Chap 1&2 *Primary pollutants: are those which This is characterized by a weak lapse which is The amount of pollutant
The amount of pollutant that the regulations
have a direct effect following emission. (e.g.. SO2
from power stations) *Secondary pollutants are
those formed by reaction in the atmosphere.
These reactions can occur between primary
pollutants and the constituents of the unpolluted
atmosphere, and result in smog, haze and many
forms of plant and material damage. Air quantity
monitoring. 1. Identification of potential problems
2. Assess trends 3. Provision of base line data 4.
Identification of pollution peaks and episodes 5.
Identification of pollutant source. AP effects on
Visibility: Most gaseous air pollutants are totally
transparent without NO2, which is brown. Some
urban smogs appear brown because of NO2
contain.
Criteria Pollutants (1) Sulphur oxides (2) Fine
Particulate matter (3) CO (4) O3, NO2 , Pb.
Hazardous AP: Asbestos, Benzene, Be, As, Hg,
Radionuclides, Vinyl Chloride. Long-term eff:
Low conc: exposures lead to chronic effects.
Short-term eff: High conc: exposures lead to
acute eff: occur only in industrial accidents. Air
pollutants Emission without monitoring 1.
Emission factors (NOx & VOCs) 2. Mass balance
considerations 3. Engineering Calculations 4.
Direct emission measurements. Influence of
Meteorology: mean wind speed, predominant
wind direction, mean mixing height (dispersion of
the pollutants), humidity, rainfall. Emission
Inventory: 1. List the type of sources for the
area; 2. Determine the type of pollutants
emission from each of the sources; 3. Find valid
emission factor; 4. Determine the # and size of
the sources by count or mean estimate; 5.
Multiply obtain the total emission for the total
area.
Conversion of PPM to g/m3
The mass rate in = 0, and mass decay rate = 0.
Mass rate out = mass emission rate in room from
cigarette smoking
Mass rate out = (flow rate) (exit concentration)
Mass emission rate = (no. of persons)(cigarettes/
person-time)(mass emission/cigarette)
Chap 3
✴Environmental Impacts of Power Plants
✴Generation of Pollutants – Quantification
✴Use of Environmental Technology
✴Introduction to Air Pollution Models
✴Simple Box Models
✴Gaussian Plume Models (basics)
Overall power plant efficiency, ηplant
Electrical energy is expressed in units of
kilowatt-hours (kW-hr); 1 MW = 1000 kW; 1 Wh =
3600 J
Formation of CO2
C + O2 CO2
CH4 + 2O2 CO2 + 2H2O
Formation of SO2 (contʼd)
Most of the sulfur (95% or more) is oxidized to
gaseous SO2:
S + O2 SO2
This SO2 is a major contributor to acid rain and a
source of adverse health effects. (Acid aerosol
from SO3)
Formation of PM
Toxic heavy metals may be found in the ash of
fossil fuels, especially coal.
Because oil and natural gas are refined before
use, they contain little or no as when
combusted .
Formation of NOx
NOx consists mainly of nitric oxide (NO) and
nitrogen dioxide (NO2) formed from high-
temperature reactions between oxygen and
nitrogen.
Solid and liquid wastes
Reducing environmental impacts:
Three basic approaches
1.Technological measures to control or remove a
pollution before it is released to the environment:
"end of pipe"
2.Application of "Green Design" principles to
increase the efficiency of electric power
generation.
3.Selection and utilization of cleaner energy
sources and alternative technologies for pollution
abatement.
Factors that Affect the Fate of Air Pollutants
Meteorology: Wind Speed and Direction;
Temperature and Humidity; Turbulence
Atmospheric Stability; Topographical Effects
Source; Process
Examples of variation of temperature and wind
speed with height Uz = Ua(Z/Za)p
Effect of Surface Roughness
Stability in Unsaturated Air
Temperature Inversion
Plumes
Unstable Condition
This is caused by a strong lapse rate with height
which is in excess of the adiabatic lapse rate.
Under these conditions, a visible continuously For Fb > 55 m4/s3
released plume will appear to exist as large
altered by condensing hygroscopic,
loops, thus the description “looping”.
Neutral Condition
If a cyclone separator is to be applied for even
decrease of temperature with height at a rate
between the dry adiabatic rate and the
isothermal condition (no change of temperature
with temperature).
Most of the turbulence in this case is usually
mechanical in nature rather than buoyant. The
appearance of this plume is cone shaped with its
vertex at the source.
Stable Condition (temperature inversion)
Under these conditions, the thermal structure
inhibits vertical motions so there is almost no
vertical dispersion. The thermal structure does
not inhibit horizontal motions so there may be a
considerable variety of horizontal plume
appearances under stable conditions from a very
narrow ribbon to a considerable amount of
horizontal spreading (fanning).
Atmospheric Motions
(1) Solar heating and (2) Spin of the earth
Chap 4&5
✴Introduction to Air Pollution Models
✴Simple Box Models
✴Gaussian Plume Models (basics)
Why do we need air pollution models?
Since it is not possible to make measurements of
specific air quality for a facility that has not yet
been constructed, air quality dispersion modeling
is about the only way to estimate this future
impact.
Transport Processes
Advection: bulk motions of the atmosphere.
Entrainment: turbulent or diffusive in nature.
Box Models
Eulerian Type: This model computes chemical
species concentrations at a fixed geographical
location.
Lagrangian Type: In this model the box is
allowed to move with air motions, thus allowing
one to follow the chemistry of an individual
parcel. These models are employed for studies
on local and regional scales.
Fixed Box Model
(Accumulation Rate) = (all flow rates in) - (all
flows rates out) + (creation rate) - (destruction
rate).
Assumptions: Homogeneous Distribution;
Constancy of the wind speed; Constant Input of
pollutants into the Box; Continuous Emissions;
Conservation of mass
So, the accumulation rate is zero.
0 = (all flow rates in) - (all flow rates
out)
Flow rate at the upwind of the city:
Flow rate in = uWHb (Volume/time
* mass/volume)
Flow rate of pollutant emitted by the
city:
Flow rate in = Q = qWL
Flow rate out = uWHc
c = b + qL/uH
Modifications: (Annual average conc.) =
∑(concentration for that meteorology)(frequency
of occurrence of that met. con.)
Drawbacks: There is no distinction between area
sources and point sources. Stack height
considerations are taken into consideration in
this model.
Diffusion Models
It assumes that
concentrations from a continuously emitting
plume are proportional to the emission rate
that these concentrations are diluted by the
wind at the point of emission at a rate
inversely proportional to the wind speed,
the time-averaged concentrations (about 1h)
crosswind and vertically near the source are
well described by Gaussian or normal (bell-
shaped) distributions. Furthermore, there is
no chemical or physical (deposition) loss of
pollutants during their transit in atmosphere.
The point-source Gaussian Plume Model
Point Source at Elevation H above the Ground,
Without Reflection
Point Source at Elevation H above the Ground,
With Reflection
The ground level concentration of a pollutant
according to Equation (13) (z = 0)
is directly downwind on centerline and the
effective stack height is zero (i.e., y = 0 and H =
0).
(15)
The maximum Ground-Level In-Line
Concentration (2)
(16)
(17)
Calculation of the Effective Stack Height
For each stability category, a calculation is first
made to determine whether the plume rise is
dominated by momentum (Fm) or buoyancy
(Fb).
(18)
Where Ts is stack gas temperature (K), Ta is
ambient air temperature (K), andre g is
acceleration due to gravity (9.8 m/s2).
(19)
If the difference between the stack gas and
ambient temperatures, (∆ T), is greater than or
equal to crossover temperature (∆ T)c, plume
rise is assumed to be buoyancy dominated;
otherwise, plume rise is assumed to be
momentum dominated.
For Fb < 55 m4/s3,
(20)
(21)
For stable conditions, the crossover temperature require further treatment or disposal.
difference is
(22)
(23)
For Fb < 55
xf = 49Fb 5/8 (24)
and the final effective plume height, H(m), is
(25)
Instantaneous Release of a Puff
The Gaussian Dispersion Equation for plumes
containing particles (26) Particle Size Distribution
Downwind concentration under a temperature
inversion
for x ! 2XL (27)
Where L = elevation of the bottom of the
inversion layer (m)
XL = the distance downwind where the
plume first encounters the inversion layer
!z = 0.47(L-H) at x = XL (28)
For distances x < XL, the standard Gaussian
plume equation can be used to estimate
downwind concentrations. For x > 2XL, C(x,0)
applies. For distances between XL and 2xL,
concentrations can be estimated by interpolating ! =
between the values computed for x = XL and x =
2XL.
Line-Source Dispersion Model
(29) overstate the effectiveness of the control device
Where q = emission rate per unit of distance
along the line (g/m-s).
Area Source Models
(Rate of change of pollutant in the box) = (Rate
of pollution entering the box) - (Rate of pollution p = p1p2……………..pn-1pn
leaving the box)
range i and Wi =1.0
steady-state solution
Time-dependent increase in pollution above the
city. Letting C(0) be the concentration for the air-
shed above the city (the box) at time t = 0, the
solution becomes
If we assume that the incoming wind blows no
pollution into the box and the initial concentration
in the box is zero
Estimation of wind-speed at the stack
Chap
(13) 6&7
Emission inventories are produced by combining Gravity Settler
information on the intensity of activities with
emission factors that specify the quantity of a
pollutant emitted per unit of activity.
Pollution control is an end-of-pipe process. It is such as smelters and metallurgical processes.
(14)after the waste is generated. It often Models used:
performed
transfers the pollutant from one environmental
medium to another.
Factors to use tall stacks:
Intermittent control scheme: Plant shutdown;
Fuel switching; Production curtailment
Control techniques for limiting pollutant
formation and emission at the sources
Pollution prevention (P2) focuses on the
reduction of pollution at the source. This implies
“up-front” limiting of waste.
Gaseous Pollutants
Removal process
Absorption
Examples: SO2, NH3, NO, and NO2
Adsorption
Examples: Hydrocarbons
Chemical Alteration of the Pollutant
Using combustion or catalytic processing of
the waste gases
Example: SO2 Emissions from stationary
sources
Three basic strategies for controlling SO2
emissions:
1. Fuel substitution
2. Fuel desulphurisation
3. Removal of SO2 from effluent gases, fuel
desulphurisation, liquefaction and
gasification of coal. (Coal: FeS2, organic
compounds, and sulphates)
Resource Recovery
Pollution control approaches
Pollution prevention
Process change
Use of a downstream (tailpipe) pollution control
device
The Ultimate fate of Pollutants
Combustion of organic compounds
Disposal of other pollutants ( non-combustible) in
a landfill
When deciding what process, method, and
equipment to use in controlling a specific air
pollutant problem, a number of environmental,
engineering, and economic factors should be
considered.
Environmental factors
allow to be emitted.
Whether or not the air pollution equipment will
produce another hazardous waste that will
Engineering factors
The chemical and physical properties of the
pollutant
Design and operational requirements
Economic factors
The initial cost of buying and installing the
equipment.
The cost of operating the equipment
Almost all particle control devices operate on the
same basic principle: The physical mechanisms
that cause collisions are mainly inertial drift,
electrostatic drift, Brownian motion, and
interception.
The main properties/characteristics of the carrier
gas are the following: Gas flow rate;
Temperature; Pressure; Density; Humidity;
Composition reactivity
The main properties and characteristics of the
particles that may influence the selection of the
control system are the following: Particle size;
Hygroscopicity; Electrical phenomena; Solubility:
Particle-size distributions are usually
represented by a cumulative weight fraction
curve in which the proportion of particles less
than or greater than a certain size is plotted
against the diameter of the particle.
log (d84.1) = log (d50) + log σg
log (d15.9) = log (d50) − log σg
d84.1 diameter such that ptcs constituting
84.1% of the total mass of ptcs are smaller
than this size
d50 geometric mean diameter
d15.9 diameter such that ptcs constituting
15.9% of the total mass of ptcs are smaller
than this size
σg geometric standard deviation
σg = d84.1∕d50 = d50∕d15.9
Control Efficiency
=
= attain the required tangential velocity Vt.
In general, coarse-particle removal is far easier
to achieve than fine-particle removal. Because
of this, the total mass removal efficiency may
Penetration
p = 100 – E, percent basis
p = 1 – E, fraction basis
For a multiple series of n collectors, the overall
penetration is simply given by:
The overall efficiency
E = W1E1+ W2E2 + W3E3 + … = WiEi i=1
where Wi = mass fraction of particles in size
complicated. Two vortices are formed, one
Collector in Series
!overall = 1-(p1p2..pn-1pn)
Collector in Parallel
cyclone, sending it to the hopper.
Q1, C1 Q1, C2
!1
Q, C1
Q, C2 cone to arrest the vortex, the vortex will extend
!2
Q2, C1 Q2, C2
Chap 8&9
The basic mechanisms used for removal of
particulate matter (PM) from gas streams:
Advantages: ease of construction and operation
and little maintenance.
Application: to treat dirty gases in industries
Block flow or Plug flow model; Back-mixed or
Mixed model
Block Flow
Vavg = Q/WH t = L/Vavg
Fractional Collection Efficiency,
η = (L*Vt)/(H*Vavg) for block flow.
For Stokeʼs Law, Vt = (ρpgD2)/(18µ)
η = (LgD2 ρp)/(HVavg18µ) for block flow.
Mixed Flow
ln[Cout/Cin] = -(VtL)/(HVavg) for mixed flow
η = 1- (Cout/Cin) = 1-exp[-(VtL)/(HVavg)]
Vt = (L ρpgD2)/(HVavg18µ) for mixed flow
ηmixed = 1-exp[-(ηblock flow)]
dp =
For small particles, for which the calculated
collection efficiencies are small, the mixed and
block flow models give practically the same
answer. For larger particles the calculated
collection efficiencies become larger, and the two
models give different answers.
Advantages
✴ Low cost of construction and maintenance
✴ Few maintenance problems
✴ Relatively low operating pressure drops, in
the range of approximately 0.1 inH2O
✴ Temperature and pressure limitations
imposed by the materi8als of construction
used
✴ Dry disposal of solid particulates
Disadvantages
✴ Large space requirement
✴ Relatively low overall collection
efficiencies (typically ranging from 20 to
60%)
Centrifugal Separators (Cyclones)
Dcut = cut diameter
η = overall collection efficiency
P = pressure drop
The cut diameter ( the diameter of particles
collected with 50% efficiency) is
Dcut = (9Wiμ/
2πNVcρp)1/2
smaller particles, there are two options that may
be considered: to make Wi smaller or Vc larger.
η = (πNVcD2ρp)/9Wiμ
(3)
!j =
overall η = ∑ηjM(%)
Pressure drop = Pin – Pout = K((ρgVi2)/
2)
If a body moves in a circular path with radius r
and velocity vc, along the path, then its angular
velocity (ω) is
ω = vc/r
Centrifugal force = mvc2/r = mω2r
Vt = vc2D2 ρp/(18µr)
Advantages:
✴ Low-cost method of removing particulate
matter from exhaust gas streams
✴ Better removal efficiency than that of
settling chambers
Disadvantages:
✴ Not as efficient as baghouses, venturi
scrubbers, and electrostatic precipitators
✴ Used as precleaners before these more
effective devices
There are three types of cyclones.
Tangential entry cyclone arrangement
Axial entry cyclones
Cyclones with bottom inlet
Inlet
Purpose: to accelerate the gas in the cyclone to
Cyclone Body and Cone
The removal efficiency of a cyclone for a given
particle size is greatly dependent on cyclone
dimensions.
The diameter of the cyclone has a large effect on
the pressure drop for a given volumetric flow
rate.
The number of turns of the vortex is determined
by the overall length. As the number of turn
increases, the removal efficiency increases.
Inlet length and width are also important. As the
inlet is made smaller, the inlet velocity increases.
This gives higher removal efficiency at the
expense of added pressure drop.
The motion of a gas in a cyclone is somewhat
descending and the other ascending. The
ascending vortex is smaller in radius, with faster
tangential velocities than the descending vortex
(the main vortex).
The cone primarily serves as a mechanism for
removing particulate matter from the walls of the
Dust Discharge System (hopper)
If the discharge bin is immediately below the
cone and nothing is added to the bottom of the
into the discharge bin. Dust can be reentrained
from the hopper into the inner vortex. If the
leaks exist in the bin, dust can be sucked back
up into the cyclone. Several methods can be
used to avoid particulate reentrainment.
Cyclone Gas Outlet
The length of the tube must extend beyond the
inlet so that eddies created in the annulus
between the tube and the cyclone walls do not
mix particulates up and into the exit tube.
Some flow straighteners can be used to reduce
the pressure drop without reducing efficiency.
Pressure Drop
As the pressure drop increases, so does the cost
for power to move the gas through the cyclone.
the removal efficiency usually increases too.
✴ Collection efficiency in a cyclone is largely
dependent on particle size distribution.
✴ Efficiency can only be guaranteed if the
particle size distribution is known.
✴ Guarantees are made when the dust
composition is constant or contains only a
small fraction of particles less than 10 m in
diameter.
Gravity Settler
Chap 10
✴ Electrostatic Precipitator
✴ Baghouse
✴ Scrubber/Venturi scrubber
✴ Comparative evaluation of all particulate
control devices
Electrostatic Precipitators (ESPs)
!!= 1 - exp(-wA/Q) (1)
where
η = collection efficiency;
w = drift velocity (average);
A = collection surface area;
Q = gas volumetric flow rate
ESPs are often used to collect fly ash from
power plants. However, fly ash can be
resistive to charging, thereby inhibiting
collection.
The nature of the ash controls the resistivity.
If resistivity is low, then the particles cannot
be sufficiently charged for collection.
If resistivity is high, not as many particles
can be charged and electrostatic
discharges from the plates can explode
sheets of particulate off.
While low resistivity particles cannot be
successfully collected, high resistivity particles
can by conductance modifications.
✴ The resistivity often decreases with
temperature
✴ High resistivity particles can also be
 conducting material to the surfaces. SO3
3NO2 + H2O 2HNO3 + NO
can be used.
Electrostatic Precipitator Operation
✴ Transfer of a negative charge to all the
particles in a gas stream.
✴ Migration of negatively charged particles
to the grounded collection plate.
✴ Collection of particles onto the positively
charged plates, creating a dust layer.
✴ Removal of the collected particles from the
plates by rapping or spraying the plates
with a liquid
Particle Charging
✴ Suspension of evenly spaced discharge
electrodes (thin wires) between large
plates called collection electrodes
(grounded).
✴ Application of a negative, high-voltage,
pulsating, direct current to the discharge
electrode creating a negative electric field.
Corona Discharge: Free Electron
Generation
The negative (gas) ions play a key role in
capturing dust particles
✴ The gas ions stick to the particles,
imparting a negative charge to them.
✴ Small particles (less than 1 m diameter)
can absorb “tens” of ions.
✴ Large particles (greater than 10 m) can
absorb “tens of thousands” of ions.
✴ Regardless of the size, the particles
encounter the plate and stick, because of
adhesive and cohesive forces.
Particle Charging Mechanisms
✴ Field charging
✴ Diffusion charging (the random Brownian
motion of the negative gas ions).
ESP design parameters and their effects
on collection efficiency
Resistivity, Specific collection area, Aspect
ration, Gas flow distribution, and Corona
power.
Particle-migration Velocity
Where,
dp = diameter of the particle, m
Eo = strength of field in which particles are
charged, V/m
Ep = strength of field in which particles are
collected
(normally the field close to the
collection plates), V/m
μ = gas viscosity, Pa. s
Where
q = particle charge(s)
Ep = strength of field in which particles are
collected (normally the field close to the
collection plates), V/m
μ = gas viscosity, Pa. s
2NO + 2CO N2 + 2CO2
r = radius of the particle, m
Deutsch-Anderson Equation
! = 1 - exp(-wA/Q)
This equation neglects three significant
process variables:
✴ First, it completely ignores the fact that
dust reentrainment may occur during the
rapping process.
✴ Second, it assumes that the particle size
and, consequently, the migration velocity
are uniform for all particles in the gas
stream.
✴ Third, it assumes that the gas flow rate is
uniform everywhere across the precipitator
and that particle sneakage (particles
escape capture) through the hopper
section does not occur.
More accurate estimates of collection
efficiency can be obtained by substituting the
effective precipitation rate, we, in place of the
migration velocity, w, or by decreasing the
calculation of collection efficiency by a factor
of k, which is constant.
Resistivity
✴ Particles that exhibit high resistivity are
difficult to charge. But once charged, they
do not readily give up their acquired
charge on arrival at the collection
electrode.
✴ On the other hand, particles wit low
resistivity easily become charged and
readily release their charge to the
grounded collection plate.
✴ ESPs work best under normal resistivity
conditions.
High resistivity can generally be reduced by
using the following:
Adjusting the temperature
Increasing moisture content
Adding conditioning agents to the gas stream
Increasing the collection surface area
Using hot-side precipitators (occasionally).
Low resistivity
Particles that have low resistivity are difficult to
collect because they are easily charged (very
conductive) and rapidly lose their charge on
arrival at the collection electrode.
Methods to overcome low resistivity
If the conductive particles are coarse, they can
be removed upstream of the precipitator by
using such as a cyclone. Baffles are often
installed on the collection plates to help
eliminate this precipitation-repulsion
phenomenon.
The addition of liquid ammonia into the gas
stream as a conditioning agent has found wide
use in recent years.; ammonia reacts with
sulfuric acid contained in the flue gas to form
an ammonium sulfate compound that
increases the resistivity of the dust.
Specific Collection Area
A/Q (total collection area/gas flow rate)
✴ Increases in the SCA of a precipitator
design will, in most cases, increase the
collection efficiency of the precipitator.
Aspect Ratio
✴ The aspect ratio, which relates the length
of an ESP to its height (L/H), is an
important factor in reducing rapping loss
(dust reentrainment).
Gas Flow Distribution
✴ Gas velocity is reduced by the expansion,
or diverging, section of the inlet plenum.
Advantages:
•Can handle large gas volumes.
NO + 0.5O2 NO2 Slow
•High collection efficiencies even for sub-micron
•Greenhouse problems
sized particles.
•Low energy input.
•High T gases can be treated.
Disadvantages:
•Relatively high capital cost.
•Precipitators are sensitive to variable dust
loadings or flow rates.
•Resistivity causes materials to be economically
uncollectible.
Filters
Mechanisms of capture in fabric filters: for
particles less than 1 micrometer the mechanisms
are inertial impaction and direct interception. For
particles less than 1 micrometer diffusion is the
mechanism.
Two types:
Deep bed filter
Bag-house
Deep bed filters: intercept low volumes of
relatively clean gases.
Bag-houses are generally used for industrial
purposes. Aerodynamic Capture of Particles
Inertial impaction
Direct Interception
Diffusion
Advantages of bag house filters
•High efficiency even for small particulates
•Easy to clean
•High capacity
•Pressure drops are reasonable and hence
energy requirement is low
•Different materials can be handled
Disadvantages of bag house filters
•Size requirement is large
•Explosion possibility
•Need to keep hygroscopic particles away to
prevent cloth cleaning problems.
Wet Scrubbers for Particulate Control
(Venturi Scrubber)
Improved efficiency compared to dry collectors
•Growth in size of small particles
•Low reentrainment
Four types of wet collection equipment
Spray tower
Cyclone spray tower
Impingement scrubber:
Venturi scrubber: water is introduced at right
angles to a high velocity gas flow in a venturi
tube ( a contraction), resulting in the formation of
very small water droplets by the flow and high
relative velocities of water and particles.
dilute SO2 streams
Problems
•Higher efficiency requires higher operating
costs; by products are difficult to recover.
•An air pollution problem can be transformed
into a water or solid waste pollution problem.
•venturi scrubbers are generally more expensive
than simple settling chambers and cyclones, but
less expensive than high-efficiency electrostatic
precipitators and baghouses.
Penetration, p
= + C∗
In the above expression, ρL is the liquid density,
ρp is the particle density, uG is the gas velocity in
the throat of the venturi, μg is the viscosity of the
air, and Q is the volumetric flow rate; KC and f
are empirical coefficients.
Disadvantages:
Corrosion problems
Meteorological problems
Difficulty of byproduct recovery
Pressure drop and power requirements
Water pollution
Summary
✴ Gravity settling chambers, cyclones, and
ESPs have similar design equations. They
work by driving the particles to a solid wall
where they form larger particles that can
be collected.
✴ Filters and scrubbers have design
equations from each other and from the
above devices; the divide the flow.
✴ The venture scrubber is the most widely
used type of co-flow scrubber to collect
small particles.
Chap 11
Removal of SOx & NOx.
The two basic approaches to controlling SOx
emissions are
remove sulfur from fuel before it is burned, or
remove SO2 from the exhaust gases.
Many crude oils are "sour", that is, they contain
sulfur
R-S + H2 -> H2S + R
where R represents any organic group.
Most sulfur recovery units use the Claus process
H2S + 3/2 O2 -> H2O + SO2
2H2S + SO2 -> 2H2O + 3S
Limestone scrubbing
CaCO3(s) + H2O + 2SO2 ! Ca2+ + 2HSO3- + CO2(g)
CaCO3(s) + 2HSO3- + Ca2+ ! 2CaSO3 + CO2 + H2O
The major advantage of limestone scrubbing is
that the absorbent is abundant and inexpensive,
and it has a wide range of commercial
acceptance. The disadvantages include scaling
inside the tower, equipment plugging, and
corrosion.
Lime scrubbing
CaO + H2O ! Ca(OH)2
SO2 + H2O ! H2SO3
H2SO3 + Ca(OH)2 ! CaSO3. 2H2O
CaSO3. 2H2O + 1/2O2 ! CaSO4.2H2O
The advantages of lime scrubbing include better
utilization of the reagent and more flexibility in
operations.
The major disadvantage is the high cost of lime
relative to limestone.
The dual alkali system was developed to
eliminate the main problems encountered with
lime and limestone scrubbing (namely, scaling
and plugging inside the scrubbing tower). The
dual alkali system uses two reagents and two
process loops to remove the SO2.
Lime-spray drying
The advantages of lime-spray drying include few
maintenance problems, low energy usage, and
low capital and operating costs.
A disadvantage is the potential to blind the fabric •
if the temperature of the flue gas approaches the
dew point.
Dry scrubbing
The advantages of dry scrubbing are low capital
costs and low maintenance requirements. The
disadvantages are high reagent costs (including
transportation) and possible waste disposal
problems (leaching of soluble sodium salts).
Flue Gas Treatment Techniques for NOx
Removal
FGT is also used where combustion controls are •
not applicable
FGT techniques are broadly classified as dry or
wet techniques, and the dry techniques are
further classified as catalytic reduction, non-
catalytic reduction, and adsorption.
Catalytic Reduction. The most advanced FGT
method is selective catalytic reduction (SCR).
In SCR, only the NOx species are reduced
(ultimately to N2 gas). Nonselective catalytic
reduction
4NO + 4NH3 + O2 ! 4N2 + 6H2O
2NO2 + 4NH3 + O2 ! 3N2 + 6H2O
Selective Non-catalytic Reduction (SNR).
At temperatures of 900 - 1000 C, NH3 will
reduce NOx to N2 without a catalyst. At NH3 :
NOx molar ratios of 1: 1 to 2: 1, Potential
problems with SNR include incomplete mixing of
NH3 with the hot flue gas, and improper
temperature control. If the temperature is low,
unreacted ammonia will be emitted; if the
temperature is too high, NH3 will be oxidized to
NO.
Adsorption.
One type of system uses activated carbon with
NH3 injection to simultaneously reduce the NOx conversion of fuel-N to NOx is the oxygen
to N2 and oxidize the SO2 to H2SO4. If no sulfur availability.
is present in the fuel, the carbon acts as a
catalyst for NOx reduction only.
Control of Sulfur Oxides
•! S (in fuel) + O2 ! SO2
•! SO2 ! ! ! ! CaSO4
•! CaCO3 + SO2 + 0.5O2 ! CaSO4 + CO2
CuFeS2 + 5/2 O2 ! Cu + FeO + 2SO2
SO2 from the principal ores of Pb, Zn, and Ni. the production and utilization of HNO3 lead to
Control methods
reduced S compounds
concentrated SO2 streams
after the flame, to convert to the NOx to N2.
Removal of reduced sulfur compounds from
petroleum and natural gas streams
Uses and limitations of absorbers and strippers time at high temperature
for APC
• The absorber system works well for H2S and Two-stage combustion or reburning
NH3 using ethanolamine and water,
respectively.
• The removal of SO2 from gas streams is
relatively easy if there are no other acid
gases present.
• removal of SO2 in N2 using NH4OH
• The removal of SO2 from combustion gases
is much more complex and difficult.
• NO and NO2 are not easily removed from
the gas streams by the above process.
• 3NO2 + H2O 2HNO3 + NO
• NO is not an acid gas.
• The regeneration of the solvent is not
necessary if the amount of material to be
collected is small.
Sulfur removal from hydrocarbons
H2S + !O2 ! S + H2O (Claus process)
Note: H2S + 3/2 O2 ! SO2 + H2O
Removal by catalytic hydro-desulfurization.
(HC containing S) + H2 HC + H2S
(Ni or Co catalyst promoted with Mo or W).
Removal of SO2 from rich waste gases
The SO2 concentrations in off-gases from the
smelting of metal sulfide ores range from 2 to
12% of SO2.
SO2 + ½O2 SO3 (in the presence of
vanadium catalyst)
SO3 + H2O H2SO4
Removal of SO2 from lean waste gases
Chemical treatment:
Scrubbing with water containing finely ground
limestone.
Drawbacks
large amount of water is needed.
emissions of SO2 from the waste water
large decline in the concentration of dissolved
O2 because of possible oxidation of SO2;
damage to aquatic life.
Scrubbing with NaOH
Problems:
fate of sodium sulfate
detergent manufacture and paper making;
purity ?
CO2 (12%, 120 times that of the SO2)
based on the Henryʼs law considerations, the
conc. of CO2 is 3.2 times higher in the
solution.
The liquid-phase reactions:
CO2(g) ! CO2(dissolved) + H2O ! H2CO3 ! H+ + HCO3- VOCs- liquids or solids containing organic
SO2(g) ! SO2(dissolved) + H2O ! H2SO3 ! H+ + HSO3- CO, CO2, and CaCO3).
The dissolution of CO2 can be minimized by the Volatility:
driving the equilibrium to the left. pH = 4 - 6
Similarities between SOx and NOx
• Released to the atmosphere largely by
combustion sources, mainly from coal fired
power plants.
• Both pollutants are regulated because of
their emissions in large quantities; both are
severe respiratory irritants in high
concentration.
• Contributors to acid rain.
• Contributors to the formation of PM10 in
urban areas.
Major Differences
• Sources of SOx: S contaminants in fuels or
the unwanted S in sulfide ores. Sources of
NOx: N contaminants in fuels (small
contributor); the reaction of atmospheric N2 air is saturated or undersaturated with respect to
with O2 in high temperature flames.
• Reduction of NOx by manipulating the time, Sources of VOCs
T and O2 content of the flames. No such
reductions are possible with Sulphur Oxides. fuel)
• Motor vehicles – a major emitter of NOx but •Solvents or chemical intermediates (vinyl
a minor source of SOx because of fuels.
• Removal mechanism:
• SO2 dissolution in water followed by reaction •Biogenic emissions
with alkali-oxidation to sulfate.
• NO very low solubility in water
•
• Fate of conversion products of the pollutants
• SO2 CaSO4 (Landfill, harmless, low-
solubility solid)
• NOx N2 + O2 (released to the
atmosphere.)
NO and NO2 Equilibrium
• Both reactions are reversible that do not go
to completion.
•
Thermal, Prompt and Fuel NOx
1. Thermal NOx:
• formed by the simple heating of O2 and
N2 either in a flame or by some other
external heating (a lightning bolt)
2. Prompt NOx:
• very quick formation of the nitrogen oxides
as a result of the interaction of N2 and O2
with some of the active carbon species
derived from the fuel in flames.
3. Fuel NOx:
• Formation of NOx by conversion of some
of the nitrogen originally present in the fuel
to NOx.
Coal and some high boiling petroleum fuels
contain significant amounts of organic nitrogen.
The most important factor affecting the
• Fuel-N + O2 NOx
• N2 + O2 NOx
The peak temperature of a flame depends on the
following:
1. The fuel and oxidizer used
2. The size of the flame
3. The degree of fuel-air mixing
4. The amount of fuel-air present
emissions of NO and NO2.
Modification of the combustion process to
prevent the formation of NOx.
Treatment of the combustion gas chemically,
aCg∗
The formation of NO is controlled by:
peak temperature
oxygen content at the high temperature
• Advantage: cheap
• Disadvantages: incomplete burning in the
second stage; unburned fuel and/or CO in
the exhaust gas is increased.
Post Flame Treatment
• add a reducing agent to the combustion gas
stream to take oxygen away from NO.
•
• in the presence of platinum-rhodium catalyst
Rhodium Catalyst
In power plants, NH3 is added to reduce NO to
N2.
6NO + 4NH3 5N2 + 6H2O
In the presence of O2
4NO + 4NH3 + O2 4N2 + 6H2O
2NO2 + 4NH3 + O2 3N2 + 6H2O
Other Approaches:
scrubbing of NO with solutions of NaOH and
KMnO4, in nitric acid solutions.
Adsorption of NO and SO2 onto activated carbon
adsorbent followed by removal and production of
S and N2 as the final products.
Summary
✴ Thermal, prompt and fuel NOx are the major
mechanisms for the formation of nitrogen
oxides in industrial processes.
✴ The rate of conversion of NO to NO2 in
flames is very slow, so that most of the NOx
in flames is NO.
✴ NO leads to air pollution problems through
NO2.
✴ NO formation in flames can be reduced to by
modifying the combustion processes
(reductions in the peak temp., the O2 content
at the peak temp. and the time at the peak
temp.).
✴ The NO in combustion gases can be
reconverted to N2 by reaction with a
reducing agent.
Chap 12
• VOCs
• Sources and effects
• Control approaches:
a) Substitution
b) Leakage control
c) Control by adsorption
d) Control by combustion
e) Control by condensation
f) Process modification
carbon which vapourise at significant rates (not
Evaporation of chemicals at significant rates
Evaporation rate is dependent on the vapour
pressure of the individual compounds.
Estimation of the vapour-phase component of a
volatile species in equilibrium with air.
Raoult's Law
yi = mol fraction of component i in the vapor
xi = mol fraction of component i in the liquid
pi = vapor pressure of pure component i
P = Total pressure
Evaporation of a VOC depends on whether the
that VOC.
•Liquid fuels (propane, gasoline, diesel fuel, jet
chloride in plastic industries for making PVC)
•Paints, nail-polishers
Effects of VOCs
•Smog problems
•Air toxicity
Control Alternatives
• Substitution
a) Replacements for oil-based paints,
coatings, and inks
b) Less toxic solvents for more toxic solvents
c) Replacement of gasoline with compressed
natural gas or propane.
• Leakage control
a) Filling, breathing, and emptying losses
VOC emission = (Vair – Vmix) (CVOC in the mix)
Concentration ci can be expressed as
b) Displacement and breathing losses for
gasoline
c) Control by Adsorption
Solid
some form of activated carbon (charcoal)
because of high surface area.
Surface area considerations
Adsorption is a particularly useful technique
when:
The pollutant gas is non-combustible or
difficult to burn
The pollutant is sufficiently valuable to warrant
recovery.
The pollutant is in very dilute concentration in
the exhaust system.
Adsorption capacity
log10X = a + b log10Ce + c[log10Ce]2
where X is the adsorption capacity (kg of
pollutant/kg of carbon); Ce is the pollutant
concentration in ppm; a , b, and c are correlation
constants.
Adsorbents: activated carbon, silica gel,
molecular sieves, activated alumina
Pollutant treated: hydrocarbons, H2S, SO2
Limitations: preferentially select water, inefficient
at high temperatures (regenerated with steam at
high temperature typically)
W =
1 + bCg∗
where
W amount of gas per unit mass of absorbent,
kg/kg
a,b constants determined by experiment
Cg equilibrium concentration of gaseous
pollutant, g/m3
In analysis of experimental data, rewritten as
follow:
Cg∗ 1 b
W a a g
Zr − δ
tB =
vf
where Zr height of bed, m
δ width of adsorption zone, m
vf velocity of adsorption zone as defined by
(Qg )(1 + bCg∗ )
vf =
aρs ρg Ac
where ρ density of solid and gas, kg/m3
Ac cross-sectional area of bed, m2
Factors that affect the effectiveness in
controlling gaseous pollutants.
Temperature:
Pressure:
Molecular weight of the gas:
Presence of other gases:
Decomposition and polymerization:
Size and surface area of the adsorbent particles
depth of the adsorbent bed,
the velocity of the gas,
the concentration of the gas and
how frequently the apparatus is operated and
regenerated.
Control by Combustion
Pollutants treated: CO and hydrocarbons
Methods: Direct flame incineration; Catalytic
combustion
Goal: To convert VOC materials from the harmful
or objectionable form, to a harmless or less
objectionable form by combustion.
Combustible pollutants: gas, mist droplet or a
solid particulate.
Incomplete combustion is a permanent problem;
intermediate products: aldehydes, dioxins, and
furans.
Control by Condensation
Condensation is not as economical as
adsorption for the following reasons:
one-stage refrigerators cannot be used
because of low temperatures.
frequent defrosting because of possible
freezing of the material being removed on the
cooling coils.
frequent defrosting because of possible
condensation of water vapour on the cooling
coils; contamination of the recovered liquid
due to water.
These condensers encounter a special fire
hazard.
Summary
1. Emissions of VOCs from a variety of sources
with a wide variety of individual components,
each with its own properties.
2. Control options: substitution, leakage control,
adsorption and recycling, incineration,
condensation, and process modification.
3. Applicability of control options for non-VOC
emissions: incineration for odour control of
H2S, adsorption of SO2 or mercury vapour,
and leakage control for any process source.