Enhanced Plant Design for the Production of

Azeotropic Nitric Acid

by

Rainer Maurer, Uwe Bartsch

Krupp Uhde GmbH,

Dortmund, Germany

Prepared for Presentation at

The Nitrogen 2000

Vienna, Austria

12 to 14 March 2000

Organized by

British Sulphur Publishing (CRU Publishing)

Copyright © Krupp Uhde GmbH

Enhanced Plant Design for the Production of Azeotropic Nitric Acid

 -2-

1 Market Situation for Azeotropic Acid

As shown in Fig. 1, about 80 % of the nitric acid production is used for fertilisers. The main
product is ammonium nitrate (AN) and its various derivatives as calcium nitrate (CN),
calcium ammonium nitrate (CAN), ammonium sulphate nitrate (ASN) and liquid N fertilisers
(UAN). The other main branch is nitrophosphate (NP) compounds.

Non-fertilisers are dominated by explosive grade ammonium nitrate (LAN). Nitric acid is also
required for chemicals, represented in this graph by caprolactam, adipic acid as an
intermediate product for nylon and toluene diisocyanate as an intermediate product for
polyurethane.

In the recent past, the world market has exhibited noticeable demand for so-called
azeotropic acid with an elevated concentration of about 68 % by weight. Obviously some
nitrations which only took place in the presence of high concentrated nitric acid in the past
can be performed under less severe conditions nowadays. That means concentrated nitric
acid can be partly or completely replaced by azeotropic acid.

Consequently, Krupp Uhde has developed an enhanced process design for the reliable
production of azeotropic acid.

FL-Bartsch Z:\DAT\FL\FL_WORK\Konferenzen\2000_akt\03_nitrogen\na&an_ugm\Bartschnitrogen.ppt page 1

Nitric Acid
80 % 20 %

Fertiliser Non-Fertiliser

AN NP AN Explosives Chemicals

Toluene
Capro- Adipic diiso-
CN CAN UAN ASN lactam Acid cyanate

Poly-
Nylon
urethane

Fig. 1: Nitric acid Applications

Enhanced Plant Design for the Production of Azeotropic Nitric Acid

 -3-

1.1 Overview
This presentation focuses on the special features of an azeotropic acid plant (Fig. 2).

1.2 Basics
The azeotropic point for the nitric acid / water system is well known as a limitation for
distillation. After some important process parameters governing the absorption have been
presented by means of a simplified model, it can be concluded that the azeotropic point is no
limitation for absorption applied in a nitric acid plant.

1.3 Limitations
Compared to a normal nitric acid plant design, certain process constraints have to be
overcome in addition to produce azeotropic acid. First a measured concentration profile is
discussed, gained during commissioning while operating an absorption tower outside the
normal range. Hereafter the problem, “When does the absorption work stably”, is discussed
thoroughly and visualised by various simulation results. Next operation at partial plant load is
identified as a critical design case, since due to reduced absorption pressure the rising NOx
content in the tailgas has to be limited. Finally, the water balance for an azeotropic acid plant
is established. As a result, the maximum absolute humidity of the intake air can be
calculated.

1.4 Technical Concepts

By means of a dual pressure plant flowsheet, important technical features of an azeotropic
acid plant are explained. The effect of a change of basic process parameters like pressure or
cooling water temperature on the absorption performance is discussed.

FL-Bartsch Z:\DAT\FL\FL_WORK\Konferenzen\2000_akt\03_nitrogen\na&an_ugm\Bartschnitrogen.ppt page 2

Introduction

Basics

Limitations
Market situation for
68 % nitric acid Technical
Significance of Concepts
azeotropic point for
•Distillation
Absorption stability
•Absorption
Part load operation
Water balance Secondary air cooling
Pressure increase
Additional cooling

Fig. 2: Azeotropic Acid plant features

Enhanced Plant Design for the Production of Azeotropic Nitric Acid

 -4-

2 Basics

2.1 Significance of the Azeotropic Point for Distillation

Fig. 3 depicts the vapour-liquid equilibrium for the nitric acid / water system. For atmospheric
pressure the well known azeotropic point occurs at a liquid concentration of 68.4 %. That
means by distillation the separation of vapour (y) and liquid with different concentration (x)
can only be performed below this azeotropic point, since the vapour concentration y is equal
to the liquid concentration x. The azeotropic point is thus a natural barrier for distillation.
The azeotropic point can be shifted slightly by a pressure change. For lower total pressure it
is shifted to a lower liquid concentration.

FL-Bartsch Z:\DAT\FL\FL_WORK\Konferenzen\2000_akt\03_nitrogen\na&an_ugm\Bartschnitrogen.ppt page 3

100

95
90

85

80
75

70

65
y [% HNO3 in vapour]

60

55

50
45

40
35

30

25
20

15

10
5

0
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80 85 90 95 100
x [% HNO3 in Liquid]

Fig. 3: Vapour Liquid Equilibrium Nitric Acid-Water

Another possibility to shift the azeotropic point is the basis for concentrating diluted nitric
acid. Fig. 4 shows the effect of addition of sulphuric acid to a nitric acid / water solution.

By increasing the H2SO4 concentration stepwise from 0 % via 20 % and 40 %, the azeotropic
point is shifted to lower liquid concentrations, and finally at a concentration of 67 % H2SO4
the azeotropic point has vanished.
Then it is possible to distillate concentrated nitric acid. The nitric acid is the lighter phase and
extracted as vapour, while the sulphuric acid will be further diluted in the liquid phase.

Enhanced Plant Design for the Production of Azeotropic Nitric Acid

 -5-

FL-Bartsch Z:\DAT\FL\FL_WORK\Konferenzen\2000_akt\03_nitrogen\na&an_ugm\Bartschnitrogen.ppt page 4

100

95

90

85

80

75

70

65
y [% HNO3 in vapour]

60

55

50

45
Reference
0 % H2SO4
40
20 % H2SO4
35
40 % H2SO4
30 67 % H2SO4
25

20

15

10

0
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80 85 90 95 100
x [% HNO3 in Liquid]

Fig. 4 Vapour Liquid Equilibrium Nitric Acid –Water (Paramater: H2SO4-Content)

2.2 Absorption Reaction Model

Is the azeotropic point also a limitation for absorption?

A simplified model for the complex reactions based on the film theory is shown in Fig. 5. NO2
is in equilibrium with N2O4 in the gas bulk as well as in the gas film. Only N2O4 is transported
through the gas film to the gas-liquid boundary and is hydrolysed, while NO2 - hydrolysis can
be neglected.

The HNO2 formed intermediately is decomposed to nitric acid, water and nitrogen monoxide.
The NO gas formed in the liquid phase limits the absorption because it has to be transported
back to the gas phase. There it is oxidised to NO2 which is in equilibrium with N2O4 to close
the circuit. The overall reaction in the liquid phase can be summed up as follows:

3 NO2 + H2O = 2 HNO3 + NO

It can be concluded that the physical laws ruling the absorption are completely different from
the distillation as discussed before. Therefore the ‘classic’significance of the azeotropic
point to limit the nitric acid strength is only valid for distillation.

For absorption the partial pressure of NO and NO2 at the absorption tower inlet is crucial.
According Krupp Uhde’s experience a certain total NOx partial pressure in the range of 1 bar
is required to produce an azeotropic acid in an absorption tower.
The technical concepts as well as physical limitations for azeotropic acid production are
discussed later.

Enhanced Plant Design for the Production of Azeotropic Nitric Acid

 -6-

FL-Bartsch Z:\DAT\FL\FL_WORK\Konferenzen\2000_akt\03_nitrogen\na&an_ugm\Bartschnitrogen.ppt page 5

2 NO + O2 2 NO2

Gas phase 2 NO2 N2O4

Gas film 2 NO2 N2O4

Liquid film N2O4 + H2O HNO3 + HNO2

Liquid phase

3 HNO2 HNO3 + H2O + 2 NO

Fig. 5: Simplified Absorption Reaction Model

3 Limitations

3.1 Special Absorption Profile Measured During Commissioning

The concentration profile shown in Fig. 6 was measured during the start-up of a mono high-
pressure nitric acid plant. Plant design is 300 MTPD with acid strength of 65 % by weight
and the absorption pressure was 9.4 bar abs.
During start-up by mistake only about 50 % of the design process water flow was supplied to
the top of the absorption tower. As a result, nitric acid of much higher strength was formed at
the bottom of the tower.
The higher concentrations result in a notch in the concentration profile at tray 12, which is
the entry point of the crude condensate delivered by the cooler condenser. This notch occurs
because the concentrations on the previous sieve trays were raised considerably.
Consequently, the crude condensate concentration at tray 12 is far too low and disturbs the
profile. Therefore the acid concentration at the subsequent absorption trays 12 to 17 rise
again, or in other words these trays show desorption. After passing a maximum at tray 17
with a concentration of approx. 66 %, the column had stabilised and absorption took place
again. Overall, the entire acid profile was shifted to the right. The absorption tower profile
was maintained for some hours, so a quasi stationary state was reached.
On the first trays, the laboratory even determined concentrations above 70 %. Even though
taking into account an inaccuracy of the density measurement of about 0.5 to 1 %, the
corrected concentration calculates to approximately 69.5 %.
So during start-up of this plant a superazeotropic nitric acid was produced in a production
absorption tower, but on the other side also the NOx-value in the tailgas measured to 370
ppm was increased above the permissible limit.

Enhanced Plant Design for the Production of Azeotropic Nitric Acid

 -7-

FL-Bartsch Z:\DAT\FL\FL_WORK\Konferenzen\2000_akt\03_nitrogen\na&an_ugm\Bartschnitrogen.ppt page 6

Concentration
[wt. %]
75

70
Start-up lab results 65

Absorber Design 60

55

50

45

40

35

30

25

20

15

10

0
0 5 10 15 20 25 30 35 40

Tray No.

Fig. 6: Measured Absorption Profile

3.2 Simulated Acid Profile for a Dual Pressure Plant

At Krupp Uhde a sophisticated computer program is used for the reliable design of the
absorption tower. Furthermore, this program is capable to predict the limits within which the
absorption will work.

Fig. 7 visualises a simulation for the absorption behaviour of a column in a dual pressure
plant, where nitric acid of two concentrations is produced. The major part of 60 % is taken
from the absorber as 68 % nitric acid, the remaining side stream as 60 % nitric acid.

Now the acid strength is shifted up to 70 % in steps of 0.5 % by simulation. The higher the
concentration, the worse the absorption tower works, resulting in a less steep concentration
profile. This effect is increased after the crude condensate has been added, since its
concentration no longer matches that of the tray acid. As a result the whole concentration
profile is shifted to the right.

Fig. 8 is a detail of the previous one, focussing on the first absorption trays Nos. 3 to 7. As
mentioned in connection with the measured profile presented earlier, another criterion of
stability is if the respective tray absorbs or desorbs. Here the trays No. 1 and 2 are so called
oxidation trays, which will only increase the NO2 content of the incoming NO gas. The raw
acid is extracted from tray 3 with the higher concentration, while the 60 % acid is taken from
a tray with similar concentration.

Regarding the slope between tray 3 and 4, below 69 % the negative slope refers to
absorption, while above 69 % the tray desorbs, characterised by a positive slope. The nearly
horizontal slope at 69 % represents the limit of stable absorption, i. e. at the particular tray
number no additional acid formation takes place nor acid decomposition.

Enhanced Plant Design for the Production of Azeotropic Nitric Acid

 -8-

Summing up these simulation results, this absorption tower works stably until a
concentration of 69 % by weight. This result is in accordance with measurements taken
during practical operation of this plant.

The absorption stability also depends on the pressure and cooling water temperature as
discussed later.

FL-Bartsch Z:\DAT\FL\FL_WORK\Konferenzen\2000_akt\03_nitrogen\na&an_ugm\Bartschnitrogen.ppt page 7

75

70

65
68,2 [Gew%]
60
68,5 [Gew%]
55 69,0 [Gew%]
69,5 [Gew%]
50
70,0 [Gew%]
Acid
Conc. 45
[wt. %]
40

35

30

25

20

15

10

0
0 5 10 15 20 25 30 35 40 45 50
Tray No.

Fig. 7: Simulated Acid Profiles for Dual Pressure Plant

FL-Bartsch Z:\DAT\FL\FL_WORK\Konferenzen\2000_akt\03_nitrogen\na&an_ugm\Bartschnitrogen.ppt page 8

71
70,12 70,38
70
69,61 69,7
69,1 69,28
69 69
68,59
68,2 68,27 68,3
68
67,69 67,74
67,23 67,29
67

66 66,05 66,18
Acid
conc.65 65,06 65,09
[wt. %]
64,33
64

63 68,2 [Gew%]
68,5 [Gew%] 62,13
62 62,1
69,0 [Gew%]
61 69,5 [Gew%]
70,0 [Gew%]
60 60,15

59 59,05

58

57 57,11
3 4 5 6 7
Tray No.

Fig. 8: Detail Simulated Acid Profiles for Dual Pressure Plant

Enhanced Plant Design for the Production of Azeotropic Nitric Acid
 -9-

3.3 Partial Load Operation

Depending on the client’s production requirements, some nitric acid plants are operated for
a longer time at partial plant load. Then the available absorption pressure is naturally lower,
depending on the characteristic machine performance curve. Therefore especially if the
production of a 68 % azeotropic acid has to be maintained, partial load operation is an
additional critical absorption tower design case.

Fig. 9 shows the acid profile of an absorption tower as derived by simulation. Due to the
decreased absorption pressure of about 9 bar abs. at partial load, compared to about 12 bar
abs. at full load, the concentration on any given tray is increased with respect to the full load
case.

The NOx-content in the tailgas also increases with respect to the deteriorated absorption
performance, in this case from 190 to 310 ppm by volume (Fig. 10).

Nowadays, most of the new nitric acid plants are equipped with a selective catalytic tailgas
treatment unit (SCR) to meet environmental standards. So the NOx-content at absorber
outlet, the so called NOx-cut, is evaluated under economical aspects. The investment costs
for the absorption tower must be compared to the costs of the SCR unit, consisting of
required catalyst volume and additional NH3-consumption and pressure drop.

For this plant the NOx-cut after the absorption was chosen to be 300 ppm by volume. The
number of sieve trays was adjusted accordingly to ensure the production of 68 % azeotropic
acid at partial load operation.

FL-Bartsch Z:\DAT\FL\FL_WORK\Konferenzen\2000_akt\03_nitrogen\na&an_ugm\Bartschnitrogen.ppt page 9

70

60

100 % plant load

50 70 % plant load
Acid Conc. [wt. %]

40

30

20

10

0
0 5 10 15 20 25 30 35 40

Tray No.

Fig. 9: Concentration Profiles

Enhanced Plant Design for the Production of Azeotropic Nitric Acid

 - 10 -

FL-Bartsch Z:\DAT\FL\FL_WORK\Konferenzen\2000_akt\03_nitrogen\na&an_ugm\Bartschnitrogen.ppt page 10

100000

100 % plant load

70 % plant load
10000
NOx [ppm]

1000

310
190

100
0 5 10 15 20 25 30 35 40
Tray No.

Fig. 10: NOx-Content in Tailgas

4 Technical Concepts

4.1 Krupp Uhde’s Dual Pressure Azeotropic Plant

Fig. 11 highlights the specific features of a dual pressure azeotropic acid plant.

To satisfy the overall water balance, it is mandatory to get rid of the water carried with the
incoming air. The measures depend on the air humidity and temperature and therefore on
the plant location / climatic conditions. Krupp Uhde is prepared to offer tailor-made solutions.

In case of a high ambient air temperature and humidity the installation of an additional air
condenser is to be recommended. In order to reduce the water partial pressure as far as
possible, this apparatus would be cooled with chilled water. As usual in Krupp Uhde dual
pressure plants, there is an extra chilled water circuit linked to the ammonia evaporation.

The machinery shown as an example is completely integrated in Krupp Uhde’s compact bull
gear concept. The first pressure level delivered by the air compressor is advantageous for
the burner, while the final pressure delivered by the NOx-compressor promotes the
absorption so that azeotropic acid can be formed.

Enhanced Plant Design for the Production of Azeotropic Nitric Acid

 - 11 -

FL-Bartsch Z:\DAT\FL\FL_WORK\Konferenzen\2000_akt\03_nitrogen\na&an_ugm\Bartschnitrogen.ppt page 11

Air Condenser

CCW CCW

Ammonia Air Mixer

Tailgas
Tailgas Heater 1
AC NOx < 50 ppm Reactor Tailgas Heater 2
Secondary Air
HP-
Air Compressor Steam STH
Tailgas- Tailgas
CW
Turbine
Process CW Process Water
Air Filter Gas WB
Cooler
Air Cooler
Tailgas NO Gas Condenser 2
CW

AmmoniaTailgas Mixer
WB
HP Steam
NOx Com- Absorption
pressor Economizer

STL/CPL
Tailgas Boiler
Feedwater Bleacher
Reactor & Dryer
Ammonia
Gas Filter
LP Steam CW
CCW Tailgas
CPL Heater 3
CW Nitic Acid
Ammonia Product
Evaporation Ammonia Gas
& Superheating
CCW CW
LP Steam Auxiliary Acid Condensate
CPL Ammonia CPL LP
AW
Ammonia Liquid Evaporation Cooler Condenser 1 &
Feedwater Preheater Steam Acid Heater

Fig. 11. Krupp Uhde Dual Pressure Plant Azeotropic Acid Product

4.2 Limitation of Acid Concentration by Air Humidity

4.2.1 Outline of the Water Balance

The water balance of the nitric acid process consists of reaction water, dilution water and
water carried with the process streams (Fig. 12).
In the burner section water is formed by the main reaction to NO (1) and the undesired side
reactions to N2 (2) and N2O (3). In the absorber section water is consumed according to the
overall reaction (4) and for dilution to the azeotropic concentration of about 68 % by weight.

Also a major part of the water may be sucked in with the process air. The air humidity
depends on the location of the plant as well as season and time of day. The remaining part
of the water balance is satisfied by process water supplied to the top of the absorption tower.

4.2.2 Derivation of the Theoretical Limit Concentration

Figure 12 highlights the specific reactions which take place in the ammonia burner section
and the absorption. Considering the desired reaction (1), 1.5 moles of water are formed per
mole of ammonia. For each mole of formed NO 0.5 moles of water are consumed in the
absorption section. Overall there is a surplus of 1 mole of H2O per 1 mole of ammonia fed to
the plant, for a 100 % burner efficiency.

Taking into account a more realistic burner efficiency of 95 %, that means 5 % of the
ammonia are converted to N2 or N2O according reaction (2) and (3) with no extra water, a
maximum HNO3-concentration of 76.6 % can be produced.

Enhanced Plant Design for the Production of Azeotropic Nitric Acid

 - 12 -

FL-Bartsch Z:\DAT\FL\FL_WORK\Konferenzen\2000_akt\03_nitrogen\na&an_ugm\Bartschnitrogen.ppt page 12

TAILGAS

NH3
PROCESS WATER

AMMONIA BURNER ABSORPTION

(1) 4 NH3 + 5 O2 4 NO+ 6 H2O 3 NO2 + H2O 2 HNO3 + NO (4)
(2) 4 NH3 + 3 O2 2 N2 + 6 H2O
(3) 4 NH3 + 4 O2 2 N2O + 6 H2O

AIR
Rel. humidity
x% to 100 %
Azeotropic Acid HNO3
68 % by weight

Fig. 12: Water balance for an Azeotropic acid plant

4.2.3 Calculation of the Limit Water Load in Intake Air

The absorption tower requires a minimum process water feed to ensure safe and stable
operation of the plant. In practical operation it is mandatory to keep the NOx content in the
tailgas within the allowed limits. The minimum required process water fed to the top of the
absorption tower can be assumed to approx. 30 kg per ton of 100 % HNO3. Considering this
value in connection with the limit concentration of 76.6 %, the final possible concentration
comes out to be 74.9 %.

Related to the desired azeotropic acid concentration of 68 %, the remaining difference in the
water balance amounts to 135 kg per ton of acid. This water is the maximum water content
allowed to be carried with the intake air. Taking into account an oxygen content in the tailgas
of 2.5 % by volume, the intake air amounts to 4950 kg per ton of acid. Thus an overall
absolute water content of about 27 g per kg dry air can be expected. Based on this figure
and an ambient pressure of 1.013 bar, Fig. 13 shows the relation between relative air
humidity and temperature. Admissible combinations of ambient air temperature and humidity
for the production of azeotropic acid lie below the limit curve.
Should the air condition lie outside the admissible area, the installation of an additional
cooling facility is required. An example of an extra chilled water cooler was given in Fig. 11.

Enhanced Plant Design for the Production of Azeotropic Nitric Acid

 - 13 -

FL-Bartsch Z:\DAT\FL\FL_WORK\Konferenzen\2000_akt\03_nitrogen\na&an_ugm\Bartschnitrogen.ppt page 13

0,9 inadmissible conditions

rel. Humidity

0,8
Pressure = 1.013 bar
Abs. Humidity = 27 g / kg dry air
admissible conditions

0,7

0,6
29 30 31 32 33 34 35 36 37 38 39

Temperature [°C]

Fig. 13: Theoretical Limit Curve for intake Air Humidity

4.3 Secondary Air Drying

Secondary air, which is about 20 % of the total air flow, is used for stripping of NOx gases
dissolved in the raw acid leaving the absorber. The secondary air carries the quantity of
water corresponding to the climatic conditions or the conditions in the air condenser if
installed. This water content would dilute the product acid leaving the sump of the bleaching
tower. In order to maintain the specified acid strength, a secondary air dryer integrated in the
sump of the bleaching column is installed.

The principle is to dry the incoming secondary air by means of the product acid, which is fed
to the top of the bleaching column (Fig. 14). In contrast to the usual configuration there is a
special drying section at the bottom where the secondary air comes in. The already bleached
total product acid flow leaves the sump of the upper part. A small amount of the total product
acid feeds the drying section below. The incoming secondary air is dried in counter-current
flow to this acid. The drying effect is physically based on the fact that the partial pressure of
water over the acid in the drying section is considerably smaller than in the compressed
secondary air.

The acid leaving the bleacher is diluted by the water contained in the secondary air.
Therefore this acid is added to the crude condensate and delivered to the appropriate
absorber tray. In this way the circuit of this extra condensate stream is closed.

Enhanced Plant Design for the Production of Azeotropic Nitric Acid

 - 14 -

FL-Bartsch Z:\DAT\FL\FL_WORK\Konferenzen\2000_akt\03_nitrogen\na&an_ugm\Bartschnitrogen.ppt page 14

Loaded Secondary Air Tailgas

12 C003
Bleacher

LIC

Product Acid 12 C001

Absorption

Secondary Air

12 E007
Cooler Condenser LIC
LIC

Fig. 14: Secondary Air Drying Configuration

4.4 Effect of Pressure Increase on Acid Concentration

An enhancement of the process pressure before absorption has two benefits. On the one
hand, the absorption is promoted by the total pressure approximately by the power of 2.2.
On the other hand, the partial pressure of the NOx gas is increased, which is necessary to
produce the desired acid strength.

Fig. 15 depicts the effect of a pressure increase. Starting point is the desired acid strength
chosen to 67.5 %, corresponding to the medium curve. The acid concentration is lower on
tray 4 than on tray 5, indicating desorption instead of absorption.

The bottom curve is derived by a pressure increase of 0.4 bar. The negative gradient
indicates absorption, meaning the desired acid strength of 67.5 % can be produced by
means of this pressure increase.

What maximum acid strength can be produced at this increased pressure? By simulation the
acid concentration has been raised until the slope is horizontal, referring to the uppermost
curve. At this concentration of 67.7 % the horizontal slope indicates the limiting value since
neither absorption nor desorption occurs.

Summing up, in this example a pressure of 0.4 bar increases the acid concentration by
0.2 %.

Enhanced Plant Design for the Production of Azeotropic Nitric Acid

 - 15 -

FL-Bartsch Z:\DAT\FL\FL_WORK\Konferenzen\2000_akt\03_nitrogen\na&an_ugm\Bartschnitrogen.ppt page 15

68

67,68 67,69

67,48 67,52
67,5
67,5PH [wt. %]
67,4 67,5 [wt. %]
67,04
67,7PH [wt. %]
Acid concentration [wt. %]

67
66,88

66,66
66,5

66,09
66
65,95

65,59
65,5

65
4 5 6 7 8 9
Tray Nr.

Fig. 15: Effect of Pressure Increase on Limit Acid Concentration

Of course the plant, especially the machine set, must be capable of providing an additional
pressure if required. The design pressures of the relevant equipment have to be raised
accordingly.
4.5 Cooling and chilled water supply
Due to the fact that the reactions governing the absorption are highly exothermic, the
appropriate cooling of the absorption tower is important. With the aid of Krupp Uhde’s
sophisticated computer program and experience, the number and distribution of the cooling
layers are determined exactly in accordance with the heat loads on every sieve tray.

The cooling water temperature available on site is fixed for a given plant and depends only
on the season. Therefore if the desired acid strength with regard to the NOx-limitation in the
tailgas cannot be achieved by cooling water only, chilled water can be used to feed the
cooling coils especially in the lower section of the absorption tower in order to increase
oxidation and acid formation.

A proven solution in Krupp Uhde plants is to use the ammonia evaporation heat to produce
chilled water in an extra circuit. In order to avoid overloading of the ammonia evaporator, this
measure is limited to maximum of approx. 80 % of the total evaporation heat.

Theoretically it is also possible to provide an external chilled water circuit if necessary.

However, this solution is expensive and therefore should only be considered if all other
measures discussed before are not sufficient.

Enhanced Plant Design for the Production of Azeotropic Nitric Acid

 - 16 -

5 Summary
Unlike for distillation, the azeotropic point itself has no significance for the production of
azeotropic acid. However, the elevated concentration of 68 % by weight implies process
constraints which have to be considered especially for the absorption section. Obviously the
NOx content in the tailgas has to be limited due to environmental requirements, especially
during partial load at decreased pressure.

The simulation runs performed were based on measured data if available. By means of a
sophisticated computer program the absorption was brought to the limit, under variation of
the respective process parameters like absorption pressure or cooling water temperature.
Thereby operation limits could be predicted reliably, at the elevated concentration and
pressure ranges which characterise an azeotropic acid plant.

For the entire azeotropic acid plant, a detailed consideration of the water balance is
mandatory. As a result, an explicit figure for the absolute humidity of the intake air was
derived. Consequently, a limit curve for the relation between relative air humidity and
temperature could be established. With the help of this tool a quick check can be made as to
whether external cooling is required. If so, Krupp Uhde is prepared to offer tailor-made
solutions. As an example, a secondary air drying configuration was discussed in more detail.

Enhanced Plant Design for the Production of Azeotropic Nitric Acid