ENGINEERING CHEMISTRY

Unit 2 Fuels Analyses: Ultimate and proximate analysis of coal, Determination of calorific value of solid and gaseous fuels by bomb and Junkers Calorimeter respectively. Calculations of calorific value based on Dulongs formula. Combustion, requirement of oxygen/ air in combustion process. Flue gas analysis by Orsats apparatus and its significance.
1. Ultimate and proximate analysis of coal Q.1:What is proximate and ultimate analysis of coal? Answer 1 : The "ultimate" analysis" gives the composition of the biomass in wt% of carbon, hydrogen and oxygen (the major components) as well as sulfur and nitrogen (if any). The carbon determination includes that present in the organic coal substance and any originally present as mineral carbonate. The hydrogen determination includes that in the organic materials in coal and in all water associated with the coal. All nitrogen determined is assumed to be part of the organic materials in coal. The "proximate" analysis gives moisture content, volatile content,consisting of gases and vapors driven off during pyrolysis (when heated to 950 C), the fixed carbon and the ash,the inorganic residue remaining after combustion in the sample and the high heating value (HHV) based on the complete combustion of the sample to carbon dioxide and liquid water. Proximate analysis is the most often used analysis for characterizing coals in connection with their utilization.

Determination of Calorific Value of solid and liquid fuel

Determination of Calorific Value of a Solid Fuel - Bomb

Calorimeter:

Construction The bomb calorimeter (shown in the fig.) consists of an outer cylindrical steel vessel (bomb) with an airtight screw and an inlet for oxygen. The bomb has a platinum crucible with a loop of wire. The ends of the wire project out and can be connected to a source of electric current. The bomb is immersed in a rectangular vessel (calorimeter) containing water, which is continuously stirred. A Beckmann thermometer is introduced into the calorimeter. Working A known mass of the fuel is made into a pellet and taken in the crucible. Oxygen is passed through the bomb. A known mass of water is taken in the calorimeter and is closed with the lid. The initial temperature of water is noted. The ends of the wire are connected to an electric source so as to ignite the fuel

The heat released is absorbed by water. The temperature of water rises. The final temperature is noted.

Calculation Let m = mass of fuel W = mass of water w = water equivalent of calorimeter t1 = initial temperature of water t2 = final temperature of water s = specific heat of water

GCV ( solid fuel)

(W+w) (t2-t1) s m

If the fuel contains x% hydrogen, NCV of the fuel is calculated as follows 2 atoms of hydrogen produce one molecule of water 2g of hydrogen produce 18 g of water x g of hydrogen produce 9 g of water x % hydrogen 9 x g of water = 0.09 x g of water 100 NCV = GCV - latent heat of steam formed = GCV - 0.09 x latent heat of steam
Latent heat of steam = 2454 kJ kg-1

1 calorie = 4.187 kJ kg-1

The calorific value of a liquid fuel can be determined using bomb calorimeter.

Procedure of bomb calorimeter experiment :

1.A known quantity of fuel sample is added in crucible. 2.Start the stirrer and not the initial temperature of water. 3.Start current through crucible and let fuel sample to burn in presence of oxygen. 4.Heat release during combustion of fuel is taken by water and temperature of it rises. Note final steady state temperature of water.

Junkers Calorimeter:
Junkers calorimeter is a device used for measuring LHV and HHV of gaseous or liquid fuels. Its working principle is based on the First Law of Thermodynamics.

The device is essentially a Bunsen burner with a cooling jacket. The jacket is cylindrical in shape, about 80cm tall, with water running through it. The burner sits inside the cylinder. The calorimeter allows the user to measure the temperature of water flowing in and flowing out. Once steady-state is reached, with those two temperatures steady, the water flowing through is collected for a specified period of time. Measuring the mass of the water and the temperature rise in the water, the operator can calculate the number of joules which went into the water to heat it. There is a flow meter on the fuel gas, so the operator can also calculate the volume of gas that was burned in the same time period. The amount of energy, in J, available per litre of gas can then be calculated.

Dulongs formula:
The fuel contains oxygen, then it is assumed that the whole amount is combined with hydrogen having mass equal to 1/8th of that of oxygen. Therefore, while finding the Calorific value of the fuel, this amount of hydrogen should be subtracted.

H.C.V = 338800 * C + 14400 * [H2 - O2 /8] + 9270 * S

Exercises of analysis and calorific value

1. Calculate the gross and net calorific value of a coal which analyses: C 74%, H 6%, N 1%, O 9%,
S 0.8%, moisture 2.2% and ash 8%.

ANS.1 GCV = 339%C + 1427(%H %O/8) + 22%S

= 32060.2 KJ/Kg NCV = GCV - 24.44(9%H + %M) = 30630.26 KJ/Kg Thus NCV = 0.955 times GCV in this case.

2. The ultimate analysis of bituminous coal (dry basis %) is : C 77, H 5.8, N 1.7, O 4.8, S 2.5 and
ash 9. The moisture content is 5 %. The gross calorific power is 7650 Kcal/Kg on dry basis. Calculate a) Gross calorific value, moist basis b) Net calorific value, dry basis c) Net calorific value, moist basis d) Gross calorific value, dry basis using Dulong formula.

ANS.2
GCV Moist basis = 33873.2 + 1422 (5.54.55/8) + 222.3 = 31804.2 KJ/Kg NCV Moist basis = GCV - 24.44 (5.59 + 5) = 30472.2 KJ/Kg NCV Dry basis = NCV moist basis100/ (100%M) = 32076 KJ/Kg GCV Dry basis Dulong formula = 77338 + 1422 (5.84.8/8) + 222.4 = 33473.2 KJ/Kg

3: Calculate the gross calorific value and net calorific value of a sample of coal 0. 5g of which when burnt in a bomb calorimeter, raised the temperature of 1000g of water from 293K to 301.6K. The water equivalent of calorimeter is 350 g. The specific heat of water is 4.187 kJ kg-1, latent heat of steam is 2457.2kJkg-1. the coal sample contains 93% carbon, 5% hydrogen and 2% ash.

ANS.3
m = mass of the fuel W = mass of water taken w = water equivalent of calorimeter t1 = initial temperature of water t2 = final temperature of water s = specific heat of water = 0.5 g = 1000 g = 350 g = 293 K = 296.4 K = 4.187 kJ kg-1K-1

GCV (solid fuel) =

(W+w) (t2-t1) s m = (1000 +350) g (296.4 -293)K 4.187 kJ kg-1K-1

0.5g
= 1350 g 3.4 K 4.187 kJ kg-1K-1

0. 5g = 3 8437 kJ kg-1
NCV (solid fuel) = GCV - latent heat = = = = G.C.V. - (0.09 % of H) latent heat 38437 kJ kg-1 - (0.09 5) 1105.7 kJ kg-1 38437 kJ kg-1 1106 kJ kg-1 37331 kJ kg-1

4: Calculate the gross calorific value and net calorific value of a gaseous fuel, 0.012m3 of which when burnt raised the temperature of 3.5kg of water by 8.2K. Specific heat of water is 4.2 kJ kg-1K-1. Latent heat of steam is 2.45 kJ kg-1. The volume of water collected is 6.5cm3 . Latent heat of steam is 2457.2kJ kg-1

ANS.4
V = volume of the gas burnt W = mass of water t2- t1 = rise in temperature s = specific heat of water v = volume of water collected GCV( gaseous fuel) = 0.015 m3 = 3.5 kg = 15.6 K = 4.2kJ kg-1K-1 = 6.5 cm3

= W s (t2- t1) V = 3.5 kg 4.2 kJkg-1K-1 15.6 K

0.012m3
= 11073 kJm-3

NCV( gaseous fuel) = GCV latent heat = G.C.V. - amount of water collected latent heat V = 11073 kJm-3 6.5 10-3 kg 2457.2kJkg-1 0.012 (1 cm3 of water 1 g of water)

= 11073 kJm-3 6.5 10-3 kg 2457.2kJkg-1 0.015 = 11073 kJm-3 1065 kJm-3

= 10008 kJm-3

Exercises of analysis and calorific value TO YOU

1. The ultimate analysis of a coal(moist basis in %): C 69.8 , H 4.6 , N 1.4, O 8.5, S 2.5, H 2O 4.5
and ash 8.7. The gross calorific value, moist basis, is 29920 KJ/Kg. Calculate, by means of the Dulong formula, the gross calorific value, moist basis, of the coal.

2. The proximate analysis of coal is: Moisture 2.4%, Volatile Matter 29.4%, Fixed Carbon 58%,
Ash 9.7% and Sulphur 0.5%. Its gross calorific value is 7650 Kcal/Kg. Calculate proximate analysis and calorific value on a) Moisture free basis b) Dry ash free basis

3. A producer gas analyses 50% N 2, 25% CO, 18% H 2, 6% CO 2 and 1% O 2. Calculate net calorific
3

power (Kcal/m ).

ANALYSIS OF FLUE GAS:

Orsats gas analysis apparatus: An Orsat gas analyser is a piece of laboratory equipment used to
analyse a gas sample (typically fossil fuel flue gas) for its oxygen, carbon monoxide and carbon dioxide content. Although largely replaced by instrumental techniques. Construction The apparatus consists essentially of a calibrated water-jacketed gas burette connected by glass capillary tubing to two or three absorption pipettes containing chemical solutions that absorb the gasses it is required to

measure. For safety and portability, the apparatus is usually encased in a wooden box. The absorbents are: Potassium Hydroxide (Caustic Potash) Alkaline pyrogallol ammoniacal Cuprous chloride The base of the gas burette is connected to a levelling bottle to enable readings to be taken at constant pressure and to transfer the gas to and from the absorption media. The burette contains slightly acidulated water with a trace of chemical indicator (typically methyl orange) for colouration.

BY: SHUBHAM KHANDELWAL (FARRE.IN)