Fuels & Combustion

Fuels Although there are many different types of fossil fuels in the world; in marine engineering coal, petroleum, and natural gas are used. Out of which petroleum fuel is most widely used and remains one of the highest single cost factors in running a ship. Petroleum is a compound made up predominantly of atoms of hydrogen and carbon; thus the name hydrocarbons and can combine in various ways to form many different compounds. As petroleum oil comes out of the ground in an unrefined or crude state it is thus termed as crude oil. This crude oil must be refined in a refinery to be separated into constituents such as gaseous fuels, gasoline (petrol), kerosene (paraffin), gas oils, distillate diesel fuels and lubricating oils etc. before it can be used by the consumer. Refining is by heating the crude oil, in a fractionating tower furnace (Fig.1) so that vapours are boiled off and then condensed at different temperatures. The constituents or fractions are collected separately in a distillation process are collected from the where they condense out at the different levels maintained at appropriate temperatures.

Figure 1. Oil refinery process The boiling process produces a residue which is very dense as the result of having lost the lighter parts. This high-density remainder has much the same

hydrocarbon make up as the lighter fractions and having concentrates of impurities and is also used as a fuel. Further this residual oil is again refined by a second process where distillation is carried out at a reduced pressure and high temperature is called Vacuum distillation. In order to meet the product demand, further refining processes were introduced. Today, a modern refinery, in addition to atmospheric and vacuum distillation, may also consist of refining processes such as cracking, which may be thermal (Vis-breaking) or with a catalyst (Catalytic cracking is a process that uses a powdered silica-alumina based catalyst with heating). This final process removes more of the lighter fractions, to leave an even heavier residue which may consists some of the catalyst powder in it. When this residue is used for blending bunker fuel oils the very abusive silica-alumina catalytic fines have caused severe engine wear when not detected and removed by slow purification in the ship's fuel treatment system. Bunkers are classified (ISO8217:2005-See Table 1 & 2) as Gas Oil, Light and Marine Diesel Oil, Intermediate Fuel Oil and Marine or Bunker (C) Fuel Oil. The quality of a fuel oil is generally determined by a number of specific parameters or proportions of metals or impurities in a given sample of the particular fuel. Such parameters include: viscosity; specific gravity; flash point; Conradson carbon; asphaltenes content; sulphur content; water content; vanadium content; and sodium content. The delivery note specifies the type of fuel, amount, viscosity, specific gravity, flash point and water content. Trouble frequently results from inferior fuels and there can be insufficient information to give warning. Some of the Classification Societies and specialist firms provide testing services and on-board testing equipment is available. A representative sample is needed to give an accurate test is obtain at test cock is fitted in the bunker manifold. Combustion is a chemical process where rapid oxidation accompanied by heat and light is released. For a successful complete combustion it requires certain ratios of air and fuel and heat is necessary if an engine or boiler is to operate. The air to fuel ratio is approximately should be 15:1 (Stoichiometric ratio) of combustion to be complete. In actual the oxygen in the air is to one that takes part in the combustion process whilst the other major constituent nitrogen is assumed to be dormant. The atmosphere may be assumed to contain 23.15 per cent of oxygen by weight and 20.96 per cent by volume. Two parameters of traditional importance have been the calorific value and viscosity. Viscosity, once the best pointer to a fuels quality or degree of heaviness, is now considered as being only partially a major quality criterion because of the possible effects of constituents of a fuel. The calorific value or heat of combustion of a fuel oil is a measure of the amount of heat released

during complete combustion of a unit mass of the fuel, expressed MJ/kg. Calorific value is usually determined by a bomb calorimeter but it can also be theoretically calculated. The calorific value can be expressed as gross or higher value which includes the latent heat of water vapour formed by the combustion of the hydrogen or as net or lower calorific value obtained from subtracting this latent heat. The difference between the gross and net values is usually about 2.53.0 MJ/kg, depending upon the hydrogen percentage. Typical gross calorific values for different fuels are: Diesel oil 50 MJ/kg Gas oil 45.62 MJ/kg Heavy fuel 43.1 MJ/kg When test data is not available the specific gravity of a fuel will provide an approximate guide to its calorific value: Specific gravity at 15oC = 0.85 0.87 0.91 0.93 Gross CV MJ/kg = 45.62 45.2 44.79 43.95 An average diesel fuel should comprise in percentages, carbon 8687(C = 33.7 MJ/kg); hydrogen 11.013.5(H = 144 MJ/kg); sulphur 0.52 (S = 9.7 MJ/kg); oxygen and nitrogen 0.51.0. The greatest energy output in the combustion of fuels is from the hydrogen content, and fuels having high hydrogen: carbon ratio generally liberates greater quantities of heat. Typical examples are given below: Carbon Element - C 12.00 Hydrogen Element H 1-H2 - 2 Oxygen Element O 16- O2 - 32.00 Nitrogen Element N 14-N2 -28.02 Sulphur Element S 32-S2- 64.14 Carbon burned to carbon dioxide C + O2 = CO2 12 kg C + 32 kg O = 44 kg CO2 Carbon burned to carbon monoxide 2C + O2 = 2(CO) 24 kg C + 32 kg O = 56 kg CO Carbon monoxide burned to carbon dioxide 2(CO) + O2 = 2(CO2) 56 kg CO + 32 kg O = 88 kg CO2 Hydrogen oxidised to steam 2H2 + O2 = 2(H2O) 4 kg H + 32 kg O = 36 kg steam (or water) Sulphur burned to sulphur dioxide S2 + 2O2 = 2(SO2) 64 kg S + 64 kg O = 128 kg SO2

Sulphur dioxide burned to sulphurous acid SO2 + H2O = H2SO3 64 kg SO2 + 18 kg H2O= 82 kg H2SO3 Sulphur dioxide burned to sulphur trioxide O2 + 2(SO2) = 2(SO3) 32 kg O + 128 kg SO2 = 160 kg SO3 Sulphur trioxide and water to form sulphuric acid SO3 + H2O = H2SO4 80 kg SO3 + 18 kg H2O = 98 kg H2SO4 Sulphur is a naturally occurring element in crude oil and concentrated in the residual component of the crude oil distillation process. Hence the amount of sulphur in the fuel oil depends mainly on the source of the crude oil and to a lesser extent on the refining process. Typically, for residual fuel on a worldwide basis, the value is in the order of 2-4% m/m. In the combustion process in a diesel engine, the presence of sulphur in the fuel can potentially give rise to corrosive wear. This can be minimized by suitable operating conditions and lubrication with alkaline lubricant for the cylinder liner. In the fuel oil there are impurities due to the place from where it is taken and during refining and transportation such as following: Vanadium which is a metal that is present in all crude oil in an oil soluble form. The levels found in residual fuels depend mainly on the crude oil source, with those from Venezuela and Mexico having the highest levels. The actual level is also related to the concentrating effect of the refinery processes used in the production of the residual fuel. The majority of residual fuels have vanadium levels of less than 150mg/kg. However some fuels have a vanadium level greater than 400mg/kg. There is no economic process for removing vanadium from either the crude oil or residue. In general, fuel as delivered contains a small amount of sodium. If not removed in the fuel treatment process, a high level of sodium will give rise to post combustion deposits in the turbocharger and on exhaust valve and lead to high temperature corrosion. Catalyst Fines are particles of spent aluminum and silicon catalyst that arise from the catalytic cracking process in the refinery. The fines are in the form of complex alumino-silicates. If not reduce by suitable fuel treatment, the abrasive nature of the fines does damage to the engine, particularly fuel pumps, injectors, piston rings and liners. The generally accepted limit amount of catalyst is by limiting the combination of aluminum and silicon in elemental form to 80mg/kg. The percentage removed by fuel treatment depends upon the size and density of the particulate matter.

Other types are the carbon residue of a fuel is the tendency to form carbon deposits under high temperature conditions in an inert atmosphere. It may be expressed as Conradson Carbon Residue (CCR) or Micro Carbon Residue. The carbon residue value depends upon the refinery processes employed in its manufacture. And ash value is related to the inorganic material in the fuel oil. The actual value depends upon three factors, firstly the inorganic material naturally present in the crude oil, secondly the refinery processes employed, and thirdly, upon possible subsequent contamination due to sand, dirt and rust scale. As stated before the Stoichiometric (air/fuel) ratio for complete combustion theoretically is 15:1, but in actual for complete combustion in an engine the air must be in excesses than the Stoichiometric air, which is about 150 percentage of the theoretical air.

Table 1: Requirements for marine distillate fuels

Table 2: Requirements for marine residual fuels