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ENGINEERING CHEMISTRY

Unit 1 General Aspects of Fuel: Organic fuels, Origin, classification and general aspects of fossil fuels. Solid fuels, Coal, carbonization of coal, manufacturing of coke by Beehive oven and by product oven method. Liquid fuels, Composition of petroleum, advantages and refining of petroleum. Cracking, reforming, polymerization and isomerization of refinery products. Synthetic petrol, Bergius and Fischer Tropsch process. Knocking, octane number and anti-knocking agents. Gaseous fuels, Advantages, manufacturing, composition and calorific value of coal, gas and oil gas. General Aspects of Fuel: Any matter which is burnt to produce heat energy is known as a fuel.
Wood, coal, domestic gas (LPG), kerosene, diesel and petrol are used as fuels. Fuels are used in homes, industries and transportation. Most of the fuels are carbon and hydrogen compounds. So, when a fuel is burnt, it combines with the oxygen of air to form carbon dioxide and water vapours.

Calorific Value of a Fuel All the fuels produce heat on burning. Some fuels produce more heat, whereas others produce less heat. The usefulness of a fuel is measured in terms of its calorific value. The higher the calorific value, the better the fuel will be. The calorific value indicates the amount of heat a fuel liberates when it is burnt. The amount of heat produced by burning one gram of a fuel completely is known as its calorific value. It is usually expressed in kilo joules per gram (kJ/g). Characteristics of a Good Fuel: A good fuel should have the following characteristics : It should have a high calorific value. It should not produce any harmful products like soot and poisonous gases on burning. It should cause minimum pollution of air. It should be cheap and readily available. It should be easy to store, transport and handle. It should have a low kindling temperature.

Gaseous fuels are excellent fuels as they satisfy most of the requirements of a good fuel.

Types of Fuels There are three types of fuels classified on the basis of their physical state: 1) Solid Fuels: Wood, charcoal, coal , coke paraffin and tallow are some of the commonly used solid fuels. Solid fuels require much space for storage and emit smoke and ash on burning.A Very important solid fuel is Coal.

2) Liquid Fuels Most of the liquid fuels are obtained from petroleum. Petrol, kerosene, diesel, fuel oil, benzene, alcohol, are some of the most common used liquid fuels. They require less storage space than solid fuels and leave no residue when burnt.A very important liquid fuel is Petroleum.

Diesel. 3) Gaseous Fuels: Gaseous fuels are used for domestic as well as industrial purposes. Some important gaseous fuels are: (i) Natural Gas:Natural gas is obtained from petroleum wells, and mainly contains methane and small quantities of ethane and propane. It is the cheapest available gaseous fuel.

(ii)

(ii) Biogas:Biogas is a mixture of methane, carbon dioxide, hydrogen and hydrogen sulphide. The major constituent of biogas is methane. It is produced by degradation of plants and animal wastes.

(iii) Water Gas:Water gas is mainly a mixture of hydrogen and carbon monoxide. It is prepared by passing steam over red hot coke. (iii) Coal Gas:Coal gas is a mixture of methane, hydrogen and carbon monoxide. It is obtained by the destructive distillation of coal.

Biogas Generator Q 1. What are the advantages and disadvantages of solid,liquid,gaseous fuels? Ans 1. Solid is not very useful because of the difficulties of moving it from the storage tank to the combustion chamber. Power plants that burn coal crush it to a powder first, as that can be pumped and handled almost like a liquid. Late model steam locomotives used the powder or used coal in small pieces and transported it via a screw conveyer. Gas is not that useful either, as you have to compress it or liquify it to store any significant amount of fuel, and then the storage for compressed gas becomes very heavy, or the storage for liquified gas becomes power intensive to keep it liquid. Liquid has the advantage of being easy to store and easy to move and pump and inject into the combustion chambers.

Organic fuels: Organic fuel is a fuel extracted or produced form organic matter and is also knwon as
bio diesel.

(1)

Typical organic triglyceride with three hydrocarbon chains

(2)

Typical carboxylic acid group terminating an organic hydrocarbon chain, to form a fatty acid. (3) the case of burning bio-diesel would be as follows :-

Fossil fuels: Fossil fuels are fuels formed by natural processes such as anaerobic decomposition of buried dead organisms.Coal, oil and gas are called "fossil fuels" because they have been formed from the organic remains of prehistoric plants and animals.

They range from volatile materials with low carbon:hydrogen ratios like methane, to liquid petroleum to nonvolatile materials composed of almost pure carbon, like anthracite coal. Fossil fuels are non-renewable resources.

Coal, one of the fossil fuels. Disadvantages : (1)Basically, the main drawback of fossil fuels is pollution. Burning any fossil fuel produces carbon dioxide, which contributes to the "greenhouse effect", warming the Earth. (2)Burning coal produces more carbon dioxide than burning oil or gas. It also produces sulphur dioxide, a gas that contributes to acid rain. We can reduce this before releasing the waste gases into the atmosphere. (3)Coal-fired power stations need huge amounts of fuel, which means train-loads of coal almost constantly. Coal: coal is a fossil fuel produced from vegetable matter under high temperature and pressure condition over millions of year .it is chiefly comaposed of C,H,O and non-combustible inorganic substance. These deposits lose moisture and volatile matter due to gradual decomposition process in absence of oxygen .final coal formation takes place about a light year.

Q.What is the advantage and disadvantage of Liquid and Gaseous Fuels over Solid Fuels? Ans. Liquid and gaseous fuels are considered better fuels than the solid fuels because of the following reasons: 1. Liquid and gaseous fuels are easier to handle than solid fuels. 2. Liquid and gaseous fuels can be transported easily through pipelines whereas solid fuels cannot be transports in this way. 3. Liquid and gaseous fuels do not leave any residue after burning. 4. Liquid and gaseous fuels have higher calorific values than the solid fuels. In other words, for a given mass of the fuel, liquid and gaseous fuels produce more heat. 5. Liquid and gaseous fuels produce little or no smoke, whereas most of the solid fuels burn with smoke. 6. Liquid and gaseous fuels have relatively low ignition temperature and hence they burn more easily than solid fuels. Disadvantages of Gaseous Fuels 1. Very large storage tanks are needed for storing gaseous fuels. 2. They are highly inflammable, so chances of fire hazards are high in their use. 3. They are more costly than solid or liquid fuels. 4. It cannot be used in IC engine.

Classification and Rank of Coal:The degree of 'metamorphisrn' or coalification


undergone by a coal, as it matures from peat to anthracite, has an important bearing on its physical and chemical properties, and is referred to as the 'rank' of the coal.

ayered between other sedimentary rocks, coal is found in seams ranging from less than a millimetre in thickness to many metres. Coal is composed mainly of carbon (50-98%), hydrogen (3-13%) and oxygen, and smaller amounts of nitrogen, sulphur and other elements. It also contains a little water and grains of inorganic matter that remain as a residue known as ash when coal is burnt. Low rank coals, such as lignite and sub-bituminous coals, are typically softer, friable materials with a dull, earthy appearance; they are characterised by high moisture levels and a low carbon content, and hence a low energy content. Higher rank coals are typically harder and stronger and often have a black vitreous lustre. Increasing rank is accompanied by a rise in the carbon and energy contents and a decrease in the moisture content of the coal. Anthracite is at the top of the rank scale and has a correspondingly higher carbon and energy content and a lower level of moisture. Coal Types Geologists also classify coal types according to the organic debris, called macerals, from which the coal is formed. Macerals are identified (microscopically) by reflected light - the reflective or translucent properties of the coal indicating the individual component macerals and the way they have combined to form the coal. Bituminous coals are dense black solids, frequently containing bands with a brilliant lustre. The carbon content of these coals ranges from 78 to 91 percent and the water content from 1.5 to 7 percent.Sub-bituminous coals usually appear dull black and waxy. They have a carbon content between 71 and 77 percent and a moisture content of up to 10 percent and are used for electricity generation or can be converted to liquid and gaseous fuels. Brown coals, found in Australia in Victoria's Latrobe Valley, are used for power generation but generally are uneconomic to transport because of their high moisture content. These coals are also susceptible to spontaneous combustion. COMPARISON OF COAL AND COKE: COAL: (1) (2) (3) (4) COKE: (1) Stronger and porous. (2) Sulpher is eliminarted during coking. Less stronger and low porosity. Sulphur is present. It has more volatile matter and burns with long flame. USED IN REVERBERATORY FURNACE.

(3) Coke burns with short flame since it has low volatile matter. (4) Used in metallurgical process. CARBONIZATION PROCESS: Carbonization or carbonisation is the term for the conversion of an organic substance into carbon.When coal is heated strongly in absence of air,it forms a strong ,porous,dense and coherent mass known as cake. This process ofconversion of coal into coke is called carbonization. There are two types of carbonization:

Low temp.
carbonization

High temp. carbonization

Carried out at 500-700'c caloific value-65009500 cal/gm.


MANUFACTURE OF METALLURGICAL COKE: (1) Beehive coke oven process. (2) Otto- Hoffmanns by product coke oven process.

Carried out at 9001000'c caloific value-55006000 cal/gm

(1) Beehive coke oven process: Beehive coke ovens were called that because they were built earth soil and then covered with earth.90% of Colombian coke is made in beehive ovens. Beehive oven: A fire brick chamber shaped like a dome is used. It is 4 m wide and 2.5 m high. The roof has a hole for charging the coal from the top. The discharging hole is provided in the circumference of the lower part of the wall. Number of ovens is built in a row with common walls between neighboring ovens. Coal is introduced from the top and produces an even layer about 60-90 cm deep (fig.4). Air is supplied initially to ignite the coal. Carbonization starts and

Beehive oven: Volatile matter burns inside the partially closed side door. Carbonization proceeds from top to bottom and is completed in 2-3 days. Heat is supplied by burning of volatile matter and hence no by-products recovered. The exhaust gases are allowed to escape to the atmosphere. The hot coke is quenched with water and discharged, manually through the side door. The walls and roof retain enough heat to initiate, carbonization of the next charge. The yield of coke is about 80%. Disadvantage of beehive coke oven: (1) The by products are not recovered and allowed to escape. (2) Lower amount of coke is produced. (3) Process is not flexible and takes more time. (4) The exhaust gases produse pollution. (5) No recovery of by-products (6) Lower coke yield due to partial combustion (7) Lack of flexibility in operation

Otto- Hoffmanns by product coke oven process:


Construction: A number of narrow rectangular chambers made of silica bricks 12-14 m in length, 4-5 m in height,
0.5 m width ire used. It is tightly closed so that no air can enter. Each chamber at the top has three holes for charging coal, a gas take off and refractory lined cast iron door for discharging the coke. The carbonization chambers are erected side by side with vertical flues or interspaced for combustion in between them. 10-100 ovens are set together. One oven is capable of holding 16-24 tones of coal.

Working Coal is charged into the chamber and closed tightly at both ends. The oven is heated to 1200C by burning gaseous fuel (coke oven gas). Waste gases produced during combustion (flue gases) passed through regenerator and then let off through a chimney to the atmosphere. The flue gases pass their sensible heat to the checker brick work until the temperature rises to 1000C. Time taken is about 11-18 hours. After completion, the red hot coke is pushed out by a ram which is electrically driven. The yield is about 75%. Quenching is done by spraying water (wet) and inert gases from boilers (dry). Dry quenching is advantageous because the coke obtained is strong and dense. Also wet quenching the sensible heat of coke is lost whereas in dry quenching the inert gases are circulated to boilers where they preheat the boiler feed water and then recalculated for cooling fresh charge of coke.

1.14; liquid fuels: (1) PETROLEUM: Petroleum (L. petroleum, from Greek: petra (rock) + Latin: oleum (oil)) or crude oil is a
naturally occurring flammable liquid consisting of a complex mixture of hydrocarbons of various molecular weights and other liquid organic compounds. petroleum includes only crude oil, but in common usage it includes all liquid, gaseous, and solid (e.g., paraffin) hydrocarbons. Under surface pressure and temperature conditions, lighter hydrocarbons methane, ethane, propane and butane occur as gases, while pentane and heavier ones are in the form of liquids or solids.

Composition by weight: Element Carbon Hydrogen Nitrogen Oxygen Sulfur Metals Percent range 83 to 87% 10 to 14% 0.1 to 2% 0.05 to 1.5% 0.05 to 6.0% < 0.1%

1.14.3REFINING OF CRUDE OIL: The refining of petroleum is done in big refineries. Washing it with acidic or basic solution first neutralizes crude oil. A furnace is used to heat up the crude oil to 650 - 675 K and then the pressure reduced. The resulting crude oil vapors are fed into a fractionating column through an inlet near the bottom of the furnace.

Fig: 1.4 - Fractional distillation of crude oil

The fractionating tower is a tall cylindrical steel structure divided into compartments by horizontal trays fitted into it. Each tray has a number of holes and a short tube with a bubble cap. Due to a regular temperature gradient along the height of the column, the fractions with lower boiling points rise up and get liquefied at different heights in the trays, depending on the boiling. These caps allow the lighter vapors to escape up the column while the progressively less volatile and heavier fraction condense and flow into the respective trays (through tray holes and overflow) in the lower section of the tower. They can then be tapped out. The major products obtained from the fractional distillation of crude oil are listed below. Gasoline obtained by this procedure is called straight run gasoline.

Cracking: The process of breaking higher hydrocarbons with high boiling points into a
variety of lower hydrocarbons that are more volatile (low boiling), is called cracking (or pyrolysis). For example, a higher hydrocarbon C10H22 splits according to the reaction. C10H22 C8H18 + C2H4

higher hydrocarbon lower hydrocarbons The process of cracking, increases the relative amounts of the lower hydrocarbons. During cracking, carbon-carbon bonds get broken in a random manner, leading to various kinds of products being formed. Types of Cracking (1)Thermal Cracking Breaking down large molecules by heating at high temperature and pressure is termed as thermal cracking. Thermal cracking is further classified into the following classes: Liquid phase thermal cracking process: The higher boiling fractions e.g., fuel oil, lubricating oil are converted into low boiling fractions by heating the liquids at a temperature of 750 K, under a pressure of about 10 atmosphere. Vapor phase thermal cracking process: Low boiling fraction e.g., kerosene is cracked in the vapor phase at a temperature of about 875 K and under a pressure of 3 atmosphere.

Catalytic Cracking:Higher hydrocarbons can also be cracked at lower temperature (600 650 K) and lower pressure (2 atm) in the presence of a suitable catalyst. Catalytic cracking produces gasoline of higher octane number and therefore this method is used for obtaining better quality gasoline. A typical catalyst used for this purpose is a mixture of silica (SiO2), 4 parts; alumina (Al2O3), 1 part, and manganese-dioxide (MnO2), 1 part

Two mathed used for catalytic cracking: 1. Fixed bed catalytic cracking 2. Moving bed catalytic cracking Steam Cracking:Here, higher hydrocarbons are mixed with steam in their vapor phase and heated for a short duration to about 900C, and cooled rapidly. This process is suitable for obtaining lower unsaturated hydrocarbons. SYNTHETIC PETROL Petrol or gasoline can be synthesized by following three methods: 1. Polymerisation 2. Fischer- Tropsch method 3. Bergius process

Polymerisation: In this method,smaller molecules of hydrocarbons are combined to form heavier molecule resembling gasoline.

Fischer- Tropsch method: The FischerTropsch process, or FischerTropsch synthesis, is a collection of chemical reactions that converts a mixture of carbon monoxide and hydrogen into liquid hydrocarbons. (2n+1) H2 + n CO CnH(2n+2) + n H2O where 'n' is a positive integer.

Bergius process: This process is used to convert low grade coals suvh as bituminous coal and lignites into liquid and gaseous fuel by hydrogenating them in presence of catalyst .

REFORMING: It is a process in which structural modifications are done in the molecules to improve the anti -knocking characteristics. These are two types: Thermal reforming: In a thermal reforming process is heated to 510-595C (950-1100F) in a furnace, much the same as a cracking furnace, with pressures from 400 to 1000 psi (2758 to 6895 kPa). The products of thermal reforming are gases, gasoline, and residual oil or tar, the latter being formed in very small amounts (about 1%). The amount and quality of gasoline, known as reformate, is very dependent on the temperature. As a rule, the higher the reforming temperature, the higher the octane number. thermal reforming, catalytic reforming converts low-octane gasoline into high-octane gasoline (reformate)

Catalytic reforming: Catalytic reforming usually is carried out by 450-520C (840-965F), and then
passed through fixed-bed catalytic reactors at hydrogen pressures of 100-1000 psi (689-6895 kPa).

The four major catalytic reforming reactions are: 1: The dehydrogenation of naphthenes to convert them into aromatics as exemplified in the conversion methylcyclohexane (a naphthene) to toluene (an aromatic), as shown below:

2: The isomerization of normal paraffins to isoparaffins as exemplified in the conversion of normal octane to 2,5-Dimethylhexane (an isoparaffin), as shown below:

3: The dehydrogenation and aromatization of paraffins to aromatics (commonly called dehydrocyclization) as exemplified in the conversion of normal heptane to toluene, as shown below:

4: The hydrocracking of paraffins into smaller molecules as exemplified by the cracking of normal heptane into isopentane and ethane, as shown below:

KNOCKING AND OCTANE NUMBER: Knocking is a sharp metallic sound produced in the internal combustion engine. Knocking is caused by the low octane number of gasoline. The metallic sound during working of an internal combustion engine is termed as knocking. The greater the compression greater will be efficiency of engine. The fuel which has minimum knocking property is always preferred.

The tendency to knock falls off in the following order : Straight chain alkanes > branched chain alkanes > olefins > cyclo alkanes > aromatic hydrocarbons.

OCTANE NUMBER:It is used for measuring the knocking character of fuel used in petrol engine. The octane number of a given sample may be defined as the percentage by volume of iso-octane present in a mixture of iso-octane and n-heptane which has the same knocking performance as the fuel itself. Octane number is a standard which determines the knocking ability and quality of gasoline. Higher is the octane number of a gasoline, lower is the knocking it produces. CH3 - CH2 - CH2 - CH2 - CH2 - CH2 - CH3 n-heptane; octane no. = 0 + CH3 | CH3 |

CH3 - C - CH2 - C - CH3 ; Octane no. = 100 | CH3 2, 2, 4-Trimethyl pentane or Iso-octane.

For example : a given sample has the knocking performance equivalent to a mixture containing 60% iso-octane and 40% heptane. The octane number of the gasoline is, therefore, 60. Presence of following types of compounds increases the octane number of gasoline. (i) In case of straight chain hydrocarbons octane number decreases with increase in the length of the chain. (ii) Branching of chain increases the value of octane number (iii) Introduction of double bond or triple bond increases the value of octane number. (iv) Cyclic alkanes have relatively higher value of octane number. (v) The octane number of aromatic hydrocarbons are exceptionally high (vi) By adding gasoline additives (eg TEL)

(3) Antiknock compounds : To reduce the knocking property or to improve the octane number of a fuel certain chemicals are added to it. These are called antiknock compounds. One such compound, which is extensively used, is tetraethyl lead (TEL). TEL is used in the form of following mixture, TEL = 63%, Ethylene bromide = 26%, Ethylene chloride = 9% and a dye = 2%. However, there is a disadvantage that the lead is deposited in the engine. To remove the free lead, the ethylene halides are added which combine with lead to form volatile lead halides. Pb + Br - CH2 - CH2 - Br Pb Br2 + CH2 = CH2 Ethylene bromide Volatile Ethylene

However, use of TEL in petrol is facing a serious problem of Lead pollution, to avoid this a new compound cyclopenta dienyl manganese carbonyl (called as AK-33-X) is used in developed countries as antiknocking compound.

(4) Cetane number : It is used for grading the diesel oils. CH3 - ( CH2 )14 - CH3 Cetane cetane no. = 100

Cetane no. = 0 - Methyl naphthalene The cetane number of a diesel oil is the percentage of cetane (hexadecane) by volume in a mixture of cetane and -methyl naphthalene which has the same ignition property as the fuel oil under consideration. GASEOUS FULES: COAL GAS: The composition of coal gas varied according to the type of coal and the temperature of
carbonisation. Typical figures were: Carbonization/Carbonisation is the term for the conversion of an organic substance into carbon or a carbon-containing residue.

Hydrogen 50% Methane 35% Carbon Monoxide 10% Ethylene 5%

OIL GAS: It calorific value is 4500-5400 kcal/m3.it is preaped by thermal cracking of mineral oil like kerosene oil.

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