ER 100:

Energy Toolkit I: Combustion

Dan Kammen

September 1, 2010
 Overview
• What do we do with fossil fuels: burn ‘em
– Combustion: impacts
• Fuels
• Balancing combustion chemical equations
• Combustion products
• Equivalence ratios
• Energy content and temperature
 Importance of fossil fuels
• The major contributors to Energy Use in the US and in the
world
Energy Supply 2000 World U.S.
Total Energy use (Quads) 428 97
Coal (%) 33 38
Natural Gas(%) 22 26
Biomass fuels (%) 13 4
Hydropower (%) 6 4
Nuclear (%) 6 8
Solar, wind, geothermal (%) <0.5 0.4

Electricity Supply 1995 World U.S.

Net generation (TWh) 12,500 3,400
Fossil fuel (%) 62 68
Hydropower (%) 19 9
Nuclear (%) 17 20
Biomass and other (%) 5 3
 Emissions: Terms of Discussion
• Mole fraction (%, ppm, ppb)
• mass/energy in (pollutant/MMBtu, Kg/KJ)
• mass/distance (g/mile) [vehicle standards]
• mass/volume = g/m3
• reference emissions to corrected oxygen content in
exhaust to prevent apparent emission reductions
by dilution
– Remember, the solution to pollution is … dilution.
 What happens in combustion?
• Fuel + oxidizer -> Products + light + heat
• Combustion, in its simplest form, e.g: methane
CH4 + 2O2  CO2 + 2H20

A clean reaction, except for the issue of carbon

dioxide and the global climate
This idealized reaction takes place in an
‘atmosphere’ (oxygen) free of impurities
Context: combustion is part of the story

(On road emissions)

Source: Brandt and Farrell (2006) Environmental Research Letters (erl.iop.org)

 Fuel: Data Summary
 Properties of Selected Fuels
CH4 C2H6 C3H8 Other HCs H2S Heating Value
(wt%) (106 J/m3)
Natural gas (No.1) 87.7 5.6 2.4 1.8 2.7 43.2
Natural gas (No.2) 88.8 6.4 2.7 2.0 0.0004 41.9

(Ultimate analysis) C H N O S Heating value

(wt%) (106 J kg-1)
Gasoline (No.2) 86.4 12.7 0.1 0.1 0.4-0.7 ~ 35

(Approximate analysis) Carbon Volatile matter Moisture Ash Heating value

(%) (%) (%) (%) (106 J kg-1)
Anthracite (PA) 77.1 3.8 5.4 13.7 27.8
Bituminous (PA) 70.0 20.5 3.3 6.2 33.3
Subbituminous (CO) 45.9 30.5 19.6 4.0 23.6
Lignite (ND) 30.8 28.2 34.8 6.2 16.8

Data from Flagan and Seinfeld, Fundamentals of Air Pollution Engineering, 1988, Prentice-Hall.
How much CO2 is produced when 1 ton of cellulose (C6H12O6) is burned?
Balance the equation:
C6H12O6 + O2  CO2 + H2O
First the carbon:
C6H12O6 + O2  6CO2 + H2O
Then the hydrogen:
C6H12O6 + O2  6CO2 + 6H2O
Last, the oxygen (because you can change the oxygen without altering other elements):
C6H12O6 + O2  6CO2 + 6H2O,

Oxygen: 6 + x Oxygen: 12 + 6 =18

So, 6 + x = 18  x = 12, or 6 O2The balanced equation is:
C6H12O6 + 6O2  6CO2 + 6H2O
What about the grams per mole of wood (molecular weight):
C6H12O6 = (6 x 12) + (12 x 1) + (6 x16) = 180 grams/mole
How much CO2 is produced when 1 metric ton of wood is burned,
continued ...
From the equation we can find out how much CO2 we get per
metric ton of wood.
So, from C6H12O6  6CO2 + 6H2O, we see that:

180g C 6H12O 6 10 6 g C 6H12O 6


264g CO 2 X gCO 2

(12+(2x16)) = 44 grams per mole of CO2


264g x 106 g
x=  1.47 x 106 g  1.47 tons of CO 2
180g
 Combustion Stoichiometry: More elegant solution

 Combustion in Oxygen

Cn H m  O2  CO2  H 2O

1. Can you balance the above equation?

2. Write the reactions for combustion of methane
and benzene in oxygen, respectively.
Answer

 m m
Cn H m   n  O2  nCO2  H 2O
 4 2

CH 4  2O2  CO2  2H 2O

C6 H 6  7.5O2  6CO2  3H 2O

10
 Combustion Stoichiometry

 Combustion in Air (O2 = 21%, N2 = 79%)

Cn H m  (O2  3.78N 2 )  CO2  H 2O  N 2

1. Can you balance the above equation?

2. Write the reactions for combustion of methane
and benzene in air, respectively.
Answer

 m m  m
Cn H m   n  (O2  3.78N 2 )  nCO2  H 2O  3.78 n   N 2
 4 2  4
CH 4  2(O2  3.78N 2 )  CO2  2H 2O  7.56N 2

C6 H 6  7.5(O2  3.78N 2 )  6CO2  3H 2O  28.35N 2

11
 Real Combustion

• If combustion occurs without complete oxidation instead,

we get:
CH4 + O2 + N2  mostly (CO2 + 2H20 +N2)
+ traces (CO + HC +NO...)
• This can occur when:
– temperature too low,
– insufficient O,
– combustion too rapid,
– poor mixing of fuel and air, etc. ...
 Real, Real (fully nasty), Combustion

• At higher temperatures, N reacts with O:

air(N2 +O2) + heat  NOx (thermal)
• So much for pure fuels, now add impurities:
enter N, S, metals and ash (non-combustibles)
What we really get:
• Fuel (C, H, N, S, ash) + air (N2 +O2) 
(CO2, H2O, CO, NOx, SOx, VOCS, particulates) +
ash
– Volatile Organic Compounds: VOCs
 Air-Fuel Ratio
 Air-Fuel (AF) ratio
AF = m Air / m Fuel
Where: m air = mass of air in the feed mixture

m fuel = mass of fuel in the feed mixture

Fuel-Air ratio: FA = m Fuel /m Air = 1/AF

 Air-Fuel molar ratio

AFmole = nAir / nFuel
Where: nair = moles of air in the feed mixture
nfuel = moles of fuel in the feed mixture
14
 Air-Fuel Ratio

 Rich mixture
- more fuel than necessary
(AF) mixture < (AF)stoich

 Lean mixture
- more air than necessary
(AF) mixture > (AF)stoich

Most combustion systems operate under lean conditions.

Why is this advantageous?
Consider the combustion of methanol in an engine.
If the Air-Fuel ratio of the actual mixture is 20, is the
engine operating under rich or lean conditions?
16
 Equivalence Ratio

Equivalence ratio: shows the deviation of an actual

mixture from stoichiometric conditions.

( FA) actual ( AF ) stoich

 
( FA) stoich ( AF ) actual

The combustion of methane has an equivalence

ratio Φ=0.8 in a certain condition. What is the
percent of excess air (EA) used in the combustion?

How does temperature change as Φ increases?

17
 Formation of NOx and CO in Combustion

 Thermal NOx
- Oxidation of atmospheric N2 at high temperatures
N 2  O2  2 NO
NO  12 O2  NO2
- Formation of thermal NOx is favorable at higher temperature

 Fuel NOx
- Oxidation of nitrogen compounds contained in the fuel

 Formation of CO
- Incomplete Combustion
- Dissociation of1 CO2 at high temperature
CO2  CO  2 O2
18
 Air Pollutants from Combustion

How do you explain the trends of the exhaust HCs, CO, and NOx as a
function of air-fuel ratio? 19

How do you minimize NOx and CO emission?

 Attainment Areas and
Nonattainment Areas
• National ambient air quality standards (NAAQS)
for six pollutants (referred to as criteria
pollutants): carbon monoxide, lead, ozone (ground
level), nitrogen dioxide, particulate matter (PM2.5
and PM10), sulfur oxides.
• Nonattainment area: a geographic area where
ambient air quality concentrations exceed NAAQS
for one or more criteria pollutants.
 Criteria Pollutants & the Clean Air Act

POLLUTANT Emissions Air Concentration

‘83 - ‘02 ‘93 - ‘02 ‘83 - ‘02 ‘93 - ‘02
CO - 41% - 21% - 65% - 42%
Pb - 93 % -5% - 94% - 57%
O3 [1 hr] - 40 % - 25% - 22% - 2%
PM10 - 34% - 22% - - 10%
PM2.5 - - 17% - - 8%
SO2 - 33% - 31% -34% - 39%
NOx - 15% -9% - 2% +.5%
Ultrafines

• Create greater inflammatory response than fine PM

• Affect heart rate variability
• Are more potent in inducing cellular damage than fine PM
• May be associated with premature death
Aerosols

http://earthobservatory.nasa.gov/Library/Aerosols/
 Aerosols:
from power plants & cars

http://earthobservatory.nasa.gov/Library/Aerosols/
 Summary: Combustion Products
• Air, N2, O2, Ar
• Products of complete combustion: CO2, H2O
• Products of incomplete combustion: trace
hydrocarbons, unburned hydrocarbons, CO, H2,
aldehydes, soot
• Fuel impurities: SO2, SO, metals, metal oxides, ash
(silica, sand)
• Nitrogen compounds: N source is the air or
the fuel, e.g.
NO, NO2, N2O, HONO, NH2
Fossil fuel combustion (chemistry)
• Coal = Carbon (C) + impurities (e.g., sulfur)
• Oil = Mixture of hydrocarbons (CxHy) + imp.
• Natural Gas = methane (CH4) + carbon dioxide (CO2) + imp.
• Combustion = oxidation, exothermic
CxHy + O2  CO2 + H2O + ENERGY + (CO+C)
N2 + O2  NOx
S + O2  SOx
• Ratio of x:y determines ratio of CO2:H2O
• CH4 has lowest x:y and thus lowest CO2 per energy
• Carbon has the highest ratio
 Solid fuels
• Peat
• Coal (moisture, volatiles, fixed carbon, ash)
(CH0.8)
• Wood (moisture, volatiles, fixed carbon, ash)
• Charcoal (devolatilized wood)
• Coke (devolatilized coal or petroleum)

• Key difference among fuels: the quantity of CO2

formed per unit of energy released. Natural gas
releases ~ 42% less CO2 than coal
Chemical Structure of Coal
 Gas and Liquid Fuels
• Natural gas: CH4, C2H6, N2, CO2
• Propane(C3), Butane (C4), LPG (mixture)
• Synthetic gases (from biomass, coal products)
• Petroleum derived fuels (~CH2);
– Gasoline (C4 to C10, avg: C8)
– Diesel (C12)
– Turbine fuels, kerosene (C10)
– Heavy fuel oils
• Shale oil derived liquids
• Alcohols, ethers (have oxygen in the fuel)
• Hydrogen
 Products
• Depend on fuel, mixing, and temperature
• At temperatures < 1250 K
– fuel + oxidizer --> O2 + CO2 + H2O + N2
• At combustion temperatures (~1400-2200 K)
– many stable species dissociate
– molecular events and elementary reactions important
• CO2 <=>CO+ 1/2 O2
• H20<=> H2 + 1/2 O2
– Actual product concentrations depend on balance
among reactions that lead to formation & consumption
of intermediate species (and the kinetics)
ER200 (preview of fuel cell session): All reactions
accompanied by absorption or release of energy

• Ideal system: adiabatic (ideal) combustion

– no heat loss or energy transfer out of the system
– constant pressure process, steady state, exothermic
– Energy expressed as enthalpy
Energy = E = U + KE + PE
But for gases changes of state require another term, too:
Enthalpy = H = U + pv
internal energy + pressure volume work
Hreactants = Hproducts for an adiabatic system
H for constant pressure reaction = heat absorbed
Reference / resource slides
 Diesel automobile
NOx emission standards
1.0

0.8 USA
Emission (gm/km)

0.6

0.4 Europe

Japan
0.2

0.0
1990 1995 2000 2005 2010 2015
Year
 Diesel automobile
particulate emission standards

0.3

0.2
Emission (gm/km)

0.2 Japan

0.1

Europe
0.1

0.0
1990 1995 2000 2005 2010 2015
Year
 Ratio of permitted diesel emissions
to gasoline emissions
7

US
6 Europe
Japan
Best diesel/best gasoline
Diesel/Gasoline Emissions

0
HCs CO NOx
 US coal S emission standards
2.5

2.0
SO2 Emission (kg/GJ)

1.5

1.0

0.5

0.0
Pre-NSPS 1971 1979 1999 FGD Advanced Average
NSPS NSPS existing
 US coal NOx emission standards
0.50

0.40
NOx Emission (kg/GJ)

0.30

0.20

0.10

0.00
Pre-NSPS 1971 1979 1997 Advanced Average
NSPS NSPS NSPS existing
 US coal particulate emission standards
100

90

80

70
PM Emission (gm/GJ)

60

50

40

30

20

10

0
Pre-NSPS 1971 1979 1999 TSP Advanced Average
NSPS NSPS existing