Air Pollutants and Their Effects

Tie the corresponding items together

CO

Irritating to lungs
Contributing to tropospheric/ground level O3

NOx

Aerosol
Mainly from transportation

VOC

Mainly from fossil fuel combustion in stationary

sources

Erosion of buildings
PM

In the form of solid or liquid

Highly water soluble

SOx

smoke

Air Pollutants: Carbon Monoxide (CO)

Colorless, odorless, tasteless gas
Produced during incomplete combustion
77% of total CO: emitted from transportation
Form carboxyhemoglobin (COHb) in the bloodstream
An indoor air pollutant

CO & Health Effects

Typical concentration

Roadway: 550 ppm

Cigarette smoke: 2400 ppm
Smoky bar: 2030 ppm (~ 1 hr ambient standard)
Smokers [COHb]: ~ 510%

[COHb] in blood and symptons

1.7% ~ 35 ppm for 1 hour
2.5%: tone signal
10%: headache
30%: fatigue, impaired judgment
60%: lost of consciousness

CO: Effects of Exposure

Source: Seinfeld, J.H. 1986, Atmospheric Chemistry and Physics of Air Pollution, published by John Wiley & Sons, Inc., New York

Sulfur Containing Pollutants

Carbonyl Sulfide (OCS, 500 ppt)

Carbonyl Sulfide
(COS, 500 ppt)

Carbon Disulfide
(CS2, 35120 ppt)
Hydrogen Sulfide
(H2S, 450840 ppt)

Wetland

Dimethyl Sulfide
(CH3SCH3, 80110 ppt)
SO2, 1500 ppt)

Global Sulfur Emissions Estimates

Source

SO2

Fossil-fuel burning
70
& industry
Biomass burning
2.8
Oceans (DMS)
-Wetlands (H2S,DMS, and CS2) -Plants + soils
-Volcanoes
78
Anthropogenic (Total)
Natural
Total

SO42-

Total Sulfur (Tg(S) yr-1)*

2.2

7177

0.1
40320
-24
24

2.23.0 (1.4/1.1)
1525 (8.4/11.6)a
0.012 (0.8/0.2)
0.250.78 (0.3/0.2)b
9.311.8 (7.6/3.0)
7380
2540
98120

*(w/o sea salta and soil dustb)

Numbers in ( ) are fluxes from Northern Hemisphere/South Hemisphere.
Source: Berresheim et al., 95

Anthropogenic Sulfur Emissions

Source: Dignon and Hameed (1989), Hameed and Dignon (1992), and Spiro et al. (1992)

Oxides of Sulfur (SOx)

~ 90% of the anthropogenic-related SOx emitting from
fossil fuel combustion
Transformation of SO2(g) to sulfuric acid (H2SO4):
- Reaction with hydroxyl radicals:
SO2 + OH

HOSO2

HOSO2 + O2

SO3 + HO2

SO3 + H2O

H2SO4

Oxides of Sulfur (SOx)

Transformation of SO2(g) to sulfuric acid (H2SO4) (ctd.):
- Reaction with O2 (needs large activation energy):
2SO2(g) + O2

2SO3(g)

SO3(g) + H2O(pte)

H2SO4(pte)

- Soluble in water:

SO2(g) + H2O(pte)

H2SO4(pte)

. (not balanced)

Neutralization reactions of SO2(g) to (NH4)2SO4:

H2SO4(pte) + 2NH3(g)

(NH4)2SO4(pte)

SOx: Effects
Precursor of sulfate particles
Most sulfate particles in urban air: 0.20.9 m
-

visibility

- easily penetrating deep in human lungs

- synergistic effects
Highly water soluble: erosion of building materials

Control of Sulfur-Containing Pollutants

(1) Sulfur oxides:
Pre-combustion control; pollution prevention
Removal of SO2 from
rich waste stream
lean waste stream
Combustion
Flue gas desulfurization (FGD):
- Wet-throwaway
- Double alkali
- Dry throwaway
- Wet-dry throwaway
- Adsorption/absorption
(2) Others (e.g., H2S):
Removal of S from natural gas and petroleum

Control of SO2: Pre-combustion Control

Unit of sulfur content emitted:
% or mass of SO2 emitted per heat energy delivered
Pre-combustion control:
Fuel switching:

30-90% emission; blending; temporary

Compliance coal or low-sulfur coal:

- Meeting NSPS without control: [emission] < 1.2 lb/MBtu
(0.5 g/MJ) (NSPS: new source performance standard)
- Organic bound: chemical/biological treatment
- Inorganic form: washing to remove pyrite (FeS2),
ash content

Control of Rich SO2 in Waste Gases

Resource Recovery
for smelting ores:
SO2 + 0.5O2 vanadium catalyst
SO3 + H2O
H2SO4

SO3;

Cost-effective if
(a) SO2 concentration is high enough
(b) the chemical conversion leads to marketable
products (H2SO4)

Control of Lean SO2 in Waste Streams

Combustion control:
Fluidized-bed combustion (FBC):
CaCO3 + SO2 + 0.5 O2
~ 90%

of S

Advanced Pressurized Fluidized-Bed Combustion (PFBC)

Source: http://www.engineering-4e.com/systems.htm

CaSO4 + CO2

Control of Lean SO2 in Waste Streams

Flue gas desulfurization (FGD)
- Often used for coal/oil power plants
Processes:
- Wet-throwaway: limestone, hydrated lime/quicklime
- Double alkali (DA): sodium (bi)carbonate (Na2CO3, NaHCO3)
- Dry-throwaway: Boiler injection (CaCO3/Ca(OH)2); Boiler/flue
gas injection (Na2CO3 or NaHCO3)

- Wet-dry: spray dryers (SD)

- Regenerative adsorption/absorption: Regenerable
adsorbents or absorbents

Control of Lean SO2 in Waste Streams

Wet-throwaway process (limestone), Wet Scrubber:
CaCO3 + SO2 + 2H2O
CaSO32H2O
~ 90% of S
CaO + SO2 + 2H2O
(CaCO3

heat

CaSO32H2O

~ 95%

of S

CaO (porous materials) + CO2)

Disadvantages of wet scrubber:

1. Expensive
2. Corrosion, scaling, plugging problems
3.
amounts of water used
4. Sludge treatment: CaSO3 CaSO4 thickening
vacuum filtration

Control of Lean SO2 in Waste Streams

Wet-throwaway processes (Quicklime/hydrated lime):
- An alternative to limestone in wet-throwaway processes
- CaO (burned lime/quicklime) hold tank hydrated to Ca(OH)2
- More reactive than CaCO3 because of higher surface area
- More expensive because of additional steps

Control of Lean SO2 in Waste Streams

Double alkali scrubber
Na2CO3 + SO2
Na2SO3 + CO2

- To solve the problems of wet scrubbing

- Solubility of sodium salts >> solubility of calcium salts
liquid w/o solid particles
regenerated with CaO/CaCO3
Na2SO3 + CaCO3 + 0.5O2

CaSO4 can be precipitates

CaSO4 + Na2CO3 (in hold tank)

Control of Lean SO2 in Waste Streams

Double alkali scrubber

(Source: Air Pollution Control Engineering by Noel De Nevers, McGraw Hill, 95)

Control of Lean SO2 in Waste Streams

Scrubber

Taken from www.induscoenviro.com/img/scrubber1.jpg

Control of Lean SO2 in Waste Streams

Scrubber

Taken from www.mikropul.com/products/wscrub...turi.gif

Control of Lean SO2 in Waste Streams

Scrubber

Taken from www.q-net.net.au/~legion/scrubber.jpg

Control of Lean SO2 in Waste Streams

Dry-throwaway process:
CaCO3

dried at high temp. CaO

SO2

CaSO3

O2

CaSO4

Disadvantages of dry system

1. More expensive by requiring excess of lime/limestone
2. Increase in solid waste
3. Less efficient than wet-throwaway (DA)

4. Mainly based on empirical tests

Control of Lean SO2 in Waste Streams

Spray dryers (SD):
dispersion from high-pressure gas atomizing nozzle
for heat-sensitive products (e.g., SO2-containing flue gases)
more like wet-lime scrubber
partly like dry sorbent injection

Picture taken from class.fst.ohio-state.edu/Dairy_T...-141.gif

Control of Lean SO2 in Waste Streams

Spray dryers (SD):

Taken from www.niro.com/NIRO/cmsresources.n...ber2.gif

Control of Lean SO2 in Waste Streams

Regenerative Systems:
Adsorbents/absorbents can be regenerated
Concurrent removal of SOx and NOx: still under study

Control of Lean SO2 in Waste Streams

CaCO3 Ca(OH)2

Reagents
Na2CO3
NaHCO3

limestone hydrated lime sodium

(quicklime) carbonate

sodium bicarbonate

Regenerable
adsorbents/
absorbents

Process
---------------------------------------------------------------------------------------------------Wet-throwaway
DA
Dry-throwaway

Wet-dry
Regenerative

Limestone / Lime scrubbing

DA

DA

Boiler
Boiler lime Boiler or flue Boiler or flue
limestone injection
injection
injection
injection
SD
SD
SD
Many kinds,
producing SO2 or S
or H2SO4. Some
control both SO2
and NOx.

Control of Sulfur in Natural Gas & Petroleum

Removal of sulfur from natural gas streams:
H2S(g)

H2S (l)

H+ + HS-

add alkali

remove H+
Removal of sulfur from hydrocarbon fuels:
H2S + O2

S (inert, harmless) + H2O

(Undesirable oxidation: H2S + 3/2 O2

HC-containing S + H2

catalysts (Ni/Co)

SO2 + H2O)
HCs + H2S

Reactions of Nitrogen and Sulfur: Comparison

Elementary oxidation & reduction
Reduction

Elemental
form

Oxidation
1st step

Oxidation
2nd step

---------------------------------------------------------------------------------------------------High pressure+
high temperature+
hydrogen gas + catalyst.
Biological processes
(low pressures
and temperatures).

reaction with O2,

at (1) high temperatures
(2) low temperatures

(1) atmosphere
(2) catalytic reactor

NH3

N2

NO

NO2

H2S

SO2

SO3

Reactions of Nitrogen and Sulfur: Comparison

Additional Reactions
Reaction( with water)

Reaction (with NH4+ or other cations)

---------------------------------------------------------------------------------------------------Rate depends on atmospheric

moisture content

Rate depends on [atmospheric cations]

HNO3

nitrate particles

H2SO4

sulfate particle

Nitrogen Containing Pollutants

N2O, NOx, HNO3, and NH3
N2O
- Colorless
- Almost completely from natural sources
- Long residence time

120 years

- Important Green-house gas

NH3
- Emitted from natural & anthropogenic sources

NO2 and Ozone

NO2
irritating the lungs, causing bronchitis and pneumonia, and
lower resistance to respiratory infections
NOx + OH

HNO3

NOx + volatile organic compounds

photochemical oxidants

Photochemical smog pollutants

O3: chest constriction & irritation of mucous membranes

Others: PAN (peroxyacetylnitrate), HCHO, acrolein, etc.

causing irritation of eyes and respiratory systems (coughing),

Control NOx: Formation

Thermal NOx
Prompt NOx
Fuel NOx

(Source: Air Pollution Control Engineering by Noel De Nevers, McGraw Hill,95)

Control NOx: Prompt NOx

During the 1st part of combustion
Mainly converted from original form in fuel
Carbon bearing radicals
CH + N2

HCN + N

N + O2

NO + O

HCN + O2

NO

HCN + NO

N2

Control NOx: Fuel NOx

Most of the fuel nitrogen is converted in the flame to HCN,
subsequently converted to NH or NH2.
NH + O2
NH2 + O2

NO + H2O, or NH + NO
NO + H2O, or NH2 + NO

N2 + H2O
N2 + H2O

[NOx] from fuel depends on [NO]/[O2] ratio in the flame zone

At high-temp. zone of flame, if [O2]

[NO]

Usually, 20-50% of fuel nitrogen is converted to NOx,

depending on (1) furnace conditions, and (2) chemical
nature of nitrogen in fuels.

Control NOx During Combustion

During combustion:
- Emitted [NOx]

with

peak temperature,
time at high temperature,
[O2] at high temperature
- Peak temperature depends on

(1) fuel and oxidizer used,

(2) flame size,
(3) degree of fuel-air premix, and
(4) amounts of fuel-air preheat

Control NOx During Combustion

During combustion:
- Peak temperature

(Source: Air Pollution Control Engineering by Noel De Nevers, McGraw Hill, 2000)

Control NOx During Combustion

Modify Combustion / Combustor Design
Low NOx burner / Two-stage combustion:
1st stage: low excess air
[O2] and max. temp.
[NOx] formed
2nd stage:
- w/ excess air;
- the max. temp. from the 1st stage is low enough to
[NO] formed
- Often add extra fuel (e.g., CH4) without N

Control NOx During Combustion

Modify Combustion / Combustor Design
Low NOx burner / Two-stage combustion (ctd.):
Disadvantages: (1) fuel consumption,
(2) [CO] emissions, and
(3) larger burner.

Control NOx During Combustion

Modify Combustion / Combustor Design
Low NOx burner / Flue gas recirculation (FGR):
When fuel gas is employed: through mixing + excess air
prevent fuel-rich
thermal NOx and prompt NOx
[NOx] formed

fuel nitrogen

If oil is employed:
prompt NOx

(Source: Air Pollution Control Engineering by Noel De Nevers, McGraw Hill, 2000)

Control NOx Post-Combustion

Chemical Treatment of Combustion Exhaust Gases
From mobile emission sources:
Adding reducing agents:
2NO + 2CO pt-rh catalysts N2 + 2CO2
3-way catalytic converter

Taken from images.gasgoo.com/MiMwMDRfMDA0Iz...rter.jpg

Control of NOx Post-Combustion

Conversion efficiency (%)

Air-to-fuel ratio & Catalytic Converter Performance

Air-to-fuel ratio
14.8:1

14.9:1

(Source: Introduction to Environmental Engineering and Science by G.M. Masters, Prentice Hall, 2008)

Control of NOx Post-Combustion

Air-to-fuel ratio for vehicle emission control

(Source: Introduction to Environmental Engineering and Science by G.M. Masters, Prentice Hall, 97)

Control NOx Post-Combustion

Chemical Treatment of Combustion Exhaust Gases
From stationary emission sources:
(1) Selective catalytic reduction (SCR) w/ reducing reagents:
6NO + 4NH3
5N2 + 6H2O
4NO + 4NH3 + O2
4N2 + 6H2O
2NO2 + 4NH3 + O2
3N2 + 6H2O
Note: @ temp. > 1800oF,
NH3 + O2
NO + 1.5H2O
dominates over other reactions

Control NOx Post-Combustion

Chemical Treatment of Combustion Exhaust Gases
From stationary emission sources (ctd.):
(2) Selective noncatalytic reduction (SNCR)
(3) Scrubbing w/ solution of NaOH & KMnO4
- Expensive electrochemical regeneration of KMnO4
- More suitable for small-scale processes

Regulating NOx in Exhausts

Preventing artificial dilution of exhausts before release:
- depending on dilution of excess air;
- standard limit/regulation based on O2% in the exhaust
(Max. 6-7% of O2, by volume)
Other units: mg/m3, lb/106 Btu, g/GJ, g/kcal

Photochemical Reactions: Ground Level O3

Most abundant photochemical oxidants, in addition to
formaldehyde (HCHO), peroxybenzoyl nitrate (PBzN),
peroxyacetyl nitrate (PAN), and acrolein (CH2CHCOH)
Health effects of photochemical pollutants
O3: chest constriction & irritation of mucous membranes
Others (PAN, HCHO, acrolein, etc.): irritation of eyes and
respiratory systems (coughing),

Photochemical Reactions: Ground Level O3

NO-NO2-O3 photochemical reaction sequence
N2 + O2
2NO
2NO + O2
2NO2
NO2 + hv
NO + O
O + O2 + M
O3 + M
O3 + NO
NO2 + O2
When RCOO + NO RCO + NO2
(RCOO & RCO : VOC radicals)

Air Pollutants and Ground Level O3

Concentrations measured in Los Angeles, CA, USA, Jul. 19, 1965

Source: U.S. HEW, 1970, Air Quality Criteria for Carbon Monoxide, AP-62, National Air Pollution Control Administration,
Washington, DC

Photochemical Reactions: Ground Level O3

Why and how do VOC emissions aggravate ground level [O3]?
Tropospheric chemical reactions!
To reduce [O3]:

both VOCs and NOx