Air Pollution Control Techniques for

Stationary Sources
EnE 250 Air Pollution
Lecture 2.2

Analiza P. Rollon, PhD

Department of Chemical Engineering
College of Engineering
University of the Philippines
Lecture Outline
1. Control of Primary Particulates
2. Control of Gases and Odorous
Compounds
3. Control of Hazardous Air Pollutants
4. Air Pollution Control for Chemical
Industries
5. Flue Gas Cleaning
 Air Pollution Sources
• Stationary sources
– Energy-Producing Industries (Power generation)
– Incineration systems
– Chemical and Metallurgical Industries
• Mobile sources
– Gasoline powered engines
– Diesel powered engines
– Gas turbines
– Jet engines
 Stationary Sources
• Energy-Producing Industries (Power
generation)
• Incineration systems
• Chemical and Metallurgical Industries
Lecture 5.2 Air Pollution Control Techniques for Stationary Sources

CONTROL DEVICES
 Control Devices

Primary Particulates: dry particulate matter (PM)

Gravity settlers cyclones Filters
scrubbers electrostatic precipitators
bag filters (fabric filters) Cyclones
electrostatic precipitators scrubbers
dry scrubbers
Odors
Dilution
Containment
Liquid droplets and mists
Chemical conversion
gaseous pollutants Filters
Absorption electrostatic precipitators
Adsorption cyclones
Condensers scrubbers
Conversion to non-pollutant substance
Biological process systems
Lecture 5.2 Air Pollution Control Techniques for Stationary Sources

CONTROL OF PRIMARY
PARTICULATES
Control of Primary
Particulates
First: 1. Gravity Settlers
Introduction on Terminal
Velocity 2. Cyclones
Next: Control devices 3. Scrubbers
4. Filters
5. Electrostatic Precipitator
 Terminal Velocity
At steady state, i.e., zero acceleration, three
forces act on a suspended particle:
1. Gravitational force
2. Drag force
3. Buoyancy
Force balance gives the terminal velocity.
(terminal gravitational settling velocity)
 Terminal Velocity
Stoke’s flow regime:
For particles in air in the size range 5 to 50 um, the
terminal velocity, Vt, is given as:
g.d (  p   g )
2

Vt  Where
p

18 g = acceleration due to gravity

dp = particle size
c = particle density
This equation can be used g = gas density
as an approximation in the
 = gas viscocity
size range 1 -100 m.
 Terminal Velocity
Terminal velocity of spherical particles in air at ambient
conditions (298 K, 101.3 kPa)
Particle size, um 0.01 0.1 1.0 10 100 1000

Terminal velocity, m/s 1.3 x 10-7 1.8 x 10-6 6x10-5 6x 10-3 0.5 7

Specific gravity: assumed 2,000 kg/m3

• Particle size with larger terminal velocity is easier to remove.

• Terminal velocity is proportional to the square of particle size.
• Fine particles are difficult to remove.
 Gravity Settlers
• Gravity settler - a chamber through which the
contaminated gas passes slowly allowing time for
particles to settle by gravity.
• Stokes’ flow regime: the terminal velocity depends
on the square of the particle diameter.
• Small particles  low terminal velocity
• 40-50 m and respirable dust is not removed
• Used for pre-cleaning
 Cyclones
Cyclone – a centrifugal
separator, where the
centrifugal force is used to
move the particles.
Centrifugal force > gravity
force
 particle velocity > terminal
velocity
 small particles can be
removed
 Cyclones
Mechanism:
Gas spirals along the outer part of
a cylindrical body, with a
downward component, then
turns, spirals upward.
Clean gas leaves at central outlet at
top.
Particles are driven to the wall by
centrifugal force, form larger
agglomerates that slide down
the wall and collect in the dust
hopper at the bottom.
Collected particles are removed
through a rotary valve at the
bottom.
 Cyclones
• Cyclones: simple construction, low investment, low
to moderate operating and maintenance costs. 
widely used.
• Useful for removing large particles (not efficient for
fine particles).
• Good efficiency for particle sizes > 10 um.
• Good for small gas flows (>10 m3/s) with coarse dust
and moderate demands on cleaning efficiency.
 Cyclones
• Small cyclones in parallel (multi-tube cyclone):
achieves better efficiency
• Centrifugal force is larger because cyclone diameter
is smaller, and the travelling distance for the particles
is short.
 Cyclones
• The efficiency of a gas cleaning device:
– Particle cut size diameter (i.e., the particle size
removed at > 50% efficiency)  see fig. 4.2
– vary between 2 and 13 um for different cyclone
designs and operating conditions.
Cyclones: Collection
effiiency
Fig. 4.2 of F&T, 2009
 Cyclones
• Cut size diameter dp50
for a standard cyclone:
Dc  A high inlet velocity and large
d p 50  0.27
Vc  p   g  particle density lowers the
Where cut size diameter. 
Dc = cyclone diameter increases the efficiency.
 = gas viscocity A high gas viscosity, large
Vc = inlet gas velocity cyclone diameter increases
c = particle density the cut size.  decreases
g = gas density the cyclone efficiency
 Cyclones
• Efficiency,, for a particle size (dp) can be
calculated given the cut size diameter (dp50).
2
dp 
 d  The total efficiency can
  p 50 
2 be obtained by
dp 
1   summation.
 d p 50 
 Scrubbers
• Scrubbers (wet collectors): liquid is used to capture
particles and soluble gaseous pollutants.
• Mechanism:
 Liquid distributed at the top of a column. Gas stream is
injected at the bottom.
 Liquid droplets 100 – 1000 m is formed.
 Contact between gas and liquid: allows transfer of particles
(and soluble gases) from gas phase to the liquid.
 Liquid droplets are separated from the gas phase.
 Scrubbers
• Fine particles (liquid, solid) 0.1 to 100 m can be
effectively removed from the gas stream.
• Mechanism of particle removal: impaction, direct
inception, diffusion
• Optimum droplet size:
• < 100 m: droplets tend to follow gas, and relative
velocity difference between particle and droplet  0
• > 1000  m: droplet concentration is small; chance of
collision with gas particles becomes smaller.
 Interceptor: liquid droplets
Streamline: gas flow
Mechanism of particle
removal in absorbers

a. Inertial Impaction
(relatively large particles
travelling on collision
course with the drops of
the liquid, the interceptor)
b. Interception (particles
travelling on streamline
but contacts interceptor
because streamline
converges)
c. Diffusion (very small
particles, < 1um, impinge
upon the drop because of
random molecular
motion.
 Spray Scrubbers & Packed Scrubbers

Spray Scrubber (Spray Tower) Packed Scrubber (Packed Tower)

 Spray Scrubbers: Design
• Common scrubbers: Spray tower or spray scrubbers
• Water (scrubbing liquid) is sprayed using nozzles to
produce small liquid droplets.
• Gas flow: co-current, counter-current or cross flow
• Particles collide with liquid droplets.
• Droplets settle by gravity at the bottom of the tower.
 Spray Scrubbers: Design
• Gas velocity at the bottom is low enough to allow
liquid droplets to settle.
• 500 m droplet: terminal velocity is about 2 m/s; gas
velocity is < 2-3 m/s.
• Mist eliminator at the top: to avoid carry-over of
liquid droplets at the top.
 Scrubbers: Design
• Liquid collected at the bottom is cleaned, recycled to
the spray nozzles at the top.
• Liquid load: 0.3 – 1.2 kg water/m3 gas.
• Pressure drop: 250-500 Pa.
• With particle > 10 m, spray scrubber is superior to
cyclones
• Packing materials: Polymers may be used but
pressure drop and operating cost is high.
 Scrubbers
Advantages (compared to dry
methods)
• Particles & gases may be
simultaneously removed.
• No risk of dust explosion.
No dust problem.
• Useful for humid gases and
sticky material.
• Corrosive particles and
droplets may be removed
and neutralized.
• Compact.
Disadvantages
• Requires separation of
particles (as sludge) from
the liquid.
• Requires wastewater
treatment.
• There is water
consumption. Account for
evaporation.
• Possible corrosion problem.
• Freezing in cold weather.
 Bag Filters
• Filter – any porous structure composed of granular of
fibrous material or a membrane that tends to retain
the particulate as the carrier gas passes through the
voids or the fine holes of the filter material.
• Material: textile, glass, polymers, ceramics, metals
 Filtration
• Filtration: Retention in a mesh

30
Bag Filters

Removal of particulate matter

 Filter Configuration
• Fixed bed or layers of granular materials
• Plain, treated or charged mats or pads
• Paper filters or multiple plies or folds
(increased surface area; cylindrical tubes)
• Rigid porous beds (for large particle removal)
• Fluidized bed
 Filtration

• Mechanical processes important to filtration:

interception, inertial impaction, electrostatic
deposition, diffusion
Yinghui Wang, , , Keting Gui, Mingheng Shi, Changfeng Li (2008) Removal of dust from flue gas in
magnetically stabilized fluidized bed. Particuology
Volume 6, Issue 2, April 2008, Pages 116–119
Mechanism of Particle
Removal
a. Inertial Impaction
b. Interception
c. Diffusion
d. Sieving
e. Electrostatic attraction
 Filter Material
• Types
– Fibrous (cloth)
– Granular (sand)
– Rigid solid (screen)
– Mat (felt pad)
• Materials: natural or synthetic
– Fibers, granules, cloth, felt, paper, ceramic,
metals, glass, plastic
 Filter Material
• Cotton, wool: cheap, but not applicable at 80 - 90C,
not resistant to acids, bases
• Many polymers stand 200C
• Higher temperature: metals, ceramics
• Fabric filters formed into cylindrical tubes (increased
surface area): Filter bag typical dimensions: 150 mm
diameter, 4 – 8 m length
 Filter Cleaning
• Filter cake formed may improve filter efficiency but
at some point increases pressure drop  filter cake
must be removed
• Removing filter cake (cleaning the filter):
– Short pulse jet of compressed air from top of each
filter bag.
– Filter bag expands during the pulsing  dust cake
breaks off, falls to the bottom, automatically
removed.
PulseJet Bag Filter
Removing filter cake (cleaning the
filter):
Short pulse jet of compressed air
from top of each filter bag.
Filter bag expands during the
pulsing  dust cake breaks off,
falls to the bottom, automatically
removed.

www.hosokawamicron.co.jp
 Filter Design
• Estimate total filter area
• Filter size- depends on the volumetric flow of
the gas; acceptable pressure drop (particle
concentration is not important).
• Frequency of pulse cleaning: depends on
particle concentration.
 Filter Design
• Capacity of a bag filter:
– volumetric flow rate per filter area (gas velocity
perpendicular to the filter surface)
• typical: 0.015 -0.02 m/s for a pulse jet filters;
• can also be 0.005 -0.04 m/s
– Air to cloth ratio
 Filters
• Pressure drop can be kept low by frequent cleaning.
• Note: filter cake helps filtration
• Frequent cleaning lowers efficiency
• For membrane filters, efficiency is not dependent on
thickness of cake
• Membrane bags (Teflon): more expensive
• Fabric filter efficiency: >99% for 0.5 m particles
 Filter for dust cleaning
Advantages
• High efficiency for all particles
• Many options for filter
materials and filter
construction
• Can be made in all sizes from
gas flows 0.05 m3/s to 500
m3/s
• Moderate pressure drop and
energy consumption
• Different types of particles can
be removed in same
installation
Disadvantages
• Large space needed
• Risk of dust explosion
• Hygroscopic material 
cleaning problems
• Humid gases must be at
temperature above dew point
to avoid condensation and bag
cleaning problems
 Electrostatic Precipitator (ESP)
Particle collection in ESP is based on movement of electrically charged
particles in an electric field.
1. The dust particles are charged.
Gas molecules are ionized by the corona of the emission electrodes.
Emission electrodes: wires (20-100 kV below ground potential)
2. The charged dust particles move in an electric field.
Gas flows horizontally between plates.
3. The dust particles are collected on oppositely charged plates
collecting electrodes.
Collection electrodes: plates (grounded)
4. The dust particles are removed from the collecting electrodes.
Electrostatic precipitator
Electrostatic precipitator
 Electrostatic Precipitator (ESP)
• Most convenient for large installation: high
investment in electrical equipment.
• The electric force in an ESP is much stronger
compared to the centrifugal force of a cyclone.
• The collection efficiency of ESP for small particles is
much better than that of a cyclone.
• Particles 0.05 – 200 m can be removed with high
efficiency (> 99% is possible).
 Electrostatic Precipitator (ESP)
• Pressure drop: 250 – 500 Pa (lower than those of
cyclones, bag filters, and efficient scrubbers).
• Typical dimension of an ESP: 16 m height, 30 m
width, 20 m length for a power plant.
• Distance between plates: 0.15 – 0.4 m.
• For 500 m3/s flow rate: use parallel units
• If high efficiency is required: use ESP units in series
 Electrostatic Precipitator (ESP)
• The migration velocity (w) is found from a force
balance (drag force = electrostatic force):

k D .E d p
2

w

where
k(D) = a constant depending on the dielectric constant (D) of the particle
E = electric field strength
dp =particle size Larger particle size, greater
 = gas viscosity electric field strength 
greater migration velocity
 higher efficiency
 Electrostatic Precipitator (ESP)
Advantages
• High efficiency for all
particle sizes
• Can be used for very large
installations, 500 m3/s gas
per unit
• Low pressure drop and low
energy consumption
• Can be used at high gas
temperatures of 400 –
500C
Disadvantages
• The properties of the
particle are important for
the removal efficiency and
the dust resistivity must be
within certain limits
• Too expensive for small
scale installation, say less
than 5-10 m3/s
• Large investment
 Comparison of Methods for Control of Particulate Air Pollutants
Gravity Cyclones Scrubbers Bag Filters Electrostatic
Settlers Precipitators
Particle sizes > 50-100 m >5-10 m >2-5 m (>0.3 All particle All particle
with a high m for Venturi sizes sizes
removal scrubbers)
efficiency
Temperature Depends on Depends on Higher water 200-250C; 400-500C
limit construction construction use at higher higher with
material material temperature metal or
(>100C is (>1000C is due to ceramic filters
possible) possible) evaporation
Effect of water Must avoid Must avoid No effect Must avoid Affects
content condensation condensation condensation efficiency

Pressure drop, 50-130 1000-2000 500-1300 1000-1500 50-130

Pa

Other remarks Can be used as Useful for Sludge and The best Not for gas
a pre-separator coarse dust waste disposal choice if high flow < 5-10
and not as final must be efficiency is m3/s (high
cleaning considered needed investment
process cost)
Lecture 5.2 Air Pollution Control Techniques for Stationary Sources

CONTROL OF GASES AND ODOROUS

COMPOUNDS
Removal of Gaseous
Pollutants
1. Absorption devices
2. Adsorption devices
3. Condensers
4. Conversion to non-pollutant
material (oxidation processes,
direct-flame afterburners,
catalytic afterburners)
5. Biological control systems
(biofilters; bioscrubbers)
Control of Gases and Odorous Compounds

OXIDATION: THERMAL OR
CATALYTIC
 Oxidation
Combustible air pollutants
Net reaction:
CmHn + (m + n/4) O2  n/2 H2O + m CO2
Reaction mechanism is complicated. Many intermediates are
formed and oxidized before the final combustion products are
formed.
Important intermediate compound is CO
CmHn + (m/2 + n/4) O2  n/2 H2O + m CO
CO + ½ O2  CO2
The oxidation of CO may be the critical design parameter.
 Oxidation
If the pollutant contains S, Cl or N, secondary pollutants like SO2,
HCl and NOx may be formed.
Thermal NOx may be formed from N2 and O2 in the air in any
case when the flame temperature is above 1300 C.
If the concentration of the combustibles is above the lower
explosion limit the gas will burn if ignited, and in this case we
have a fuel and not an air pollution problem.
A mixture of air and combustible gases can explode if the
concentration is between the explosion limits. In this interval
the mixture can burn if ignited.
 Explosion limits for selected compounds

Compound Lower explosion limit, Upper explosion limit,

vol% vol %
Ethylene 2.7 34.0
Carbon monoxide 12.5 74.0
Methane 4.6 14.2
Methanol 6.4 37.0
Propane 2.4 8.5
Toluene 1.2 7.0
Hydrogen 4.0 76.0
 Oxidation
The explosion limits depend on the chemical compound, the
composition of the mixture, the temperature, the pressure,
and the ignition temperature or energy.
If the temperature is outside the explosion limits, the gas will not
burn when ignited.
If the concentration is above the explosion limit, the mixture
may be diluted with air, as is the case with other gaseous fuels
in combustion processes.
If the concentration is below the lower explosion limit, the gas
must be either reheated to the temperature necessary for
oxidation to take place or add a fuel to the combustion
chamber.
 Oxidation
Oxidation may be either
• Thermal at high temperature of 850 – 1000 C
• Catalytic at a lower temperature of 250 – 400
C
 Thermal Treatment Processes
• Incineration (does not destroy heavy metals)
– Time, temperature, turbulence
• Hydrocarbons + O2 + energy(?)  CO2 + H2O + energy (?)
• Hydrocarbons + O2 + energy(?) + Cl or heavy metals +
inorganic salts + N compounds + sulfur compounds + P
compounds + S compounds  CO2 + H2O + energy (?)+
chlorinated hydrocarbons or heavy metals + inorganic salts +
N compounds + sulfur compounds + P compounds + S
compounds
 Advantages of thermal systems
• Potential energy recovery
• Volume reduction of the contaminant
• Detoxification of selected molecules
• Applicable to most organic contaminants
• Small land area requirement
 Chemical Changes
• For most thermal processes
C20 H 32O10  x1O2  x2 H 2O 
y1C  y2 CO2  y3CO  y4 H 2  y5CH 4  y6 H 2O  y7Cn H m

• CnHm: alkanes, benzene

 Thermal Oxidation (Incineration)
• For safety reasons, the concentration must be 25% of
the lower explosion limit if an oxidation process is
used for control of air pollutants, and usually the
concentration is well below this limit.
• Polluted gas is preheated through heat exchange
with cleaned gas.
 Thermal Oxidation (Incineration)
Cleaning efficiency Important parameters 3 T’s:
depends on • Temperature
• Combustion • Time
temperature • Turbulence
• Residence time
• Flow conditions • Design: refer to Chemical
• Flow concentration Reaction Engineering and
• Type of pollutants Unit Operations of ChE
 Thermal Oxidation (Incineration)
• If the concentration of the pollutant is above 10-15 g/m3 of
solvents, the adiabatic temperature rise of combustion may
be 200 – 350 C and the hot cleaned gas may be used for
heating of water or steam production (waste heat recovery
boiler)
• If the concentration of the pollutant is below about 5 g/m3
fuel consumption is high, because it is not possible to preheat
the gas to a high temperature in a counter-current heat
exchanger (HE).
– HE is large, expensive
– Combustion would initiate at the HE, damaging
 use regenerative heat exchangers
Combustion Chamber with
Heat Exchanger
Combustion Chamber with
Heat Exchanger
High Efficiency Furnace
Combustion with
regenerative heat
exchange
 Guidelines for Incineration
• Liquid purely organic contaminants
• Chlorine-containing organic materials: special
considerations (special materials), long combustion time,
high temperature (> 1600C), continuous mixing
• Feedstock containing heavy metals: should not be
incinerated
• S compounds  SO2 emission, needs control
• Minimize formation of NOx: T > 1100 C
 Catalytic Combustion
By the use of catalyst the rate of reaction can be increased and
the oxidation can be carried out at a lower temperature and
in a more compact unit (i.e. smaller space requirement).

Catalytic material:
• Noble metals like Pt or Pd
• Oxides of the transition metals: CuO, Cr2O3, NiO

Catalyst shapes:
Spheres, cylinders or rings, monoliths

Catalyst lifetime: 25,000 h

 Catalytic Combustion
• Temperature: 250 – 350C (compared to 900-
1000 C in thermal combustion)  cheaper
construction material
• Space velocity (m3 gas per second per m3 of
catalyst): 4 – 5 s-1
• Residence time: 0.2 s (for thermal
combustion: 0.5 – 1 s)
Catalytic combustion with
heat exchanger for raw
gas heating
Catalytic Combustion
Catalysts for Combustion
Catalytic Oxidation
 Oxidation: Summary
• Oxidation is an attractive process: high removal efficiencies, >
99%
• If concentration is high enough to give sufficient adiabatic
temperature rise, no additional fuel is needed.
• If the concentration is low, fuel must be burned to heat the
gas and compensate for the losses. Regenerative heat
exchange may be used to reduce fuel costs.
 Oxidation
Advantages
• Can obtain very good removal of organic
and combustible inorganic compounds
• Process is not sensitive to moderate
changes in gas flow or pollutant
concentration
• Performance is not dependent on type of
pollutant if temperature and residence
time are high enough
• Heat recovery is possible
• Fuel consumption may be low at high
pollutant concentration or using
regenerative heat exchange
Disadvantages
• Relatively large investment
• High operating cost if additional fuel is
needed and heat recovery is not an option
• Valuable compounds cannot be recovered
• Secondary pollutants may be formed if gas
contains S or Cl. SO2 and HCl must be
removed before emission.
• NOx may form if the burner zone
temperature is high or the gas contains
nitrogen.
 Other Thermal Processes
• Pyrolysis – chemical decomposition induced in
organic material by heat in the absence of
oxygen (produces gaseous materials, liquid,
coke)
• Semi-volatile organic compounds, pesticides,
PCBs, dioxins, PAHs
 Other Thermal Processes
• High-pressure oxidation (combines wet air
oxidation and supercritical water oxidation,
high temperature and high pressure)
Control of Gases and Odorous Compounds

ABSORPTION
 Absorption Process
absorption a component in a gaseous mixture becomes absorbed
as a solute in a liquid (bulk gas to bulk liquid)

liquid phase gas phase: air or steam

absorption

For compounds that are highly soluble in water (absorbent liquid)

Solubility of the absorbate (pollutant) is enhanced by chemical or biological
reaction in the liquid.
Example: absorption of SO2 in a solution or slurry of CaCO3 in water.
81
Absorbers

Packing
•provides surface or interfacial contact
area between liquid and gas
•Ensure an even distribution of liquid
over the cross section

Height absorption tower: 50 m for flue

gas desulfurization in a power plant
 Absorbers
• Spray tower (without packing):
– Not clogged by particles
– Low pressured drop, <1000 Pa (low energy usage)
– Gas velocity may be 3 m/s, column diameter may be
smaller than packed towers
• Packed tower
– Enhanced cleaning efficiency
– May be clogged by particles
– Higher installation cost
– Higher pressure drop
 Design of Absorbers
• ChE unit operation equipment design: treats
absorption as physical absorption
• Industrial gaseous emissions of low concentration
of the soluble pollutant to be removed:
– If physical absorption: high water requirement
(consider phase equilibrium principle: concentration
in the gas phase is in general directly correlated with
concentration in the liquid phase)
– Absorption with chemical reaction (needs chemical
reaction engineering)
Absorption liquids and reactive compounds used for air pollution control
Pollutant Absorption liquid or reactive compound
HCl, HF, NH3 Water
SO2, NO2 NaOH, NH3, CaCO3, Ca(OH) 2
H2S NaOH, NaOCl
NH3 H2SO4, HNO3
Organic acids NaOH
Phenols, cresols NaOH
Phosgene NaOH
Cl2 NaOH, NaSO3, Na2S2O3
Mercaptans NaOCl, H2O2, O3, KMNO4, Cl2
Amines NaOH
Polar solvents Microorganisms
Non-polar solvents Oil
Odorous compounds Water, NaOCl, H2O2, O3, KMnO4, Cl2, microorganisms
 Absorption with a Chemical Reaction
• Advantages:
– Absorption is fast  dimensions of the absorption
tower becomes smaller compred to physical
absorption
– The capacity of the absorption liquid is not limited
by the solubility of the gas in water because the
pollutants react in the liquid phase, and the water
consumption is reduced.
 Absorption
Advantages
• Simple, cheap compared to
oxidation and adsorption
• The pollutant may be
recovered, recycled to the
process, or be converted to
useful byproducts
• Not sensitive to the
humidity of the gas
Disadvantages
• Cleaned gas is saturated
with water
• Wastewater must be
treated
• There is consumption of
chemicals
• Consumption of water
Control of Gases and Odorous Compounds

ADSORPTION
 Adsorption
• Adsorption process uses the ability of a solid surface to
remove one or more gases or liquids selectively from a
mixture.
• In air pollution control, the gaseous pollutant (the adsorbate)
is adsorbed on the solid phase (adsorbent).
 Adsorption Principles
• Partitioning to solids: Sorption (adsorption)
– A (solution ) + solid  A-solid
– The interaction of the solute (chemical being sorbed) with
the surface of a solid surface can be complex and
dependent on the properties of the chemical (solute) and
water (solvent)
– Adsorption may be
• Physical (adsorption)
• Chemical (Chemisorption)
 Adsorption & Desorption
 Adsorption: deposition or attachment on a solid surface

carbon

Adsorbate;
organic/inorganic

91
 Adsorption
• Physical adsorption:
– Molecules stick to surface because of van der Waals
forces.
– Exothermic: enthalpy change is 1.5 to 2 times the
enthalpy change of condensation, i.e., 2-20 kJ/mol
– Reversible: increasing the temperature or lowering
the concentration, pollutant is desorbed without any
chemical conversion
 Adsorbent can be recycled; adsorbate can be
recovered.
 Adsorption
Adsorbents: Activated carbon (AC)
– Activated carbon • Porous, High specific surface 500-1000
m2/g in small pores
(most common in
air pollution • Macropores facilitate transport of
pollutants to the micropores where
control)
adsorption takes place
– Zeolites • Finest micropore: size of a few molecule
– Polymers diamater
– Silica gel • Adsorption is not restricted to monolayers
on the surface and the fine pores may
become filled with pollutants
• Used as a tablet or granular (2-5 mm)
• Widely used to remove non-polar solvents
 Adsorption
• Gas passes through a layer of
activated carbon contained as fixed
bed in a vessel or cylinder
• Height: 0.2 – 1 m depending on the
concentration of the pollutant and the
layout
• At low pollutant concentration 1-10
ppmv: shallow layer with a low
pressure drop (long period before AC
is saturated and must be changed)
• At high pollutant concentration, AC is
regenerated using steam,p ollutant
may be recycled
 Adsorption
• Adsorption is carried out at room
temperature;
• Desorption or regeneration: done with steam
at 100 to 150 C
• Design of adsorption unit depends on the
adsorption capacity of the AC
• For easily adsorbed compounds: AC may take
up 30% of their own weight, but the capacity
depends on the type of compound (the
adsorbate).
• Relationship between the concentration of
the compound (adsorbate) in the gas phase
and that in the solid phase  adsorption
isotherm
 Adsorption
• Adsorption is most effective for non-polar
(hydrophobic) organic compounds (example:
hydrocarbons) and less effective for polar
(hydrophilic) compounds (example: organic acids and
lower alcohols).
 Adsorption: Partition Coefficients
Sorption isotherms: S = KDCw

• S = concentration of the solute in the solid phase (mass of

solute per mass of soil or sediment or adorbent)

• Cw = concentration of the contaminant in the liquid phase

(mass of solute per volume of pore water or liquid solution)

• KD = partition coefficient
 Adsorption: Partition Coefficients
• Estimating the KD:

KD = KOCOC

• KOC = the organic carbon partition coefficient (volume of pore

water per mass of organic carbon)
 Adsorption Isotherms
• Deriving KD: CS
KD 
CW
Adsorption isotherm fig
4.15
 Theoretical adsorption capacity for a given activated carbon for
selected organic compounds at different concentrations in the gas
 Adsorption
• Adsorption is especially well suited to control
air pollution in the cases when
– The pollutant is not combustible or forms a
harmful secondary pollutant upon combustion
– The pollutant is valuable and recycling to the
production process is possible
– Adsorption without regeneration can be used at
low pollutant concentrations
 Adsorption
Advantages
• High removal efficiency for
polar compounds
• Recycling of the pollutants
to the production process at
high pollutant
concentration  short
payback period
• No chemicals needed
Disadvantages
• High investment and
operating costs in units with
regeneration
• The activated carbon must
be supplemented or
changed; lifetime – few
years
• Wastewater from the
condensation of steam must
be treated if the pollutants
are (partly) water solluble
Control of Gases and Odorous Compounds

BIOLOGICAL METHODS
 Biological Methods
Carried out by microorganism
• Air pollutants + O2 biomass + CO2 + H2O

Biological methods: well suited for removal of

odorous compounds at relatively low
concentration.
Two types:
– Biological filters
– Biological scrubbers
 Biological Filters
Biological filters
• Microorganisms are fixed to a porous organic material
• Gas flows through a layer (example: peat moss mixed with
twigs and small branches to give stability and porosity).
• The odorous substances are adsorbed to the organic material
and used as feedstock by the organisms.
• The microorganisms adapt to the pollutants after some time
and “suitable” microorganisms grow. In some cases special
microorganisms grown on the target compound to be treated
is put on the filter to ensure filter performance.
• Nutrients to support microbial growth are also added.
 Biofilter Media
Table 2. Biofilter media characteristics
Moisture Nutrient
Material Porosity Useful Life Comments
Capacity Capacity
Peat Average Good Good Good Good
Microorganis
Soil (heavy Poor Good Good Good m Sources
loam)
Average Good Good Good
Compost
(yard waste)
Wood Chips Good Average Average Average Good
Additions
Straw Good Average Poor Poor
for Porosity
Biofilters
Biofilters
 Biological Scrubbers
Biological Scrubbers
• Similar principles as scrubbers with chemical
reaction, but, instead of chemical reaction,
biological reactions carried out by
microorganisms
– present in the scrubbing liquid or
– fixed to the packing or filter material in the
scrubber
Horizontal and Vertical Biofilters

Figure 2. Horizontal flat-bed biofilter (left) and vertical biofilter (right)

Degradability of VOCs

HAPs
 Aerobic Degradation by Pure
Culture
Organism Compound
Hypomicrobium Methyl chloride
Pseudomonas DM I dichloromethane
Alcaligenes A 175 1,4 dichlorobenzene
Bacillus TPI Thiophenol
Pseudomaomas putida BU2 Butraldehyde
Rhodococcus Sk Scatole
Mycobacterium L1 Vinyl chloride
Coryneformic bacterium 2 ethyl hexanol
 Biological Filters
Advantages Disadvantages
• High efficiency • Requires large space
• Low pressure drop • Filter materials may need to
• No expenses forchemicals be changed after a few
• Simple operation years (it may also be
degraded)
• Clean gas is saturated with
water, has ambient
temperature  needs
reheating to enhance
thermal rise
 Comparison of methods to control gaseous air pollutants
Properties of Thermal Catalytic Absorption Adsorption Biological Biological
the gas at the Oxidation Oxidation Scrubbers filters
inlet
Compounds VOC and other VOC and other Water-soluble VOCs, HCs, Water-soluble biodegradable
removed with combustibles combustibles compounds nonpolar and compounds,
high efficiency (HCs, solvents, (HCs, solvents, (SO2, HCl, NH3, solvents, biodegradable odorous
odorous odorous organic acids, odorous compounds, substances
compounds compounds mercaptans, substances odorous
amines substances

Dust content A low dust A low dust No harm Dust must be No harm Dust must be
load is load is pre-removed pre-removed
tolerable tolerable
Water content Increases the Increases the Lowers water Tolerates up to Increases the Increases the
operation cost operation cost consumption 70% relative operation cost operation cost
humidity

High Good for heat Good for heat May lower Cooling is Cooling is Cooling is
temperature recovery recovery efficiency needed needed needed
 Comparison of methods to control gaseous air pollutants
Thermal Catalytic Absorption Adsorption Biological Biological
Oxidation Oxidation Scrubbers filters

Advantages Potential for Potential for Simple process Possible to Simple process Simple process
heat recovery heat recovery reuse
adsorbed
compounds

Disadvantages High costs High cost, risk Wastewater High cost in Wastewater Large space
High fuel costs of catalyst and/or sludge plants with and/or sludge requirement
in some cases poisoning in regeneration
special cases
Air Pollution Control Techniques for Stationary Sources

CONTROL OF HAZARDOUS AIR

POLLUTANTS
 Considerations
• Estimating contaminant migration
• Treatability tests
• Contaminant treatment and control
– Source, release, transport, exposure, response
Air Pollution Control Techniques from Stationary Sources

POLLUTION CONTROL TECHNIQUES

FOR CHEMICAL INDUSTRIES
 Inorganic Acid Manufacture
Acid Manufacturing Process Air Pollutant Control methods
emissions
Hydrochloric Byproducts of organic HCl absorption
chlorination, salt process,
and synthetic HCl
Hydrofluoric Fluorspar-sulfuric acid SiF4, HF Scrubbers (some with
caustic)
Nitric Pressure process & direct NO, NO2, N2O4 Catalytic reduction,
strong acid adsorption, absorption
Phosphoric Elemental P Particulate matter,
fluorides
Thermal process H3PO4, H2S Mist eliminators, alkaline
scrubbers
Wet process SiF4, HF
Superphosphoric Fluorides
Sulfuric contact SO2, acid mist Scrubbers with mist
eliminators
 Base Manufacture
Base Manufacturing Air Pollutant Control methods
Process emissions
Calcium oxide Rotary kiln, vertical PM Cyclones +
(lime) and shaft kiln, 2collectors
fluidized bed (baghouse, ESP),
furnace wet scrubbers,
granular bed filters,
wet cyclones
Sodium carbonate Solvay (ammonia PM Wet scrubbers
(soda ash) soda)
Sodium hydroxide, electrolytic Chlorine, mercury Alkaline scrubbers,
caustic soda chemical scrubbers
and adsorbers
Pollution Control Techniques for Chemical Industries

FLUE GAS CLEANING

Flue Gas Cleaning
• Desulfurization
• NOx Removal
– Power Plants
– Boilers in Industries
– Biomass Combustion
– Waste Incinerators
 Flue Gas Desulfurization (FGD)
• 88% wet scrubbers
• Sorbent injection processes
• Spray dry scrubbers
• Regenerable processes
• Combined SO2/NOx removal processes
 Flue Gas Desulfurization (FGD)
• SO2 has a low solubility in water and reaction with basic
reagent is necessary to obtain high degree of desulfurization
(small absorption tower, low water use)
• Example: limestone with a high content of CaCO3 (>95%)
• SO2 (g) + ½ O2 (g) + CaCO3 (s) + 2 H2O (l)  CaSO4.2H2O (s) gypsum +
CO2 (g)
Limestone based FGD
plant on a coal-fired
boiler

Inlet gas temperature: 100-

120  C, 99% or more of the
fly ash has been removed
(in an ESP, upstream).

The flue gas is cooled to 70 -

80C in a heat exchanger
counter-currently with the
cleaned flue gas.
Limestone based FGD
plant on a coal-fired
boiler

Inlet gas temperature: 100-

120  C, 99% or more of the
fly ash has been removed
(in an ESP, upstream).

The flue gas is cooled to 70 -

80C in a heat exchanger
counter-currently with the
cleaned flue gas.
Limestone based FGD
plant on a coal-fired
boiler

Flue gas goes through

absorption spray tower
(without packing) where
the following takes place:
•SO2 from the gas phase is
absorbed by the scrubbing
liquid.
•HSO3- is oxidized to SO42-
•CaCO3 is dissolved.
•Crystals of CaSO4 .2H2O
(gypsum) are formed.
Limestone based FGD
plant on a coal-fired
boiler
Limestone is added at the
bottom of the absorption
tower and is partly
dissolved in the scrubbing
liquid, which is pumped to
the top of the scrubber and
distributed over the cross
section using spray nozzles.
The liquid is recycled over
the tower and part of the
limestone dissolves during
contact between gas and
liquid in the tower.
Limestone based FGD
plant on a coal-fired
boiler
Limestone is added at the
bottom of the absorption
tower and is partly
dissolved in the scrubbing
liquid, which is pumped to
the top of the scrubber and
distributed over the cross
section using spray nozzles.
The liquid is recycled over
the tower and part of the
limestone dissolves during
contact between gas and
liquid in the tower.
Limestone based FGD
plant on a coal-fired
boiler

Air is blown to the bottom

of the absorber to ensure
complete oxidation of
sulfite to sulfate.

A side stream is taken out

for removal of gypsum using
hydro cyclones and vacuum
filters.
Limestone based FGD
plant on a coal-fired
boiler

Air is blown to the bottom

of the absorber to ensure
complete oxidation of
sulfite to sulfate.

A side stream is taken out

for removal of gypsum using
hydro cyclones and vacuum
filters.
Limestone based FGD
plant on a coal-fired
boiler

All the sulfur removed from

the flue gas leaves the
process as gypsum of high
quality.

The gypsum is washed with

water, and this water is
partly recycled to the
process and partly taken
out for wastewater
treatment, where heavy
metals, mainly from small
amount of fly ash, are
removed.
Limestone based FGD
plant on a coal-fired
boiler

The cleaned flue gas is

heated to 70 – 80C by heat
exchange with incoming
flue gas to ensure a proper
plume rise and good
dispersion of the remaining
air pollutants in the
atmosphere.

The efficiency of the flue

gas desulfurization with
scrubbers is typically about
95% removal of SO2; 99% in
newer plants.
 Lime-Limestone FGD
A typical
lime/limestone
Flue Gas
Desulfurization
(FGD) system
consists of three
major sub-
systems:
• The reagent (lime
or limestone
slurry)
preparation;
• The scrubber/SO2
absorber and mist
eliminator, and
• slurry/solid waste
disposal systems.
http://www.cgscgs.com/
 NOx Removal from Flue Gas
Clean Technology approach: use of low-NOx burner
• But, flue gas still contains NOx
NOx: 95% NO, the rest is NO2
• NO is not an acid, has low solubility in water

Commercial process for NO removal:

• Reduction of NO and NO2 to N2
 NOx Removal from Flue Gas
Reduction of NO and NO2 to N2
Most common reactant for this reaction: NH3, the
reaction can be carried out
• at low temperature (300-400 C) using a catalyst, i.e.,
the selective catalytic Reduction (SCR) process
• Or at high temperature (850-1000 C) without a
catalyst, the selective non-catalytic reduction (SNCR)
process
 NOx Removal from Flue Gas
Selective Catalytic Reduction
(SCR) process:
Main reactions
6 NO + 4 NH3  5 N2 + 6 H2O
6 NO + 8 NH3  7 N2 + 12 H2O
Side reactions
3 O2 + 4 NH3  2 N2 + 6 H2O
Overall Reaction:
4 NO + 4 NH3 + O2  4 N2 + 6 H2O
These reactions take place
on the surface of a solid
catalyst.
Catalyst is porous to give a
large specific surface
and most of the reaction
takes place on the
interior surfaces.
Most common catalyst:
TiO2 as catalyst, and
V2O5 and WO3 as carrier
material.
 NOx Removal from Flue Gas
SCR Process: Optimum temperature is 350 –
370 C. The catalyst is placed
Show fig. 4.19 F&T in the flue gas stream before
the air preheater, where the
usually the flue gas has this
temperature.
At this point (which is before the
electrostatic precipitator),
the flue gas has high content
of flys ash. Thus the catalyst
is in blocks with small
channels to ensure tha the
ash will not deposit on the
catalyst surface.
NH3 Injection in DeNOx Reactor
NOx Removal from Flue Gas

www.advatechllc.com
NOx Removal from Flue Gas

www.power-eng.com
urs-processtechnologies.com
 NOx Removal from Flue Gas
Selective Non-Catalytic Reduction (SNCR) process:
Same reactions but without catalyst  higher temperature 900 –
1,000C.
Another reaction is possible: 4 NH3 + 5 O2  4 NO + 6 H2O (This
undesirable, detrimental reaction takes place > 950C and
dominates at 1,000C.
Below 900C, the reaction of NO with NO3 becomes low.  Flue
gas may contain un-reacted NH3.
 NOx Removal from Flue Gas
Selective Non-Catalytic Reduction (SNCR) process:
It is important to inject NH3 at the proper place in the boiler
where the optimum temperatures (about 950C) prevail.
Temperature changes with fuel type, boiler load, fouling of heat
transfer surfaces.  NH3 consumption is higher
 efficiency is lower compared to SCR process.

This SNCR
method is not
used in coal-fired
power plant. !!!
 Waste Incinerators
• Flue gas contains potassium (K) and other catalyst poisons.
• Thus, in waste combustion, it is not possible to place the SCR
process before the particle and gas cleaning process.
• In this case, the cleaned and cooled gas may be reheated
before the SCR reactor (i.e., tail-end placement of SCR).
• But higher operating cost.
• Thus, most waste incinerators use SNCR process.
 Biomass Combustion
• Biomass combustion (Waste-to-Energy)
• Biomass fuels: straw and wood have
potassium (K). This is a catalyst poison for the
vanadium based SCR catalyst.
• Deactivation of the catalyst by K is fast. But
may reactivate it by washing with water or
acid.
 FG Cleaning: Summary
Air Pollution Control Costs for Coal-fired Power Stations
Capital Cost Running Cost

ECU/kW As % of 0.001 ECU As % of the

capital cost per kWh cost of
of the plant electricity

Low-Nox burners + over- 20-40 2-3 1-2 1-4

fire air
SCR 70-110 5-8 4-5 6-12

Particulate Control 40-50 3-4 2-3 4-8

FGD 130-220 10-17 5-6 8-14

Total 260-420 20-32 12-16 19-38

Main Reference:
Jess Fenger & Jens Christian Tjell (Eds.) Air Pollution – from a local to a
global perspective. Royal Society of Chemistry (RSC) Publishing &
Polyteknisk Forlag, Denmark. 2009. 488 pp.

Thank you!!
QUESTIONS ??