Influence of the purification process on the stability of <Emphasis Type="Italic">Jatropha curcas</Emphasis> biodiesel

The aim of this work was to evaluate the influence of the purification process on the stability of Jatropha curcas biodiesel. The biodiesel was obtained using a variety of purification processes: three wet methods with different drying processes (vacuum oven, conventional oven and anhydrous sodium sulfate) and one dry method (purification with adsorbent magnesium silicate). Biodiesel was characterized through the analysis of carbon residue, acidity index, infrared and gas chromatography. The composition J. curcas oil indicated 56.3 % of unsaturated fatty acids and 43.7 % of saturated fatty acids. Jatropha oil presented high quantity of saturated acids, which are less susceptible at oxidation. The biodiesel sample that was chemically purified (PUsq) presented better purity, indicating be the process more efficient in remove the residues of synthesis. Thermogravimetric curves of purified biodiesel by wet method, PUsq, with chemical drying using anhydrous sodium sulfate, and PUsv, with vacuum drying, showed the highest initial decomposition temperatures, indicating higher thermal stability. The carbon residue and infrared analyses suggested that contamination by catalyst residue is a determining factor in reduction of the oxidative stability of biodiesel. The oxidative stability was evaluated using Rancimat and pressure differential scanning calorimetry. Biodiesel samples showing better oxidative stability were purified using PUsq and PUsv, which obtained stability of 6 h using the Rancimat technique, the minimum limit set by Brazilian legislation, without the addition of antioxidant, suggesting that these methods least influenced the stability of biodiesel.     

Comparison of the oxidative stability of soybean and sunflower oils enriched with herbal plant extracts

The present study was conducted to determine and compare the oxidative stability of soybean and sunflower oils using differential scanning calorimetry (DSC). These edible oils were enriched with marjoram (Origanum majorana L.), thyme (Thymus vulgaris L.), and oregano (Origanum vulgare L.) extracts at three different concentrations and synthetic antioxidant (BHA). The fatty acid composition of studied oils was determined by gas chromatography mass spectrometry to evaluate the content of unsaturated fatty acids that are sensitive to oxidation process. Oil samples were heated in the DSC at different heating rates (4.0, 7.5, 10.0, 12.5, and 15.0 °C min^?1) and oxidation kinetic parameters (activation energy, pre-exponential factor, and oxidation rate constant) were calculated. The results showed that the oxidative stability of sunflower oil samples enriched with oregano extracts and soybean oil supplemented with thyme extracts was improved compared to samples without the addition of herbal plant extracts and the synthetic antioxidant.     

Effect of temperature and composition on density,viscosity and thermal conductivity of fatty acid methyl esters from soybean,castor and Jatropha curcas oils

This work is focused on experimental determination of density, viscosity and thermal conductivity as a function of temperature and composition for fatty acid methyl esters (FAME) from soybean, castor and Jatropha curcas oils. Results show that an increase in temperature, over the range of (273 to 363) K, resulted in a decrease of all properties studied. FAME from soybean and J. curcas oils presented similar rheological behaviour, while FAME from castor oil presented higher values for density and viscosity. Density, dynamic viscosity and thermal conductivity data for all systems obtained here were correlated using empirical equations with good agreement between experimental and calculated values. Experimental data presented here may be useful as a database for specification purposes and equipment design and plant operation in the biodiesel industry.     

Rosemary (Rosmarinus officinalis L.) extract

The restriction to the use of synthetic antioxidants has fostered the research on natural antioxidants, taking into account that the prolonged usage of these substances can harm seriously the human being provoking degenerative diseases. In the present study, the antioxidant effect of the ethanolic rosemary (Rosmarinus officinalis L.) extract on the oxidative stability of edible vegetable oils was investigated by means of the pressurized differential scanning calorimetry (PDSC) and oven test techniques. The rosemary extract, at the concentration of 2,000 mg kg^?1, as well as the synthetic antioxidant tert-butylhydroquinone (TBHQ) at the concentrations of 100 and 200 mg kg^?1 were added to samples of sunflower oil, corn oil, and soybean oil. The fatty acid profiles of the vegetable oils were determined by gas chromatography–mass spectrometry confirming the elevated contents of unsaturated fatty acids. The thermogravimetric analysis showed that the rosemary extract is stable at the frying temperature of the oils. The results of the oxidative stability demonstrated that the extract of Rosmarinus officinalis displayed a more effective protective action in the PDSC technique, when compared with the synthetic antioxidant TBHQ, indicating that it is a promising source of natural antioxidants for edible vegetable oils.     

Evaluating antioxidants efficiency during storage of ethylic and methylic biodiesel by low pressurized DSC and Rancimat methods

Efficiencies of four commercial antioxidants used during the storage of two biodiesel, BS-ethyl and BS-methyl, respectively obtained from soybean oil by ethylic and methylic routes, were evaluated by measuring their oxidative stability using a low pressurized DSC (low P-DSC) method developed by the authors and by Rancimat method, which is specified by the American ASTM D6751 and European EN 14214 standard methods. The operating temperature of the low P-DSC method was the same as that used in the Rancimat procedure (110 °C). The antioxidants, used in 500 mg kg^?1 content, have the following active components: phenol, biphenol, phenol + amine mixture, and a hydroquinone + organic acid mixture. Samples of each biodiesel–antioxidant mixture were evaluated simultaneously by the two methods, right after their preparation and 30, 60, 90, and 120 days of storage at 23 ± 1 °C. A non-dimensional oxidative induction time parameter, defined as the ratio between the oxidation induction time (OIT) or induction time (IT) values at a storage time t and at t = 0, was used to evaluate the antioxidant activity. For the same mixture, changes of this non-dimensional parameter calculated from OIT or IT show a similar trend with storage time, indicating that it can be determined either from low P-DSC or Rancimat method data. As the efficiency of the studied antioxidants depends on their composition, their interaction with each biodiesel, and on the storage time, this parameter can be used to indicate the best storage time for each antioxidant–biodiesel mixture.     

Comparative study of oxidative stability of sunflower and cotton biodiesel through P-DSC

Biodiesel can contain unsaturated fatty acids, which are susceptible to oxidation, being able to change into polymerized compounds. Oxidative stability is very important in the quality control of oils and biodiesel. In this study, biodiesel samples were produced through the methyl route, using a homogeneous catalyst. The determination of methyl esters was performed by gas chromatography in order to confirm the conversion of the carboxylic acids present in the raw material for the methyl esters. Also proved the presence of methyl linoleate and methyl oleate to the major constituent of biodiesel. The thermal and oxidative stability of sunflower and cotton oils and their biodiesel, using TG and P-DSC techniques were investigated. The use of P-DSC to measure the oxidative induction time was very important. These measurements were used to evaluate the cotton and sunflower oils, and their respective biodiesel. It was found that the thermal-oxidative stability of vegetable oils and their biodiesel were similar, due to the fact that both presented chemical composition and percentages of fatty acids similar.     

Antioxidative properties of hydrogenated cardanol for cotton biodiesel by PDSC and UV/VIS

Biodiesel is a non-toxic biodegradable fuel that consists of alkyl esters produced from renewable sources, vegetal oils and animal fats, and low molecular mass alcohols, and it is a potential substitute for petroleum-derived diesel. Depending on the raw materials used, the amount of unsaturated fatty acids can vary in the biodiesel composition. Those substances are widely susceptible to oxidation processes, yielding polymeric compounds, which are harmful to the engines. Based on such difficulty, this work aims to evaluate the antioxidant activity of cashew nut shell liquid (cardanol), as additive for cotton biodiesel. The oxidative stability was investigated by the pressure differential scanning calorimetry (PDSC) and UV/Vis spectrophotometer techniques. The evaluated samples were: as-synthesized biodiesel — Bio T₀, additivated and heated biodiesel — Bio A (800 ppm L⁻¹ of hydrogenated cardanol, 150°C for 1 h), and a heated biodiesel — Bio B (150°C, 1 h). The oxidative induction time (OIT) analyses were carried out employing the constant volume operation mode (203 psi oxygen) at isothermal temperatures of 80, 85, 90, 100°C. The high pressure OIT (HPOIT) were: 7.6, 15.7, 22.7, 64.6, 124.0 min for Bio T₀; 41.5, 77.0, 98.6, 106.6, 171.9 min for Bio A and 1.7, 8.2, 14.8, 28.3, 56.3 min for Bio B. The activation energy (E) values for oxidative processes were 150.0±1.6 (Bio T₀), 583.8±1.5 (Bio A) and 140.6±0.1 kJ mol⁻¹(Bio B). For all samples, the intensities of the band around 230 nm were proportional to the inverse of E, indicating small formation of hyper conjugated compounds. As observed, cardanol has improved approximately four times the cotton biodiesel oxidative stability, even after the heating process.     

Chemical,thermal and rheological properties and stability of sapucaia (<Emphasis Type="Italic">Lecythis pisonis</Emphasis>) nut oils

Sapucaia (Lecythis pisonis) is a tree that grows in Colombia, Venezuela and the Guyanas and is widely distributed in Brazil. This work presents a study of sapucaia nut oils (SO) that were obtained by Bligh and Dyer (LP1) and Soxhlet (LP2) methods and were evaluated for their fatty acid composition, rheological and thermal properties, total phenolic compounds (TPC), antioxidant properties and oxidative stability using Rancimat and ATR-FTIR spectroscopy. The analyses showed that the method of extraction impacts the fatty acid profiles of SO. Oil extracts present considerable TPC content and antioxidant properties. Thermal analysis revealed three degradation steps for SO in the air atmosphere, starting at around 130 °C, being thermally stable up to 300 °C (with a ~ 5% mass loss) and reaching total degradation near 620 °C. Thermal analysis under N₂ produced two degradation steps, initiating at around 130 °C and finishing at 500 °C. Rancimat also confirmed the high thermal stability of SO, with induction periods of 13.28 h (LP1) and 7.18 h (LP2). The DSC parameters of SO were similar among each other. Crystallization (? 8.04 to ? 73.93 °C) and melting (? 31.34 to 8.28 °C) phases occurred over a large temperature range. SO presented FTIR spectral features with characteristic bands for vegetable oils. Ostwald–de Waele and Herschel–Bulkley rheological models indicated major pseudoplastic behavior for SO, with a predominant viscous component. These results reinforce that SO are appropriate for human consumption and open up new possibilities for their industrial exploitation, such as for food and the cosmetic, pharmaceutical and biodiesel industries.     

High oleic safflower biolubricant through double transesterification with methanol and pentaerythritol: Production,characterization, and antioxidant addition

Double transesterification from vegetable oils could play an important role in biodiesel and biolubricant production, with the possible implementation of biorefineries to replace refineries based on petroleum. The oxidative stability of the original sample will influence the quality of the intermediate and final products, recommending highly stable raw materials or the use of antioxidants to keep quality parameters during storage. The aim of this work was to obtain a stable biolubricant, assessing its production through a double transesterification with methanol and pentaerythritol from high-oleic safflower oil and adding antioxidants, paying attention to quality parameters. Consequently, a biorefinery that produced high-quality products was proposed. In conclusion, high biodiesel and biolubricant yields were obtained (>97 and >94%, respectively) with the following chemical conditions for the latter: FAME/alcohol ratio, 1:0.33; pressure, 260 mmHg; catalyst concentration, 1.0%; temperature, 160 °C. The oxidative stability of biodiesel complied with the standard (10.78 h) due to its high methyl oleate content (exceeding 80%), whereas this parameter was shorter for the biolubricant (2.86 h), possibly due to its molecular structure. Consequently, antioxidant addition was needed, and tert-Butylhydroquinone at low concentration (500 ppm) kept viscosity and acid number of high-oleic safflower biolubricant during oxidation conditions (up to 8 h). However, tannic acid did not keep these properties in biolubricant. In conclusion, by using the right antioxidant, all the products of the proposed biorefinery were stable during oxidizing conditions, making this biorefinery more competitive.     

Comparison of the effect of <Emphasis Type="Italic">Pleurotus citrinopileatus</Emphasis> extract and vitamin E on the stabilization properties of camellia oil

We selected Camellia tenuifolia (Hayata) seed oil to compare the effects of mushroom extract and vitamin E on its stabilization properties. Camellia tenuifolia was selected for its higher oil content, but its proportions of unsaturated fatty acids and natural antioxidants as well as its oxidation stability are lower than those of Camellia oleifera oil. Our aim was to improve the oxidation stability, thermal stability, and photodegradation of C. tenuifolia seed oil and then compare the advantages of mixing traditional antioxidant (vitamin E) and mushroom natural antioxidant components (mushroom extract) in the oil. The focus was on the analysis of the effects of Pleurotus citrinopileatus (Singer) extract and vitamin E on the stabilization properties of C. tenuifolia seed oil, which involved some degradation research, such as evaluating the thermal, oxidation, and antioxidant effects as well as the irradiative (pulsed light) stability of the original oil and oil mixed with additives for comparing the differences by differential scanning calorimetry tests and isothermal microcalorimeter (TAM Air) analyses. We determined the effects of stabilization additives vitamin E and various PC extract doses by using pulsed light irradiation (0, 30, and 60 pulses) and found that the 3 mass% PC extract had the best antiphotodegradation characteristics, and the 0.1 mass% vitamin E indicated the outstanding oxidation stability for among all of the additives in this study. Overall, we obtained the following suitable conditions to stabilize camellia oil: addition of vitamin E, addition of 3 mass% PC extract, and a nitrogen atmosphere.     

Sunflower biodiesel

The higher is the degree of unsaturation in ester chain of a biodiesel, the smaller is its oxidation stability. Sunflower biodiesel obtained by the ethyl route possesses a high amount of unsaturated fatty acids, mainly oleic acid (C18:1) and linoleic acid (C18:2), thus being more prone to the oxidation process. In Brazil, with the purpose of meeting the specifications of the Brazilian National Agency of Petroleum, Natural Gas and Biofuels (ANP), antioxidant additives, from synthetic and natural origins, have been added to the biofuel. Antioxidants are an alternative to prevent the oxidative deterioration of the fatty acid derivatives, as they are substances able to reduce the oxidation rate. In this study, the oxidative stability of sunflower biodiesel, obtained by the ethyl route and additivated with different concentrations of the antioxidants butylated hydroxytoluene (BHT) and t-butylhydroquinone (TBHQ), was evaluated by means of Pressure differential scanning calorimetry (P-DSC) and the Accelerated oxidative stability test (Rancimat, Method EN 14112). The results obtained by the two techniques showed the same oxidation tendency. Thus, P-DSC can be used as an alternative to determine the oxidative stability of biodiesel. The antioxidant TBHQ, added to biodiesel at the concentrations of 2000 and 2500 mg kg⁻¹, raised the oxidation induction time to a value higher than 6 h, the limit established by the Resolution ANP number 7/2008, thus being the best alternative among the studied antioxidants.     

Evaluation of antioxidants on the thermo-oxidative stability of soybean biodiesel

This work shows the evaluation of three antioxidants (2,6-di-t-butyl-4-methylphenol (BHT)—synthetic antioxidant, hydrogenated cardanol (HC), and alkyl hydrogenated cardanol (AHC)—both derived from cashew nut shell liquid) on the thermo-oxidative stability of the soybean biodiesel. The antioxidants were added at concentrations of 200, 300, and 400 ppm, and the oxidative stability of the biofuel with and without antioxidants were investigated by thermogravimetric analysis (TG-DTG and IPDT) and Metrohm 743 Rancimat per the EN 14112 method. The results showed that all antioxidants contributed for the thermo-oxidative stability of the soybean biodiesel as follows: soybean biodiesel < soybean biodiesel + BHT < soybean biodiesel + HC < soybean biodiesel + AHC. In the Rancimat method, the results showed that the antioxidants influenced the biodiesel stability with an increase of at least 71 %.     

A complete evaluation of thermal and oxidative stability of chia oil

Chia (Salvia hispanica L.) seed oil is the richest natural source of α-linolenic acid, an n ? 3 polyunsaturated fatty acid (ω-3 PUFA), contributing to its use as functional and nutraceutical food in large part of Latin America. However, a food with such fatty acid composition could be highly susceptible to lipid oxidation. Thus, the present study was conducted to determine the thermal and oxidative stability of chia oil by various methods. Rancimat method was used to evaluate the effect of synthetic and natural antioxidants in the oxidative stability. Pressurized differential scanning calorimetry (PDSC), Schaal test and ¹H NMR spectroscopy were used to assess the thermal stability. The effect of frying temperature and/or heating time on fatty acid composition was assessed by ¹H NMR. The results show that tert-butylhydroquinone (TBHQ) and a mixture of TBHQ and rosemary extract were effective in increasing the oxidative stability of chia oil. Concerning the storage conditions, PDSC, Schaal test and ¹H NMR data showed that chia oil is stable at 60 °C; hence, there is no need for special storage conditions. PDSC and ¹H NMR results indicate that chia oil cannot be used in cooking and frying, because at high temperatures severe degradation of the unsaturated groups and loss of the nutritional properties of the oil occur.     

Determination of nutrients and potentially toxic elements in Jatropha curcas seeds, oil and biodiesel using inductively coupled plasma mass spectrometry

Biodiesel is a renewable and biodegradable fuel that can be used in diesel engines as a replacement for fossil diesel. A suitable alternative is to produce it from Jatropha curcas, which has high quality oil concentration. Nevertheless, the presence of particular chemical elements above certain limits can affect the product quality, leading to vehicle engine problems and acting as air pollution source. The objective of this work is to develop a method for the simultaneous determination of B, Na, Mg, P, S, K, Ca, Cr, Mn, Fe, Co, Ni, Cu, Zn, Cd, Ba, and Pb in J. curcas seeds, oil and biodiesel using the inductively coupled plasma mass spectrometry (ICP-MS) technique. This material was evaluated because has been successfully employed in India for biodiesel production as well as in other places where there is an incentive to family farming, without affect the food chain. The oil was obtained from seeds via mechanical extraction and the biodiesel was achieved by oil transesterification. After optimization of the microwave digestion method for the different sample types, the samples were analyzed by ICP-MS. The certified reference material NIST SRM 1515 (apple leaves) and the recovery tests were carried out to ensure the accuracy of the proposed method, which made possible the quantification of several nutrients and potentially toxic elements in J. curcas seeds, oil and biodiesel, especially Na, K, Ca, Mg, P and S in biodiesel which are mandatory analyzed by Petroleum, Natural Gas and Biofuel National Agency (ANP). This work highlights the findings of the first study of potentially toxic and nutrient elements in the production chain steps seed–oil–biodiesel from J. curcas.     

Dihydromyricetin

A study on the efficiency of bio-based compound as stabilizer for linear low density polyethylene (LLDPE) is reported. A water extract from Ampelopsis grossedentata (Dihydromyricetin) is used. Its stabilizing activity is compared with two commercial phenolic antioxidants: methyl gallate (MG) and Irganox 1010. Based on the measurement of the oxidation onset temperature (OOT) of LLDPE/antioxidant samples, it is found that the antioxidant ability of the three kinds of antioxidants is in the following order: DMY > 1010 > MG. The antioxidant ability and thermal decomposition activation energy (E _a) of antioxidants are further examined by thermal gravimetric analysis. The effects of water extraction on the migration resistance of LLDPE/antioxidants are also evaluated by monitoring the OOT change, demonstrating that DMY retained high stability against migration.     

Harnessing Indigenous Plant Seed Oil for the Production of Bio-fuel by an Oleaginous Fungus,Cunninghamella blakesleeana- JSK2, Isolated from Tropical Soil

Cunninghamella blakesleeana- JSK2, a gamma-linolenic acid (GLA) producing tropical fungal isolate, was utilized as a tool to evaluate the influence of various plant seed oils on biomass, oleagenicity and bio-fuel production. The fungus accumulated 26 % total lipid of their dry biomass (2 g/l) and 13 % of GLA in its total fatty acid. Among the various plant seed oils tested as carbon sources for biotransformation studies, watermelon oil had an effect on biomass and total lipid increasing up to 9.24 g/l and 34 % respectively. Sunflower, pumpkin, and onion oil increased GLA content between 15–18 %. Interestingly, an indigenous biodiesel commodity, Pongamia pinnata oil showed tremendous effect on fatty acid profile in C. blakesleeana- JSK2, when used as a sole source of carbon. There was complete inhibition of GLA from 13 to 0 % and increase in oleic acid content, one of the key components of biodiesel to 70 % (from 20 % in control). Our results suggest the potential application of indigenous plant seed oils, particularly P. pinnata oil, for the production of economically valuable bio-fuel in oleaginous fungi in general, and C. blakesleeana- JSK2, in particular.     

Thermal behaviors of soy biodiesel

Biodiesel is a prospective and promising fuel for diesel engines. However, some aspects need improvement, to develop into an ideal fuel, such as flow properties at low temperatures and storage stability at high temperatures with exposure to the air. Thermal analysis is an efficient tool for measuring properties, such as crystallization temperature, and thermal and oxidative stabilities. In this study, the thermal behaviors of biodiesel at low and high temperatures were investigated by using thermogravimetric analyzer, differential scanning calorimetry, pressurized differential scanning calorimetry (PDSC), and sorption analyzer (SA). The soy biodiesel was obtained through a transesterification reaction with a homogeneous catalyst. The constituents of the soy biodiesel as determined by gas chromatography show that methyl esters content was 99?% and of these 84?% were unsaturated fatty acids. TG results illustrate that the total weight loss of the biodiesel was 99?% below 300?°C under nitrogen flow, indicating a high purity biodiesel. The onset decomposition temperature and the peak temperatrue of the soy biodiesel were 193 and 225?°C, respectively, implying the biodiesel has good thermal stability. PDSC results show that the oxidation onset temperature of the soy biodiesel was 152?°C, and the oxidative induction time was 24?min. DSC results demonstrate that the onset crystallization temperature of the soy biodiesel was 1.0?°C. The SA results point out that with increasing temperature and humidity, the soy biodiesel absorbed more water, and in which humidity was the dominant factor. The water absorption and desorption of the soy biodiesel is a non-reversible process. The preferable storage conditions for soy biodiesel occur when humidity is less than 30?% and the temperature is less than 30?°C. In summary, thermal analysis is a faster alternative for thermal behavior studies as compared with conventional standard methods.     

Thermal decomposition of biodiesel fuels produced from rapeseed, jatropha, and coffee oils with different alcohols

Thermal behaviors and the effects of various alcohols on biodiesel fuel (BDF) derived from edible oil such as rapeseed oil and inedible oils such as coffee oil and jatropha oil, were studied. TG curves in air and N₂ of rapeseed BDF, jatropha BDF, drip coffee, and BDF espresso coffee BDF synthesized from the methanol presented similar results which exhibited only one mass loss step, which is attributed to vaporization or combustion of the methyl esters. The decomposition temperature (T _d) of rapeseed, jatropha and coffee Bt-BDF were high by about 30 °C compared with the standard, Me-BDF. The amount of decomposition residue at 400 °C was found to be related to the number of carbon atoms in the alcohol, with the residue becoming greater with more carbons in the alcohol. The oxidation stability of rapeseed BDF depended on the carbon chain of the alcohol. However, coffee and jatropha BDFs were stable in spite of the long chain alcohol.     

Determination of the oxidation stability of biodiesel and oils by spectrofluorimetry and multivariate calibration

Oxidation stability is an important quality parameter for biodiesel. In general, the methods used to evaluate the oxidation stability of oils and biodiesels are time-consuming. This work reports the use of spectrofluorimetry, a fast analytical technique, associated with multivariate data analysis as a powerful analytical tool to prediction of the oxidation stability. The prediction of the oxidation stability showed a good agreement with the results obtained by the EN14112 reference method Rancimat. The models presented high correlation (0.99276 and 0.97951) between real and predicted values. The R² values of 0.98557 and 0.95943 indicated the accuracy of the models to predict the oxidation stability of soy oil and soy biodiesel, respectively. The residual distribution does not follow a trend with respect to the predicted variables indicating the good quality of the fits.     

Industrial Waste Utilization for Low-Cost Production of Raw Material Oil Through Microbial Fermentation

In view of ever-growing demand of biodiesel, there is an urgent need to look for inexpensive and promising renewable raw material oils for its production. In this context, the aim of this study was to evaluate the potential use of industrial wastes for low-cost production of oils through microbial fermentation. Among the strains tested, Yarrowia lipolytica grew best and produced highest lipid when grown on decanter effluent from palm oil mill. When crude glycerol by-product from a biodiesel plant was added into the effluent as a co-substrate, Y. lipolytica produced a higher biomass of 3.21 g/L and a higher amount of lipid of 2.21 g/L which was 68 % of the dry weight. The scale up and process improvement in a 5-L bioreactor increased the biomass and lipid up to 5.53 and 2.81 g/L, respectively. A semi-continuous mode of operation was an effective mode for biomass enhancement while a fed-batch mode was effective for lipid enhancement. These yeast lipids have potential to be used as biodiesel feedstocks because of their similar fatty acid composition to that of plant oil.