Emissions

Presentation by
Peter Kay

Senior Lecturer
Leaning Objectives
By the end of this lecture you should be able to:
• Describe how unwanted emissions are formed
• Understand the health and environmental impact of the emissions
• Describe how emissions change with equivalence ratio
• Calculate the air to fuel ratio based on the emissions
• Broadly discuss the UK policy on reducing emissions
Combustion Chemistry
• Combustion chemistry is complex and there are many intermediate
products that are formed.
• Consequently, often end up with unwanted products.
Emissions
• Rarely get perfect combustion and often get a range of unwanted
emissions:
o Carbon Monoxide (CO)
o Unburnt hydrocarbons (UBHC)
o Particulate Matter (PM)
o Nitrogen Oxides (NOx)
o Sulphur Dioxide (SO2)
Emission Formation &
Health Effects
Carbon Monoxide
• Formed due to incomplete combustion
• The CO is higher when the mixture is fuel rich/oxygen lean.

• Carbon monoxide, colourless an odourless, is toxic to humans.

o 25 people in England and Wales are killed by CO poisoning (NHS).
o CO has killed many campers who put ‘extinguished’ BBQ in porch
Unburnt Hydrocarbons
• Unburnt Hydrocarbons (UBHC) are formed when the fuel isn’t
properly burnt.
• UBHC’s can be formed in a number of ways:
o The fuel ‘avoiding’ the flame zone by leaking into crevasses, poor
mixing, etc
o Weak flame front, that have a low combustion temperature, due to
fuel-lean or fuel-rich areas
• Unburnt hydrocarbons can form ground level Ozone which is harmful
to health they can also form petrochemical smog
• Unburnt hydrocarbons are not to be mixed up with particulate matter.
Particulate Matter
• Particulate matter (PM) is formed due to incomplete combustion.
• The exact formation mechanisms are still not fully understood. But
essentially formed by nucleation.
• PM10 and PM2.5 refer to particles that are less than 10 and 2.5 microns
respectively.
• Small particulates can get penetrate the lungs, even the bloodstream.
Causing harmful effects such as asthma and lung cancer.
Particulate Matter
1600000 1.6
• Particulate matter is linked to the
equivalence ratio, as shown. 1400000 1.4
• As the mixture gets leaner …

Number Concentration [#/cc]

Mass Concentration [mg/cc]

1200000 1.2
o The mass decreases
1000000 1
o The number increases
800000 0.8
o By definition the droplet size
has to decrease 600000 0.6

• Therefore leaner mixture mean 400000 0.4

less CO2 but more ultra fine 200000 0.2
particulates.
0 0
0.8 1 1.2 1.4 1.6 1.8 2 2.2 2.4 2.6
Fuel-air Equivalence Ratio [-]

Number Concentration Mass Concentration

Nitrogen Oxides
• NOx can be formed in three ways:
o Thermal NOx: High temperature oxidation of the nitrogen in the
combustion air

o Fuel NOx: Nitrogen Oxides that are formed by nitrogen carrying fuels.
o Prompt NOx: Usual term for NOx that are formed by processes other than
those above. For example, nitrogen in the air reacts with radicals such as
C, CH and CH2.
• Cause or exacerbate a number of health conditions, such as inflammation of
the lungs. Also contribute to acid rain.
Sulphur Dioxide
• Sulphur Dioxide is predominately formed by combustion of fossil fuels
to generate electricity

• When inhaled irritates the nose, throat and airways to cause

shortness of breath
o Asthmatics and similar conditions are most at risk of developing
further problems
• SO2 also reacts with the atmosphere to cause acid rain:
Emission Production
Compression v Spark-Ignition
• Compression Ignition:
o Ignition occurs when the temperature of the
compressed air is above the auto-ignition
temperature of the fuel
o Fuel is injected directly into the cylinder
o “Diffusion” flame
• Spark Ignition:
o Ignition controlled by a spark
o Fuel is often mixed with air before cylinder
o “Pre-mixed” Flame
Compression v Spark-Ignition
• Goto https://www.youtube.com/watch?v=Zph5usgWkN0
Emissions
Comparative %vol in exhaust

HC
NOx

CO

Rich Lean

Air-fuel equivalence ratio, λ.

Emission Measurement &
Calculation
Emissions Measurement
• Carbon Monoxide/Dioxide: Measured by infra-red absorption
o The fraction of light absorbed by a sample is proportional to the
concentration of the species.
o Light at the particular absorption spectrum must be used.
• NOx: Measured by chemiluminescence.
o Chemiluminescence is the production of light from a chemical
reaction.
o The intensity of the light is proportional to the species
• Unburnt Hydrocarbons: Measured by flame Ionisation Detection
o When hydrocarbons are burned, ions are formed
o If this is done in an electric field then the current flow corresponds
closely to the number of carbon atoms present.
Emissions Measurement
• Particulate Matter: Typically measured using a Condensation
Particulate Counter (CPC)
o The sample is heated and then passed through a chamber that is
saturated with a fluid, typically butanol.
o The particulates act a nucleation site and the butanol condenses
on the particles
o This causes the particles to ‘grow’ to a suitable size to then be
counted by a laser-based counter.
Emissions Calculation
• So far only complete combustion has been considered.
• However, real exhaust gases contain a soup of products:

• Often all but carbon dioxide, water, excess oxygen and nitrogen are negligible in
the exhaust.
Emissions Calculation
• The composition of the exhaust gases can be used to determine the AFR and vice
versa.
• Consider the example of propane:

• If propane is combusted with excess air then oxygen will be present in the
exhaust:
Predicting Exhaust Composition
• If propane is combusted with excess air then oxygen will be present in the
exhaust:

• The exhaust gases are typically analysed as ‘dry’ samples. In other words with the
water removed. For our example the total number of moles in the dry exhaust is:

• We can also predict the concentrations of the exhaust products. For example, if
10 % excess air is burnt with propane then what is the expected oxygen
concentration, by volume in the dry exhaust?

• Solving gives:
Calculating AFR
• If propane is combusted with excess air then oxygen will be present in the
exhaust:

• The exhaust gases are typically analysed as ‘dry’ samples. In other words with the
water removed. For our example the total number of moles in the dry exhaust is:

• If we know the percentage of one of the products in the exhaust then we can
calculate the excess air. Say the percentage of CO 2 is 10 % by-volume. Then:

• Rearranging gives
• Therefore:
Solution
• From previous slide:

• Therefore AFR is:

Exercise
• A biomass furnace burns a wood chip fuel whose dry combustible
matter has the equivalent chemical formula C6H10O5.
o Write a balanced chemical equation for the combustion for the
biomass with air
• A sample of the dry flue gas is found to contain 14% carbon dioxide
and 7% oxygen by volume.
o Determine the actual air to fuel ratio by volume.
 Solution
• Write a balanced equation for stoichiometric combustion of the wood
chips (C6H10O5)

Reactants Products

Carbon: 6 Carbon: 𝑦 =6

Hydrogen: 10 Hydrogen: 2𝑧 = 10

Oxygen: 2 𝑥 +5 Oxygen:
2 𝑦 +𝑧
= 17
• Therefore:
Solution
• For stoichiometry:

• With excess air:

• Dry exhaust number of moles is:

• Based on percentage of CO2:

• Solving for gives, 49

• Therefore the AFR is 9.
Solution
• With excess air:

Gravimetric AFR is:

Emission Policy
Policy
• Air quality was first recognised in the UK, following the
London Great Smog of 1952
o As many as 12,000 people may have died as a result of
the smog
• In 1956 the Clean Air Act was passed, introducing a
number of measures to reduce air pollution
• The environment act of 1995 led to the implementation of
the National Air Quality Strategy in 1997
o The aim is to provide a framework by which key
pollutants could be reduced and monitored.
Air Quality Management Areas
• Since 1997 each local authority has been reviewing
and assessing the quality of air in their area
• If the air quality is unlikely to meet the National
objectives then a plan must be produced.
• The National objectives set daily and annual limits
for pollutants hazardous to human health
• Bristol set out its own AQMA in 2011.
 National Air Quality Objectives
Pollutant Concentration Averaging Period Permitted Exceedances per annum
PM2.5 25 μg/m3 1 year N/A
PM10 40 μg/m3 1 year N/A
50 μg/m3 24 hours 35
NOx 40 μg/m3 1 year N/A
200 μg/m3 1 hour 18
SO2 125 μg/m3 24 hours 3
350 μg/m3 24 18
Air Quality Management Areas
• Bristol has several stations throughout the city
monitoring emissions
• Bristol is implementing plans to reduce emissions
• These include hybrid buses – Number 72 to UWE
o The has ‘geo-fencing’ technology
o When in the AQMA the bus runs on batteries
o Inductive charging plate at UWE East
entrance
Policy
• In July 2017 the latest UK Air Quality plan was
introduced by Michael Gove
• The main points were:
o The ban of conventional petrol and diesel cars
by 2040.
o Didn’t introduce scrappage scheme, but many
manufactures offering it anyway
o Help authorities with:
̶ Implementation fund to help authorities to
prepare plans (£255m)
̶ Clean air fund for authorities to bid for
additional funding to implement measures
̶ Retrofitting & new low emission buses
(£100m)
Emission Management
Emissions Targets - Automotive
• Because of the ultra fine particles produced during lean combustion
• A Particulate Measurement Programme, commissioned by the
European Joint Research Centre, was completed in 2007 to address
this.
• The permitted PM from vehicles is going to change from a
measurement by mass to number.
• The new measurement is now 6x1011 #/km
o The new number assumes that for typical average size particle
then the mass won’t be exceeded.
Emissions Control
Catalytic converter: either two-way (CO & HC control) or three-way
(CO, HC and NOx):
• Catalytic converters usually contain precious metals contained on a
substrate
• The three-way catalyst has 3 simultaneous tasks:

• However, three way catalytic converters have to operate in a narrow

band of equivalence ratios.
 Emissions Control
• Three way catalytic converters are unsuitable for diesel engines
because of the narrow operational band
• Therefore CO and HC are treated with a two-way catalyst, Diesel
Oxidation Catalyst (DOC).
• A Selective Catalytic Reduction (SCR) device is used to treat NO x.
o The SCR uses aqueous urea to reduce the NO x to Nitrogen, Water
and Carbon Dioxide

• A Diesel Particulate filter is often used to remove PM from the

exhaust. Urea Dosing
System
PM PM
CO2
CO Oxidation CO2 Diesel Particulate Selective Catalytic
Engine H2O
HC Catalyst H2O Filter Reduction N2
NOx NOx
Emissions Control
• SO2 is removed by a simple process called Flue-gas Desulphurisation
(FGD)
• SO2 is an acidic gas and so can be reacted with an alkaline material,
limestone slurry is commonly used.

• Calcium sulphate is has industrial uses such as the production of

gypsum and used as a preservative in the food industry
Leaning Objectives
By the end of this lecture you should be able to:
• Describe how unwanted emissions are formed
• Understand the health and environmental impact of the emissions
• Describe how emissions change with equivalence ratio
• Calculate the air to fuel ratio based on the emissions
• Broadly discuss the UK policy on reducing emissions
 Emissions
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