Top Catal

DOI 10.1007/s11244-016-0568-0

ORIGINAL PAPER

A System Simulation Study of the Enhanced-SCR Reaction

F. Marchitti1 • I. Nova1 • P. Forzatti1 • E. Tronconi1 • S. Adelberg2 •

V. Strots2

 Springer Science+Business Media New York 2016

Abstract This study addresses fundamental and practical solutions of NH4NO3 (AN) to a NO–NH3 containing feed
aspects of the Enhanced-SCR reaction over a Fe-zeolite SCR results in the ‘‘Enhanced-SCR’’ (E-SCR) reaction,
catalyst. The key mechanistic steps responsible for the 2NH3 + 2NO + NH4 NO3 ! 3N2 þ 5H2 O; ðR:1Þ
improvement of the DeNOx activity at low temperatures are
analysed, and a system simulation model is developed to over V2O5–WO3/TiO2 and Fe-zeolites. The E-SCR reac-
assess its potential for NOx conversion improvement in tion is associated with high DeNOx efficiencies, similar to
heavy-duty aftertreatment systems. It was found that the those of the Fast-SCR, in the 180–350 C T-range without
ammonium nitrate additive can dramatically improve the upstream oxidation of NO–NO2. The aim of the present
low-temperature DeNOx activity of a Fe-zeolite catalyst, by work is to clarify both fundamental and practical aspects of
generating in situ NO2 readily. Such NO2 can then react in the E-SCR reactivity, with particular focus on the key
the Fast-SCR reaction, which explains the enhanced low-T mechanistic steps responsible for the improvement of the
SCR activity. The simulation of a complete heavy-duty DeNOx activity. Further, a system simulation model is
aftertreatment system with a dedicated AN injection showed developed to semi-quantitatively describe the E-SCR
the potential of the apparatus, in both cold and hot WHTC. chemistry and to assess its potential for NOx conversion
improvement in heavy-duty aftertreatment systems.
Keywords NH3/urea SCR
Ammonium nitrate

Enhanced-SCR
Fe-zeolite
Simulation
2 Materials and Methods

1 Introduction 2.1 Lab Scale Test Rig Runs

NH3/urea SCR is nowadays a well-established technology The catalytic material used for the investigation herein
for the control of NOx emissions from diesel vehicles, but reported is a commercial Fe-zeolite SCR catalyst, coated on
the reduction of the emission limits and the lower exhaust a 400 cpsi honeycomb substrate and provided by Umicore.
temperatures due to more efficient engines require more The tested sample was a small core monolith cut down from
effective DeNOx systems, especially at low temperatures. It the central part of the original brick. The tested sample had a
has been demonstrated [1, 2] that addition of aqueous square cross section (6 9 6 cells, 7.7 9 7.7 9 65 mm3).
In order to fully analyze the Fe-zeolite catalyst behavior
with and without the ammonium nitrate (AN) additive,
& V. Strots both steady-state and transient runs were performed. First,
[email protected] the catalyst behavior was characterized under pure NH3-
1
Laboratory of Catalysis and Catalytic Processes,
SCR conditions, collecting a complete SCR baseline data
Dipartimento di Energia, Politecnico di Milano, Via La Masa set. Then, proceeding according to a hierarchical approach,
34, 20156 Milan, Italy an increasing amount of AN was added to the reacting
2
IAV GmbH, Carnotstrasse 1, 10587 Berlin, Germany system. During the investigation, the following effects on

123
 Top Catal

the DeNOx performances were addressed: effect of tem- connecting pipes have been created using axisuite soft-
perature, GHSV, AN feed concentration, and co-presence ware by exothermia, and integrated with the models for
of NO2 in the feed mixture. The Fe-zeolite catalyst was sensors, injection of aqueous solutions of urea and AN, and
tested under both degreened and aged conditions. Before with the injection control strategy using Simulink-based
being used for activity runs, the Fe-zeolite catalyst was VeLoDyn software by IAV. The system model has been
conditioned in the reactor by feeding 10 % of both O2 and used for the analysis and comparison of SCR and SCR/DPF
H2O; N2 was the balance gas to keep the GHSV at system performances in the WHTC test cycle used for
35,000 h-1. The reactor temperature was progressively heavy-duty engine certification for Euro VI, as well as in a
increased from room temperature up to 550 C and held for driving cycle simulating bus operation in city traffic [4].
3 h. Isothermal steady-state and transient runs were
carried out in the T = 150–550 C and GHSVs = 2.4 Simplified Model for AN Adsorption
35,000–1,00,000 h-1 ranges. Typical feed concentrations and Reaction with NO
of NOx (NO2/NOx = 0–0.5) and NH3 were 500 ppm, with
8 % O2, 5 % H2O v/v and N2 as balance gas. In E-SCR Following the analysis of the experimental results and the
runs, a calibrated aqueous solution of AN was also dosed mechanistic findings, a simplified model of the AN reac-
by means of a peristaltic pump, upstream of the SCR cat- tions was developed. The sub-model included just one
alyst. The solution concentrations and the pump flow rates global gas phase reaction, i.e. NO oxidation by AN via:
were selected to result in AN feed concentrations of NH4 NO3 + NO ! NO2 + N2 + 2H2 O ðR:2Þ
100–350 ppm. The concentrations of NO, NH3, NO2, and
N2O in the outlet gases from the test reactor were contin- Following experimental observations, an assumption
uously monitored by a UV-analyzer and a ND-IR-analyzer, was made that step (R.2) proceeds instantaneously and with
respectively. More details can be found in [1, 2]. 100 % efficiency at the entrance to the SCR catalyst. The
assumption enabled direct implementation of the AN-re-
2.2 Aftertreatment System Variants lated steps on a system level, without the modification of
the kinetic model of the SCR catalyst. While lacking in
Figure 1 shows three SCR system configurations consid- accuracy, especially with regard to AN decomposition at
ered. System 1 represents a standard architecture com- temperatures exceeding 230 C, the simple model enabled
monly used in commercial heavy-duty exhaust systems preliminary simulation and comparison of the performance
meeting Euro VI or US EPA 2010 requirements, with the of systems shown in Fig. 1.
injection of aqueous urea solution used to deliver ammonia
for the reduction of nitrogen oxides. The system includes a 2.5 Reductant Injection Strategy
Pt-based diesel oxidation catalyst (DOC), a Pt-coated die-
sel particulate filter (cDPF), an SCR catalyst, and an Two different strategies have been developed and imple-
ammonia slip catalyst combining the functions of ammonia mented in the system model, one for single-fluid injection
oxidation and SCR. This system also assumes injection of a (Systems 1 and 3), another for the System 2 with two
single solution of AN and urea in water. System 2 uses injectors. In the single-fluid systems, the urea or AN-urea
separate injections of urea solution and AN solution. Sys- solution is injected as needed to maintain the required SCR
tem 3 uses reductant injection similar to System 1 but does catalyst coverage by ammonia, defined by the balance
not include the DOC and Pt coating of the DPF. between high SCR reaction rates and avoidance of
ammonia slip in transient system operation. Injection of
2.3 System Model four solutions has been simulated, with AN-to-urea ratio of
0.0, 0.3, 0.6, and 0.9. The portion of water was reduced
The modeling and simulation approach for heavy-duty with increased AN concentration, in order to keep the
SCR-based diesel aftertreatment systems has been pre- injected volume roughly the same. However, higher water
sented in [3]. The models for the catalyst monoliths and contents might be required for systems with high AN

Urea + AN + Urea + AN +
H2O Urea + H2O AN + H2O H2O
DOC

DOC

ASC
ASC

ASC

cDPF SCR cDPF SCR DPF SCR

(1) (2) (3)

Fig. 1 Schematic diagrams of the investigated diesel aftertreatment systems

123
Top Catal

concentration, in order to maintain stability of the liquid each of NO and NO2, 5 % of H2O and 8 % of O2) are also
and avoid crystallization. shown as a lower and upper bound, respectively.
In the dual-injection system, urea solution is injected as As expected the Standard-SCR (red line) reaction is
described above, while the injection of the AN solution is associated with the lowest NOx conversion in the whole
governed by the following rules: temperature range; instead, the Fast-SCR reaction (black
line) achieves 83 % of NOx conversion already at 175 C.
• Exhaust temperature at the SCR inlet must be between
Adding just 100 ppm of AN, the performance of the cat-
175 and 350 C.
alyst is enhanced with a gain in NO conversions of about
• Molar ratio of NO2 to NOx (NO ? NO2) at the SCR
35 % at 180 C if compared to the case of the Standard-
inlet must be \0.5
SCR where no AN was fed to the reactor. The improve-
• The injected quantity is calculated to allow the reaction
ment associated with the AN injection increases linearly
of NO oxidation by AN to proceed until
with growing AN feed concentration. Thus, when feeding
NO2:NOx = 0.5
200 ppm of AN, the conversion is incremented from
The required triggers and calculations have been approximately 10–80 %, with a further 35 % increment. If
implemented in Simulink and then integrated with the urea the AN feed concentration increases up to 250 ppm (the
solution injection strategy and the SCR system model. stoichiometric value for reaction (R.1), the DeNOx per-
formance improves up to 85 %, that is still lower than that
of the Fast-SCR.
3 Results and Discussion Further, the effect of co-feeding NO2 and AN to the Fe-
zeolite catalyst has been addressed. Figure 3a reports the
3.1 Lab Scale Test Rig Runs results obtained feeding 200 ppm of AN, in the presence of
250 ppm of NO2 and ammonia, oxygen and water, while in
First, the potential benefits due to the AN additive on the Fig. 3b the results of the well-know NO2 SCR reacting
DeNOx performance of the investigated commercial Fe- system, obtained feeding 500 ppm of both NO2 and NH3
zeolite catalyst were analyzed. Figure 2 reports the impact plus O2 and H2O, are shown.
of different AN feed concentrations (100, 200, 250 ppm) Figure 3a clearly demonstrates that there is a NOx
on the NOx conversion at GHSV = 75,000 h-1. The typ- conversion even in the co-presence of NO2 and AN, which,
ical feed composition for the steady-state runs are: however, is associated with a significant production of N2O
500 ppm of both NH3 and NO, 5 % of H2O and 8 % of O2 at temperatures below 400 C. The results however are not
in the presence of 100, 200 and 250 ppm of AN. Both the very different from those obtained at NO2 SCR conditions
curve of the Standard-SCR reaction (500 ppm of both NH3 (Fig. 3b). In this case, the reacting system resulted in lower
and NO, 5 % of H2O and 8 % of O2) and of the Fast-SCR NOx and ammonia conversions, and in a higher production
reaction (500 ppm of both NH3 and NOx, with 250 ppm of N2O in the whole investigated temperature range.
Based on the positive results from the steady-state runs,
a set of transient (TRM = Transient Response Method)
runs and steady-state experiments were performed in order
to address the mechanistic aspects of the Enhanced-SCR
100 F-SCR
chemistry [3, 4], in relation to the interaction between NO
and AN, and to identify its key steps. In order to eliminate
80 +250AN
NOx Conversion, %

+200AN
the contributions of Standard-SCR and/or NO oxidation, all
the TRM runs were performed without O2, at T = 200 C,
60 GHSV = 75,000 h-1 and H2O = 5 %. A typical TRM
result in which NO was fed to the reactor is shown in
+100AN
40 Fig. 4. At time t = 0 s the H2O pump was switched on to
feed 5 % of H2O ? about 250 ppm of AN. The NO con-
20 centration dropped instantaneously to roughly 270 ppm,
S-SCR
and, at the same time, NO2 formation started and its outlet
0 concentration promptly increased up to an average value of
100 150 200 250 300 350 400 450 500 550 600 230 ppm. This is clear evidence that AN is able to oxidize
Temperature, °C NO–NO2 very rapidly already at this low temperature
Fig. 2 NOx conversion over degreened Fe-zeolite under different SCR
according to the stoichiometry of reaction (R.2).
and E-SCR conditions versus catalyst T: GHSV = 75,000 h-1, Subsequently (t = 1700 s) 500 ppm of NH3 was also
H2O = 5 % (v/v), O2 = 8 % (v/v), NH3 = 500 ppm, NOx = 500 ppm added to the reactor feed stream, and the NO2 outlet

123
 Top Catal

500 500
A B

Concentration, ppm
Concentration, ppm 400 400

300 300
NH3
200 200
NO2 NO2
NO N2O
NO
100 NH3 100

N2O
0 0
200 250 300 350 400 450 500 550 200 250 300 350 400 450 500 550
Temperature, °C Temperature, °C

Fig. 3 Co-presence of AN and NO2 in the feed stream: GHSV = 75,000 kh-1; O2 = 8 % v/v; H2O = 5 % v/v NH3 = 500 ppm;
a NO2 = 250 ppm, NH4NO3 = 200 ppm; b NO2 = 500 ppm

600 2NH3 + NO2 + NO ! 2N2 + 3H2 O; ðR:3Þ

start feeding 250ppm AN
500 and the Standard-SCR,
NO 4NH3 + 4NO + O2 ! 4N2 + 6H2 O; ðR:4Þ
Concentration, ppm

400 start feeding 500ppm NH3

NOave=270ppm
a 0th kinetic order in ammonia was assumed as NH3 was
300 not a limiting reactant in our runs. A more detailed
description of the kinetic model fit results is presented in
200
NOave=60ppm
[5].
NO2ave=230ppm
Figure 5 shows the model fit at different temperatures
100
NO2 and for different amounts of injected AN as a function of
NH3 space velocity. In all cases, the very simple model was able
0
to account for the experimental results. The rate parameter
0 1000 2000 3000 estimates for (R.2) confirmed that NO oxidation by AN is
Time, s very fast at all conditions. This simple kinetic approach
was the first step in the development of a simulation tool
Fig. 4 AN (250 ppm AN) TRM runs versus time: T = 200 C,
GHSV = 75,000 h-1, H2O = 5 % (v/v), O2 = 0 % (v/v),
aimed at predicting the SCR catalyst performance in the
NH3 = 0–500 ppm, NO = 500 ppm real case scenario, accounting also for AN co-feed.

concentration quickly dropped to zero. After a transient, 3.2 Simulation Study

the NH3 and NO outlet concentrations achieved a steady-
state value around 60 ppm. The simultaneous consumption Figure 6 shows the system simulation results as integrated
of NO, NO2, and NH3 is strongly linked with the occur- NOx emissions in the World Harmonized Transient Cycle
rence of the Fast-SCR reaction. (WHTC) used for certification of heavy-duty vehicles for
Overall, the TRM run in Fig. 4 demonstrates that AN Euro VI. The cycle consists of cold and hot portions,
generates a good amount of NO2 by in situ oxidation of defined by the initial state of the engine and the exhaust
NO. NO2 is then consumed according to the Fast-SCR system. In the graphs, the point with AN:urea ratio = 0
stoichiometry. This suggests that there must be a direct corresponds to a system fed with standard AdBlue solution.
equivalence between AN and NO2, as feeding AN is a As the AN:urea ratio increases to 0.3, the NOx emissions
different way to supply NO2 to the system in order to are reduced in both cold and hot portion of the WHTC,
enable the Fast-SCR reaction. which indicates that the NO:NOx ratio in the exhaust gas at
Having identified such a simple reaction scheme, we the SCR catalyst inlet becomes closer to the optimum.
further proceeded in modeling this process. The adopted With further increase of AN content, the NOx emission
kinetic scheme consists of three reactions in which the key level increases, reflecting the fact that the excess of NO2 in
step is the oxidation of NO to NO2 by AN (R.2), followed the gas reduces the SCR catalyst activity.
by the Fast SCR reaction,

123
Top Catal

500 500
A B
concentration, ppm 400 400

300 NO 300

200 200
NO
100 100

NO2 NO2
0 0

500 500
C D
400 400
concentration, ppm

300 300

200 200

NO NO 100
100

NO2 NO2
0 0
40000 60000 80000 100000 40000 60000 80000 100000

GHSV, h-1 GHSV, h-1

Fig. 5 Comparison between model fit (solid line) and experimental NO = 500 ppm, a T = 180 C, AN = 100 ppm; b T = 250 C,
data (dots): species concentrations as a function of GHSV; AN = 100 ppm; c T = 225 C, AN = 200 ppm; d T = 180 C,
H2O = 5 %(v/v) ? AN, O2 = 8 %(v/v), NH3 = 500 ppm, AN = 250 ppm

0.7 0.7
NOx emissions, cold WHTC, g/kWh

NOx emissions, hot WHTC, g/kWh

A B
0.6 0.6 System 1
System 2
0.5 0.5
System 3
0.4 0.4

0.3 System 1 0.3

System 2
0.2 0.2
System 3
0.1 0.1

0.0 0.0
0.00 0.20 0.40 0.60 0.80 1.00 0.00 0.20 0.40 0.60 0.80 1.00
AN : Urea ratio AN : Urea ratio

Fig. 6 Cycle average NOx emissions versus the ratio of injected AN:Urea for three system architectures (Fig. 1) for cold (a) and hot (b) WHTC
simulation. Cycle averaged value is given for System 2

The System 2, with separate injection of urea and AN, is necessary for supporting NO oxidation, and only in the
shows roughly the same performance as the System 1 with necessary amount. Figure 7 shows the time-dependent
AN:urea = 0.3, but using much smaller quantity of injec- simulated values of NO:NOx ratio at the inlet to the SCR
ted AN. This is apparently the result of greater flexibility of catalyst, where the System 3 operates at the NO:NOx = 0.5
the dual injection system, which supplies AN only when it for a significant portion of the cycle.

123
 Top Catal

NO2 / NOx ratio NH4NO3, ppm TSCR in, °C

300
200
100

400

200

0
1.0
0.8
0.6
0.4
0.2
0.0
0 500 1000 1500 2000 2500 3000 3500 4000
time [s]

Fig. 7 SCR inlet temperature (upper plot), concentration of injected AN (middle plot), and NO2/NOx ratio at the SCR inlet (lower plot) versus
time in cold and hot WHTC for System 2. For NO2/NOx ratio, blue line corresponds to urea injection and red line corresponds to AN injection

The system simulation also indicates that the injection possibility for a reduction of Pt content in DOC and of the
of AN has a potential for reducing the size and cost of an corresponding cost of the aftertreatment system has been
SCR system while further improving its performance. The indicated. However, the feasibility of such a system needs a
results for System 3 in Fig. 6 show lower NOx emissions solution for soot oxidation in the DPF, usually supported
compared to Systems 1 and 2, and the increased optimum by the DOC and Pt coating of the DPF.
AN:urea ratio. The reduced NOx emissions can be attrib- Due to the significantly simplified nature of the model of
uted to increased temperature at the SCR catalyst inlet in AN reactions used for system simulation, the simulation
System 3 that, in the absence of the DOC and heat losses results should be considered at this stage as an indication of
from the DOC and connecting pipes, is heated up faster and trends. Further improvement of the model and experi-
operates at elevated temperature, compared to Systems 1 mental validation is necessary to more accurately define the
and 2. The removal of the DOC and of Pt coating form the potential for improvement of the system performance and
DPF results in lower NO2 concentrations at the DPF outlet costs resulting from AN addition to AdBlue.
(NO2:NOx ratio stays typically in the range of 0.05–0.1 for
heavy-duty engines), which increases the demand for AN Acknowledgments Financial support from the EU FP7-284909
Project ‘‘CORE—CO2 reduction for long distance transport’’ is
to provide for closer to optimal NO2:NOx ratio at the SCR gratefully acknowledged.
inlet.

References
4 Conclusions
1. Forzatti P, Nova I, Tronconi E (2010) Ind Eng Chem Res
Our study suggests that the AN additive can dramatically 49(21):10386
2. Forzatti P, Nova I, Tronconi E, Kustov A, Thøgersen JR (2012)
improve the low-T DeNOx activity of a Fe-zeolite SCR Catal Today 184:153
catalyst. Essentially, the role of AN is to generate NO2 3. Adelberg S, Schirmer S, Monteforte M, Schrade F, Bunar F, Kishi
readily in situ. Such NO2 can then react in the Fast-SCR A (2014) SAE Paper 2014-01-1554, SAE
reaction, which explains the enhanced low-T SCR activity. 4. Strots V, Kishi A, Adelberg S, Krämer L (2014) JSAE Paper
20145174, JSAE
The simulation of heavy-duty aftertreatment systems with 5. Marchitti F, Hemings EB, Nova I, Forzatti P, Tronconi E (2015)
AN additive indicates significant DeNOx performance Emiss Control Sci Technol 2:1–9
improvement potential, in both cold and hot WHTC. A

123