Investigation of the effect of detergent–dispersant additives on the oxidation stability of biodiesel,diesel fuel and their blends

Basic materials of biodiesels and molecular structure of different biodiesels were discussed with special focus on their oxidation stability and post-additization. Commercial biodiesels produced from rapeseed oil and used cooking oil were blended to diesel fuel in 5%, 7%, and 10% mass fraction. The samples were stored at ambient temperature for one year to simulate the effects of strategic storage and/or long stock turnover rate. Following the one year storage period the samples were treated with BHT antioxidant and/or succinic type detergent–dispersant additives in 300 mg kg⁻¹, 600 mg kg⁻¹ and 900 mg kg⁻¹ concentrations. BHT was applied as antioxidant additive, while the detergent–dispersant additives were either newly developed additives (polyisobutylene succinic anhydride derivatives containing fatty acid methyl ester in their molecular structure) or commercial ones. Structure of the developed additives and their mechanism is described in detail. Rancimat and Seta TOST devices were applied to evaluate the effect of the additives on the oxidation stability of the samples. It was found that the decrease of oxidation stability during storage can be partially compensated with post-additization by suitable detergent–dispersant additives. Oxidation of biodiesels during Rancimat measurement was investigated with infrared spectroscopy. The results showed that during the thermal oxidation fatty acid methyl esters decompose to carbonyl, carboxyl and hydroxyl compounds, while cis-trans isomerization also occurs.     

The role of viscosity in the fluorescence behavior of the diesel/biodiesel blends

Recently, the potentiality of fluorescence spectroscopy to be used in the quantification of biodiesel content in diesel/biodiesel blends (DBB) was demonstrated. However, the source of the fluorescence dependence of the DBB with biodiesel concentration remains unanswered. In the present paper, a close analysis of the optical properties of the DBB was performed over a wide composition range. The findings suggest that the alterations in the fluorescence intensity can be accounted for only after taking into account changes in viscosity as well as absorbance, in a model where the fluorophores were considered as molecular rotors.     

Detailed chemical kinetic oxidation mechanism for a biodiesel surrogate

A detailed chemical kinetic mechanism has been developed and used to study the oxidation of methyl decanoate, a surrogate for biodiesel fuels. This model has been built by following the rules established by Curran and co-workers for the oxidation of n-heptane and it includes all the reactions known to be pertinent to both low and high temperatures. Computed results have been compared with methyl decanoate experiments in an engine and oxidation of rapeseed oil methyl esters in a jet-stirred reactor. An important feature of this mechanism is its ability to reproduce the early formation of carbon dioxide that is unique to biofuels and due to the presence of the ester group in the reactant. The model also predicts ignition delay times and OH profiles very close to observed values in shock tube experiments fueled by n-decane. These model capabilities indicate that large n-alkanes can be good surrogates for large methyl esters and biodiesel fuels to predict overall reactivity, but some kinetic details, including early CO₂ production from biodiesel fuels, can be predicted only by a detailed kinetic mechanism for a true methyl ester fuel. The present methyl decanoate mechanism provides a realistic kinetic tool for simulation of biodiesel fuels.     

Experimental study of the oxidation of large surrogates for diesel and biodiesel fuels

The experimental study of the oxidation of two blend surrogates for diesel and biodiesel fuels, n-decane/n-hexadecane and n-decane/methyl palmitate (74/26 mol/mol), has been performed in a jet-stirred reactor over a wide range of temperatures covering both low, and high-temperature regions (550-1100 K), at a residence time of 1.5 s, at quasi atmospheric pressure with high dilution in helium (hydrocarbon inlet mole fraction of 0.002) and at stoichiometric conditions.Numerous reaction products have been identified and quantified. At low and intermediate temperatures (less than 1000 K), the formation of oxygenated species such as cyclic ethers, aldehydes and ketones has been observed for n-decane, n-hexadecane, and methyl palmitate. At higher temperature, the formation of these species was not observed any more, and small amounts of unsaturated species (olefins and unsaturated methyl esters) have been detected.Results obtained with methyl palmitate and n-hexadecane have been compared in order to highlight similarities and differences between large n-alkanes and methyl esters.     

Performance of a diesel engine fueled by waste cooking oil biodiesel

A direct injection diesel engine fueled by a diesel/biodiesel blend from waste cooking oil up to B100 (a blend of 100% biodiesel content) indicated a combustion efficiency rise by 1.8% at full load. The soot peak volume fraction was reduced by 15.2%, while CO and HC concentrations respectively decreased by 20 and 28.5%. The physical and chemical delay periods respectively diminished by 1.2 and 15.8% for engine noise to pronounce 6.5% reduction. Injection retarding by 5° reduced NO_x to those original levels of B0 (a blend of zero biodiesel content) and combined respective reduction magnitudes of 10 and 7% in CO and HC at 75% load. Increasing the speed reduced CO and HC respectively by 26 and 42% at 2.36 times the droplet average strain rate. By coupling the turbulence model to the spray break-up and chemical kinetics models, increasing the injection pressure simultaneously reduced CO, HC and NO_x at 17% exhaust gas recirculation ratio.     

Assessment of tree seed oil biodiesel: A comparative review based on biodiesel of a locally available tree seed

The present investigation is undertaken to investigate prospect of seeds of a locally available tree (koroch) for biodiesel production. The middle-size, evergreen koroch tree with spreading branches are available in Assam. The characteristics of koroch biodiesel and engine performance fueled by koroch biodiesel are also analyzed reviewing similar results available in the literature so as to ascertain its status. Twelve number of different tree seed oils, reported earlier, are considered for making the present comparative assessment. Though transesterification has been the common process for converting tree seed oil into biodiesel, as evidenced from the literature consulted in this study, but there have been variations of the chemical processes. Variations of the transesterification are attributed to (i) types of catalysis viz., acid (H₂SO₄) or base (KOH, NaOH, and NaOCH₃), (ii) reaction temperature, (iii) molar ratio, (iv) nature of reaction viz., single stage or multi-stage. The outputs of the reaction have also been found varying in terms of yield as well as quality. Quality of biodiesel, however, was found to influence by the nature of feedstock. The assessment of quality parameters was made either by ASTM D 6751 or EN 14214 standards. The major fuel properties such as calorific value, kinematic viscosity, cetane number and cloud point of the reference biodiesel (koroch biodiesel) are compared with the properties of five biodiesel obtained from non-edible tree seed (karanja, mahua, polonga, jatropha and rubber seed) and then ranked them in order of desirable property. No single biodiesel type could be found at top rank with reference to more than one property. With regards to viscosity, except rubber seed biodiesel, all other biodiesels (karanja, mahua, polonga, jatropha and koroch) fulfilled the ASTM D 6751 (1.9-6 cSt) as well as EN14214 (3.5-5) standards. Koroch biodiesel ranks 3rd, 3rd and 6th in case of kinematic viscosity, cetane number and calorific value amongst the biodiesel types considered for the present study. Cloud point of koroch, polanga, mahua, rubber, karanja and jatropha biodiesels are 4, 13.2, 5, 4, 12 and 4 °C. Further, properties of biodiesel were found to have influencing correlation with the fatty acid characteristics of the feedstock. Therefore, biodiesel with desirable properties could be expected form optimum mixing of different feedstock.Eleven number of different engine performance results pertaining to uses of biodiesel are also reviewed in this paper. Varying test conditions with reference to fuel types and blends, engine size and loading pattern are discussed. Engine performance results of koroch biodiesel were then compared with five similar tree-based biodiesel. It is observed that tree seed oil with more unsaturated fatty acids exhibits lower thermal efficiency compared to biodiesel having more saturated acids.     

Degradation of physical properties of different elastomers upon exposure to palm biodiesel

Biodiesel, as an alternative fuel, is gradually receiving more popularity for use in internal combustion engines. However questions continue to arise with regard to its compatibility with elastomeric materials. The present work aims to investigate the comparative degradation of physical properties for different elastomers [e.g. ethylene propylene diene monomer (EPDM), silicone rubber (SR), polychloroprene (CR), polytetrafluroethylene (PTFE) and nitrile rubber (NBR)] upon exposure to diesel and palm biodiesel. Static immersion tests in B0(diesel), B10 (10% biodiesel in diesel), B20, B50 and B100(biodiesel) were carried out at room temperature (25 °C) for 1000 h. Different physical properties like, changes in weight and volume, hardness and tensile strength were measured at every 250 h of immersion time. Compositional changes in biodiesel due to exposure of different elastomers were investigated by Gas chromatography mass spectroscopy (GCMS). The overall sequence of compatible elastomers in palm biodiesel is found to be PTFE > SR > NBR > EPDM > CR.     

Simulation of HCCI combustion in air-cooled off-road engines fuelled with diesel and biodiesel

The present work describes the elaboration of a predictive tool consisting on a phenomenological multi-zone model, applicable to the simulation of HCCI combustion of both diesel and biodiesel fuels. The mentioned predictive tool is created with the aim to be applied in the future to perform engine characterization during both pre-design and post-design stages. The methodology applied to obtain the proposed predictive model is based on the generation of an analytical mechanism that, given a set of regression variables representing the engine operative conditions, provides the user with the optimal figures for the scaling coefficients needed to particularize both the ignition delay and the heat release rate functional laws, which rule the combustion development in the proposed multi-zone model for HCCI engines. The validation of the proposed predictive multi-zone model consists on the comparison between chamber pressure curve derived from the simulations and experimental data based on a DEUTZ FL1 906 unit modified in order to allow HCCI combustion operation mode using diesel EN590 and rapeseed biodiesel. Finally, evidences of the capabilities of the proposed model to be used as a predictive tool applicable to the analysis of off-road engines under HCCI conditions are provided, consisting in the characterization and optimization of the operational maps related to both Brake Specific Fuel Consumption and NOx emissions.     

The effect of biodiesel and bioethanol blended diesel fuel on nanoparticles and exhaust emissions from CRDI diesel engine

Biofuel (biodiesel, bioethanol) is considered one of the most promising alternative fuels to petrol fuels. The objective of the work is to study the characteristics of the particle size distribution, the reaction characteristics of nanoparticles on the catalyst, and the exhaust emission characteristics when a common rail direct injection (CRDI) diesel engine is run on biofuel-blended diesel fuels. In this study, the engine performance, emission characteristics, and particle size distribution of a CRDI diesel engine that was equipped with a warm-up catalytic converters (WCC) or a catalyzed particulate filter (CPF) were examined in an ECE (Economic Commission Europe) R49 test and a European stationary cycle (ESC) test. The engine performance under a biofuel-blended diesel fuel was similar to that under D100 fuel, and the high fuel consumption was due to the lowered calorific value that ensued from mixing with biofuels. The use of a biodiesel–diesel blend fuel reduced the total hydrocarbon (THC) and carbon monoxide (CO) emissions but increased nitrogen oxide (NO_x) emissions due to the increased oxygen content in the fuel. The smoke emission was reduced by 50% with the use of the bioethanol–diesel blend. Emission conversion efficiencies in the WCC and CPF under biofuel-blended diesel fuels were similar to those under D100 fuel. The use of biofuel-blended diesel fuel reduced the total number of particles emitted from the engine; however, the use of biodiesel–diesel blends resulted in more emissions of particles that were smaller than 50 nm, when compared with the use of D100. The use of a mixed fuel of biodiesel and bioethanol (BD15E5) was much more effective for the reduction of the particle number and particle mass, when compared to the use of BD20 fuel.     

Autoignition reactivity of blends of diesel and biodiesel fuels with butanol isomers

The effect of n-butanol replacement by iso, sec or tert-butanol on the autoignition reactivity of diesel and biodiesel/butanol blends (the total alcohol content being 40% by vol.) was analysed. The study was performed in a constant volume combustion chamber under different initial temperatures (535 °C, ∼600 °C and 650 °C) and n-butanol substitutions. Results show that the effect of the alcohol in both pseudo-binary (diesel fuel/normal, sec, iso or tert-butanol) and pseudo-ternary (diesel fuel/n-butanol/iso, sec or tert-butanol) blends is not that expected from the autoignition properties of the pure isomers. When blended either with diesel or biodiesel fuels, tert-butanol increases the autoignition reactivity of the blend while the other two isomers reduce it. The partial substitution of n-butanol by tert-butanol could be an attractive method for increasing the alcohol content while keeping safe engine operation. Partial substitutions with iso or sec-butanol would promote partially premixed combustion conditions with limited pressure gradient peaks. Chemical kinetics simulations corroborate that the different consumption rates of active radicals from the butanol isomers are responsible for the observed trends. Biodiesel blends are less sensitive to the isomer replacing n-butanol due to its higher number of secondary CH bonds when compared to diesel fuel.     

Study of the oxidation stability and exhaust emission analysis of Moringa olifera biodiesel in a multi-cylinder diesel engine with aromatic amine antioxidants

In this study, the two most effective aromatic amine antioxidants N,N′-diphenyl-1,4-phenylenediamine (DPPD) and N-phenyl-1,4-phenylenediamine (NPPD), were used at a concentration of 2000 ppm. The impact of antioxidants on the oxidation stability, exhaust emission and engine performance of a multi-cylinder diesel engine fuelled with MB20 (20% Moringa oil methyl ester and 80% diesel fuel blend) were analysed at varying speed conditions at an interval of 500 rpm and a constant load. It was observed that, blending with diesel enhanced the oxidation stability of the moringa biodiesel by approximately 6.97 h, and the addition of DPPD and NPPD to MB20 increased the oxidation stability up to 34.5 and 18.4 h, respectively. The results also showed that the DPPD- and NPPD-treated blends reduced the NOx emission by 7.4% and 3.04%, respectively, compared to the untreated blend. However, they do have higher carbon monoxide (CO) and hydrocarbon (HC) levels and smoke opacities, but it should be noted that these emissions are still well below the diesel fuel emission level. The results show that the addition of antioxidant with MB20 also improves the engine's performance characteristics. Based on this study, MB20 blends with amine antioxidants can be used in diesel engines without any modification.     

Effect of biodiesel fuels on diesel engine emissions

The call for the use of biofuels which is being made by most governments following international energy policies is presently finding some resistance from car and components manufacturing companies, private users and local administrations. This opposition makes it more difficult to reach the targets of increased shares of use of biofuels in internal combustion engines. One of the reasons for this resistance is a certain lack of knowledge about the effect of biofuels on engine emissions. This paper collects and analyzes the body of work written mainly in scientific journals about diesel engine emissions when using biodiesel fuels as opposed to conventional diesel fuels. Since the basis for comparison is to maintain engine performance, the first section is dedicated to the effect of biodiesel fuel on engine power, fuel consumption and thermal efficiency. The highest consensus lies in an increase in fuel consumption in approximate proportion to the loss of heating value. In the subsequent sections, the engine emissions from biodiesel and diesel fuels are compared, paying special attention to the most concerning emissions: nitric oxides and particulate matter, the latter not only in mass and composition but also in size distributions. In this case the highest consensus was found in the sharp reduction in particulate emissions.     

Impact of physical properties of biodiesel on the injection process in a common-rail direct injection system

This paper presents the influence of biodiesel fuel properties on the injection mass flow rate of a diesel common-rail injection system. Simulations are first performed with ISO 4113 diesel fuel on a four-cylinder common-rail system to evaluate a single and triple injection strategies. For each injection strategy, the impact of modifying a single fuel property at a time is evaluated so as to quantify its influence on the injection process. The results show that fuel density is the main property that affects the injection process, such as total mass injected and pressure wave in the common-rail system. The fuel’s viscosity and bulk modulus also influence, but to a lessen degree, the mass flow rate of the injector notably during multiple injection strategies as individual properties change the fuel’s dampening property and friction coefficient.     

Effect of temperature on tribological properties of palm biodiesel

Biodiesel, as an alternative fuel is steadily gaining attention to replace petroleum diesel partially or completely. The tribological performance of biodiesel is crucial for its application in automobiles. In the present study, effect of temperature on the tribological performance of palm biodiesel was investigated by using four ball wear machine. Tests were conducted at temperatures 30, 45, 60 and 75 °C, under a normal load of 40 kg for 1 h at speed 1200 rpm. For each temperature, the tribological properties of petroleum diesel (B0) and three biodiesel blends like B10, B20, B50 were investigated and compared. During the wear test, frictional torque was recorded on line. Wear scars in tested ball were investigated by optical microscopy. Results show that friction and wear increase with increasing temperature.     

A cycle simulation model for predicting the performance of a diesel engine fuelled by diesel and biodiesel blends

Among the alternative fuels, biodiesel and its blends are considered suitable and the most promising fuel for diesel engine. The properties of biodiesel are found similar to that of diesel. Many researchers have experimentally evaluated the performance characteristics of conventional diesel engines fuelled by biodiesel and its blends. However, experiments require enormous effort, money and time. Hence, a cycle simulation model incorporating a thermodynamic based single zone combustion model is developed to predict the performance of diesel engine. The effect of engine speed and compression ratio on brake power and brake thermal efficiency is analysed through the model. The fuel considered for the analysis are diesel, 20%, 40%, 60% blending of diesel and biodiesel derived from Karanja oil (Pongamia Glabra). The model predicts similar performance with diesel, 20% and 40% blending. However, with 60% blending, it reveals better performance in terms of brake power and brake thermal efficiency.     

Impact of waste cooking oil in biodiesel blends on particle size distributions from a city-car engine

Using biodiesel as a blending component in diesel engine has demonstrated to reduce hydrocarbon and particulate matter emissions. Literature showed that biodiesel type, engine architecture and test conditions deeply affect performance and emission characteristics. Among suitable biodiesel fuels, waste cooking oil (WCO) is considered very attractive due to the reduced environmental impact without sacrificing engine performance.This paper aims at investigating how mixing ratio of biodiesel from WCO and mineral diesel affects the particle size distributions of a current state of art small displacement diesel engine.Experimental tests have been performed on an up-to date light common rail diesel engine. Its complete operative field has been investigated. The results obtained show that the use of biodiesel blends from WCO reduces the total number of particles emitted from the engine with respect to the diesel fuel; the reduction is more evident as the percentage of biodiesel in the blend increases. The number of particles in WCO biodiesel soot with diameter smaller than 10 nm is reduced as compared to diesel fuel; the same trend is observed for diameters larger than 200 nm; comparable particle numbers were obtained in the ultrafine range (Dp < 100 nm).     

On droplet combustion of biodiesel fuel mixed with diesel/alkanes in microgravity condition

The burning characteristics of a biodiesel droplet mixed with diesel or alkanes such as dodecane and hexadecane were experimentally studied in a reduced-gravity environment so as to create a spherically symmetrical flame without the influence of natural convection due to buoyancy. Small droplets on the order of 500 μm in diameter were initially injected via a piezoelectric technique onto the cross point intersected by two thin carbon fibers; these were prepared inside a combustion chamber that was housed in a drag shield, which was freely dropped onto a foam cushion. It was found that, for single component droplets, the tendency to form a rigid soot shell was relatively small for biodiesel fuel as compared to that exhibited by the other tested fuels. The soot created drifted away readily, showing a puffing phenomenon; this could be related to the distinct molecular structure of biodiesel leading to unique soot layers that were more vulnerable to oxidative reactivity as compared to the soot generated by diesel or alkanes. The addition of biodiesel to these more traditional fuels also presented better performance with respect to annihilating the soot shell, particularly for diesel. The burning rate generally follows that of multi-component fuels, by some means in terms of a lever rule, whereas the mixture of biodiesel and dodecane exhibits a somewhat nonlinear relation with the added fraction of dodecane. This might be related to the formation of a soot shell.     

Comprehensive study of biodiesel fuel for HSDI engines in conventional and low temperature combustion conditions

In this research, an experimental investigation has been performed to give insight into the potential of biodiesel as an alternative fuel for High Speed Direct Injection (HSDI) diesel engines. The scope of this work has been broadened by comparing the combustion characteristics of diesel and biodiesel fuels in a wide range of engine loads and EGR conditions, including the high EGR rates expected for future diesel engines operating in the low temperature combustion (LTC) regime.The experimental work has been carried out in a single-cylinder engine running alternatively with diesel and biodiesel fuels. Conventional diesel fuel and neat biodiesel have been compared in terms of their combustion performance through a new methodology designed for isolating the actual effects of each fuel on diesel combustion, aside from their intrinsic differences in chemical composition.The analysis of the results has been sequentially divided into two progressive and complementary steps. Initially, the overall combustion performance of each fuel has been critically evaluated based on a set of parameters used as tracers of the combustion quality, such as the combustion duration or the indicated efficiency. With the knowledge obtained from this previous overview, the analysis focuses on the detailed influence of biodiesel on the different diesel combustion stages known ignition delay, premixed combustion and mixing controlled combustion, considering also the impact on CO and UHC pollutant emissions.The results of this research explain why the biodiesel fuel accelerates the diesel combustion process in all engine loads and EGR rates, even in those corresponding with LTC conditions, increasing its possibilities as alternative fuel for future DI diesel engines.     

Modeling study of soot formation and oxidation in DI diesel engine using an improved soot model

Particulate emission is one of the most deleterious pollutants generated by Diesel fuel combustion. The ability to predict soot formation is one of the key elements needed to optimize the engine performance and minimize soot emissions. This paper reports work on developing, a phenomenological soot model to better model the physical and chemical processes of soot formation in Diesel fuel combustion. This hybrid model features that the effect of turbulence on the chemical reaction rate was considered in soot oxidation. Soot formation and oxidation processes were modeled with the application of a hybrid method involving particle turbulent transport controlled rate and soot oxidation rate. Compared with the original soot model, the in-cylinder pressures, heat release rate and soot emissions predicted by this hybrid model agreed better with the experimental results. The verified hybrid model was used to investigate the effect of injection timing on engine performance. The results show that the new soot model predicted reasonable soot spatial profiles within the combustion chamber. The high temperature gas zone in cylinder for hybrid model case is distributed broadly soot and NOx emission dependence on the start-of-injection (SOI) timing. Retarded SOI timing increased the portion of diffusion combustion and the soot concentration increased significantly with retarding of the fuel injection timing. The predicted distributions of soot concentration and particle mass provide some new insights on the soot formation and oxidation processes in direct injection (DI) engines. The hybrid phenomenological soot model shows greater potential for enhancing understanding of combustion and soot formation processes in DI diesel engines.