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Fuels are all those substance which on combustion give large amount of heat. It contain carbon as main constituent. Combustion Reaction =
WOOD
Fuels are defined as Substance which Undergoes Combustion in the presence of air to produce a large amount of heat that can Be used Economically For industrial and Domestic PurPose. For e.g.: Wood, Coal; Kerosene, Petrol, Diesel, Natural gas (LPG), etc.
FUELS
Primary/Natural
Solid E.g. Wood, Caol Gaseous E.g. Natural gas
Secondary/Derived
Solid E.g. Charcoal Gaseous E.g. Coal gas
E.g. Petroleum
Liquid
High
Moderate velocity
of
combustion.
Product Low
Easy
Combustion Should
Controllable.
Fuels play an important role in our everyday life because they are used in homes, vehicles and industries for providing energy. Domestic Usage: Fuels like wood, coal, kerosene, cow dung etc are used domestically.
For Vehicles: Coal, diesel and petrol are used as fuel for road, sea and air transport in automobiles and locomotives. For industry: Fuels like coal and natural gas are used. For Air Space Centre: Specially prepared fuels like hydrazine (Rocket fuels) [NH2-NH2] are used.
Definition:
The number of units of heat evolved during complete combustion of unit weight of the fuel is called as calorific value. Calorific value can also defined as, the number of parts of water which gets heated through 1C by the heat evolved by the complete combustion of one unit weight fuel under the conditions such as: Whole of heat evolved is absorbed by water The product formed leave the system at atmospheric temperature & pressure.
From both the above definitions, it is clear that a fuel, to be most useful, must possess high calorific value because the heat evolved by combustion of definite weight of fuel is directly related/proportional to the calorific value of the fuel.
Definition:
Ignition temperature is defined as minimum temperature to which a substance must be heated before its burns spontaneously independent of the source of heat. E.g.: Ethanol has an ignition temperature of 425C/798F and flash point of 12C/54F. Each fuel should be brought above its Ignition Temperature for starting the combustion process. The minimum ignition temperature at atmospheric pressure for some substances are:
o o o o o
Carbon: 400C Gasoline: 260C Hydrogen: 580C Carbon monoxide: 610C Methane: 630C
The calorific value of solid fuels is expressed as British Thermal Units per Pound (B.T.U. per 1b) or Kilogram Centigram Unit per Kilogram (K.C.U. per kg.). A British Thermal Unit may defined as, the heat required to raise the temperature of one pound of water from 60F to 61F. Calorie, a unit of heat, may be defined as, the heat required to raise the temperature of one kilogram of water from 15C to 16C.
Taking both above definitions of these units, a correlation between them can be written as; 1 B.T.U = 2.252 k.cals = 252 cals 1 k.cal = 1000 cals 1 k.cal = 3.968 B.T.U. The calorific value can be also expressed as Centigrade Heat Unit (C.H.U.) which is the amount of heat required to raise temperature of 1 pound water through one degree centigrade. Thus, 1 k.cal = 2.2 C.H.U = 3.968 B.T.U. Also 1 k.cal/kg = 1.8 BTU/1b 1 k.cal/m3 = 0.1077 BTU/ft3 1 BTU/ft3 = 9.3 k.cals/m3
High Calorific Value is defined as the total amount of heat produced when one unit of the fuel has been burnt completely and the products of combustion have been cooled to 16C or 60F. Low Calorific Value is defined as the net heat produced when unit mass or volume of fuel is completely burnt and products of combustion are allowed to escape into the atmosphere.
The calorific value of fuels is determined theoretically by Dulong formula or I.A. Davies formula.
According to Dulong, the calorific value of a fuel is the sum of the calorific values of all the elements present . The calorific values of different elements are given as under:
Calorific Value of C = 8080 cal/g Calorific Value of H = 34500 cal/g Calorific Value of S = 2240 cal/g Thus, Dulongs Formula is given as: H.C.V. (G.C.V.) = 1/100 [8080C + 34500 (H O/8) + 2240S] where C, H, O & S are the % of C, H, O & S respectively. In this formula, oxygen is assumed to be present in combination with hydrogen as water; and: L.C.V. (N.C.V.) = H.C.V. 0.09H X 587
The solid fuels are available in nature (primary fuels) and also prepared artificially know as (secondary fuels). The common natural solid fuels are wood, peat, lignite coal. The artificial solid fuels are charcoal, coal, briquettes. The other industrial fuels are fossil coals, oil shales, furnace slags, peat, boiler slags, anthracite etc. Coal is a combustible solid fuel. By and large, all the solid fuels are formed in nature from cellulose, lignin, proteins, resins, fats and waxes. and
All these raw materials, which are formed under the earth y the burials of partially decomposed vegetation, undergo fermentation liberating CH4, CO2 and H2 gas and form peat, which is slowly converted into lignite and then by further pressure and heat, anthracite is formed.
A) Banded Coals
This type of coal is a variety of bituminous or sub-bituminous coal. These are generally formed from peat. The structure of this type contains layers or bands of coal forming materials.
B) Splint Coals
This is also variety of bituminous of sub-bituminous coal, with dull lustre and greyish-black colour. The bands of different coal forming materials are more irregular in this variety, as a result it breaks with irregular rough fracture. There is no swelling on burning, but burns freely.
C) Cannal coals
A variety of bituminous or sub-bituminous coal with compact fine grained texture instead of bands. The colour varies from dark grey to black; possesses high volatile matter, non-coking type, ignites easily and burns with luminous smoky flame.
D) Bog-head coals
A variety of bituminous or sub-bituminous coal similar to Cannel coal in appearance as well as combustibility, but posses high content of volatile matter and algal remains. When subjected to distillation it gives high yield of tar and oil.
With minimum 92-98% fixed carbon and maximum 2-8% volatile matter. 87-91% fixed carbon, 9-13% volatile matter. 86% fixed carbon, 14% volatile matter.
Low rack coals are graded further on the basis of their moist B.T.U., indicating natural moisture
Coal :
A mined sample of coal contains the coal substance, intermixed with mineral constituents such as kaolin, shale, chloride, sulphides, etc. The major constituents of coal are carbon, hydrogen and oxygen. The properties of coal depend upon these constituents. There are hundreds of varieties of coal, depending upon its origin and chemical constituents of coal. The important types of coal are peat, lignite, bituminous and anthracite. The conversion of wood into coal takes place progressively. Depending upon extent of transformation, coals are divided into 4 types (or grades or ranks):
Increase in - Carbon percentage, calorific value, density, lustre, hardness, black colour intensity. Decrease in - Moisture, volatile matter, % of N, H, O, S & Ash.
Peat is brown and fibrous in texture. Freshly mined out peat contains large quantity of water as it is found in water logged areas. Air dried peat contains 15-25% moisture and it crumbles into powder during air drying. Calorific value of peat is about 5400 cal/gm. It has low density. It contains 57% C, 6% H, 35% O & 3-6% ash.
Uses
Peat type of coal gets powdered during combustion, therefore it is used after briquetting, as domestic and industrial fuel. It is used for soil conditioning. It can be used for steam raising, thermal insulation, packing, gas purification and some times for power generation.
It is intermediate stage between peat and black coal. It is brownish black and more compact than peat. It contains 45-50% volatile matter and burns with long flame. It has Calorific value of 6000-6700 cal/gm. It cantains 65-70% C, 5% H, 20% O & 10-15% ash.
Uses
After briquetting it is used as domestic and industrial fuel. Lignite is used for making ' producer gas It can be used for power generation.
These coal burns with smoky yellow flame and are dark grey to black. They contains 7090% C and therefore they are classified as:
A)
Sub-bituminous coal:
This coal has characters between lignite and bituminous coal. It is harder and denser than lignite. It is grey black and has dull waxy lustre. It contains 70-75% C and large volatile matter upto 35-40%. It has Calorific value of 7000 cal/gm. It is non-caking coal.
Uses
B)Bituminous coal:
This coal has banded or laminated structure with alternate bright and dull layers. It has cubical fracture. It is black, dense and hard. It contains 75-80% carbon. It has Calorific value of 8000-8500 cal/gm.
Uses
It is used most widely for domestic and industrial purposes. It is used for steam generation and power generation.
C)
Semi-bituminous coal:
It has characteristics between bituminous and anthracite. It has low volatile matter and 75-85% C. It has low caking property. It has Calorific value of 8400 cal/gm.
Uses
Making of coke, high temperature heatings, coal gas for tar and chemicals.
This is highest rank or grade of coal. It has calorific value about 8700 cal/gm. It has 92-98% C. It contains very low volatile matter, ash and moisture. It is highly lustrous, black and hard coal.
Being costly coal, it is used for specific industrial purposes. It is used as metallurgical fuel. It is used for making electrodes. It is used for high temperature heating.
Uses
The liquid fuels are generally the products obtained from petroleum refining.
The main constituents of crude or raw petroleum are paraffin, naphthalene and aromatic hydrocarbons. The concentration of all there vary. The characteristic features of the liquid fuels are,
a) Liquid fuels possess low flash and fire point. b) The calorific value of liquid fuels is generally very high. c) The viscosity of liquid fuel is very low at ordinary temperature. d) The moisture and sulphur content of liquid fuels is low.
Petroleum or crude oil is the main source of almost all liquid fuels used now and a large number of petrochemicals such as plastics, rubbers, fibres, organic chemicals, hydrogen etc. can be manufactured from crude oil fraction. It has negligible percentage of ash and moisture and has minute quality of Sulphur. It has very high calorific value such as 40,000 kJ/kg.
Origin of petroleum
As per modern theory, petroleum is formed from buried debris of plants and animals (organic matter), under favorable condition. The burial of the organic matter during volcano, upheavals in earth surface should take place along with large quantity of water and under a dome of hard, impervious rock. The anaerobic bacteria, higher temperature and radioactive substances enables degradation of organic matter, in the presence of water, under the dome, to form highly alkane rich matter as crude oil. The anaerobic bacteria take out oxygen atoms from cellulose, protein, oil molecules and forms alkane rich crude oil. For example:
Petroleum, commonly known as rock oil or mineral oil, is obtained from nature, under the earth, in the form of deeply coloured highly viscous liquid. It contains a large number of different individual chemicals ranging from methane to asphalt.
Average elemental composition of crude petroleum is: C = 80 to 87% H = 11 to 15% S = 0.1 to 3% O = 0.1 to 0.9% N = 0.4 to 0.9%
Open chain alkanes: Both straight chain and branched chain alkanes are present in crude oil.
Cycloalkanes: Crude oil contains cycloalkanes like cyclopentane, cyclohexane and their alkyl substituted products.
Aromatics: In all the crude oil benzene and alkyl substituted benzenes are upto 2%. Asphaltenes: All the crude oils contain the small amount of polycondensed aromatic solids as colloidal dispersion in crude oil.
Resins: These are the polymeric substances. They are gummy and are lower molecular weight polymers.
Petroleum gets formed collected under the earth. The depth of such a storage of petroleum varies from few hundreds to few thousands of feet below the surface of the earth. It is surrounded by layers of natural gas, under the earth. In short, the crude petroleum thus formed floats upon a layer of salt water and is surrounded by layer of natural gas, deep below the impervious rock. Mining of oil is done by drilling holes in earths crust and sinking pipe up to the oil bearing rocks.
Due to the hydrostatic pressure exerted by natural gas, surrounding to the stock of petroleum helps to get petroleum piped out with pressure.
Crude oil coming from the petroleum wells consists of a viscous, dark coloured frothing mixture of solid, liquid and gaseous hydrocarbons containing sand and water in suspension. In order to make it into a marketable product, the oil is made free from impurities like water, dissolved salts, sulphur etc.
The process by which petroleum is made free from impurities and separated into various useful fraction having different boiling points and further treated to remove undesirable tendencies and to impart specific properties to them is broadly called REFINING OF PETROLIUM.
The crude oil from the oil well is an extremely stable emulsion of oil and salt water. The process of removing oil from water consists in allowing the crude to flow between two highly charged electrodes. The colloidal water droplets aggregates to form large drop, which separate out from the oil. To remove the persistent impurities, colour etc., various fractions are passed over adsorbents like Kieselgure clay etc. and the resultant oils are generally pure. (2) REMOVAL OF HARMFUL IMPURITIES
NaCl and MgCl2 can corrode the refining equipment and can cause scale formation in the heating pips. Hence special care should be taken to remove them. Modern techniques of electrical desalting and dehydration are developed for this purpose. Then oil is treated with copper-oxide. The reaction occurs with sulphur compound, which result in the formation of copper sulphide (a solid), which is then removed by filtration.
(3)
FRACTIONAL DISTILLATION
Fractional distillation is a combination of distillation and rectification. Rectification process consists of counter flow contacting of the vapour formed in distillation with the liquid obtained by condensation of vapuor. For effective rectification in distillation column, it is essential to see that an ascending flow of vapour (formed due to the heat supplied at the bottom section) meets the descending flow of liquid (formed due to cold spraying in the top section). These principles are used in the FRACTIONTING TOWER widely used in petroleum refining. Fractionating Tower (in figure) consists of a pipe still and bubble tower. In pipe still the crude petroleum is heated and is fractionated in bubble tower.
Bubble tower consists of horizontal stainless steel trays or plates at short distances. Each tray is provided with a small chimney covered with loose cap though which vapour rises up. These small chimneys are covered with loose bubble caps. Crude oil is piped through a pipe still where it is heated to about 400*C and the vapours are the introduced near the bottom of the bubble tower. As the vapour move upwards, the 3 higher boiling fractions condense at lower plats and only the lower boiling fractions move to higher plates. The vapour are allowed to pass up through higher plates via bubble caps. The heavier component having high boiling fraction condense and the condensate flows down to the next lower tray through the down comers. The vapour which condenses give out the latent heat of condensation to the liquid in the tray, from which more volatile components moves up the column. This process of condensation and vapourization takes place many time causing separation of the fractions according to their boiling points. Thus higher boiling fractions condense at the lower parts of the column and lower boiling fractions condense at the higher parts of the column. Thus the crude oil is fractionated into different fractions depending on their boiling ranges and are collected at different heights in the column. In this way mixture of vapours and liquids of different boiling points are separated. This fractionation gives uncondensed gases, gasoline, kerosene and gas oil fraction.
Fractionating tower
Cracking is a process of converting heavy oil with higher molecular weight hydrocarbons to the oil with lower molecular weight hydrocarbon which is known as gasoline.
Thus, heavy oil is heated at a high temperature under pressure or in the presence of catalyst to obtain gasoline.
For example: C10H22 (Decane) C5H12 n-Pentane + C5H10 Pentene
Thermal cracking
Catalytic cracking
liquid phase or
vapour phase
Fixed bed
Moving bed
By this method, any type of oil can be cracked. In this method, the oil is pumped into the coil kept at 420C-550C under a pressure of 15-100 kg/cm2. As the temperature increases, a better quality of gasoline is produced. The octane value of this gasoline is low, i.e. 6570. Therefore, it is mixed with higher octane value gasoline and then used I engine.
Vapour phase thermal cracking:
In this method, the heavy oil is heated in the heater at 400C to convert it into the vapours and then these vapous are passed to the reaction chamber which is maintained at 600C-650C and under a pressure of 10-20 kg/cm2. At this stage, the higher hydrocarbons are converted into lower hydrocarbons easily and the octane value to petrol is usually 75-80.
Catalytic Cracking
Fixed bed catalytic cracking:
In this method, vapours of the heavy oil are heated in the presence of catalyst due to which a better yield of petrol is obtained.
In this method, heavy oil is vaporised by heating in an electrical heater. Then the vapours are passed over a series of trays containing catalyst. Generally, the catalyst used are crystalline alumina-silicate, bentonite, bauxite and zeolites. The reaction chamber is maintained at 425C-540C and under a pressure of 1.5 kg/cm2. The cracked gases are taken out from the top of the reaction chamber (cracker) and allowed to pass into fractionating tower, where gasoline fraction is collected. The octane value of this gasoline is about 80-85. During the cracking, free carbon is also formed which deposits on catalyst, then the flow of vapours of heavy oil is passed over the second set of reaction chamber and the catalyst is earlier chamber is regenerated by burning the carbon deposits with the help of air and reused.
Process:
In this method, a mixture of heavy oil and catalyst is heated in the still to convert the heavy oil into vapours. There vapours along with hot catalyst are brought to the cracker. The cracker is maintained at a temperature of 550-570C and atmospheric pressure. In the cracker, the vapours of the heavy oil and hot catalyst come in intimate contact with each other and the breaking of higher molecular weight hydrocarbons into lower hydrocarbon (Gasoline) takes place. The low boiling hydrocarbons move up to the top of the cracker are passed through the cyclone separator while the catalyst remains in the cracker. These cracked gases are further passed through the fractionating column to have three major fractions: Gasoline, middle oil & heavy oil. The gasoline is further cooled and purified to remove the impurities of sulphur, unsaturated hydrocarbons and colouring matter, if present. The catalyst performs two functions: (1) To get a better quality gasoline during cracking process & (2) to carry heat during process.
2
3
Pressure
Octane value
1.5 kg/cm2
80-85
Around 1 kg/cm2
85-90
and pressure.
The cracking is specific in nature and can give proper quality of gasoline.
4 5
6
7
Chemical nature:
Chemically biodiesel is the methyl esters of long chain carboxylic acids. Biodiesel is obtained by transesterification of vegetable oil or animal fat with methyl alcohol using sodium metal or sodium methoxide, as catalyst .
Transesterificaion
Transesterificaion is the process of converting one ester to another ester. A molecule of oil or fat is the trimester of glycerol and three molecules of long chain carboxylic acids. This triester is converted into methyl ester of the fatty acids by the following reaction: Vegetable oil/Animal fat
1. 2.
Filter the cheap or waste vegetable oil/fat. Heat it at 110C with stirring to remove any water from it.
3.
Prepare sodium methoxide from sodium metal and methanol. Add the sodium
methoxide about 2% by weight to the vegetable oil or fat. Add methanol about 20% stirring for 30 minutes. Cool and mix sufficient water, stir well. The glycerol and soap dissolve in water phase. Separate the water insoluble phase (biodiesel) from water phase. Add antioxidant to the biodiesel to avoid it to become gummy due to oxidation and polymerization. Biodiesel can be obtained from various vegetable oils like soyabeen oil, palm oil, groundnut oil , cottonseed oil, mustard oil, sunflower oil etc.
4. 5.
6. 7.
8.
Biodiesel can be used as good fuel for diesel engines but generally it is used as its 20% mixture with diesel. Biodiesel is cheaper. It has high cetane numbers 46 to 54 and high C.V. of about 40kJ/gm. It is regenerative and environment friendly. It does not give out particulate and CO pollutants. It has certain extent of lubricity. It is clean to use biodiesel in diesel engines.
A propellant is a chemical which is used in the production of energy and pressurized gas that is used to create movement of a fluid or to generate propulsion of a vehicle or projectile or other object. In rockets and aircraft, propellants are used to produce a gas that can be directed through a nozzle, thereby producing thrust. In rockets, rocket propellant produces an exhaust and the exhausted material is usually expelled under pressure through a nozzle. The pressure may be from a compressed gas, or a gas produced by a chemical reaction. The exhaust material may be a gas, liquid, plasma, or, before the chemical reaction, a solid or liquid.
In this method of propulsion techniques, propellants used are basically chemicals, which produces high amount of energy on burning. Depending upon the physical state of the propellant used, they can be classified as: Propulsion using solid propellants: - Here solid propellants (see solid propellants) are used to propel the rocket When the solid fuel is ignited, it burns along the walls of the combustion chamber. As discussed earlier, solid fuels have perforation. This is to increase the surface area and eventually to increase the thrust produced by the rocket. As the combustion proceeds, the perforation shape changes into a circle. This provides high thrust initially and thrust lowers during the middle of the flight.
Types of Propellant
Solid Propellants Liquid Propellants Hybrid Propellants
Any solid propellant consists of two parts: An oxidizer A fuel or a reducer. In solid propellants, the fuel and oxidizer components are prepared separately and are then mixed together. This is because the oxidizer is in powder form and the fuel is a fluid of varying consistency. They are then blended together and poured into the rocket case under carefully controlled conditions. In addition to fuel and oxidizer, some other compounds are added to increase the efficiency of the propellants.
The oxidizer is ammonium per chlorate (NH4ClO4) (69.93 %). The fuel is a form of powdered aluminum (16 %).
SOLID PROPELLANTS
Homogeneous Solid Propellants
Liquid propellants are nothing but rocket propulsion fuels in liquid state.
Liquid propellants used in launch vehicles can be classified into: Petroleum Cryogenic propellants Hypergolic propellants
In a cryogenic propellant the fuel and the oxidizer are in the form of very cold, liquefied gases. These liquefied gases are referred to as super cooled as they stay in liquid form even though they are at a temperature lower than the freezing point. Thus we can say that super cooled gases used as liquid fuels are called cryogenic fuels. These propellants are gases at normal atmospheric conditions. But to store these propellants aboard a rocket is a very difficult task as they have very low densities. Hence extremely huge tanks will be required to store the propellants. Thus by cooling and compressing them into liquids, we can vastly increase their density and make it possible to store them in large quantities in smaller tanks. Normally the propellant combination used is that of liquid oxygen and liquid hydrogen, Liquid oxygen being the oxidizer and liquid hydrogen being the fuel. Liquid oxygen boils at 297oF and liquid hydrogen boils at 423oF.
Hybrid propellants are those propellants, which are a mixture of solid and liquid propellants. In these propellants, one of the two components (oxidizer and fuel) is solid (usually fuel) whereas the other is liquid (usually oxidizer). In a hybrid propellant rocket engine, the liquid part is injected into the solid part. Thus the storage chamber of the solid part acts as the combustion chamber. In a hybrid rocket the oxidizer flows down the perforation (see solid propellants) (This is not a part of the site tour) in the solid fuel grain and reacts with the solid fuel. This produces the hot exhaust gases required to produce thrust. This process can be seen in the following image: In many hybrid motor designs, the oxidizer is pressurized liquefied nitrous oxide (N2O) while the fuel is cellulose (C6H10O5 ).