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Acid rain
Traffic
Nitrogen oxides
7.1
General
7.1.1
NOx forming
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Flue-gas Purification
7.2
Background
With the formation of any type of nitric oxide the temperature plays a
key role. With extreme energy supply so-called radicals can originate
from molecules.
Radicals are reactive particles which have one electron too many or are
one proton short, which makes them react with other molecules very
quickly.
N2 + Oisn
Nisn + O2
NO + Nisn
NO + Oisn
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Flue-gas Purification
ENERGY
Oisn
+
Oisn
Oisw
+
Oisw
O
+
O
2 Oxygen radicals
Oisn stands for in statu nascendi. Oisw is the Dutch version and stands
for in staat van wording which means: in state of being
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Flue-gas Purification
Nitro
gen
oxide
NO
Thermal
Main influence
factor NOx forming
Place of
forming
Reaction
Flame
a. From the
incineration air:
Oisw+N2 NO+Nisw
Nisw+O2 NO+Oisw
Pre reaction
zone
Fuel
Prompt
Flame
CN+H2 HCN*+Hisw
CN+H2O HCN*+OHCN+N2 HCN*+Nisw
Fuel
Flame
Flame
NO+HO2 NO2+OH-
Flue gas
channel and
chimney
2NO+O2 2NO2
NO2
Atmosphere
* produces NOx
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Flue-gas Purification
Ozone
Nitric acid
This nitric acid (HNO3) comes into contact with water vapour in the air,
which is condensing and comes down as precipitation.
The originated acid precipitation is a threat for forests, crops,
surface-, and groundwater.
We must assume that if the emission of acidifying substances in the
Netherlands would stop, the quantity of acid rain would decrease by
only 25 %. The rest of the pollution drifts over from other countries.
Conversely of course it would also mean that measures on our side
would decrease the acid rain in our neighbouring countries because
75% of the emitted NOx from the Netherlands blows over to our
neighbouring countries.
Because of the fact that the combustion temperatures with domestic
waste incineration dont normally exceed 1100 C, the NOx formation is
limited. Normally the concentration in the flue gases with domestic
waste is not more than 250 mg/Nm3.
To illustrate: per ton waste, approximately 2 kg NOx is formed.
Summarising we can say that the NOx formation depends on a number
of parameters, namely:
The flame temperature
The air factor
The shape of the flame
The heat load of the furnace hearth
Temperature of the incineration air
The geometry of the furnace hearth
Residing time
The most important cause however is the flame temperature. On
illustration 2, you can see the influence of this. Also schematically
shown, is how the various types of NOx relate.
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Flue-gas Purification
350
Thermal NOx
Fuel NOx
Prompt
600 C
1050 C
2000 C
Flame temperature in C
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Flue-gas Purification
Now, if we put the circulation pump aside, after all we have natural
circulation, then this applies:
cl
cg
tr
cfly ash
cslag
mb
H0
Mltheoretically
cb
mfly ash
T flame
mslag
t slag
tl
tb
=
=
=
=
=
1.005 kJ/(kgK)
1.0 kJ/(kgK)
25 C
0.84 kJ/(kgK)
1 kJ/(kgK)
= 25 ton/hour
= 10,000 kJ/kg
= 3.5 kg/kg waste
= 2 kJ/kg
=3%
= Flame temperature
= 25 %
= 500 C
= 30 C
= 50 C
Now we can say that the added energy to the furnace must be equal to
the one that leaves the furnace.
So, the supplied heat is the sum of the heat in the flue gases, that of
the heat in the slag and of the heat in the fly ash.
Or:
25000
25000
25000
10000 +
2 (50 25) +
1.5 3.5 1.005 (30 25)
3600
3600
3600
Qto = 69974.8 kW
The mass flue gas becomes:
m g = 41.66 kg/s
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Flue-gas Purification
Q fluegas = m g cg T flame
Qfluegas = 41.66 1.2 Tflame
25000
1.0 500
3600
Qslag = 868 kW
The heat with the fly ash:
Q flyash= 0.03
25000
0.84 Tflame
3600
25000
0.84 Tflame
3600
T flame =
1377 C
25000
25000
25000
10000 +
2 (50 25) +
1.2 3.5 1.005 (30 25)
3600
3600
3600
Qto = 69938.2 kW
The heat in the flue gas becomes now:
g = (25000 0.25 25000 ) + (25000 1.2 3,5)
m
3600
3600
3600
m g = 29.16 kg/s
Qfluegas = 29.16 1.2 Tflame
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Flue-gas Purification
The heat in the slag and the fly ash remains the same, so now follows:
69938.2 = 29.16 1.2 Tflame + 868 + 0, 03
25000
0.84 Tflame
3600
T flame = 1964 C
This is only meant as an example, however it is demonstrated that with
a decreased air factor, the flame temperature initially increases.
However, if the air factor, prior to burning, becomes lower than 1, the
flame temperature reduces due to lack of oxygen.
Pay attention: This calculation applies to an adiabatic burning in a
furnace with refractory fire proofing as walls and a downstream boiler.
In a downstream boiler, approximately 10 to 15 % of the contributed
energy is removed from the furnace hearth, due of flame radiation to
the furnace walls, so this is accompanied by a temperature reduction.
7.3
7.3.1
7.3.2
7.3.3
Here one uses flue gas which is branched off downstream of the ESP.
Then we mix the flue gas with primary or secondary air. Here we also
create a deprived oxygen environment.
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Flue-gas Purification
7.4
Carbon monoxide
7.4.1
Cold CO
7.4.2
Warm CO
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Flue-gas Purification
7.5
Reduction
The SNCR-system
This is a process, where ammonia or urea is sprayed into the flue gas
flow as a reaction agent, to reduce the nitrogen oxides (NOx) to
molecular nitrogen and vapour. Nowadays they experiment with
injecting various derivatives of ammonia (for example organic amines)
into the hearth to expand the temperature window. Animal manure
contains ammonia and organic compounds and in principal after
processing, it can be a good replacement of an ammonia solution.
The reduction takes place in a temperature range of 850 - 950 C and
is subject to the following reactions:
4 NO + 4 NH3 + O2 4 N2 + 6 H2O
6 NO2 + 8 NH3 7 N2 + 12 H2O
The mechanism of this reaction is based on nitrification/nitration, which
is a specific reaction of NOx. As a by-product a small quantity of nitrous
oxide N2O laughing gas can arise.
The reaction above is also called the over all reaction. The actual
reaction takes place in stages these are as follows:
4 NH3
NH3
NH2
+ 6 O2 4 NH2 + 4 OH
+ OH NH2 + H2O
+ NO N2
+ H2O
If the temperature falls below 850 C, then less NH2 radicals will be
formed. Because there are less NH2 radicals formed, less nitrogen
oxides are converted into molecular nitrogen and vapour. The result is
that the ammonia concentration in the flue gases increases.
In a SNCR-DeNOx, the reaction above takes place in a relatively closely
defined temperature range of approximately 850-950 C. At higher
temperatures the injected NH3 is converted (burned) into NOx.
At temperatures above 1000 C, the equation is:
4NH3 + 5O2 4NO + 6H2O
Reaction speed
Ammonia
In general the ammonia or urea is injected into the furnace in the form
of a 25% solution. To cover a large surface area sprinkler nozzles are
built in on the left and the right side of the furnace / boiler.
The feed tank for the 25% ammonia is designed pressure free.
An adjustable dosage pump pumps the ammonia to a steam injector,
through which the steam- NH3-mixture is added.
There can only be a high degree of NOx separation achieved when the
quantity of NH3 is added above the stoichiometric value. The largest
part of the NH3 surplus ends up in a scrubber as molecular ammonia,
where it is washed. In the acid scrubber water the ammonia converts
directly into NH4+.
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Flue-gas Purification
Aerosols
Boiler
NaOH or Ca(OH)2
To vacuum pump
Condenser
NH4OH
Neutralisation
NH3 Stripper
Ammonia
Heating
Page 156
Quench
Flue-gas Purification
Sprinkler pressure
Refractory
Urea
Flow
Urea
Sluice
Water supply
Mixer
Level gauge
Pump
Quantity measurement
8. Check valves
9. Mixer
10. Mixing vessel
11. Pump
12. Check valves
13. Pressure measurement
14. Sprinkler nozzles
Disadvantage
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Flue-gas Purification
Temperature
For correct operation of the SNCR it is important that one works in a
narrow temperature window (optimal at approximately 850 C), see
illustration 5.
This requires an accurate dosage at the various spray levels, where
injection of ammonia takes place. By adding additives the lowest
operation temperature can be decreased to nearly 700 C. Applicable
additives include multiple alcohols and ammonia compounds.
Reduction (%)
850 C
Reference temperature C
Laughing gas
Ammonia salts
Page 158
Consumption ammonia
To reach a good efficiency, a large excess of ammonia will have to be
applied (a stoichiometric ratio of approximately 2 to 4 for a removal of
80%). This excess will be retrieved on the fly ash and in the salt/fly
ash mixture (in a semi-dry method) or in the wastewater (wet
scrubbing). A consequence is that the application possibilities of the fly
ash can decrease (odour problems).
The wastewater will have to be treated: in principle, the ammonia will
be stripped and can then be recycled.
Application of urea instead of ammonia is not desirable, because
recirculation is not possible and laughing gas can be formed.
Salt deposits
In applying the necessary excess of ammonia there is a risk that in the
cold section of the boiler salt deposition will occur. In addition (very
fine) aerosols of ammonia salts originate that are difficult to remove
from the flue gases and that possibly require an additional treatment
stage in the RGR.
An SNCR can only meet the values of BVA if a significant excess of
ammonia, with the above mentioned risks will be applied. The
advantage of SNCR is that no extra components have to be added to
the RGR.
SNCR is very sensitive to variations of the boiler temperature, including
variations in the calorific value and composition of the waste. A good
mixture of the waste and a constant combustion is necessary.
Flue-gas Purification
7.5.1
Ion form
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Flue-gas Purification
7.5.2
Cold steam
Temperature
1100 C
Without SNCR
With SNCR
200 C
Injection point
Boiler route
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Flue-gas Purification
Heat content
(Enthalpy)
100%
Without SNCR
With SNCR
25 30%
Heat increase
20%
Injection point
Boiler route
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Flue-gas Purification
7.6
Re-heater
Injection of
coke/lime-mixture
Compressed
Air
Catalyst
Wet scrubber
Fabric filter
ESP
From Boiler
Steam
ID fan
Chemicals
Steam
Fly ash +
Operation
Heavy
metals
Salt
water
to
effluent
NaCl
or
HCl
Chemicals
Insoluble
Ca-salt or
gypsum
To chimney
Polluted Coke
or carbon dust
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Flue-gas Purification
Substance content
Catalyst
Tail-end SCR is generally applied for the removal of NOx from flue
gases at various industries. The advantage of this is that the flue gas is
already highly purified and the risk of contaminating the catalyst is low.
Moreover, a catalyst with smaller distance between the plates is chosen
(larger specific surface area) due to the very low residue content and
the risk of salt deposits (especially NH4HSO4) is significantly smaller so
that a lower operating temperature is possible.
Temperature
In general, an SCR is operated at a temperature of 300 up to 350 C.
At lower temperatures, the reaction speed will be significantly lower
and another type of catalyst will have to be applied and / or a larger
resistance time will be required. The risk of a lower temperature is that
the formation of SO3 increases and more salt deposition can occur.
With a low dust SCR the temperature cannot be reduced lower than
approximately 260 C.
With a tail end this problem is less present (see above) so that a
further temperature decrease (to approximately 180 C) can be
implemented and the re-heating of the flue gases can take place in an
energetically favourable manner. There is still few practice data known
of SCRs at such low temperatures. The development of LTSCR
however is progressing very quickly and is promising. At AVR
Rozenburg, an LTSCR is in use.
Number of layers
The number of layers catalyst stipulates to an important degree the
pressure loss on the SCR. With tail end SCR's, operating at 300 up to
350 C, 2 to 4 layers are applied with a total pressure loss of
approximately 2 kPa. Due to the decrease in activity of the catalyst, a
reserve capacity needs to be built in. There is often a space reserved
for an extra layer, which will be introduced after a period of time.
If the flue gases contain (almost) no more substance, a packed bed
can be applied. The advantage of a packed bed is that the specific
surface is significantly larger and the reactor becomes smaller and
simpler. In relation to the risk of dust contamination, packed beds are
not yet applied.
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Flue-gas Purification
Dioxins
Re-heating
Page 164
Flue-gas Purification
The heat exchanger consists of two stages. The lower heat exchange
stage (cold side) is fabricated acid resistant (Alloy 59). This section is
at the acid dew point. The second heat exchanger stage consists of
normal steel (St. 12.03).
The plate heat exchanger operates without an external energy source.
Upstream and downstream of the inlet respectively outlet of the plate
heat exchanger, on the hot and the cold side, temperature gauges are
installed.
With these operational measurement points, the company staff can
monitor the warming up of the DeNOx installation. Decrease of the flue
gas entry temperature down to below the design temperature
(t = 85 C) leads to the acid dew point shifting to the unprotected
range of the plate heat exchanger.
Differential pressure The differential pressure gauge over the plate heat exchanger is to
check if the pressure loss increases at the purified gas side due of
deposits. The raw gas side of the plate heat exchanger is monitored
with help of the differential pressure gauge.
When the pressure loss decreases at the plate heat exchanger by 30%,
then the plate heat exchanger can be cleaned when the installation is
in standstill.
Then it is also possible to clean the heating surfaces.
Natural gas burner
The flue gases recuperated from the pre-heater in the plate heat
exchanger can be heated with a natural gas burner to the required
operation temperature of the catalysts. The natural gas burner can be
designed as a channel surface burner and can be connected to the flue
gas line upstream of the NH4OH-injection.
The natural gas burner consists of:
Air storage with gas burner element
Ignition burner
Redundantly executed combustion fan
Compound regulator
Burner control
The natural gas burner is adjusted in accordance with the flue gas
temperature for the catalyst. In accordance with the established
temperature of the temperature regulator (normal operational
temperature 300 C), the quantity of fuel and air is adjusted by means
of the compound regulator.
Lances
NH4OH-quantity regulation
The NH4OH-injection often consists of lances with a sprinkler for two
substances (NH4OH/compressed air).
The NH4OH-sprinklers are implemented between the natural gas
burner and the catalyst in the flue gas channel. Via a static mixing
system (Delta wing) the NH4OH which is injected with atomized air is
distributed into the flue gas in accordance with the required
homogeneous.
Via the control valve, in accordance with the NOx disposal rate, flue gas
volume flow, the NH4OH that is introduced into the flue gas is injected
as atomizer medium with help of compressed air. The injected quantity
of NH4OH is registered at the measuring point and indicated on the
central switchboard.
With the manual control valves and the local flow meters it is possible
to correct both sprinklers.
Both the NH4OH-line and the atomizer air injector pipe are closed off
through help of the quick closing valves isolating the flue gas line when
stagnation or breakdown occurs.
Page 165
Flue-gas Purification
7.6.1
Catalyst deactivation
+ SO3 + H2O
(NH4)2SO4
+ SO3 + H2O
NH4HSO4
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Flue-gas Purification
7.6.2
Desorbed
With this method, the NOx is removed by allowing the flue gases to
pass through an active carbon filter. Because the active carbon acts as
a catalyst, this method is known as the low temperature SCR method.
Upstream of the filter NH3 must be dosed to make the conversion of
NOx into N2 possible. Because the active carbon from the catalyst
(SAK) works absorbing for the other residue pollutions that are present
in the flue gases, the filter will quickly loose its affectivity when no
measures are taken. An option is to place the active carbon filter
(HOK) upstream of the SAK-filter. The HOK-filter must then remove
the residue pollutions from the flue gases so that the SAK-filter has a
very low consumption of active carbon. Because of the very low
velocity of the flue gas flow inside the filter, the placement space that
this installation requires will be very large. One can calculate with a
filter capacity of 360 m30 per hour for each m2 filter surface.
Research indicates however that the feasibility of BVA for NOx with
ACCR is questionable. Besides, ACCR gives a substantial increase of the
CO-degree in the flue gases, especially at higher temperatures. This
increase can even amount to 20 up to 30 mg/m30, which makes the
requirement from the BVA (maximum 50 mg/m30 CO) difficult to
achieve.
This system works well at temperatures up to 70 C, when the
temperature becomes 95 C or higher, then the NOx is desorbed by the
active carbon.
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Flue-gas Purification
7.6.3
Page 168
Flue-gas Purification
7.7
Ammonia (NH3)
7.7.1
What is ammonia
7.7.2
Physical qualities
Triple point:
-77.74 C
0.0607 bar
(0.00607 MPa)
Critical point:
132.4 C
114.8 bar
(11.48 MPa)
Boiling point:
-33.4 C
1.013 bar
(0.1013 MPa)
Page 169