Pollutants

Particulates
Lead
Hydrogen chloride
Beryllium
Mercury
Dioxins
Sulfur dioxides
Nitrogen oxides
Carbon monoxide
Carbon dioxide

Unburnt hydrocarbons
Volatile Organic compounds
Methylene chloride
Chloroform
Carbon tetrachloride
Benezene
Formaldehyde
Xylene

Health Concerns
Carbon Dioxide:produces greenhouse effect.CO2 molecules interact with infrared heat energy preventing normal radiation from earth,leading to warming of
atmosphere.Coastal flooding,melting of antartic ice and agricultural disruption
could result. CO2 from coal-207, oil-160, nat gas-111 lb/MM Btu
Carbon Monoxide:Dangerous to health besides being indicative of inefficient
combustion.Passes through lungs,directly into blood,causes fainting and even
death.At an exposure of 0.1% in air by volume,a human will be comotose in 2
hours. Exposure is limited 9 ppm for an 8 hour period and 13 ppm for any 1 hour
Oxides of Nitrogen: NOx is mainly NO;remainder is NO2.NO converts to
NO2.Reduces ability of blood stream to carry oxygen.NO2 is more toxic than
NO.On absorbing light in the UV range,dissociates into NO and atomic
oxygen,which reacts with O2 to form ozone and smog.Affects plant life.Also NO2
reacts with H2o to form HNO3-a constituent of acid rain
Oxides of sulfur:Causes acid rain and damage to plant life,structures.Also an
eye irritant and causes respiratory diseases such as emphysema,bronhitis and
lung cancer.Causes smog,haze.
Particulates:Affect visibility,haze,smog;affects lungs,digestion.

POWER PLANT EMISSIONS

Item

Efficiency,%

42

40

46

46

52

Coal/nat gas(g/kwh)

340

335

220/47

310

140

Co2,g/kwh

830

810

660

760

380

So2,g/kwh

600

585

380

150

No2,g/kwh

600

585

270

300

350

Gypsum,g/kwh

20

62

13

Ash,g/kwh

34

22

32

Rejected heat,mj/kwh

4.3

3.6

3.4

3.2

2.6

1.Coal fired 2.FBC 3.nat gas/coal fired CC 4.ICGCC 5.nat gas CC

Pollutants in MSW plants

Dioxins: Generated in MSW applications. These are
typically family of organic compounds. Almost all
dioxins are removed when exposed to a temperature
of 1500 F for 21 sec. At higher temperatures, shorter
residence times are required.
SO2-30 ppm at 12 % CO2
NOx-140-200
CO-400
THC-70
TSP-0.01 g/dscf
4

Thermal and Catalytic incineration

Chemical & petrochemical plants;Metal
coating, paints,
pharmaceuticals
Exhaust from many
processes contain
VOCs.They form ozone
when released to
atmosphere.
Incineration is effective
way to destroy
them.VOCs are
converted to CO2 and
H2O.There are two
types,catalytic and
Thermal
Catalytic: needs lower oxidation
temperatures.500-700 F.lower fuel
consumption.

. 1500-1800
Thermal: combustion at
F. Residence time 2 secs destroys
pollutants. aux fuel used if vapor has
lower heating values

Hazardous waste incineration

The temperature profile
for hazardous waste
steam generator
process can be tailored
to achieve any
DRE.One is ADEF and
the other is ADEGH.
The first profile achieves
a DRE of 99.99 % and
the second a DRE of
99.9999%.The increase
in residence time helps
achieve a higher
destruction of wastes.

Devices for pollution control

BAG HOUSE

ESP

Low emissions

Low emissions

High capital cost

Low gas pressure drop

High gas pressure drop

High capital cost

Requires significant real estate

Requires significant real estate

Fuel sensitive

Emissions from IGCC

Item

Efficiency,%

42

46

52

CO2,g/kwh

830

760

380

SO2,g/kwh

600

150

NOx,g/kwh

600

300

350

1-coal fired steam plant 2-IGCC 3-nat gas fired CC plant

NOx formation
NOx is produced through oxidation of fuel bound and atmospheric
nitrogen.There are 3 kinds:Fuel NOx,prompt NOx and thermal NOx.
Fuel NOx: nitrogen in fuel combines with oxygen in air .gaseous fuels have
little fuel bound nitrogen,while coal/oil have.Fuel bound nitrogen can
account for 50% of the NOx emissions.Most NOx control technologies have
little impact on fuel-NOx,which is controlled by fuel switching or fuel
treatment.Fuel NOx is insensitive to flame temperature.
Prompt NOx:results when fuel hydrocarbons break down and recombine
with nitrogen in air.Chemically produced.Accounts for 15-20 ppm and forms
ahead of flame tip.
Thermal NOx:forms when atmospheric nitrogen combines with
oxygen.Rate of formation increases exponentially with temperature and
directly proportional to oxygen concentration.Keeping flame temperature low
reduces it.Residence time,turbulence and excess air are the other factors
affecting it.

NOx Reduction in Boilers & HRSGs

Several methods available. Best solution

is arrived at on a case to case basis
10

NOx reduction methods

Boilers

Gas Turbines/HRSGs

Gas recirculation

Water/steam injection

Staged combustion

SCR deNOx

SNCR
Burner modification
SCR
Steam/water injection

11

Gas Reburn
One of the methods to reduce NOx in large industrial boilers is natural gas
reburning,which lowers NOx by 50-70%. Nat gas is injected into the upper
furnace region to convert the NOx formed in the primary fuels combustion
gases to molecular nitrogen.
Primary zone:burners fuelled by coal/oil/gas are turned
by 10-20 %
Gas reburning zone:natural gas between 10-20% of
boiler heat input is injected above the primary
zone.This creates a fuel rich region where
hydrocarbon radicals react with NOx to form molecular
nitrogen.Recirculated flue gases may be mixed in .
Burnout zone:A separate overfire zone system
redirects air from primary combustion zone to a
location above the gas burning zone to ensure
complete combustion.There must be room for overfire
air and for burnout.Also emissions of SO2,CO2 are
reduced as nat gas replaces coal/oil.

12

NOx,CO conversions-Boilers
Exs air,%

10

20

30

10

20

30

Fuel

n.gas

n.gas

n.gas

n.gas

#2oil

#2oil

#2oil

#2oil

% vol co2

9.47

8.68

8.02

7.45

13.49

12.33

11.35

10.51

H2o

19.91

18.38

17.08

15.96

12.88

11.9

11.07

10.36

N2

70.62

71.22

71.73

72.16

73.63

74.02

74.34

74.62

O2

1.72

3.18

4.43

1.76

3.24

4.5

MW

27.52

27.62

27.68

27.77

28.87

28.85

28.84

28.82

Wgm

768

841

914

986

790

864

938

1011

Nat gas:% vol C1=97,C2=2,C3=1.HHV=23789,LHV=21462 Btu/lb

# 2oil:C=87.5,H2=12.5,deg API=32.HHV=19727,LHV=18512 Btu/lb
13

NOx,CO conversionsBoilers
ppmvdN=106xYx(N/46)x(MW/wgm)x(21-3)/(21-O2Y) where
Y=100/(100-%h2o),wgm=flue gas produced per MM Btu fired,lb
and N=lb of NOx per MM Btu generated. At 0 % excess air for nat
gas,Y=100/(100-9.9)=1.248.
ppmvdN=106x1.248xNx27.52x18/(46x769x21)=832N
Similarly at 30 % excess air,wgm=986,Y=1.189,MW=27.77,Y=1.189
ppmvdN=106x1.189x(N/46)x(27.7/986)x18/(21-4.43x1.189)=832N
ppmvdC=1367C as ratio of MW of CO and NOx=28/46.C=lb CO/MM Btu.

Hence for nat gas:ppmvdN=832N and ppmvdC=1367C

For oil:

ppmvdN=783N and ppmvdC=1286C

14

Converting Pollutants in gas turbine exhaust

If w lb/h is the flow of NOx(NO2),the following expression gives V,the NOx on dry
volumetric basis:

V=100x[(w/46)/W/MW]/(100-%H2O)

(1)

%H2O=volume of water vapor in exhaust gases

W,MW=exhaust gas flow and its molecular weight
Converting to 15 % oxygen basis,dry:

Vn=Vx(21-15)x106/[21-100x%O2/(100- %H2O)]

(2)

Where %O2 =oxygen present in wet exhaust gases.

Similarly, ppm of CO converted to 15%oxygen basis is Vc=1.642Vn for the same w
lb/h of CO.
Example: 25 lb/h of NOx and 15 lb/h of CO are present in 550,000 lb/h of exhaust
gases whose analysis is:% vol CO2 =3.5,H2O=10,N2=75,O2 =11.5.
MW=2.5x44+10x18+75x28+11.5x32=28.0 V=100x(25/46)/(550,000/28)/(10010)=30.74x10-6 Vn=30.74x6/[21-100x11.5/(100-10)]=22.4 ppmvd
Vc=(15/25)x1.642x22.4=22 ppmvd

15

Converting Hydrocarbons
Let U be the emission of UHC(treated as methane) in lb/MM Btu in flue
gases of natural gas at 20% excess air.
Vu=Ux106xYxMWx(21-3)/[16xWgmx(21-O2xY). From earlier slide,at 20%
excess air,flue gas MW=27.68,% water vapor=17.08,16 is mol wt of
methane,Wgm =914 and % O2 wet=3.18. Hence,
Vu=Ux106x(100/82.92)x27.68x18/[16x914x(21-3.18x100/82.92)]=2394 U
ppmvd
For excess air at 10%:
Vu=Ux106x(100/82.62)x27.62x18/[16x841x(21-1.72x100/82.62)]=2365U
ppmvd. Hence if UHC is0.1lb/MM Btu for natural gas,it is 237 ppmvd.
For # 2 oil at 20% excess air,Wgm=938,O2=3.24,MW flue
gas=28.84,%H2O=11.07.
Vu=Ux106x(100/88.93)x28.84x18/[18x938x(21-3.24x100/88.93)]=2240U
ppmvd.
If U=0.1 lb/MM Btu for # 2 oil,it is 224 ppmvd

16

Converting SOx from mass to volume

Each lb of Sulfur converts to 2 lb of SO2. S+O2=SO2
[32+32=64]
Using natural gas at 20% excess air,
Vs=Sx106x(100/82.92)x27.68x18/[64x914x(213.18x100/82.92)]
=598 S ppmvd. Hence 0.1 lb/Mm Btu SOx=60 ppmvd
Similarly for # 2 oil at 20 % excess air:
Vs=Sx106x(100/88.93)x28.84x18/[64x(213.24x100/82.92)]=534S ppmvd
If a fuel oil with 19000 Btu/lb HHV having 3 % sulfur is
fired,what is the SO2 in lb/MM Btu?
SO2 =2x106x0.03/HHV=2x106x0.03/19000=3.15 lb/Mm Btu
17

Sulfur Compounds
SOx reacts with water vapor in the flue gas/atmosphere to
form sulfuric acid mist.air borne sulfuric acid is found in
fog,smog,acid rain and snow. About 95 % of sulfur in fuel
converts to SO2,1-5 % as SO3 and 1-3 % as sulfate
particulates. SOx pollution has been controlled by either
dispersion(tall stack) or reduction-switching to low sulfur
fuel,desulfurizing the fuel and using FGD system.It
involves use of scrubbers. These are classified as non
regenerable or regenerable. RFGD converts waste
byproduct into a marketable product such as sulfur or
sulfuric acid. SOx reduction of 90-95 % can be achieved
by FGD. Fuel desulfurization and FGD are used in large
utility boilers and not in small boilers.
18

Reference Oxygen Level

In emission calculations, 3% oxygen dry reference is used in
oil/gas fired boilers and in gas turbine emission calculations,15
% oxygen is used. However actual oxygen levels during
measurement of pollutants may be different. How do we
convert?
ppm(3% oxygen dry)=ppm(actual)x(21-3)/(21-oxygen(actual
dry)
If dry oxygen in flue gases=1.7% and 12 ppmvd of a pollutant is
measured, then at 3 % oxygen it will be =12x(21-3)/(211.7)=11.2 ppmvd
Similarly, if NOx is 30 ppmvd at 14 % oxygen dry in a GT
exhaust, it will be = 30x(21-15)-(21-14)=25.7 ppmvd at 15 %
oxygen dry level. Sometimes emissions are limited on mass
basis and sometimes on ppmvd basis.
19

Effect of firing on NOx

Firing temp,F

900

1100

1300

1500

MM Btu/h HHV

35.4

96.6

160.4

226.8

Burner NOx,lb/h

3.5

9.7

16.0

22.7

Turbine NOx,lb/h

48.8

48.8

48.8

48.8

Total NOx,lb/h

52.3

58.5

64.8

71.5

Stack NOx,ppmvd

41.9

41.8

41.7

41.6

Depending on initial exhaust gas analysis,NOx in ppmvd

may increases or decrease with firing.However NOx in
lb/h will be higher.
20

Typical Emissions from various fuels

Gas

NOx(lb/MM Btu

CO(lb/MM Btu

Natural gas

0.1

0.08

Hydrogen gas

0.15

Refinery gas

0.1-0.15

0.03-0.08

Blast furnace gas

0.03-0.05

0.12

Producer gas

0.05-0.1

0.08

[Emissions from Duct burners]

21

NOx vs FGR

22

NOx formation vs Flame temperature

N2+O2 NOx

d(NO)=Ae-b/T [O2]0.5 [N2]dt

NOx=f(T,[O2],t)

Thermal NOx is nearly 40

times higher at 2700 F
compared to that at 2250 F.
NOx at 3000 F /2700 23
F=6.6

Effect of Excess air on NOx and CO

As excess air increases the CO decreases. NOx increases as

combustion temperature increases and falls off with further
increase due to dilution and cooling of the mixture. FGR
has the same effect.

24

Effect of Oxygen on NOx

This is a general chart. Mixing and burner type affect NOx formation
significantly

25

Combustion temperature vs
FGR

26

FGR and Fuel Staging

Eliminating air heaters
helps lower flame
temperature and hence
NOx. It also lowers
furnace heat flux and
total fan power
consumption via lower
gas/air pressure drops

Burner suppliers offer fuel and

air staging concepts to decrease
NOx
27

Boiler Arrangement using FGR and SCR

28

Fuel Nitrogen conversion

As the nitrogen % weight in liquid fuel

increases,the fraction converted to NOx
decreases

29

Ranking of fuels for NOx potential

GASES
Landfill gas
Natural gas
propane
butanes
hydrogen
CO

LIQUIDS SOLIDS
methanol
Ethanol
gasoline
# 2 fuel oil
# 6 fuel oil
MSW
RDF
coal

30

SNCR process
Uses ammonia or
urea.Operates in a
narrow range of
temperatures,typically
1800-2000 F. Variable
load and gas temperature
affects performance and
efficiency.

Advantages:Low energy consumption ,20-40 kw and its ability to

control ammonia slip
31

A Comparison of Options
Method

NOx removal %

10-30

$/kw

<1

Oper cost

<1

2
30-50
10-15
<1

15-30

40-60

60-90

30-70

5-10

35-45

75-150

10-20

<1

1-6

5-9

1-4

(mills/kwh)
1-Combustion adjustments 2-Low NOx burners 3-Overfire air
4-Reburning

5-SCR

6-SNCR

32

SCR in Packaged Steam generator

A gas bypass system
may be required to
maintain 600-700 F
gas temperature at the
catalyst at all loads.At
low loads,the gas
temperature drops
off.Portion of the
evaporator is bypassed
using dampers.

33

Catalyst reactions

SO3+NH3+H2O NH4HSO4
SO3+2NH3+H2O (NH4) 2SO4
In a vertical gas flow HRSG as in forced circulation units,water
washing of surfaces downstream of SCR is a problem as it can
affect the catalyst.

SO2
converts to
SO3 at the
catalyst
A major
advantage of
natural
circulation
HRSGs is the
ability to water
wash highly
soluble
ammonia
compounds
formed
downstream of
the SCR when
operating with
a sulfur
containing fuel.
34

Ammonia Feeding systems

35

SCR location

SCR efficiency drops off at lower gas temperatures and also at very high
temperatures. Optimum is in 600-750 F range. Also catalyst size, gas pressure
drop and cost increases with higher temperature or flue gas volume. Hence an
optimum design is arrived at by discussion with SCR suppliers.

36

HRSG Temperature profiles

37

HRSG with CO and NOx

Catalysts

38

Ammonium Sulfate

Tdp(deg C)=503.4+10.922ln(pso3 xpnh3x10-12xp2) :p-gas pressure,bara, pso3 &

pnh3-ppmv of so3 and nh3
Eg:p=1 bara,pso3 = 0.25 , pnh3 =40, then Tdp=503.4+10.922ln(.25x40x10-12)=226.7
39 C

Cleaning of HRSG tubes

External fouling of HRSG tubes is caused by deposition of compounds formed in
turbine exhaust gas from contaminants and ammonia injected for SCR. With oil firing
,serious problems arise. Unreacted ammonia can react with SO3 to form ammoniam
salts ,principally ammonium bisulfate and ammonium sufate,that deposit downstream
of HRSG tubes. Slip of 1 ppm prevents formation of salts but that is difficult an
impairs SCR performance and NOx reduction.Fouling also increases back pressure
of the HRSG.
The potential for deposit formation is increased with CO calalyst since CO oxidizes
SO2 to SO3.The CO catalyst should be locate downstream of SCR as it permits
operation at lower gas temperatures and lower ammonia slip.
Traditional cleaning methods are high pressure water washing and sand blasting;
these damage the tubes and fins and also generate secondary waste which must be
disposed off. A new process is is to use CO2 pellets or dry ice.These pellets shock
the deposits severing their bond with the tubes without damaging the tube fins. The
pellets sublimate into vapor,leaving only the contaminants and no cleaning media like
water or sand to dispose. Cleaning not effective at corners.

40

Variables affecting SCR

NH3 slip should be
large enough to
ensure reactions
but small enough
not to cause
sulfate formation. It
is also a pollutant
and monitored.
Ammonium sulfate
is a sticky
substance which
can deposit on
downstream
equipment causing
plugging.

Experience indicates that when NH3 slip is less than 10 ppm and
SO3 is less than 5 ppm,formation of ammonium sulfate is nil unless
41
gas temperature is very low <200 C.

Steam Injection in gas

Turbines and Boilers

42

Steam/water injection in Turbines

Water/fuel

0.2

0.4

.6

Heat rate
(Btu/kwh-l)

11,137

11,238

11,139

11,441

NOx-lb/h

209

141

95

64

NOx-ppmv

120

81.5

55

37

CO2-lb/h

129

157

207

297

CO2-ppmv

122

149

197

283

THC-lb/h

16.3

20

29

52

THC-ppmv

26.9

33.7

49

87.5

Item

water/fuel
0.15

steam/fuel

Ratio

Kw

20,100 20,365 20,890

36,400 38,650

Heat rate-L

9453

11,211

9505

0.5

9560

0.7

10,878

43

Limitations of control methods

Lo-NOx burner:Furnace size,fuel nitrogen content,FD fan
limits,superheater performance,CO formation
FGR:Flame stability,Efficiency loss,erosion,FGr
fan,duct,operating cost
Reburn:availability of secondary fuel,pressure part
modification,furnace geometry,superheater
performance,space limitations
SCR:Variable load operation,additional gas pr drop,ammonia
handling,slip,variable gas temperature,deposits

44

Particulate Matter
PM consists of compounds such as nitrates, sulfates,
carbon,oxides.PM can be corrosive,toxic to plants and life.
They are classified as PM and PM10. PM10 is a particulate
matter with diameter less than 10 microns.This is considered
severe as it can pass through a bodys filtering system
because of its size. PM levels from natural gas are lower
than those from residual fuel oils.
Methods of particulate control vary depending on boiler size
and fuels. For utility boilers,ESP,scrubbers and bag houses
are used. For smaller boilers, it is better to use cleaner fuels.

45

Emission monitoring methods

Constituent

CEM technology

Particulate matter

transmissometer,B ray absorption

SO2

UV absorption,IR pulsed fluorescence

Nitrogen oxides

Chemiluminescence

Hydrogen chloride

IR with gas filter

CO

IR

CO2

IR

VOCs

flame ionization detection

Organic air toxics

chromotography

Ammonia

same as NOx

46

Technology for monitoring

Infra radiation: an infra red beam passes thro a measurement filter and is
absorbed by the gas.A light detector creates a signal which monitors
concentrations
UV absorption: A split beam with optical filters,phototubes and amplifiers
measures differences in light beam absorption between reference and
sample
Chemiluminescence:Ozone is injected into the sample to react with NOx
generating light that is measured by a photocell
Flame ionization: hydrocarbons are ionized with strong light.Signals are
received by flame ionization detector
Electrochemical cells:voltage measured when an o2 sample into a sample
with a strong base is compared to a reference voltage
Chromotography:A sample gas sent thro a column.Output measured by a
flame photometric cell is compared
Transmissometer:Light is passed through a stack where it is reflected by a
mirror on opposite side.Quantity of light returned is proportional to the47