Topics in Catalysis Vols. 30/31, Nos.

14, July 2004 ( 2004) 37

Control of NOx emissions from diesel engine by selective catalytic

reduction (SCR) with urea
Joon Hyun Baika, Sung Dae Yima, In-Sik Nama,* Young Sun Mokb, Jong-Hwan Leec,
Byong K. Choc, and Se H. Ohc
a
Department of Chemical Engineering/School of Environmental Science and Engineering, Pohang University of Science and Technology
(POSTECH), Pohang, Korea
b
Department of Chemical Engineering, Cheju National University, Jeju, Korea
c
General Motors R&D Center, Warren, MI, USA

Among the catalysts screened, Cu-ion exchanged ZSM5 zeolite exhibited the highest NO removal activity, particularly at low
reaction temperatures below 200 C, maintaining a wide operating temperature window. The hydrothermal stability of the
CuZSM5 catalyst can be improved by the optimization of metal content of the catalyst. Through the variation of reactor operating
conditions, NO conversion of better than 90% could be achieved with a minimum NH3 slip. The decomposition of urea was also
examined and a kinetic model for both thermal and catalytic decomposition of urea was developed. Urea-SCR over the CuZSM5
catalyst exhibited that the NO removal activity is competitive to that by NH3-SCR, indicating urea can be eectively utilized in
SCR reactor system as the reducing agent.
KEY WORDS: urea-SCR; decomposition of urea; CuZSM5.

1. Introduction In the present study, a variety of candidate catalysts

The selective catalytic reduction (SCR) of NOx with
NH3 has been widely used for the removal of NOx
emissions from stationary sources. However, the tech-
nology is not suitable for controlling NOx emissions
from automotive diesel engines mainly due to the
diculty in handling and transportation of NH3. For
its application to mobile source, urea has received
considerable attention as a NH3 carrier for the SCR
technology [13].
When the urea solution is atomized and injected into
the hot exhaust gas stream containing NOx, the droplets
are heated, and water evaporates rst. Pure urea will
then be thermally decomposed into one molecule of
ammonia and one molecule of isocyanic acid. The
isocyanic acid formed by the thermal decomposition of
urea can readily undergo hydrolysis on the catalyst
surface to produce one more molecule of ammonia.
Thus, the complete decomposition of 1 mol of urea
produces 2 mol of ammonia and 1 mol of carbon
dioxide. This leads to the corresponding overall reaction
for the SCR of NO by urea:
2H2 N
CO
NH2 4NO O2 ! 4N2 4H2 O 2CO2
1 tiveness of an automotive three-way catalyst under lean
It has been reported that the rate of HNCO hydrolysis is
much faster than the rate of the SCR reaction within the
range of low to medium temperature over active SCR
catalysts [4,5].
* To whom correspondence should be addressed.
E-mail: isnam@postech.ac.kr
have been evaluated for their fresh NO removal activity
and hydrothermal stability as well as the eect of reactor
operating conditions. The thermal and catalytic decom-
position of urea has been also examined to quantify the
production of NH3, the reductant required. The eec-
tiveness of the urea-SCR technology for the control of
NOx exhaust emission has been demonstrated in this
study.
2. Experimental
2.1. Catalysts preparation
Cu-zeolite catalysts, including ZSM5, Mordenite,
HY, USY and Ferrierite, were prepared by the ion-
exchange method using Cu(CH3COO)2 H2O solution.
The content of copper was controlled by varying the
number of the ion-exchange steps. The other metal
exchanged zeolites, such as FeZSM5 and PtZSM5, were
also prepared by the identical method using FeCl3 and
Pt(NH3)4(NO3)2 solution, respectively. V2O5/TiO2,
Pt/Al2O3, CrOx/TiO2 and MnOx/TiO2 were prepared
by wet impregnation method. It should be noted that
Pt/Al2O3 catalyst was prepared to examine the eec-
conditions. CrOx/TiO2 and MnOx/TiO2 have also been
reported as low-temperature SCR catalysts [68].
All the catalysts prepared in the present study were
dried at 110 C for 12 h and calcined in air at 500 C for
5 h. They were again pretreated in air at 500 C for 1 h
prior to each experiment. Listed in table 1 are the
physicochemical properties of the catalysts prepared and
screened in the present study.

1022-5528/04/07000037/0 2004 Plenum Publishing Corporation

38 J.H. Baik et al./NOx reduction with urea

Table 1
Physicochemical properties of the catalysts employed in the present study

Metal content (wt%) Ion- Surface

exchange area
Catalysts PMa V W Pt Cr Mn Cu Fe Si/Al level (%) (m2/g)

V2O5/TiO2 WI 2.0 66
Com Ab 1.6 7.3 60
Pt/Al2O3 WI 1.7 290
CrOx/TiO2 WI 11.9 117
MnOx/TiO2 WI 9.6 190
CuHM IE 2.3 5 31 400
CuHY IE 6.6 3 80
CuUSY IE 3.2 15 100
CuFER IE 1.1 9 24 300
CuZSM5-14-97 IE 2.9 14 97 340
CuZSM5-14-117 IE 3.5 14 117 330
FeZSM5-14-96 IE 2.4 14 96 340
PtZSM5-14-20 IE 0.5 14 20
a
Preparation method, WI: wet impregnation, IE: ion exchange.
b
Commercial catalyst.

2.2. Reactor system and experimental procedure

The NO removal activity of the catalysts prepared
has been evaluated for NH3-SCR in a packed-bed ow
reactor system [9]. A feed gas mixture containing NO
(500 ppm), NH3 (500 ppm), O2 (5%), H2O (10%) and
N2 (balance) was supplied through mass ow controllers
(Brooks 5850E) to the reactor. The concentrations of
NO and NH3 were analyzed by an on-line chemilumi-
nescence NONOx analyzer (Thermo Electron Co.,
Model 42H) and an NH3 analyzer with NDIR (Rose-
mount Analytical, Model 880A), respectively.
The reactor system for the urea-decomposition reac-
tion and urea-SCR consists of a urea (commonly 1 M
aqueous solution) injection part, a reactor for urea
thermal decomposition, a catalytic reactor, and an Figure 1. Activity of promising SCR catalysts for the reduction of NO
analysis part for remained NH3 (and/or NO), urea and by NH3. Feed: 500 ppm NO, 500 ppm NH3, 5% O2, 10% H2O and N2
HNCO [10]. balance; Reactor SV: 100,000 h)1.
The concentration of urea was adjusted to 250 ppm
throughout the present study. To analyze the urea
that is critical for the application to automotive diesel
remaining unconverted and HNCO produced by the
engines. The catalyst exhibited NO conversion higher than
decomposition reaction and urea-SCR, a part of the
60% at 150 C and 100,000 h)1, maintaining a wide
reacted gas was absorbed into a series of the absorption
operating temperature window from 200 to 400 C
bottles containing deionized water. The concentrations
revealing NO conversion higher than 90%. At comparable
of urea and HNCO absorbed into the water were then
Cu loadings, CuHM, CuUSY and CuFER showed
analyzed by HPLC with a UV detector (Younglin
relatively lower deNOx activity than the CuZSM5 catalyst
UV730D) as reported previously [11].
at the reaction temperatures covered in the present study,
as shown in gure 2. This suggests that ZSM5 is the best
support among other types of zeolites tested in the present
3. Results and discussion study as a zeolite catalyst for the removal of NO by NH3.
3.1. Catalyst screening for NH3-SCR
3.2. Eect of reaction conditions on deNOx performance
The NO conversion activities of a variety of SCR
of CuZSM5 catalyst
catalysts prepared in the present study are compared in
gure 1. Among the catalysts, the CuZSM5 catalyst Figure 3 shows that an increase in the residence time
revealed the highest performance of NO removal activity, of the feed gas stream in the reactor signicantly
particularly at low reaction temperatures below 250 C improves NO conversion particularly at low reaction