FUEL L-1

Fuels and combustion, Fuels-Classification of fuels, calorific value LCV, HCV; measurement of calorific value using bomb calorimeter (numerical problems). Combustion: Calculation of air qualities (problems). Solid fuel, proximate and ultimate analysis ( problems). Carbonization of coal. Liquid Fuels: Knocking and anti-knocking for petrol and diesel (octane number and cetane number) - diesel index. Refining of liquid fuels, cracking of petroleum. Gaseous fuels: LPG, natural gas, CNG: Composition and applications. Biofuels: Biodiesel and Biogas -composition and applications. Next generation fuels.

Fuels
Fuel is a combustible substance which during combustion gives large amount of heat.

There are chemical fuels, nuclear fuels and fossil fuels.

Classification of Fuels These can be classified on the basis of their occurrence and physical state On the basis of occurrence they are of two types: Primary Fuels: Fuels which occur in nature as such are called primary fuels. E.g., wood, peat, coal, petroleum, and natural gas.

Secondary Fuels: The fuels which are derived from the primary fuels by further chemical processing are called secondary fuels. E,g., coke, charcoal, kerosene, coal gas, producer gas etc.

(ii) On the basis of physical state these may be classified as:

Solid Fuels Liquid Fuels Gaseous Fuels

Calorific value: It is defined as the total quantity of heat liberated when a unit mass of a fuel is burnt completely.

Units of Calorific value: System CGS MKS B.T.U Solid/Liquid Gaseous Fuels Fuels Calories/gm k cal/kg BTU/lb Calories/cm3 k cal/m3 BTU/ft3

The quantity of heat can be measured in the following units: (i) Calorie: It is defined as the amount of heat required to raise the temperature of 1gm of water by 1 oC 1 calorie = 4.184 Joules

(ii) Kilo Calorie: 1 k cal = 1000 cal (iii) British thermal unit: (B. T. U.) It is defined as the amount of heat required to raise the temperature of 1 pound of water through 1oF. 1 B.T.U. = 252 Cal = 0.252 k cal (IV) Centigrade heat unit (C.H.U): It is defined as the amount of heat required to raise the temperature of 1 pound of water through 1oC. 1k cal = 3.968 B.T.U.

= 2.2 C.H.U.

Characteristics of Good Fuel:

(i) Suitability: The fuel selected should be most suitable for the process. E.g., coke made out of bituminous coal is most suitable for blast furnace.

(ii) High Calorific value

(iii) Ignition Temperature: A good fuel should have moderate ignition temperature. (iv) Moisture content: Should be low (v) Non combustible matter content (vi) Velocity of combustion: It should be moderate (vii) Nature of the products (viii) Cost of fuel, (ix) Smoke, (x) Control of the process

Gross and net calorific Value

Gross Calorific Value: It is the total amount of heat generated when a unit quantity of fuel is completely burnt in oxygen and the products of combustion are cooled down to the room temperature.
As the products of combustion are cooled down to room temperature, the steam gets condensed into water and latent heat is evolved. Thus in the determination of gross calorific value, the latent heat also gets included in the measured heat. Therefore, gross calorific value is also called the higher calorific value. The calorific value which is determined by Bomb calorimeter gives the higher calorific value (HCV)

Net Calorific Value: It is defined as the net heat produced when a unit quantity of fuel is completely burnt and the products of combustion are allowed to escape.

The water vapour do not condense and escape with hot combustion gases. Hence, lesser amount than gross calorific value is available. It is also known as lower calorific value (LCV).
LCV=HCV-Latent heat of water vapours formed Since 1 part by weight of hydrogen gives nine parts by weight of water i.e. H 1O H O 2 2 2 2

Therefore,

LCV=HCV-weight of hydrogen x 9 x latent heat of steam

= HCV-weight of hydrogen x 9 x 587 Determination of Calorific value 1. Determination of calorific value of solid and non volatile liquid fuels: It is determined by bomb calorimeter. Principle: A known amount of the fuel is burnt in excess of oxygen and heat liberated is transferred to a known amount of water. The calorific value of the fuel is then determined by applying the principle of calorimetery i.e. Heat gained = Heat lost

Bomb Calorimeter

Calculations
Let weight of the fuel sample taken = x g Weight of water in the calorimeter = W g

Water equivalent of the Calorimeter, stirrer, bomb, thermometer = w g

Initial temperature of water = t1oC Final temperature of water = t2oC Higher or gross calorific value = C cal/g Heat gained by water = W x Dt x specific heat of water = W (t2-t1) x 1 cal

Heat gained by Calorimeter = w (t2-t1) cal Heat liberated by the fuel = x C cal Heat liberated by the fuel = Heat gained by water and calorimeter x C = (W+w) (t2-t1) cal C=(W+W)(t2-t1) cal/g x

Net Calorific value: Let percentage of hydrogen in the fuel = H Weight of water produced from 1 gm of the fuel = 9H/100 gm Heat liberated during condensation of steam = 0.09H 587 cal Net (Lower calorific value) = GCV-Latent heat of water formed

= C-0.09H 587 cal/gm

Corrections: For accurate results the following corrections are also incorporated:

(a)Fuse wire correction: As Mg wire is used for ignition, the heat generated by burning of Mg wire is also included in the gross calorific value. Hence this amount of heat has to be subtracted from the total value. (b)Acid Correction: During combustion, sulphur and nitrogen present in the fuel are oxidized to their corresponding acids under high pressure and temperature.

S O SO 2 2 2SO O 2H O 2H SO 2 2 2 2 4 2 N 5O 2H O 4HNO 2 2 2 3

DH = -144,000 Cal
DH = -57,160 Cal

The corrections must be made for the heat liberated in the bomb by the formation of H2SO4 and HNO3. The amount of H2SO4 and HNO3 is analyzed by washings of the calorimeter.

For each ml of 0.1 N H2SO4 formed, 3.6 calories should be subtracted.

For each ml of 0.01 HNO3 formed, 1.43 calories must be subtracted.

(C) Cooling correction: As the temperature rises above the room temperature, the loss of heat does

occur due to radiation, and the highest temperature recorded will be slightly less than that obtained. A temperature correction is therefore necessary to get the correct rise in temperature. If the time taken for the water in the calorimeter to cool down from the maximum temperature attained, to the room temperature is x minutes and the rate of cooling is dt/min, then the cooling correction = x dt. This should be added to the observed rise in temperature. Therefore, Gross calorific value C=(W+w)(t2-t1+Cooling correction)-[Acid+ fuse corrections] / Mass of the fuel.

Theoretical calculation of Calorific value of a Fuel: The calorific value of a fuel can be calculated if the percentages of the constituent elements are known. Substrate Carbon Hydrogen Sulphur Calorific value 8080 34500 2240

If oxygen is also present, it combines with hydrogen to form H2O. Thus the hydrogen in the combined form is not available for combustion and is called fixed hydrogen.

Amount of hydrogen available for combustion = Total mass of hydrogen-hydrogen combined with oxygen.
1 H 2 O2 H 2O 2 1g 8g 9g

Fixed Hydrogen = Mass of oxygen in the fuel Therefore, mass of hydrogen available for combustion = Total mass of hydrogen-1/8 mass of oxygen in fuel =H-O/8

Dulongs formula for calculating the calorific value is given as: Gross calorific Value (HCV) 1 O [8080C 34,500( H ) 2,240S ]kcal / kg 100 8 Net Calorific value (LCV) 9H [ HCV 587]kcal / kg 100 [ HCV 0.09 H 587]kcal / kg

Solid Fuels: Primary as well as secondary are widely used in domestic and industrial purposes. e.g., wood, coal, charcoal and coke. Wood: Wood has been used as a fuel from ancient times. Due to large scale deforestation, wood is no longer used except in forest areas where wood is available at a low cost.

Wood when freshly cut contains 25-50% moisture. Normally it is used in air dried condition with 10-15 percent moisture content. The calorific value of air dried wood is about 35004500 kcal/kg. When wood burns, the ash content is low but the oxygen content is very high. This makes even dry wood a fuel of low calorific value. Wood charcoal is obtained by destructive distillation of wood. The major use of wood charcoal is for producing activated carbon.

Coal: coal is regarded as a fossil fuel produced from the vegetable debris under conditions of high temperature and pressure over million of years. The transformation of the vegetable debris to coal takes place in two stages: (a)Biochemical or peat stage: During this stage, the plant materials were attacked by various micro organisms. (b)Chemical stage or metamorphism: In this stage, the peat deposit buried under sedimentary deposits lose moisture and volatile components under the effect of high temperature and pressure. The peat gets enriched in carbon whereas its oxygen content decreases.

The spongy peat transforms into hard brittle coal gradually. The time required for the formation of young brown coal is of the order of 107 years. Classification of Coal: Coals are mainly classified on the basis of their degree of coalification from the parent material, wood. When wood is converted into coal, there is gradual increase in the concentration of carbon and decrease in the percentage of oxygen and nitrogen. Coal is given a ranking depending upon the carbon content of the coal from wood to anthracite.

Type of coal

Percentage (dry, mineral matter free basis) C H O N VM -

% calorific moist value ure

Wood Peat

45-50 5-6

20-40 0-0.5

70-90

45-60 3.5-6.5 20-45 0.75-3 45-75 70-90

Brown Coal 60-75 4.5-5.5 17-35 0.75-2 45-60 30-50

Bituminous 75-90 4.0-5.5 20-30 0.75-2 11-50 10-20 coal Anthracite 90-95 3-4 2-3 0.5-2

40004500 41255280 66007100 66008800

84703.8-10 1.5-3.5 8800

Analysis of Coal Coal is analysed in two ways: 1. Proximate analysis

2. Ultimate analysis
The results of analysis are generally reported in the following ways: As received basis Air dried basis

Moisture free basis (oven dried)

Moisture and ash free basis

Proximate Analysis The data varies with the procedure adopted and hence it is called proximate analysis. It gives information about the practical utility of coal. Proximate analysis of coal determines the moisture, ash, volatile matter and fixed carbon of coal. 1. Moisture Content: Air dried moisture is determined by heating a known amount of coal to 105-110 oC in an electric hot air oven for about one hour. After one hour, it is taken out from the oven and cooled in a dessicator and weighed.

Percentage of moisture= Loss in weight

Weight of coal taken

100

Excess of moisture is undesirable in coal.

Moisture lowers the heating value of coal and takes away appreciable amount of the liberated heat in the form of latent heat of vapourisation. Excessive surface moisture may cause difficulty in handling the coal. Presence of excessive moisture quenches fire in the furnace. 2. Volatile Matter: consists of a complex mixture of gaseous and liquid products resulting from the thermal decomposition of the coal.

It is determined by heating a known weight of moisture free coal sample in a covered platinum crucible at 950 20oC for 7 minutes. Percentage of volatile matter = Loss of weight due to volatile matter 100 Weight of coal sample taken

Significance
A high percent of volatile matter indicates that a large proportion of fuel is burnt as a gas. The high volatile content gives long flames, high smoke and relatively low heating values.

For efficient use of fuel, the outgoing combustible gases has to be burnt by supplying secondary air. High volatile matter content is desirable in coal gas manufacture because volatile matter in a coal denotes the proportion of the coal which will be converted into gas and tar products by heat. Ash: Coal contains inorganic mineral substances which are converted into ash by chemical reactions during the combustion of coal. Ash usually consists of silica, alumina, iron oxide and small quantities of lime, magnesia etc. Ash content is determined by heating the residue left after the removal of volatile matter at 700 50oC for an hour without covering

Weight of the residue left Percentage of ash = Weight of the coal

100

Ash can be classified as intrinsic ash and extrinsic ash. The mineral matter originally present in vegetable matter from which the coal was formed is called intrinsic ash. It consists of oxides of Na, K, Mg, Ca and Si. The mineral matter like clay, gypsum, dirt which gets mixed up during mining and handling of coal constitute the extrinsic ash which remains as a residue after the combustion. E.g., CaSO4, CaCO3, Fe2O3 etc.

The high percentage of ash is undesirable. It reduces the calorific value of coal.
In furnace grate, the ash may restrict the passage of air and lower the rate of combustion. High ash leads to large heat losses and leads to formation of ash lumps. The composition of ash and fusion range also influences the efficiency of coal.

When coal is used in boiler, the fusion temperature of ash is very significant. Ash having fusion temperature below 1200oC is called fusible ash and above 1430oC is called refractory ash.

Apart from loss of efficiency of coal, clinker formation also leads to loss of fuel because some coal particles also get embedded in the clinkers. Fixed Carbon: Fixed carbon content increases from lignite to anthracite. Higher the percentage of fixed carbon greater is its calorific value and better is the quality of coal.

The percentage of fixed carbon is given by:

Percentage of fixed carbon = 100-[% of moisture+volatile matter+ash] Significance: Higher the percentage of fixed carbon, greater its calorific value

The percentage of fixed carbon helps in designing the furnace and shape of the fire-box because it is the fixed carbon that burns in the solid state. Ultimate analysis: It is carried out to ascertain the composition of coal. Ultimate analysis includes the estimation of carbon, hydrogen, sulphur, nitrogen and oxygen. 1. Carbon and Hydrogen: A known amount of coal is taken in a combustion tube and is burnt in excess of pure oxygen. C O CO 2 2 H 1O H O 2 2 2 2

Fig 3. Estimation of carbon and hydrogen

2KOH CO K CO H O 2 2 3 2 CaCl 7 H O CaCl .7 H O 2 2 2 2

44 g of CO2 contain = 12 g of carbon Y g of CO2 contain = 12 y 44

y 100 Percentage of carbon 12 44 weight of coal taken

18 g of water contain = 2 g of hydrogen Z g of water contain 2 zg of hydrogen 18 z 100 Percentage of hydrogen 2 18 weight of coal taken Significance: Calorific value of a fuel is directly related to its carbon content. A higher percentage of carbon reduces the size of the combustion chamber

High percentage of hydrogen also increases the calorific value of coal. The content of hydrogen in coals varies between 4.5 to 6.5 percent from peat to bituminous stage.

2. Nitrogen: Nitrogen present in coal sample can be estimated by Kjeldahls method. Nitrogen H SO Heat ( NH ) SO 2 4 42 4 The contents are then transferred to a round bottomed flask and solution is heated with excess of NaOH.
The ammonia gas thus liberated is absorbed in a known volume of a standard solution of acid used.

Fig 4. Estimation of nitrogen by Kjeldahls method

The unused acid is then determined by titrating with NaOH. From the volume of acid used by NH3 liberated, the percentage of nitrogen can be calculated.

NaOH ( NH ) SO 2 Na SO 2 NH 2H O 42 4 2 4 3 2 NH H SO ( NH ) SO 3 2 4 42 4

Carbonization of Coal (Manufacture of Coke) It is the process of heating the coal in absence of air to a sufficiently high temperature, so that the coal undergoes decomposition and yields a residue which is richer in carbon content than the original fuel. Caking and coking of coals: some coals have a tendency to soften and swell at higher temperatures, to form a solid coherent mass with porous structure. Such coals are called caking coals. The residue formed is called coke.

If the coke is hard, porous and strong, than the coal, from which it is formed, it is called coking coal.
This property is found only in bituminous type of coal.

Coals with a high percentage of volatile matter are not fit for coking and are used for gas making. The coals having 20-30 % volatile matter are good coking coals. Process of carbonization: First moisture and occluded gases are driven off. At about 260-270oC carbon, water, H2S, some low molecular alkenes and alkanes are evolved. At about 350oC the decomposition of coal is accompanied by evolution of gases and elimination of vapours takes place. At about 400oC, caking coal becomes soft and plastic. At about 700oC, hydrogen is evolved

Above 800oC, main gaseous products are evolved Gases evolved from the plastic mass, expand it to give foam like appearance. At further high temperatures this foam like mass solidifies to form a solid mass with porous structure called coke. Types of carbonization (i) Low temperature carbonization (ii) High temperature carbonization (i) Low temperature carbonization: When the destructive distillation of coal is carried out at temperatures between 500-700oC.

It is practiced for the production of semi coke. Which is also called soft coke. The yield of coke is about 75-80 %. The coke thus produced contains 5 to 15 % volatile matter. The various products of low temperature carbonization are semi coke, low temperature tar, crude low temperature spirit and gas. LTC plants normally use low rank coals. These low rank coals produce excessive smoke on burning. Semi coke from LTC is highly reactive and can be easily ignited into a smokeless flame

The gas which is obtained as a byproduct has higher calorific value of about 6500-9500 kcal/m3. (ii) High temperature carbonization: It is carried out at 900-1200oC. HTC is used for the production of pure, hard, strong and porous metallurgical coke containing 1-3 % volatile matter. The yield of the coke is 65-75%. The byproducts-gas and tar have greater amounts of aromatic hydrocarbons. The gas which is obtained has lower calorific value of about 5000-6000 kcal/m3 than that produced in LTC; but the yield of the gas is higher.

The coke obtained is very much harder than the coke obtained from LTC process and hence is called hard coke.

Metallurgical coke: The properties of coke depend on porosity, reactivity and the amount of volatile matter retained by coke during carbonization. Coke is mainly used as a heat source and reducing agent in metallurgy. A good coke in metallurgical process should possess the following characteristics: (i) Purity: The metallurgical coke should contain lower percentage of moisture, ash, sulphur and phosphorous. (ii) Porosity: The coke should be porous so as to provide contact between carbon and oxygen. (iii)Strength: The coke used in metallurgical process should have high strength so as to withstand the

weight of the ore, flux etc. in the furnace. (iv) size: Metallurgical coke should be of medium size. (v) Combustibility: Coke should burn easily. The combustibility of coke depends on the nature of the coal, carbonization temperature and reaction temperature. (vi) Calorific value: It should be high. (vii) Reactivity: Reactivity of coke is its ability to react with CO2, steam, air and oxygen. The reactivity should not be too high. The reactivity toward CO2 represent the reduction of CO2 CO ( g ) C(s) 2CO( g ) 2

Cost: Coke should be cheap and easily available. Manufacture of Metallurgical Coke: (i) Beehive Oven

(ii) Otto Hoffmann oven

(i) Beehive oven: A beehive oven is a fire-brick chamber having a dome-shaped structure. The dimensions of a typical oven are 4m and 2.5m high. The roof is provided with a hole for charging the coal from the top. Another hole, the discharging hole is provided in the circumference of the lower part of the wall. A number of ovens are built in a row with common walls between neighbouring ovens.

Fig. 5: Beehive coke oven

Demerits of Beehive ovens: The demerits are No recovery of byproducts, which are useful chemicals and are allowed to escape. Lower coke yield due to partial combustion Lack of flexibility of operation (ii) Otto-Hoffmanns oven or By-product Oven: The beehive ovens have been replaced by chamber ovens which works on regenerative principle of heat economy. All the valuable products are recovered from the outgoing flue gases. Construction: It consists of no. of narrow rectangular chambers made of silica bricks.

Fig. 6: A single chamber of Otto Hoffmanns oven

Working: Coal is charged into the chamber. The coke ovens are heated to 1200oC by burning gaseous fuels. The process of carbonization takes place layer by layer in the coal charge. As the coal adjacent to the oven walls gets heated, a plastic zone is formed which moves away from the walls towards the central zone. As the coal is converted into coke, there is decrease in volume. This is because of the removal of volatile matter in the form of tar and gas at about 500oC. At further high temperature, the plastic mass solidifies into hard and porous mass called coke.

Regenerative principle is employed to achieve as economical heating as possible. Regenerators are built underneath the ovens.The flue gases pass their heat to the checker brick work of regenerators until the temperature rises to 1000oC. Regenerators work on the principle of alternate heating and cooling cycles. This is achieved by periodically changing the direction of flow of gases through the vertical flues every 30 min or so. Carbonization of a charge of coal takes about 11-18 hours. After the process is complete, red hot coke is pushed outside by means of a ram which is electrically driven. The coke falls into a quenching car. The yield is 75 % of coal.

Fig. 7: Otto Hoffmanns Byproduct coke oven

Recovery of byproducts: The gases and vapours evolved on carbonization in coke ovens are not allowed to mix with the combustion and are collected separately.The coke oven gas is treated separately for the recovery of the valuable byproducts.

Fig. 8: Coke-Oven gas treatment plant

(i) Recovery of Tar: The gas from the coke ovens is passed through a tower in which liquor ammonia is sprayed.Tar and dust get collected in a tank. The tank is provided with a heating coils to recover back ammonia. (ii) Recovery of ammonia: The gases are then passed through a tower where water is sprayed to recover ammonia. The ammonia can also be recovered by dissolving it in H2SO4 to form (NH4)2SO4, which is then used as a fertilizer.

(iii) Recovery of Naphthalene: The gases are passed through a cooling tower, where water at a low temperature is sprayed.The gas is scrubbed with water until its temp. reduces.

(iv) Recovery of Benzol: The gases are then introduced into a light oil or benzol scrubber, where benzene along with its homologue is removed and is collected at the bottom. (v) Recovery of H2S and other S compounds: are removed from the coke oven gas after the light oil has been separated out.

Fe O 3H S Fe S 3H O 2 3 2 2 3 2 2Fe S 4O 2FeO 3SO 2 3 2 2 4FeO O 2Fe O 2 2 3 The SO2 obtained can be used for the manufacturing of sulphuric acid, which can be used to absorb NH3 from the coal gas.