ISSN 1070-4272, Russian Journal of Applied Chemistry, 2014, Vol. 87, No. 4, pp. 434−438. © Pleiades Publishing, Ltd.

, 2014.
Original Russian Text © E.A. Spetsow, L.A. Nefedova, S.A. Lavrishcheva, 2014, published in Zhurnal Prikladnoi Khimii, 2014, Vol. 87, No. 4, pp. 440−445.

SORPTION
AND ION EXCHANGE PROCESSES

Chemisorption of Microimpurities of Nitrogen(II)

and (IV) Oxides in the Presence of an Excess Amount of Oxygen
E. A. Spetsow, L. A. Nefedova, and S. A. Lavrishcheva

St. Petersburg State Technological Institute (Technical University), Moskovskii pr. 26, St. Petersburg, 190013 Russia
e-mail: evgeniispetsow@yandex.ru

Received January 13, 2014

Abstract—Chemisorbents and chemical absorbents synthesized by impregnation of a γ-Al2O3 substrate with

active components in the form of transition metal oxides and potassium salts of metallic acids are recommended
for application. The sorbents are intended for neutralization of microconcentrated nitrogen mono- and dioxides
from an oxygen-enriched medium. The synthesis parameters and physicochemical properties of the sorbents are
presented and the conditions of the most effective operation of each type of sorbents are specified.
DOI: 10.1134/S1070427214040065

Various industrial processes (welding, maintenance of
the rolling stock and fuel reservoirs and functioning of
nitrogen industry shops, thermal power plants, and cata-
lytic generators of artificial atmosphere) are accompanied
by both local and general contamination of air in a work
station by toxic nitrogen oxides. However, lowering the
oxygen of NO and NO2 (NOx) in the working-area atmo-
sphere to the maximum permissible concentration level
(2–5 mg m–3) by organization of an inlet-and-exhaust
ventilation and by using the classical methods of absorp-
tion catching or selective catalytic reduction are, as a rule,
inefficient. The optimal solution to the given problem is
to include filters of design containing a cartridge with
a high-efficiency adsorbent into the purification process.
The main industrial adsorbents for absorption of NOx
are activated carbons, carbon fibers, and high-porosity
metal oxide systems [1–3]. NO and NO2 molecules are
adsorbed on these materials under the action of intermo-
lecular interaction (Van der Waals) forces of the orienta-
tion and induction types. However, at a substantial excess
of molecular oxygen relative to NOx microimpurities in
the gas being purified, the selectivity of the adsorption
process with respect to O2 is substantially higher. This
circumstance leads to a nearly full blocking of the active
surface and, as a consequence, makes impossible provid-
ing the required purification level.
It is known [4, 5] that CeO2 has oxygen-exchange
properties and, combined with active sorbents of nitro-
gen dioxide (e.g., Mn, Cu, or FE oxides) in an oxygen-
enriched medium, can promote oxidation of NO delivered
from the gas flow, with its simultaneous transition to the
state of a surface complex firmly retained by chemisorp-
tion interaction forces.
The patent [6] suggested using potassium permanga-
nate that deposited onto an aluminum oxide support and
serves as an active oxidant of NO to NO2 due to the high
reactivity of oxygen in the active phase. It was noted that
manganese present in the composition can exhibit sorp-
tion properties with respect to the product being formed.
A high chemical activity toward nitrogen oxides can
also be exhibited by other substances in whose presence
the activity of the surface oxygen in the lattice is enhanced
under the influence of an alkali metal cation, e.g., in po-
tassium metavanadate [7, 8].
One of the most important texture characteristics
responsible for the efficiency of sorption materials is
the active surface area of a sorbent. It is possible to use
for this purpose a high-porosity support, e.g., γ-Al2O3
with a large degree of accessibility of the inner surface
of pores in grains and with a low hydraulic resistance of
a stock bed.

434
 CHEMISORPTION OF MICROIMPURITIES
The goal of our present study was to synthesize sup-
ported sorption materials and examine their physico-
chemical properties in purification of an air medium to
remove microscopic concentrations of NO and NO2. In
doing so, we considered new methods for their neutraliza-
tion: by chemisorption on the surface of a mixed oxide
matrix, one of whose components is an ionic conductor
of oxygen, and also by chemical absorption with the use
of strong oxidizing agents.
EXPERIMENTAL
We studied the sorption, texture, and structural proper-
ties of samples of supported chemisorbents and chemical
absorbers. As the starting support was chosen γ-Al2O3,
among the previously suggested materials produced from
gibbsite, pseudoboehmite, and anhydrous α-Al2O3 [9].
The specific inner pore surface area Ssp of the sup-
ports and sorbents were determined chromatographically
from the thermal desorption of nitrogen. The pore radii
and the pore size distribution over equivalent pore radii
were determined by mercury porosimetry on a PA-3M
device in the range 3.5–3 500 000 nm. Surface groups of
elements and intermediate complexes were identified by
IR spectroscopy (spectral range 4000–400 cm–1, resolu-
tion 0.1 cm–1) with an appropriate software processing.
The phase states of the components in the samples were
determined on a DRON-2 X-ray diffractometer with
CuKα radiation and N-filter. The temperature of phase
changes in the structure of solids were found by using
the thermogravimetric method in the temperature range
50–750°C in air on a Q-1500D derivatograph (Hungary)
equipped with software. The wear strength Sw of grains
was calculated as the ratio between the mass of grains
disintegrated in a centrifugal mill to their initial mass.
The mechanical strength of grains along the generatrix,
Sg, was determined on an IPG-2 tensimeter at a fixed
limiting load related to the impact area.
The sorption of NO and NO2 was performed on a flow-
through dynamic installation with a single-channel tubular
adsorber with a combined electric-heating unit. Experi-
mental conditions: volumetric air flow rate 0.3 m3 h–1;
water vapor content in dried air flow, up to 10 mg m–3;
concentration of nitrogen(II) and (IV) oxides (in terms
of NO), 110–220 mg m–3; variable NO/NO2 ratio; atmo-
spheric pressure; inner absorber diameter 30 mm; sorbent
charge volume 30 cm3. The process temperature was
measured and controlled with a PID controller of TRM
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 87 No. 4 2014
435
brand (OVEN OOO, St. Petersburg) and a Chromel–Co-
pel thermocouple. The NO and NO2 concentrations were
recorded with a R-310S chemiluminescent gas analyzer
(OPTEK ZAO, St. Petersburg) with a preliminary prepa-
ration of samples from the gas flow being analyzed. The
sorption efficiency was calculated as the ratio between the
amount of the oxides NOx absorbed from unit volume and
their initial concentration in the flow. The catalytic activ-
ity was determined as the ratio of the difference between
the NO concentrations before and after the reaction to
the initial NO concentration. The total pore volume was
found by the pycnometric method against distilled water.
Among the already developed supports, we chose as
having the most pronounced texture properties the alumi-
num oxide support based on pseudoboehmite to synthe-
size on its basis chemisorbents and chemical absorbents
of nitrogen(II) and (IV) oxides, with various qualitative
and quantitative compositions.
Texture properties of the support for chemisorbents
and chemical absorbents: final processing temperature
520–540°C; specific surface area 228 m2 g–1; total pore
volume 0.70–0.80 cm3 g–1, wear resistance 99.8%, crash-
ing strength along the generatrix, 9.0 ± 1.0 MPa; grain
size 0.8–1.25 mm. Pore radius distribution (nm, %):
3.5–10, 85–90; 10–100, 1.5–2; 100–1000, 0.3; 103–104,
0.5; (1–5) × 104, 0.5–1.
The chosen support is intended to provide a high effi-
ciency of the competitive sorption of NOx, compared with
O2 molecules, as well as an increased sorption capacity
for the target components. The high temperature of the
final thermal treatment of the support makes it possible
not only to perform the NOx sorption process in a wide
temperature range, but also create materials capable of
being thermally regenerated on performing a desorption
purification cycle.
The composition and the texture properties of pilot
sorbent samples are listed in the table.
The samples under consideration were obtained by
a single deposition onto the chosen support of salts pre-
cursors of the active phase from their aqueous solutions,
followed by stepwise thermal treatment in air.
The conditions chosen for forming the sorption matrix
for sample CS and chemical absorbent CO2 is substanti-
ated by the results of a preliminary differential-thermal
analysis (DTA) of supported salts (Fig. 1).
When a mixture of nitrates is heated, two endothermic
peaks reflecting the general process of water desorption
and decomposition of salts are observed in the tempera-
436 SPETSOW et al.

Composition and properties of adsorbent samples

Mass fraction of an active component, %
Sample Ssp, m2 g–1 VΣ, cm3 g–1
MnO2 CeO2 KMnO4 K2MnO4 KVO3
CS 5 5 – – – 173 0.65
CO1 – – 7.9 – – 249 –
CO2 2.2 – – 5.0 – 234 0.67
CO3 – – – – 9.7 227 –

ture range 58–490°C. No effects at higher temperatures,
whose could indicate that a new phase is formed from
Mn and Ce oxides, were observed, just as reflections
associated with crystallization of individual oxides. In
decomposition of supported potassium permanganate,
peaks of water desorption at 120°C and formation of the
potassium manganate and manganese dioxide phases at
280–380°C are observed in addition to release of oxy-
(a)
TG
DTA
T, °C
TG (b)
DTA
T, °C
Fig. 1. Derivatograms of samples (a) [Ce(NO3)3 + Mn(NO3)2]/γ-
Al2O3 and (b) KMnO4/γ-Al2O3. (T) Temperature.
gen. At temperatures higher than 400°C, potassium salts
presumably interact with the structure of the support.
Thus, the process of phase transformation of sup-
ported nitrate salts of Mn and Ce for the CS sorbent was
performed in the following thermal treatment mode:
curing (20–25°C, 24 h), drying (100°C, 4 h), stepwise
thermal treatment up to 500°C (heating rate not exceed-
ing 25 deg min–1).
The conditions chosen for thermal treatment of
samples containing potassium permanganate and meta-
vanadate are substantiated by the data on the temperature
stability of their aggregative and phase state. On being
heated, KVO3 does not change its qualitative composition
and its melting begins at 520°C [10], and, therefore, it is
advisable to perform the thermal treatment of sample CO3
up to 300°C to only exclude physically bound water from
the material. In accordance with the DTA data (Fig. 1b),
375°C was chosen as the highest treatment temperature
for sample CO2.
Figure 2 shows X-ray diffraction patterns of the
synthesized CS chemisorbent, reference samples with
a single-component active matrix, and support. Accord-
ing to the results of an X-ray phase analysis, the systems
containing manganese oxide are insufficiently structured
under the given thermal treatment conditions and have
a mostly amorphized structure.
For example, the pronounced peaks in X-ray diffrac-
tion patterns 1 and 2 (Fig. 2) indicate that the phases of
the support and supported cerium dioxide, respectively,
are sufficiently crystallized. In this case, the dioxide
CeO2 has a structure of the fluorite type. The sample with
a supported manganese dioxide (diffraction pattern 2) is
mostly composed of anamorphous phase, even though
there are low-intensity reflections with the corresponding
interplanar spacings d/n of 3.23, 2.48, and 1.65 nm. The
simultaneous presence of manganese and cerium dioxide
phases in sample CS (diffraction pattern 4) results in an

RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 87 No. 4 2014

 CHEMISORPTION OF MICROIMPURITIES 437

increased amorphicity of the given solid solution, which

must probably have a positive effect on the sorption ca-
pacity of the formulation under consideration. It is also
noteworthy that making the thermal treatment at 450°C
longer did not raise the degree of crystallinity of the active
phase of sample CS, i.e., the structure is at equilibrium in
the temperature range under consideration.

RESULTS AND DISCUSSION

The main stage in our study of the sorption properties

of the samples consisted in their testing under the condi-
tions of a varied process temperature. The goal of these
experiments was to examine the effect of this temperature
on the rate of sorption processes and to find the optimal
temperature conditions for neutralization of NOx under
isothermal conditions.
The sorption properties of the materials were studied
in the temperature range 20–500°C. It is noteworthy
that, among the samples presented here, CO1 does not
possess the high thermal stability of supported potassium
permanganate, and, therefore, its sorption properties were
examined only at room temperature. In particular, a high
activity of CO1 in sorption of both NO and NO2 was
observed: the degree of extraction of these components
from an air flow during 3.5 of operation of the sorbent
was 97.5–99.9 and 82–96%, respectively, with the time
in which the maximum operation efficiency is reached
being 0.5 h.
At the same time, near full absence of sorption effects
in the temperature range 20–540°C was noted for sample
CO3, for which only catalytic oxidation of NO into
NO2 occurs. In this case, the process is characterized by
a degree of oxidation X for the exothermic reaction that
has the maximum value of about 26% at 420°C (Fig. 3).
This circumstance indicates that the ambient oxygen
has no effect on sorption processes occurring on sample
CO1, for which a high degree of NOx neutralization is
reached via their chemical interaction with the component
of the active phase, rather than via formation of surface
associates with structural oxygen.
It is known [11] that, depending on temperature, the
interaction of chemisorbed species with the active phase
of semiconductors, including metal oxides, can be char-
acterized by two kinds of chemisorption: molecular and
dissociative. The transition between the given states, ac-
companied by a rearrangement of bonds between solutes
and the sorbent, is manifested in a certain decrease in
the process rate for the target substances. The effect of
2θ, deg
Fig. 2. X-ray diffraction patterns of Mn–Ce–Al oxide for-
mulations. (2θ) Bragg angle. (1) γ-Al2O3, (2) MnO2/γ-Al2O3,
(3) CeO2/γ-Al2O3, (4) CS ([MnO2 + CeO2]/γ-Al2O3).
temperature on the course of particular processes on the
surface of the chemisorbents under study can be traced
using the plots in Fig. 4.
With the temperature increasing to 100–120°C, the
sorption rate of both components by sample CS decreases.
As, however, the temperature increases further, the sorp-
tion capacity again grows due to the processes described
above. It is important to note that presence of oxygen is a
positive factor for the given system, which is confirmed
by the experiment on NO chemisorption from nitrogen.
The maximum degree of neutralization of about 86%
was observed in the given case and it decreased to 54%
in 1.3 h. An experiment on chemisorption of NOx from
air at room temperature (20°C) demonstrated that the
system under consideration can 94–96% neutralize the
given components during 4 h.
X, %
T, °C
Fig. 3. Effect of temperature T on the degree X of NO xida-
tion on sample CO3. The NO/NO2 mass ratio in the starting
mixture was 4.2.

RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 87 No. 4 2014

438
ω, mg NOx/(cm3 h) (a)
ω, mg NOx/(cm3 h) (b)
Fig. 4. Sorption rate ω of (a) NO and (b) NO2 for samples (1)
CS and (2) CO2 vs. temperature T.
By contrast, sample CO2 was less susceptible to
the effect of temperature and retained a high sorption
efficiency (96–98%) for total NOx nearly in the whole
temperature range 20–250°C. An insignificant decrease
in the sorption rate could be only observed on exceeding
the temperature of 170°C. It should, however, be noted
that tests of the duration of the protective effect at room
temperature demonstrated that the maximum sorption
efficiency decreases already after 1.8 h of operation of
the given material.
CONCLUSIONS
Microconcentrated nitrogen mono- and dioxide can be
neutralized with nearly the same efficiencies (94–98%)
by two methods: chemisorption on a Mn–Ce oxide matrix
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 87 No. 4 2014
SPETSOW et al.
or on a mixture of potassium manganate and magnesium
dioxide, deposited onto a high-porosity aluminum oxide
support. In the first case, a high sorption capacity is
provided by oxygen-exchange properties of cerium ox-
ide, and in thec second, due to the high dispersity of the
sample surface formed in decomposition of the supported
potassium permanganate. The service characteristics of
the chemisorbents imply that they are capable of being
thermally regenerated after performing a cycle of purifi-
catuionj to remove NOx. The process of chemisorptinon
T, °C both materialsis the most fficient at room temperatures
20–50°C.
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