D.Mishra Sr.A.Chemist NTPC-Vindhyachal email@example.com 94258-23647
A Fully Fossilized Fuel
What is coal? Formation, sources, applications. Coal combustion description. Ash Characterization
Coal – what is it?
65-95% 2-7% <25% <10%
H O S
principally organic of carbon, •Consists Heterogeneous fuel hydrogen, oxygen, with lesser formed and mainly from decomposed amounts of sulfur and nitrogen. plant matter.
•• Over 1200 coals have been Coalification forms different classified. coal types: (Peat) Lignite Bituminous coal Time, Temperature Coal Rank Anthracite (Graphite)
Origin of Coal
Coal has been formed by the partial decay of plant materials accumulated million of years ago and further altered by the action of heat and pressure In situ Theory: coal occupies the same site where the original plants grew Drift Theory: plants were uprooted and drifted by rivers to get deposited
World Coal Reserves (1989)
7% 5% 7% 8% 12% 29% 32%
United States Russia China Australia Germany South Africa Poland
. Recoverable world coal reserves are estimated at about 1X1012 tons.Coal Sources
Coal is the world’s most plentiful fossil fuel.
Homes – heat and cooking Transportation – steam engines Industry – metal works Electricity – power plants
Low rank coals may not be suitable for some applications as the higher ranked ones. One way is to Rank the coal. It indicates the degree or extent of maturation. It is a qualitative measure of carbon content. Although they may be superior to them in other applications
. Thus lignites and sub-bituminous are low rank coals While bituminous and anthracite are high rank coals. Rank is not synonymous with grade which implies quality.Coal Classification
There are a number ways to classify coals.
• Peat :
• Lignite: soft coal and the youngest
• Anthracite: hard and geologically the oldest composed mainly of carbon
Anthracite coal refers to coal with 92-95% fixed carbon .COAL SAMPLES
Lignite refers to coal with a fixed carbon content of fewer than 40%. Bituminous coal refers to coal with 50-86% fixed carbon .
hydrogen. sulphur. oxygen.g flame temperature. flue duct design)
• Laboratory analysis
. volatile matter. etc • Useful for furnace design (e.Coal Analysis
Proximate analysis of coal
• Determines only fixed carbon. moisture and ash
• Useful to find out heating value (GCV)
• Simple analysis equipment
Ultimate analysis of coal • Determines all coal component elements: carbon.
handled and stored Since it replaces combustible matter.Proximate analysis
Moisture Content : Moisture in coal must be transported. it decreases the heat content per kg of coal Aids radiation heat transfer 1-2 gm 72 mesh coal at 105-110 C till constant weight
and helps in easier ignition of coal Sets minimum limit on the furnace height and volume 72 mesh coal 900-950 C for 7 minutes
. and incombustible gases like CO2 and N2 Proportionately increases flame length. hydrocarbons.Proximate analysis
Volatile Matter: Consist of CH4. H2 and CO.
• Affects combustion efficiency and boiler efficiency • Causes clinkering • 1-2 gm 72 mesh 800 C (burned)
. • Increases handling costs.Proximate analysis
Ash Content : • Ash is an impurity that will not burn • Reduces handling and burning capacity.
Fixed carbon: Solid fuel left in the furnace after volatile matter is removed consists mostly of carbon may contains some H2. O2. S and N2 gives a rough estimate of heating value of coal
Beginning of Fossilization
The oldest peats are about 1 million years old. Composition depends on type.
. It is regarded as the borderline between vegetation (biomass) and a fossil fuel. depth of deposit and age. fibrous mass of partially decayed plant material accumulated in situ under water-logged conditions. When wood is subjected to bacterial processes under nearly stagnant water. lignin and protein are decomposed. Peat is believed to have formed from wood. the cellulose.Peat
Peat is the first stage in the formation of coal. Residuals combine to form dopplerite. It is a brown.
Reduces to 90% when cut. Wet peat contains 95% moisture. Ash is about 3%. Reduces to less than 25% when air dried.900 kJ/kg.
.700 and 20.Peat (Continued)
Contains 70-90% dopplerite and 5-30% resins and waxes. Calorific value varies between 16.
.Peat (Continued) Combustion Characteristics:
1. Its low bulk density (320 kg/m3) reduces capacity of furnace and increases storage and handling capacity due to its high volume.
Its low calorific value and high moisture content reduces furnace temperature and efficiency of combustion.
2. Its friable nature (can be easily crumbled) causes appreciable loss in handling.
Ultimate Analysis of Peat on wet basis with ash:
Carbon: 84.8% Ash: 3.2% Hydrogen: 1.1% Moisture: 3.0% Calorific Value : 16.9% Oxygen + Nitrogen: 7.700-20.900 kJ/kg
It is intermediate in composition between peat and bituminous coal. It is an immature form of coal.
. Believed to be between 10 and 40 million years old.Lignite
Forms the first phase of fossilization of vegetable matter. Most immature lignites are chemically similar to most mature peats.
5-78.900-29.5-30% 20-75% 12-20% 3-30% 40-50% 1-12% 20.300 kJ/kg
.Composition of typical Lignites:
Carbon: Oxygen + Nitrogen +Sulfur Water (as mined) Water (dried) Ash Volatile matter Sulfur Calorific value (dry) Used raw or dried in furnaces Pulverized and used in mills 64.5% 16.
. A progressive loss of volatile matter.
With increasing Rank. Generally. A progressive decrease in equilibrium moisture content. a progressive increase in calorific value. This increases with increase in depth of deposit. the following characteristics are noticed: Age of coal is increased. with a corresponding increase in carbon.
4. a progressive increase of ash content.
3. In some cases. A progressive loss of oxygen.Rank of Coal
1. hydrogen and in some cases sulfur.
Proximate Analysis of some typical anthracite coals
Class and group Meta-anthracite
Fixed Carbon % Volatile Matter % Age in million years Cal. value kJ/kg
. % 14-22 Age in million years 100 Calorific Value kJ/kg 36520
High volatile: A.B.Proximate Analysis of some typical bituminous coals
Class and group Fixed Carbon. % 78-86 Volatile Matter.
Proximate Analysis of some typical sub-bituminous coals
Class and group Fixed Carbon. % 69-72 Volatile Matter. % 28-31 Age in million years 40 Calorific Value kJ/kg 36050
Proximate Analysis of some typical Lignites
Class and group Fixed Carbon. % 58-64 Volatile Matter. % 36-42 Age in million years 1 Calorific Value kJ/kg 36050
Balance (Data not available)
1.Ultimate Analysis of some typical anthracite coals
C H O N+S Ash % Moisture %
7 5.0-5.0-4. ash-free) Typical Subbituminous C 91-93 80-91 82.75 2.Bituminous Typical Sub-bituminous (dry.1
18.5-6.9 75-80 78 74.5 4.1 5 5.0 H 4.1
5.26 4.Ultimate Analysis of some typical Carbonaceous and Bituminous coals
Fuel Type Carbonaceous Bituminous Typical Bituminous Sub.9 O N+S Ash Moisture
Data not given Data not given Data not given Data not given 4 2.0 5.9 13 13.01 9.4
Data not given
0-5.7 4.7 5 25.72
5.5 25 2 O N+S Ash Moisture Data not given Data not given Dry.Ultimate Analysis of Some Typical Lignite.8 38 44 44
Data not given 1 Tr Dry.62
4.8 68 H 5. ash-free
Typical Peat Typical Peat Typical Wood Typical Wood
56.6 6 6 6.7
60. Peat and Wood
Fuel Type Lignite Typical Lignite Typical Lignite C 60-75 68.89
33.5 55 50 49. ash-free Data not given
. ash-free Dry.
Mineral Elements and Chlorine in Pine and Bituminous Coals
Element Ca Na K Pine (Ave. values) (ppm) 760 28 39 Illinois Coal >5000 200-5000 200-5000 (ppm)
Mn Fe P Si Al Cl
97 10 40 6 48
6-210 >5000 10-340 >5000 >5000 200-1000
Coal gradually loses its volatility and goes deeper whereas petroleum becomes progressively lighter as it cracks and rises. increasing temperature affect in opposite ways.
.Co-existence of coal and petroleum
Where coal and petroleum co-exist. Thus the best coals are deeper in the ground whereas the best petroleum are nearer the ground level.
But thermal decomposition begins at a much lower temperature. and leaves a solid residue whose composition and properties depend on heat treatment temperature. Evolves water.Coal Combustion
When heated to progressively higher temperatures in inert atmosphere (very little oxygen present). coal decomposes. Can be divided into 3 stages. tar and gas.
. Temperature range in which volatilization proceeds very rapidly is 350-500oC.
Combustion of Coal
the carbonaceous material undergoes several different processes: The pyrolysis (or devolatilization) process occurs as the carbonaceous particle heats up. resulting in up to 70% weight loss for coal.
. The combustion process occurs as the volatile products and some of the char reacts with oxygen to form carbon dioxide and carbon monoxide. which provides heat for the subsequent combustion reactions. The process is dependent on the properties of the carbonaceous material and determines the structure and composition of the char. Volatiles are released and char is produced.
. H2O.Main Processes in Coal Combustion
p-coal. H2O. …
heat conduction Pyrolysis (T > 400° C) Ignition of volatiles.Processes at coal combustion
The carbon particle is preheated – heat radiation. temperature 1000-1700 °C Coal particles (char) are ignited
evaporation of volatiles and homogeneous ignition
.Processes during coal combustionStructural change of coal particles during ignition
Radiative heat transfer between the gas and coal particles and between the coal/air mixture and the furnace walls.The physical processes influencing pulverized coal combustion
Turbulent/swirling flow of air and coal. Turbulent/convective/molecular diffusion of gaseous reactants and products.
. Convective heat transfer through the gas and between the gas and coal particles.
Coal Combustion~ Air Pollutants
CO2 CO NOx SOx Particulate matter Trace metals Organic compounds
Carbon Dioxide. Meanwhile.
C + O2 CO2
Almost 99% of C in coal is converted to CO2. CO2 sequestration is being tested. coal power plants will have to leave steam-based systems (37% efficiency) and go towards coal gasification technology (60% efficiency). In order to lower CO2 emission levels.
temperature or turbulence).Carbon monoxide. CO
C + ½O2 CO
CO is minimized by control of the combustion process (air/fuel ratio.
. residence time.
4. since combustion is almost complete. 3. Pollution control equipment. Coal properties.Particulate Matter
PM composition and emission levels are a complex function of: 1.
In PC power plants. 2. Boiler firing configuration. the emitted PM is primarily composed of inorganic ash residues.
. Boiler operation.
9% Electrostatic precipitator (ESP)
Wet scrubber Cyclone 95-99% 90-95% (d(m)>10)
.1<d (m)<10) Fabric filter (or bag house) As high as 99.1>d(m)>10) <99% (for 0.PM controls (AP-42. EPA)
Mainly post combustion methods:
99% (for 0.
Collection of fine particles. Be. Pb. Cd. Cr)
Class 2 Elements that are enriched in fly ash relative to bottom ash (Ar. combustion conditions.
Class 1 Elements that are approximately equally concentrated in the fly ash and bottom ash (Mn. physical and chemical properties of the metal.
Control of total particulate matter emissions
Class 3 Elements which are emitted in the gas phase (mainly Hg).Trace metals
FORMATION Concentration of metal in coal.
The main groups of environmental concern are: 1) Tetra-chloro.
Emissions dependent on combustion behavior in the boiler (air/fuel ratio. Characterized by hydrocarbon class: alkanes. 2) Polycyclic organic matter (POM). alcohols and substituted benzenes. semi volatile and condensable organic compounds either present in the coal or formed as a product of incomplete combustion.
. residence time. temperature or turbulence).through octa-chloro.dioxins and furans. alkenes. aldehydes.Organic Compounds
Sulfur in coal (<10%)
Organic sulfur (40%) Chemically bonded to the hydrocarbon matrix in the forms of thiophene, thiopyrone, sulfides and thiol. Inorganic sulfur (60%) Imbedded in the coal, as loose pyrite - FeS2 or marcasite, and calcium/iron/barium sulfates. Sources of sulfur in coal: Seawater sulfates, Limestone
radicals Coal-S (CS, S2, S, SH) SO
Nitrogen Oxides, NOx
Nitrogen in Coal (1-2%)
Name Pyridine1 Structure ~ Relative amount 15-40% Stability More stable
structures made up of 2-5 fused aromatic rings.
Main NO Mechanisms
Fuel NO: volatiles-NO and char-NO
N2 + O NO + N N + O2 NO + O
Strong temperature-dependence: >1300-1500°C Not a major source of NO in coal utility boilers.
N2 + CHx HCN + N + …
N + OH NO + H Prevalent only in fuel-rich systems.
. Not a major source of NO in coal utility boilers.
.Fuel NO (-N in volatiles)
HCN/NH3 + O2 NO + HCN/NH3
The major source of NO in coal utility boilers (>80%).
Char NO (-N in the char)
Char-N + ½O2 NO
Char-C + NO ½N2 + Char(O)
[char-NO = ~25%] < [volatiles-NO = ~75%]
1% of total CO emissions. 39% of total NOx emissions.1) Coal combustion in India has tripled since 1990. 62% of total CO2 emissions. Almost all of coal use is for electricity production. 2) Coal combustion emissions in India: 71% of total SO2 emissions.
. 38% of total SPM emissions.
FeCo3 FeS Nacl Na2So4 Cacl2 MgCl2 Quartz Kaolinite Calcite Siderite Dolomite Ankerite Pyrite Alkali Metals Melting Point Deg.2H2O CaCo3 FeCo3 CaCo3. C 1983 2083 1200 800 1050 1000 1075 700-850
.MgCo3 CaCo3.Minerals Present in Coal
Minerals Chemical Formula Sio2 Al2o3.
Minerals in Coal Ash
Low Fusible Compounds (700-850Deg. Al2o3
. Mgcl2 Medium Fusible Compounds(900-1000) FeS .K2So4.Cacl2.Na2So4.Fe2o3 High Melting Compounds(1600-2800) Sio2. C) Nacl.
6 mm in height
. C) HT –Hemispherical Temperature (1200-1400 Deg C) FT.Ash Fusion Temperature
ID –Initial Deformation Temperature (1000-1200 Deg.Fusion Temperature (1400-1600 Deg C)
Name Initial deformation temperature (IT) Softening temperature (ST) also sometimes called the spherical temperature Hemispherical temperature (HT) Fluid temperature (FT)
is the temperature at which the point of cone begins to round the base of the cone is equal to its height the base of the cone is twice its height the cone has spread to a fused mass no more than 1.
Effect of Low Fusibles
Condense on the surface of clean tubes Form primary sticky layer Solid particles adhere to this layer Dense internal layer and loose external layer
SiO2) whose melting point is 1205 Deg C . Minerals like CaO & MgO are also good Fluxing agents.Effect of Medium Fusibles
Fe2O3 gets reduced to FeO .
. Fayalite(2FeO.SiO2 and Al2O3 gives compounds of different melting points. Different mixture of FeO .P of FeO is 200 above and of SiO2 is 500 Deg C above this.M.
Individually they are harmless.
.Effect of Compounds having high melting point
Participate in agglomeration.
Slagging and Fouling
Platten Fouling Reheater Slagging
Base/Acid Ratio: (Fe2O3 +CaO +MgO+K2O+ Na2O) (SiO2 +Al2O3+TiO2)
Silica Percentage: (SiO2 * 100) ( SiO2 +Fe2O3 +CaO+ MgO) A smaller Base/ Acid ratio and higher silica percentage makes coal less slag prone
Severe slagging of pulverised coal fired boilers is usually associated with coal ashes rich in iron.
Fouling means building up of bonded & sintered deposits on super-heater and re-heater tubes in the convection heat transfer passage of boiler. The ash deposit on heat exchange surface in the combustion chamber is termed as slag.
Toacoal Copper-Oxy-Chloride. These additives either increase the ash fusion temperature or change its Theological behavior by way of changing its sticking properties and viscosity. Thermosol. clinkering.
.E. three possible remedial measures can be adopted :Additive dosing :Thermomix.Control of Slagging &Fouling
To minimize slagging. & deposit formation.
Boiler Efficiency Steam Output
Heat Input is Pulverised Coal Heat Output is Superheated Steam
Losses in Boilers
Second Pass Furnace ESP
1) Loss due to dry flue gas = 4.928%
Losses in Boilers Contd.
2) Loss due to Un-burnt Carbon = 0.331%
Second Pass ESP
3) Due to Sen.Losses in Boilers Contd.102%
.071% = 0. Heat of Bottom Ash 4) Due to Sen. Heat of Fly Ash
5) Radiation Losses
= 0.Losses in Boilers Contd.
074% = 1.263% = 0.83%
.537% 8) Loss due to Moisture in Air 9) Unaccounted Losses Total Losses
= 13.Losses Related to Coal & Ambient Air Quality
Loss due to moisture in Fuel
7) Loss due to Hydrogen in Fuel = 5.
Heat loss due to dry flue gas
Dry Flue Gas Loss
Heat loss due to wet flue gas Heat loss due to moisture in fuel Heat loss due to moisture in air Heat loss due to unburnts in residue Heat loss due to radiation & other unaccounted loss
Heat 100% from Fuel
0.5% 4.Boiler Heat Balance
5.3% 1% 1%
Boiler Efficiency (Heat in Steam)
.Thank you and Questions?