EXPERIMENT NO - 01

AIM:
To determine proximate analysis and calorific value of coal (solid fuel).

APPARATUS REQUIRED:

Coal sample, VM crucible, silica crucible, electronic hot air oven, muffle furnace, analytical balance,
metal tongs, desiccator

THEORY:

PROXIMATE ANALYSIS

Coal Analysis techniques are specific analytical methods designed to measure the particular physical and
chemical properties of coal. Proximate Analysis is one of them. It comprises of determination of moisture
content, ash, volatile matter and fixed carbon.

Moisture: It is an important property of coal, as all coals are mined wet. Groundwater and other
extraneous moisture are known as adventitious moisture and is readily evaporated. Moisture held within
the coal itself is known as inherent moisture and is analyzed quantitatively. Moisture may occur in four
possible forms within coal:
1. Surface moisture: water held on the surface of coal particles or macerals
2. Hydroscopic moisture: water held by capillary action within the microfractures of the coal
3. Decomposition moisture: water held within the coal's decomposed organic compounds
4. Mineral moisture: water that comprises part of the crystal structure of hydrous silicates such as
clays.
Total moisture is analyzed by loss of mass between an untreated sample and the sample once analyzed.
This is achieved by any of the following methods:
1. Heating the coal with toluene
2. Drying in a minimum free-space oven at 150 °C (300 °F) within a nitrogen atmosphere
3. Drying in the air at 100 to 105 °C (210 to 220 °F) and relative loss of mass determined
Methods 1 and 2 are suitable for low-rank coals but method 3 is only suitable for high-rank coals as free
air drying low-rank coals may promote oxidation. Inherent moisture is analyzed similarly, though it may
be done in a vacuum. 1 g of a finely powdered airdried sample taken in a crucible and heated in an
electrically heated hot air oven at 105°C-110°C for 1 hr. and again weighed after desiccation till constant
weight.
The percentage of moisture is given by,

% Moisture in coal = {loss in wt. of coal X 100}/ wt. of coal initially taken

Volatile Matter: Volatile matter in coal refers to the components of coal, except for moisture, which is
liberated at high temperatures in the absence of air. This is usually a mixture of short Page | 9 and long-
chain hydrocarbons, aromatic hydrocarbons and some sulfur. The volatile matter of coal is determined
under rigidly controlled standards. Any coal which has high volatile matter content:
● Can ignite easily.
● Burns with long smoky yellow flame.
● Has low calorific value.
● Needs a large furnace volume for combustion.
● The high tendency of catching fire.
It is defined as the loss in weight of moisture-free powdered coal when heated in a crucible fitted with
cover in a muffle furnace at 925˚C for 7 minutes.

% Volatile matter = {Loss in wt. of moisture-free coal X 100}/ wt. of moisture-free coal taken

Ash: Ash content of coal is the non-combustible residue left after coal is burnt. It represents the bulk
mineral matter after carbon, oxygen, sulfur and water (including from clays) has been driven off during
combustion. The analysis is fairly straightforward, with the coal thoroughly burnt and the ash material
expressed as a percentage of the original weight.
The residual sample after the two above experiments in the crucible is heated in the furnace at 700°C
+50°C for 1 or 2 hours without the lid. Then it is cooled, left in the desiccator and weighed to constant
weight.

% Ash in coal = {wt. of residue ash formed X 100} / wt. of coal initially taken

Fixed Carbon: The fixed carbon content of the coal is the carbon found in the material which is left after
volatile materials are driven off. This differs from the ultimate carbon content of the coal because some
carbon is lost in hydrocarbons with the volatiles. Fixed carbon is used as an estimate of the amount of
coke that will be yielded from a sample of coal. Fixed carbon is determined by removing the mass of
volatiles determined by the volatility test, above, from the original mass of the coal sample. It is
determined indirectly by deducting the total of moisture, Volatile matter, and ash percentage from 100.

% Fixed carbon in coal = 100- (% Moisture+% Ash+% Volatile matter)

The different expressions for calorific values are:

1. The amount of heat generated by the combustion of the unit amount of fuel is known as Gross
Calorific Value (GCV). Gross or High calorific value is the quantity of heat evolved by the
combustion of unit mass fuel in the presence of oxygen, the original material and final product
being at a temperature of 25℃, and the water obtained is in liquid form, represented by GCV.
2. Net Calorific Value (NCV) is the quantity of heat liberated when a unit amount of fuel is burnt
in presence of oxygen, the original material and final product being at a temperature of 25℃, and
the water obtained is in the vapour phase. The Net Calorific Value is always less than Gross
calorific Value, (i.e., NCV<GCV), by the amount corresponding to the heat of condensation of
water vapours i.e., 587 kcal/kg.
Therefore, NCV = HCV - Latent Heat of water vapour formed
 = HCV - Mass of Hydrogen x an x Latent heat of steam
Since 1 part by mass of hydrogen produces ‘a’ part by mass of water
Units: It is expressed in either calorie/gm (Cal/gm) or kilocalorie/kg (kcal/kg) or British Thermal unit/lb.
(B.T.U/lb.) in case of solid or liquid fuel. In the case of gaseous fuel, the unit is kcal/m 3 or B.T.U/ft3.

Determination of Calorific Value

Bomb calorimeter:
The apparatus which is used to determine the calorific value of solid and liquid fuels is known as a Bomb
calorimeter.
The apparatus consists of a cylindrical stainless
stool bomb, the lid of which is screwed to the
body to make it air-tight. Through the lid, there
is one oxygen inlet valve and two electrodes. In
the bomb, there is a nickel crucible attached to a
ring. The sample of fuel is placed in the
crucible. An electrically heated magnesium wire
touches the sample. The bomb is placed in a
copper calorimeter, which is surrounded by an
air jacket and water jacket which minimizes the
heat loss due to radiation. There is a stirrer and a
Beckmann's thermometer which can accurately
measure the temperature up to n/100th of a
degree.

A weighed mass of a fuel placed in the crucible is allowed to burn in oxygen by electric spark across the
electrode and the heat liberated is measured by the principle of calorimetry i.e., the heat liberated is taken
by calorimeter and water. The initial and final temperatures of the calorimeter are noted.

Calculation: m = mass of fuel pellet (g)

W= mass of water in the calorimeter (g)
w = water equivalent of calorimeter (g)
t₁ = initial temperature of calorimeter.
t₂ = final temperature of calorimeter.
HCV = gross calorific value of fuel.
(W −w)(t 2−t 1)
L = HCV = cal/gm
m

The water equivalent of the calorimeter is determined by burning fuel of known calorific value and using
the above equation. The fuels used in the above purpose are benzoic acid (GCV = 6325 kcal/kg) and
naphthalene (GCV = 9688 kcal/(kg). The correction factors used to get accurate results include:
1. Fuse wire correction. The heat liberated during sparking should be subtracted from heat liberated.
2. Acid correction. Fuels containing Sulphur and Nitrogen if oxidized, the heats of formation of
H₂SO, and HNO, should be subtracted (as the acid formations are exothermic reactions).
 3. Cooling correction. The rate of cooling of the calorimeter from maximum temperature to room
temperature is noted. From this rate of cooling (i.e., dt°/min) and the actual time taken for cooling
(t min) then correction (dt x t) is called cooling correction and is added to the (t₂-t₁) term.

(W + w)(t 2−t 1 +Cooling correction)−( Acid + fuse correction)

∴ L=
m

The approximate calorific value of a fuel can be determined by knowing the amount of constituents
present: Gross or higher calorific value (HCV) from elemental constituents of a fuel.

H=34500 kcal/kg C=8080 kcal/kg S=2240 kcal/kg

Oxygen present in the fuel is assumed to be present as water (fixed hydrogen). Available H in the
combustion of the fuel in
= Total hydrogen - Fixed hydrogen
1
= Total hydrogen - mass of oxygen in fuel.
8

Dulong's formula for calorific value from the chemical composition of fuel is,
1 0
HCV = [8080C + 34500(H - ) + 2240S] kcal/kg
100 8

where C, H, O, S are the percentages of carbon, hydrogen, oxygen and sulfur in the fuel. Oxygen is
assumed to be present in combination with hydrogen as water,
∴ LCV = [HCV - 0.09H x 587] kcal/kg.

(∴1 part of H gives 9 parts of water and the latent heat of steam is 587 kcal/kg)

PROCEDURE:

PROXIMATE ANALYSIS:

Moisture determination:
 The silica dish was dried in the oven and weighed
 1gm of 20 mesh coal sample was spread over the dish
 The dish was weighed again to find the weight of the sample
 The dish was heated in the oven without any cover at about 105±5oC for about 1 hour.
 The dish was taken out from the oven and then was covered with a lid and set aside to cool.
 The dish was then weighed again so as to find the loss in weight of coal sample due to the
presence of moisture.
Volatile matter:
 A clean crucible with its lid was heated at 900±15oC for 7 minutes straight in a muffle furnace.
 The crucible and the lid were then allowed to cool separately on a metal plate for a minute and
then in a desiccator.
 The crucible and the lid were weighed together.
 Approximately 1 gm of sample was put again and weighed so as to determine the exact mass.
 The crucible with the lid was then put inside the furnace at 900oC and then keep there for a
period of 7 minutes.
 The crucible with the lid was weighed again so to determine the loss in weight due to the
expulsion of volatile matter.

Ash determination:
 The silica dish was dried in the oven and then weighed.
 1gm of 20 mesh coal sample was spread over the dish.
 The weight of the dish was taken again to find the exact weight of the sample.
 The open dish was inserted into the furnace at 815°C for an hour.
 The dish was then removed; and was allowed to be cooled for 10 minutes on the slab and then for
15 minutes in the desiccator.
 The mass of the residue in the dish was weighed, which is the ash content of the coal sample.

CALORIFIC VALUE OF COAL USING BOMB CALORIMETER

Calorific value determination:

 About 1 g of coal pellet was weighed and then introduced into the bomb.
 1 ml of distilled water was added and then the fuse was connected to the lid wires.
 The bomb was pressurized with oxygen and placed inside the jacket.
 The jacket was filled with 2000ml of water. Temperature of water was kept 2oC less than the
room temperature.
 The calorimeter was then assembled and the motor was run for 5 minutes.
 The temperature of the water bath was recorded accurately using a precision thermometer at an
interval of 1 minute for 5 minutes and the charge was ignited at the start of 6th minute.
 The temperature was recorded for every minute until a constant temperature was attained.
 The bomb was then opened carefully.
  All the interior surfaces of the bomb were washed with a jet of distilled water and the washings
were collected in a beaker.
 All unburned pieces of the fuse wire were removed and the length of the pieces was measured.
 The residual ash was collected and then weighed.

REPORT:

 The moisture content (in wt.%) in coal samples was determined, as received basis.
 The ash content, V.M. and fixed carbon in percentages in both samples was calculated along with
the dry basis results and put all the results and data in a tabular form.
 The temperature versus time graph was plotted for the bomb calorimeter.
 The calorific value of coal was then calculated from the recorded data using Dulong's formula.

CALCULATIONS:
APPLICATION:
 Proximate analysis helps in determining the qualities of coal, the most extensively used primary
energy source, which is essential for deciding the application area and technology to be used.

 It gives quick and valuable information regarding the commercial classification of different
grades of coal.

 It is used to calculate the Gross Calorific Value (GCV)

CONCLUSION:

Proximate analysis is one of the first analyses performed on coal after mining. The test involves heating
the coal under various conditions for variable amounts of time to determine moisture, volatile matter,
fixed carbon, and ash yield. The procedure for proximate analysis is not that complex and hence does not
require elaborate and costly equipment. Thus, this analysis is widely used for industrial purpose.