Coal Combustion

D.Mishra Sr.A.Chemist NTPC-Vindhyachal dileepmishra@ntpc.co.in 94258-23647

Coal

A Fully Fossilized Fuel

Contents

What is coal? Formation, sources, applications. Coal combustion description. Ash Characterization

Coal what is it?

C
Elemental Composition

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.

N
Ash H2O

1-2%
5-35% 2-15%

Char 20-55%

Proximate Analysis

VM

20-25%

Over 1200 coals have been Coalification forms different classified. coal types: (Peat) Lignite Bituminous coal Time, Temperature Coal Rank Anthracite (Graphite)

Coal

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

Coal Sources

Coal is the worlds most plentiful fossil fuel. Recoverable world coal reserves are estimated at about 1X1012 tons.

World Coal Reserves (1989)

7% 5% 7% 8% 12% 29% 32%
United States Russia China Australia Germany South Africa Poland

Coal Applications

Homes heat and cooking Transportation steam engines Industry metal works Electricity power plants

Coal Classification
There are a number ways to classify coals. One way is to Rank the coal. It indicates the degree or extent of maturation. It is a qualitative measure of carbon content. 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. Low rank coals may not be suitable for some applications as the higher ranked ones. Although they may be superior to them in other applications

Coal classification
Peat :
Lignite: soft coal and the youngest

sub-bituminous
Bituminous:

semi-bituminous:
Anthracite: hard and geologically the oldest composed mainly of 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 . Anthracite coal refers to coal with 92-95% fixed carbon .

Lignite

Bituminous

Anthracite

Coal Analysis
Proximate analysis of coal

Determines only fixed carbon, volatile matter, moisture and ash

Useful to find out heating value (GCV)

Simple analysis equipment

Ultimate analysis of coal Determines all coal component elements: carbon, hydrogen, oxygen, sulphur, etc Useful for furnace design (e.g flame temperature, flue duct design)

Laboratory analysis

Proximate analysis

Moisture Content : Moisture in coal must be transported, handled and stored Since it replaces combustible matter, 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

Proximate analysis

Volatile Matter: Consist of CH4, hydrocarbons, H2 and CO, and incombustible gases like CO2 and N2 Proportionately increases flame length, 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

Proximate analysis
Ash Content : Ash is an impurity that will not burn Reduces handling and burning capacity. Increases handling costs. Affects combustion efficiency and boiler efficiency Causes clinkering 1-2 gm 72 mesh 800 C (burned)

Proximate analysis

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

Peat

Beginning of Fossilization

Peat

Peat is the first stage in the formation of coal. It is regarded as the borderline between vegetation (biomass) and a fossil fuel. It is a brown, fibrous mass of partially decayed plant material accumulated in situ under water-logged conditions. Composition depends on type, depth of deposit and age. The oldest peats are about 1 million years old. Peat is believed to have formed from wood. When wood is subjected to bacterial processes under nearly stagnant water, the cellulose, lignin and protein are decomposed. Residuals combine to form dopplerite.

Peat (Continued)

Contains 70-90% dopplerite and 5-30% resins and waxes. Wet peat contains 95% moisture. Reduces to 90% when cut. Reduces to less than 25% when air dried. Ash is about 3%. Calorific value varies between 16,700 and 20,900 kJ/kg.

Peat (Continued) Combustion Characteristics:

1.

2.

3.

Its low calorific value and high moisture content reduces furnace temperature and efficiency of combustion. Its low bulk density (320 kg/m3) reduces capacity of furnace and increases storage and handling capacity due to its high volume. Its friable nature (can be easily crumbled) causes appreciable loss in handling.

Ultimate Analysis of Peat on wet basis with ash:

Carbon: 84.2% Hydrogen: 1.9% Oxygen + Nitrogen: 7.8% Ash: 3.1% Moisture: 3.0% Calorific Value : 16,700-20,900 kJ/kg

Lignite

Lignite

Forms the first phase of fossilization of vegetable matter. It is an immature form of coal. Believed to be between 10 and 40 million years old. It is intermediate in composition between peat and bituminous coal. Most immature lignites are chemically similar to most mature peats.

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 64.5-78.5% 16.5-30% 20-75% 12-20% 3-30% 40-50% 1-12% 20,900-29,300 kJ/kg

Rank of Coal
1.

2.

3.

4.
5.

6.

With increasing Rank, the following characteristics are noticed: Age of coal is increased. This increases with increase in depth of deposit. A progressive loss of oxygen, hydrogen and in some cases sulfur, with a corresponding increase in carbon. A progressive decrease in equilibrium moisture content. A progressive loss of volatile matter. Generally, a progressive increase in calorific value. In some cases, a progressive increase of ash content.

Proximate Analysis of some typical anthracite coals

Class and group Meta-anthracite
Fixed Carbon % Volatile Matter % Age in million years Cal. value kJ/kg

>98

<2

180

35820

Anthracite

92-98

2-8

To

40700

Semi-anthracite

86-92

6-14

250

36750

Proximate Analysis of some typical bituminous coals

Class and group Fixed Carbon, % 78-86 Volatile Matter, % 14-22 Age in million years 100 Calorific Value kJ/kg 36520

Low volatile

Medium volatile

69-78

22-31

To

-do-

High volatile: A,B,C

<69

>31

180

-do-

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

Sub-bituminous A

Sub-bituminous B

64-69

31-36

To

35000

Sub-bituminous C

<64

>36

100

-do-

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

Lignite A

Lignite B

51-57

42-49

To

35000

Lignite C

41-51

49-59

40

-do-

Ultimate Analysis of some typical anthracite coals

Fuel
C H O N+S Ash % Moisture %

Anthracite

93-95

3-4

1-2

1-2

~2

~2

Typical Anthracite

90.27

3.0

2.32

1.44

2.97

1.0

Typical Anthracite

93.7

2.0

2.2

Balance (Data not available)

Ultimate Analysis of some typical Carbonaceous and Bituminous coals

Fuel Type Carbonaceous Bituminous Typical Bituminous Sub- Bituminous Typical Sub-bituminous (dry, ash-free) Typical Subbituminous C 91-93 80-91 82.9 75-80 78 74.0 H 4.0-4.5 4.5-6.0 5.7 5.0-5.1 5 5.9 13 13.01 9.9 O N+S Ash Moisture

Data not given Data not given Data not given Data not given 4 2.26 4.75 2.1

Typical Subbituminous

73.3

5.1

18.4

Data not given

Ultimate Analysis of Some Typical Lignite, Peat and Wood

Fuel Type Lignite Typical Lignite Typical Lignite C 60-75 68.8 68 H 5.0-5.7 4.7 5 25.5 25 2 O N+S Ash Moisture Data not given Data not given Dry, ash-free

Typical Lignite
Typical Peat Typical Peat Typical Wood Typical Wood

56.52
60.5 55 50 49.3

5.72
5.6 6 6 6.7

31.89
33.8 38 44 44

1.62

4.25

15.0

Data not given 1 Tr Dry, ash-free Dry, ash-free Data not given

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)

Mg
Mn Fe P Si Al Cl

110
97 10 40 6 48

200-5000
6-210 >5000 10-340 >5000 >5000 200-1000

Co-existence of coal and petroleum

Where coal and petroleum co-exist, increasing temperature affect in opposite ways. Coal gradually loses its volatility and goes deeper whereas petroleum becomes progressively lighter as it cracks and rises. Thus the best coals are deeper in the ground whereas the best petroleum are nearer the ground level.

Coal Combustion

When heated to progressively higher temperatures in inert atmosphere (very little oxygen present), coal decomposes. Evolves water, tar and gas, and leaves a solid residue whose composition and properties depend on heat treatment temperature. Temperature range in which volatilization proceeds very rapidly is 350-500oC. But thermal decomposition begins at a much lower temperature. Can be divided into 3 stages.

Combustion of Coal

the carbonaceous material undergoes several different processes: The pyrolysis (or devolatilization) process occurs as the carbonaceous particle heats up. Volatiles are released and char is produced, resulting in up to 70% weight loss for coal. The process is dependent on the properties of the carbonaceous material and determines the structure and composition of the char. 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.

Main Processes in Coal Combustion

homogeneous combustion

volatiles
p-coal, d=30-70m

CO2, H2O,

coal particle

char

heterogeneous combustion

CO2, H2O,

devolatilization

tdevolatile=1-5ms

tvolatiles=50-100ms

tchar=1-2sec

Processes at coal combustion

The carbon particle is preheated heat radiation, heat conduction Pyrolysis (T > 400 C) Ignition of volatiles, temperature 1000-1700 C Coal particles (char) are ignited

Processes during coal combustionStructural change of coal particles during ignition

Rapid heating, evaporation of volatiles and homogeneous ignition

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. Radiative heat transfer between the gas and coal particles and between the coal/air mixture and the furnace walls.

Coal Combustion~ Air Pollutants

CO2 CO NOx SOx Particulate matter Trace metals Organic compounds

Carbon Dioxide, CO2

C + O2 CO2

Almost 99% of C in coal is converted to CO2. In order to lower CO2 emission levels, coal power plants will have to leave steam-based systems (37% efficiency) and go towards coal gasification technology (60% efficiency). Meanwhile, CO2 sequestration is being tested.

Carbon monoxide, CO
C + O2 CO

CO is minimized by control of the combustion process (air/fuel ratio, residence time, temperature or turbulence).

Particulate Matter
Bottom Ash

Fly Ash

PM composition and emission levels are a complex function of: 1. Coal properties, 2. Boiler firing configuration, 3. Boiler operation, 4. Pollution control equipment.
In PC power plants, since combustion is almost complete, the emitted PM is primarily composed of inorganic ash residues.

PM controls (AP-42, EPA)

Mainly post combustion methods:

99% (for 0.1>d(m)>10) <99% (for 0.1<d (m)<10) Fabric filter (or bag house) As high as 99.9% Electrostatic precipitator (ESP)
Wet scrubber Cyclone 95-99% 90-95% (d(m)>10)

Trace metals
FORMATION Concentration of metal in coal, physical and chemical properties of the metal, combustion conditions.
Class 1 Elements that are approximately equally concentrated in the fly ash and bottom ash (Mn, Be, Co, Cr)
CONTROL

Class 2 Elements that are enriched in fly ash relative to bottom ash (Ar, Cd, Pb, An)
Collection of fine particles.

Class 3 Elements which are emitted in the gas phase (mainly Hg).

Control of total particulate matter emissions

Sorbents ???

Organic Compounds
Include volatile, semi volatile and condensable organic compounds either present in the coal or formed as a product of incomplete combustion. Characterized by hydrocarbon class: alkanes, alkenes, aldehydes, alcohols and substituted benzenes. The main groups of environmental concern are: 1) Tetra-chloro- through octa-chloro- dioxins and furans. 2) Polycyclic organic matter (POM).
Emissions dependent on combustion behavior in the boiler (air/fuel ratio, residence time, temperature or turbulence).

Sulfur Oxides, SOx

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

SOx Formation
-SO4
radicals Coal-S (CS, S2, S, SH) SO

O2, M

SO2

SO3

char H2S

SO2 molecule

COS, CS2

Nitrogen Oxides, NOx

Nitrogen in Coal (1-2%)

Name Pyridine1 Structure ~ Relative amount 15-40% Stability More stable

Pyrrole1

N H

60%

Less stable

Aromatic amines
1Including

NH2

6-10%

Stable

structures made up of 2-5 fused aromatic rings.

Main NO Mechanisms
1.

Thermal NO
Prompt NO

2.

3.

Fuel NO: volatiles-NO and char-NO

Thermal NO
(Zeldovich mechanism)
N2 + O NO + N N + O2 NO + O
Strong temperature-dependence: >1300-1500C Not a major source of NO in coal utility boilers.

Prompt NO
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)

volatiles

Fuel-N
HCN/NH3 + O2 NO + HCN/NH3

HCN/NH3
NO N2
(formation) (destruction)

The major source of NO in coal utility boilers (>80%).

Char NO (-N in the char)

Char-N + O2 NO
Char-C + NO N2 + Char(O)
(formation)
(destruction)

[char-NO = ~25%] < [volatiles-NO = ~75%]

1) Coal combustion in India has tripled since 1990. Almost all of coal use is for electricity production. 2) Coal combustion emissions in India: 71% of total SO2 emissions. 62% of total CO2 emissions. 39% of total NOx emissions. 38% of total SPM emissions. 1% of total CO emissions.

Coal Ash

Minerals Present in Coal

Minerals Chemical Formula Sio2 Al2o3.2H2O CaCo3 FeCo3 CaCo3.MgCo3 CaCo3.FeCo3 FeS Nacl Na2So4 Cacl2 MgCl2 Quartz Kaolinite Calcite Siderite Dolomite Ankerite Pyrite Alkali Metals Melting Point Deg. C 1983 2083 1200 800 1050 1000 1075 700-850

Minerals in Coal Ash

Low Fusible Compounds (700-850Deg. C) Nacl,Na2So4,Cacl2, Mgcl2 Medium Fusible Compounds(900-1000) FeS ,K2So4,Fe2o3 High Melting Compounds(1600-2800) Sio2, Al2o3

Ash Fusion Temperature

ID Initial Deformation Temperature (1000-1200 Deg. C) HT Hemispherical Temperature (1200-1400 Deg C) FT- 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 1.6 mm in height

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

Effect of Medium Fusibles

Fe2O3 gets reduced to FeO . Different mixture of FeO ,SiO2 and Al2O3 gives compounds of different melting points. Fayalite(2FeO.SiO2) whose melting point is 1205 Deg C .M.P of FeO is 200 above and of SiO2 is 500 Deg C above this. Minerals like CaO & MgO are also good Fluxing agents.

Effect of Compounds having high melting point

Participate in agglomeration. Individually they are harmless.

Slagging and Fouling

Platten Fouling Reheater Slagging

Reheater

Economiser Burners

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

Fouling

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. Severe slagging of pulverised coal fired boilers is usually associated with coal ashes rich in iron.

Control of Slagging &Fouling

To minimize slagging, clinkering, & deposit formation, three possible remedial measures can be adopted :Additive dosing :Thermomix- E, Thermosol, 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.
Coal

cleaning

Furnace temperature:
Furnace temperature

Boiler Efficiency Steam Output

Radiation Loss

Second Pass

Heat Input

ESP Furnace

Heat Input is Pulverised Coal Heat Output is Superheated Steam

Losses in Boilers

Heat Input

Second Pass Furnace ESP

1) Loss due to dry flue gas = 4.928%

Losses in Boilers Contd.

Second Pass

Heat Input

Furnace

ESP

2) Loss due to Un-burnt Carbon = 0.331%

Losses in Boilers Contd.

Heat Input
Furnace

Second Pass ESP

3) Due to Sen. Heat of Bottom Ash 4) Due to Sen. Heat of Fly Ash

= 0.071% = 0.102%

Losses in Boilers Contd.

Heat Input
Furnace

Second Pass

ESP

5) Radiation Losses

= 0.200%

Losses Related to Coal & Ambient Air Quality

6)

Loss due to moisture in Fuel

= 1.263% = 0.074% = 1.327%

7) Loss due to Hydrogen in Fuel = 5.537% 8) Loss due to Moisture in Air 9) Unaccounted Losses Total Losses

= 13.83%

Boiler Heat Balance

5.5% 4.2%

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

1%

BOILER

0.3% 1% 1%

87%

Boiler Efficiency (Heat in Steam)

Thank you and Questions?

dileepmishra@ntpc.co.in 94258-23647