00.01.

50 - 010

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.

Contents of the lesson

1 2 3 What is combustion? Fuels Flue gases

The copyright in this material is vested in Shell Global Solutions International B.V., The Hague, The Netherlands and Shell Netherlands Raffinaderij B.V. All rights reserved. Neither the whole or any part of this document may be reproduced, stored in any retrieval system or transmitted in any form by any means (electronic, mechanical, reprographic, recording or otherwise) without the prior written consent of the copyright owner.

Process engineering / 00.01.50 - 010

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

1.1 Combustion conditions

Before combustion can take place a number of conditions must be fulfilled: - in the gas phase fuel and oxygen must be thoroughly mixed. The mixing ratio of fuel and oxygen must be within the explosion limits; - the combustible mixture that meets this condition must be ignited. Initiating a combustion reaction requires ignition energy. If only a small amount of heat is required, a spark from a sparkplug can suffice. However, if larger amounts of heat are required, because the fuel must first be evaporated, the use of a pilot flame is necessary. The explosion limits define the range within which the mixing ratio must lie to form a combustible mixture. A term used in this connection is the Upper Explosion Limit A mixture with a mixing ratio exceeding the Upper Explosion . Limit contains too much fuel and is called rich The too . Lower Explosion Limitcorresponds to the minimum amount of fuel in the mixture. A mixture with a mixing ratio below the lower limit contains too little fuel and is called lean too . As the atmospheric combustion in furnaces and boilers always uses air, the explosion limits are often indicated for a mixture of fuel and air. If a combustible mixture is introduced into a chamber and is gradually heated, it will ignite spontaneously at some given temperature. This temperature, which is dependent on the type of fuel, is called the self-ignition temperature. For natural gas, for instance, this temperature is about 595C. When combustion has started, the reaction can be maintained by continuously supplying fuel and oxygen (air). In this way a continuos combustion reaction can be maintained. The volume in which the reaction takes place is governed by several factors, including the amount of fuel to be burnt per unit time and the reaction rate.

- explosion limit - ignition energy

- Upper Explosion Limit (UEL) - Lower Explosion Limit (LEL)

- self-ignition temperature

Process engineering / 00.01.50 - 010

1.2 Flame properties

- flame 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. The flame speed is determined inter alia by the air/fuel ratio. The flame speed is very important in connection with the stabilisation of the flame. The colour of the flame is dependent, inter alia, on the carbon/hydrogen ratio. In general, a large contribution of hydrogen gives a less clearly visible flame. The colour of the flame is also dependent on the flame temperature. 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 fuels. 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. By adiabatic is meant that the combustion is considered without any exchange of heat with the environment. Since burning with pure oxygen produces less flue gas per kilogram of fuel than combustion with air, the adiabatic flame temperature will be considerably higher in the former case. Question 2 What processes are active in the flame? Question 3 Why is the adiabatic flame temperature higher if combustion takes place using pure oxygen?

- flame speed

- flame colour

- adiabatic flame temperature

1.3 Combustion air requirement

- theoretical air air requirement The theoretical air requirement is the amount of air per kilogram of fuel which contains just enough oxygen to burn all of the fuel. If we were to conduct combustion processes with the theoretical air requirement, the flue gas would not contain oxygen any more. In practice, it is impossible to burn the fuel at the theoretical air requirement. This is mainly because it is impossible to obtain an ideal mixture of fuel and air. If in spite of that, combustion would still be conducted at the theoretical air requirement, then the flue gases would contain (partially) burnt fuel (soot and carbon monoxide) (CO)). As a result, afterburning would take place at some other point in the plant, instead of in the furnace.

- afterburning

Process engineering / 00.01.50 - 010

- energy loss - environmental pollution

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?

- Standard Refinery Fuel (SRF)

- excess air - air factor (N)

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)

Process engineering / 00.01.50 - 010

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)

Process engineering / 00.01.50 - 010

5811-010-001-P

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?

Process engineering / 00.01.50 - 010

5811-010-002-P

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

= 2.75 kg CO2 per kg CH4

16 = 2.25 kg H2O per kg CH4

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.
7

Process engineering / 00.01.50 - 010

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.

Process engineering / 00.01.50 - 010

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.
9

Process engineering / 00.01.50 - 010

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.

10

Process engineering / 00.01.50 - 010

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?

2. 3.

4.

5. 6.

Answers to the questions in the lesson

1. Reactions in which heat is released are called exothermic reactions. Most combustion reactions are reactions in which heat is released. The process that takes place within the flame 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. As burning with pure oxygen produces less flue gas per kilogram of fuel than combustion with air, the adiabatic flame temperature is considerably higher in the former case. If combustion were to be conducted on a technical scale at the theoretical air requirement, then the flue gases would contain (partially) burnt fuel (soot and carbon monoxide) (CO)). A possible result would be afterburning at a point in the plant other than in the furnace. 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.

2.

3.

4.

11

Process engineering / 00.01.50 - 010

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.

6.

7.

Answers to the exercises

1. A liquid fuel with a low carbon/hydrogen ratio gives a clearly visible orange-yellow flame. At excess air of 4%, the air factor 1.04. The air factor for a gaseous fuel is roughly in the range N = 1.05 - 1.1. The full combustion of a liquid fuel, however, requires an air factor of N = 1.20 - 1.30. The difference between the lower calorific value and the higher calorific value 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. 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. Flue gases obtained from liquid fuels mostly contain an amount of flyash. This ash contains various substances, which are composed, for instance, of sand, salts and heavy metals. SRF means Standard Refinery Fuel; this is a liquid fuel of a fixed quality with regard to the combustion properties.

2. 3.

4.

5.

6.

12