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Presented to:
EPRI-DOE-EPA-AWMA
Combined Power Plant Air Pollutant Control
Mega Symposium
August 28-31, 2006
Baltimore, Maryland, U.S.A.
Introduction
Over the past decade, efforts to remove nitrogen oxides (NOx)
through the use of selective catalytic reduction (SCR) technology
have resulted in increased sulfur trioxide (SO3) concentrations in
the flue gas stream of utility boilers that fire fossil fuels or other
specialty fuels. This same problem has been encountered when
firing fuels with high vanadium content which increase the SO2 to
SO3 conversion in the boiler. When flue gases containing as low as
10 ppmdv of SO3 are treated in a wet flue gas desulfurization
system (WFGD) the potential exists for a visible secondary plume
to occur. The primary plume is due to water droplets which dissipate readily. The secondary plume is less visible and typically
only becomes apparent after the primary plume has dissipated.
The secondary plume is caused by aerosols, primarily sulfuric acid
but also ammonium bisulfate and other compounds. The color of
the secondary plume is typically blue, but brown and other colors
have been noted depending upon meteorological conditions, angle
of the sun, other compounds, etc.
When establishing the design criteria for SO3 mitigation systems, it is important to understand the factors that affect SO3
formation in the boiler and also to have an understanding of where
H2SO4 is removed in the backend equipment of the boiler island.
SO3 forms in two areas of a fossil fuel fired power plant, the boiler
proper and across the SCR catalyst.
Combustion of fuel liberates elemental sulfur, which oxidizes to
form SO2. At typical combustion temperatures, very little SO2 is
converted to SO3, approximately 0.1%, because thermodynamic
equilibrium at these temperatures favors SO2 formation. As the
temperature drops the equilibrium changes so that more SO3 can be
formed. The formation of SO3 is dependent on the existence of
atomic oxygen which is present down to approximately 1500F. So
SO3 is formed in a lower temperature window as long as there is
atomic oxygen available. SO3 formation is increased by catalytic
effect of metal oxides on the boiler tubes or surfaces. The percent
of SO2 that is oxidized to SO3 in the furnace and convection pass of
the boiler is defined as the boiler SO2 to SO3 conversion rate, or the
boiler conversion rate. The boiler conversion rate is dependent
upon many variables including: furnace geometry (surface area),
oxygen concentration (excess air), fuel vanadium levels, fuel sulfur
levels and the ash composition. Metal oxides in the ash can increase the conversion of SO2. Ash with high alkalinity will react
with SO3 in the boiler and economizer and lower the measured
conversion. That is, approximately the same amount of SO3 is
formed but it reacts with the alkali in the boiler. As the SO3 concentration is measured at the economizer exit, the amount of SO3
measured will be less than that formed. The conversion determined
from the measurement is the apparent conversion which is less
than the actual.
The SO3 in the flue gas begins to hydrolyze to form H2SO4
vapor as the temperature drops below about 1000F. This reaction
is complete at gas temperatures between about 350 and 400F. The
bulk of the reaction is taking place within the air heater. The H2SO4
can condense out on cold end surfaces, which can be below the acid
due point. Acid aerosols can also form if local gas temperatures
drop below the dew point due to air in-leakage or damage to the
insulation.
For a coal fired boiler, typically 0.5 to 1.5% of the SO2 in the
flue gas is oxidized to SO3. Firing fuels with high vanadium content, such as fuel oil or Orimulsion, results in higher boiler conversion rates due to the catalytic effect of the vanadium. Conversion
measurements when firing fuels with high alkali content (sodium,
potassium, calcium in the ash) indicate relatively lower apparent
conversions. The actual conversion is unknown because of the
reaction of the SO3 and alkali in the boiler. As a result, the SO3
concentration in the flue gas is relatively lower with higher alkali
flyash and the calculated conversion is lower.
Boiler operation has an effect on SO3 formation. Operating the
unit with higher excess air can provide additional oxygen radicals
for oxidizing SO2. However, lowering the excess air level must be
balanced against higher unburned carbon levels in the ash.
Selective catalytic reduction (SCR) technology contributes additional SO3 to the flue gas and ultimately higher SO3 emissions.
The rate of SO2 to SO3 oxidation is defined as the SCR conversion
rate. The SCR catalyst consists primarily of vanadium pentoxide
(V2O5), tungsten trioxide (WO3) and titanium dioxide (TiO2). Vanadium pentoxide is the active compound in the catalyst and is the
ingredient responsible for the conversion of SO2 to SO3. Catalyst
composition is carefully selected based on the operating conditions, the SO2 concentration, the ammonia slip and the target ammonium bisulfate concentration. SCR catalysts can be designed for
a range of conversions, about 0.20% to 0.8% per layer. This results
in conversions of 0.60% to 2.4% with 3 layers of catalyst. The
conversion rate varies greatly with catalyst temperature. The combination of catalyst operating temperature and the baseline catalyst
conversion rate results in significant variability from site to site.
Thus, when selecting an SCR catalyst it is important to evaluate
both the benefits of using a low conversion catalyst and providing
means to lower economizer outlet (SCR inlet) temperature. Selecting a low conversion rate catalyst or lowering the catalyst operating
temperature can substantially reduce the SO3 content after the SCR
and can reduce the cost of the mitigation equipment if required.
For a given boiler that was originally designed for a low sulfur
fuel but will burn higher sulfur fuels in conjunction with the use of
a WFGD system, the potential exists for increased slagging in the
boiler. As a result, a higher economizer exit (SCR inlet) temperature may occur. As this temperature increases, the SCR conversion
rate increases, resulting in a higher SO3 concentration at the SCR
outlet. Some units minimize this increase in flue gas temperature at
the economizer outlet by employing water cannons and/or
sootblowers.
Similar to the ESP, the fabric filter can also remove SO3. However,
there is a major difference that makes a fabric filter more efficient
than an ESP. The ESP captures ash that has adsorbed some acid.
The same thing occurs in the fabric filter. However, as ash is
removed in the fabric filter, a cake builds up on the bag. As the acid
passes through the cake it is exposed to more ash, so the adsorption
of the acid is increased over that occurring naturally in the flue gas.
This enhanced removal does not require additional alkalinity in the
ash. If there is additional alkalinity in the ash, such as when firing
PRB coals, additional removal will occur. Tests have indicated that
removals as high as 40% can be achieved in a fabric filter when
firing eastern bituminous coals. Acid removals above 90% are
achieved when firing PRB fuels. Flue gas temperature, fabric material, acid dew point and alkalinity in the ash, all play a key role in
the performance of the fabric filter.
Removal in WFGD
A WFGD provides the ideal conditions for aerosol formation.
As the flue gas enters the scrubber quench zone, the H2SO4 vapor is
quickly cooled below its dew point and now exists entirely as an
aerosol. The size of the H2SO4 aerosol particle is dependent on
how fast it is condensed. The rapid condensation that takes place
in the scrubber results in ultra-fine (sub-micron) aerosols. The
overall removal of the acid in the scrubber increases as the aerosol
particle size increases. Therefore, the removal of H2SO4 in the wet
scrubber can be enhanced by forming larger particles.
Precipitator design and operation also play a role in the removal
of acid in the scrubber.
Ash loading to the FGD may increase due to ash carryover from
an ESP with high resistivity ash, i.e., ash with little to no SO3 for
conditioning. The capture of SO3 by ash and/or sorbent in the
precipitator may also reduce the H2SO4 loading to the FGD. Limited data with lowering the inlet loading to the FGD has shown a
reduction in FGD acid aerosol capture rate.
The capture of H2SO4 in the WFGD system ranges from below
30% to 75%. Most test data indicates good repeatability at the
same unit and operating conditions. However, there are units for
which the test data is highly variable even at seemingly identical
operating conditions. The parameters controlling the H2SO4 removal in the wet scrubber are not fully understood.
Although the resultant secondary (SO3/ H2SO4) plume can be
quite visible, the actual concentration is very low, measured in
parts per million. In cases where the WFGD technology is utilized
in conjunction with SCRs on high sulfur coals or with high vanadium petroleum fuels, the sulfuric acid aerosols at the stack exit can
be as low as 6 to 10 ppm dry volume, yet are readily visible under
the right meteorological conditions.
Sorbent technologies
There are several sorbents that can be utilized to control the SO3
emissions from a combustion source. These sorbent control methods include injecting chemicals in either the fuel or in the flue gas.
These sorbents react in the flue gas to form a solid compound that
can be removed in the particulate collection device such as an ESP
or baghouse.
Sorbent injection technologies for the mitigation of SO3 typically utilize alkaline-based reagents that contain calcium, magnesium, sodium or ammonia. Depending on the reagent used, these
reagents can be injected dry or wet, either in aqueous or slurry
form. Dry injection typically uses pneumatic conveying equipment to transport dry solids from a storage silo to the flue gas.
Injection of solutions and slurries has some disadvantages when
compared to dry injection. Wet injection generally requires longer
residence times since the reaction typically occurs after evaporation. Also, poor atomization can result in agglomeration of ash on
internal supports or other boiler island equipment depending on
injection location.
Several chemicals have been found to be successful at reducing
SO3 concentrations when added downstream of the boiler furnace
(i.e., upstream or downstream of the air heater), SCR, ESP or scrubber. These chemicals include magnesium oxide, calcium hydroxide,
sodium bisulfate, ammonia, and sodium sesquicarbonate (Trona).
Each of these chemicals is effective in reducing SO3 emissions, but
extreme care must be exercised in selecting the proper additive for a
specific site. Due consideration should be given to: temperature
distribution across flues, characteristics of the additives and resulting salt formation, available residence time, amount and availability
of additive, physical limitations of ductwork, internal structural
supports, particle size of additive, flow distribution in ductwork
and potential impacts on flyash sales as well as reagent cost. Sorbents that are injected downstream of the SCR have an advantage in
the fact that the sorbent removes the SO3 generated from both the
boiler and SCR. Sorbents injected in the furnace can remove SO3
before the SCR but there could still be a visible sulfuric acid plume
because of the SO3 generated across the SCR, especially with a high
conversion catalyst.
Injection in the furnace and/or in the ductwork before an SCR is
assumed to only remove the SO3 formed in the boiler. The addition
of sufficient excess alkali with furnace injection may continue to
remove the SCR-generated SO3 if the alkali is still present and
reactive before and after the SCR. For example, some magnesiumbased sorbents injected into the furnace become unreactive before
the SCR. Furthermore, it is important with this option to select a
sorbent that will not poison the SCR catalyst.
Injection in the ductwork after the SCR reduces the total SO3
formed in both the boiler and the SCR and therefore reduces the
existing SO3 to the air heater. This minimizes the impact of ammonium bisulfate formation and other means for pluggage. This injection location also reduces the impact, such as corrosion, from operating near the dew point temperature. By reducing the SO3 concentration prior to the air heater, the average cold end temperature can
be reduced to achieve greater boiler efficiency (improved heat rate).
Alkali injection either before or after the ESP provides effective
control of SO3 plume at either location. These injection locations
do not address the potential for ammonium bisulfate deposition in
the air heater or the potential to lower the air heaters average cold
end temperature. Injection prior to the ESP will minimize the potential for a visible SO3 plume, minimize ESP corrosion from higher
acid dew point, but can possibly degrade ESP performance depending on the sorbent and its effect on ash resistivity. Injection
after the ESP will also minimize the potential for a visible SO3
plume and provide downstream corrosion protection. However,
there is a potential regulatory issue with injecting a sorbent that
reacts to form a solid downstream of the particulate collection
device.
Typical sorbents
Table 1 summarizes the various sorbents typically employed in
power plant SO3 mitigation applications.
Table 1
Typical Sorbents
Sorbent
Effectiveness
Relative
O&M
Costs
Relative
Capital
Costs
Low
LowNH3 already
in use w/SCR
Low
High
Moderateslurry
Moderate
Low
Low
Moderate
to low
High
Relative
Maintenance
High Surface
Area Lime
Good to
excellent
Low
Moderate
Low
High
Moderate
ESP concerns
Trona
Excellent
Low
Low
Low
Ammonia
Ammonia has generally been used as the reagent for NOx control
in SCR systems and also for flue gas conditioning to enhance ESP
performance. Ammonia can also be an effective means for SO3 removal when lower concentrations of SO3 are present in the flue gas.
It is typically injected downstream of the air heater and upstream
of the ESP to form ammonium bisulfate and/or ammonium sulfate.
High removal efficiencies can be achieved if injected in front of the
air heater but ABS formation can produce a sticky ash that fouls the
air heater basket elements. Ammonia has minimal capital and O&M
costs compared with other technologies. Many plants with an SCR
system already have ammonia on site that could be utilized for SO3
mitigation.
The use of ammonia for SO3 mitigation can impact flyash sales
due to high ammonia content in the ash. Ammonia off-gassing from
flyash is another concern. Sites that stabilize scrubber sludge by
mixing it with flyash and lime could experience odor problems.
Additionally, ammonium bisulfate formation may cause buildup in
the air heater and flues, and cause ESP operational problems from
ammonia salts which may cause solid particulate related opacity
issues rather than H2SO4 issues. There is also a risk of increased
ammonia slip.
Magnesium Hydroxide
Trona
SBS
Table 2
Coal Analysis and Heat Input Used
Ultimate Analysis
%
Example
Ash
S
H2
C
H 2O
N2
O2
Cl
Total
17.61
3.10
4.13
64.24
5.5
1.15
4.19
0.08
100.00
5625.3
11,500
Table 3
Flue Gas Flow Rates
Component
CO 2
H 2O
SO 2
N2
O2
HCl
1,151,349
290,706
30,297
3,960,526
198,420
402
Total
5,631,700
Table 4
Base Condition
Entering ESP
348 lb/hr H2SO4
Entering Stack
261 lb/hr H2SO4
14.7 ppmvd
Entering ESP
372 lb/hr H2SO4
Entering Stack
297 lb/hr H2SO4
16.7 ppmvd
to SO3, the SO3 flow rate entering the air heater is 566 lb/hr compared to the base case of 379 lb/hr (with no SCR). If a catalyst
designed for 1% conversion is selected, the SO3 flow rate entering
the air heater increases to 754 lb/hr compared to the base case of
379 lb/hr. Using the same H2SO4 removal efficiency for the air
heater and ESP as used in the base case, for the 300F case, the
H2SO4 flow rate entering the WFGD for the 0.5% and 1% case is
390 lb/hr and 519 lb/hr respectively. When the air heater design
outlet temperature is increased to 330F, the H2SO4 flow rate entering the WFGD increases to 444 lb/hr for the 0.5% conversion case
and 591 lb/hr for the 1% conversion case. For this example, 40%
removal across the WFGD will be used. For the 300F air heater
outlet design, when the catalyst is designed for 0.5% conversion, a
concentration 234 lb/hr or 13.4 ppmvd of H2SO4 enters the stack
and when the catalyst is designed for 1% conversion, the H2SO4
concentration entering the stack is 312 lb/hr or 17.8 ppmvd. For the
330F air heater outlet design, when the catalyst is designed for
0.5% conversion, a concentration 266 lb/hr or 15.1 ppmvd of H2SO4
enters the stack and when the catalyst is designed for 1% conversion, the H2SO4 concentration entering the stack is 354 lb/hr or 20.1
ppmvd. Table 5 summarizes the above discussion.
U.S.$75,000 per year for a single boiler unit. The savings will
propagate for plants with multiple boilers. Table 6 summarizes
this discussion.
Conclusions
When a plant is considering the use of SO3 mitigation technologies, several areas of the boiler island and air quality control system
need to be investigated to optimize the SO3 mitigation philosophy
employed. For example, most users plan to use higher sulfur coals
after the retrofit of a Wet FGD system. This can impact boiler
conversion of SO2 to SO3 and economizer outlet temperature. Both
of these issues could substantially affect stack H2SO4 emissions by
increasing values. Air heater operation (temperature and operating
conditions) has a large effect on the amount of SO3 exiting the air
heater and even the Dry ESP. Operating conditions and equipment
sizing are important considerations in SO3 mitigation. Wet FGDs
do collect some H2SO4 but not to the levels that provide optimal
stack condition on higher sulfur coals. Selection of a low SO2 to
SO3 conversion catalyst could reduce both the cost of mitigation
equipment as well as sorbent costs.
Several sorbents are effective in removing H2SO4 from the flue
gas stream but careful consideration is required on location of injection, cost and reliability of the handling and injection system and
sorbent costs. In some cases, use of alternate sorbents should be
considered in design of the sorbent handling system allowing flexibility to switch to a different sorbent if supply interruptions occur and/or price increases occur. In conclusion, a system approach
to SO3 mitigation based on plant-specific conditions may reduce
the overall cost of mitigation equipment.
References
1. Erickson, Clayton A. and Jambhekar Rajaram, Current work
on the impacts and control of SO3 emissions from Selective Catalytic Reduction systems, 2002 Conference on SCR and SNCR for
NOx Control, Pittsburgh, Pennsylvania, May 2002.
2. Damle, A. S., Ensor, D. S., Sparks, L. E., Prediction of the
opacity of detached plumes formed by condensation of vapors,
Atmospheric Environment, Volume 18, No. 2, (1984).
3. Maziuk, John, Successful Mitigation of SO3 by Employing Dry Srobent Injection of Trona Upstream of the ESP, Air
Quality 5 Conference, Baltimore, Maryland, 2005.
4. White, Harry J., Industrial Electrostatic Precipitation,
Addison-Wesley Publishing Company, Boston, Massachusetts,
1963.
Table 6
Trona Evaluation
Trona Flow Rates
300F A/H Outlet Temp, 0.5% Conversion Catalyst
300F A/H Outlet Temp, 1.0% Conversion Catalyst
330F A/H Outlet Temp, 0.5% Conversion Catalyst
330F A/H Outlet Temp, 1.0% Conversion Catalyst
572 lb/hr
651 lb/hr
605 lb/hr
695 lb/hr