The basics of diesel engines and diesel fuels

Jon Van Gerpen University of Idaho Department of Biological and Agricultural Engineering Moscow, ID 83844
The diesel engine has been the engine of choice for heavy-duty applications in agriculture, construction, industrial, and on-highway transport for over 50 years. Its early popularity could be attributed to its ability to use the portion of the petroleum crude oil that had previously been considered a waste product from the refining of gasoline. Later, the diesels durability, high torque capacity, and fuel efficiency assured its role in the most demanding applications. While diesels have not been widely used in passenger cars in the United States (less than 1%), they have achieved widespread acceptance in Europe with over 33% of the total market [1]. In the United States, on-highway diesel engines now consume over 30 billion gallons of diesel fuel per year and virtually all of this is in trucks [2]. At the present time, only a minute fraction of this fue l is biodiesel. However, as petroleum becomes more expensive to locate and extract, and environmental concerns about diesel exhaust emissions and global warming increase, biodiesel is likely to emerge as one of several potential alternative diesel fuels. In order to understand the requirements of a diesel fuel and how biodiesel can be considered a desirable substitute, it is important to understand the basic operating principles of the diesel engine. This chapter describes these principles, particularly in light of the fuel used and the ways in which biodiesel provides advantages over conventional petroleum-based fuels. Diesel Combustion The operating principles of diesel engines are significantly different from those of the spark-ignited engines that dominate the U.S. passenger car market. In a spark- ignited engine, fuel and air that are close to the chemically correct, or stoichiometric, mixture are inducted into the engine cylinder, compressed, and then ignited by a spark. The power of the engine is controlled by limiting the quantity of fuel-air mixture that enters the cylinder using a flow-restricting valve called a throttle. In a diesel engine, also known as a compression-ignited engine, only air enters the cylinder through the intake system. This air is compressed to a high temperature and pressure and then finely atomized fuel is sprayed into the air at high velocity. When it contacts the high temperature air, the fuel vaporizes quickly, mixes with the air, and undergoes a series of spontaneous che mical reactions that result in a self- ignition or autoignition. No spark plug is required, although some diesel engines are equipped with electrically heated glow plugs to assist with starting the engine under cold conditions. The power of the engine is controlled by

Documents/Basics of Diesel Engines.doc

varying the volume of fuel injected into the cylinder, so there is no need for a throttle.

Figure 1. Cross section of a diesel engine combustion chamber Figure 1 shows a cross section of the diesel combustion chamber with the fuel injector positioned between the intake and exhaust valves. The timing of the combustion process must be precisely controlled to provide low emissions with optimum fuel efficiency. This timing is determined by the fuel injection timing plus the short time period between the start of fuel injection and the autoignition, called the ignition delay. When the autoignition occurs, the portion of the fuel that had been prepared for combustion burns very rapidly during a period known as premixed combustion. When the fuel that had been prepared during the ignition delay is exhausted, the remaining fuel burns at a rate determined by the mixing of the fuel and air. This period is known as mixing-controlled combustion. The heterogeneous fuel-air mixture in the cylinder during the diesel combustion process contributes to the formation of soot particles, one of the most difficult challenges for diesel engine designers. These particles are formed in high temperature regions of the combustion chamber where the air- fuel ratio is fuel-rich and consists mostly of carbon with small amounts of hydrogen and inorganic compounds. Although the mechanism is still not understood, biodiesel reduces the amount of soot produced and this appears to be associated with the bound oxygen in the fuel [3]. The particulate level in the engine exhaust is composed of these soot particles along with high molecular weight hydrocarbons that adsorb to the particles as the gas temperature decreases during the expansion process and in the exhaust pipe. This hydrocarbon material, called the soluble organic fraction, usually increases when biodiesel is used, offsetting some of the decrease in soot [4]. Biodiesels low volatility apparently causes a small portion of the fuel to survive the combustion process, probably by coating the cylinder walls, where it is then released during the exhaust process. Documents/Basics of Diesel Engines.doc 2

A second difficult challenge for diesel engine designers is oxides of nitrogen (NOx) emissions. NOx emissions are associated with high gas temperatures and fuel lean conditions and, in contrast to most other pollutants, are usually observed to increase when biodiesel is used [4]. NOx contributes to smog formation and is difficult to control in diesel engines because reductions in NOx tend to be accompanied by increases in particulate emissions and fuel consumption. While the bound oxygen on the biodiesel molecule may play a role in leaning the air-fuel ratio in NOx formation regions, the dominant mechanism seems to be the effect of changes in the physical properties of biodiesel, such as the speed of sound and bulk modulus, on the fuel injection timing [5]. One of the most important properties of a diesel fuel is its readiness to autoignite at the temperatures and pressures present in the cylinder when the fuel is injected. The laboratory test that is used to measure this tendency is the Cetane Number Test (ASTM D 613). The test compares the tendency to autoignite of the test fuel with a blend of two reference fuels, cetane (hexadecane) and heptamethylnonane. Fue ls with a high cetane number will have short ignition delays and a small amount of premixed combustion since little time is available to prepare the fuel for combustion. Most biodiesel fuels have higher cetane numbers than petroleum-based diesel fuels. Biodiesel fuels from more saturated feedstocks have higher cetane numbers than from less saturated feedstocks [6]. Biodiesel from soybean oil is usually reported to have a cetane number of 48 to 52, while biodiesel from yellow grease, containing more saturated esters, is normally between 60 and 65 [7]. Energy Content The energy content of the fuel is not controlled during manufacturing. The actual value of the lower heating value for diesel fuel will vary depending on the refinery in which it was produced, the time of year, and the source of the petroleum feedstock as all of these variables affect the composition of the fuel. Diesel fuels with high percentages of aromatics tend to have high energy contents per liter even though the aromatics have low heating values per kg. Their high density more than compensates for their lower energy content on a weight basis. This is of special importance for diesel engines because fuel is metered to the engine volumetrically. A fuel with lower energy content per liter will cause the engine to produce less peak power. At part load conditions the engine operator will still be able to meet the demand for power but a greater volume of fuel will need to be injected. The fuel injection system may advance the fuel injection timing when the fuel flow rate increases and this can cause an increase in the NOx emissions. In addition to the compressibility effects mentioned earlier, this effect is another reason for the higher NOx emissions observed with biodiesel [8]. Biodiesel fuels do not contain aromatics but they contain methyl esters with different levels of saturation. Unsaturated esters have lower energy content on a weight basis, but due to their higher density, they have more energy per unit volume. For example, methyl stearate has a higher heating value of 40.10 MJ/kg, which is 0.41% higher than methyl oleates higher heating value of 39.93 MJ/kg. However, on a volume basis (at 40 C),

Documents/Basics of Diesel Engines.doc

methyl stearate has an energy content of 34.07 MJ/liter, which is 0.7% less than methyl oleates higher heating value of 34.32 MJ/liter [9,10]. These differences are small enough that feedstock differences are difficult to detect in actual use. Biodiesel has a lower energy content (lower heating value of 37.2 MJ/kg for soy biodiesel) than No. 2 diesel fuel (42.6 MJ/kg for No. 2 diesel fuel). On a weight basis, the energy level is 12.5% less. Since biodiesel is more dense than the diesel fuel, the energy content is only 8% less on a per gallon basis (32.9 MJ/liter compared with 36.0 MJ/liter). Since diesel engines will inject equal volumes of fuel, diesel engine operators may see a power loss of about 8.4%. In some cases, the power loss may be even less than this because biodiesel's higher viscosity can decrease the amount of fuel that leaks past the plungers in the diesel fuel injection pump leaving more fuel to be injected. Tests have shown that the actual efficiency at which the energy in the fuel is converted to power is the same for biodiesel and petroleum-based diesel fuel [11]. Therefore, the brake specific fuel consumption (BSFC), which is the fuel flow rate divided by the engines output power and is the parameter most often used by engine manufacturers to characterize fuel economy, will be at least 12.5% higher for biodiesel. Low Temperature Operation Diesel fuel contains small amounts of long chain hydrocarbons, called waxes, that crystallize at temperatures within the normal diesel engine operating range. If temperatures are low enough, these wax crystals will agglomerate and plug fuel filters and prevent engine operation. At a low enough temperature, the fuel will actually solidify. This phenomenon also occurs with biodiesel. The saturated fatty acids produce methyl esters that will start to crystallize at about 0C for soybean oil and as high as 1315C for animal fats and frying oils [12, 13]. The most common measure of this tendency to crystallize is the cloud point. This is the temperature where the onset of crystallization is observed visually as a cloudiness in the fuel. A more extreme test is the pour point, which is the lowest temperature at which the fuel can still be poured from a vessel. ASTM D 2500 and D 97 are used to determine the Cloud Point and Pour Points of the fuels, respectively. Other tests are used to measure the tendency of the fuel to plug fuel filters. Additives, known as pour point depressants, can be used to inhibit the agglomeration of the wax crystals, which then lowers the point at which fuel filter plugging occurs. It is also common to add No. 1 diesel fuel to No. 2 diesel fuel to lower its operating point. No. 1 diesel fuel has a very low level of waxes and dilutes the waxes in No. 2 diesel fuel, which lowers the temperature at which they cause the fuel to solidify. Both No. 1 and No. 2 diesel fuels can be blended with biodiesel to lower the operating temperature of the fuel. When biodiesel is used at the 1-2% level as a lubricity additive, there does not seem to be any measurable effect on the cloud point. The allowable operating temperature for B20 blends is higher than the original diesel fuel, but many B20 users have been able to operate in cold climates without problems.

Documents/Basics of Diesel Engines.doc

Corrosion Many of the parts in the diesel fuel injection system are made of high-carbon steels and thus are prone to corrosion when in contact with water. Water damage is a leading cause of premature failure of fuel injection systems. Diesel fuel containing excessive water that enters the injection system can cause irreversible damage in a very short time. Many diesel engines are equipped with water separators that cause small water droplets to coalesce until they are large enough to drop out of the fuel flow where they can be removed. There are some reports that these water separators are not effective when used with biodiesel. Water can be present in fuels as dissolved water and free water. Petroleum-based diesel fuel can only absorb about 50 ppm of dissolved water while biodiesel can absorb as much as 1500 ppm [14]. While this dissolved water can affect the stability of the fuel, free water is more strongly associated with corrosion concerns. ASTM D 2709 is used to measure the total amount of free water and sediment in a diesel fuel sample. The method uses a centrifuge to collect the water and the specifications on both diesel fuel and biodiesel limit the amount of water and sediment to 0.05 %. Some compounds in diesel fuel, especially sulfur compounds, can be corrosive. Since copper compounds are particularly susceptible to this type of corrosion, copper is used as an indicator of the tendency of the fuel to cause corrosion. In ASTM D 130, polished copper strips are soaked in the fuel to characterize the tendency to corrode metals. Some tarnish is typically allowed, but corrosion causes the fuel to fail the test. Sediment Diesel fuel filters are designed to capture particles that are larger than 10 microns in size. Some newer engines are even equipped with filters that capture particles as small as 2 microns. These filters should stop foreign materials from entering the fuel injection system. However, when fuels are exposed to high temperatures and the oxygen in air, they can undergo chemical changes that form compounds that are insoluble in the fuel. These compounds form varnish deposits and sediments that can plug orifices and coat moving parts causing them to stick. Several test procedures have been developed that attempt to measure the tendency of diesel fuels to produce these sediments, such as ASTM D 2274, but none have gained the acceptance needed to be included in the diesel fuel specification (ASTM D 975). Because of its high concentration of unsaturated compounds, biodiesel is expected to be more susceptible to oxidative degradation than petroleum-based diesel fuel. Inorganic materials present in the fuel may produce ash that can be abrasive and contribute to wear between the piston and cylinder. ASTM D 482 is used to characterize ash from diesel fuels. The ASTM specification for biodiesel, D 6751, requires that ASTM D 874 be used. This method measures sulfated ash, which is specified because it is more sensitive to ash from sodium and potassium. These metals originate from the catalyst

Documents/Basics of Diesel Engines.doc

used in the biodiesel production process and are likely to be the main sources for ash in biodiesel. When fuel is exposed to high temperatures in the absence of oxygen, it can pyrolyze to a carbon-rich residue. While this should not occur in the cylinder of a properly operating engine, some injection systems have the potential to create a region within the injection nozzle where this residue can collect and limit the range of motion of moving parts. Various test procedures such as ASTM D 189, D 524, and D 4530 have been developed as an attempt to predict the tendency of a fuel to form in-cylinder carbon deposits. Unfortunately, it is very difficult to reproduce in-cylinder conditions in a test, so the correlation of these procedures to actual engine deposits is limited. Diesel fuel injection systems have very closely fitting parts that are subjected to high loads. These parts require lubrication to prevent rapid wear. All diesel injection systems rely on the fuel itself to provide this lubrication. While the mechanism is still a topic for debate, it is known that as refiners reduce the sulfur content of diesel fuel the ability of the fuel to provide the necessary lubrication decreases. The property that characterizes the ability of the fuel to lubricate is the lubricity. There are two methods that are commonly used to measure diesel fuel lubricity, the Scuffing Load Ball On Cylinder Lubricity Evaluator (SLBOCLE - ASTM D 6078-99) and the High Frequency Reciprocating Rig (HFRR - ASTM D 6079-99) but they have not been widely accepted or required as part of the ASTM specification for diesel fuel. This is primarily due to the lack of correlation between the test procedures and the large amount of test-to-test variability. Biodiesel has excellent lubricity and as little as 1 to 2% biodiesel can raise the lubricity of a poor lubricity fuel to an acceptable level [15]. Emissions Under ideal circumstances, all of the carbon in the diesel fuel will burn to carbon dioxide and all of the hydrogen will burn to water vapor. In most cases, virtually all of the fuel follows this path. However, if sulfur is present in the fuel, it will be oxidized to sulfur dioxide and sulfur trioxide. These oxides of sulfur can react with water vapor to form sulfuric acid and other sulfate compounds. The sulfates can form particles in the exhaust and elevate the exhaust particulate level. In 1993, the Environmental Protection Agency mandated that diesel fuel should contain no more than 500 ppm of sulfur. This was a factor of 10 reduction in sulfur level and greatly reduced sulfur as a source of exhaust particulate. In 2006, the EPA has mandated a new reduction in sulfur to 15 ppm. This will eliminate sulfur as a component of exhaust particulate and allow the introduction of catalytic aftertreatment for diesel engines. Sulfur is a powerful catalyst poison and limits the options available for controlling emissions on future engines. Biodiesel from soybean oil is very low in sulfur. However, biodiesel from some animal fat feedstocks has sulfur levels that exceed the 2006 mandate and will require further treatment. Aromatics are a class of hydrocarbon compounds that are characterized by stable chemical structures. They are usually present in diesel fuel at levels between 25 to 35%. They are desired by diesel engine operators because they provide greater energy per liter

Documents/Basics of Diesel Engines.doc

of fuel but they are believed to contribute to higher emissions of particulate and NOx, and have lower cetane numbers. In the early 1990s, the California Air Resources Board (CARB) implemented standards that limited the aromatic content of diesel fuels sold in California to 10%. CARB later allowed the aromatic content to be higher if fuel producers could show that their fuels produced equivalent or lower emissions than the low aromatic fuel. Biodiesel contains no aromatic compounds. Viscosity Fuel viscosity is specified in the standard for diesel fuel within a fairly narrow range. Hydrocarbon fuels in the diesel boiling range easily meet this viscosity requirement. Most diesel fuel injection systems compress the fuel for injection using a simple piston and cylinder pump called the plunger and barrel. In order to develop the high pressures needed in modern injection systems, the clearances between the plunger and barrel are approximately one ten-thousandth of an inch. In spite of this small clearance, a substantial fraction of the fuel leaks past the plunger during compression. If fuel viscosity is low, the leakage will correspond to a power loss for the engine. If fuel viscosity is high, the injection pump will be unable to supply sufficient fuel to fill the pumping chamber. Again, the effect will be a loss in power. The viscosity range for typical biodiesel fuels overlaps the diesel fuel range with some biodiesels having viscosities above the limit [16]. If fuel viscosity is extremely excessive, as is the case with vegetable oils, there will be a degradation of the spray in the cylinder causing poor atomization, contamination of the lubricating oil, and the production of black smoke. Flashpoint Diesel engine operators are accustomed to treating diesel fuel as is it were nonflammable. The volatility of both No. 1 and No. 2 diesel fuel are low enough that the air-vapor mixture above the fuel is below the flammability limit. The property that characterizes this behavior is the flashpoint. The temperature at which the fuel will give off enough vapor to produce a flammable mixture is the flashpoint. This temperature is 52C to 66C for diesel fuel and below -40C for gasoline. An important advantage of biodiesel is that its very high flashpoint, over 150C, means that biodiesel presents a very low fire hazard. New Technologies Requirements for lower emissions and continued demands for improved fuel economy have driven the engine industry to technical advances that incorporate state-of-the-art electronics and manufacturing technology. Electronically controlled cam-actuated unit injection has pushed the limits for fuel injection pressures to more than 2000 bar. The rapid mixing provided by the high spray velocity resulting from this extreme injection pressure provides low particulate formation and virtually complete soot oxidation while allowing retarded injection timing settings for reduced NOx. The introduction of common rail injection systems for light and medium duty engines has allowed new flexibility in programming the injection event. These systems allow multiple

Documents/Basics of Diesel Engines.doc

injections within a single engine cycle. A common strategy is to start the combustion with two brief injections, called the pilot- and pre- injections. These injections produce an environment in the cylinder so that when the main injection occurs, the ignition delay will be shorter, the amount of premixed combustion will be less, and the NOx production will be reduced. These small injections that precede the main injection also reduce engine noise and vibration. Immediately following the main injection, a small amount of fuel may be injected to assist in oxidizing the soot particles. Then, later in the expansion process a post- injection provides the elevated exhaust hydrocarbon level needed by the after-treatment equipment. The high degree of control offered by common rail injection systems would have been useless without the electronic control provided by the electronic control unit. The application of powerful on-board computers to diesel engines initially lagged behind their use on spark- ignition engines but current engines have corrected this deficiency. With the exception of some oxidation catalysts, diesel engines have traditionally not used exhaust after-treatment for emission control. The three-way catalyst technology that is widely used for spark- ignited vehicles is not suitable for use on diesel engines because it requires a near stoichiometric fuel-air mixture to get simultaneous reductions in carbon monoxide, unburned hydrocarbons, and oxides of nitrogen. Diesels always operate with excess oxygen so the reducing catalyst needed to eliminate NOx cannot operate. The oxidation catalysts provided on some diesel engines are able to reduce particulate levels by oxidizing some of the adsorbed hydrocarbons from the soot particles but they are not effective at reducing the solid portion of the particulate and they do nothing to reduce NOx. Recent innovations include catalyzed diesel particulate filters or traps. These devices force the exhaust to pass through a porous ceramic material that captures the exhaust particles. The surface of the ceramic is coated with a catalyst that oxidizes the particles as they are collected. NOx traps and absorbers are also being developed. These devices catalytically convert the NOx to stable compound s that are collected within the catalyst and then periodically removed during regeneration cycles. The catalysts used in both the particulate traps and the NOx absorbers are very sensitive to fuel sulfur. To allow this technology to develop, the U.S. Environmental Protection Agency has mandated the reduction in fuel sulfur from 500 ppm to 15 ppm by 2006 that was mentioned earlier. To improve the engines air supply, variable geometry turbochargers have been developed to extend the engine operating range over which adequate air is provided to keep particulate emissions low. Air-to-air after-coolers are also used to lower intake air temperatures to reduce both NOx and particulate emissions. Very little experience has been accumulated with biodiesel use in advanced technology engines. While the addition of exhaust aftertreatment systems to control particulate and NOx emissions may reduce one of the driving forces for biodiesel use, there is no indication that biodiesel will not be fully compatible with the new engine systems.

Documents/Basics of Diesel Engines.doc

References: 1. Broge, J.L., Revving Up For Diesel, Automotive Engineering International, V. 110, No. 2, February 2002, pp. 40-49. 2. Energy Information Administration, www.eia.doe.gov 3. McCormick, R.L., J.D. Ross, and M.S. Graboski, Effect of Several Oxygenates on Regulated Emissions from Heavy-Duty Diesel Engines, Environ. Sci. and Technol. V. 31, No. 4, 1997, pp. 1144-1150. 4. Sharp, C.A., S.A. Howell, and J. Jobe, "The Effect of Biodiesel Fuels on Transient Emissions from Modern Diesel Engines, Part I Regulated Emissions and Performance," SAE 2000-01-1967, 2000. 5. Tat, M.E., J.H. Van Gerpen, S. Soylu, M. Canakci, A, Monyem, and S. Wormley, The Speed of Sound and Isentropic Bulk Modulus of Biodiesel at 21C from Atmospheric Pressure to 35 Mpa, Journal of the American Oil Chemists Society, V. 77, No. 3, 2000, pp. 285-289. 6. Knothe, G., M.O. Bagby, and T.W. Ryan, III, Cetane Numbers of Fatty Compounds: Influence of Compound Structure and of Various Potential Cetane Improvers, SAE Paper 971681, (SP-1274), 1997. 7. Van Gerpen, J., Cetane Number Testing of Biodiesel, Liquid Fuels and Industrial Products from Renewable Resources Proceedings of the Third Liquid Fuels Conference, Nashville, Tenn., Sept. 15-17, 1996. 8. Tat, M.E and J.H. Van Gerpen, Fuel Property Effects on Biodiesel, ASAE Paper 036034, presented at the American Society of Agricultural Engineers 2003 Annual Meeting, Las Vegas, NV, July 27-30, 2003. 9. Freedman, B. and M.O. Bagby, Heats of Combustion of Fatty Esters and Triglycerides, JAOCS, V. 66, No. 11, November 1989, p. 1601-1605. 10. Weast, R.C., Editor, Handbook of Chemistry and Physics, 51 st Edition, Chemical Rubber Company, Cleveland, Ohio, 1970-1971. 11. Monyem, A. and J.H. Van Gerpen, The Effect of Biodiesel Oxidation on Engine Performance and Emissions, Biomass and Bioenergy, V. 20, No. 4, 2001, pp. 317-325. 12. Lee, I., L.A. Johnson, and E.G. Hammond, Use of Branched-Chain Esters to Reduce the Crystallization Temperature of Biodiesel, Journal of the American Oil Chemists Society, V. 72, No. 10, 1995, pp. 1155-1160.

Documents/Basics of Diesel Engines.doc

13. Dunn, R.O. and M.O. Bagby, Low-Temperature Properties of TriglycerideBased Diesel Fuels: Transesterified Methyl Esters and Petroleum Middle Distillate/Ester Blends, Journal of the American Oil Chemists Society, V. 72, No. 8, 1995, pp. 895-904. 14. Van Gerpen, J.H., E.G. Hammond, L. Yu, and A. Monyem, Determining the Influence of Contaminants on Biodiesel Properties, Society of Automotive Engineers Technical Paper Serie s No. 971685, SAE, Warrendale, PA, 1997. 15. Schumacher, L.G. and B.T. Adams, Using Biodiesel as a Lubricity Additive for Petroleum Diesel Fuel, ASAE Paper 026085, July 2002. 16. Tat, M.E. and J.H. Van Gerpen, The Kinematic Viscosity of Biodiesel and Its Blends with Diesel Fuel, Journal of the American Oil Chemists Society, V. 76, No. 12, 1999, pp. 1511-1513.

Documents/Basics of Diesel Engines.doc

10