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Process engineering
Combustion technique
Combustion
This is the first lesson on the subject of combustion technique, in which the various aspects of fired equipment are described. The process industry uses vast amounts of energy in the form of heat. This heat is mostly obtained by the combustion of oil, gas or coal. In this lesson a start is made with the description of the conditions under which the combustion process should take place.
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Lesson
1. What is combustion?
Combustion is a chemical reaction between a combustible material and oxygen, as a result of which various combustion products are formed (one of them being flue gas). A combustion reaction produces heat. Reactions in which heat is produced are called exothermic reactions. We could describe a combustion reaction by means of the following equation: fuel + oxygen flue gas + heat Question 1 What is meant by an exothermic reaction?
- exothermic reactions
- self-ignition temperature
- flame speed
- flame colour
- afterburning
Another effect would be the loss of energy since the chemically bound heat of this fuel would not be fully used. Finally, the incompletely burnt constituents of the flue gas would contribute to pollution of the environment. The theoretical air supply rate is fully governed by the composition of the fuel. For Standard Refinery Fuel (SRF) this value is about 14 kg air per kg oil. For standard fuel gas it is about 16 kg per kg gas. To fully burn all of the fuel we must add an extra amount of air to the theoretical requirement. In other words: we conduct the combustion process with an excess of air. This excess air is expressed in the factor(N). The amount of air air actually used in the combustion process equals N * the theoretical requirement. The concepts of excess air and air factor can cause confusion. If the air factor is 1.2, then we speak of an excess air of 20%. In such a situation N-1 = 0.2 * the theoretical air requirement is supplied in addition. In practice, it is found that fuel gas can be mixed with air rather well. As a result, it is sufficient to use only a slight excess air, N = 1.05 - 1.1. The complete combustion of heavy liquid fuel often requires an air factor of N = 1.20 - 1.30. Question 4 What are the effects if a combustion is conducted on a technical scale at a theoretical air requirement?
2. Fuels
- fuel - calorific value - higher (gross) calorific value - lower (nett) calorific value A fuel is characterised by the release of heat in a reaction with oxygen. The calorific value of a fuel is defined as the amount of heat released in the combustion of one kilogram of fuel. A distinction is made between the lower calorific value and the higher calorific value. The higher calorific value is the amount of heat actually released in a combustion. The lower calorific value indicates the fraction of the heat released that can actually be used. The difference between these calorific values is due to the presence of water. The water can be present in the fuel or can be formed during combustion. The water present leaves the plant in the form of water vapour (the temperature is usually higher than 200 C). However, the heat used for the evaporation cannot be recovered by condensing the water vapour. This energy is lost and cannot be used for the generation of heat. Table 1 gives the higher calorific values of the elements C, H and S. Table 2 summarises the higher and lower calorific values of a number of gases. For liquid fuels these values can be based on the density and the sulphur content of the oil. This relationship is shown in figure 1. Fora Standard Refinery Fuel we could use a lower calorific value of 40.2 (MJ/kg)
Table 1 Higher calorific values of the elements C, H and S Element Combustion product Calorific value (MJ/kg) Carbon carbon dioxide 34 Hydrogen water 144 Sulphur sulphur dioxide 10.5 Table 2 Calorific values of various gaseous fuels SI units Fuel Specific mass kg/m3* Calorific value
Conventional units Density (air = 1.0) Calorific value higher kcal/kg 34,400 13,100 11,900 12,300 11,600 11,900 11,500 11,700 11,600 2,430 lower kcal/kg 29,000 11,800 11,100 11,200 10,800 10,900 10,700 10,800 10,700 2,430 -
higher lower MJ/kg MJ/kg H2 0.0899 144 121 CH4 0.717 54.8 49.4 C 2 H4 1.262 49.8 46.5 C 2 H6 1.356 51.5 46.9 C 3 H6 1.937 48.6 45.2 C 3 H8 2.015 49.8 45.6 C 4 H8 2.583 48.1 44.8 C4H10 2.696 49.0 45.2 C3H12 3.40 48.6 .8 CO 1.25 10.2 10.0 CO2 1.98 N2 1.25 H2 O 0.80 * at 0C and 760 mm Hg (ca. 1.01325 bar)
0.069 0.55 0.975 1.05 1.50 1.56 2.03 2.07 2.63 0.967 1.528 0.967 0.621
For every constituent of the total fuel composition it can be calculated how much oxygen is theoretically required to give a complete combustion. By way of example we will calculate the value for the combustion of methane (CH4). The combustion reaction is given by: CH4 + 2O2 CO2 + 2H2O + heat (16) + (64) (44) + (36)
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Figure 1 Relation between lower calorific value and composition of liquid fuels
In other words: 1 kmol methane reacts with 2 kmol oxygen and forms, with heat being produced, 1 kmol carbon dioxide and 2 kmol water (vapour). The reaction equation further shows that the combustion of 16 kg CH4 requires 2 * 32 = 64 kg O2. So, the theoretical oxygen supply rate for burning methane equals 4 kg oxygen per kg methane. The combustion is not conducted with pure oxygen, but with air. As air contains 23 percent by weight oxygen, the theoretical air supply 100% rate is * 4 kg = 17.4 kg air per kg methane. 23% The calorific value of fuels used at a refinery is mainly governed by the carbon/hydrogen ratio. As matter of fact, such fuels consist mainly of the elements carbon and hydrogen. The element hydrogen has a higher calorific value than the element carbon. Hence, a lower C/H ratio means a higher calorific value. This is shown in figure 2. With the aid of this figure it is found that for a standard refinery oil, which has a lower calorific value of 40.2 kJ/kg, the C/H ratio is approx. 9.2. Question 5 Why has a fuel with a higher C/H ratio a lower calorific value?
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Figure 2 Relation between the lower calorific value and the C/H ratio of liquid fuel
3. Flue gases
A closer look at the reaction equation for methane and oxygen shows that at theoretical combustion the flue gas consists of carbon dioxide (CO2) and water (vapour) (H2O). CH4 + 2O2 CO2 + 2H2O (16) (64) (44) (36) The mass ratio's relative to the mass of methane equal:
(1 44) 16 (2 18) 16
Of course, the mass balance of the reaction equation must tally: 1 kg CH4 + 4 kg O2 = 2.75 kg CO2 + 2.25 kg H2O However, in practice use is made of air instead of pure oxygen, so that we find in the flue gases large amounts of nitrogen (N2) (about 77% mass of the air is nitrogen). As combustion in practice is always with a excess air, the flue gases will also contain oxygen, since ultimately, only the theoretical amount of oxygen can be used.
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So, if we burn 1 kg methane with air, with the air factor being 1.1 (10% excess air), the flue gas composition is:
(1 44) 16 (2 18) 16 (0.1 23) 100 (1.1 77)
= 2.75 kg CO2
= 2.25 kg H2O
* 17.4 = 0.40 kg O2
100
* 17.4 = 14.74 kg N2
Hence, the combustion of 1 kg CH4 yields: 2.75 + 2.25 + 0.4 + 14.74 = 20.14 kg flue gas. It should be added that the flue gas composition is mostly expressed in percent volume. In the measurement of oxygen, too, the amount of oxygen present in the flue gas is indicated as percent volume. - environmental pollution In addition to possibly causing the above-mentioned air pollution (due to partially burnt fuel), the flue gases can contain other noxious substances. Thus, the fuel oil usually contains other materials (sand, salts and heavy metals) that leave the stack in the form of solid particles (fly ash). Further, the sulphur present in the oil is converted into sulphur dioxide (SO2) and sulphur trioxide (SO3). Finally in a combustion plant nitrogen monoxide (NO) and nitrogen dioxide (NO2) are formed. All the substances mentioned above are harmful to the environment. Obviously, efforts are made to minimise these emissions. Question 6 Why does flue gas always contain oxygen? Question 7 Mention a number of substances that cause environmental pollution and which are released in combustion processes.
Summary
Combustion is a chemical reaction between a combustible material and oxygen, in which various combustion products are formed. We can describe a combustion reaction with the following equation: fuel + oxygen flue gas + heat. Combustion can take place if the following conditions are fulfilled: - in the gas phase fuel and oxygen must be thoroughly mixed. The mixing ratio must be within the explosion limits; - the combustible mixture that meets this condition must be ignited. Initiating a combustion reaction requires ignition energy. The explosion limits determine the range within which the mixing ratio of fuel and oxygen must lie to obtain a combustible mixture. A mixture with a mixing ratio exceeding the upper explosion limit contains too much fuel and is called rich A mixture with a mixing ratio below the lower explosion limit too . contains too little fuel and is called lean too . The self-ignition temperature is the temperature at which a combustible mixture that is slowly heated spontaneously ignites. A flame is visible part of an exothermic reaction between fuel and oxygen the . The process that takes place within the flame area is characterised by: - the emission of (visible) light; - the prevalence of temperatures higher than 1100C; - the oxidation of carbon, hydrogen and sulphur to carbon dioxide (CO2), water (H2O) and sulphur dioxide (SO2); - the continuation of the initiated reaction. The flame speed is defined as the speed with which the flame front propagates. Depending on the rate of oxygen supply, the flame colour will vary from: - red/orange to yellow for liquid fuel; - yellow to blue for gaseous fuel. The adiabatic flame temperature is determined by the amount of heat released per kilogram of fuel and also by the amount and composition of the combustion products formed per kilogram of fuel. The theoretical air requirement is the amount of air per kilogram of fuel which contains just enough oxygen to burn all of the fuel. The calorific value of a fuel is defined as the amount of heat released in the combustion of one kilogram of fuel. The higher calorific value is the amount of heat actually released in a combustion.
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The lower calorific value indicates the fraction of the heat released that can actually be used. In addition to causing the above-mentioned air pollution (due to partially burnt fuel), such as hydrocarbons, soot and carbon monoxide, the flue gases can contain other noxious substances. The sulphur present in the oil is burnt to sulphur dioxide (SO2) and sulphur trioxide (SO3). Finally, the operation of a combustion plant is accompanied by the formation of nitrogen monoxide (NO) and nitrogen dioxide (NO2). Finally, various materials (sand, salts and heavy metals) leave the stack in the form of solid particles.
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Test
Exercises
Do not send in your answers for correction 1. What is the flame colour produced by a liquid fuel with a low carbon/hydrogen ratio? What is the air factor if it is given that the excess air is 4%? Give a rough indication of the air factor for a gaseous fuel and for a liquid one. How do you explain the difference between the lower calorific value and the higher calorific value? What substances leave the stack in the form of flyash? What is the meaning of SRF?
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5.
The element hydrogen has a higher calorific value than the element carbon. Hence, a lower C/H ratio means a higher calorific value. The carbon/hydrogen ratio is also one of the factors determining the colour of the flame. In general, a lower contribution of hydrogen gives a more clearly visible flame. In practice, combustion is always done with excess air. As ultimately, only the theoretical amount of oxygen is used, there will always be oxygen present in the flue gases. In addition to possibly causing the above-mentioned air pollution (due to partially burnt fuel), such as hydrocarbons, soot and carbon monoxide, the flue gases can contain other noxious substances. The sulphur present in the oil is burnt to sulphur dioxide (SO2) and sulphur trioxide (SO3). Further, the operation of a combustion plant is attended with the formation of nitrogen monoxide (NO) and nitrogen dioxide (NO2). Finally, various materials (sand, salts and heavy metals) leave the stack in the form of solid particles.
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