Attempts to reduce NOx exhaust emissions by using reformulated biodiesel

Biodiesel is a renewable, domestically produced fuel that has been shown to reduce particulate, hydrocarbon, and carbon monoxide emissions from diesel engines. Under some conditions, however, biodiesel produced from certain feedstocks has been shown to cause an increase in nitrogen oxides (NO_x). This is of special concern in urban areas that are subject to strict environmental regulations. Although soy-based biodiesel may increase the emission of nitrogen oxides, it is the most easily accessible in North America. We investigated two routes to reformulate soy-based biodiesel in an effort to reduce nitrogen oxide emissions. In one of these, soy-oil methyl esters were modified by conversion of a proportion of the cis bonds in the fatty acid chains of its methyl esters to their trans isomers. In the other approach, polyol derivatives of soybean oil were transesterified to form soy methyl polyol fatty acid esters. The NO_x emissions of these modified biodiesels were then examined, using a Yanmar L100 single cylinder, four stroke, naturally aspirated, air cooled, direct injection diesel engine. Using either isomerized methyl oleate or isomerized soy biodiesel, at 20% blend level in petroleum diesel (‘B20’), nitrogen oxide emissions were elevated by between 1.5 and 3 percentage points relative to the combustion of a B20 blend of commercial biodiesel. Nitrogen oxide emissions were reduced in proportion to blend level during the combustion of polyol biodiesel, with a 20% blend in petrodiesel resulting in a reduction of about 4.5 percentage points relative to the emissions of a comparable blend of commercial soy biodiesel.     

Adiabatic flame temperature from biofuels and fossil fuels and derived effect on NOx emissions

There is currently a sustained interest in biofuels as they represent a potential alternative to petroleum derived fuels. Biofuels are likely to help decrease greenhouse gas emissions and the dependence on oil resources. Biodiesels are Fatty Acid Methyl Esters (FAMEs) that are mainly derived from vegetable oils; their compositions depend on the parent vegetables: rapeseed (“RME”), soybean (“SME”), sunflower, palm etc. A fraction of biodiesel has also an animal origin (“tallow”). A key factor for the use of biofuels in gas turbines is their emission indices (NOx, CO, VOC, and PM) in comparison with those of conventional “petroleum gasoils”. While biodiesels reduce carbon-containing pollutants, experimental data from diesel engines show a slight increase in NOx. The literature relating to gas turbines is very scarce. Two recent, independent field tests carried out in Europe (RME) and in the USA (SME) showed slightly lower NOx while a lab test on a microturbine showed the opposite effect. To clarify the NOx index of biodiesels in gas turbines, a study has been undertaken, taking gasoil and natural gas (NG) as reference fuels. In this study, a calculation of the flame temperature developed by the 3 classes of fuels has been performed and the effect of their respective compositions has been investigated. The five FAMEs studied were RME, SME and methyl esters of sunflower, palm and tallow; these are representative of most widespread vegetable and animal oil bases worldwide. The software THERGAS has been used to calculate the enthalpy and free energy properties of the fuels and GASEQ for the flame temperature (T_f), acknowledging the fact that “thermal NOx” represents the predominant form of NOx in gas turbines. To complete the approach to structural effects, we have modeled two NG compositions (rich and weak gases) and three types of gasoil using variable blends of eleven linear/branched/cyclic molecules. The results are consistent with the two recent field tests and show that the FAMEs lie close to petroleum gasoils and higher than NG in terms of NOx emission. The composition of the biodiesel and regular diesel fuel influences their combustion heat: methyl esters with double bonds see a slight increase of their T_f and their NOx index while that of gasoil is sensitive to the aromatic content.     

Evaluation of formulation strategies to eliminate the biodiesel NOx effect

In this paper, we explore the efficacy of (1) reducing the iodine value of soy-derived biodiesel fuels through increasing the methyl oleate (methyl ester of oleic acid) content and (2) addition of cetane improvers, as strategies to combat the biodiesel NO_x effect: the increase in NO_x emissions observed in most studies of biodiesel and biodiesel blends. This is accomplished by spiking a conventional soy-derived biodiesel fuel with methyl oleate or with cetane improver. The impact on bulk modulus of compressibility, fuel injection timing, cetane number, combustion, and emissions were examined. The conventional B20 blend produced a NO_x increase of 3–5% relative to petroleum diesel, depending on injection timing. However, by using a B20 blend where the biodiesel portion contained 76% methyl oleate, the biodiesel NO_x effect was eliminated and a NO_x neutral blend was produced. The bulk modulus of petroleum diesel was measured to be 2% lower than B20, yielding a shift in fuel injection timing of 0.1–0.3 crank angle. The bulk modulus of the high methyl oleate B20 blend was measured to be 0.5% lower than B20, not enough to have a measurable impact on fuel injection timing. Increasing the methyl oleate portion of the biodiesel to 76% also had the effect of increasing the cetane number from 48.2 for conventional B20 to 50.4, but this effect is small compared to the increase to 53.5 achieved by adding 1000 ppm of 2-ethylhexyl nitrate (EHN) to B20. For the particular engine tested, NO_x emissions were found to be insensitive to ignition delay, maximum cylinder temperature, and maximum rate of heat release. The dominant effect on NO_x emissions was the timing of the combustion process, initiated by the start of injection, and propagated through the timing of maximum heat release rate and maximum temperature.     

A numerical investigation into the anomalous slight NOx increase when burning biodiesel; A new (old) theory

Biodiesel is a notable alternative to petroleum derived diesel fuel because it comes from natural domestic sources and thus reduces dependence on diminishing petroleum fuel from foreign sources, it likely lowers lifecycle greenhouse gas emissions, and it lowers an engine's emission of most pollutants as compared to petroleum derived diesel. However, the use of biodiesel often slightly increases a diesel engine's emission of smog forming nitrogen oxides (NO_x) relative to petroleum diesel. In this paper, previously proposed theories for this slight NO_x increase are reviewed, including theories based on biodiesel's cetane number, which leads to differing amounts of charge preheating, and theories based on the fuel's bulk modulus, which affects injection timing. This paper proposes an additional theory for the slight NO_x increase of biodiesel. Biodiesel typically contains more double bonded molecules than petroleum derived diesel. These double bonded molecules have a slightly higher adiabatic flame temperature, which leads to the increase in NO_x production for biodiesel. Our theory was verified using numerical simulations to show a NO_x increase, due to the double bonded molecules, that is consistent with observation. Further, the details of these numerical simulations show that NO_x is predominantly due to the Zeldovich mechanism.     

Experimental study on the hazards of the jet diffusion flame of liquefied dimethyl ether

Dimethyl ether (DME) has been considered as a substitute for diesel fuel because it has a low auto-ignition temperature and produces less NO_x, SO_x, and particulate matter. However, the introduction of DME vehicles needs widely available DME supply stations. Moreover, the preparation of safety regulations for DME supply stations is very important, and so safety data is needed. Therefore, the present paper reports the hazards of the DME jet diffusion flame, which is one of several hazardous properties of DME, by studying the results of leaking gas and liquid DME. DME jets were released horizontally from circular nozzles whose diameters were 0.2, 0.4, 0.8 and 2 mm, and the release pressure was varied from the saturated vapor pressure to 2 MPa. When gaseous DME was released at the saturated vapor pressure, the flame was blown out. However, when liquefied DME was released, the flame formed. We obtained the experimental equations for estimating the scale and thermal hazards of DME diffusion flames.     

Mitigation of NOx emissions from a jatropha biodiesel fuelled DI diesel engine using antioxidant additives

Biodiesel offers cleaner combustion over conventional diesel fuel including reduced particulate matter, carbon monoxide and unburned hydrocarbon emissions. However, several studies point to slight increase in NO_x emissions (about 10%) for biodiesel fuel compared with conventional diesel fuel. Use of antioxidant additives is one of the most cost-effective ways to mitigate the formation of prompt NO_x. In this study, the effect of antioxidant additives on NO_x emissions in a jatropha methyl ester fuelled direct injection diesel engine have been investigated experimentally and compared. A survey of literature regarding the causes of biodiesel NO_x effect and control strategies is presented. The antioxidant additives L-ascorbic acid, α tocopherol acetate, butylated hydroxytoluene, p-phenylenediamine and ethylenediamine were tested on computerised Kirloskar-make 4 stroke water cooled single cylinder diesel engine of 4.4 kW rated power. Results showed that antioxidants considered in the present study are effective in controlling the NO_x emissions of biodiesel fuelled diesel engines. A 0.025%-m concentration of p-phenylenediamine additive was optimal as NO_x levels were substantially reduced in the whole load range in comparison with neat biodiesel. However, hydrocarbon and CO emissions were found to have increased by the addition of antioxidants.     

Biodiesel engine performance and emissions in low temperature combustion

Engine performance and emission comparisons were made between the use of soy, Canola and yellow grease derived B100 biodiesel fuels and an ultra-low sulphur diesel fuel in the high load engine operating conditions. Compared to the diesel fuel engine-out emissions of nitrogen oxides (NO_x), a high-cetane number (CN) biodiesel fuel produced comparable NO_x while the biodiesel with a CN similar to the diesel fuel produced relatively higher NO_x at a fixed start of injection. The soot, carbon monoxide and un-burnt hydrocarbon emissions were generally lower for the biodiesel-fuelled engine. Exhaust gas recirculation (EGR) was then extensively applied to initiate low temperature combustion (LTC) mode at medium and low load conditions. An intake throttling valve was implemented to increase the differential pressure between the intake and exhaust in order to increase and enhance the EGR. Simultaneous reduction of NO_x and soot was achieved when the ignition delay was prolonged by more than 50% from the case with 0% EGR at low load conditions. Furthermore, a preliminary ignition delay correlation under the influence of EGR at steady-state conditions was developed. The correlation considered the fuel CN and oxygen concentrations in the intake air and fuel. The research intends to achieve simultaneous reductions of NO_x and soot emissions in modern production diesel engines when biodiesel is applied.     

Fuel properties and nitrogen oxide emission levels of biodiesel produced from animal fats

FAME of lard, beef tallow, and chicken fat were prepared by base-catalyzed transesterification for use as biodiesel fuels. Selected fuel properties of the neat fat-derived methyl esters (B100) were determined and found to meet ASTM specifications. The cold-flow properties, lubricity, and oxidative stability of the B100 fat-derived fuels also were measured. In general, the cold-flow properties of the fat-based fuels were less desirable than those of soy-based biodiesel, but the lubricity and oxidative stability of the fat-based biodiesels were comparable to or better than soy-based biodiesel. Nitrogen oxide (NO_x) emission tests also were conducted with the animal fat-derived esters and compared with soybean oil biodiesel as 20 vol% blends (B20) in petroleum diesel. The data indicated that the three animal fat-based B20 fuels had lower NO_x emission levels (3.2–6.2%) than did the soy-based B20 fuel.     

Parametric study of combined premixed and non-premixed flame coal burner

A combined gas/air mixture–coal burner was developed to include heat recirculation by utilizing a radiative solid material with premixed flame jets impinging onto the downstream side to preheat the fuel/air jet on the upstream side. Providing the heat recirculation mechanism at different air staging degrees enhanced the destruction rates of the fuel nitrogen oxides. Concentric elliptical premixed gas/air and coal/air jets had a stronger preheating effect and a consequent increased NO_x reduction effectiveness as compared to concentric circular jets, where the inner elliptical jets enlarged the contact diffusion area and entrainment thus increasing the preheating time. The parametric variation in the feeding ports to the coal combustor affected the exhaust emissions, wherein the use of an inclined or shifted injection from the centre-line contributed to the NO_x reduction. Increasing the jet angle in the upstream direction reduced the CO concentrations, while the NO_x emissions varied depending on the degree of staging. The inverse/normal flame configuration was found more effective than the normal flame configuration with respect to NO_x reduction that was enhanced at higher heat input ratios. Utilizing inverse triple flames led to a further NO_x reduction since higher temperatures prevailed in the initial flame region with a five reaction zone structure. Finer particles produced less NO_x, which was further reduced by blending the coal with biomass.     

Combustion, performance and emission characteristics of a DI diesel engine fueled with ethanol-biodiesel blends

In this study, Euro V diesel fuel, biodiesel, and ethanol-biodiesel blends (BE) were tested in a 4-cylinder direct-injection diesel engine to investigate the combustion, performance and emission characteristics of the engine under five engine loads at the maximum torque engine speed of 1800 rpm. The results indicate that when compared with biodiesel, the combustion characteristics of ethanol-biodiesel blends changed; the engine performance has improved slightly with 5% ethanol in biodiesel (BE5). In comparison with Euro V diesel fuel, the biodiesel and BE blends have higher brake thermal efficiency. On the whole, compared with Euro V diesel fuel, the BE blends could lead to reduction of both NO_x and particulate emissions of the diesel engine. The effectiveness of NO_x and particulate reductions increases with increasing ethanol in the blends. With high percentage of ethanol in the BE blends, the HC, CO emissions could increase. But the use of BE5 could reduce the HC and CO emissions as well.     

Various strategies for reducing Nox emissions of biodiesel fuel used in conventional diesel engines: A review

Energy demand, decreasing fossil fuel reserves, and health-related issues about pollutants have led researchers to search for renewable alternative fuels to either partially or fully replace fossil fuels. Among many alternative fuels, biodiesel became one of the most popular choices due to similar properties to that of conventional diesel. Biodiesel produces slightly lower brake thermal efficiency compared to that of conventional biodiesel, but has an advantage of reduced emissions of CO₂, CO, HC, and smoke. However, biodiesel shows higher NOx emission which, when used in increased biodiesel market, may become a serious problem. Various strategies were attempted by different researcher to reduce NOx emissions. In this paper, various strategies, adapted for reducing NOx emissions of biodiesel fuel used in diesel engines for automobile applications, are reviewed and discussed. The strategies are grouped into three major groups, namely combustion treatments, exhaust after-treatments, and fuel treatments. Among various strategies discussed, fuel treatments, such as low temperature combustion, mixing fuel additives and reformulating fuel composition, reduce NOx emission without compromising other emission and performance characteristics and they seem to be promising for future biodiesel fuel.     

Solubility of a diesel–biodiesel–ethanol blend,its fuel properties,and its emission characteristics from diesel engine

In this work, we studied the phase diagram of diesel–biodiesel–ethanol blends at different purities of ethanol and different temperatures. Fuel properties (such as density, heat of combustion, cetane number, flash point and pour point) of the selected blends and their emissions performance in a diesel engine were examined and compared to those of base diesel. It was found that the fuel properties were close to the standard limit for diesel fuel; however, the flash point of blends containing ethanol was quite different from that of conventional diesel. The high cetane value of biodiesel could compensate for the decrease of the cetane number of the blends caused by the presence of ethanol. The heating value of the blends containing lower than 10% ethanol was not significantly different from that of diesel. As for the emissions of the blends, it was found that CO and HC reduced significantly at high engine load, whereas NO_x increased, when compared to those of diesel. Taking these facts into account, a blend of 80% diesel, 15% biodiesel and 5% ethanol was the most suitable ratio for diesohol production because of the acceptable fuel properties (except flash point) and the reduction of emissions.     

Engine performance and emission characteristics of a three-phase emulsion of biodiesel produced by peroxidation

Biodiesel, which is produced from vegetable oils, animal fats or used cooking oils, can be used as an alternative fuel for diesel engines. The high oxygen content of biodiesel not only enhances its burning efficiency, but also generally promotes the formation of more nitrogen oxides (NO_x) during the burning process. Fuel emulsification and the use of NO_x inhibitor agents in fuel are considered to be effective in reducing NO_x emissions. In the study reported herein, soybean oil was used as raw oil to produce biodiesel by transesterification reaction accompanied by peroxidation to further improve the fuel properties of the biodiesel, which was water washed and distilled to remove un-reacted methanol, water, and other impurities. The biodiesel product was then emulsified with distilled water and emulsifying surfactant by a high-speed mechanical homogenizer to produce a three-phase oil-droplets-in-water-droplets-in-oil (i.e. O/W/O) biodiesel emulsion and an O/W/O emulsion that contained aqueous ammonia, which is a NO_x inhibitor agent. A four-stroke diesel engine, in combination with an eddy-current dynamometer, was used to investigate the engine performance and emission characteristics of the biodiesel, the O/W/O biodiesel emulsion, the O/W/O biodiesel emulsion that contained aqueous ammonia, and ASTM No. 2D diesel. The experimental results show that the O/W/O emulsion has the lowest carbon dioxide (CO₂) emissions, exhaust gas temperature, and heating value, and the largest brake specific fuel consumption, fuel consumption rate, and kinematic viscosity of the four tested fuels. The increase of engine speed causes the increase of equivalence ratio, exhaust gas temperature, CO₂ emissions, fuel consumption rate, and brake specific fuel consumption, but a decrease of NO_x emissions. Moreover, the existence of aqueous ammonia in the O/W/O biodiesel emulsion curtails NO_x formation, thus resulting in the lowest NO_x emissions among the four tested fuels in burning the O/W/O biodiesel emulsion that contained aqueous ammonia.     

Atomization and combustion of canola methyl ester biofuel spray

The spray atomization and combustion characteristics of canola methyl ester (CME) biofuel are compared to those of petroleum based No. 2 diesel fuel in this paper. The spray flame was contained in an optically accessible combustor which was operated at atmospheric pressure with a co-flow of heated air. Fuel was delivered through a swirl-type air-blast atomizer with an injector orifice diameter of 300 μm. A two-component phase Doppler particle analyzer was used to measure the spray droplet size, axial velocity, and radial velocity distributions. Radial and axial distributions of NO, CO, CO₂ and O₂ concentrations were also obtained. Axial and radial distributions of flame temperature were recorded with a Pt–Pt/13%Rh (type R) thermocouple. The volumetric flow rates of fuel, atomization air and co-flow air were kept constant for both fuels. The droplet Sauter mean diameter (SMD) at the nozzle exit for CME biofuel spray was smaller than that of the No. 2 diesel fuel spray, implying faster vaporization rates for the former. The flame temperature decreased more rapidly for the CME biofuel spray flame than for the No. 2 diesel fuel spray flame in both axial and radial directions. CME biofuel spray flames produced lower in-flame NO and CO peak concentrations than No. 2 diesel fuel spray flames.     

Performance of compression ignition engine with mahua (Madhuca indica) biodiesel

The performance of biodiesel obtained from mahua oil and its blend with high speed diesel in a Ricardo E6 engine has been presented in this paper together with some of its fuel properties. These properties were found to be comparable to diesel and confirming to both the American and European standards. Engine performance (brake specific fuel consumption, brake thermal efficiency and exhaust gas temperature) and emissions (CO, smoke density and NO_x) were measured to evaluate and compute the behaviour of the diesel engine running on biodiesel. The reductions in exhaust emissions and brake specific fuel consumption together with increase brake power, brake thermal efficiency made the blend of biodiesel (B20) a suitable alternative fuel for diesel and thus could help in controlling air pollution.     

Effects of injection angles on combustion processes using multiple injection strategies in an HSDI diesel engine

Effects of injection angles and injection pressure on the combustion processes employing multiple injection strategies in a high-speed direct-injection (HSDI) diesel engine are presented in this work. Whole-cycle combustion and liquid spray evolution processes were visualized using a high-speed video camera. NO_x emissions were measured in the exhaust pipe. Different heat release patterns are seen for two different injectors with a 70-degree tip and a 150-degree tip. No evidence of fuel-wall impingement is found for the first injection of the 150-degree tip, but for the 70-degree tip, some fuel impinges on the bowl wall and a fuel film is formed. For the second injection, a large amount of fuel deposition is observed for the 70-degree tip. Weak flame is seen for the first injection of the 150-degree tip while two sorts of flames are seen for the first injection of the 70-degree tip including an early weak flame and a late luminous film combustion flame. Ignition occurs near the spray tip in the vicinity of the bowl wall for the second injection events of the 150-degree tip, however, it is near the injector tip in the central region of the bowl for the 70-degree tip. The flame is more homogeneous for the 150-degree tip with higher injection pressure with little soot formation similar to a premixed-charge-compression-ignition (PCCI) combustion. For other cases, liquid fuel is injected into flames showing diffusion flame combustion. More soot luminosity is seen for the 70-degree tip due to significant fuel film deposition on the piston wall with fuel film combustion for both injection events. Lower NO_x emissions were obtained for the narrow-angle injector due to the rich air–fuel mixture near the bowl wall during the combustion process. Increasing injection pressure leads to increased NO_x emissions for both injection angles because of the relatively leaner and faster combustion process with higher in-cylinder temperature for the increased injection pressure.     

Experimental studies of bluff-body stabilized LPG diffusion flames

Bluff-body stabilized turbulent jet diffusion flame has received renewed attention in recent years due to its practical applications. An experimental study is carried out to investigate the effect of coaxial air velocity, U_a, and lip-thickness, δ of the bluff-body on the flame stability limits and emission levels. The stability limits of a typical diffusion flame can be characterized in terms of two parameters namely flame lift-off height and blow-off velocity. It is experimentally observed that lift-off height is not linearly dependent on the fuel exit velocity, U_f, as compared to the simple jet. The flame stability is found to be improved for larger lip-thickness bluff-body because of the presence of lower pressure in the wake region behind the bluff-body. Flame length is observed to be dominated by buoyancy and momentum regimes. The transition from buoyancy to momentum regime is found to be extended with increase in lip-thickness. It is also observed that the blow-off limit is also extended further by 10% as compared to simple jet diffusion flames under similar conditions. The emissions data are reported in terms of mass based emission index, EINO_x (g [NO_x]/kg [fuel]) for a wide range of flow conditions. It is concluded that the addition of coaxial air in the larger lip-thickness bluff-body flames causes a marginal reduction in emission levels relative to smaller lip-thickness bluff-body.     

Use of branched-chain esters to reduce the crystallization temperature of biodiesel

To reduce the tendency of biodiesel to crystallize at low temperatures, branched-chain alcohols were used to esterify various fats and oils, and the crystallization properties of the branched esters were compared with those of methyl esters by using differential scanning calorimetry (DSC), cloud point, and pour point. Compared with the methyl esters that are commonly used in biodiesel, branched-chain esters greatly reduced the crystallization onset temperature (T_CO) of neat esters and their corresponding ester diesel fuel blends. Isopropyl and 2-butyl esters of normal (∼10 wt% palmitate) soybean oil (SBO) crystallized 7–11 and 12–14°C lower, respectively, than the corresponding methyl esters. The benefit of the branched-chain esters in lowering T_CO increased when the esters were blended with diesel fuel. Esters made from a low-palmitate (3.8%) SBO crystallized 5–6°C lower than those of normal SBO. Isopropyl esters of lard and tallow had T_CO values similar to that of methyl esters of SBO. DSC provided an accurate means of monitoring crystallization, and the DSC results correlated with cloud and pour point measurements.     

Comparative evaluation of performance and emission characteristics of jatropha, karanja and polanga based biodiesel as fuel in a tractor engine

Non-edible jatropha (Jatropha curcas), karanja (Pongamia pinnata) and polanga (Calophyllum inophyllum) oil based methyl esters were produced and blended with conventional diesel having sulphur content less than 10 mg/kg. Ten fuel blends (Diesel, B20, B50 and B100) were tested for their use as substitute fuel for a water-cooled three cylinder tractor engine. Test data were generated under full/part throttle position for different engine speeds (1200, 1800 and 2200 rev/min). Change in exhaust emissions (Smoke, CO, HC, NO_x, and PM) were also analyzed for determining the optimum test fuel at various operating conditions. The maximum increase in power is observed for 50% jatropha biodiesel and diesel blend at rated speed. Brake specific fuel consumptions for all the biodiesel blends with diesel increases with blends and decreases with speed. There is a reduction in smoke for all the biodiesel and their blends when compared with diesel. Smoke emission reduces with blends and speeds during full throttle performance test.