Heats of combustion of biofuels obtained by pyrolysis and by transesterification and of biofuel/diesel blends

The obtained heats of combustion were 46.65 ± 0.20; 38.09 ± 0.31; 39.67 ± 0.22; 41.88 ± 0.31; 37.86 ± 0.46; 39.89 ± 0.09; 41.28 ± 0.31 MJ/kg for diesel, transesterified soybean oil, pyrolysed soybean oil and crude soybean oil, transesterified palm tree oil (Elaeis sp.), pyrolysed palm tree oil, crude palm tree oil, respectively. The results show the heats of combustion of biofuels are approximately 17% smaller than traditional diesel. The data also show the heats of combustion depend on the methodology used for the biofuel production. Addition of biofuels to traditional diesel fuel results in a linear decrease of the heat of combustion with the amount of the alternative fuel added to the diesel. However, for blends with 5% biofuels, which is the limit demanded by Brazilian legislation, no significant decrease of the heat of combustion of the commercial diesel was observed.     

Adsorption and preconcentration of divalent metal ions in fossil fuels and biofuels: gasoline, diesel, biodiesel, diesel-like and ethanol by using chitosan microspheres and thermodynamic approach

Biodiesel and diesel-like have been obtained from soybean oil by transesterification and thermal cracking process, respectively. These biofuels were characterized as according to ANP standards by using specific ASTM methods. Ethanol, gasoline, and diesel were purchased from a gas station. Deacetylation degree of chitosan was determined by three distinct methods (conductimetry, FTIR and NMR), and the average degree was 78.95%. The chitosan microspheres were prepared from chitosan by split-coating and these spheres were crosslinked using glutaraldehyde. The surface area of microspheres was determined by BET method, and the surface area of crosslinked microspheres was 9.2 m² g⁻¹. The adsorption isotherms of cooper, nickel and zinc on microspheres of chitosan were determined in petroleum derivatives (gasoline and diesel oil), as well as in biofuels (alcohol, biodiesel and diesel-like). The adsorption order in all fuels was: Cu > Ni > Zn. The elution tests presented the following preconcentration degrees: >4.5 to ethanol, >4.4 to gasoline, >4.0 to diesel, >3.8 to biodiesel and >3.6 to diesel-like. The application of chitosan microspheres in the metal ions preconcentration showed the potential of this biopolymer to enrich fuel sample in order to be analyzed by flame atomic absorption spectrometry.     

Thermal diesel-like analysis

Biofuel has been obtained by cracking of soybean (Glycine sp.) oil, which is characterized by acidity index, density, cetane index, copper corrosion, carbon residue, fulgor point, and heat of combustion. In order to evaluate the quality of biofuel as well as detect its adulteration with vegetable oil, partial least squares regression calibration models based on thermogravimetric (TG) analysis were used as a precise and an accurate method. Thirty mixtures of biofuel/diesel/vegetable oil standards were prepared. Twenty of them were used for calibration, and ten for validation. The results have shown that the thermogravimetric analysis, PLS/TG, presented the best performance for the detection of vegetable oil contamination with a root mean square error of prediction (RMSEC% w/w) of 0.23, with a relative error of prediction of 3.6%, corroborating with the success of TG analysis application to determine the quality of biofuels and diesel/biofuel blends, showing that the TG analysis is an excellent tool to control quality of biofuels.     

Soybean biodiesel methyl esters,free glycerin and acid number quantification by 1H nuclear magnetic resonance spectroscopy

Production of alternative fuels, such as biodiesel, from transesterification of vegetable oil driven by heterogeneous catalysts is a promising alternative to fossil diesel. However, achieving a successful substitution for a new renewable fuel depends on several quality parameters. ¹H NMR spectroscopy was used to determine the amount of methyl esters, free glycerin and acid number in the transesterification of soybean oil with methanol in the presence of hydrotalcite‐type catalyst to produce biodiesel. Reaction parameters, such as temperature and time, were used to evaluate soybean oil methyl esters rate conversion. Temperatures of 100 to 180 °C and times of 20 to 240 min were tested on a 1 : 12 molar ratio soybean oil/methanol reaction. At 180 °C/240 min conditions, a rate of 94.5 wt% of methyl esters was obtained, where free glycerin and free fatty acids were not detected. Copyright © 2012 John Wiley & Sons, Ltd.     

Oxygen storage capacity of substituted YBaCo4O7+δ oxygen carriers

Depletion of non-renewable energy sources are at elevated manner due to the rapid growth of industrialization and transportation sector in last few decades and leads to further energy demand. Biodiesels especially second-generation fuels from non-edible oil resources are alternate sources for replacement of diesel fuel in CI engines due to their considerable environmental benefits. In the present work, non-edible feedstock of Calophyllum inophyllum seed oil (tamanu oil) is used for biodiesel production. Transesterification method is used for preparation of biodiesel in the existence of methanol with NaOH as catalyst. The copper nanoparticles are synthesized by electrochemical method, and it is characterized by using X-ray diffraction analysis (XRD) and scanning electron microscopy (SEM). XRD and SEM results confirm the presence of copper nanoparticle and size of around 30 nm. This paper aims to investigate the effects of the copper additive nanoparticles with biodiesel blends on the engine performance, combustion and emission characteristics of single-cylinder direct-injection diesel engine and compared that with diesel fuel. The results showed that the addition of nano-additives enhances brake thermal efficiency and reduces specific fuel consumption compared to biodiesel blends but slightly lower than diesel. Combustion characteristics also are enhanced by improved oxidation reaction inside the combustion chamber which resulted in higher heat release rate. The emissions of HC, NO_x and O₂ are significantly reduced for nano-additive blends compared to diesel but increased CO₂ emission was observed. It is noticed that higher CO₂ emission and substantial reduction of unused O₂ emissions from engine fueled with nano-additive are evident for enhanced oxidation and better combustion. Energy and exergy analysis of the diesel engine is carried out to estimate the effect of using nanoparticle additive with biodiesel.

     

Investigation on the performance,emissions and combustion characteristics of CRDI engine fueled with tallow methyl ester biodiesel blends with exhaust gas recirculation

This paper demonstrates the study of performance, combustion and emission characteristics of a common rail diesel injection (CRDI) engine with the influence of exhaust gas recirculation (EGR) (5, 15 and 25%) at various fuel injection pressures (400, 500 and 600 bar) under the effective load conditions (0, 25, 50, 75 and 100%). The experiments were carried out in a controlled manner using the CRDI engine fuelled with 80% (D80) diesel (98% purity) blended with 20% (B20) tallow biodiesel. The engine has been operated at a rated speed of 1500 rpm on all load conditions, fuel injection timings of 10°, 15° and 20° bTDC, fuel injection pressures of 400, 500 and 600 bar, respectively. Combustion-influenced performance characteristics such as variation of in-cylinder pressure and net heat release rate in J deg^?1 are also studied with the above operating conditions. It was observed that the usage of 20% biofuel blend shows considerable improvement in combustion, and it further enhances with an increase in the injection pressures. Besides, EGR (up to 25%) reduced significant pollutants at higher operating pressures (600 bar) at higher load conditions. It was also observed that CO₂ emission increased with increase in the % EGR with an increase in the load conditions. However, for CO emission increased up to 50% load condition and subsequently tends to decrease due to improved combustion at higher load; hence higher temperature. NO_x, smoke opacity continue to increase with the increase in pressure and the percentage increase in EGR due to its attainment of adiabatic temperature, which leads to the pathway for the Zeldovich mechanism. The present work shows light on the usage of tallow methyl ester produced from the wastes in the tannery industry as alternate biofuel operating the CRDI engines without compromising its combustion and emission characteristics to deliver the same power as petro-diesel.

     

Multivariate control charts based on NAS and mid‐infrared spectroscopy for quality control of B5 blends of methyl soybean biodiesel in diesel

In this work, mid‐infrared spectroscopy and multivariate control charts based on net analyte signal were applied for quality control of B5 blends of biodiesel/diesel (5% biodiesel/95% diesel). Control charts were constructed using instrumental signal decomposition, generating three charts: the net analyte signal chart for monitoring the analyte of interest (methyl soybean biodiesel); the interference chart, which corresponds to the contribution of all other compounds in the diesel sample (diesel); and the residual chart, which corresponds to non‐systematic variations. Statistical limits were established for each developed chart, using samples inside quality specifications (normal operation conditions). To validate multivariate control charts, new samples were analyzed. The new samples represented samples in‐control and samples out‐of‐control in relation to the content of biodiesel, adulterated biodiesel with severe vegetable oils and adulterated diesel with residual automotive lubricant oil, kerosene, and gasoline. The results obtained show an excellent distinction between the samples inside and out of the quality specifications, with 91% and 100% correctly classified, respectively, which demonstrates that the methodology developed is a viable alternative for quality monitoring of this type of fuel. Copyright © 2015 John Wiley & Sons, Ltd.     

Evacuating liquid coatings from a diffusive oblique fin in micro-/mini-channels

The present work emphasis on to estimate the theoretical findings of energy and exergy analysis of biodiesel fueled with diesel on variable compression ratio engine at various combinations of fuel blend at different compression ratios. This study aims to identify the optimum engine settings based on compression ratio and biodiesel blends. The engine is operated with methyl esters of rubber seed oil and its 20, 40, 60 and 80% blends with diesel on volume basis. The compression ratio is varied from 18:1 to 22:1 at five compression ratios at 80% load in 3.5 kW, 1500 rpm, single cylinder water-cooled direct injection engine. The variables analyzed are energy and exergy potential of fuel input, shaft work, cooling water, maximum pressure, heat release rate, exergy destruction, brake-specific energy consumption, brake thermal efficiency, second law efficiency, entropy generation, exhaust gas temperature and various emissions. It is observed that the combination of CR 20, B20 and B40 at 80% load gives a better performance in thermodynamic analysis of methyl esters of rubber seed oil blended with diesel in VCR engine.

     

Biofuels–Renewable Energy Sources: A Review

Biodiesel is biodegradable and nontoxic, and it significantly reduces toxic and other emissions when burned as a fuel. The advantages of biodiesel as diesel fuel are its portability, ready availability, renewability, higher combustion efficiency, non-toxicity, higher flash point, and lower sulfur and aromatic content, higher cetane number, and higher biodegradability. The major disadvantages of biodiesel are its higher viscosity, lower energy content, higher cloud point and pour point, higher nitrogen oxide (NO_x) emissions, lower engine speed and power, injector coking, engine compatibility, high price, and greater engine wear. The technical disadvantages of biodiesel/fossil diesel blends include problems with fuel freezing in cold weather, reduced energy density, and degradation of fuel under storage for prolonged periods. The sources of biodiesel are vegetable oils and fats. The direct use of vegetable oils and/or oil blends is generally considered to be unsatisfactory and impractical for both direct injection and indirect type diesel engines because of their high viscosities and low volatilities injector coking and trumpet formation on the injectors, higher level of carbon deposits, oil ring sticking, and thickening and gelling of the engine lubricant oil, acid composition. Biodiesel is obtained by transesterifying triglycerides with methanol. A popular variation of the batch transesterification process which needs high alcohol/acid ratio (several separation problems and high corrosivity and toxicity) is the use of continuous stirred tank reactors in series. This continuous process is heterogeneous and is based on reactive distillation. The key factor is the selection of the right and effective solid catalyst which leads to reduction of energy consumption and investments at all.     

A novel method for the synthesis of biodiesel from soybean oil and urea

The increasing demand for energy has encouraged the development of renewable resources and environmentally benign fuel such as biodiesel. In this study, ethyl fatty esters (EFEs), a major component of biodiesel fuel, were synthesized from soybean oil using sodium ethoxide as a catalyst. By-products were glycerol and difatty acyl urea (DFAU), which has biological characteristics, as antibiotics and antifungal medications. Both EFEs and DFAU have been characterized using Fourier transform infrared (FTIR) spectroscopy, and ¹H nuclear magnetic resonance (NMR) technique. The optimum conditions were studied as a function of reaction time, reactant molar ratios, catalyst percentage and the effect of organic solvents. The conversion ratio of soybean oil into pure EFEs was 76% after 10 h of reaction. The highest conversion yield of EFEs is obtained when the urea/soybean oil ratio was from 6.2 mmol to 1 mmol, while the highest production of DFAU is obtained when the ethoxide (as a catalyst)/soybean oil ratio is from 6.4 mmol to 1 mmol in hexane as the reaction medium.     

Montmorillonite-supported KF/CaO: a new solid base catalyst for biodiesel production

Biodiesel is an alternative to petroleum-derived diesel fuel; development of a high-efficiency base catalyst to be used in heterogeneous biodiesel production is still a challenge. In this paper, a novel solid base catalyst, KF- and CaO-supported montmorillonite (KCa/MMT) was successfully synthesized by a facile impregnation method, and used for producing biodiesel in transesterification of commercial soybean oil with methanol. The catalysts were characterized by X-ray diffraction, carbon dioxide temperature-programmed desorption and scanning electron microscopy. Effects of the parameters, such as the loading amount of KF, the amount of KCa/MMT, and the methanol to oil molar ratios, on the yield of biodiesel were investigated. A maximum biodiesel yield of 98 % was obtained under the optimal reaction conditions. The separated catalyst can be directly used in the next round of reactions and gave a satisfactory yield. Furthermore, analysis of the catalyst's tolerance to oil-containing water or free fatty acids, and a kinetic study were also carried out. Koros–Nowak tests were designed and conducted, and it was proven that the heat and mass transfer were not limited by the reaction rate.     

Thermal transformation of micro-crystalline cellulose in phosphoric acid

Use of crude oil derivatives such as diesel and gasoline is becoming unsuitable due to their detriment to environment and to the increasing worldwide energy demand which is driving crude oil reservoirs towards exhaustion. Replacement of diesel and gasoline with biofuels (i.e. biodiesel and bioethanol, respectively) is very desirable. In fact, biofuels are not only environmentally sustainable, but also potentially inexhaustible due to the large amounts of waste biomasses from which they can be retrieved. In the present study, a model compound (micro-crystalline cellulose) was dissolved in phosphoric acid and converted at 80 °C to glucose, thereby providing the possible substrate for fermentation to bioethanol. Results revealed that after 1 h heating, the reaction had the largest glucose yield as compared to similar studies done by using other acid catalysts. In addition, the temperature applied here was from 40 to 60 °C lower than those already reported in literature for acid-driven cellulose degradations. Phosphoric acid allowed both glucose and levulinic acid achievement. The latter is usually used to synthesize fuel additives, catalysts, solvents and herbicides, thereby enhancing the added value of the conversion of cellulose to glucose in phosphoric acid. Finally, ¹H T₁ NMR relaxometry showed its suitability to monitor cellulose degradation. The advantages of relaxomety are its quickness since only few minutes are needed to obtain relaxograms, and the possibility to use raw mixtures without the needing of sample preparation.     

The flash points and thermal behaviors of diesel blends with biodiesels, α-pinene,d-limonene and caffeic acid as antioxidants

The present study assessed the effects of antioxidants on the flash point and thermal behavior of diesel fuel blended with 3–10 vol% biodiesel made from spent coffee grounds oil (SCGO) or Jatropha seed oil (JSO) extracted using with n-hexane or acetone, with or without α-pinene and d-limonene (as volatile antioxidants) or caffeic acid (as a non-volatile antioxidant). Effects were evaluated by assessing flash points and by thermogravimetry/differential thermogravimetry and differential thermal analysis (DTA). The flash points of the JSO and SCGO biodiesels obtained from oils extracted using n-hexane were higher than those extracted using acetone, and the addition of 10 vol% JSO or SCGO biodiesel made using acetone extraction increased the flash point by up to 2 °C. The DTA results for JSO and SCGO biodiesels also changed according to the extraction solvent. The flash points of diesel/α-pinene/d-limonene mixtures decreased as the amount of α-pinene was increased up to 10 vol%. TG peaks obtained from 10% α-pinene/d-limonene (50 vol%/50 vol%) in diesel were lowered by approximately 20 °C. The addition of 100–1000 mg kg^?1 caffeic acid to diesel lowered the flash point by 2 °C and shifted the TG peak to approximately 75 °C from the value of 66 °C for pure diesel. This effect was constant regardless of the caffeic acid content, while DTA results were largely unaffected by this additive. The results of this work confirm that both flash point and thermal behavior are dependent on the particular type of antioxidant employed.

     

The Obtaining Biodiesel from Used Vegetable Oil and Animal Waste Oil by Two Stages Transesterification Reaction

The biodiesel was obtained from used vegetable oil (UVO) and animal waste oil (AWO) by the two stages transesterification reaction. Also chemical and technical properties of feed and products were determined. Conditions of transesterification reaction for each of the oil samples were determined as a result of several sets of experiments. The suitable conditions of transesterification reaction were the following. Hereto a molar ratio of oil: methanol: catalyst was 1: 6: 1/40, for 30 min, at temperature of 600°C. To obtain biodiesel directly by the one stage transesterification, in case of using UVO sample, when the acidity number of feed oil had to less than 3 mg KOH/g. The biodiesel from UVO and AWO was prepared by mixing 5, 10, 20% of volume in the summer and winter diesel fuel. However, the product from mixture of UVO and winter diesel fuel met the technique requirements both of winter and summer diesel fuel, but the product from mixture of AWO and summer diesel fuel did not satisfy technical requirements of diesel fuel.     

Enhancing Clostridial Acetone-Butanol-Ethanol (ABE) Production and Improving Fuel Properties of ABE-enriched Biodiesel by Extractive Fermentation with Biodiesel

The extractive acetone–butanol–ethanol (ABE) fermentations of Clostridium acetobutylicum were evaluated using biodiesel as the in situ extractant. The biodiesel preferentially extracted butanol, minimized product inhibition, and increased production of butanol (from 11.6 to 16.5 gL⁻¹) and total solvents (from 20.0 to 29.9 gL⁻¹) by 42% and 50%, respectively. The fuel properties of the ABE-enriched biodiesel obtained from the extractive fermentations were analyzed. The key quality indicators of diesel fuel, such as the cetane number (increased from 48 to 54) and the cold filter plugging point (decreased from 5.8 to 0.2 °C), were significantly improved for the ABE-enriched biodiesel. Thus, the application of biodiesel as the extractant for ABE fermentation would increase ABE production, bypass the energy intensive butanol recovery process, and result in an ABE-enriched biodiesel with improved fuel properties.     

Biofuel Combustion Chemistry: From Ethanol to Biodiesel

Biofuels, such as bio‐ethanol, bio‐butanol, and biodiesel, are of increasing interest as alternatives to petroleum‐based transportation fuels because they offer the long‐term promise of fuel‐source regenerability and reduced climatic impact. Current discussions emphasize the processes to make such alternative fuels and fuel additives, the compatibility of these substances with current fuel‐delivery infrastructure and engine performance, and the competition between biofuel and food production. However, the combustion chemistry of the compounds that constitute typical biofuels, including alcohols, ethers, and esters, has not received similar public attention. Herein we highlight some characteristic aspects of the chemical pathways in the combustion of prototypical representatives of potential biofuels. The discussion focuses on the decomposition and oxidation mechanisms and the formation of undesired, harmful, or toxic emissions, with an emphasis on transportation fuels. New insights into the vastly diverse and complex chemical reaction networks of biofuel combustion are enabled by recent experimental investigations and complementary combustion modeling. Understanding key elements of this chemistry is an important step towards the intelligent selection of next‐generation alternative fuels.     

Pyrolysis oil from fast pyrolysis of maize stalk

Maize stalk was fast pyrolysed at temperatures between 420 °C and 580 °C in a fluidized-bed, and the main product of pyrolysis oil was obtained. The experimental results showed that the highest pyrolysis oil yield of 66 wt.% was obtained at 500 °C for maize stalk. Chemical composition of the pyrolysis oil acquired was analyzed by GC–MS and its heat value, stability, miscibility and corrosion characteristics were determined. These results showed that the pyrolysis oil could be directly used as a fuel oil for combustion in a boiler or a furnace without any upgrading. Alternatively, the fuel could be refined to be used by vehicles.     

Thermal and rheological behavior of diesel and methanol biodiesel blends

The most feasible alternative among fuels derived from biomass seems to be the biodiesel, having the required characteristics for a total or partial substitution of diesel oil. Therefore, the aim of this work is to evaluate the thermal and rheological behavior of the blends of diesel with the methanol biodiesel obtained from soybean oil, using B5, B15 and B25 blends. All thermogravimetric curves exhibited one overlapping mass loss step in the 35–280°C temperature range at air atmosphere and one step between 37–265°C in nitrogen. The rheological study showed a Newtonian behavior (n=1) for all blends.     

Thermal characterization of oil and biodiesel from oiticica (<Emphasis Type="Italic">Licania rigida</Emphasis> Benth)

Searching for other alternative sources, which are not part of the food chain, and which are able to supply the biofuel market is a promising option. In this context, it has been searched to investigate the oiticica oil, approaching its availability to the biodiesel synthesis, as well as its thermal stability. Few works retreat parameters such as: the optimization of the biodiesel synthesis, its physical–chemical properties, and thermal parameters etc. The characterization results revealed that the oil showed very high kinematic viscosity, and acidity value around 13 mg KOH/g, requiring a pre-treatment. To reduce the acid in the oil, it has been done the esterification of oil, which was studied in different molar ratios oiticica oil/ethanol (1:9) and 2.0% catalyst, in order to get the best reduction the index of acidity. The lowest level of acidity of the oil obtained after the esterification was 4.4 mg KOH/g. The reaction rate for the synthesis of biodiesel, compared to the initial mass of oiticica oil ester was 85%. This income can be overcome by pursuing an even smaller reduction of acid value of biodiesel oiticica. The acid value of biodiesel was 1.8 mg KOH/g. The results have revealed that the oiticica oil and biodiesel are stable at 224 and 179 °C, respectively.     

酯交换法制备生物柴油的研究进展

作为一种对环境友好的可再生燃料生物柴油,对解决日益枯竭的石油资源和由石化柴油燃烧带来的环境问题具有重要意义.综述了运用酯交换反应制备生物柴油的几种方法的研究进展,对其优、缺点和研究趋势进行了归纳总结和展望.