270 Chem. Eng. Technol.

I4 (1991) 270-274

Absorption of Nitric Oxide in Dilute Nitric Acid

Werner Weisweiler, Klaus Eidam, Michael Thiemann, Erich Scheibler and

Karl Wilhelm Wiegand*

This paper presents laboratory-scale measurements on the absorption of nitric oxide in dilute
nitric acid. The NO concentration in the gas feed varied from 250 to 10 000 ppm. Nitrogen was
used as carrier gas. The concentration of nitric acid was between 30 and 60 mass-%.
Temperature during the measurements was set at 25 “C. In order to determine mass flow rates,
experiments were performed in a double-stirred cell. This type of absorber has a defined gash-
quid interface as the mass transfer area. The liquid phase is introduced periodically and the gas
phase continuously. A well-known model was used to describe the phenomenon of NO absorp-
tion. Several balance equations were established and solved. The calculated mass transfer rates
were compared with those obtained experimentally. The empirical and theoretical data are in
satisfactory agreement.

1 Introduction K,
2 NO + HNO, + H,O $ 3 HNO, .
The production of nitric acid according to the Ostwald process
involves the combustion of ammonia to nitric oxide which, in They suggested the following mechanism:
turn, becomes oxidized to NO,. The last step of the process is
the absorption of nitrogen oxides in water to produce HNO,. HNO, + H + + NO; $ N20, + H,O , (2)
There is still scope for elucidation of the absorption step of this
process, although it has been applied since the beginning of this
2 NO + N,O, + 2 H,O 4 HNO, . (3)
century and should, therefore, be well-known in all its details. Reaction (2) was assumed to be slow and, thus, rate determin-
The worldwide demand for environmental protection enforces ing. Reaction (3) may be regarded as a series of elementary
a reduction in the concentration of noxious components of steps and it is known to be fast. Neglecting the reverse reactions
waste gases by as much as possible. Hence, the dimension of of (2) and (3), the rate expression is given by’’:
the absorption tower has to be optimized accordingly.
1 d[NO] 1 d[HNO,]
In view of this, more sophisticated calculation methods for I=-- ___ - ~= k [ H + ] [NO;] [HNO,] .
2 dt 3 dt
designing the absorption step of the nitric acid production pro- (4)
cess are being developed. The physico-chemical data, which
The equilibrium system of NO, NO,/N,O,, HNO,, HNO, and
are required for this purpose, refer to the chemisorption of NO
H,O was measured by Theobald [4].Carta and Pigford [5] cor-
and NO,/N,O, in water. These reactions are only relevant at
related Theobald’s data in terms of two independent reactions:
the water inlet to the absorption tower. However, increasing
reaction between the noxious gases and the liquid phase leads K2
to increasing concentrations of reaction products in water. 3 NO, + H,O 2 HNO, + NO (5)

A kinetic investigation of the chemisorption of NO,/N,O, in K3

diluted and concentrated nitric acid has already been published NO + NO, + H,O $ 2 HNO,
in this journal. The aim of the present study is to examine the
kinetics of absorption of nitric oxide in nitric acid of different Empirical equilibrium constants are obtained for reactions (5)
concentrations. and (6):

(7)
2 Reactions of NO in Nitric Acid

Several researchers investigated the reactions of NO in nitric

acid. Abel and co-workers [l -31 found that nitrous acid is
formed:
~.
Combining (7) and (8), the equilibrium constant of reaction (1)
* Prof. Dr. W. Weisweiler, Dip1.-Chem. K. Eidam, Institut fur
Chemische Technik, Universitat Karlsruhe, KaiserstraBe 12, D-7500 is defined as
Karlsruhe 1, Dr.-Ing. M. Thiemann, Dip].-Ing. E. Scheibler and Dr.-
Ing. K. W. Wiegand, Uhde GmbH, Friedrich-Uhde-StraBe 15, D-4600
Dortmund 1. 1) List of symbols at the end of the paper.

0 VCH Verlagsgesellschaft mbH, D-6940 Weinheim, 1991 0930-7516/91/0408-0270 $03.50+ ,2510

Chem. Eng. Technol. 14 (1991) 270-274 27 1

On the liquid side, the above chemical reactions have to be

(9) taken into account. Therefore, Eqs (15) and (16) are valid:

d2cNO
The values of K , are given by Carta and Pigford [ S ] for a DNo,l ~ = kl CHN02 9
temperature of 25 “C: dY2

In K , = 10.359 -

3 Theory of Mass Transfer with boundary conditions

The description of the mass transfer phenomena is based on the dCHN02

film model of Lewis and Whitman [6]. The assumptions in-
for y = 0: cNo = cRo and ~ = o ,
dY
clude steady-state diffusion of the participating species and con-
stant concentration of nitric acid. In the gas phase, Ficks’s first and y = L: cNo = 0 and CHN02 = CHN02,L ,

law is the basis of the film model:

The solutions of these differential equations yield the correla-
d2PN0 - tion between the concentration and the distance from the gas/
DNO,g 7-
- (1 1)
liquid interface for NO and HNO, (see Fig. 1):

with boundary conditions 2 CHN02

cNOb) = CxO + 7 (1 - cos a y ) +

Solution of Eq. (1 1) yields the relationship between the concen-

tration and the thickness of the gas-side film (see Fig. 1): CHN02,L
=)
C H N O ~ ~ cos a cos a y
X
PNO (x) = P a 0 + (P60 -PNO,bulk) ~ ’ (12)
6,
There is no chemical reaction in the gas phase. Therefore, the
mass flow rate is represented only by the diffusion process: Eqs (17) and (18) contain c ~and L.~ In order
~ to obtain
~ ,
these two values, additional balance equations have to be
established:

Using Eq. (12) and k,,,,l(RT) = DNo,g/6g,

the mass transfer
rate is given by the following equation:
L
C H N 0 2 , L - CHN02,0
DHN02,1 3 ki C H N O ~dy . (20)
6,-L 0

gas phase interface liquid phase Their solutions are:

bulk I film film , ~ bulk
CHN02,L 3 12
-
’ (21)
cgo 1 -(l/(cos a L ) ) + a L tan a L

CHNO~,O
~-
[
1 - (6, - L ) tan a L]
- (22)
4 0 1 - (l/(cos a L ) ) + a L tan a L
NO
P The following equation is valid for the mass transfer rate:

JNO = - DNO,I
-
-

Fig. 1. Relationships between NO and HNO, during absorption in liquid

phase.
272 Chem. Eng. Techno]. 14 (1991) 270-274

4 Experimental

In this paper, the absorption of NO into nitric acid is examined,

IfI '
with NO concentration in carrier flow of nitrogen being well
defined. The concentration of HNO, as the absorbent was
chosen in accordance with the concentration, maintained in the
absorption column of a nitric acid plant. The temperature was
set at 25 "C. The apparatus used was the same as employed in
[lo].

A double stirred cell (Fig. 2) made of glass and PTFE was usecl TC
as the laboratory-scale absorber. Stirrer speeds in the gas and
liquid phases can be controlled separately. Ideal mixing may hc
assumed if the gas phase is agitated at 1 000 min- and the li-
quid phase at 130 min-'. The advantage of this type of ah-
sorber lies in the fact that the mass transfer area is known exact-
ly. This area is identical to the upper surface area of the liquid Fig. 3. Experimental set-up. CTC thermostat, DSC double-stirred cell, GA
phase. gas analyzer, I mixing chamber, R1. R2 flowmeters, REC recorder, RV
regulating valve.

The complete set-up is shown in Fig. 3. To vary the concentra-

tions, NO gas must be diluted with nitrogen. The N, flow rate The values of kg,s02 and k,,c02 may be adapted for any kind of
is measured by a flowmeter ( R I ) .When the gas mixture reaches species i in aqueous systems, via equations of Calderbank and
the mixing chamber, a homogeneous composition is achieved. Moo-Young [7]
The reactor itself forms part of a bypass. Alternatively, the gas
composition may be determined at the inlet and outlet of the
double stirred cell. During analysis, the absolute gas
throughput is measured by a second flowmeter (R2). For deter-
mining the gas composition, an NO/NO, analyzer (GA) is used.

Mass transfer coefficients for gas and liquid sides of the inter-
face are obtained by measuring model absorptions. The gas-
side mass transfer coefficient k, is first determined for SO, by
where D are the diffusion coefficients.
absorption in NaOH solution, representing physical absorption,
followed by a fast chemical reaction. In this case, k, is propor-
tional to the gas velocity uG. The liquid-side mass transfer coef-
5 Results
ficient k , is measured by absorption of CO, in water saturated
with nitrogen which represents a purely physical process.
The aim of this investigation was to develop a method for
k,,,02 depends on the speed of the liquid-phase stirrer.
calculating the mass transfer rate JNo.The computational pro-
cedure is outlined in Fig. 4.

To solve Eqs (2 1) to (23), the reaction rate constant is needed,

PLAIN BEARING which is contained in a defined as (3 k,/DHN02)1/2. Schmid and
Krichel [8] measured k , . The results are shown in Fig. 5 . The
relationship between the rate constant and the concentration of
nitric acid may be described as:

OUR-BLADE STIRRER
with cHNO3
expressed in mass-%.

In addition, the solubility data of nitric oxide in nitric acid are

needed. The following equation reflects the correlation between
the solubility of nitric oxide and nitric acid concentration:
LIQUID OUT1
L HNo = (1.9302 - 0.0002108 cHNO,)x l o - " (27)

MAGNETIC STIRRER with cHNO,expressed in mass-%

The concentration of nitrous acid in the employed nitric acid

Fig. 2. Laboratory-scale double-stirred cell absorber. solutions was 2 x 10- moIiI.
Chem. Eng. Technol. 14 (1991) 270-274 273

--- -- - - -- - - - kg values determined by

experiments o r c o r r e l a t i o n s
P*NO from Eq. (14)

-- - - -- - --- - - - - - - Henry’s law

C*NO = HNO P*NO

experiments o r c o r r e l a t i o n s ,
hence s
= D N O .I /ki f o l l o w s

publication of Park and Lee [9]. Fig. 7 presents the mass

Fig. 6 presents a plot of mass transfer rate J,, as a function of
partial pressure p&, of NO at the interface. The data were ob-
tained with the experimental apparatus. It can be seen that J,,
is proportional to @ & o ) ’ / 2 . The solubility and decomposition
kinetics of nitrous acid in aqueous solutions may be found in the
transfer rate as a function of nitrous acid concentration in dif-
ferent nitric acid solutions. It is seen that J N O is proportional
to between ( c ~ , ~ 1/3 ~ , (~c )~ , , ~ , ~ Finally,
and ) ” ~ . it can be con-
firmed that the film theory is well suited to describe the NO ab-
sorption in dilute nitric acid.

100 1OL

1010 mol
HNO3 conientration ’ ‘ I
’1s s cm

10
10

k
, ,J 10‘

10

OJ 1 I 1 1
0 10 20 30 mass-% 50
1 10 lo2 Pa lo3
C(HN031 G
Fig. 5. Reaction rate constant as a function of nitric acid concentration. Fig. 6. Mass flow rate J,, as a function of partial pressure of NO at gas/
x : data of Schmid and Krichel [8], -: calculated from Eq. (26). liquid interface pZo, at 25 “C.
274 Chem. Eng. Technol. I 4 (1991) 270-274

Received: August 29, 1990 [CET 3201

Symbols used

clHNO,)
Fig. 7. Mass flow rate J,, as a function of nitrous acid concentration for
different nitric acid solutions at 25 "C.
C concentration
D diffusion coefficient
H Henry's coefficient
J mass transfer rate
K equilibrium constant
k reaction rate constant
kz '1 gas-side mass transfer coefficient
kl liquid-side mass transfer coefficient
L distance from gashquid interface
P pressure
R universal gas constant
r rate of chemical reaction
T temperature
t time
gas flow rate
"G
mass
IV

x gas-side space coordinate

liquid-side space coordinate
6 Conclusions and Prospects film thickness

The object of this study was to examine the kinetics of NO ab-

sorption in nitric acid of different concentrations. The study
culminated in a description of NO mass transfer during nitric
acid production, according to the Ostwald process. A computa- Indices
tional procedure is outlined.
* at interface
bulk in bulk
A previous publication [ 101 dealt with the kinetics of absorption g gas-side
of N 0 2 / N 2 0 4in nitric acid. In conjunction with the present in- I liquid-side
vestigation, it is possible to develop a dynamic calculation
method for the design of large-scale NO, absorption columns.
The advantage of the dynamic over the static methods lies in the
fact that introduction of empirical adaptation parameters, such References
as efficiencies, is not necessary. The dynamic methods are bas-
ed only on physico-chemical laws and data. Abel, E., Schmid, H . , 2. Phys. Chem. 132 (1928) p. 55.
[I]
Abel, E., Schmid, H., Z. Phys. Chem. 134 (1928) p. 279.
[2]
Schmid, G., Bahr, G . , 2. Phys. Chem. N.F. 41 (1964) p. 8.
[3]
In future studies, the kinetics of absorption of N 2 0 3 in nitric Theobald, H., Chem.-Ing.-Tech. 40 (1968) p. 15.
[4]
acid should be examined. N 2 0 3 is formed in reactions, both in [5]
Carta, G., Pigford, R.L., Ind. Eng Chem. Fundam. 22 (1983) p. 329.
gas phase and at gashiquid interface when NO and N 0 2 / N 2 0 4 Lewis, W.K., Whitman, W.G., Ind. Eng Chem. 16 (1924) p. 1215.
[6]
are both present. It would be of interest to elucidate the role of Calderbank, P.H., Moo-Young, M.B., Chem. Eng Sci. 16 (1961) p.
[7]
N 2 0 3 in NO, absorption during nitric acid production, because 39.
[8] Schmid, G., Krichel, G., Ber. Bunsenges. Phys. Chem. 68 (1964) p.
N203 has properties analogous to those of N20, and should 677.
yield a significant contribution to the NO, mass transfer rate [9] Park, J.Y., Lee, Y.N., J . Phys. Chem. 92 (1988) p. 6294.
with respect to NO content in the gas feed to the absorption col- [lo] Weisweiler, W., Eidam, K., Thiemann, M., Scheibler, E., Wiegand,
umn of nitric acid production plant. K.W., Chem. Eng. Technol. 13 (1990) No. 2, p. 91.