CHAPTER 9

EMISSION CONTROL
9.1.Introduction:

As with any combustion process, the by-product or the exhaust from a gas turbine
contains elements that have been deemed as pollutants. These emissions or pollutants are
basically unwanted products. The ideal hydrocarbon combustion products, water vapor and
carbon dioxide, exist commonly in nature and have no ill effects on the environment. Other
than the current concern for build-up of carbon dioxide in the atmosphere, these products are
generally considered to be harmless.

The main emission products of concern are

 Nitrogen oxides ( Nox)

 Carbon-monoxide (CO)
 Volatile Hydrocarbon Compounds (VHC)
 Sulphur oxide (SOx )
 Particulate Matter (PM)

In some areas, most notably in U.S., Japan, and Germany, the NOx emission restrictions
are pushing the limits of commercially available control technologies. Meeting them without
sacrificing emissions of other pollutants, fuel-to-energy efficiency, load following capability,
supplementary-fuel firing flexibility and ultimately, the competitive economics of a given
project-is the seemingly impossible task of designers and users today.

Historically, emissions of Nitrogen oxides (NO x) have been the challenge for gas
turbines. Regulations continue to change and combustion technology continues to improve,
resulting in a steady decline in the allowable rate of NOX emissions.

In general control schemes for NOx fall into three categories: water/steam injection
into the combustor, selective catalytic reduction and non-catalytic reduction systems (SCR
and SNR), and combustor modifications. The most stringent control requirements can be met
with a combination of all technologies.

-110-
9.2. Nitrogen Oxides Emissions and Control:

9.2.1 Formation Oxides of nitrogen (NOx) from gas turbines are composed of two types:
Fuel NOx and Thermal NOx. Fuel NOx is formed by the gas phase oxidation of char nitrogen
(CN-compounds) in the fuel, and is largely independent of combustion temperature or the
nature of the organic compounds. Thermal NOx is the result of the high temperature reaction
between the nitrogen and oxygen in the combustion air. Formation of thermal NOx is a function
of combustion chamber design and turbine operating parameters, including flame temperature,
residence time, combustion pressure and fuel /air ratios in the primary combustion zone. Since
nitrogen is low in natural gas, thermal NOx is the primary concern for natural gas fired gas
turbines. Formation of nitrogen oxides can be limited by lowering combustion temperatures
and staging combustion. (Using a reducing atmosphere followed by an oxidized atmosphere).

9.2.2 Water or Steam Injection:

The use of water or steam injection in the combustion zones of a gas turbine is
commonly used to limit the amount of NOx formed. The concept is straightforward. The
injection of water or steam in the combustion zone lowers the flame and gas temperatures so
thermal NOx formation is inhibited. The degree of reduction in NOx formation is somewhat
proportional to the amount of water or steam injected into the combustor.

Consequences on the design and operation are, however, not straightforward at all. In
fact, in the interest of justifying water/steam injection over SCR, these consequences have not
been appreciated to the extent they perhaps should have been by users, designers, and system
suppliers.

In particular, water injection can:

 Increase CO and unburned hydrocarbon emissions especially at lower

loads.
 Increase in fuel consumption by up to 5% to make up for the latent heat
of vaporization lost in the water vapor going out the stack.
 Result in the loss of water that had been extensively treated.
 Increasing in the complexity of engine control and monitoring systems.

-111-
  Shorten the life of major turbine components.

Water quality and the water supply system are both critical to successful water
injection. One common problem is corrosion and plugging of the fuel nozzles, a condition that
leads to overfiring and more wear and tear on the vanes behind the combustor. Turbine
suppliers have put much effort in recent years to develop specifications for water quality that
minimize or avoid these impacts.

Likewise, the water system must balance the delivery to each combustor in case of
multiple combustor units and meter the water flow in proportion to the fuel flow. If not, high
pressure and temperature differentials are created between combustors affecting the component
life and the ability of the combustors to operate in a concerted fashion.

Economic analyses indicate that system costs increase as the water injection rate
increases for the above reasons. The compelling result is that, beyond a certain emission level,
operating costs for incremental amounts of NOx removal rise dramatically.

Since the gas turbine New Source Performance Standards (NSPS) was last revised in
1982, gas turbines have significantly improved their tolerance to negative maintenance impacts
from the water necessary to control NOx emissions below the current NSPS level. Steam or
water injection can be used to control gas turbine NOx emission levels without significant
impact on reliability or power output.

Due to the temperature lowering mechanism of water or steam injection, it can be an

effective NOx control method for a turbine burning either natural gas or fuel oil. However, de-
mineralized water must be used and additional capital cost is required because an onsite
demineralization plant must be built and the annual operation of this system can be a
significant expense in unit operation.

9.2.3 Improved Low NOx Combustors:

For many applications, emissions levels achievable by water or steam injection are still
too high. Other methods have been devised to reduce the combustion flame temperature, and
most of these can be used either by themselves or in combination with water or steam injection.
Gas turbine manufacturers now offer burner designs that, when compared to earlier combustor

-112-
technology, provides improved air/fuel mixing and reduced flame temperature. These dry low-
NOx (DLN) combustors achieve a low flame temperature by maintaining a low fuel-to-air ratio
in the main combustion zone. The lower combustion temperatures prevent thermal NO x
formation when firing natural gas and No.2 fuel oil in comparison to the earlier standard
combustion chamber design.

Three main types of DLN combustors have been developed. These are lean premixed
combustion, rich/quench/lean combustion and catalytic combustion.

9.2.3.1 Lean Premixed Combustion:

Lean premixed combustion is the most developed of the three DLN types. The concept
of lean premixed combustion is to have a uniform, lean fuel-air mixture throughout the
combustion zone, with no fuel-rich pockets where high flame temperatures would cause NOx
formation. The challenges to making this process work are threefold: maintaining a uniform,
learn mixture, yet having enough fuel to have a stable flame; achieving the uniform fuel-air
mixture over a wide range of power outputs; and providing adequate residence time for
oxidation of the CO to CO2 and for burnout of the unburned hydrocarbons (UHC).

The flame stability issue has been approached in several ways, including swirl
stabilization and use of a continuous pilot flame. The latter approach is the most popular, with
ignition of the premixed lean mixture typically provided by a small pilot flame which creates
only a small amount of NOx.

In order to maintain careful control of the lean fuel-air mixture over a practical range of
power operations, designers have had to find ways to vary the geometry of the combustion
chamber. Siemens has developed variable guide vanes to control the fuel-air mixture. Others,
such as General Electric (GE), have opted to make the combustion chamber into a series of
small, lean premixed chambers that can be staged in some manner to achieve low-emissions
operation over an extended power range. That is, all of the chambers operate at full power, but
at lower power levels combustion takes place only in selected chambers. Commercial lean
premix combustors can reach NOx levels as low as 15 or even 9 ppmv. The lower of these
numbers is adequate to meet the most stringent regulations now in place.

-113-
 Murphy’s law says that reducing NOx emissions will increase other emissions. In the
case of lean premix combustors the low flame temperature necessary to preclude NO x
formation also slows down the oxidation of CO to CO 2 and the complete combustion of the
hydrocarbon fuel. In order to meet regulations on CO and UHC emissions, these species must
spend more time in the combustion zone. The straightforward way to accomplish this is to
design a combustor, which has a large volume downstream of the main combustion zone. A can
or silo combustor can usually be enlarged to increase this down-low-NO x combustor to an
engine with an annular combustor is a bit more challenging.

9.2.3.2 Rich/Quench/Lean Combustion:

In the rich/quench/lean combustion process a stable flame, which is so fuel rich that
there is not enough oxygen to form NO x, is established in the first region of the combustor. The
fuel-rich mixture is carried downstream where air is added to cool the flame and dilute the fuel
to a lean mixture. Then combustion is completed within the mixture that is so lean the flame
temperature remains low enough to prevent significant NOx production. This method is unique
in that it reduces the formation of NOx from fuel-bound nitrogen as well as thermal NOx in
gaseous fuels. There has been much promising laboratory work on this concept, most notably
with the Westinghouse Multi Annular Swirl Burner.

9.2.3.3 Catalytic Combustion:

Catalytic combustion resembles lean premixed combustion. In the ideal case of

catalytic combustion, however, no pilot flame is necessary. Instead, combustion is initiated by
the catalyst interacting with a fuel-air mixture that is, otherwise, too lean to burn. Because even
low combustion temperatures are greater than metals can withstand, early attempts at catalytic
combustion used a ceramic-based catalyst placed in the combustion zone. This subjected the
catalysts to thermal sintering and vaporization, and the ceramic substrate, while able to
withstand the high temperatures, could not stand the thermal cycling of repeated hot and cold
conditions. This led to cracking and the unacceptable risk of sending abrasive particles through
the turbine after a few startup and shutdown cycles.

At least one catalyst Technology Company, Catalytic Inc. has addressed the problem by
designing a catalyst that carefully limits the combustion temperature in the catalyst zone, with

-114-
combustion subsequently going to completion downstream. This requires very exacting control
of the flow conditions and the fuel-air mixture, but does allow the use of a catalyst with a
metallic substrate. Laboratory and test cell data are encouraging, indicating NO x emissions as
low as 1 ppmv can be attained with this technology, with adequate catalyst life expected.

Over the past several years the gas-turbine industry has focused extensive development
efforts on DLN technologies, and many of these combustors are commercially available now.
The use of dry low NOx burners eliminates the need for water de-mineralizing systems with the
associated capital and operating costs. Because of this and the negligible differential cost, dry
low NOx burners are becoming standard equipment for NOx control on new natural gas fueled
turbine units.

9.2.4 Selective Catalytic Reduction (SCR):

SCR is a post combustion method for NOx emissions control. The SCR process
combines vaporized ammonia with NOx in the exhaust gases in the presence of a catalyst to
form nitrogen and water. The vaporized ammonia is injected into the exhaust gases before it
passes through the catalyst bed. The SCR process can achieve in excess of 90% NOx reduction.

At NOx inlet concentrations below approximately 150 ppm, a non-linear relationship

exists between removal and inlet concentration. This is a significant factor in sizing the
catalyst because gas turbine exhaust frequently contains less than 150 ppm NO x especially
when water injection or dry low NOx burners are also used. The NH 3/NOx mole ratios,
concentration of O2 in the exhaust gas, and space velocity (inverse of residence time) are
important factors in determining removal efficiency. The temperature specificity of a given
catalyst is also important.

Most SCR systems on turbines in operation in the United States are on combined cycle
units, and ammonia injection and SCR catalyst are integrated into the HRSG.

Catalysts are usually located within the evaporator section of the HRSG because the
temperature profile is in the range needed for the desired chemical reactions. The catalyst
location is determined on a project specific basis.

-115-
 Exhaust gas temperatures from simple cycle gas turbines generally are too high for
vanadium-based catalysts, so zeolite must be used. Zeolite catalyst will operate effectively at
temperatures up to 600oC.

The most common commercial SCR catalysts for NO x reduction are vanadium-based.
Vanadium pentoxide (V2O5) is generally used as the active compound. It is normally supported
by titanium or a mixture of titanium and silica. Oxides of tungsten and molybdenum are often
incorporated as promoters.

Zeolites, which are crystalline aluminosilicate compounds, are another catalyst used in
high temperature, simple cycle applications. Zeolite crystals are characterized by an inner
connected system of pores, and absorb only those compounds with molecular sizes comparable
to the pore size. The small pore size creates a very high internal surface area. Zeolites are also
called molecular sieves. Although operating experience with zeolite catalyst is currently
limited to relatively small turbines, zeolite does offer a high temperature NO x control
alternative that has not been previously available.

Platinum is also used as the active compound in SCR catalysts. In NO x reduction-only

applications, platinum-based catalysts are not generally cost competitive with vanadium based
catalysts. However, in dual NOx and carbon monoxide SCR applications, platinum is generally
the preferred catalyst. The optimum temperature range for the CO reduction catalytic reaction
is lower than for the NO x reaction. At least one manufacturer has developed a dual application
catalyst that is platinum based.

In gas turbine applications, the main causes of catalyst deactivation are thermal
degradation and poisoning. Thermal degradation occurs when maximum design Temperatures
is exceeded. Exhaust gases above the design temperature sinter the catalyst and cause a
permanent loss of active surface area at temperature above 425oC.

Primary poisons for SCR catalyst are arsenic, sulfur oxides, sodium, potassium, and
calcium. Arsenic is generally not a problem for turbines firing natural gas or low sulfur oil.
However, it can be present if refinery gas is burned. At low temperatures (less than 275 oC),
Sulfur in the form of SO3 (oxidized SO2) can combine with catalytic compounds to form
sulfates which block the catalyst, pores. The SO 3, can also react with the NH3 to form

-116-
ammonium sulfate and bisulfate which coats the catalyst surface. Ammonium sulfate and
bisulfate deposition on downstream equipment can result in other problems such as corrosion
and plugging.

These poisoning effects do not occur suddenly; these are continual processes over the
life of the catalyst. As the catalyst becomes less active, the ratio of ammonia injected to NO x
removed must be increased to compensate for the lower activity level and maintain required
NOx emissions. The increase in stoichiometric ratio results in increased ammonia slip. In turn,
the increased ammonia slip can cause ammonium sulfate or bisulfate deposition problems.

Eventually, the SCR catalyst will no longer meet performance requirements. However,
it is unlikely that the entire array of catalyst will need to be replaced at any one time. The
exception to this would be if severe mechanical damage resulted from a thermal excursion.
The probability of such a failure is extremely low.

The use of an SCR system could result in a negative environmental impact because of
the release of unreacted ammonia to the atmosphere. Ammonia and number of amine
compounds are recognized hazardous air pollutants. Ammonia is also a hazardous material.
Accordingly, this material must be handled and stored with extreme care.

If fuel oil is the primary fuel for the gas turbine, the use of SCR also has the potential to
increase particulate emissions in the form of ammonia sulfate compounds. Because of the
inherently higher sulfur content in fuel oil, SCR oxidizes more of the SO 2 to SO3, and in the
presence of unreacted ammonia, sulfate compounds are formed. Once the flue gas cools, the
sulfate compounds precipitate out in the form of particulate and cause plugging and corrosion
of downstream equipment.

9.3.Carbon Monoxide and Volatile Organic Compound Emissions:

Typically, measures taken to minimize the formation of NO x inhibit complete

combustion, which in turn increases the emissions of CO and volatile organic compounds
(VOCs).

CO is formed during the combustion process as a result of incomplete oxidation of the

carbon in the fuel. CO and VOC formation are reduced by ensuring complete and efficient

-117-
combustion of the fuel in the turbines. High combustion temperatures, adequate excess air, and
good fuel/air mixing during combustion minimize CO and VOC emissions. Therefore, staging
combustion and lowering combustion temperatures by water or steam injection or low-NO x
burners (which are used for NOx emission control) can be counter-productive with regard to
CO and VOC emissions.

9.3.1 Catalytic Oxidation:

Catalytic oxidation is a post-combustion method for reduction of CO and VOC

emissions. The Process oxidizes CO to CO 2 with the use of a catalyst and oxidizes VOC
hydrocarbons to CO2 and H2O. A CO control catalyst uses a precious metal base to promote
the oxidation process. None of the catalyst components are considered toxic.

The optimum exhaust gas temperature (range) for CO and VOC catalyst operation is
between 470oC and 600oC. Exhaust gas from the gas turbine is typically between 510oC and
600oC. Therefore a CO and VOC catalyst, if used, would be installed at the discharge of the gas
turbine. Oxidizing catalysts are capable of reducing CO and VOC emissions by approximately
95% and 50% respectively.

If the fuel contains sulfur, then the use of an oxidizing CO catalyst in conjunction with
SCR catalyst must be carefully examined. Oxidation catalyst can convert up to 60% of the SO 2
into SO3. When this SO3 comes in contact with the ammonia required for SCR operation, then
ammonium sulfate and ammonium sulfite will be formed. Although the operating temperature
is too high for these salts to deposit and foul the catalyst, they will condense and collect onto
the cooler back-end of the HRSG. Also, the salts that do not condense can form particulate
matter, which will be emitted from the stack.

9.4. Sulfur Dioxide and Acid Gas Mist Emissions:

The NSPS established by Environmental Protection Agency for emissions from gas
turbines sets a maximum SO2 level in the flue gas of 150 ppmdv (at 15% O2) and a maximum
fuel sulfur content of 0.8% by weight (40 Code of Federal Regulations (CFR) 60.333). The
EPA has not established a gas turbine NSPS for acid gas mist (H 2SO4). The turbine,

-118-
manufacturer’s emission data indicate that on average, approximately 3% of the SO 2 in the flue
gas are oxidized to SO3 which combines with water to form H2SO4.

Typically, natural gas has only a trace of sulfur (2,000 grains per million standard cubic
feet or less) and no supplemental SO2 or acid gas mist emission controls have been
imposed on natural gas fired gas turbines. Permits for NO.2 fuel oil fired gas turbines
typically have included limits on maximum allowable fuel sulfur contents.

As discussed in the previous section, the use of CO oxidation catalyst in the presence of
sulfur bearing fuels will lead to an increase in SO 3 production. If oxidation catalyst is to be
used, this increase must be included in the determination of acid mist emissions.

9.5. Particulate Matter Emissions:

The emission of particulate matter from the gas turbine facility is controlled by
ensuring complete combustion of the fuel. The NSPS for gas turbines do not establish an
emission limit for particulate matter. The natural gas and No. 2 fuel oil fuels to be used in gas
turbines will contain only trace quantities of noncombustible material. The manufacturers
standard gas turbine operating procedures ensure as complete combustion of the fuel as
possible.

Particulate matter can also be formed by the use of post combustion catalyst used on
turbines fired by sulfur bearing fuels.

9.6. Summary of Emissions Control:

The SCR process can achieve in excess of 90% NO x reduction. Because flue gas
temperature affects catalyst performance, installation of the catalyst in an area in which the flue
gas is between 315oC and 400oC is essential.

SCR catalysts are designed to provide optimum activity, selectivity and chemical
stability. Catalysts with high activity offer high NO x conversion. Catalysts with optimum
selectivity reduce the undesired chemical reaction. Chemically stable catalysts protect against
catalyst deactivation and ensure acceptable service life.

-119-
 Typically measures taken to minimize formation of NO x during combustion inhibit
complete combustion and result in increased emissions of CO and VOCs. Catalytic oxidation is
a post combustion method that can be used to reduce CO and VOC emissions. The control of
SO2 emissions from gas turbines is accomplished by using natural gas that contains only trace
amounts of sulfur content in fuel. Particulate emissions are controlled by the complete
combustion of the fuel using proper operating procedures.

-oO:Oo-

-120-