UNIT 5 - Fuel and Combustion

Fuel is a combustible substance, containing carbon as main constituent, which on proper burning gives large amount of heat, which can be used economically for domestic and industrial purposes. Eg., Wood, Charcoal, Coal, Kerosene, Petrol, Producer gas, Oil gas, LPG etc.,

During the process of combustion of a fuel (like coal), the atoms of carbon, hydrogen, etc. combine with oxygen with the simultaneous liberation of heat at a rapid rate.

Fuel + Oxygen ---> Products + Heat

Calorific Value

Calorific value of a fuel is “the total quantity of heat liberated, when a unit mass (or volume) of the fuel is burnt completely”

Units of Heat: (1) Calorie - is the amount of heat required to raise the temperature of one gram of water through one degree centigrade (15-16° C).

(2) Kilocalorie – is equal to 1,000 calories. This is the unit of metric system and may be defined as “the quantity of heat required to raise the temperature of one kilogram of water through one degree centigrade. Thus, 1 kcal = 1,000 calories.

(3) British Thermal Unit (BTU)-

(4) Centigrade heat unit (CHU)

Gross Calorific Value (GCV)

It is the total amount of heat produced, when unit mass/volume of the fuel has been burnt completely and the products of combustion have been cooled to room temperature (15° C or 60° F).

Net Calorific Value (NCV)

It is the net heat produced, when unit mass/volume of the fuel is burnt completely and the products are permitted to escape.

In actual practice of any fuel, the water vapour and moisture, etc., are not condensed and escape as such along with hot combustion gases. Hence, a lesser amount of heat is available.

COAL

Coal is a highly carbonaceous matter that has been formed as a result of alteration of vegetable matter (eg., plants) under certain favourable conditions. It is chiefly composed of C, H, N and O besides non-combustible inorganic matter.

The successive stages in the transformation of vegetable matter into coal are – wood, peat, lignite, bituminous coal, steam coal and anthracite. Anthracite is probably the purest form of coal and contains 95 % carbon.

Analysis of Coal

Proximate Analysis

It is called ‘proximate’ because the data collected vary with the procedure adopted. It is an empirical but important analysis dealing with the determination of

Moisture content

Volatile matter

Ash content

Fixed carbon.

(i) Determination of moisture content in coal: It is the loss in weight of coal caused by heating a known quantity of coal for one hour at 105˚C.

% of moisture content= Loss in wt of coal x 100

Wt of coal taken initially

Significance of Moisture:

1) Reduces the calorific value of coal

2) Increases the consumption of coal for heating purpose.

3) Lengthens the time of heating.

(ii) Determination of volatile matter in coal:

It is the loss in weight of moisture free powdered coal when heated in a muffle furnace at 950˚C for seven minutes.

% of volatile matter in coal = Loss in wt of moisture free coal x 100

Wt of coal taken

Significance of volatile matter:

1) During burning of coal, gases like CO, CO2, CH4, N2, O2, hydrocarbons etc. that come out are called volatile matter of the coal.

2) It has been found that the coal with higher volatile matter content ignites easily.

iii) Determination of ash in coal:

It is the weight of residue obtained after burning a known weight of coal in an open crucible in the presence of air at 750˚C for 30 minutes.

% of ash in coal = Weight of residue ash formed x 100

Weight of coal taken

Significance of ash content:

1) It consists mainly SiO2, Al2O3 and Fe2O3 with varying amount of other oxides such as Na2O, CaO, MgO etc.

2) High ash content in coal is undesirable because it

i) increases transporting, handling and storage costs

ii) is harder and stronger

iii) has lower calorific value

(iv) Determination of fixed carbon:

It is determined indirectly by deducting the sum total of moisture, volatile matter and ash percentage from 100.

% of fixed carbon in coal= 100 - %(moisture + volatile matter + ash)

Significance of Fixed carbon:

It is the pure carbon present in coal. Higher the fixed carbon content of the coal, higher will be the calorific value of the sample.

ULTIMATE ANALYSIS

Ultimate analysis refers the determination of weight percentage of carbon, hydrogen, nitrogen, oxygen and sulphur of pure, dry coal.

a) Determination of carbon and hydrogen in coal:

A known amount of coal is burnt in presence of oxygen thereby converting carbon and hydrogen of coal into-

(i) CO2 (C +O2 CO2) and (ii) H2O (H2 + ½ O2 H2O) respectively. The products of combustion CO2 and H2O are passing over weighed tubes of anhydrous CaCl2 and KOH which absorb H2O and CO2 respectively.

The increase in the weight of CaCl2 tube represents the wt of water formed while the increase in the wt of KOH tube represents the wt of CO2 formed.

Significance of fixed carbon: It is the sum total of fixed carbon and the carbon present in the volatile matters like CO, CO2, hydrocarbons. Thus, total carbon is always more than fixed carbon in any coal. High total carbon containing coal will have higher calorific value.

Significance of hydrogen: It increases the calorific value of the coal. It is associated with the volatile matter of the coal. When the coal containing more of hydrogen is heated, it combines with nitrogen present in coal forming ammonia. Ammonia is usually recovered as (NH4)2SO4, a valuable fertilizer.

(ii) Determination of nitrogen:

This is done by Kjeldhal’s method. A known amount of powdered coal is heated with concentrated sulphuric acid in the presence of K2SO4 and CuSO4 in a long necked Kjeldhal’s fask. This converts nitrogen of coal to ammonium sulphate. When the clear solution is obtained (ie., the whole of nitrogen is converted into ammonium sulphate), it is heated with 50 % NaOH solution, thus the ammonia formed is distilled over and is absorbed in a known quantity of standard 0.1 N H 2SO4

solution. The volume of unused 0.1 N H2SO4 is then determined by titrating against standard NaOH solution. Thus, the amount of acid neutralized by liberated ammonia from coal is determined using the formula.

Significance: Presence of nitrogen decreases the calorific value of the coal. However, when coal is carbonized, its N2 and H2 combine and form NH3. Ammonia is recovered as (NH4)2SO4, a valuable fertilizer.

(iii) Determination of Sulphur: A known amount of coal is burnt completely in Bomb calorimeter in presence of oxygen. Ash thus obtained contains sulphur of coal as sulphate which is extracted with dil. HCl. The acid extract is then treated with BaCl2 solution to precipitate sulphate as BaSO 4. The precipitate is filtered, washed, dried and weighed. From the weight of BaSO4, the percentage of sulphur in coal is calculated

Significance: It increases the calorific value of the coal, yet it has the following undesirable effect- The oxidation products of sulphur (SO2, SO3) especially in presence of moisture forms sulphuric acid which corrodes the equipment and pollutes the atmosphere.

(iv) Determination of oxygen: It is calculated indirectly in the following way-

% of oxygen in coal = 100 - % (C + H + N + S + ash).

Significance: The less the oxygen content, the better is the coal. As the oxygen content increases, its moisture holding capacity also increases.

METALLURGICAL COKE

When bituminous coal (coal containing about 90 % carbon) is heated strongly in absence of air, the volatile matter escapes out and a while, lustrous, dense, strong, porous and coherent mass is left which is called metallurgical coke.

Metallurgical coke is superior to coal for the following reasons:

• Coke is stronger and more porous than coal

• Coke contains lesser amount of sulphur than coal

• Coke does not contain much volatile matter.

Manufacture of Metallurgical coke by Otto Hoffmann’s method:

In order to (i) save the fuel for heating purpose and (ii) recover valuable by-products like coal gas, ammonia, benzol oil, tar etc. Otto Hoffmann developed a modern by-product coke oven.

The oven consists of a number of narrow silica chambers, each about 10-12 m long, 3-4 m tall and 0.4-0.45 m wide.

Each chamber has a hole at the top to introduce the charge, a gas off take and a refractory lined cast iron door at each end for coke discharge.

The oven works on heat regenerative principle ie., the waste gas produced during carbonization is utilized for heating.

The ovens are charged from the top and closed to restrict the entry of air.

Finely powdered, crushed coal is charged through hole at the top of the chambers.

The ovens are heated to 1200°C by burning producer gas.

The air required for the combustion of the fuel is preheated in regenerators.

The cycle goes on and the heating is continued until all the volatile matter has escaped. It takes nearly 18 hours for carbonization of a charge.

When the carbonization is over, the red hot coke is pushed out into truck by a massive ram. It is then quenched by spraying water (wet quenching).

The yield is about 70 %.

Recovery of by-products:

i) Recovery of tar: The coke oven gas is first passed through liquid ammonia. Tar and dust get collected in a tank below, which is heated by a steam coil to recover back the ammonia sprayed.

ii) Recovery of ammonia: The coke oven gas is passed through another tower in which water is sprayed. Gaseous ammonia goes into solution as NH4OH.

iii) Recovery of naphthalene: After recovering ammonia, the remaining gases are led through water when naphthalene gets condensed.

iv) Recovery of benzene: The resultant gas from the previous step is sprayed with petroleum whereby benzene.

v) Recovery of H2S: The gases are then passed through a Fe2O3. Hydrogen sulphide is retained here.

PETROLEUM PROCESSING AND FRACTIONS:

Petroleum or crude oil is a dark greenish-brown, viscous oil found deep in earth crust. It is composed mainly of various hydrocarbons (like straight-chain paraffins, cycloparaffins or naphthalenes, olefins and aromatics), together with small amounts of organic compounds containing oxygen, nitrogen and sulphur.

Mining of petroleum

Refining of crude oil:

Step 1: Separation of water (Cottrell’s process):

Step 2: Removal of harmful sulphur compounds:

Step 3: Fractional distillation: Uncondensed gas, Petroleum ether, Gasoline or petrol, Naphtha, Kerosene oil, Diesel oil, Heavy oil and Residue may be either i) Asphalt or ii) Petroleum coke

CRACKING

It is defined as the decomposition of bigger hydrocarbon molecules into simpler low boiling hydrocarbons of lower molecular weight. For example,

C10H22 (Decane) C5H12(n-Pentane) + C5H10 (Pentane)

Boiling Point=174°C B.Pt. = 36°C

Catalytic cracking

The quality and yield of gasoline produced by cracking can be greatly improved by using a catalyst like aluminium silicate [Al2(SiO3)3] or alumina [Al2O3].

KNOCKING

Due to the presence of some constituents in the gasoline used, the rate of oxidation becomes so great that the last portion of the fuel air mixture gets ignited instantaneously producing an explosive violence known as knocking.

Antiknocking agents are TEL and olefines added compounds.

OCTANE NUMBER

Octane number of a gasoline (or any other internal combustion engine fuel) is the percentage of iso-octane in a mixture of iso-octane and n-heptane.

If a sample of petrol gives as much of knocking as a mixture of 75 parts of iso-octane and 25 parts of n-heptane, then its octane number is taken as 75.

CETANE NUMBER

It is the percentage of hexadecane in a mixture of hexadecane and 2-methyl naphthalene.

The cetane number of a diesel fuel can be raised by the addition of small quantity of certain ethyl nitrite, isoamyl nitrite and acetone peroxide.

SYNTHETIC PETROL

BERGIUS PROCESS: (HYDROGENATION OF COAL)

It consists of converting low grade coals such as bituminuous coal into liquid and gaseous fuels by hydrogenation in presence of iron oxide as catalyst.

The raw materials are coal dust, heavy oil and nickel oleate or tin oleate.

A coal paste is prepared by mixing coal dust with heavy oil and catalyst.

It is then pumped into the converter where the paste is heated to 450˚C under 200-250 atmosphere in pressure of hydrogen.

Coal dust in heavy oil + H2 Mixture of hydrocarbons Crude oil Condensation

Reaction is exothermic, the vapour leaving the converters is condensed in the condenser to give synthetic petroleum or crude oil.

The oil is then fractionally distilled to give (i) petrol (ii) middle oil (iii) heavy oil.

Middle oil is again hydrogenated to produce more amount of petroleum and Heavy oil is used for making paste with fresh coal dust which is required for this process.

GASEOUS FUELS

WATER GAS

It is essentially a mixture of CO and H2. Its calorific value is 2800 kcal/m3. The average composition of water gas is H2 (51 %); CO (41 %); N2 (4 %); CO2 (4 %).

Manufacture: A water gas generator is a steel cylindrical vessel. At the top, it is provided with a hopper for adding coke.

Water gas outlet is provided near the top.

At the bottom, an arrangement of taking out ash formed.

Water gas is obtained by the action of steam on a bed of coal

C + H2O → CO + H2 – 28 kcal.

Since the above reaction is endothermic, the coal cools down after a few minutes and the reaction proceeds in a different way to form CO2 and H2, instead of water gas (CO + H2).

Due to exothermic reactions, the temperature of the bed rises and when the temperature increases to 1000˚C, air entry is stopped and steam is again passed.

Thus, steam and air are blown alternatively. Therefore, the manufacture of water gas is intermittent.

Uses: It is used i) As a source of hydrogen gas ii) In the manufacture of NH 3 by Haber’s process iii) As an illuminating gas iv) As a fuel gas v) For welding purposes

PRODUCER GAS

Producer gas is essentially a mixture of combustible gases (CO and N2). The calorific value is only 1800 k cal/m3. The average composition of producer gas is 50 % N2; 30 % CO; 10 % H2 and rest CO2 and CH4.

Manufacture:

The reactor consists of large airtight mild steel cylindrical towers lined inside with refractory bricks.

At the bottom, it is provided with pipe for blowing air and an arrangement for removing air.

Coal is added through a hopper at the top and producer gas comes out from an exit near the top.

The formation of producer gas involves the following:

Combustion or oxidation zone: C + O2 → CO2 + 97 kcal.

Reduction zone: CO2 + C → 2 CO - 36 kcal

C + H2O → CO + H2 - 29 kcal

C + 2 H2O → CO2 + 2H2 - 19 kcal

Producer gas is a poisonous gas; insoluble in water and heavier than air.

Uses: It is a cheap, clean and used for heating open hearth furnaces (in steel and glass manufacture); muffle furnaces, retorts etc., and used as a reducing agent in metallurgical operations.

COMPRESSED NATURAL GAS (CNG)

CNG is natural gas compressed to a high pressure of about 1000 atmospheres. It is derived from natural gas and the main constituent of CNG is methane.

Properties:

CNG is comparatively much less pollution causing fuel as it produces less CO, ozone and hydrocarbons during combustion.

No sulphur and nitrogen gases are evolved.

No carbon particles are ejected during combustion

LIQUIFIED PETROLEUM GAS (LPG)

LPG or bottled gas or refinery gas is obtained as a by-product during the cracking of heavy oils. LPG is dehydrated, desulphurised and traces of odorous organic sulphides (mercaptans) are added to give warning of gas leak.

Its calorific value is about 27,800 kcal/m3.

The main constituents of LPG are n-butane, isobutene, butylenes and propane, with little or no propylene and ethane.

Uses: As a domestic fuel, industrial fuel and as motor fuel.

Power Alcohol

When ethyl alcohol is blended with petrol at concentration of 5-10%.

100% ethyl alcohol is also called power alcohol.

Ethyl alcohol is used in an internal combustion engine.

The addition of ethanol to petrol increases its octane number.

When ethanol is blended with diesel is called E diesel.

Properties:

1. Lower calorific values of 7000 kcal/kg.

2. High octane number (90).

3. Anti knocking properties are good.

4. Generates 10% more power than the gasoline of same quantity.

5. Compression ratio is also higher.

Uses: Good fuel in motors.

Advantages:

1. Cheaper than petrol.

2. If any moisture is present, power alcohol absorbs it.

3. Ethanol contains oxygen atom, complete combustion occurs, so emission of CO, HC and particulates are reduced.

Disadvantages:

1. Low calorific value of power alcohol than petrol (petrol: 11500 kcal/ kg) special engine and carburetor is required.

2. Output power is reduced upto 35%. Corrosion occurs at engine.3. Due to its high surface tension, atomization of power alcohol is difficult, so it causes

starting trouble.

Bio-diesel

Vegetable oil/methyl esters of fatty acids is called bio-diesel.

Biodiesel is defined as mono alkyl esters of long chain fatty acids.

Biodiesel can be blended with petroleum diesel.

Vegetable coil comprise of 90-95% triglycerides, small amount of diglycerides, free fatty acids, phospholipids etc.

Triglycerides are esters of long chain fatty acids like stearic acid and palmitic acid.

Viscosity of vegetable oil is higher and their molecular weight is in the range of 600-900, which are about 3 times higher than those of the diesel fuel.

Manufacture:

Vegetable oil undergoes trans-esterification or alcoholysis.

Involves treatment of vegetable oil with excess of methanol in presence of catalyst to give monoethyl esters of long chain fatty acid and glycerine. It is allowed to stand for some time and glycerine is separated.

Advantages:

1. It is bio-degradable.

2. Prepared from renewable resources.

3. Gaseous pollutants are lesser as compared to the compared to the conventional diesel fuel.

4. Produced from all types of vegetable oils.

5. Best engine performance and less smoke emission.

Disadvantages:

1. Gel formation in cold weather.

2. It decreases the horse power of the engine.

3. As bio-materials are hygroscopic, bio-diesel can absorb the water from atmosphere.

4. Degrades and soften the rubber and plastics that are used in old cars.

5. It has about 10% higher NOx emission than conventional petroleum.

FLUE GAS ANALYSIS: (Orsat’s Apparatus)

The mixture of gases like SO2, CO2, O2, CO etc. coming out from the combustion chamber is called flue gas.

Importance of Flue Gas Analysis:

The analysis gives the idea of whether a combustion process is complete or not.

The C and H present in a fuel undergo combustion forming CO2 and H2O respectively.

If analysis of a flue gas indicates the presence of CO because of incomplete combustion.

If there is considerable amount of oxygen, it shows that there is excess supply of O2.

Analysis:

The flue gas analysis is carried out by using Orsat’s apparatus. The analysis of flue gas generally deals with the determination of CO2, O2 and CO by absorbing them in the respective solution of KOH, alkaline pyrogallol and ammonium cuprous chloride.

It is essential to follow the order of absorbing the gases- CO2 first; O2 second and CO last.

This is because the absorbent used for O2 (ie., alkaline pyrogallol) can also absorb some amount of CO2 and the percentage of CO2 left would be less.

Description of Orsat’s apparatus:

Orsat’s apparatus consists of a horizontal tube having 3 way stopcock at one end and a water jacketed measuring burette at the other end.

The horizontal tube is connected to three different absorption bulbs for the absorption of CO2, O2 and CO respectively.

The lower end of the burette is connected to the leveling bottle by means of rubber tube.

The level of water in the leveling bottle (water reservoir) can be raised or lowered by raising or lowering the water reservoir

By changing the level of water, the flue gas can be moved into various parts of the apparatus during analysis.

a) Absorption of CO2: Flue gas is passed into the bulb A via its stopcock by raising the water reservoir. CO2 present in the flue gas is absorbed by KOH.

The difference between original volume and the volume of the gases after CO2 absorption gives the volume of CO2 absorbed.

b) Absorption of O2: Stopcock of bulb A is closed and bulb B is opened. Oxygen present in the flue gas is absorbed by alkaline pyrogallol.

c) Absorption of CO: Now the stopcock of bulb B is closed and stopcock of bulb C is opened. Carbon monoxide present in the flue gas is absorbed by ammoniacal cuprous chloride.

Since the total volume of the gas taken for analysis is 100 mL, the volume of the constituents are their percentage.

Further, as the content of CO in the flue gas would be very low, it should be measured quite carefully.

Combustion of Fuels

Combustion is a process of rapid exothermic oxidation, in which a fuel burns in the presence of oxygen with the evolution of heat and light.

Theoretical calculation of calorific value

Dulong’s formula for GCV or HCV is

= 1/100 [8080 C + 34500 (H – O/8) + 2240 S] kcal/kg

Dulong’s formula for LCV or NCV is

= [HCV – 9/100 H x 587] kcal/kg

Combustion Air Calculation problems

Problem 1:

Calculate the volume of air (volume % of O2 in air = 21) required for complete combustion of 1 litre of CO.

Solution:

The combustion equation of CO is written as

CO (1 vol) + ½ O2 (0.5 Vol) → CO2

One volume (litre) of CO requires 0.5 volume (litre) of O2 for complete combustion.

WKT: 21 litres of O2 is supplied by 100 litres of air

Therefore 0.5 litre of O2 is supplied by 100 x 0.5/21 litres of air

= 2.38 litres of air.

The volume of air required for complete combustion of 1 litre of CO = 2.38 litres._____________________________________________________________________________Problem 2:

A coal sample was found to contain the following: C=81%, H=4%, O=2%, N=1% and the remaining being ash. Estimate the quantity of minimum air required for the complete combustion of 1 kg of coal sample, if 40% of excess air is required.

Solution:

1. 1 kg of the fuel contains

81/100 = 0.81 kg of carbon4/100 = 0.04 kg of hydrogen2/100 = 0.02 kg of oxygen1/100 = 0.01 kg of nitrogen

2. N2 is non-combustible constituent, it does not burn and not require any O2.

3. The combustion equations of the remaining constituents are written as

(a) C (12 kg) + O2 (32 kg) → CO2

(b) H2 ( 2 kg) + ½ O2 (16 kg) → H2O

(a) 12 kg of C requires 32 kg of O2

Therefore 0.81 kg of carbon requires=32 x 0.81/12= 2.16 kg

(b) 2 kg of H2 requires 16 kg of O2

Therefore 0.04 kg of H2 requires = 16 x 0.04/2= 0.32 kg of O2

Therefore total amount of O2 required = 2.16+0.32= 2.48 kg

But the amount of O2 already present 0.02 kg

Therefore net amount of O2 required=2.48-0.02=2.46 kg

WKT; 23 kg of O2 is supplied by 100 kg of air

Therefore 2.46 kg of O2 is supplied by 100 x 2.46/23 = 10.696 kg of air

The amount of air required if 40% excess of air used

= Theoretical air x 100 + excess air/100

= 10.696 x 100 + 40/100= 14.696 kg of air.

_________________________________________________________________________________Problem 3:

Calculate the minimum amount of air required for complete combustion of 50 kg of fuel containing 80% C, 60% H, 2% S and the rest nitrogen by weight.

Solution:

1. 1 kg of the fuel contains

80/100 = 0.8 kg of C6/100 = 0.06 kg of H2/100 = 0.02 kg of S

2. Nitrogen is a non-combustible constituent; they do not burn and do not require any O2.

3. The combustion equations of the remaining constituents are as

(a) C (12 kg) + O2 (32 kg) → CO2

(b) H2 (2 kg) + ½ O2 (16 kg) → H2O

(c) S (32 kg) + O2 (32 kg) → SO2

(a) 12 kg of C requires 32 kg of O2

Therefore 0.8 kg of C requires= 32 x 0.8/12=2.13 kg of O2

(b) 2 kg of H2 requires 16 kg of O2

Therefore 0.06 kg of H2 requires= 16 x 0.06/2=0.48 kg of O2

(a) 32 kg of S requires 32 kg of O2

Therefore 0.02 kg of S requires= 32 x 0.02/32= 0.02 kg of O2

Therefore, total amount of O2 required=2.13+0.48+0.02=2.63 kg

WKT; 23 kg of O2 is supplied by 100 kg of air

Therefore 2.63 kg of O2 is supplied by =100 x2.63/23=11.43 kg of air

The minimum amount of air required for the complete combustion of 1 kg of fuel = 11.43 kg

Therefore, the minimum amount of air required for the

complete combustion of 50 kg of fuel = 11.43 x 50 kg=571.5 kg