ABSTRACT
Selective Catalytic Reduction (SCR) of NO
x
using
reductants such as urea continues to be of high interest to
meet impending regulations. Vanadia supported on anatase
titania is a well-established catalyst for stationary and heavy-
duty-diesel truck deNO
x
applications. However, traditional
anatase titania-based materials are regarded to have limited
thermal stability in the most demanding applications such as
those where the SCR catalyst is located downstream of a
regenerating DPF, in which the catalyst could be exposed to
very high temperatures. More recently, state-of-the-art
titania-based vanadia catalysts have shown good cold-start
performance and are capable of surviving accelerated aging
treatments of up to 64 hrs at 670°C [ 1 ], good performance in
a configuration upstream of a DOC/DPF [ 2 ], good low
temperature NO
x
conversion on par with Cu-zeolite SCR
catalysts and superior resistance to sulfur poisoning [ 3 ]. We
report here new, highly engineered titania-based materials
with substantially improved stability and/or activity
compared to the state-of-the-art commercial titania-based
vanadia SCR catalysts. New synthetic approaches were used
to prepare catalyst support materials that are predominantly
anatase TiO
2
in composition. The thermal and hydrothermal
stabilities of the new materials were characterized using a
combination of x-ray powder diffraction with Rietveld
Refinement, transmission and scanning electron
microscopies, and N
2
porosimetry. Vanadia-loaded catalysts
in powder form were thermally- or hydrothermally-aged and
evaluated for NO conversion activity and selectivity in
model-gas bench-scale reactors using NH
3
as the reductant,
and were compared to commercial titania-based vanadia
powders. The new materials fall into two classes. In the first,
the materials exhibit substantially improved thermal stability,
anatase phase stability and higher porosity, while exhibiting
deNO
x
activity comparable to commercial materials. In the
second class, the activity and stability of the new materials
can be tuned to yield higher deNO
x
activity, particularly
after exposure to high temperatures, while maintaining crystal
phase stability and porosity at least as good as that of state-
of-the art commercial titania-based vanadia catalysts. In a
bench test under severe conditions that simulate lifetime
catalyst exposure, no detectable vanadium is lost from the
new catalysts to the vapor phase. The new, highly engineered
materials should provide the catalyst formulator with new
options to achieve robust and active SCR systems.
INTRODUCTION
The selective catalytic reduction (SCR) of nitrogen oxides
produced during combustion processes using reductants such
as NH
3
has been a commercially successful technology for
over 30 years [ 4]. Over the last several years there has been
extensive development of SCR catalysts for mobile-source
applications. Titania-based vanadia catalysts have been
employed widely on a commercial basis in stationary-source
applications for many years, and more recently in heavy duty
diesel mobile-source applications [ 5]. Recent SAE papers on
titania-based vanadia catalysts have shown that these
catalysts offer good cold-start performance, and are capable
of surviving accelerated aging treatments of up to 64 hrs at
670°C [ 1], good performance in a configuration upstream of a
DOC/DPF [ 2] and superior resistance to sulfur poisoning [ 3].
However, it is commonly accepted that the main limitation of
titania-based vanadia catalysts is a relative lack of thermal
durability relative to zeolite-based catalysts [ 6]. The titania
New Titania Materials with Improved Stability and
Activity for Vanadia-Based Selective Catalytic
Reduction of NOx
2010-01-1179
Published
04/12/2010
David Monroe Chapman, Guoyi Fu, Steve Augustine, Mark Watson, Jennifer Crouse, Lubov
Zavalij and Dale Perkins-Banks
Millennium Inorganic Chemicals
Copyright © 2010 SAE International
SAE Int. J. Fuels Lubr. | Volume 3 | Issue 1 643