Diesel Fuel Characteristics. Rudolph Diesel (1858-1913) developed a theory that revolutionized the engines of his day.

He envisioned an engine in which air is compressed to such a degree that there is an extreme rise in temperature. When fuel is injected into the piston chamber with this air, the fuel is ignited by the high temperature of the air, igniting it, forcing the piston down. Diesel designed his engine in response to the heavy resource consumption and inefficiency of the steam engine, which only produced 12% efficiency. On February 27, 1892, Diesel filed for a patent at the Imperial Patent Office in Germany. Within a year, he was granted Patent No. 67207 for a "Working Method and Design for Combustion Engines, a new efficient, thermal engine. With contracts from Frederick Krupp and other machine manufacturers, Diesel began experimenting and building working models of his engine. In 1893, the first model ran under its own power with 26% efficiency, remarkably more than double the efficiency of the steam engines of his day. Finally, in February of 1897, he ran the "first diesel engine suitable for practical use, which operated at an unbelievable efficiency of 75% using peanut oil as a fuel. The crowning achievement for Rudolph Diesel's invention came at the 1900 Paris Exposition where the diesel engine took the Grand Prix. To the amazement of all in attendance his engine was fueled by 100% peanut oil. It is essential to understand that Diesel believed the utilization of a biomass fuel to be the real future of his engine. He wanted to provide farmers, small industries and those in isolated communities the opportunity to produce their own fuel and to compete with the large monopolies that controlled all energy production at that time.

In the early days, exclusively stationary diesel engines were built and from 1903 onward both small and larger seagoing ships equipped with diesel engines began to appear. Another focus was on the propulsion of submarines. Here, dimensions and weight did not play a decisive role. Diesel engines weighed up to 250 Kilograms per horsepower in those days, a much lower horsepower to weight ratio than the OTTO cycle gas engines of the day. The main reason for this lies in the introduction of the fuel into the cylinder under high pressure. The only feasible method was to induce fuel using pressurised air, and this was only possible with auxiliaries that were not only heavy but also a very large part of the engine Rudolph Diesel literally disappeared in 1913. There is some question of the timing of Diesel's death. Some think it might have been accidental or even a suicide. However, others considered a possible political motivation. Diesel did not agree with the politics of Germany and was reluctant to see his engine used by their naval fleet. With his political support directed towards France and Britain, he was on his way to England to arrange for them to use his engine when he inexplicably disappeared over the side of the ship in the English Channel. Peanut or vegetable oils were used as fuel for the diesel engine until the early 1920's, when diesel engine manufacturers modified the injection system of the engine to handle the lower viscosity of distillate fossil fuels, which were widely available and low in cost. The oil tycoons of the day also wielded influence over every aspect of the transportation industry and shaped the development of the engine to favor their interests. This distillate fuel became known as diesel fuel although Rudolph himself never used it! The use of diesels as on road power plants did not occur until the late 1920s after Robert Bosch had designed his compact liquid, (solid), fuel injection system in 1927. From that point on diesels were also powering on road vehicles. Diesel fuel keeps the country moving. From consumer goods moved cross-country, to the generation of electric power, to increased efficiency on the nation's farms, diesel fuel plays a vital role in the nation's economy and standard of living. Today, both the engine and the fuel still bear Diesels name.

The major uses of diesel fuel include: On-road transportation (Trucks, buses, cars), farming, rail transportation, marine shipping, off-road uses (mainly mining, construction, and logging), electric power generation and military transportation. In the early days of diesels no standards or formula for what diesel fuel should be was clearly defined. What was available was a collection of petroleum distillates that varied widely in composition and quality. Performance criteria have since been established by the American Society for Testing Materials (ASTM). The standards for diesel fuel composition are defined in the document D-975 Diesel Fuel Specification. The ASTM is one of the world's largest voluntary standards development systems. Its standards for materials, products, systems, and services have been adopted by the oil industry. However, ASTM defines only regular diesel fuel. Premium diesel has been left to other organizations, one being the National Conference on Weights and Measures (NCWM), sponsored by the National Institute of Standards and Technology (NIST).

Other standards for fuel are outlined by individual countries and organizations. Europe and Japan for example have different fuel classification standards and criteria. The Recommended Maintenance Practices Manual, which is produced by the The Maintenance Council, a group which includes members of the ATA, OEMs, Governments and other stakeholders in the trucking industry, has its own recommendations for diesel fuel including RP3O4A (preferred) and RP3O4B (minimum) Diesel Fuel Specifications, these represent the TMC's opinion of what is required for a regular diesel fuel. Bio Diesel is covered under a separate classification, ASTM D-6751
Table-6: ASTM Specification (D6751) for B100 Property Flash Point Water & Sediment Kinematic Viscosity (40 C) Sulfated Ash Sulphur CopperStrip Corrosion Cetane Cloud Point Carbon Residue (100% Sample) Acid Number Free Glycerin Total Glycerin Phosphorous Content Distillation Temperature (90% Recovered) *The carbon residue shall be run out on the 100% sample. The standards for Bio Diesel have just been set 2005 and are subject to frequent review as new developments come along ASTM Method D93 D2709 D445 D874 D5453 D130 D613 D2500 D4530* D664 D6584 D6584 D4951 D1160 Limits 130 min. 0.050 max. 1.9-6.0 0.020 max. 0.05 max. No.3 max. 47 min. Report 0.050 max. 0.80 max. 0.020 max. 0.240 max. 0.001 max. 360 max. Degrees C % mass Mg KOH/gm % mass % mass % mass Degrees C Units Degrees C % Volume mm2/sec % mass % mass

Diesel Fuel is a petroleum product distilled between finished kerosene and heating oil.

Combustion of diesel fuel is a chemical reaction called oxidization, the carbon in the fuel will react with oxygen in the air and change to carbon dioxide and the hydrogen in the fuel reacts with the oxygen to form H2O or water in fact if combustion conditions were ideal these are the only two compounds that would result. Unfortunately combustion in an engine is rarely ideal and many more compound are produced such as non-combusted fuel, (HC), partially combusted carbon, (carbon Monoxide, CO) and Aldehydes, Nitric oxide, (NO), Nitrogen Dioxide, (NO2), Sulphur Dioxide, (SO2) and various volatile organic compounds as particulate matter both solid and liquid. When fuel combusts it is an exothermic reaction, that is, heat is given off as the molecular bonds holding the carbon and hydrogen together are broken. This process begins when there is sufficient heat present and the correct mixture of vaporized fuel and air. As long as sufficient heat is maintained and there are enough reactants the process will become self sustaining until all of the fuel is combusted. Note that fuels with higher heat content per pound of weight have a greater number of atomic/molecular bonds, so more heat will be released by these fuels during combustion.

The term diesel fuel is generic; it refers to any fuel for a compression ignition engine. However, in common use, it refers to the fuels made commercially for diesel-powered vehicles. In North America, this is primarily Grade No. 2-D diesel fuel. However, two other grades, Grade No. 1-D and Grade No. 4-D, are also in commercial use. These grade designations are established by the American Society for Testing and Materials (ASTM). The grades are numbered in order of increasing density and viscosity, with No. 1-D the lightest and No. 4-D the heaviest Some petroleum products have similar, but not identical, specifications and physical properties. For example, No. 2 fuel oil and No. 2-GT gas turbine fuel are similar to No. 2-D diesel fuel. And No. 1-GT gas turbine fuel oil, Jet-A Aviation Turbine Fuel, and kerosene, the product specifically sold for use in lamps and stoves are similar to No. 1-D diesel fuel.

Several organizations issue marine fuel specifications. Standard 8217 of the International Standards Organization (ISO) is the primary standard. ASTM maintains a parallel specification, D 2069. The shipping industry increasingly prefers higher-viscosity residual fuels because they are less expensive. Although residual fuels don't burn as readily as distillate fuels, the slow speeds (60-200 rpm) of the large marine engines allow more time for combustion to occur. The specifications for each product are developed to ensure that it is suitable for the intended use. The fuel properties needed to keep a lamp burning are not nearly as stringent as those required to keep a jet aircraft aloft. Products with similar physical properties should not be used interchangeably without a complete understanding of the requirements of the intended use. Bio-Diesel SME or SOME 'Soy Methyl Ester' Diesel is the most common bio diesel in the U.S. and is derived from soybean oil. Soy Diesel is a biodiesel/petrodiesel blend based on SME. One bushel of soybeans will produce about one (US) gallon of fuel.

Soy beans

RME or RSME 'Rapeseed Methyl Ester' Diesel is the most common biodiesel in Europe and is derived from rapeseed oil. These fuels are collectively known as Fatty Acid Methyl Esters (FAME). Biodiesel fuels are methyl/ethyl ester-based oxygenates derived from a broad variety of renewable sources such as vegetable oils, animal fats, and cooking oils. Their properties are similar to diesel fuel, as opposed to gasoline or gaseous fuels, and thus are capable of being used in compression ignition engines with little or no modifications. Bio-diesel refers to the pure fuel before blending with petroleum diesel fuel. Blends of bio-diesel are denoted as, "BXX" with "XX" representing the percentage of biodiesel contained in the blend (i.e.: B20 is 20% biodiesel, 80% petroleum diesel). The primary advantage of using biodiesel is that it has favourable emission characteristics compared to straight petro diesel. Rapeseed or canola Biodiesel is considered less toxic than table salt and biodegrades as fast as sugar. At this time most manufacturers still consider biodiesel to be an experimental fuel and do not recommend or prohibit its use although they are coming around. Some OEMs suggest that if using biodiesel the maximum concentration should be a 5% solution with petrodiesel others do not suggest a limit on the concentration but all will refuse warranty coverage to any failure attributed to the use of a biodiesel. With that said there are significant benefits to the fuels lubricity when using a biodiesel blend of as little as 2% biodiesel. This has become a subject of immense debate with the advent of ULS or ultra low sulphur fuels coming in 2006. There are specifications for FAME under ASTM Specification D 6751 and in Germany under DIN V 51606 however these standards are under development and may be subject to change. Another form of biodiesel is filtered and purified used cooking oil. This needs to be processed similarly to new oil. Bio-diesel however is not the god send it seems to be when the carbon footprint of biodiesel is considered the amount of energy and carbon expended to make bio-diesel approaches the amount of energy we receive from the completed fuel so as a method to reduce greenhouse gases it is questionable at best.

Although there are significant advantages in terms of emission reductions when using biodiesel there are precautions to be taken, the following are Caterpillars recommendations when switching to biodiesel: The oil change interval can be affected by the use of biodiesel fuel. Use Scheduled Oil Sampling (SOS) to monitor the engine oil condition and to determine the optimum oil change interval. Biodiesel provides approximately 5-7% less energy per gallon of fuel when compared to distillate fuels. To avoid engine problems when the engine is converted back to 100% distillate diesel fuel, do not change the engine rating to compensate for the power loss. Elastomer compatibility with biodiesel is still being monitored. The condition of seals and hoses should be monitored regularly. Biodiesel fuels may pose low ambient temperature problems for both storage and operation. At low ambient temperatures, fuel may need to be stored in a heated building or a heated storage tank. The fuel system may require heated fuel lines, filters, and tanks. Filters may plug and fuel in the tank may solidify at low ambient temperatures if precautions are not taken. Consult your biodiesel supplier for assistance in the blending and attainment of the proper cloud point fuel. Biodiesel has poor oxidation stability, which can result in long term storage problems. The poor oxidation stability qualities may accelerate fuel oxidation in the fuel system. This is especially true in engines with electronic fuel systems because they operate at higher temperatures. Consult the fuel supplier for oxidation stability additives. Biodiesel fuel is an excellent medium for microbial growth. Microbes cause fuel system corrosion and premature filter plugging. The effectiveness of conventional anti-microbial additives, when used in biodiesel is not known. Consult your fuel and additive supplier for assistance. Care must be taken to remove water from fuel tanks. Water accelerates microbial growth. Water is naturally more prevalent in biodiesel fuels than in distillate fuels. Cetane Rating Cetane Rating of diesel fuel is a measure of the ignition quality of the fuel. The faster the fuel ignites the higher the cetane rating. When injected into the combustion chamber of the cylinder, fuel must quickly mix with air then ignite through absorbing heat as the ignition source. The time between the beginning of fuel injection and the start of combustion is called "ignition delay." Higher cetane number fuels result in shorter ignition delay, providing improved combustion, lower combustion noise, easier cold starting, faster

warm-up, less white smoke, and, in many engines, reduction of some emissions. To measure cetane number properly is rather difficult, as it requires burning the fuel in a special, hard-to-find, diesel engine called a Cooperative Fuel Research (CFR) engine, under standard test conditions. The operator of the CFR engine uses a hand-wheel to increase the pressure within the cylinder of the engine until the time between fuel injection and ignition is 2.407ms. The resulting cetane number is then calculated by determining which mixture of cetane (hexadecane) and isocetane (2,2,4,4,6,8,8heptamethylnonane) will result in the same ignition delay. Testing for cetane number is not performed in the field but fuel cetane number can be estimated by checking the API gravity index of the fuel, this will be discussed below. The higher the cetane rating the faster ignition takes place during the compression stroke in a diesel. This is opposite to the octane rating of gasoline. Octane is a measure of gasolines resistance to auto-ignition the higher the octane number the less likely the gasoline will self ignite or detonate during the compression stroke. Many opinions exist as to the benefits of high octane gasoline but the following should dispel some myths about its use. High octane gasoline has for all intents and purposes exactly the same potential heat energy as its low octane counterpart therefore it is not more powerful. Certain gasoline engines require a higher octane fuel to perform at their optimum, these are mostly higher compression engines, turbocharged and supercharged engines ingest more air under load than their naturally aspirated counterparts and therefore will have elevated compression ratios under load these too may require high octane fuel but always check the owners manual. High octane fuel will not increase the performance of an engine designed to run on lower octane fuel and if you use it you are only wasting the extra ten to twelve cents per litre. That said all engines will ping or pre-ignite under given circumstances especially with todays lean running engines. The engines knock sensor picks up the vibration from the ping and the ECM adjusts the timing automatically to prevent engine damage. This adjustment of engine timing will cause a slight reduction in engine performance during this event and yes higher octane fuel will result is less of these events occurring however the benefits are extremely limited and do not warrant the extra cost of the fuel. In fact some people who drive cars with high compression engines are taking the opposite tack that is they are starting to run low octane fuel in their engines and letting the knock sensor compensate by adjusting the timing thereby saving the extra cost of fuel! High cetane rating of fuel is necessary to facilitate good starting qualities, and smooth running. Low cetane fuel will cause excessive fuel knock and excessive white smoke after start-up. The exhaust smoke can be darker when the engine is warmed up due to incomplete combustion from excessive ignition delay. Nitrate based fuel additives can be added to increase the cetane ratings. A small quantity of amyl or hexyl nitrate will add as much as 6 points to the cetane rating. The average cetane number for 2D diesel fuel is 44. Most engines do not benefit from improved starting above a 40 cetane but performance and emission benefits are improved if higher cetane fuel is used. The City of Toronto purchases #1D fuel to achieve better emission characteristics from their diesel-powered vehicles. Since #1D has a naturally higher cetane number it has better cold weather starting and running characteristics. Adding cetane booster to #2D would likely be a better strategy since the energy value is preserved delivering more power and better fuel economy. The minimum cetane rating for number 1 and number 2 diesel according to the D-975 standard is 40 however number 2 D in Canada averages about 44 and number 1 D averages about 47-48.

Specific Gravity API Index For a repair technician the specific gravity of a fuel is a good indication of the grade of fuel. Typically the specific gravity will correspond to the grade of fuel and more obviously, the heat content. If a fuel lacks density it will not have the same energy content as a denser fuel. In colder climates the specific gravity will indicate whether the fuel has been blended with kerosene or #1D. Although fuel density does not specifically relate to diesel fuel cetane number higher cetane fuels tend to have higher API gravities that is they are less dense and a technician can use the gravity as an indicator of the fuels quality. It should be noted however that checking the gravity is by no means a scientific measure of the fuels quality it is used for comparison purposes only. It should also be noted that fuels are seasonally adjusted for operation in different ambient temperatures so number 2D diesels API gravity will range from approximately 34 to 37. Flashpoint: The flash point of a fuel is defined as the temperature to which the fuel must be heated to produce a vapour that will ignite when exposed to a spark or flame. If the flash point of a fuel is too low, the fuel is considered a fire hazard, which is prone to flashing, possible ignition, and even explosion. For most diesel fuel this is from 38 to 52 C depending on the grade of fuel. Different from the flashpoint is the auto ignition temperature the temperature the fuel will ignite at when heated. The minimum auto-ignition temperature of diesel fuel sold in North America is 292C. Typically diesel ignites at 250C. It should be noted that gasoline although being more volatile than diesel fuel it has quite a bit higher auto-ignition temperature. Thus, if gasoline is mixed with diesel fuel a significantly longer ignition delay time is the result. Volatility Volatility for diesel is measured as the amount of fuel as a percentage evaporated at a particular temperature. This is similar to the boiling point of the fuel. Volatility is also related to cetane rating. Higher cetane fuels are more volatile since its molecules are lighter and more easily evaporated and burned. Lower cetane fuel is less volatile having larger more complex hydrocarbon molecules (more aromatic content). These larger molecules contain more potential heat energy but are more difficult to vaporize and burn and are limited to no more than 20% content by weight in most jurisdictions, in California the California Air Resources Board, (CARB), restricts aromatic content to 10%.

The Gelling Phenomenon At low temperatures, paraffin wax crystals can start to form in diesel fuel. The fuel starts to look hazy, not the pristine clear that it is when warm. This is caused by the congealing of paraffin or wax molecules in the fuel. In a vehicle's fuel system these wax crystals can collect on fuel filters and plug them, causing engine stumbling or stalling. The temperature at which filter plugging occurs is called the low temperature operability limit of the fuel and vehicle. Both fuel system design and fuel properties are important factors in determining this minimum temperature for acceptable operation. Pour & Cloud Point: Pour and cloud point should be tailored for specific climate needs. The cloud point refers to the fuel's temperature as it begins to thicken and "cloud." The pour point refers to the temperature of the diesel fuel as it thickens and will no longer pour. Some engines will fail to run at the cloud point, but all engines will fail at the pour point. Usually the cloud and pour point are 20F degrees apart. Normal cloud point often occurs at 40 F, (4.4 C) and pour point at 15-20 F, (-9 to -6 C) with #2D fuel. If you are in a cold climate, use winterized fuel or winter blended diesel fuel, which is a mixture of #1D and #2D. #1D has a lower pour point, but also has a lower viscosity, or weight, and is harder on the fuel injectors, which is why blended mixture is recommended for cooler climates. Most fuel suppliers will automatically blend their fuel for use in the ambient climate. Lubricity: Just like a bearing needs oil to continue working smoothly; fuel must be capable of lubricating the system components in order to prolong the fuel system. Moving parts within nozzles, pumps etc. of the fuel system require lubrication to prevent galling, seizure and to prolong component life. Three methods were developed which are now available for measuring fuel lubricity; namely, the Scuffing Load Ball on Cylinder Lubricity Evaluator (SLBOCLE), the High Frequency Reciprocating Wear Rig (HFRR), and the Ball on Three Seats Method (BOTS). Lubrication capabilities are expressed as lubricity in grams of load. Many engine manufacturers require a minimum SL BOCLE rating of 3,100 grams, the higher the value, the better the lubricating ability. A huge debate over lubricity has erupted since the advent of low sulphur fuels in 1993 in the US and 1994 in Canada it seems that the removal of sulphur renders the fuel less capable to lubricate the parts it flows through. However this is not caused by the lack of sulphur but rather by the hydro-treating process used to remove it. During this process the fuel is reduced to some of its base constituents and re-blended the resulting blend does not have the lubricating capability of the original product. After many years of discussions back and forth between the two major stakeholders, (the producers of the fuel and the manufacturers of diesel fuel injection systems), the consensus is that todays fuel can benefit from the addition of a lubricity enhancer and the ULS or ultra low sulphur fuel introduced in 2006 has a lubricity additive. One enhancer is a form of biodiesel blended into the fuel at a 2% concentration. John Deere Australia is using this blend as its stock fuel for farm equipment coming off their assembly lines since March 1 2005. The main drawback of this approach is that bio-diesel is relatively expensive so many other lubricity additives are being used and considered.

Diesel Fuel Heat Content The heat content of a fuel refers to its potential energy listed in BTUs per pound or per gallon. One of the fundamental advantages of diesel engines is the inherent approximate 13% increase in heat content. This means that just the fuel alone has the potential to produce more work than its gasoline counterpart. A BTU is the amount of heat energy required to raise the temperature of one pound of water at 60 degrees Fahrenheit to 61 degrees. One BTU also has the ability to perform 778 foot pounds of work so by understanding the energy or heat content of a fuel we can calculate the potential work it is capable of. The chart above refers to American gallons when looking at the heating value. In Canada #2 Diesel fuel has approximately 140,000 BTUs per gallon #1 diesel has approximately 135,000. The fuels heat content is directly related to its density as can be seen in the earlier API chart. Number 2 diesel is denser than number 1 and number 4 would be denser than number 2, (number 4 is primarily used in stationary constant load engines). From a fleet operators standpoint it makes economic sense to run #2 all year to take advantage of its higher energy content however in certain areas the lower low temperature operability limit of number 1 is a necessity.

Above: diesel fuel is made up of more than 50 different hydrocarbons, each one will add its own characteristic to the particular blend

Sulphur Content of Diesel Fuel. Sulphur naturally occurs in most of all crude oils, which includes diesel fuel. Although the removal of sulphur has negative effects on the lubricating capabilities of the fuel, sulphur itself also has negative effects to the life of the fuel system components (forms acids) and raises emissions. When sulphur burns, it creates sulphur dioxide (SO2), which has an unpleasant odour and is a precursor to acid rain. The SO2 reacts with free oxygen to become SO3 and then with H2O to become H2SO4 or sulphuric acid. SO2 and particulate emission can be significantly decreased with the removal of sulphur from the fuel. The EPA has a mandated reduction schedule regarding sulphur content, which is defined in parts per million (ppm). Since 1993 in the US and 1994 in Canada the allowable maximum was 500-ppm, which is equivalent to .05% by weight. As of October 2006, the limit is 15ppm with ULS or Ultra Low Sulphur fuel. Off road vehicles will have to run on ULS by 2010 and rail and marine by 2014. Most engine OEMs are designing their off road engines to run on ULS already and will be compliant long before the legislation. Green Diesel Technology (Navistar) calls for sulphur levels below 15ppm right now for on highway but as mentioned before these fuels require a lubricity additive to meet the ASTM standards for viscosity and the OEM standards for boundary lubrication. In Europe sulphur levels are restricted to 350 PPM since 2001, and were reduced to 50 PPM in November 2005. 10 PPM fuel had to be available to the marketplace from Jan 1 2005. The idea is to charge slightly more for the higher sulphur content fuel to encourage the use of ULS. At this time mandatory implementation of their ultra low PPM is slated for Jan 1 2009.

Fuel Colour In order to distinguish between fuels having a high sulphur content, fuel with taxes to be paid and non-taxable fuel, diesel fuel is often coloured. Retail fuel sold in Ontario is clear. Fuel that is low in sulphur content but is not taxed is coloured red (farm vehicles some government vehicles). In the US both non taxed and high sulphur fuel are coloured red but at different concentrations of dye. Suspected high sulphur fuel must be analyzed before fines can be levied. Many different colour dyes have been used by different jurisdictions so identification has become confusing. In many parts of Canada only non taxed fuel is dyed. A proposal is being analyzed to colour low sulphur fuel, (500 PPM), yellow to differentiate it from ULSD in the US where all three sulphur levels of fuel may be available until 2010. Diesel Fuel Additives Diesel fuel additives are used for a wide variety of purposes; however they can be grouped into four major categories: Engine Performance Fuel stability Fuel handling Contaminant Control

Engine Performance Additives These additives are commonly a cetane number improver, detergent additives or lubricity additives. (Diesel Ignition Improvers) Cetane number improvers can reduce combustion noise and smoke. The magnitude of the benefit varies among engine designs and operating modes, ranging from no effect to readily perceptible improvement. These increase the cetane number of the fuels by as much as 7 points in small concentrations (0.2%) These are also termed ignition accelerators by lowering the ignition temperature required for the fuel. By minimizing the ignition delay, improvements to cold starting, acceleration, and smoke emissions can be made. 2-Ethylhexyl nitrate (EHN) is the most widely used cetane number improver. It is sometimes also called octyl nitrate. EHN is thermally unstable and decomposes rapidly at the high temperatures in the combustion chamber. The products of decomposition help initiate fuel combustion and, thus, shorten the ignition delay period from that of the fuel without the additive. The increase in cetane number from a given concentration of EHN varies from one fuel to another. It is greater for a fuel whose natural cetane number is already relatively high. The incremental increase gets smaller as more EHN is added, so there is little benefit to exceeding a certain concentration. EHN typically is used in the concentration range of 0.05% mass to 0.4% mass and may yield a 3 to 8 cetane number benefit. Other alkyl nitrates, as well as ether nitrates and some nitroso compounds, also have been found to be effective cetane number improvers, but they are not currently used commercially. Di-tertiary butyl peroxide was recently introduced as a commercial cetane number improver. A disadvantage of EHN is that it decreases the thermal stability of some fuels. The effect of the other cetane number improvers on thermal stability is unknown, but it seems likely that they will be similarly disadvantaged. Several laboratories are investigating this issue. Detergent or Injector Cleanliness Additives Fuel and/or crankcase lubricant can form deposits in the nozzle area of injectors the area exposed to high cylinder temperatures. The extent of deposit formation varies with engine design, fuel composition, lubricant composition, and operating conditions. Excessive deposits may upset the injector spray pattern (see Figure 7-1) which, in turn, may hinder the fuel-air mixing process. In some engines, this may result in decreased fuel economy and increased emissions. Ash less polymeric detergent additives can clean up fuel injector deposits and/or keep injectors clean. These additives are composed of a polar group that bonds to deposits and deposit precursors, and a non-polar group that dissolves in the fuel. Thus, the additive can re-dissolve deposits that already have formed and reduce the opportunity for deposit precursors to form deposits. Detergent additives typically are used in the concentration range of 50 ppm to 300 ppm. High doses can clean an already-coked nozzle, while smaller doses maintain clean operation.

The ability of an injector to stay clean will be more important as manufacturers attempt to meet emission regulations, performance requirements and maximize engine efficiencies. The Engine Manufacturers Association endorsed a detergent requirement using the test method, L-10 Injector Depositing Test. This test was developed by Cummins to evaluate fuel and fuel additive effectiveness in reducing deposits on direct-injection nozzles typically found in heavy-duty engines. The test utilizes a Cummins 1988 turbocharged L40 engine with Pressure Time (PT) injectors. The engine is cycled at 15-sec intervals between closed rack and partial rack (full and part throttle) for a total of 125 hours. At the end of the test, the injectors are flow-tested to determine the percent of fuel flow lost. Plungers in the injector bodies are removed and visually rated for deposits using the Coordinated Research Council (CRC) scale. Typically a "dirty" fuel, with no additives, will have CRC ratings over 20; a fuel with additives will have ratings below 10. Lubricity Additives Lubricity additives are used to compensate for the poor lubricity of severely hydro-treated diesel fuels. There have been numerous examples from the field where lack of lubricity in the fuel has caused premature equipment breakdown and in some cases, catastrophic failures. This problem will be more dramatic as EPA moves to further reduce the sulphur levels in petrodiesel fuel. There are two basic elements to lubrication, hydro-dynamic lubrication where the two components in contact are separated by a wedge or wall of fluid and boundary lubrication when extreme pressure between the two components squeezes the fluid from between the two components. Boundary lubrication is dependant on film strength of the fluid, if the film shears then metal to metal contact will occur followed very quickly by component failure. Blending 2% biodiesel with the new ULS petrodiesel addresses the hydrodynamic lubrication issue but the boundary HYDRODYNAMIC lubrication issue is still up in the air. LUBRICATION Most lubricity additives contain a molecule that is attracted to metal surfaces, causing the additive to form a thin surface film. The film acts as a boundary lubricant when two metal surfaces come in contact. Two additive chemistries, fatty acids and esters, are commonly used. The fatty acid type is typically used in the concentration range of 10 ppm to 50 ppm. Since esters are less polar, they require a higher concentration range of 50 ppm to 250 ppm.

Smoke Suppressants. Some organo-metallic compounds act as combustion catalysts. Adding these compounds to fuel can reduce the black smoke emissions that result from incomplete combustion. During the 1960s Act and the formation of the EPA, certain barium organo-metallics were used occasionally as smoke suppressants. The EPA subsequently banned them because of the potential health hazard of barium in the exhaust. Smoke suppressants based on other metals, e.g., iron, cerium, or platinum, are used in other parts of the world; but have not been approved by the EPA for use in North America. These additives are often used in vehicles equipped with particulate traps to lower particulate emissions even further. Fuel Handling Additives Antifoam Additives Some diesel fuels tend to foam as they are pumped into vehicle tanks. The foaming can interfere with filling the tank completely, or result in a spill. Most antifoam additives are organo-silicone compounds and are typically used at concentrations of 10 ppm or lower. De-Icing Additives Free water in diesel fuel freezes at low temperatures. The resulting ice crystals can plug fuel lines or filters, blocking fuel flow. Low molecular weight alcohols or glycols can be added to diesel fuel to prevent ice formation. The alcohols/glycols preferentially dissolve in the free water, giving the resulting mixture a lower freezing point than that of pure water. Low Temperature Operability Additives There are additives that can lower a diesel fuel's pour point (gel point) or cloud point, or improve its cold flow properties. Most of these additives are polymers that interact with the wax crystals that form in diesel fuel when it is cooled below the cloud point. The polymers mitigate the effect of the wax crystals on fuel flow by modifying their size, shape, and/or degree of agglomeration. The polymer-wax interactions are fairly specific, so a particular additive generally will not perform equally well in all fuels. To be effective, the additives must be blended into the fuel before any wax has formed, i.e., when the fuel is above its cloud point. The best additive and treat rate for a particular fuel can not be predicted; it must be determined experimentally. Fuel Stability Additives Fuel instability results in the formation of gums that can lead to injector deposits or particulates that can plug fuel filters or the fuel injection system. The need for a stability additive varies widely from one fuel to another. It depends on how the fuel was made the crude oil source and the refinery processing and blending. Stability additives typically work by blocking one step in a multi-step reaction pathway. Because of the complex chemistry involved, an additive that is effective in one fuel may not work as well in another. If a fuel needs to be stabilized, it should be tested to select an effective additive and treat rate. Best results are obtained when the additive is added immediately after the fuel is manufactured. Antioxidants One mode of fuel instability is oxidation, in which oxygen in the small amount of dissolved air attacks reactive compounds in the fuel. This initial attack sets off complex chain reactions. Antioxidants work by interrupting the chains. Hindered phenols and certain amines, such as phenylenediamine, are the most commonly used antioxidants. Stabilizers Acid-base reactions are another mode of fuel instability. The stabilizers used to prevent these reactions typically are strongly basic amines and are used in the concentration range of 50 ppm to 150 ppm. They react with weakly acidic compounds to form products that remain dissolved in the fuel, but do not react further Metal Deactivators When trace amounts of certain metals, especially copper and iron, are dissolved in diesel fuel, they catalyze (accelerate) the reactions involved in fuel instability. Metal deactivators tie up (chelate) these metals, neutralizing their catalytic effect.

Dispersants Multi-component fuel stabilizer packages may contain a dispersant. The dispersant doesn't prevent the fuel instability reactions, but it does disperse the particulates that form, preventing them from clustering into aggregates large enough to plug fuel filters or injectors. In other words it make sure that any particles that form remain small enough that they dont cause problems. Biocides The high temperatures involved in refinery processing effectively sterilize diesel fuel. But the fuel quickly becomes contaminated with micro-organisms present in air or water. These microorganisms include bacteria and fungi (yeasts and moulds). The most common way for these to enter the diesel fuel is through condensation of water in the diesel tank. This much more prevalent in stationary tank installations with low fuel turnover rates but it can occur in mobile tanks as well. As the fuel in the tank warms due to radiant heat from the sun or warm fuel returning from the injection system air and vapours leave the tank, as the tank cools air is drawn in and this air contains moisture which will then condense an the tank walls and sink to the bottom, (this is a good reason to fill your tanks at the end of a workday). Since most micro-organisms need free water to grow, bio-growth is usually concentrated at the fuel-water interface. In addition to the fuel and water, they also need certain elemental nutrients in order to grow. Of these nutrients, phosphorous is the only one whose concentration might be low enough in a fuel system to limit bio-growth. Higher ambient temperatures also favour growth. Some organisms need air to grow (aerobic), while others only grow in the absence of air (anaerobic).

The time available for growth also is important. A few, or even a few thousand, organisms don't pose a problem. Only when the colony has had time to grow much larger will it have produced enough acidic by-product to accelerate tank corrosion or enough biomass (microbial slime) to plug filters. Although growth can occur in working fuel tanks, static tanks where fuel is being stored for an extended period of time are a much better growth environment when water is present. Biocides can be used when micro-organisms reach problem levels. The best choice is an additive that dissolves in both the fuel and the water so it can attack the microbes in both phases.

Biocides typically are used in the concentration range of 200 ppm to 600 ppm. A biocide may not work if a heavy bio-film has accumulated on the surface of the tank or other equipment, because then it doesn't reach the organisms living deep within the film. In such cases, the tank must be drained and mechanically cleaned. Even if the biocide effectively stops bio-growth, it still may be necessary to remove the accumulated biomass to avoid filter plugging. Since biocides are toxic, any water bottoms that contain biocides must be disposed of appropriately. The best approach to microbial contamination is prevention. And the most important preventative step is keeping the amount of water in a fuel storage tank as low as possible, preferably zero. Demulsifiers Normally, hydrocarbons and water separate rapidly and cleanly. But if the fuel contains polar compounds that behave like surfactants and if free water is present, the fuel and water can form an emulsion. Any operation which subjects the mixture to high shear forces, like pumping the fuel, can stabilize the emulsion. Demulsifiers are surfactants that break up emulsions and allow the fuel and water to separate more easily. Corrosion Inhibitors Since most petroleum pipes and tanks are made of steel, the most common corrosion is the formation of rust in the presence of water. Over time, severe rusting can eat holes in steel walls, creating leaks. More immediately, the fuel is contaminated by rust particles, which can plug fuel filters or increase fuel pump and injector wear. Corrosion inhibitors are compounds that attach to metal surfaces and form a barrier that prevents attack by corrosive agents. Additives may be added to diesel fuel at the refinery, during distribution, or after the fuel has left the terminal. During distribution, additives may be injected prior to pipeline transit (if the fuel is distributed by pipeline), or at the terminal. When the fuel leaves the terminal, its ownership generally transfers from the refiner or marketer to the customer, who may be a reseller (jobber) or the ultimate user. For this reason, additives added to the fuel after it leaves the terminal are called aftermarket additives. Refinery Additization. The quality of all diesel fuels is not the same hence the need for these additive to bring a fuel up to certain standards. Fuel is the single largest operating expense for a diesel truck fleet; many users make their purchase decisions based on price alone. Refiners have a legal requirement to provide a product that meets specifications. Beyond that, reputable refiners ensure that non-specification properties, such as stability, lubricity, and low temperature operability are suitable for the intended use. The refiner has several options on how to achieve the desired properties: choice of crude oil, refinery processing, refinery blending, or the use of additives. The balance between refining actions and additive use is driven by economics. Since there are no legal requirements that diesel fuel contain additives, except red dye in high sulphur, (blue in Canada), and red for tax-exempt fuel some refiners may use no additives at all and still provide a high quality fuel.

Aftermarket Additives It would be convenient for the user if a finished diesel fuel could satisfy all his or her requirements without the use of supplemental additives. Although this is often the case, some users must use aftermarket additives because the low temperature conditions in their region are more severe than those for which the fuel was designed, or because of other special circumstances. Other users feel that they need a higher quality diesel than regular diesel. And, finally, there are users who regard the cost of an additive as cheap insurance for their big investment in equipment. A large number of aftermarket additive products are available to meet these real or perceived needs. Some are aggressively marketed with testimonials and bold performance claims that seem "too good to be true." So, as with any purchase, it is wise to remember the advice, caveat emptor let the buyer beware. It may be helpful to regard additives as medicine for fuel. Like medicine, they should be prescribed by an expert who has made an effort to diagnose the problem. And they should be used in accordance with the recommendations of the engine manufacturer and the instructions of the additive supplier. Sometimes indiscriminate use of additives can do more harm than good because of unexpected interactions.