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VADE-MECUM
7. ENVIRONMENT
Rev. 2002
SECTION 7 ENVIRONMENT
Table of Contents
1.
2.
3.
4.
5.
Index - i
Rev. 2002
SECTION 7 ENVIRONMENT
This section covers NOx, SOx, CO2, CKD, alternative materials, waste fuels and to some extent, PMx. SOx which
have been partially addressed in section 6.7.3 (SO2 / SO3). More and more plants are required to have CEMS
(Continuous Emission Monitoring System) which are different from the process analysers, especially for dilution
purpose. You may have to convert some results for standard conditions. Standards (as %O2) vary worldwide (see
section 7.4).
1. NOx
1.1 NOx Generalities
Gross NOx emissions are typically in the range of 500 to 1,500 ppm being closely related to kiln combustion
conditions.
In the cement industry normally, 95% of NOx formed is nitric oxide (NO). This gas is colourless and is readily
transformed into NO2 in air.
Nitrogen dioxide (NO2) is a reddish-brown gas and is the principal component of smog. The toxic effects of
NO2 are not completely known, but an exposure to 15 ppm NO2 causes eye and nose irritations and 25 ppm
causes pulmonary discomfort.
Nitrous Oxide (N2O) represents <1% (typically 10 - 20 ppm) of NOx produced in a cement kiln. It is very
stable and is considered to play a role in the destruction of ozone.
In an oxidising atmosphere NO is formed. ALL steps listed above are reversible in a reducing atmosphere,
depending on exact temperature and partial pressure conditions at a given point in the flame.
Thermal NO formation kinetics are slow compared with fuel oxidation reactions and may be disassociated
from the combustion process. Thus final NO concentrations never reach levels predicted by thermodynamic
equilibrium at temperatures used.
Note that some studies (Fenimore, Bowman,...1971) found that the rates of thermal NOx formation in the
primary flame zone were considerably higher than those in the post flame zone. This fast NO formation
occurred at rates greatly exceeding the rate predicted by the O, N atom equilibrium mechanism. Some NO is
formed before the O atom has equilibrated with O2 (second hypothesis).
Prompt NO is the breaking of N2 bonds by CH hydrocarbonaceous radicals instead of O2. No discussion of
NO formation is complete without discussing Prompt NO, but in practical terms the amounts are negligible.
b. Fuel NOx
Many fuels contain significant quantities of chemically bound nitrogen. Some oils can have nitrogen in excess
of 2-4% N and many liquid hazardous wastes may have nitrogen much higher than that. The solid fuel
nitrogen content can be between .5 and 3%.
The fuel NOx is due to the nitrogen conversion in the flame during the combustion. Nitrogen is mainly
contained in aromatic compounds.
7.1
Rev. 2002
SECTION 7 ENVIRONMENT
The following diagrams show the ratio between the different sources of NOx in a lab furnace. The lower curve
was measured in an atmosphere without nitrogen and shows the fuel source of nitrogen oxide.
400
NO (ppm)
Air
300
NO thermal
Ar/O2
200
NO combustible
100
0
0
10
20
Excess air
30
40
Rule of thumb
0.2 to 2% N in fuel may yield 60 to 2100 ppm NO
0.8
0.6
0.4
0.2
0
21
20
Air
400
Thermal NOx
300
Ar/O2
200
18
500
Fuel NOx
100
19
600
NO, ppm
10
20
30
Excess air
40
50
Comparison of this figure with the previous one shows that the preheated air is effective on thermal NOx but
not on the fuel NOx mechanism.
In fact, the formation of thermal NOx is strongly dependent on the flame temperature and a few factors can
affect it.
7.2
Rev. 2002
SECTION 7 ENVIRONMENT
4
Q2 = K 2 * SKG * T f4 Tm , with
Q2:
K2:
-7
Flame Shape
The hotter the flame, the higher the NOx emission so the burner pipe settings affecting the flame shape also
have an impact on the NOx emission: i.e. primary air, combustible fineness, volatiles content...
Nitrogen Fuel
About 60% of the fuel nitrogen is converted into NOx in a PH/PC tower so the nitrogen content is also an
important factor in NOx generation (cf. Davenport Kiln audit 1997, 64%).
During the combustion process, the NOx generated in the calciner is mainly fuel related. Thus wed rather use
low N content fuel.
7.3
Rev. 2002
SECTION 7 ENVIRONMENT
Technique
Red effic.
Flame cooling
All
0-50%
Low-NOx burner
All
0-30%
Staged comb
Preca/preheat 10-50%
Mid-kiln firing
Long
20-40%
Easy to burn
All
10-15%
SNCR
Preca/preheat 10-85%
SCR (one plant)
All
89-95%
SNCR : selective non catalytic reduction
Reported
Reported
emissions mg/m3 emissions kg/tkk
4000.84000.8< 500-1000
<1.0-2.0
200-800
100-200
0.4-1.6
0.2-0.4
Operating
cost in $/tkk
0-0.5
0
0
0.2-0.4
Investment
in M US$
0-0.2
0.15-0.8
0.1-2/1-4
0.8-1.7
0.5-1.5
2.5-4.5
7.4
Rev. 2002
SECTION 7 ENVIRONMENT
2. SO2
(see also chapter Volatile in section pyroprocessing)
1% sulfur in heavy fuel oil yields 700 ppm SO2 in the dry stoichiometric product of combustion.
Best Available Control Technologies (BACT) for SO2 emissions
(see IPPC, Feb 2000, EC)
Technique
Kiln
Red effic.
Reported
syst
emissions
app
mg/m3
Absorbant addition
All
60-80%
400
(limestone or lime)
Dry scrubber
Dry
Up to 90%
<400
Wet scrubber
All
>90%
<200
Activated Carbon
dry
Up to 95%
<50
C4 lime reinjection
Fullers patent
PH/PC
30%
Reported
emissions
kg/tck
0.8
Operating
cost in
$/tck
0.1-0.4
Investment
in MUS$
<0.8
<0.4
<0.1
1.4-1.6
0.5-1.0
11
6-10
0.2
0.2
0.2-0.3
7.5
Rev. 2002
SECTION 7 ENVIRONMENT
3. Dust
3.1 What Affects the Dust Production
3.2 ESP
(Sources: Air Pollution Engineering manual, A.J. Buonicore, W.T.Davis)
a. Principles of operation
The ESPs perform by applying proper electrical forces in the space between the high voltage system and
ground of each gas passage. These electrical inputs involve a voltage level based on gas passage spacing and
gas and particle characteristics. The flow of electric current through this space will depend on the resistance it
encounters before reaching ground potential, identified as the collecting surface or plate. The electron flow
through the gas passage is known as corona current and will impact a negative charge bias to the particles
carried in the flue gas causing these particles to migrate toward positive side.
Rules of thumb
Operating voltage: 30 to 70 kV, dependent on design factors
Operating current density: 5 to 50 mA/cm2
Dust layer thickness: to 1 in.
b. Load and particle size
The higher the voltage, the better the collection. Usually, the first field will collect the biggest particles and
consequently, the finest will be found in the last field. Alkalis have a tendency to settle on fines and preferably
you want to waste your CKD from the last field.
7.6
Rev. 2002
SECTION 7 ENVIRONMENT
Rule of thumb: For a four field ESP with 80% collection efficiency, you will get an overall efficiency of 99.8%.
Field #
Entering
(kg)
100.0
20.0
4.0
0.8
1
2
3
4
Collected
(kg)
80.0
16.0
3.2
0.6
Cumulative
Collection
Efficiency
80.0 %
96.0 %
99.2 %
99.8 %
C
O
L
L
E
C
T
I
O
N
E
F
F
I
C
I
E
N
C
Y
,
%
5.0
c. Collection efficiency
Rules of thumb
Gas velocity impacts treatment time and power density (range from 0.6 1.5 m/s).
Specific collecting area (SCA) in ranges from .017 to .051 m2/Rm3/h (300 920 ft2/kCFM).
Migration velocity W (Lafarge NA cement kilns) : 30 to 110 cm/s.
Collection Efficiency
Eff. = 1 (exp {(A/Q)*W}0.5), where
where
- Q is the gas flow through precipitator,
- A is the Collection area and SCA is usually
calculated to reach the efficiency problem to
Process
Range of migration velocity
(cm/s)
Wet Kilns
Dry Kilns
PH/PC Kilns
30 80
30 60
45 110
*To get units in m2/(m3/s), multiply by 3600. To get them in ft2/kCFM, multiply by 5.019 and then 3600. 100 ft2/kCFM is a small SCA, 400 is medium and
900 is considered large.
7.7
Rev. 2002
SECTION 7 ENVIRONMENT
01
01
01
01
F erutarepmeT
006
004
002
01
R
e
s
i
s
t
i
v
i
t
y
(
O
h
m
c
m
)
R
E
S
I
S
T
I
V
I
T
Y
(
O
H
M
.
c
m
)
Fo ERUTAREPMET
3.3 Baghouse
(see Priority Study for more information)
a. Principles of operation
Dust gas flows through a fiber filter media. Clean air gets out and dust is caught at the surface of the media as
a dust cake. This cake is then removed by cleaning the surface bag by either shaking, reversing the air flow or
sending a pulse jet that extend the filter media for a short period of time.
b. Filter media
There are two types of filter media:
- Woven
- Felt
7.8
Rev. 2002
SECTION 7 ENVIRONMENT
Cloth type and weight are selected, based on temperature, moisture (because of hydrolysis) and resistance
(acid, alkali, oxydation and abrasion). Mostly used in cement industries are:
Generic name type
Trade name type
Max. temp. on
Application
Lifetime guarantee
continuous op.
(years)
(C)
Polypropylene
Herculon
125
General
2
Polyester
Dacron
130
General, mills
2
Glass
Fiberglass
260
Kiln, cooler
3
Polytetrafluorethylene (PTFE)
Teflon
250
Kiln, cement
4
Expanded PTFE
Rastex, Gore-tex
250
Kiln
34
Expanded PTFE/Glass
Superflex
250
Kiln
56
Aromatic Aramid
Nomex
190
Kiln, cooler
23
Polymide
P 84
240
Kiln
23
Dedusting
Shaker type
Reverse air
0.6 (2)
0.6 (2)
Pulse-jet
1.2 1.8 (4 6)
1.2 (4)
Coolers
Pressure drop
P
mm Hg (wg)
7.5 11 (4 6)
7.5 11(4 6)
9 19 (5 10)
Configuration
Styles
3.4 CKD
Lafarge NA data
(9 plants out of 15 waste CKD)
PLANT
1999
Alpena*
Bath*
Brookfield*
Davenport*
Exshaw*
Fredonia*
Joppa
Paulding*
Seattle
8.4%
2.9%
16.8%
2.6%
1.7%
11.7%
5.8%
10.3%
12.9%
% Dust Wasting
1998
1997
12.3%
3.2%
13.0%
3.9%
2.6%
9.8%
4.7%
15.3%
11.1%
4.7%
12.6%
4.2%
1.7%
8.6%
8.6%
20.6%
7.9
Rev. 2002
SECTION 7 ENVIRONMENT
4. CO2
The greenhouse gases are becoming a major concern for the cement industry. CO2 comes from three sources:
1- Decarbonation 2- Combustion of the carbon content in the fuel and 3- Same as #2 but from the Power plant
which provide our power needs.
Since 1990, Lafarge NA has emitted 1,0 tCO2/t kk for total emission (0,9 tCO22/t cement), which is : 0,5
tCO2/t kk coming from decarbonation, between 0,3 0,4 tCO2/t kk from fuel and between 0,0 0,2 tCO2/t
kk from power (indirect calculation, CO2 is generated at the Power plant).
5. Others
5.1 Correction to Standard Oxygen Conditions
2.62
2.86
1.15
1.8
1.23
1.88
2.05
3.27
1.5
mg/m3 @
0.21 [O 2 ]1
x[NO ]l
SO2
SO2
CO
CO2
NO
NO2
NO2
SO2
HCl
0.21 [O2 ]2
1 ppm of
[NO]2 =
[NO]2 : ?
[O2 ]1 : 0.08
450 ppm NO
8% O2
Standard condition:
6% O2
Question: What is the corresponding NO with the
6% O2 dilution (instead of 8%)?
Measurements:
Temp
(C)
25
0
25
25
25
25
0
25
25
Kg/tonne clinker
<0.4-6
<0.02-7
0.01-0.4
1-4
800-1040
0.01-1
5.4 Analysers
Two types of analysers : CEMS (continuous emission monitoring system) for Environment and Process
analysers.
7.10
Rev. 2002
SECTION 7 ENVIRONMENT
CO
Uras 14
Uras 3G
Uras 3G
Uras 3G
Servomex 700B
Uras 14
Uras 4
Combustibles
Uras 10P (methane)
O2
Magnos 17
Magnos 7G
Magnos 7G
Magnos 6G
Magnos 7G
Magnos 7G
Servomex 700B
Magnos 17
Magnos 7G
NO
Uras 14
Radas 1G
Radas 1G
Radas 1G
Uras 14
Radas 2
SO2
Radas 2
Uras 4
Uras 14
Uras 3G
Uras 10P
ZRF
Uras 14
Ultramat 22P (also
CO2)
Rosemount
88003702010
Sick GM950
Ultramat 6
Ultramat 21P
Thermox
Magnos 7G
Magnos 16
TAI-9710-20-2x
Magnos 7G
Radas 2
Radas 1G
Radas 2
Uras 14
ZRF
Uras 14
-
Uras 14
-
Magnos 7
Magnos 17
Leeds & Northrup
803-G2-R005-D
Rosemount 3001NH
Rosemount 3001NH
Oxymat 6
Thermox WDG III
Uras 14
Thermox WDG IV
Magnos 17
Ultramat 6
Thermo
Environmental 10 AR
Uras 14
Ultramat 6
Western Research
721 AT
Uras 14
Uras 4
Thermox WDG IV
Thermox WDG IV
Magnos 7G
Radas 2
Radas 2
Thermox WDG IV
Hagan 240R2
Notes: 1. Uras, Magnos, and Radas are Hartmann & Braun models;
2. Ultramat, Oxymat are Siemens models; 3. TAI-9700 series is a Teledyne model;
4. Hagen is a Rosemount model; 5. ZRF is a California Analytical model
7.10
Rev. 2002
SECTION 7 ENVIRONMENT
SO2
THC
Radas 1G
Radas 1G
MIR 9000
MIR 9000
MIR 9000
MIR 9000
MIR 9000
N/A
N/A
MIR 9000
MIR 9000
MIR 9000
MIR 9000
MIR 9000
JUM VE-7
JUM VE-7
Magnos 6
Radas 2
Radas 2
N/A
N/A
N/A
Radas 2
Radas 2
N/A
Fredonia K1/K2
Uras 3G
Magnos 6G
Joppa K1/K2
N/A
N/A
N/A
Uras 4
Kamloops
Paulding K1/K2
Uras 14
Magnos 16
N/A
N/A
Richmond
Seattle
(11)
St. Constant K1
Uras 3G
N/A
Magnos 6G
Magnos 6G
Rsmnt 3001NH
(11)
Uras 3G
Uras 3G
N/A
Uras 3G
N/A
Lear Siegler
SM8100
Uras 3G
Ultramat 6(8)
Rsmnt 3001NH
& Magnos 7G
Oxymat 6(8)
Radas 1G
Radas 1G
Lear Siegler
SM8100
Uras 3G
N/A
N/A
Plant
CO
Alpena - RG14
Alpena - RG15
Alpena - K19
Alpena - K20
Alpena - K21
Alpena - K22
Alpena - K23
Alpena K22/K23
Bath
Brookfield
Davenport
Uras 4
Exshaw K4 / K5
O2
St. Constant K2
Sugar Creek II
(7)
Whitehall K2 / K3
Woodstock
MIR 9000
MIR 9000
MIR 9000
MIR 9000
MIR 9000
Uras 10E
Uras 10E
Ametek CEM/IQ
Ametek CEM/IQ
Ametek CEM/IQ
Ametek CEM/IQ
Ametek CEM/IQ
Uras 10P
MIR 9000
MIR 9000
MIR 9000
MIR 9000
MIR 9000
Compur
MultiFID 100
N/A
N/A
Western
Research
721AT
HCl
N/A
flow monitor
USI 100
USI 100
N/A
N/A
N/A
USI
100
USI
100
USI
100
USI
100
USI
100
N/A
USI
100
USI
100
opacity
DAS version
Front end
N/A
N/A
(3)
USI 500C
(3)
USI 500C
(3)
USI 500C
(6)
L&N
(6)
L&N
(5)
USI 500C
USI 500C
USI 500C
Ultraflow USI 500C
Cirrus v. 3.04.09
Cirrus v. 3.04.09
Cirrus v. 3.04.09
Cirrus v. 3.04.09
Cirrus v. 3.04.09
Cirrus v. 3.04.09
Cirrus v. 3.04.09
Cirrus v. 3.04.09
A-B PLC-5
A-B PLC-5
A-B PLC-5
A-B PLC-5
A-B PLC-5
A-B PLC-5
A-B PLC-5
A-B PLC-5
Fluor Daniel
A-B PLC 5
Cirrus v. 3.5
Quantum
140CPU
Cirrus v. 3.03
RS3
Cirrus v. 3.03
A-B PLC 5
USI 500C
Ultraflow USI 500C
Cirrus v. 3.04
TI 555
USI 500C
USI 500C
USI 500C
Anarad
Cirrus v. 3.5
Fix app
Quantum
140CPU-53414
GE Series 90-70
Rsmnt 2000A
Notes: 1. Uras, Magnos, and Radas are Hartmann & Braun models; 2. N/A; 3. ID Fan; 4. N/A; 5. K22 / K23 Common stack; 6. Breech; 7. Scheduled for installation 1Q2001; 8. Ultramat and Oxymat are
Siemens models; 9. MIR 9000 is a Environnement S.A. Gas Filter Correlation analyzer; 10. Ametek CEM/IQ is a zirconium oxide O2 analyzer; 11. Gas analyzers downstream from ESP
7.11
Rev. 2002