Chapter 3 concentrations and emissions

• Concentration units: ppm, ppmv, mg/m3, μg/m3

• Equations of State:
pV = m.R.T
pv = R.T
pV = n.Ru.T
R = 287 J/Kg.K
Ru= 8.314 J/mol.K = 0.08206 l.atm/mol.K
Ru = R.MW
MW- molecular weight

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• At STP: T = (0, 15, 20, 25) Degrees Celcius
(T = 60 degree F) and p = 1 atm,
T(F) = 1.8 T(C) + 32 and ΔT(F) = 1.8 ΔT(K)
1 mol of air occupies a volume

• The conversion between ppmv and mg/m3

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 Example of calculation

The US AQS (Air Quality Standard) for CO-

based on 8-hour is 9 ppmv
Express this standard as a % by volume and as
mg/m3 at US STP (T = 25 deg.C and p = 1atm)
Answers:
%CO = 0.0009 %
Concentration of CO in mg/m3 = 10.3 mg/m3

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 Two fields of measurement and estimation
 Ambient measurement: Concentration of pollutants in
ambient air. Ambient monitoring
 Source measurement: concentration/emission from air
pollution source. Source-testing
Representative sample
 EPA guidelines for proper placement of samplers (ex. CO
sampler should be at street level)
 Separate measurements and averaged for source testing
(ex. Stack, where v,c,T,p = f(x,y,z,t))
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 Components of typical ambient-monitoring or
source-sampling device.

If the detector functions in real time (not cumulative), then the gas
meter is not needed, but some kind of signal integrator or recorder is.
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Illustration of some of the problems of choosing a
sampler site to measure ambient CO in a city.

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 Emission estimation methodology

• Several methodologies are available for

calculating emissions from boilers. The method
used is dependent upon available data,
available resources, and the degree of
accuracy required in the estimate.
• In general, site-specific data that are
representative of normal operation at that site
are preferred over industry-averaged data such
as AP-42 emission factors
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 Emission estimation methodology
• Continuous Emission Monitoring System
• Prediction emission monitoring
• Stack sampling
• Fuel analysis
• Emission factor method

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 Continuous Emission Monitoring System

• A CEMS provides a continuous record of emissions

over an extended and uninterrupted period of time.
Various principles are employed to measure the
concentration of pollutants in the gas stream; they are
usually based on photometric measurements.
• Once the pollutant concentration is known, emission
rates are obtained by multiplying the pollutant
concentration by the volumetric stack gas flow rate.
• The accuracy of this method may be problematic at
low pollutant concentrations.
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 CEMS- formula, interference, reference and
equivalent methods, averaging
• Formula

Where: m-mass flow rate (emission) of the

pollutant in mg/s, Kg/h, MT(metric ton)/h or
tonne/h, ton(short ton)/h.
1 Kg = 2.205 lbm, 1 ton = 2000 lbm, 1 ton =
0.91 MT
C- pollutant concentration in mg/m3
Q- flue gas flow rate in m3/s
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 CEMS- formula, interference, reference and
equivalent methods, averaging
• Interference example SO2 measurement
In nitrogen gas: SO2 + 2NaOH Na2SO3 +H2O
In air, CO2 interferes: CO2 + 2NaOH Na2CO3 +H2O
Ambient air SO2: West-Gaeke method (ASTM D2914)
Power plant stack SO2: EPA reference method 6
• Reference method is considered the standard
• Equivalent/alternative method should be checked
against the reference method

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 U.S. EPA "Method 6" sampling train for SO2

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U.S. EPA "Method 6" sampling train for SO2
• Glass wool excludes particulate matter from the rest of the sampling
train.
• The midget bubbler contains an aqueous isopropanol solution, which
removes S03 but not SO2; its contents are discarded after the sampling
is completed.
• The first two midget impingers contain an aqueous solution of
hydrogen peroxide; the third impinger is empty and traps carryover
liquid from the second.
• At the end of the test, the contents of the three midget impingers, plus
the water used to rinse them, are combined and titrated with barium
perchlorate, using a thorin indicator.
• The silica gel drying tube protects the pump, rotameter, and dry gas
meter from moisture carried over from the impingers

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 CEMS- formula, interference, reference and
equivalent methods, averaging
• Averaging

Real-time instruments present results as electronic signals

that can be easily averaged by built-in electronics for any Δt

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Measured velocities and particle mass flow rates (velocity x concentration) in a
complex duct. The values shown are the ratio of the observed value to the average
value for the whole duct. For example, near the bend, where the velocity is shown as
1.2, the measured velocity was 1.2 x 39 ft/s = 47 ft/s = 14.3

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 CEMS- formula, interference, reference and
equivalent methods, averaging
In a source test, the stack was divided into four sectors, each
of which had the same cross-sectional area. The following
velocities and pollutant concentrations were measured in
these sectors: What is the average concentration in the gas
flowing in this stack?

Answer: Cav = 616 mg/m3

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 CEMS- formula, interference, reference and
equivalent methods, averaging
The SO2 sampling train shows that The concentration
of SO2 in a stack is 600 ppmv, the average velocity of
the flue gas v = 12.2 m/s (measured using Pitot tube),
the stack diameter d = 1.5 m, the stack temperature
T = 232 deg. C and the pressure p = 1 atm
Determine:
1- SO2 concentration in mg/m3
2- Q in m3/s
3- SO2 emission in Kg/h, MT,year

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 S Pitot Tube Manometer Assembly

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 Isokinetik sampling

• In stack sampling for PM, one must maintain

isokinetic flow into the sampling probe

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 PM2.5 measurement
• The older instruments for gases as well as the current
instruments for particulates are not real-time instruments but
rather are averaging instruments.
• For example, one EPA-required method for ambient particulate
sampling is the PM2.5 sampler.
• It consists of a special inlet that excludes particles larger than 2.5
in diameter, a filter, a fan, a flow-measuring device, and a suitable
housing. A preweighed filter is placed in the filter holder, and air
is sucked through it for 24 hours at a measured rate.
• The concentration of particles is computed from equation :
Cav = (increase in filter weight):(airflow rate x Δt)

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 PM2.5 measurement
A PM2.5 sampler ran for 24 hours at an average flow rate
of 16.7 L/min. The tare weight of the fresh filter was
0.1400 g, and the gross weight of the filter, dried to the
same humidity as the fresh filter, was 0.1405 g. What was
the average PM2.5 concentration in the air drawn through
the sampler? Answer: 20.8 microgram/m3
N.B. The 16.7 L/min flow rate for PM2.5 samplers is close
to the average human breathing rate, so that the sample
weight increase, 500 micrograms is close to the mass of
fine particles breathed in per day by an average person
when the PM2.5 concentration is 20.8 micrograms/m3

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 Prediction Emission Monitoring
• PEM is based on developing a correlation between pollutant
emission rates and process parameters and could be considered a
hybrid of continuous monitoring, emission factors, and stack
tests.
• A correlation test must first be performed to develop this
relationship.
• Emissions at a later time can then be estimated or predicted
using process parameters to predict emission rates based on the
results of the initial source test.
• For example, emissions from a boiler controlled by an SO2
scrubber could be predicted, based on the correlation of the
scrubbing solution to the pH and flow rate.

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 Stack Sampling

• Stack sampling provides a “snapshot” of

emissions during the period of the test.
• Samples are collected using probes inserted into
the stack, and pollutants are collected in or on
various media and sent to a laboratory for
analysis.
• Some stack test methods provide real time data
where the gas sample is analyzed on-site by
continuous analysis (e.g., EPA Method 6C and 7E).

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 Stack Sampling

• Pollutant concentrations are obtained by dividing the

amount of pollutant collected during the test by the
volume of the sample.
• Emission rates are then determined by multiplying the
pollutant concentration by the volumetric stack flow
rate.
• Only experienced stack testers should perform the
stack tests.
• The accuracy of this method may be problematic at
low pollutant concentrations
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 U.S. EPA METHOD 17
Determination of Particulate (Pm) Emissions from Stationary
Sources (In-Stack Filtration)

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 Fuel Analysis

• Fuel analysis data can be used to predict emissions by

applying mass conservation laws.
• For example, if the concentration of a pollutant, or
pollutant precursor, in a fuel is known, emissions of that
pollutant can be calculated by assuming that all of the
pollutant is emitted.
• This approach is appropriate for pollutants such as metals,
SO2, and CO2.
• It should be noted, however, that some of the pollutant
may end up in physical or chemical states (ash, unburned
hydrocarbons, etc.) not emitted to the atmosphere.
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 EPA Emission Factor Method

• Emission factors are available for many source

categories and are based on the results of source tests
performed at one or more facilities within an industry.
• Basically, an emission factor is the pollutant emission
rate relative to the level of source activity.
• EPA provides compiled emission factors for criteria
and HAPs in AP-42, the locating and estimating (L&E)
series of documents, and the Factor Information
Retrieval (FIRE) System. These may be found online at:
www.epa.gov/ttn/chief/
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 General EPA emission factor formula

E = A x EF x (1-ER/100)
where:
E = emissions;
A = activity rate;
EF = emission factor, and
ER =overall emission reduction efficiency, %

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 Summary of preferred and alternative emission
estimation method for boilers

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 Summary of preferred and alternative emission
estimation method for boilers

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Summary of preferred and alternative emission
estimation method for boilers

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EPA Emission Factor, example of calculation

m- pollutant emission lbm/h

X- emission factor lbm/ton
m(fuel)- fuel/coal rate ton/h
Using EPA tables for coal emission factors method of calculation, estimate
the emission from a 500 MWe coal-fired power plant at full load burning
a typical Pittsburgh seam coal with 35% efficiency. The power plant boiler
is PC (pulverized coal), wall-fired, dry-bottom type boiler
Pth = Pe/eff
Pth = HHV x Mass flow rate
Mass flow rate = Pth / HHV (kg/s)

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 Ash content in the coal
• Practically 25 % of ash falls to the bottom of the funace and this
is called Bottom Ash
• Another 25 % falls to the bottom of the economizer, also called
Bottom Ash
• While the remaining 50 % is carried along with the gas stream
and this called Flying Ash
• If all of the ash in the coal were emitted with the gas stream, the
emission factor for the PM would be: Ash content = (A/100) x
(1000 Kg/Tonne) = 10A (Kg/Tonne) instead of 5A in the table
Ash content = (A/100) x (2000 lbm/ton) = 20A (lbm.ton) instead
of 10A in the table

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 Answers:
• m (coal) = 179 ton/h
• m (PM) = 7.8 ton/h
• m (PM10) = 23% of PM
• m (SO2) = 5.4 ton/h
• m (CO) = 89.5 lbm/h = 0.045 ton/h
• m (NOx) = 1.942 ton/h

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Attention

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 Rankine Cycle

1-2 Isentropic compression in a pump

2-3 p = cst, heat addition in a boiler
3-4 Isentropic expansion in a turbine
4-5 p = cst, heat rejection in a condenser

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 Schematic Diagram of a coal-fired steam
power plant

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 Schematic diagram of the boiler

  1 – pulverizers, 2 – steam
drum, 3 – downcomer, 4 –
water wall, 5 – FD-fan, 6 –
primary air fan, 7 – platen
superheater, 8 – high
temperature superheater, 9
– high temperature reheater,
10 – low temperature
superheater, 11 – low
temperature reheater, 12 –
economizer

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