D.

Shishkov,
P. Bozadjiev,
D. Djambov,
Ts. Velinova,
JournalP.ofDjambov,
the University
of Chemical
Technology
and Metallurgy,
46, P.
2, Vasilev
2011, 161-164

INTEGRATION BETWEEN HIGH PRESSURE

AND LOW PRESSURE NITRIC ACID PRODUCTIONS
P. Djambov, D. Shishkov, P. Bozadjiev, D. Djambov, Ts. Velinova, P. Vasilev
University of Chemical Technology and Metallurgy

8 Kl. Ohridski, 1756 Sofia, Bulgaria

E-mail: jambov@uctm.edu

Received 15 March 2011

Accepted 20 May 2011

ABSTRACT
On the basis of an unique mathematical model and specialized computer package, the steady-state behaviour of
plant columns for nitric acid production has been carried out. The investigation of the column at high productivity
permitted to propose two variants for integration between high-pressure and low-pressure nitric acid productions in
NEOCHIM PLD. The method has been patented. The results were confirmed by experimental data and in 2008 the
proposal has been realized with ecological and large economical effects.
Keywords: nitric acid production, nitrogen oxides absorption, steady-state modelling.

INTRODUCTION
The nitric acid is an important heavy chemical,
produced on a very large scale, exclusively by oxidation
of ammonia and absorption of the nitrous gas with water.
A simplified scheme of the dual-pressure nitric
acid production in Neochim PLC, Dimitrovgrad is shown
in Fig.1. It includes: 1) oxidation low-pressure part, where
nitrogen oxides are produced by oxidation of ammonia
with atmospheric air over platinium catalyst. The exit gas
stream is cooled at several steps. In a flush column (C.27)
the nitrous gas is washing from ammonia and ammonium
nitrate by recycling acid condensate; 2) in the absorption
high-pressure part of the plant the nitrous gas after
compression and cooling constitute the feed at the bottom
of the absorption column C.31, which receives process
water at the top.
In this paper we present an implementation of
an idea: integration between high-pressure (AK-72) and
low-pressure (TZ-300) nitric acid production plants in
the fertilizer part of Neochim PLC, Dimitrovgrad, Bulgaria. The diluted (43 %) nitric acid from atmospheric
technology requires in the next stage (the ammonium
nitrate production) using of an vacuum evaporation section, which, on the other hand, leads to serious ecological problems. The essence of the idea is: up-concentra-

tion of the nitric acid from atmospheric-pressure technology TZ-300 at the absorption system of the nextdoor high-pressure nitric acid production AK-72. The
right answer of this possibility can be achieved by the
investigation of the absorption column of the production AK-72, shown in Fig. 2.
The main constructive parameters of the column
are: diameter 4 m, hight 57 m, sieve plates 55, feed
plate - No 6, 7, 8, cooling plates 25 (cooling water
flows through coils, layer in the froth of the plates).
Concerning to the performance of the absorption column at higher productivity, the next questions
are arising: 1) What changes of the NOx absorption will
appear at the new productivity, because in this case the
liquid streams will increase at the lower part of the column
and will decrease nearly two times at the upper part of the
column?; 2) What will happened with the temperature
profiles, especially at the upper part of the column?; 3)
How the nitric acid concentration profile will changed?
The answer of these questions will give the numbers of
the nitric condensate feed plates, because the
concentrations on the plates have to be the same as the
nitric acid concentrations of the external liquid streams.
The right answer of these questions have to be given only
by mathematical modelling and simulation of the
processes, which take place in the absorption column.

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Journal of the University of Chemical Technology and Metallurgy, 46, 2, 2011

Fig. 1. Technological scheme of HNO3 production AK-72 in Neochim PLC.

BASIS OF THE MODEL
The absorption column serves as combined masstransfer equipment and chemical reactors. The full
mathematical model has been given in [2]. Here only some
main equations will be discussed.
A separate plate of the column is shown in Fig.3.
In the picture, also, the chemical reactions and the main
operating conditions can be seen. The plate consists: 1)
oxidation part in fact homogeneous reactor between two
consequent plates, where the important gas-reactions
are: No (1) oxidation of NO to nitrogen dioxide and
No (2) dimerization of NO2. Solving the integral kinetic equation with respect to (degree of NO conversion), the composition of nitrous gas leaving oxidation
part can be calculated.

o
(
O ,i 0,5NO ,i )i
1
1 i
2

+ln
i Pi k,i (t,i ) =
(Oo ,i 0,5NOo ,i )2 (1i )0,5NOo ,i 1 0,5NOo ,i i
Oo ,i
(1)

Fig.2. Absorption column from AK-72.

162

where: is residence time; P total pressure; - molar

part of components; tcp average temperature, kp rate
constant; 0 refers to the output of the oxidation part.;
2) absorption part the froth of the plate, where gas-

P. Djambov, D. Shishkov, P. Bozadjiev, D. Djambov, Ts. Velinova, P. Vasilev

Fig. 3. Separate plate of the column.

liquid phase reactions occur. The theoretically calculated amount of nitrogen oxides absorbed in the plate
(respectively nitric acid account fk) are corrected by a
semi-empirical plate efficiency a function of both of
constructive and operating conditions [2,10], varies at
2
every plate.
*
3 2( pNO,i )
0
0
*
(pNO,i + pNO,i )K1,i (pNO,i )
p*NO,i
K
2,i
0
0
fk,i =(GNO
i
,i +GNO,i )
0
0
+
pNO
p
,i
NO,i
(2)

A program package NEOAK-01J for modeling and steady-state simulation the behaviour of the sieve
plate column of the nitric acid production AK-72 in
NEOHIM PLC is created [7]. It includes two modes of
operation: (I) Estimation of several model parameters
by experimental data; (II) simulation of column performance. As an illustration of the possibilities of the package NEOAK-01J it may be marked: 1) the suitable available input data, formed by a dialog with the user; 2) the
results ( more than 2000 process variables): parameters
of the input and leaving streams; in a table are presented several profiles along the column nitric acid
concentration; NOx concentration; O2 concentration;
temperatures of the gas and liquid phases; plate efficiency, produced acid in the plate and NOx removal.
There are also possibilities for graphical representation
of some profiles.
The validity of the model was tested by comparing
the calculated results with measured values.
A lot of runs by program package NEOK-01J have
been carried out to investigate the influence of the main
input variables on the column performance.

RESULTS

i = A

,1
Pi 0 ,15 C (0NO
0 ,4 h10 ,15 c a0 ,,1i
+ NO 2 )i i

w 0 ,26 d 0 ,15 s 0 ,13 (t i + 273 )0 ,87

(3)

where K1, K2 are equilibrium constant of the reactions

[10], p partial pressure.
Using equations for calculations of nine heats
[2,9], the overall heat transfer coefficient between cooling water in the coils and the froth on the plate may be
calculated and used as data-fitting parameter of the
model [2].
SIMULATION OF ABSORBTION COLUMN
PERFORMANCE
Using the above discussion from the elementary
processes, which take place in the NOx absorption, an
overall model of the absorption column is created [2,7].
The model is equilibrium type model [1] and the
equations are solved by plate-to-plate method, started
from the bottom of the column.

The final step was the investigation of column

behaviour at higher productivity to answer of the ask
questions in the beginning for combining of the two nitric
acid productions in NEOCHIM PLC.
Two variants for integration between the next door
nitric acid production plants AK-72 and TZ 300 have been
proposed [5] and are presented in Fig. 4:
Variant A the diluted acid (43%) from the lowpressure nitric acid plant TZ-300 is added directly as a
second intermediate liquid stream into absorption column
of the high-pressure nitric acid plant AK-72;
Variant B the same diluted nitric acid is added to
the recycle stream of the flush column C.27 and also two
acid streams with different parameters are fed to the
absorption column C.31.
The main results for column simulation for Variant B are as following:1) the worst temperature conditions for NOx absorption are assumed (as is summer
time); 2) feed plates for the external liquid streams are
No 9 and 15( No 8 is for the basic run without connection between both plants); 3) the volume rate of pro-

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Journal of the University of Chemical Technology and Metallurgy, 46, 2, 2011

Fig. 4. Technological scheme of HNO3 production AK-72 in Neochim PLC.

cess water is 9.62 m3/h, which is nearly two times less,
than the basic run; 4) the NOx concentration in the
tail-grass (247 ppm) is satisfactory (in the basic run
236 ppm) ; Nearly the same results were obtained for
Variant A.
These results for the higher productivity of the
absorption column in nitric acid plant AK-72 were
confirmed by experimental data. The proposed method was
patented [5] and in 2008 was realized in NEOCHIM PLC
Dimitrovgrad with ecological and large economical effects.
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