Chapter 2

Air pollution audits and inventories

• Chapter 2 Part 1

– Mass Balance Method

– Emission Factor Method

2
 2.1 Mass Balance Method

Example: Combustion/Incineration

Burning of fuel (e.g. hydrocarbons, biomass) in the

presence of an excess amount of oxygen

3
 Example 1
Bituminous coal is burnt in a pulverized coal combustor for energy
Example – Mass balance method for estimating emissions
production. On the basis of 100 kg fuel, use the mass balance
method to estimate the concentrations of PM and NOx in the flue
Bituminous coal is burnt in a pulverized coal combustor for energy production. On the basis of 10
gas, in mg/acm and mg/dscm. Also, estimate SO emission in kg/GJ
fuel, use the mass balance method to estimate the concentrations of2 PM, NOx and SO2 in the flue ga
input energy (based on LHV of the fuel).
mg/acm and mg/dscm. Also, estimate SO2 emission in kg/GJ input energy (based on LHV of the fue

wt%, or mass (kg) based on 100 kg solid fuel (wet basis) kJ/kg
H2 O C H S O N Ash LHV
Bituminous coal 3.3 80.7 4.5 1.8 2.4 1.1 6.2 29000

acm: actual cubic meter (m3)

Assumptions:
volume of wet flue gas under actual stack conditions
dscm: dry standard cubic meter (m3)
• Complete combustion, with 20% excess air
volumeo of dry flue gas under standard conditions
• Flue gas: 150 C temperature, 1 atm pressure
• 50 wt% of ash in the fuel pellets will form fly ash (PM)
4
• NO emission is expressed as NOx emission, and thermal NOx is insignificant
5
Solution
Sample calculations

Per 100 kg fuel,

C + O2 à CO2
C: (80.7 kg * 1000 g/kg) / 12 g/mol = 6725 moles
O2 required = 6725 moles
CO2 = 6725 moles

4H + O2 à 2H2O
H: 4.5 * 1000/1 = 4500 moles
O2 required = 4500/4 = 1125 moles
H2O (water produced from burning hydrogen in the fuel) = 4500/2 = 2250 moles
H2O (water in flue gas that originates from moisture in the fuel) = 3.3*1000/18 = 183 moles

S + O2 à SO2
S: 1.8 * 1000/32 = 56 moles 6
H2O (water produced from burning hydrogen in the fuel) = 4500/2 = 2250 moles
H2O (water in flue gas that originates from moisture in the fuel) = 3.3*1000/18 = 183 mole

S + O2 à SO2
S: 1.8 * 1000/32 = 56 moles
O2 required = 56 moles
SO2 = 56 moles

2N + O2 à 2NO
(Generally, 95-99 vol% of NOx in the combustion flue gas is in the form of NO)
N: 1.1 * 1000/14 = 79 moles
O2 required = 79/2 ~ 40 moles
NO = 79 moles

Moles of oxygen atoms in the fuel = 2.4*1000/16 = 150

Hence, deduct 150/2 = 75 moles O2 required (input) for combustion

Total O2 required = 6725 + 1125 + 56 + 40 – 75 = 7871 moles

Total O2 input = 7871 * 1.2 = 9445 moles (20% excess air is used for combustion)7
 Total O2 required = 6725 + 1125 + 56 + 40 – 75 = 7871 moles
Total O2 input = 7871 * 1.2 = 9445 moles (20% excess air is used for combustion)
à N2 input = 9445 * 78/21 = 35080 moles (air contains ~ 78 vol% N2 and 21 vol% O2)

O2 in the flue gas = 9445 – 7871 = 1574 moles

flue
flue gasgas species HH2O
species 2O CO22
CO SO
SO22 OO2 2 NO
NO N2N2
number
number ofofmoles
moles 2250
2250++ 6725
6725 56
56 1574
1574 7979 35080
35080
183
183

X, the number of moles of wet flue gas

X, the number of moles of wet flue gas
= (2250+183) + 6725 + 56 + 1574 + 79 + 35080 = 45947
= (2250+183) + 6725 + 56 + 1574 + 79 + 35080 = 45947

Y, the number of moles of dry flue gas

Y, the number of moles of dry flue gas
= 45947 – (2250+183) = 43514
= 45947 – (2250+183) = 43514
Amount of fly ash (PM) = 0.5 * 6.2 = 3.1 kg = 3.1 * 106 mg
Amount of fly ash (PM) = 0.5 * 1.5 = 0.75 kg = 0.75 * 106 mg
8
Applying PV = nRT to calculate the volume of flue gas
 o
Forwet
For wetflue
fluegas
gasatatTT==150
150oC C==423
423K,
K,

V=XRT/P
XRT/P==45947
45947**8.315
8.315**423/101300
423/101300==1594
1594mm3 3 = 1594 acm
V= = 1594 acm
(volumeof
(volume offlue
fluegas
gasunder
underactual
actualstack
stackconditions)
conditions)

Pollutant
Pollutantconcentration
concentration
PM
PM==3.1 1066/1594
3.1**10 /1594==1944
1944mg/acm
mg/acm
NO
NOxx==7979**(14+16)
(14+16)**1000/1594
1000/1594==1478
1478mg/acm
mg/acm ANS.
ANS.

For
Fordry
dryflue
fluegas 20oC
gasatatTT==20 o = 293 K,
C = 293 K,

33
V=
V=YRT/P
YRT/P==43514
43514**8.315
8.315**293/101300
293/101300==1064
1064mm ==1064
1064dscm
dscm
(volume
(volumeof
offlue
fluegas
gasunder
underdry
dryand
andstandard
standardconditions)
conditions)

Pollutant
Pollutantconcentration
concentration
6
PM
PM==3.13.1**10
106/1064
/1064==2914
2914mg/dscm
mg/dscm
NO
NOxx==79
79**30
30*1000/1064
*1000/1064==2216
1944mg/dscm
mg/dscm ANS.
ANS.

9
SO2 emission

= mass of SO2 emission/energy content of fuel

Mass of SO2 emission = (#moles * MW) of SO2 = 56 * (32+32)/1000 kg = 3.6 kg

Energy content of fuel = (LHV * mass) of fuel = 29000 * 100 = 2.9E6 kJ = 2.9 GJ

Hence, SO2 emission = 3.6/2.9 = 1.24 kg/GJ input energy ANS.

10
Fuel: Bituminous coal H2O C H S O N Ash LHV, kJ/kg
29000
wt% or mass based on 100 kg fuel 3.3 80.7 4.5 1.8 2.4 1.1 6.2
atomic or molecular wt, g 18 12 1 32 16 14

number of moles 183 6725 4500 56 150 79

O2 required, no. of moles 0 6725 1125 56 -75 39.3 7871
O2 input (20% in excess), no. of moles 9445
N2 input, no. of moles 35080

Flue gas composition

Species H2O CO2 H2O SO2 O2 NO N2 PM (kg) Total (wet) Total (dry)
number of moles 183 6725 2250 56 1574 79 35080 3.1 45947 43514
mol/mol (wet basis) 0.004 0.146 0.049 0.0012 0.034 0.0017 0.763
mol/mol (dry basis) 0.155 0.0013 0.036 0.0018 0.806
o
T, C 150
P, atm 1
V, acm (wet basis) 1594
V, dscm (dry basis) 1064

PM conc. (mg/acm) 1944

PM conc. (mg/dscm) 2914
NOx (mg/acm) 1478
NOx (mg/dscm) 2216
Energy content of fuel, kJ 2.9E+06
SO2 (kg/GJ) 1.24
 Formation of NOx
Thermal NOx

– According to the Zeldovich mechanism, N2

reacts with O2 to form oxygen radicals and
nitrogen radicals in a sequence of reactions at
high temperatures (e.g. flames), leading to the
formation of NOx, called thermal NOx.
– NO formation rate is proportional to the
concentrations of N2 and O2, as well as the
reaction temperature.

12
Fuel NOx

• Some fuels contain nitrogen (up to 2% in coal

and oil shale).
• Most fuel nitrogen is converted to HCN in the
flame, which then converts to NH and NH2.
• NH and NH2 further react with oxygen to
produce NO.
• Typically, fuel NOx ranges from 20 to 50% of
total NOx, depending on the furnace conditions
and the chemical nature of N in the fuel.

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Prompt NOx

• During combustion, the carbon-bearing radicals

from the fuel can react with nitrogen in air by:

CH (CH2 and C) + N2 à HCN + N

• N radicals then react with O2 to promote the

formation of NO.
• Although there is no simple treatment for the
formation of prompt NO, it is generally believed
that prompt NO mechanism is significant at low-
temperature flames (e.g. in gas stove).

14
 Relative contributions of
Thermal NO, Fuel NO and Prompt NO

15
 Local/regional emission standards
Example – Lower Mainland, B.C.

Emission standards set by Metro Vancouver (GVRD):

All companies must obtain a permit by meeting the
emission standard before the plant can be put into
operation, and the permit needs to be renewed regularly.

• Some large emitters have to install on-line monitoring

systems to ensure the emission standard is always met.
 Metro Vancouver Air Quality Permits
Current permits:
[Link]
quality-regulatory-program/current-permits-and-approvals

• Industrial and commercial air contaminants

Air Quality Management Bylaw:

A permitting system is used to manage the nature and quantity of air

emissions from large industrial and commercial emitters of air
contaminants. Operations are charged a fee to:
1) fully cover the costs of monitoring and the compliance process, and
2) to provide an incentive for reducing emissions.
BC Ministry of Environment
Guideline for air emissions from MSW combustion

Factsheet (2011) summarizing key information in the Ministry of

Environment's guideline for emissions from Municipal Solid
Waste Combustion.

[Link]
waste/industrial-waste/[Link]
NOTES:
Concentration units: Mass per reference cubic metre (Rm3) corrected to 11% oxygen.
Reference conditions: 20 oC, 101.3 kPa, dry gas N.D. = Not Defined
(1) 97% of the ½ hour average values over an annual operating rolling average will not
exceed 9 mg/m3 . The 28 mg/m3 ½ hour average value is never to be exceeded.
(2) This requirement may be omitted at the discretion of the director should
treatment stages for HCl demonstrate that the emission limit for HCl is not exceeded.
(3) Proponents may be able to demonstrate that monitoring both Total Organic
Carbon and Total Dioxins and Furans could negate the need to monitor Chlorophenols,
Chlorobenzenes, Polycyclic Aromatic Hydrocarbons and Polychlorinated Biphenyls.
(4) Opacity will not be required for compliance purposes for facilities utilizing
continuous particulate monitoring systems. Opacity monitoring is recommended for
operational monitoring purposes. However, opacity monitoring can be used as a
temporary surrogate for total particulate monitoring in the event of a particulate
monitoring system failure. Under these circumstances, the emission limit of 5%
opacity over a ½ hour averaging period should apply.
Consider a situation where the flue gas is emitted from
a combustion process for power production
Without diluting the gas emission by air at the
source, Stack exit
Q1 = Q2 C1 = C2 Q1, C1

If the facility is using air to dilute the gas

emission with an aim to reduce the pollutant
concentration Air (for dilution)
Q1 > Q2 C1 < C2 at 21% O2
But Q1 C1 = Q2 C2 Hence E remains the same
à no change in impact on downwind receptors
What does this imply?
Flue gas
E=QC Q2, C2
where
Here,
Q is the volumetric flow rate (m3/h)
C2 is the concentration before dilution
C is the pollutant concentration (mg/m3)
E is the emission rate (mg/h) C1 is the concentration after dilution
21
 O2 correction
Stack exit
The O2 correction factor was originally specified by USEPA for
Cx (at x% O2)
proper comparison of the source pollutant concentration with the
Cy (at y% O2)
emission standard à To discourage using air to dilute the flue gas
instead of installing pollution control/prevention equipment
before discharging to the atmosphere

21 − 𝑦
𝐶! = 𝐶"
21 − 𝑥
Here,
Cy is the (reported) concentration corrected to y% O2
Cx is the (measured) stack exit concentration at x% O2
under dry standard conditions, i.e. dscm at 20oC and 1 atm
Flue gas

The correction factor of 11% O2 (i.e. y=11) is specified by BCMOE for MSW as fuel
Examples of other correction factors: 3% O2 (for natural gas and fuel oil)
8% O2 (for wood fuel); 15% O2 (for turbines)
22
Example 2 O2 correction factor
A source must meet a standard for PM of 30 mg/dscm corrected to 8%
O2. An in-situ stack monitor measures 20 mg/acm (i.e. mg/m3) PM at
stack conditions. The stack gas is at 200oC and 1 atm pressure and
contains 20% moisture by volume. Determine whether this source is
meeting the emission standard if the stack gas contains 6% O2 by
volume.

Note:

acm: actual cubic meter

dscm: dry standard cubic meter

• The measurement technique for oxygen automatically reports the O2

content at dry conditions.

• For stack sampling, standard conditions refer to 20 oC and 1 atm pressure

Solution
 This is Cx

This is Cy
 2.2 Emission Factor Method

• To facilitate the estimation of industrial emissions, average

emission factors have been developed by various
environmental agencies.
• An emission factor is a representative value that attempts
to relate the quantity of a pollutant released to the
atmosphere with an activity associated with the release of
that pollutant.

• One source of emission factors is the “Compilation of Air

Pollutant Emission Factors” (USEPA Publication AP42)

26
The general equation for emission estimation is:
Ec = A x EFc = A x EFuc x (1 - η/100)
Euc = A x EFuc when η = 0
where:
E = emission rate
A = activity rate
EF = emission factor
η = overall emission reduction efficiency, %

Subscript
uc: uncontrolled emission
c: controlled emission
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USEPA
Technology Transfer Network
Clearinghouse for Inventories & Emissions Factors

Emission Inventories
[Link]

Emission factors were developed based on extensive tests on specific

commercial facilities.

The USEPA WebFIRE (Factor Information Retrievals System) application website

provides online access to EPA’s air emissions factors information (Publication AP 42).
[Link]/webfire/SearchEmissionFactor/[Link]

28
One or more search terms from each of the dropdown menus
(categories) below can be selected to retrieve emissions factors for
criteria air pollutants, GHGs and hazardous air pollutants for industrial
and non-industrial processes.

29
 US EPA Publication AP42, 5th Ed.
Compilation of Air Pollutant Emission Factors
Stationary Point and Area Sources
Chapter

1 External Combustion Sources 8 Inorganic Chemical Industry

2 Solid Waste Disposal 9 Food and Agricultural Industries
3 Stationary Internal Combustion 10 Wood Products Industry
Sources 11 Mineral Products Industry
4 Evaporation Loss Sources 12 Metallurgical Industry
5 Petroleum Industry 13 Miscellaneous Sources
6 Organic Chemical Process Sources
14 Greenhouse Gas Biogenic Sources
7 Liquid Storage Tanks
15 Ordnance Detonation

30
Example of WebFIRE search results
Selected WebFIRE Factors
External Combustion Boilers
EF:
Material: Natural Gas lb NOx/106 ft3 natural gas
Pollutant: Nitrogen oxides, NOx

Source classificationLEVEL4
LEVEL2 code Control device
CONTROL FACTOR QUALITY
Lb/million ft^3
Electric Generation Boilers > 100 Million Btu/hr UNCONTROLLED 280.0 A
except Tangential UNCONTROLLED 190.0 A
FLUE GAS RECIRCULATION 100.0 D
LOW NOX BURNERS 140.0 A
UNCONTROLLED 100.0 B
LOW NOX BURNERS 50.0 D
FLUE GAS RECIRCULATION 32.0 C
LOW NOX BURNERS 32.0 C
Tangentially Fired Units UNCONTROLLED 170.0 A
FLUE GAS RECIRCULATION 76.0 D
Industrial 10-100 Million Btu/hr UNCONTROLLED 100.0 B
LOW NOX BURNERS 50.0 D
FLUE GAS RECIRCULATION 32.0 C
LOW NOX BURNERS 32.0 C
> 100 Million Btu/hr UNCONTROLLED 280.0 A
UNCONTROLLED 190.0 A
FLUE GAS RECIRCULATION 100.0 D
LOW NOX BURNERS 140.0 A
< 10 Million Btu/hr UNCONTROLLED 100.0 A
Cogeneration UNCONTROLLED 170.0 A 31
Example of EF
(not from WebFIRE)