SEPARATION SCIENCE AND ENGINEERING

Chinese Journal of Chemical Engineering, 18(2) 244ü248 (2010)

Absorption of NOx into Nitric Acid Solution in Rotating Packed Bed*

LI Yu (ह၆)1, LIU Youzhi (ঞပᄦ)1,**, ZHANG Luyao (჆াྊ)2, SU Qiang (പஜ)2 and
JIN Guoliang (ࠡ‫ڳ‬॥)2
1
Research Center of Shanxi Province for High Gravity Engineering and Technology, Institute of Chemical Engi-
neering and Environment, North University of China, Taiyuan 030051, China
2
Gansu Yinguang Chemical Group Co., Ltd., Baiyin 730900, China

Abstract Absorption of NOx into nitric acid solutions was studied in the presence of ozone by using a rotating
packed bed (RPB) contactor. The influences of operating parameters, such as high gravity number, amount of ozone,
gas velocity, liquid spray density and inlet concentration of NOx, on the removal efficiency of NOx were investi-
gated, among which the high gravity number and ozone amount are more important. Ozone was introduced to oxi-
dize HNO2 to HNO3 to prevent the decomposition of HNO2 in the liquid phase. The high gravity number presents
the effective external force for enhancing the mass transfer of ozone from gas phase to liquid phase. Under the ex-
perimental condition, the removal efficiency of NOx is higher than 90% and the concentration of nitric acid product
exceeds 45%.
Keywords nitrogen oxides, rotating packed bed, ozone oxidation, absorption

1 INTRODUCTION NO (g)  NO2 (g) YZZZZX N2O3 (g) (3)

The removal of NOx in industrial tail gas, mainly
arising from nitric acid towers, nitration reactors, de-
vices for catalyst sintering, has drawn extensive atten-
tion [1, 2]. The catalytic reduction method, a dry tech-
nique, for direct conversion of NOx to N2 has been
studied extensively [3, 4], which needs additional heat
consumption or has technological complexity. More
attention is paid to the wet method, in which NOx with
higher concentration is absorbed and oxidized to pro-
duce nitric acid, without generating other polluting
byproducts. The main drawbacks of these wet tech-
niques are that the solubility of NOx in water is low and
nitric acid is too dilute to recycle. The NOx absorption
process is primarily affected by its oxidation degree
that depends on the composition of nitrous gas [5]. To
increase the overall NOx absorption rate, oxidizing
agents are usually introduced either in the gas phase
(chlorine dioxide, chlorine, and oxygen gas) or in the
liquid phase (potassium permanganate, sodium chlo-
rite, potassium dichromate, and hydrogen peroxide)
[68]. As well known, ozone is a clean oxidant and can
enhance the NOx removal efficiency and increase the
concentration of nitric acid solutions, because it con-
verts NOx to absorbable species.
The absorption of NOx mixture into aqueous so-
lutions is carried out generally in packed columns or
plate columns [9, 10]. The chemical species in the gas
phase are NO, NO2, N2O3, N2O4, O2, and other inert gas
species. The gas phase reactions considered in this
study are:
2NO (g)  O2 (g)  o 2NO2 (g) (1)
ZZX N2O4 (g)
2 NO2 (g) YZZ
The mass transfer processes between the gas
phase and liquid phase are as follows,
NO2 (g)  o NO2 (l) (4)
N2O3 (g) 
o N2O3 (l) (5)
N2O4 (g)  o N2O4 (l) (6)
The gaseous components are absorbed into the
liquid phase. For pure water or nitric acid solution, the
following reactions are considered.
ZZX HNO2 (l)  HNO3 (l) (7)
2NO2 (l)  H2O (l) YZZ
N2O3 (l)  H2O (l) 
o 2HNO2 (l) (8)
2N2O4 (l)  H2O (l)  o HNO2 (l)  HNO3 (l)(9)
3HNO2 (l) YZZZZX 2NO  HNO3 (l)  H2O (l) (10)
The presence of ozone in the liquid phase im-
proves the NOx absorption by oxidizing HNO2 in the
liquid instantaneously. In an acidic system at ambient
temperature, the reaction is
3HNO2 (l)  O3 (l)  o 3HNO3 (l) (11)
HNO2 is unstable in liquid phase, as shown in
reaction (10), and decomposes with the release of NO.
HNO2 is oxidized to HNO3 in the presence of ozone,
increasing the NOx absorption. Reaction (11) is a fast
reaction and the mass transfer of ozone is the control-
ling step. In a conventional tower, the mass transfer
resistance is relatively large owing to the thick liquid
film and slow surface renewal. Rotating packed bed
(RPB) is a novel effective device to intensify the mass
transfer in multiphase systems, in which the volumet-
ric mass transfer coefficient is 13 orders of magnitude
larger than that in conventional towers. RBP has been
(2) applied in distillation [11], absorption [12], adsorption [13],

Received 2009-06-19, accepted 2009-11-09.

* Supported by the Fund of Science and Technology of Shanxi for Young Scholars (2007021012) and Research Project of
Shanxi Provincial Science and Technology Department (20090321113).
** To whom correspondence should be addressed. E-mail: hgliyu@nuc.edu.cn
 Chin. J. Chem. Eng., Vol. 18, No. 2, April 2010 245

reaction, etc [14]. Table 1 Specification of RPB used in the experiment

In this work, RBP is applied as a contactor for
Items Value Unit
NOx absorption into nitric acid solution in the pres-
ence of ozone. The performance of absorption is evalu- shell diameter of casing 300 mm
ated. The influences of operating parameters, such as inner diameter of packing 100 mm
high gravity number, ozone amount, gas velocity, liq- outer diameter of packing 290 mm
uid spray density and inlet concentration of NOx, on
the NOx removal efficiency are investigated.. axial height of packing 200 mm
density of packing 8500 kg·m3
2 EXPERIMENTAL specific area of packing 1200 m2·m3
void fraction of packing 0.95 m3·m3
2.1 Materials
type of packing steel wire mesh

The NOx tail gas was from nitration reaction de-

vice (Yinguang Chemical Industry Co., Gansu, China),
and the NOx concentrations in the inlet and outlet gas
streams were measured with the chemical analysis and
a flue automatic analysis apparatus (Model KN9106,
Kane Quintox Co., UK). The ozone gas was from an
ozone generator (Liu Bang Photoelectric Equipment
Co., Shandong, China), and the ozone concentrations
in the inlet and outlet gas streams were measured with
an ozone monitor (GM-6000-OEM, Anseros, Germany).
The nitric acid concentration was determined by chemi-
cal analysis. Deionized water was used throughout the
experiment.
2.2 Setup
A schematic diagram of the setup is shown in Fig. 1.
The RPB consists of a rotator and a case. The speed of
the rotator is controlled by a regulator. The specifica-
at the inner edge. The dilute nitric acid (pure water at
the beginning) influent is introduced from the circu-
lating tank into the inner edge of the rotor through a
distributor, which is a tube with holes on the wall, at a
relatively high velocity. The liquid moves outwards
due to the centrifugal force and leaves the rotor at the
outer edge. Finally, the liquid is discharged from the
bottom of RPB. To prevent the gas stream exiting from
the liquid outlet, a liquid level controller is used in the
buffer tank. The temperature of liquid feed is controlled
by a heat exchanger operated counter-currently with
water coolant. The experimental conditions are pre-
sented in Table 2.
Table 2 Experimental parameters in the study
Items Value Unit
gas velocity İ1700 m ·m2·h1
3

tion of the RPB contactor is given in Table 1.

liquid spray density İ30 m3·m2·h1
inlet concentration of NOx (NO2) 200240 g·m3
2.3 Procedure
inlet concentration of oxygen 16% mol·mol1
absorption temperature 283295 K
In normal operations, the NOx tail gas from the
nitration reactor is mixed with the ozone gas from the total pressure (absolute) 78 kPa
ozone generator in baffler vessel and then enters the mitric acid concentration İ48 % (by mass)
RPB. The gas flows inwardly from the outer edge of amount of ozone added İ10 g·m3
the rotor by pressure driving force and leaves the rotor

Figure 1 Diagram of experimental setup

1üoxygen cylinder; 2üozone generator; 3übuffer vessel; 4üheat exchanger; 5ürotating packed bed; 6üdilute nitric acid circu-
lating tank
246 Chin. J. Chem. Eng., Vol. 18, No. 2, April 2010
3 RESULTS AND DISCUSSION
3.1 Effect of high gravity number and amount of
ozone
To show the effect of structural factors of RPB on
the removal efficiency, high gravity number is em-
ployed as a group of variables including the rotating
speed and the mean value of packing diameter [15].
The rotor speed ranges from 0 to 1500 r·min1 and the
high gravity number is between 0 and 250.
The effects of high gravity number and ozone
amount on the removal efficiency are shown in Fig. 2.
The effect of high gravity number has a similar trend
for different amount of ozone, while the effect is little
without ozone added. The removal efficiency in-
creases with the amount of ozone added when it is
below 6 g·h1, but it increases little when the ozone
amount changes from 6 to 10 g·h1. The removal effi-
ciency increases sharply and then changes little with
the increase of high gravity number, and the removal
efficiency reaches 95% at high gravity number of 110.
Thus ozone plays an important role in the absorption
of NOx into nitric acid solutions, and the high gravity
number is an effective external force for enhancing the
ozone oxidation, providing an additional positive ef-
fect on the mass transfer of ozone. The high gravity
number increases the interfacial area and reduces the
mass transfer resistance of ozone by decreasing the
thickness of liquid films and the size of droplets. The
optimum operating condition is that the high gravity
number is larger than 110 and ozone is added with a
rate higher than 6 g·h1.
Figure 2 Effect of high gravity number on removal effi-
ciency at different ozone velocity
(Average inlet NOx concentration 220 g·m3, gas velocity 800
m3·m2·h1, liquid spray density 18 m3·m2·h1, nitric acid con-
centration 20%, absorption temperature 280290 K, absolute
pressure 78kPa)
adding ozone/g·h1:ƺ0; 1; 2; 3;ƿ4; 5;ƻ6; +8; × 10
3.2 Effect of gas velocity and liquid spray density
Figure 3 shows the effects of gas velocity and
liquid spray density on the removal efficiency. The
removal efficiency decreases with the increase of gas
flow velocity at these liquid spray densities. An in-
crease in the gas velocity reduces the mass transfer
Figure 3 Effect of gas velocity on removal efficiency at
various liquid spray densities
(Average inlet NOx concentration 220 g·m3, high gravity
number 110, ozone amount added 8 g·h1 liquid, nitric acid
concentration 20%, absorption temperature 280290 K, abso-
lute pressure 78 kPa)
liquid spray density/m3·m2·h1: ƺ 45; 40; 35; 30;
20; 5;ƻ10; +15
resistance and the contact time between gas and liquid.
The former enhances the mass-transfer rate, but the
latter exhibits a reverse effect. The observation indi-
cates that a reduction in the contact time has more
effects on absorption than a decrease in the mass
transfer resistance. Therefore, moderate gas velocity is
more favorable for NOx removal, but it is no more
than 800 m3·m2·h1 in the experimental RPB contactor.
The removal efficiency increases markedly with the
liquid spray density, but it varies little when the liquid
spray density is higher than 20 m3·m2˜h1. An increase
in liquid spray density reduces mass transfer resis-
tance on the liquid side and provides more absorbent,
which is favorable in the NOx absorption. The optimal
liquid spray density is 20 m3·m2·h1 in this study.
3.3 Effect of inlet NOx concentration at various
nitric acid concentrations
Figure 4 shows that the removal efficiency
Figure 4 Effect of inlet NOx concentration on removal
efficiency at various nitric acid concentrations
(Absorption temperature 280290 K, absolute pressure 78
kPa, gas velocity of 800 m3·m2·h1, liquid spray density 18
m3·m2·h1, high gravity number 110, ozone amount added 8
g·h1 liquid)
water;Ƹ HNO3 15%;ͪHNO3 30%; ƺHNO3 45%
 Chin. J. Chem. Eng., Vol. 18, No. 2, April 2010 247

Table 3 Comparison for NOx absorption into aqueous solution

Partial pressure of Gas velocity Nitric acid Removal
Reference Contactor Absorbent
NOx in the feed/Pa /m3·m2·h1 concentration/mol·L1 /%
Paiva et al. [10] 1211336 2160 packed column H2O2(0.05 mol·L1)+H2O 01 İ63
1
Thomas et al. [6] 50500 630 packed column H2O2(0.02 mol·L )+H2O 04 İ70
Pollo et al. [16] 1131134 ü packed column O3+H2O ü İ85
Li et al. (this article) 200900 1700 RPB O3+H2O 04 ı90

Figure 5 Mechanism of NOx absorption into acid solution in the presence of ozone

decreases nearly linearly as the initial concentration of
NOx increases. The removal efficiencies at nitric acid
concentration of 15%45% are close. This implies that
although there exists absorption reaction equilibrium,
the ozone oxidizes nitrous acid in the liquid phase to
prevent its decomposition, in which the oxidation re-
action is catalyzed by hydrogen ions, resulting in ni-
tric acid product with higher concentration.
3.4 Comparison for the NOx removal in this work
with those in literature
Table 3 compares the NOx removal in this work
with those in literature. In the NOx absorption process,
oxidation of nitrogen mono-oxide by oxygen is a very
slow third order reaction, and at concentrations nor-
mally encountered the absorption time and volume of
absorber would be prohibiting. In the presence of hy-
drogen peroxide or ozone the equilibrium state is
shifted, the oxidation is much faster and then nitrogen
oxides in water as well as in nitric acid of higher con-
centrations can be treated. The strong oxidant ozone
accelerated the oxidation, the slowest stage of absorp-
tion in nitric acid. It appears that the contribution of
ozone to absorption of NOx is more prominent than
the hydrogen peroxide. The high gravity number pre-
sents the effective external force for enhancing the
mass transfer of ozone from gas phase to liquid phase.
4 CONCLUSIONS
A novel method for removal of NOx in industrial
tail gas was investigated with a RPB contactor. Under
the experimental condition, the optimum operating
condition is that the gas velocity is less than 800
m3·m2·h1, the high gravity number is larger than 110,
and the liquid spray density is higher than 20
m3·m2·h1. The removal efficiency of NOx is higher
than 90% and the concentration of nitric acid product
is higher than 45% in the presence of ozone oxidation.
The dissolution of HNO2 is accompanied by a
rapid reaction with ozone in the liquid phase and in-
tensified in the RPB contactor, so that the absorption
amount of NOx is increased. The mechanism of NOx
absorption into nitric acid solutions in the presence of
ozone is represented in Fig. 5.
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