Combustion

(Lecture 3)
Lecture prepared for course in laserbased combustion diagnostics by Per-Erik Bengtsson and Joakim Bood

What is combustion?
Combustion takes place in a flame characterized by: Exothermic reactions Oxidation processes
Oxygen in air is usually the oxidizer Reactants Products + Energy

High temperatures of the products

Typically above 2000 K

Radiation
Chemiluminiscence, Planck radiation

Joakim Bood

Types of flames
Fuel/oxidizer mixing Fluid motion Examples
Spark-Ignited gasoline engines Low-NOx stationary gas turbine Flat flame Bunsen flame (followed by a nonpremixed candle for >1) Diesel engine Aircraft turbine H2/O2 rocket engine Wood fire Candle Radiant burners for heating

Turbulent Premixed Laminar Nonpremixed (Diffusion) Turbulent Laminar

Joakim Bood

Premixed flames - Diffusion flames

Premixed flames
Fuel and air is mixed before combustion
Product zone Reaction zone Pre-heat zone Unburned gas zone Porous-plug burner

Nonpremixed flames (Diffusion flames)

Fuel and air burn when they meet

Fuel + air Air Fuel

Air

Per-Erik Bengtsson and Joakim Bood

Premixed flames
Gaseous fuel and oxidizer are mixed on a molecular level prior to combustion Hydrocarbon/air flames have burning velocities around 0.5 m/s
Example: Spark-Ignition Engine

Joakim Bood

Nonpremixed flames (Diffusion flames)

Fuel and oxidizer are introduced separately and mix during combustion Energy release rate limited by mixing process Reaction zone between oxidant and fuel zone
Joakim Bood

Example: Diesel Engine

Laminar flames
Premixed e.g. Bunsen flame Rather low flame velocity

Nonpremixed (Diffusion) e.g. candle flame Fuel: wax, Oxidizer: air Reaction zone between wax vapors and air

Photo: Per-Erik Bengtsson

Photo: Per-Erik Bengtsson

Joakim Bood

Bunsen flame structure

The flame is stationary, thus the following relation is valid: SL =v sin SL is a property of a fuel/oxidant mixture at certain T and p, and it is around 0.5 m/s for hydrocarbon/air mixtures.

Reaction zone

SL v

Photo: Per-Erik Bengtsson

cold flow velocity half the cone angle SL laminar flame speed
(the velocity of a reaction zone orthogonal to its surface)

Per-Erik Bengtsson

Zones of a premixed flame

Temperature profile along x

~2000 K v sin SL

300 K
Unburned gas zone Preheat zone

Radicals, such as H, OH, and O, are formed here! Reaction zone Product zone

Photo: Per-Erik Bengtsson

The reaction zone moves towards the unburned gas at velocity SL, mainly because H atoms diffuse towards the unburned gas and react with unburned oxygen

H + O2

OH + O
Per-Erik Bengtsson

Turbulent flames
Premixed
Fast heat release Increased flame propagation rate e.g. Spark-Ignition Engine
Turbulent diffusion flame

Diffusion
Can obtain high rates of energy release per unit volume Modeling is very complex, no well established approach e.g. Diesel Engine
Photo: Per-Erik Bengtsson Joakim Bood

Flame propagation

Spark plug

Adiabatic assumptions
No heat losses to the surroundings All heat produced by the combustion is available to heat the product gas Adiabatic flame temperature may be calculated

Joakim Bood

Adiabatic flame temperature

Highest possible temperature that a flame can attain Never achieved in practice
No realistic combustion chamber is adiabatic Dissociation of product lowers temperature

Useful design parameter

Sets the upper temperature limit of the exhaust

Joakim Bood

Maximum laminar flame speed

Fuel Laminar flame speed [m/s] Adiabatic flame temperature [K]

Alkanes
Methane/air Ethane/air Propane/air 0.45 0.47 0.46 2225 2260 2267

Alkenes
Ethene/air Propene/air 0.75 0.72 2370 2334

Alkynes
Ethyne/air 1.58 2539
Per-Erik Bengtsson

Flat flame on porous-plug burner

The flat premixed flame on a porous-plug burner is a proper research flame.
Product zone Reaction zone Preheat zone
Photo: Per-Erik Bengtsson
Sintered porous-plug

Each height represents a certain time in the combustion process. The flame in the picture is very fuel-rich and soot is formed in the product zone.

Fuel + Air

Per-Erik Bengtsson

Stoichiometry
Stoichiometry expresses the ratio between the fuel and oxidant concentration in a mixture. The equivalence ratio, , is used to specify this relationship:

(# moles fuel /# moles oxygen ) in real mixture (# moles fuel / # moles oxygen ) in stoichiometric mixture

The stoichiometric relation for propane combustion: 1 C3H8 + 5 O2 + 18.8 N2 3 CO2 + 4 H2O + 18.8 N2 Example: Calculate the equivalence ratio for a mixture with the molar ratio 1:4 between propane and oxygen:

1/ 4 1/ 5

= 1.2
Per-Erik Bengtsson

Stoichiometry (2)
The stoichiometric relation for propane combustion: 1 C3H8 + 5 O2 + 18.8 N2 3 CO2 + 4 H2O + 18.8 N2 A stoichiometric hydrocarbon mixture gives a flame that ideally gives the products CO2 and H2O only. For such a flame =1. The mole fraction of propane:

X propane =

1 = 0.040 1 + 5 + 18.8
O2 in the exhaust CO and H2 in the exhaust

Xpropane= 0.040 the mixture is stoichiometric Xpropane< 0.040 the mixture is fuel-lean Xpropane> 0.040 the mixture is fuel-rich

Per-Erik Bengtsson

Flammability limits
C2H2 + air n-C4H10 + air C3H8 + air C2H6 + air CH4 + air CH4 + O2 H2 + air H2 + O2

It must be remembered that combustion is always a competition between heatgenerating reactions and cooling processes!

0%

20%

40%

60%

80%

100%

Fuel concentration in mixture

Per-Erik Bengtsson

Temperatures in flames
Temperature in ethane-air flames
2500

2000

Temperature / K

The highest temperature for a premixed hydrocarbon/air flame often obtained at the slightly rich side of stoichiometric. Temperature decreases when decreases from around 1, since the heat released also must be used to heat up surviving oxygen and increasing amounts of nitrogen.

1500

1000

500

0 0.6 0.7 0.8 0.9 1 1.1 1.2 1.3 1.4

Equivalence ratio

Per-Erik Bengtsson

Major species concentrations in product gases

Concentrations in ethane-air flames
0,18 0,16

Water and carbon dioxide have high concentrations over a large range of equivalence ratios.

0,14

Mole fraction

H2O

0,12 0,1 0,08 0,06 0,04 0,02 0 0.6 0.7 0.8 0.9 1 1.1 1.2 1.3 1.4

CO2

Equivalence ratio

Per-Erik Bengtsson

10

Species concentrations in product gases

Concentrations of CO and H2 increase when is raised above 1.
Mole fraction

Concentrations in ethane-air flame

0,09 0,08 0,07

O2

CO

Concentration of O2 increases when is lowered below 1.

0,06 0,05 0,04 0,03 0,02 0,01 0,00 0.6 0.7 0.8 0.9 1 1.1 1.2 1.3 1.4

H2

At =1 CO, H2, and O2 have mole fraction above zero due to equilibrium considerations.

Equivalence ratio

Per-Erik Bengtsson

Concentrations profiles across reaction zone (1)

Per-Erik Bengtsson

11

Concentrations across the reaction zone (2)

Per-Erik Bengtsson

Concentration distributions in diffusion flames

The figure illustrates the concentration distribution of major species in a diffusion flame on methane and air.

The figure illustrates the concentration distribution of additional species in a diffusion flame on methane and air.
Per-Erik Bengtsson

12

Combustion Chemistry (1)

A global reaction is a reaction that shows the reactants and products. However nothing is said about how the reactions occur on a molecular level. An example is The question is now how does the reaction between hydrogen and oxygen start? The reaction starts from two molecules colliding and breaking apart. For example, H2 collides with another molecule in the gas, arbitrarily called M. The hydrogen molecule and the other molecule must both have a very high energy, i.e. a high velocity, to create the first radicals.
Per-Erik Bengtsson

2 H 2 + 1 O2

2 H2O

H2+ M

H+H+M

Combustion Chemistry (2)

Rates of chemical reactions
xAA + xBB + . xPP + xQQ + . Rate law:

1 d [A] 1 d [B ] 1 d [P ] 1 d [Q ] a b = = = = k [A] [B ] x A dt xB dt xP dt xQ dt
Rate constant

a: reaction order with respect to species A b: reaction order with respect to species B a + b: overall order of reaction

Joakim Bood

13

Combustion Chemistry (3)

Temperature dependence of the rate constant

k = A exp( E / RT ) Arrhenius equation (two-parameter repr.)

A: Pre-exponential factor, E: Activation energy, R: ideal gas const, T: Temp

Experiment
CH4exp OH k=A +
E / RT

Three-parameter Arrhenius expression fitted to the measured data:

k = A' T n exp( E / RT )

Joakim Bood

Combustion chemistry (4)

A detailed chemical mechanism for hydrogen combustion contains 19 reactions.

Per-Erik Bengtsson & Joakim Bood

14

How does combustion proceed?

Combustion of methane: 1 CH4 + 2 O2 1 CO2 + 2 H2O Methane oxidation mechanism:

Per-Erik Bengtsson

Full methane mechanism

149 reactions

Per-Erik Bengtsson

15

Summary: Premixed flames

Per-Erik Bengtsson

Planck radiation
4.5E+11 4E+11 Signal intensity (W/m ) 3.5E+11 3E+11 2.5E+11 2E+11 1.5E+11 1E+11 5E+10 0 400 800 1200 1600 2000 2400 2800 Wavelength (nm)
Photo: Per-Erik Bengtsson
3

T=1600K T=2000K

Visible spectral range

Per-Erik Bengtsson

16

The blue-green emission from flames

UV Visible The blue-green emission from the reaction zone has its origin in radicals that have been produced in an excited electronic state from chemical reactions, so-called chemiluminescence. CH contributes in the blue spectral region, and C2 contributes in the blue and green spectral regions.

Per-Erik Bengtsson

17