4 SCR mechanism
At present, many catalysts have been researched, but most of them lack enough clear knowledge of the reaction
mechanism. In this paper, the development progress of the mechanisms which remove NOx by different reducing
agents was summarized.
4.1 H2 and CO as the reducing agent
Some researchers use H2 and CO as the reducing agent to remove NOx in SCR,105107 which can get a high
conversion rate. According to a study, the effect of CO and NO is to reduce the bond length and separate the bond of
NO. The mechanism is as follows:105
NO(a) + CO(a) N(a) + CO2(a) (11)
NO(a) + H(a) N(a) + OH(a) (12)
N(a) + N(a) N2(g) (13)
Another possibility is:
CO(a) + NO(a) + HH(a) COO(a) + NH2(a) (14)
4.2 Hydrocarbons as the reducing agent
Some researchers studied the mechanism of a hydrocarbon as the reducing agent, because of the practicability and
cost-effectiveness. We can use the unburned hydrocarbons already present in the exhaust gas. In the process of
catalytic reduction, NOy,108 CH3NO109 or CH3NON2 109,110 can be formed from NOx. Due to the effect of the
catalysts of Y2O3, the first step is the formation of CH3 radicals from CH4, then these will react with NOx to form
CH3NO2, finally, CH3NO2 will become N2 via the intermediates of CH2NOH, CN, NCO and N2O. 109 At present,
the hydrocarbons used as a reducing agent to remove NOx mainly include methane, propane, propylene.
Aylor et al.111 analyzed the mechanism using MnZSM-5 as the catalyst and methane as the reducing
agent. First, the NO was oxidized to NO2, then NO2 adsorbed on the surface of the catalyst and reacted with CH4.
In the process of the reaction, CN and NCO were formed, and CN would react with NO2 quickly to generate N2 and
CO2. They suggested that cyanide is the active intermediate. Lobree et al.112 studied the mechanism that removed
NOx with C3H8 as the reducing agent (Fig. 3), but they did not explain the detailed reaction process between C3
H8 and nitrates, and did not reveal the rate controlling steps in the process of the reaction.
Fig. 3 Proposed mechanism for the reduction of NO by C3H8 over FeZSM-5.112
Satsuma et al.113 researched the catalysts involving Al2O3 as the carrier, including CuAl2O3 and AgAl2O3, for
the removal of NOx. They reported that the NO was oxidized by O2 to NO2, and then formed a nitrate species
which had a stronger oxidizing ability that could be adsorbed on the catalyst's surface. At the same time, C3H6 was
partially oxidized to an acetic salt species or other oxide. Then the species will react with nitrate to form NCO and
CN, which will continue to react with nitrate to finally form N2 and CO2. The author pointed out that the generated
N2 was the rate controlling step. Yu Yunbo et al.114 did similar research and got similar results, but Yu thought the
NCO's reaction was the rate controlling step.
In practice, hydrocarbons are composed of many kinds of alkanes, alkenes and alkynes. However, in the laboratory,
we generally use one of them to test and analyse. Different possible synergistic effects or antagonistic effects would
happen with the hydrocarbons during the catalysis. This can change the path which the catalysts react with NOx, so
it needs further research. Of course, it is difficult to completely simulate the physical truth, but it is also important to
reveal active intermediates in the process of the reaction and the rate controlling steps, taking into account the key
factors which affect the rate controlling step.
NH3 as the reducing agent
Many researchers have studied the mechanism of SCR by NH3. Concerning the reaction pathway over metal oxide
catalysts, most researchers suggested that NH3 was adsorbed to the Lewis acid center and intermediates like NH2
115,116 or adsorbed NH3 117,118 formed, then they reacted with aerial NO and NO2 through an ER (Eley-Rideal)
mechanism producing N2 and H2O. They can also react with activated nitrite intermediate adsorbed on the surface
of the catalysts through a LH (Langmuir-Hinshelwood) mechanism.
Marban et al.118 proposed an ER mechanism over carbon supported Mn3O4 catalyst, in which surface-active NH3
species reacted with NO2, and to a lesser extent NO, from the gas phase (see Fig. 4). Richter et al.119 supposed
symmetric O=NON=O species formed on the MnOx/NaY catalyst after contact with NO. They suggested a
diazotization mechanism, in which NH3 was protonated to NH4 +, NO interacts with the catalyst, and nitrite and
nitrate surface species formed in the presence of O2. Followed by NH4 + reacting with NO2_ to produce N2 and
H2O. However, a parallel amide/nitrosamide SCR reaction route was possible since prevailing Lewis acid sites on
these catalysts should enable NH3 activation via amide species. Meanwhile, some researchers investigated the
mechanisms of Cu and Fe on zeolite catalysts. For Fe/zeolite catalysts, it is supposed that Fe3+ ions with oxo-Fe3+
sites,29 binuclear ions [HOFeOFeOH]2+ 120 and others were the active sites for the SCR reaction.
Fig Mechanism of the steady-state SCR reaction in the absence of oxygen;
Fig. 4 Mechanism of the steady-state SCR reaction in the presence of oxygen.118
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