst. The biodiesel obtained with 4% wt. of KNO3/Al2O3 it was what obtained a better cinematic viscosity 8,3 mm2/s, comparing with the norms of ANP, and it also presented the best conversion tax in ethyl ésteres, in accordance with the quantitative measure starting from TG, that was of 60%. While the biodiesel with 6% wt. and with 8% wt. of KNO3/Al2O3 it was it that no transesterificou, because it was observed in the analysis termogravimétrica of those two materials, a single thermal event, that it corresponds the decomposition or volatilization of the triglycerides

Extração e análise da fração lipídica da microalga monoraphidium sp., síntese e caracterização do seu biodiesel

The cultivation of microalgae biomass in order to produce biodiesel arises as an extremely promising aspect, in that the microalgae culture includes short cycle of reproduction, smaller areas for planting and residual biomass rich in protein content. The present dissertation evaluates the performance and features, through spectrometry in the region of infrared with transformed Fourier (FTIR) and spectrometry in the region of UVvisible (UV-Vis), of the extracted lipid material (LM) using different techniques of cell wall disruption (mechanical agitation at low and at high spin and agitation associated with cavitation). The technique of gas chromatography (GC) brought to light the success of alkaline transesterification in the conversion of oil into methyl monoesters (MME), which was also analyzed by spectroscopic techniques (FTIR, proton magnetic resonance (1H NMR) and carbon (13C NMR). Through thermogravimetric analysis (TGA) were analyzed the lipid material (LM), biodiesel and the microalgae biomass. The method which provided the best results concerning the efficiency in extraction of the LP of Monoraphidium sp. (12,51%) was by mechanical agitation at high spin (14 000 rpm), for 2 hours being the ideal time, as shown by the t test. The spectroscopic techniques (1H NMR, 13C NMR and FTIR) confirmed that the structure of methyl monoesters and the chromatographic data (CG) revealed a high content of saturated fatty acid esters (about 70%) being the major constituent eicosanoic acid (33,7%), which justifies the high thermal stability of microalgae biodiesel. The TGA also ratified the conversion rate (96%) of LM into MME, pointing out the quantitative results compatible with the values obtained through GC (about 98%) and confirmed the efficiency of the extraction methods used, showing that may be a good technique to confirm the extraction of these materials. The content of LM microalgae obtained (12,51%) indicates good potential for using such material as a raw material for biodiesel production, when compared to oil content which can be obtained from traditional oil for this use, since the productivity of microalgae per hectare is much larger and requires an extremely reduced period to renew its cultivation

Avaliação da estabilidade térmica e oxidativa do biodiesel de algodão e do efeito da adição de antioxidantes (α-tocoferol e BHT)

This work aims to study the effects of adding antioxidants, such as, α- tocopherol and BHT on the thermal and oxidative stability of biodiesel from cottonseed (B100). The Biodiesel was obtained through the methylical and ethylical routes. The main physical and chemical properties of cotton seed oil and the B100 were determined and characterized by FTIR and GC. The study of the efficiency of antioxidants, mentioned above, in concentrations of 200, 500, 1000, 1500, 2000ppm, to thermal and oxidative stability, was achieved by Thermogravimetry (TG), Differential Thermal Analysis (DTA), Differential Scanning Calorimetry (DSC), Differential Scanning Calorimetry - Hi-Pressure (P-DSC) and Rancimat. The Biodiesel obtained are within the specifications laid down by Resolution of ANP No7/2008. The results of TG curves show that the addition of both antioxidants, even in the lowest concentration, increases the thermal stability of Biodieseis. Through the DTA and DSC it was possible to study the physical and chemical transitions occurred in the process of volatilization and decomposition of the material under study. The initial time (OT) and temperature (Tp) of oxidation were determined through the P-DSC curve and they showed that the α-tocopherol has a pro-oxidant behavior for some high concentrations. The BHT showed better results than the α-tocopherol, with regard to the resistance to oxidation

Avaliação oxidativa do biodiesel de pinhão manso em diferentes processos de purificação

The objective of this study was to analyze the oxidative stability of biodiesel from jatropha obtained from different purification processes, three wet processes with different drying (in a vacuum oven, conventional oven and in anhydrous sodium sulfate) and dry (purification with magnesium silicate adsorbent). Raw materials of different qualities (jatropha crop ancient and recent crop) were used. The Jatropha oil was extracted by mechanical extraction and refined. The Jatropha biodiesel was obtained by the transesterification reaction in ethyl route using alkaline catalysis. The biodiesel samples were characterized by analysis of water content, carbon residue, Absorption Spectroscopy in the Infrared Region and Thermogravimetry. Thermogravimetric curves of purified PUsv* PUsq* and had higher initial decomposition temperatures, indicating that the most stable, followed by samples PU* and PUSC*. Besides the sample SP* is a smaller initial temperature, confirming the sample without purification to be less thermally stable. The percentage mass loss of the purified samples showed conversion of about 98.5%. The results of analyzes carbon residue and infrared suggested that contamination by impurities is the main factor for decreased oxidative stability of biodiesel. The oxidative stability was assessed from periodic monitoring, using the techniques of Rancimat, peroxide index, acid value and Pressurized Differential Scanning Calorimetry. Samples of biodiesel from jatropha which showed better oxidative stability were of the best quality raw material and wet scrubbing: PUsq* with dry chemical, using anhydrous sodium sulfate and PUsv* with vacuum drying, which had oxidative stability 6 hours in Rancimat time 0 days, within the limits established by the Technical Regulation No. 4/2012 of the ANP, without the addition of antioxidant, suggesting that these procedures the least influence on the oxidative stability of biodiesel

Síntese e caracterização de óxidos de zinco e de magnésio suportados em A1SBA-15 para produção de biodiesel

To overcome the challenge of meeting growing energy demand in a sustainable way, biodiesel has shown very promising as alternative energy can replace fossil fuels, even partially. Industrially, the biodiesel is produced by homogeneous transesterification reaction of vegetable oils in the presence of basic species used as catalysts. However, this process is the need for purification of the esters obtained and the removal of glycerin formed after the reaction. This context, the alternative catalysts have that can improve the process of biodiesel production, aiming to reduce costs and facilitate its production. In this study, the AlSBA-15 support with Si / Al ratio = 50 was synthesized, as like as the heterogeneous catalysts of zinc oxide and magnesium supported on mesoporous AlSBA-15 silica, in the concentrations of 5, 10, 15 and 30 %, relative to the support. The textural properties and structural characterization of catalysts and supports were determined by techniques: X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) coupled to the chemical analyzer, adsorption / desorption of N2, thermal analysis (TG / DTG), absorption spectroscopy in the infrared (FTIR) and X-ray photoelectron spectroscopy (XPS). Characterization results indicated that the support AlSBA-15 retained the hexagonal ordered after the incorporation of zinc oxide and magnesium oxide in the holder. For heterogeneous catalysts, ZnO-AlSBA-15, that was observed the presence of zinc oxide nanoparticles dispersed in the surface and interior channels of the mesoporous and microporous support. The catalytic activity was evaluated by the transesterification reaction of sunflower oil via methylic route, and some reaction parameters were optimized with the most active catalyst in biodiesel production by sunflower oil. For the series of heterogeneous catalysts, the sample with 30 % ZnO supported on AlSBA-15 showed a better conversion of triglyceride to methyl esters, about 95.41 % of reaction conditions: temperature 175 °C, with molar ratio of 42:1, stirring at 200 rpm and under a pressure of 14 bar for 6 h. The catalyst MgO-AlSBA-15 showed no catalytic activity in the studied reactions

Estudo da influência do biodiesel de mamona como aditivo antioxidante para o biodiesel de girassol e soja

Biodiesel is a fuel made up by mono-alkyl-esters of long chain fatty acids, derived from vegetable oils or animal fat. This fuel can be used in compression ignition engines for automotive propulsion or energy generation, as a partial or total substitute of fossil diesel fuel. Biodiesel can be processed from different mechanisms. Transesterification is the most common process for obtaining biodiesel, in which an ester compound reacts with an alcohol to form a new ester and a new alcohol. These reactions are normally catalyzed by the addition of an acid or a base. Initially sunflower, castor and soybean oil physicochemical properties are determined according to standard test methods, to evaluate if they had favorable conditions for use as raw material in the transesterification reaction. Sunflower, castor and soybean biodiesel were obtained by the methylic transesterification route in the presence of KOH and presented a yield above 93% m/m. The sunflower/castor and soybean/castor blends were studied with the aim of evaluating the thermal and oxidative stability of the biofuels. The biodiesel and blends were characterized by acid value, iodine value, density, flash point, sulfur content, and content of methanol and esters by gas chromatography (GC). Also studies of thermal and oxidative stability by Thermogravimetry (TG), Differential Scanning Calorimetry High Pressure (P-DSC) and dynamic method exothermic and Rancimat were carried out. Biodiesel sunflower and soybean are presented according to the specifications established by the Resolution ANP no 7/2008. Biodiesel from castor oil, as expected, showed a high density and kinematic viscosity. For the blends studied, the concentration of castor biodiesel to increased the density, kinematic viscosity and flash point. The addition of castor biodiesel as antioxidant in sunflower and soybean biodiesels is promising, for a significant improvement in resistance to autoxidation and therefore on its oxidative stability. The blends showed that compliance with the requirements of the ANP have been included in the range of 20-40%. This form may be used as a partial substitute of fossil diesel

Usos potenciais de moringa oleifera lam., uma matriz para produção de biodiesel e tratamento de água no semiárido nordestino

The current environmental crisis demands transformations in the relations among society, nature and development, considering sustainability. In this context, an important theme is replacing fossil fuels with biofuels, such as biodiesel. Moringa oleifera Lam. is a species that can be used as a raw material to produce biodiesel. Besides, it is a multiple purposes plant, which can be used also in water treatment. Thus, the aims of this work were to analyze the anatomical adaptations found in the stem and in the leaf and the seed s oil stores of M. oleifera., to investigate chemical characteristics of M. oleifera s seed oil, considering biodiesel production, and to evaluate the coagulation activity of these seeds in water treatment. Semipermanent histological laminas were made and it follows that the stem has thick cuticle, stomata whose cells guard are below the epidermis line, hollow medulla, druses and tector trichomes as adaptations to climate and soil conditions in which the species is found and the leaf is dorsiventral and it has thick cuticle, tector trichomes and druses. The seed has great reserves of oil. These features favor the use of Moringa oleifera Lam. as a raw material to produce biodiesel in Brazil s Northeast semiarid region. Chemical analysis were made through oil solvent extraction using mechanic stirrer. The oil was analyzed in UV spectrophotometer. A transesterification was made and biodiesel was analyzed in gas chromatography. Oil yield was high and good quality biodiesel was obtained. To evaluate seeds coagulantion activity, coagulation and flocculation essays in jartest were made, using seed extract to treat raw water. Seeds were efficient in cogulation process to treat water. So, they can be used in rudimentary systems or as a raw material to coagulant proteins extraction, as an alternative to traditional coagulants. M. oleifera has characteristics that favor its use to biodiesel production and water treatment

Synergistic effect in the catalytic activity of lipase Rhizomucor miehei immobilized on zeolites for the production of biodiesel

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

Three-dimensional structure of ribonuclease T-1 complexed with an isosteric phosphonate substrate analogue of GpU: Alternate substrate binding modes and catalysis

The X-ray crystal structure of a complex between ribonuclease T-1 and guanylyl(3'-6')-6'-deoxyhomouridine (GpcU) has been determined at 2.0 Angstrom resolution. This Ligand is an isosteric analogue of the minimal RNA substrate, guanylyl(3'-5')uridine (GpU), where a methylene is substituted for the uridine 5'-oxygen atom. Two protein molecules are part of the asymmetric unit and both have a GpcU bound at the active site in the same manner. The protein-protein interface reveals an extended aromatic stack involving both guanines and three enzyme phenolic groups. A third GpcU has its guanine moiety stacked on His92 at the active site on enzyme molecule A and interacts with GpcU on molecule B in a neighboring unit via hydrogen bonding between uridine ribose 2'- and 3'-OH groups. None of the uridine moieties of the three GpcU molecules in the asymmetric unit interacts directly with the protein. GpcU-active-site interactions involve extensive hydrogen bonding of the guanine moiety at the primary recognition site and of the guanosine 2'-hydroxyl group with His40 and Glu58. on the other hand, the phosphonate group is weakly bound only by a single hydrogen bond with Tyr38, unlike ligand phosphate groups of other substrate analogues and 3'-GMP, which hydrogen-bonded with three additional active-site residues. Hydrogen bonding of the guanylyl 2'-OH group and the phosphonate moiety is essentially the same as that recently observed for a novel structure of a RNase T-1-3'-GMP complex obtained immediately after in situ hydrolysis of exo-(S-p)-guanosine 2',3'-cyclophosphorothioate [Zegers et al. (1998) Nature Struct. Biol. 5, 280-283]. It is likely that GpcU at the active site represents a nonproductive binding mode for GpU [:Steyaert, J., and Engleborghs (1995) fur. J. Biochem. 233, 140-144]. The results suggest that the active site of ribonuclease T-1 is adapted for optimal tight binding of both the guanylyl 2'-OH and phosphate groups (of GpU) only in the transition state for catalytic transesterification, which is stabilized by adjacent binding of the leaving nucleoside (U) group.