Proceedings of

2000 International Joint Power Generation Conference

Miami Beach, Florida, July 23-26, 2000

IJPGC2000-15067
SCR Catalyst Design Issues and Operating Experience:
Coals with High Arsenic Concentrations and Coals from the Powder River Basin
Dr. Karina Rigby, Siemens KPW
Mr. Robert Johnson, Siemens Westinghouse
Dr. Ronald Neufert, Siemens KPW
Dr. GUnther Pajonk, Siemens KPW
Dr. Erich Hums, Siemens KPW
Mr. Andreas Klatt, Siemens KPW
Mr. Ralf Sigling, Siemens Westinghouse
Selective Catalytic Reduction (SCR) for Nitrogen Oxide emission control is a preferred
technology for coal-fired Utility compliance strategies. A large number of installations are
scheduled for commercial operation before May, 2003. Within the United States, there is
experience on only several installations, and thus many of the SCR-related decisions have
been made on the basis of extrapolated data from units with dissimilar operating
experience.
T w o significant issues currently dominate decision-making for SCR catalyst technology
and system engineering: first, the need for catalyst that provides high-efficiency
performance under high or varying gaseous arsenic conditions; and second, the need
for a technology solution for SCR installations on units firing Powder River Basin (PRB)
coal.

1. Gaseous Arsenic and SCR Catalyst Performance

It is well-known that arsenic in gaseous form will poison vanadia-titanium SCR
catalysts.
The first and most evident cases of poisoning were observed on wetbottom boilers with fly ash reinjection. In the 1980's, Siemens conducted numerous
studies on this phenomenon in German Utility installations. These studies resulted in
the development of Siemens' arsenic resistant plate catalyst.
Arsenic in the coal will be vaporized into arsenic oxides, preferably to As-(lll), in the
boiler. These are very volatile at the operating temperatures of the boiler. These
arsenic oxide molecules are very small relative to the typical pore diameters in SCR
catalysts. As a result, these can readily penetrate into the pore system of the catalyst
where these molecules will react with the vanadia in the catalyst.
The resultant
vanadia-arsenate compound is so stable that the activity of the vanadia site is lost.
This catalyst deactivation can be quite rapid for vanadia-tungsten based catalysts,
depending on the concentration of gaseous arsenic in the flue gas.
This catalyst deactivation on w e t - b o t t o m boilers in Germany caused some Utilities to
install tail-end SCR systems in order to provide a comparatively clean gas (ie low
sulfur, dust and arsenic Ioadings) for the catalyst. These kinds of SCR systems are

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generally more expensive to install, due to the requirements for heat exchangers, and
to operate, due to the costs associated with reheating the flue gas. At that time,
however, this system became the only option for Utilities to maintain high efficiency
SCR performance and relatively long catalyst operating life.
Siemens developed an arsenic resistant catalyst to improve catalyst performance in
high dust applications. For German utilities, this catalyst allowed them to choose a
high dust SCR for the wet bottom boilers, or to improve operating performance of
installed SCRs by maintaining higher removal efficiencies over a longer operating
period.

Arsenic Resistance

Deactivation caused by arsenic in the flue gas is a chemical reaction. To make an

SCR catalyst resistant to arsenic requires a change in the chemical composition of the
catalyst. The purpose is to provide a reaction site for the arsenic oxide other than the
vanadia in the pore structure. Research and development work by Siemens proved
that the addition of molybdenum to the catalyst composition is effective in protecting
the vanadia sites against arsenic attack. The amount of molybdenum and the extent
of arsenic resistance are directly proportional. Catalysts with very high molybdenum
content deactivate very slowly and show excellent k(t) / k(o) ratios over time. Initial
catalyst activity is lower, however.
In a catalyst with molybdenum added, the Mo site is more reactive with arsenic than
vanadia. As a result, the vanadia site is shielded from the arsenic since the arsenic
will form a stable compound with the molybdenum. Without molybdenum, the arsenic
will quickly react with the vanadia. Since the concentration of vanadia in the chemical
composition of the catalyst is small, typically less than 1.5%, the deactivation of
vanadia sites is quite rapid.
In the same flue gas, ie arsenic concentrations, tungsten-based catalysts will
deactivate much faster than a catalyst containing molybdenum.
In some German
installations, 50% loss of activity has been reported within 10,000 to 15,000
operating hours.
With a Siemens titanium molybdenum catalyst on similar
applications, the relative activity of the catalyst has declined only 20 to 25%.
Siemens' field experience with tungsten and molybdenum-based catalysts shows the
tendencies for lower deactivation rates for Siemens' arsenic-resistant catalysts, and
the rapid deactivation for those that are tungsten-based. The trends shown in Figure
1 are based on catalyst samples from full-scale installations, as tested by Siemens or
reported by other companies. As arsenic concentrations on the catalyst increase, as a
function of operating time and arsenic levels in the flue gas, the relative deactivation
between molybdenum and tungsten-based catalysts diverges rapidly.

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high

E
m
TiO2/WO3

'G

8
>

TiO2/MoO 3 based arsenic

resistant SiNOx plate catalysts

III

low
low

Figure 1.

Arsenic content of the catalyst

high

Comparisonof Catalyst Deactivation Rates as a Function of Arsenic Content

SCR system design is significantly affected by the catalyst decision, especially on

units expected to have high arsenic concentrations. A decision based on an incorrect
assessment of expected catalyst deactivation will impact expected operating periods
for the catalyst and result in more frequent exchange of catalyst. Understanding the
important variables before a catalyst decision will give a Utility a better basis for
evaluating expected operation and performance.
The Effect o f Calcium Oxide
Extensive development work by Siemens in the late 1980's and early 1990's showed
that gaseous arsenic levels in a flue gas are a function of the calcium oxide (CaO)
percentage in the coal. Correlations have been formed among these t w o constituents,
boiler type and fly ash recirculation to predict gaseous arsenic concentrations in the
flue gas. The importance of this determination is to accurately assess the deactivation
rate of the catalyst for catalyst design and volume calculations. Failing to choose the
correct deactivation rate will lead to an insufficient initial catalyst volume, a possibly
undersized SCR reactor arrangement, and a flawed evaluation of life-cycle operating
costs related to catalyst management.
Previous interpretations of these variables by many in the industry, primarily drawn
from SCR catalyst performance from Japanese installations firing low arsenic coals
and German coals from the Ruhr and Saar Regions with high CaO contents, assumed
that catalyst deactivation on dry bottom boilers would be relatively slow. However,
Siemens' experience in the United States has shown that arsenic concentrations in the
flue gas, based on arsenic content on SCR catalyst samples, vary considerably for dry
bottom boilers. Considering the fuel flexibility desired by many Utilities, the impact on
catalyst selection is significant. A tungsten-based catalyst will not be able to provide
the long-term reduction efficiencies nor control ammonia slip if it deactivates more
rapidly due to the high arsenic concentrations. Remedial actions, such as limestone

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injection, limitations on coal selection and a higher frequency of catalyst exchanges,

are expensive.

2. Powder River Basin (PRB) Coals and SCR Catalyst Considerations

Cost saving measures as well as strict SO 3 emissions limits have led to an increase in
the number of US Utilities burning PRB coal. The subject of PRB coal use is therefore
a significant issue in the US Utility market, considering the number of units possibly
affected by Title I regulations. Many utilities burning PRB coal are now confronted
with the necessity of installing SCR units to meet strict NOx emissions limits.
The uncertainty of long term performance has affected decision-making processes
pertaining to SCR system arrangement, life cycle operating costs and commercial
guarantees. This situation has prompted Siemens to engage in an extensive research
program to study the effects of PRB fly ash on SCR catalysts in high-dust applications,
both through independent testing at Siemens as well as through the involvement in
partnership research programs with US utilities.
As part of the Siemens PRB research program, more than 400 Siemens test samples
have been installed in numerous PRB coal plants across the US. These PRB plants
include both pulverized coal (PC) and cyclone power plants. Additional test
installations are planned.
The Siemens catalyst samples can be grouped into the following categories:

Full-size slip-stream samples tested under actual conditions

Smaller sized slip-stream samples tested under actual conditions
Coupon samples tested under actual conditions
Coupon samples tested in flue gas ducts

The goals of the Siemens catalyst testing program for PRB applications are threefold.
Our first goal is to quantify the catalyst deactivation rate for various types of PRB
applications. Knowledge about catalyst deactivation rates associated with PRB coal
forms the basis for a decision on whether a high-dust or tail-end SCR reactor is
appropriate and what type of catalyst management plan is necessary.
The second goal of the Siemens catalyst testing program is to gain information on the
catalyst deactivation mechanism resulting from PRB fly ash exposure. Knowledge of
the physical and/or chemical process leading to catalyst deactivation will provide
information on the expected magnitude of activity loss associated with PRB fly ash
exposure.
Information on the catalyst deactivation process is also the basis for developing
measures to counteract catalyst deactivation in PRB applications. This goal will be
addressed in the third phase of the Siemens catalyst testing program.

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Catalyst Deactivation Rate

Activity testing in Siemens semi-bench and pilot scale reactors has been performed on
reference catalyst samples and catalyst samples exposed in both PC and cyclone PRB
plants under actual SCR conditions. In general, activity testing showed that under worstcase conditions catalyst deactivation can reach more than 50% in less than 5000 operating
hours.
Catalysts tested under worst-case conditions showed a sharp initial decrease in
activity and a subsequent flattening of the deactivation curve as operating hours
increased. This phenomenon will be discussed in more detail below. Deactivation
information will continue to be updated as more operating hours on Siemens catalyst test
samples are gathered as part of the PRB test program.

Catalyst Deactivation Mechanism

As part of the Siemens PRB investigation, exposed catalyst samples and fly ash
specimens were analyzed in order to determine which deactivation mechanism
contributes to catalyst deactivation in PRB applications. Catalyst poisoning effects
resulting from PRB fly ash were evaluated by performing leaching experiments on fly
ash collected from numerous US and European coal plants burning PRB coal, US highsulfur coal and German hard coal. Leaching tests were performed using water and
sulfuric acid to simulate operating conditions in which water or sulfuric acid
condenses on the fly ash on the surface of the catalyst. The leached elements were
analyzed in both cases and the pH of the leaching solution was measured after the
tests performed with water.
The results of the fly ash leaching experiments showed that, except for Na, the
concentrations of poisoning constituents in PRB fly ash are lower than or similar to
those of other common coal types. The Na concentration will vary depending on the
type of PRB fly ash tested. These results show that, although deactivation from
poisoning will take place to a limited extent in PRB applications, the extreme catalyst
deactivation associated with PRB coal cannot be explained solely be chemical
poisoning.
The extent of catalyst masking and plugging resulting from PRB fly ash exposure was
also examined as part of the Siemens PRB investigation. Optical microscopy was used
to examine the large fly ash particles present on the surface of exposed catalyst
samples and scanning electron microscopy (SEM) was used to examine the
microscopic surface structure of the catalyst samples (including surface pores,
plugging and masking phases). Energy dispersive X-ray analysis (EDX) was used to
examine the chemical composition of the catalyst surface and to obtain information
about the flue gas constituents deposited on the surface of the catalyst samples.

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Optical microscopy and SEM results showed that the PRB fly ash on the surface of the
exposed catalyst samples can generally be divided into two categories. Macroscopic
fly ash deposits, observable as ash clumps on the catalyst surface and between the
catalyst plates or walls, were found to be loose and showed no signs of cementing.
Extreme plugging or fly ash cementation should therefore not be a significant problem
in plate- catalyst PRB applications.
However, SEM analysis showed that on a
microscopic scale, not observable using the naked eye, fly ash on the catalyst surface
had reacted to form a masking layer which in some cases was found to be extremely
dense. The formation of the masking layer was not found to be connected with
catalyst pores, i.e. no individual fly ash particles lodged in catalyst pores were
detected. Chemical analysis of the catalyst surface showed that the masking layer
formed on the catalyst surface consisted nearly completely of calcium and sulfur.
This masking layer prevents nitrogen oxides and ammonia from diffusing into the
catalyst sites, resulting in significant catalyst deactivation (Figure 2).

PRB deactivation mechanism:

Macroscopic blockage of
catalyst surface by
calcium sulfate coating
Calcium sulfate coating
Pore
System
CatalystSurface~

Figure 2:

Schematic showing calcium sulfate masking, the main catalyst deactivation mechanism
for PRB applications.

If one examines the chemistry of PRB fly ash it is clear why PRB applications are
especially susceptible to calcium sulfate surface masking. As discussed previously,
one of the main factors driving more and more utilities to switch to PRB coal is the
low sulfur content, allowing utilities to meet emissions limits. However, this apparent
advantage results in a disadvantage from the standpoint of SCR catalyst operation.
The CaO content of PRB coals can be nearly three times that of anthracite or
bituminous US coals. When high-sulfur coal having a low CaO content is burned, the
calcium compounds react nearly completely with the excess SO3 present in the boiler
to form calcium sulfate and other phases. The calcium sulfate itself is no longer
reactive and blows through the catalyst channels as non-reactive fly ash. However,
because of the extremely low sulfur content and the extremely high CaO content in
PRB coal, there is not enough SO3 available in the boiler to completely transform the

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CaO phases to calcium sulfate in the boiler. The result is a large percentage of "free"
or "active" CaO in PRB fly ash.
The presence of large amounts of free CaO is the essential factor in the calcium
sulfate formation mechanism leading to catalyst deactivation in PRB applications. This
is illustrated in figure 3.

(1)

Free CaO (in fly ash) is deposited onto catalyst surface

(2)

SO2 (in exhaus t gas) ~

(3)

Free CaO (on catalyst surface) + SO3 (g)

SO3 (on catalyst surface)

GAS04

calcium sulfate coating

Figure 3:

Mechanism leading to the formation of a calcium sulfate surface coating on SCR catalysts
in PRB applications

In step 1, the PRB fly ash lands on the catalyst surface as the flue gas passes through
the catalyst, as is the case for any type of fly ash. However, as described above, PRB
fly ash contains large amounts of reactive free CaO. In step 2, the small amounts of
SO2 present in the flue gas react to SO3 on the catalyst surface. The presence of
both free CaO and SO3 at the catalyst surface leads to reaction 3, the formation of a
CaSO4 layer on the catalyst surface. Because both free CaO and SO3 are continuously
available at the catalyst surface, the CaSO4 layer continues to build up as SCR
operating hours increase.
Deactivation resulting from the formation of a calcium sulfate layer on the surface of
the catalyst physically explains the sharp initial decrease in catalyst activity and the
subsequent flattening of the deactivation curve as operating hours increase. During
initial exposure, any calcium sulfate formation which takes place occurs on the active
catalyst surface, resulting in deactivation of this surface. As exposure time increases,
calcium sulfate formation occurs partially on fresh catalyst surface, but also on top of
the already formed calcium sulfate layer, resulting in only a minor increase in
deactivation due to thickening of the already present calcium sulfate diffusion barrier.
Therefore, for PRB applications, the calcium sulfate formation model is in agreement
with the sharp initial activity decrease and subsequent slower catalyst deactivation
discussed above. It is expected that continued calcium sulfate formation will result in
complete catalyst masking with increased operating hours. As supported by SEM
results, fly ash trapping in catalyst pores does not contribute significantly to
deactivation.

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Measures to Counteract Catalyst Deactivation

Results gained from the Siemens PRB investigation to date indicate that, in most
cases, a high-dust SCR application will result in catalyst deactivation rates which are
significantly higher than expected for other coal applications. As discussed above, in
such cases a strict catalyst management plan or a tail-end SCR solution may be
necessary. A third option, however, is to develop measures to counteract catalyst
deactivation resulting from PRB fly ash exposure.
Possible counteraction measures include:

Coal blending to increase the sulfur to calcium ratio in the fly ash, thereby
minimizing free CaO content
Neutralization of the free CaO before it reaches the catalyst
Decreasing the SO3 availability at the catalyst surface
Removal of the calcium sulfate from the catalyst surface after deposition

These possibilities are currently being investigated as part of the Siemens catalyst
testing program for PRB applications.

Conclusions and Catalyst Design Impact for PRB Applications

Commercial SCR catalyst operating experience for PRB applications is very limited at
this time, however there has been a substantial amount of development w o r k recently.
Siemens has been extensively involved in this area, and has come to some preliminary
conclusions.
The work indicates that a masking of the catalyst will occur if the
catalyst is installed in a conventional high dust location.
This masking in essence
deactivates the catalyst rapidly, and long term projections of performance become
very subjective.
Based on this currently available deactivation information, a tail-end SCR installation
would most likely be the best option for meeting the emission limits required at some
US utilities burning PRB coal. High-dust SCR systems with deactivation rates as high
as those presented here would require an extremely strict catalyst management plan.
The pros and cons of a tail-end vs. a high-dust SCR solution will have to be examined
by utilities and catalyst manufacturers on a case-by-case basis.

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