Dual Pressure Nitric Acid Process Simulation Results ProSim PDF

PROSIMPLUS HNO3 APPLICATION EXAMPLE
DUAL-PRESSURE NITRIC ACID

MANUFACTURING PROCESS
INTEREST OF THIS EXAMPLE
This example corresponds to the simulation of a manufacturing unit of nitric acid by a dual-pressure process. It is a
rather traditional process of nitric acid industrial production. The main modules specific to the simulator ProSimPlus
HNO3 are implemented: absorption column of nitrous vapors, nitrous vapors condensers, oxidation reactors, heat
exchangers with oxidation volumes, nitrous vapor compressors, etc.
The particular points which are detailed in this example are:
The use of a constraint management module in order to reach a specification and the management of
information streams;
The use of an information stream to split a heat exchanger between a temperature set point and a simple
exchanger in order to avoid a stream recycling.
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CORRESPONDING PROSIMPLUS HNO3 FILE HNO3 dual pressure process.pmp
Reader is reminded that this use case is only an example and should not be used for other purposes. Although this example is based on actual case it
may not be considered as typical nor are the data used always the most accurate available. ProSim shall have no responsibility or liability for damages
arising out of or related to the use of the results of calculations based on this example.
Copyright 2011 ProSim, Labge, France - Tous droits rservs www.prosim.net

Dual-pressure nitric acid manufacturing process
Version : December 2011 Page : 2 / 25
TABLE OF CONTENTS
1. PROCESS MODELING 3
1.1. Process description 3
1.2. Process flow diagram 5
1.3. Specifications 5
1.4. Components 6
1.5. Thermodynamic model 6
1.6. Operating conditions 7
1.7. "Hints and Tips" 13
1.7.1. Constraints and Recycles modules 13
1.7.2. Information stream handler module 14
1.7.3. Heat exchanger splitting 15
1.7.4. Changing of the thermodynamic model 15
2. RESULTS 16
2.1. Comments on results 16
2.2. Mass and energy balances 17
2.3. Column C101 profiles 22
2.4. Column C102 profiles 24
3. REFERENCES 25

1. PROCESS MODELING
1.1. Process description
This example is extracted from the publications [1] and [2], which describe the process summarily.
The manufacture of nitric acid includes three principal stages:
Oxidation of ammonia:
4 NH3 5 O 2 4 NO 6 H2 O
Condensation of the water of combustion and oxidation of nitric oxide
H2 O gaz H2 O liq.
2 NO O 2 2 NO 2 N2 O 4
Absorption of nitrogen dioxide and Nitrogen Tetroxide:
3 NO 2 H2 O 2 HNO 3 NO
N2 O 4 1/ 2O 2 H2 O 2 HNO 3
The mathematical modeling of chemical equilibrium and kinetics of the above reactions are complex and secondary
reactions occur, in particular the formation of N2O3:
NO NO 2 N2 O 3
The dual-pressure process (pressure of the absorption appreciably higher than that of catalytic combustion) rest on
the reaction:
3 NO 2 H2 O 2 HNO 3 NO
The principal characteristic of this reaction is that, each time two molecules of nitric acid are formed, there is also
production of a nitric oxide molecule NO, that it is required to oxide in NO2 then to absorb and so on. These
successive oxidations are done mainly in gas phase, in absorption towers where are in parallel carried out the
reaction of formation of the nitric acid and that of oxidation of NO:
NO 1/ 2 O 2 NO 2
This process is characterized mainly by the use:
of two different pressures for oxidation from ammonia and the absorption of nitrogen oxides, which ensures a
high nitrogen yield and low consumption of platinum;
of a system of high-output absorption which, combined with the high pressure of operation, makes it possible
to obtain a final low NOx content of tail gas (lower than 150 ppm in volume).

The process diagram is provided hereafter.
The liquid ammonia is vaporized by cooling water (E101), then heated (E102), filtered and sent in a mixer air-
ammonia (M101). The filtered atmospheric air is compressed (K101), then is divided into two currents, the primary
air (HP Air S2) which goes to the mixer air-ammonia (M101) and secondary air which goes to the bleacher (C102).
The air-ammonia mixture is directed towards the NH3 converter (R101).
The model of the reactor takes into account three reactions:
4 NH3 5 O 2 4 NO 6 H2 O
4 NH3 3 O 2 2 N2 6 H2 O
2 NH3 2 O 2 N2 O 3 H2 O
The gas after combustion contains nitrogen oxides, nitrogen and oxygen. Its significant heat content is recovered in
a series of exchangers (E107, E106, E108, E105, E109). After condensation (E110), a large quantity of acid with
weak concentration is formed and sent to the absorption tower (C101). The gas mixed with secondary air is
compressed (K102) and is cooled (E104 and E111). The gas and the acid are directed on the perforated plates of
the absorption column (C101) equipped in particular with cooling coils. Process water is introduced at the top and
the acid with the desired concentration is recovered at its bottom. This acid then goes to the bleaching column
(C102) equipped with plates. There is a stripping by secondary air (Air S2). The outgoing gases at the top of the
C101 absorber are sent in a series of gas-gas heat exchangers (E103, E104, E105 and E106), then in an expander
(T101) and finally in the stack.
In parallel, steam is produced by heat recovery. For that feed water is preheated (E109 and E108) then steam is
produced in the boiler (E112) and is overheated (E113). Part of this steam is turbinated (T102) to bring mechanical
power necessary to the process before being condensed (E114). For simplification purposes, that is not
represented on the diagram below, but in practice the two compressors (K101 and K102) are placed on the same
shaft as the turbines (T101 and T102).
The objective of this process is to produce 1.000 T/day of nitric acid (equivalent 100%) to a concentration of 58%
mass. The oxygen contents of tail gases are fixed at 2,5% in volume (mol.). The temperature at exit of the burner is
fixed at 890 C.
The process water feed flowrate, as well as the ammonia and air feed flowrates are automatically adjusted in order
to ensure this production.
On the level of the production of steam, the unit produces steam at 15 bars.

1.2. Process flow diagram
Dual-pressure process flow diagram
1.3. Specifications
The specifications imposed on the process are as follows:
Production of 1000 Tons/day (equivalent 100%) of nitric acid with 58% mass.
Production of 30 bars steam
The oxygen content of tail gas is fixed at 2.5% in volume (mol.)
The temperature at the output of the burner is fixed at 890 C
Mechanical energy required by the two compressors for air (K101) and NOx (K102) is provided by the
turbines of tail gas (T101) and 30 bars steam (T102)
One also seeks to optimize the energy production by recoveries between hot streams and cold streams.

1.4. Components
Properties of components involved in the simulation are taken from the specific HNO3 database, provided with
ProSimPlus HNO3 software. Nine components are taken into account:
Water (H2O)
Nitric oxide (NO)
Nitrogen dioxide (NO2)
Nitrogen Tetroxide (N2O4)
Nitrogen(N2)
Oxygen (O2)
Nitric Acid (HNO3)
Ammonia (NH3)
Nitrous oxide (N2O)
1.5. Thermodynamic model
For the main part of the process the thermodynamic model taken into account is the default model of the software
ProSimPlus HNO3 (see User's manual - chapter 2).
Two exceptions to that:
- at the level of the bleaching column, the model of Engels is used. Indeed, this model is particularly
adapted to the concentrated strong acids. Furthermore, this model must be modified in order to use
the same enthalpy basis as the HNO3 specific model :
H*=DH0f, ideal gas, 25C, 1 atm.
- at the level of the production of steam, a specific model for water and steam is used.

1.6. Operating conditions
Process feeds
Ammonia Air Process water Water for steam

(NH3) (LP AIR) (Water) (Water Utility S2)
Temperature (C) 10 25 20 20
Pressure (bar) 14 1 10 15
Adjusted so as to Adjusted so as to
Adjusted so as to satisfy
Total flow rate (t/d) satisfy the satisfy the 1 130
the specifications
specifications specifications
Reactor R101
Operating parameters Value
Type of reactor simple
Ammonia conversion rate (%) 5 O2 + 4 NH3 6 H2O + 4 NO 96.2
3 O2 + 4 NH3 6 H2O + 2N2 3.7
2 O2 + 2 NH3 3 H2O + N2O 0.1
Pressure drop (bar) 0.05
Output temperature adiabatic
Heat exchangers
Output Pressure drop Oxidation

Name Type 3
temperature (C) (bar) volume (m )
E101 Cooler/Heater Dew temp. 8 -
E102 Cooler/Heater 80 0.05 -
E103a Cooler/Heater 70 0.05 -
E103b Simple heat exchanger - 0.05 -
E104a Cooler/Heater 125 0.05 1.8

E107 Cooler/Heater 440 0.05 -
E112 Cooler/Heater Dew temp. 0.05 -
E113 Simple heat exchanger - 0.05 -
E114 Cooler/Heater Dew temp. 0.05 -
For the heat exchangers in which the chemical reactions are taken into account (reaction volume not equal to
zero), one adopts:
- a plug flow pattern
- an oxidation efficiency of 1
- the calculation of the oxidation reaction rate by the model of Koukolik
- the calculation of the dimerization equilibrium constant by the model of Koukolik.
Condenser E110
Length of the tubes (m) 6
Number of tubes 840
Vapors flow Inside the tubes
Internal diameter of the tubes (mm) 25.4
Cooling water temperature (C) 15
Cooling water flow rate (t/d) 9000
Flow direction Counter-current

2
Overall heat exchange coefficient (kcal/h/m /K) 300
Moreover, one adopts:

- the calculation of the dimerization equilibrium constant by the model of Koukolik
- the calculation of the constant of absorption of N2O4 in water by the method based on the
equation of Miller (bubble caps).

Condenser E111
Length of the tubes (m) 6
Number of tubes 250
Vapors flow Inside the tubes
Internal diameter of the tubes (mm) 25.4
Cooling water temperature (C) 15
Cooling water flow rate (t/d) 6 500
Flow direction Counter-current

2
Overall heat exchange coefficient (kcal/h/m /K) 600

- the calculation of the dimerization equilibrium constant by the model of Koukolik
- the calculation of the constant of absorption of N2O4 in water by the method based on the
equation of Miller (bubble caps).
Compressor K101
Isentropic efficiency 0,845
Mechanical efficiency 1
Discharge pressure (bar) 4.6
Taking into account of the chemical reaction no
Compressor K102
Isentropic efficiency 0,795
Discharge pressure (bar) 10
Taking into account of the chemical reaction yes


- the calculation of the equilibrium constant for the N2O3 formation by the model of Miller.
Oxidation volumes
Oxidation volume Pressure drop Temperature

Nom 3
(m ) (bar) (C)
O101 20 0.0125 Adiabatic
O104 20 0.0125 85

- a plug-flow pattern
- an oxidation efficiency of 1
- the calculation of the dimerisation equilibrium constant by the model of Koukolik
Column C101
Type of column Plate oxido-absorption column
Number of stages 30
25
Weak acid feed stage
(stages numbered from top to bottom)
Column diameter (m) 5
Diameter of the holes (mm) 5
Free section 4.82 %
Pressure drop in the column (bar) 0,8
Output temperature of the acid in the bottom (C) 25

Temperature Temperature
Stage Oxidation Stage Oxidation
3 3
C) volume (m ) (C) volume (m )
1 (top) 22 23.2 16 33 11.6

2 - 23.2 17 35 11.6
3 - 23.2 18 37 11.6
4 - 23.2 19 38 11.6
5 - 23.2 20 38 11.6
6 - 23.2 21 39 11.6
7 - 23.2 22 40 11.6
8 - 23.2 23 40 11.6
9 - 23.2 24 40 11.6
10 - 23.2 25 40 11.6
11 - 23.2 26 41 11.6
12 - 23.2 27 42 11.6
13 - 23.2 28 43 11.6
14 - 23.2 29 44 11.6
15 31 23.2 30 (bottom) 45 11.62

- the calculation of the temperature profile in the column from the provided temperatures
- the dissolution of NOx is not taken into account and for NOx in liquid phase the oxidation of
NO is taken to 0%
- the calculation of the dimerisation equilibrium constant by the model of Koukolik
- the calculation of the equilibrium of the system nitrogen oxideswaternitric acid by the
equation of Zhidkov
- the efficiency of oxidation of each plate is equal to 1
- the hydrodynamic model on each plate is that of a plug-flow reactor
- the absorption efficiency on each plate is calculated by the equation of Atroshenko 3 with a
height of liquid on the trays of 10 cm.
Column C102
Type of column Absorber
Number of theoretical stages 5
Overhead pressure (bar) 4.2
Pressure drop in the column (bar) 0.2

Pump P101
Exhaust pressure (bar) 11
Volumetric efficiency 0.65
Expander T101
Discharge pressure (bar) 1
Isentropic efficiency 0.83
Turbine T102
Discharge pressure (bar) 1.05
Isentropic efficiency 0.85
Valve V101
Operating parameters Value Comments
Three way
Type of valve
valve
Splitting rate for the stream This rate will be adjusted in

80
AIR HP2 (%) order to reach the specifications
Valve V102
Operating parameters Value Comments
Three way
Type of valve
valve
This rate will be adjusted in order to
Splitting rate of the stream
90 expand sufficient steam to balance the
Steam S5 (%)
power required by the compressors

1.7. "Hints and Tips"
1.7.1. Constraints and Recycles modules
It is possible with ProSimPlus HNO3 to implement on the same flowsheet several modules of constraint
management. Here for example, for clarification of the diagram of simulation purposes, two modules of constraint
management are implemented:
- one for the process itself: SPEC01
- the other for the production of steam: SPEC02
The implementation of several modules of constraint management affects the order of calculation of the modules
(list of calculation automatically determined in ProSimPlus HNO3) and the convergence of each cycle, but does not
have any influence on the results obtained when convergence is reached. This possibility can be used in certain
very complex cases to facilitate convergence of flowsheets, or like here in order to simplify the representation of the
process.
The operation of the modules of Constraint Management in ProSimPlus HNO3 is described at the level of the user's
manual and illustrated in the application example of ProSimPlus E02 (Cyclohexane Plant).
In this case, at the level of the module SPEC01, 4 specifications (constraints) are imposed:
- the partial mass flowrate of pure nitric acid produced in bleaching column C102 bottom is fixed at
1000 T/d (measurement module MEAS03)
- the mass composition of the produced nitric acid (bleaching column C102 bottom) is fixed at 58%
(measurement module MEAS01)
- the oxygen volume composition (molar) in tail gas (TG S6) is fixed at 2.5% (measurement module
MEAS04)
- the output temperature of the reactor R101 (stream PG01) is fixed at 890C (measurement module
MEAS02)
With ProSimPlus HNO3, the module Constraint Management module SPEC01 then will adjust 4 parameters
simultaneously (action variables) to satisfy these specifications:
- ammonia feed flowrate (feed module NH3 feed)
- air feed flowrate (feed module Air feed)
- process water feed flowrate (feed module Process water feed)
- the value of the splitting ratio of the air in V101 valve between the air used the reactor R101 and the
air used in the bleaching column C102.
Moreover, this module SPEC01 also manages the convergence of the recycling streams.

1.7.2. Information stream handler module
At the module of constraint management SPEC02 level, the turbinated steam flowrate is adjusted by action on the
opening of the valve V102, in order to balance the power consumption of the compressors K101 and K102 with that
produced by the turbines T101 and T102. For that, several Information stream handler modules are implemented.
The Information stream handler module makes it possible in ProSimPlus HNO3 to make simple operations on a
information stream: to add (B) or of to withdraw (C) a constant, to multiply (A and P=1) or to divide (A and P=-1) its
content by a constant or to raise at power (P). The result of this operation is available in the information stream
leaving the Information stream handler module:
P
Output = A * (Input) + B C
In this formulation, A, B, C and P are constants fixed by the user. Entering several information streams in a
Information stream handler module and exploiting their position in the parameter area of the module it is possible to
make them take the place of constant A, B, C and P and thus to make operations between several information
streams (see below).
While implementing several modules of this type it is thus possible to make more complicated operations. For more
complex calculations on the information streams it is however recommended to implement a Windows Script
module.
Here, the Information stream handler module H102 receives in entry:
- power of the K102 compressor as value to be handled (WK102)
- power of the K101 compressor as additive factor (B)
A and P are fixed at 1 and C at 0. Thus the leaving information stream (Power compressors) will contain the total
power consumed by the two compressors.
In the same way, the Information stream handler module H103 receives in entry:
- power produced by the T101 turbine as value to be handled (WT101)
- power produced by the T102 turbine as additive factor (B)
A and P are fixed at 1 and C at 0. Thus the leaving information stream (Power turbines) will contain the total power
produced by the two turbines.
These two information streams (Power compressors and Power turbines) are then sent towards the Information
stream handler module H104 to make the sum of them. The stream Power compressors as value to be handled
and the stream Power turbines as additive factor (B). A and P are fixed at 1 and C at 0. Thus the leaving information
stream (Power difference) will contain the difference between the power of the turbines (negative) and that of the
compressors (positive). This information stream Power difference is then sent towards the module SPEC02 which
will take in charge to make converge towards zero the value of Power difference by action on the rate of division of
the V102 valve.

1.7.3. Heat exchanger splitting
In this example, most of the heat exchangers are simulated by uncoupling the hot stream and the cold stream. This
modeling of a heat exchanger between two streams makes it possible to avoid a recycling stream which would
penalize calculations by uncoupling the heat exchanger in two parts. This modeling is illustrated in the example of
application of ProSimPlus E02 (Cyclohexane Plant).
1.7.4. Changing of the thermodynamic model
In order of insure the consistency in the calculation of the enthalpies between the column C101 (oxido-absorption)
and the column C102 (bleacher) which are using different thermodynamic models (HNO3 specific for the first and
Engels for the latter), it is necessary to insert on the C102 inlet stream (Acid S1+S2) a dummy module which will
allow to change the thermodynamic model. The unit operation generally used for this purpose is a Cooler/Heater in
which the output temperature is taken equal to the inlet temperature. Thus only the enthalpy is recalculated. The
heat duty printed in the simulation report must be, of course, ignored as it corresponds only to the difference in the
enthalpies calculated by both models. In the present case, both models give enthalpy values which are very close
(deviation < 0.7 %), however this deviation must be multiplied by the value of the flowrate, that could lead, by the
end, to have some influence on the column C102.

2. RESULTS
2.1. Comments on results
The sequence of calculation (the order of calculation of the modules) is generated automatically. At the level of
recycling, no stream is initialized and ProSimPlus HNO3 chooses to make converge the stream Air S3.
The convergence of the first cycle is obtained in 4 iterations, that is to say 20 runs in the Maximum Cyclic Network.
The convergence of the second module of specification is obtained in 1 iteration, that is to say 4 passages in the
Maximum Cyclic Network.
When convergence is reached, the values obtained of the various parameters adjusted automatically by
ProSimPlus HNO3 to reach the specifications are as follows:
- ammonia feed flowrate: 283.616 t/d
- air feed flowrate: 4999.89 t/d
- process water feed flowrate: 367.240 t/d
- air splitting ratio in V101 valve:
air used in the R101 reactor: 83.83 %
air used in the C102 bleaching column: 16.17 %.
Regarding the absorption column (C101), convergence is obtained in 9 iterations, without any initialization.
Regarding the bleaching column (C102), it converges in 2 iterations, also without any initialization.

2.2. Mass and energy balances
Streams Acid S1 Acid S1+S2 Acid S2 Acid S3 Acid S4

From E111 Acids mixer C101 Dummy E110
To Acids mixer Dummy Acids mixer C102 P01
Partial flows t/d t/d t/d t/d t/d
WATER 110.330629 719.0267179 608.696089 719.0267179 209.963131
NITRIC OXIDE 0 0 0 0 0
NITROGEN DIOXIDE 0 0.171242013 0.171242013 0.171242013 0
NITROGEN 0 26.5555056 26.5555056 26.5555056 0
TETROXIDE
NITROGEN 0 0 0 0 0
OXYGEN 0 0 0 0 0
NITRIC ACID 50.70934 1002.750981 952.0416409 1002.750981 48.4400512
AMMONIA 0 0 0 0 0
NITROUS OXIDE 0 0 0 0 0
Total flow t/d 161.039969 1748.504446 1587.464477 1748.504446 258.403182
Total flow kmol/h 288.70913 2338.240064 2049.530933 2338.240064 517.643508
Temperature C 91.9381166 52.59991071 45 52.59991071 81.6451604
Pressure bar 9.89999732 9.899997325 9.899997325 9.899997325 4.21249886
Enthalpic flow kcal/h -18692289.6 -143427975 -124735685 -142520016 -34196144.9
Vapor fraction 0 0 0 0 0
Streams Acid S5 AIR S1 AIR S2 AIR S3 Condensate

s
From P01 V101 E103a C102 E114
To C101 E103a C102 K102 >>>>
WATER 209.963131 9.150953613 9.150953613 4.436011318 959.536085
NITROGEN DIOXIDE 0 0 0 22.50500389 0
NITROGEN 0 0 0 4.222192633 0
TETROXIDE
NITROGEN 0 613.4532114 613.4532114 613.2970848 0
OXYGEN 0 186.0172684 186.0172684 185.7742049 0
NITRIC ACID 48.4400512 0 0 2.755109167 0
AMMONIA 0 0 0 0 0
Total flow t/d 258.403182 808.6214333 808.6214333 832.9896067 959.536085
Total flow kmol/h 517.643508 1175.820719 1175.820719 1188.483363 2219.26197
Temperature C 81.9068606 215.7343361 70 47.07917229 99.6325065
Pressure bar 10.999997 4.599998757 4.54999877 4.199998865 0.99999973
Enthalpic flow kcal/h -34193628.8 359264.567 -852795.401 -300693.485 1220318.93

Streams HP AIR1 HP AIR2 LP AIR NH3 NH3 S2

From K101 V101 >>>> >>>> E101
To V101 Mixer K101 E101 E102
Air+NH3
WATER 56.5824732 47.43151958 56.5824732 0 0
NITROGEN DIOXIDE 0 0 0 0 0
NITROGEN 0 0 0 0 0
TETROXIDE
NITROGEN 3793.12379 3179.670583 3793.123794 0 0
OXYGEN 1150.18801 964.1707389 1150.188007 0 0
NITRIC ACID 0 0 0 0 0
AMMONIA 0 0 0 283.6165392 283.616539
Total flow t/d 4999.89427 4191.272841 4999.894275 283.6165392 283.616539
Total flow kmol/h 7270.37281 6094.552088 7270.372806 693.8895752 693.889575
Temperature C 215.734336 215.7343361 25 10 9.36352185
Pressure bar 4.59999876 4.599998757 0.992984732 13.99999622 5.99999838
Enthalpic flow kcal/h 2221416.32 1862151.757 -7563428.45 -11101866.5 -7703546.38
Streams NH3 S3 Nitric Acid PG00 PG01 PG02

Production
From E102 MEAS03 Mixer MEAS02 E107
Air+NH3
To Mixer >>>> R101 E107 E106a
Air+NH3
WATER 0 723.7416218 47.43151958 497.4541587 497.454159
NITRIC OXIDE 0 0 0 480.7134005 480.713401
NITROGEN DIOXIDE 0 0.000204006 0 0 0
NITROGEN 0 0 0 0 0
TETROXIDE
NITROGEN 0 0.155163048 3179.670583 3188.301177 3188.30118
OXYGEN 0 0.242766129 964.1707389 308.053362 308.053362
NITRIC ACID 0 999.9960371 0 0 0
AMMONIA 283.616539 0 283.6165392 0 0
NITROUS OXIDE 0 0 0 0.36648111 0.36648111
Total flow t/d 283.616539 1724.135792 4474.889381 4474.88858 4474.88858
Total flow kmol/h 693.889575 2335.689738 6788.441663 6961.740584 6961.74058
Temperature C 80 51.93127648 198.0812614 889.9999211 440
Pressure bar 5.94999839 4.399998811 4.599998757 4.54999877 4.49999878
Enthalpic flow kcal/h -7280058.65 -143072111 -5417906.89 -5417908.71 -30796025.4

Streams PG03 PG04 PG05 PG06 PG07

From E106a O101 E108a O102 E105a
To O101 E108a O102 E105a OXI 03
WATER 497.454159 497.4541587 497.4541587 497.4541587 497.454159
NITRIC OXIDE 471.416336 376.4039363 368.8073881 282.2212567 277.264103
NITROGEN DIOXIDE 14.2542765 159.9260257 171.5512153 304.2980458 311.662956
NITROGEN 2.8829E-05 0.001757513 0.02363313 0.0310847 0.2665072
TETROXIDE
NITROGEN 3188.30118 3188.301177 3188.301177 3188.301177 3188.30118
OXYGEN 303.096121 252.435043 248.3845261 202.2163753 199.573196
NITRIC ACID 0 0 0 0 0
AMMONIA 0 0 0 0 0
NITROUS OXIDE 0.36648111 0.36648111 0.36648111 0.36648111 0.36648111
Total flow t/d 4474.88858 4474.88858 4474.88858 4474.88858 4474.88858
Total flow kmol/h 6955.28559 6889.317386 6884.033172 6823.912763 6820.36439
Temperature C 290 325.3800873 220 252.7245814 180
Pressure bar 4.4499988 4.437498801 4.387498814 4.374998818 4.32499883
Enthalpic flow kcal/h -38871910.2 -38871910.2 -44442115.9 -44442115.9 -48230234.8
Streams PG08 PG09 PG10 PG11 PG13

From OXI 03 E109a E110 O104 K102
To E109a E110 O104 K102 E104a
WATER 497.454159 497.4541587 280.5665562 280.5665562 285.002567
NITRIC OXIDE 228.148186 223.6229539 222.0586562 150.6022616 150.602262
NITROGEN DIOXIDE 387.010908 387.5943842 338.5782304 439.0036651 496.534591
NITROGEN 0.22332033 6.57795939 22.62660588 31.75847658 0.95470962
TETROXIDE
NITROGEN 3188.30118 3188.301177 3188.301177 3188.301177 3801.59826
OXYGEN 173.384348 170.9714722 163.9877533 125.8868524 311.661057
NITRIC ACID 0 0 0 0 2.75510917
AMMONIA 0 0 0 0 0
NITROUS OXIDE 0.36648111 0.36648111 0.36648111 0.36648111 0.36648111
Total flow t/d 4474.88858 4474.888587 4216.48546 4216.48547 5049.47504
Total flow kmol/h 6786.2826 6780.263058 6230.243037 6176.495317 7380.83997
Temperature C 198.72224 110 81.64516041 85 192.339758
Pressure bar 4.31249883 4.262498848 4.212498862 4.199998865 9.9999973
Enthalpic flow kcal/h -48230234.8 -52799109.1 -25845022.8 -27112834.5 -21102233.3

Streams PG14 PG15 Steam S1 Steam S2 Steam S3

From E104a E111 E112 E113 V102
To E111 C101 E113 V102 T102
WATER 285.002567 167.4230739 1130 1130 959.536085
NITRIC OXIDE 123.490504 119.2119249 0 0 0
NITROGEN DIOXIDE 525.913527 458.7435962 0 0 0
NITROGEN 13.1436659 49.85086208 0 0 0
TETROXIDE
NITROGEN 3801.59826 3801.598262 0 0 0
OXYGEN 297.204935 288.4858539 0 0 0
NITRIC ACID 2.75510917 2.755109167 0 0 0
AMMONIA 0 0 0 0 0
NITROUS OXIDE 0.36648111 0.36648111 0 0 0
Total flow t/d 5049.47505 4888.435163 1130 1130 959.536085
Total flow kmol/h 7356.4965 7023.045811 2613.519249 2613.519249 2219.26197
Temperature C 125 91.93811658 197.8505116 393.1981727 393.198173
Pressure bar 9.94999731 9.899997325 14.84999599 14.799996 14.799996
Enthalpic flow kcal/h -25332332.1 -12128773.1 2743214.284 7808092.881 6630218.48
Streams Steam S4 Steam S5 TG S1 TG S2 TG S3

From T102 V102 C101 E103b E104b
To E114 >>>> E103b E104b E105b
WATER 959.536085 170.4639145 7.154859967 7.154859967 7.15485997
NITRIC OXIDE 0 0 2.334332508 2.334332508 2.33433251
NITROGEN DIOXIDE 0 0 3.129031469 3.323380347 3.35275238
NITROGEN 0 0 0.223896879 0.029547791 0.00017573
TETROXIDE
NITROGEN 0 0 3801.598262 3801.598262 3801.59826
OXYGEN 0 0 111.7994054 111.7994054 111.799405
NITRIC ACID 0 0 0.000525795 0.000525795 0.00052579
AMMONIA 0 0 0 0 0
NITROUS OXIDE 0 0 0.36648111 0.36648111 0.36648111
Total flow t/d 959.536085 170.4639145 3926.606795 3926.606795 3926.60679
Total flow kmol/h 2219.26197 394.257276 5823.063828 5823.151838 5823.16514
Temperature C 128.789291 393.1981727 22 51.83759596 155.728602
Pressure bar 1.04999972 14.799996 9.099997541 9.049997554 8.99999757
Enthalpic flow kcal/h 1777553.49 1177874.405 -978694.335 233365.6391 4463464.37

Streams TG S4 TG S5 TG S6 Water Water Utility

S2
From E105b E106b MEAS04 >>>> >>>>
To E106b T101 >>>> C101 E109b
WATER 7.15485997 7.154859967 7.154859967 367.2407048 1130
NITRIC OXIDE 2.33433251 2.334332508 2.334332508 0 0
NITROGEN DIOXIDE 3.35291791 3.352927815 3.352927815 0 0
NITROGEN 1.0196E-05 2.89804E-07 2.89804E-07 0 0
TETROXIDE
NITROGEN 3801.59826 3801.598262 3801.598262 0 0
OXYGEN 111.799405 111.7994054 111.7994054 0 0
NITRIC ACID 0.00052579 0.000525795 0.000525795 0 0
AMMONIA 0 0 0 0 0
NITROUS OXIDE 0.36648111 0.36648111 0.36648111 0 0
Total flow t/d 3926.60679 3926.606795 3926.606795 367.2407048 1130
Total flow kmol/h 5823.16521 5823.165218 5823.165218 849.3722577 2613.51925
Temperature C 247.85697 439.3442294 171.0302931 20 20
Pressure bar 8.94999758 8.899997595 0.99999973 9.999997298 14.9999959
Enthalpic flow kcal/h 8251581.95 16327464.53 5089518.327 -58071654.3 -27707366.3
Streams Water Utility Water utility

S3 S4
From E109b E108b
To E108b E112
Partial flows t/d t/d
WATER 1130 1130
NITRIC OXIDE 0 0
NITROGEN DIOXIDE 0 0
NITROGEN 0 0
TETROXIDE
NITROGEN 0 0
OXYGEN 0 0
NITRIC ACID 0 0
AMMONIA 0 0
NITROUS OXIDE 0 0
Total flow t/d 1130 1130
Total flow kmol/h 2613.51925 2613.519249
Temperature C 116.833991 198.0095633
Pressure bar 14.949996 14.89999597
Enthalpic flow kcal/h -23138491.9 -17568286.2
Vapor fraction 0 0.07331793

2.3. Column C101 profiles
Heat duty
-1.1E+07
-1.0E+07
-9.0E+06
-8.0E+06
-7.0E+06
Heat duty (kcal/h)
-6.0E+06
-5.0E+06
-4.0E+06
-3.0E+06
-2.0E+06
-1.0E+06
0.0E+00
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30
Tray
NOx vapor mass flowrates
800
700
600
NOx mass flowrates (t/d)
500
400
300
200
100
0
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30
Tray
NO NO2 N2O4 NOx (NO+NO2+2N2O4)

Amount of NOx amount (ppmv)
90000
80000
70000
60000
NOx amount (ppmv)
50000
40000
30000
20000
10000
0
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30
Tray
Liquid mass fractions
0.7
0.6
0.5
Mass fraction
0.4
0.3
0.2
0.1
0.0
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30
Tray
HNO3 NOx

2.4. Column C102 profiles
Liquid mass-fractions
0.60
0.58
0.56
0.54
Mass-fraction
0.52
0.50
0.48
0.46
0.44
0.42
0.40
1 2 3 4 5
Stage
WATER NITRIC ACID
Vapor mass-fractions
0.030
0.025
0.020
Mass-fraction
0.015
0.010
0.005
0.000
1 2 3 4 5
Stage
NITROGEN DIOXIDE NITROGEN TETROXI

3. REFERENCES
[1] Badoual C.
Acide Nitrique
Techniques de l'Ingnieur, trait de Gnie des Procds
[2] Clarke Stephen I. and Mazzafro William J.

Nitric Acid
Kirk-Othmer Encyclopedia of Chemical Technology, 4th edition
[3] Joulia X.
"Contribution au dveloppement d'un programme gnral de simulation. Application l'analyse du
fonctionnement d'un atelier de production d'acide nitrique"
Thse INPT 1981

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PROSIMPLUS HNO3 APPLICATION EXAMPLE

DUAL-PRESSURE NITRIC ACID

INTEREST OF THIS EXAMPLE

The particular points which are detailed in this example are:

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CORRESPONDING PROSIMPLUS HNO3 FILE HNO3 dual pressure process.pmp

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1.1. Process description

The manufacture of nitric acid includes three principal stages:

Condensation of the water of combustion and oxidation of nitric oxide

Absorption of nitrogen dioxide and Nitrogen Tetroxide:

This process is characterized mainly by the use:

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The process diagram is provided hereafter.

The model of the reactor takes into account three reactions:

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1.2. Process flow diagram

Dual-pressure process flow diagram

The specifications imposed on the process are as follows:

Production of 30 bars steam

The oxygen content of tail gas is fixed at 2.5% in volume (mol.)

The temperature at the output of the burner is fixed at 890 C

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Nitric oxide (NO)

Nitrogen dioxide (NO2)

Nitrogen Tetroxide (N2O4)

Nitric Acid (HNO3)

Nitrous oxide (N2O)

1.5. Thermodynamic model

Two exceptions to that:

H*=DH0f, ideal gas, 25C, 1 atm.

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1.6. Operating conditions

Ammonia Air Process water Water for steam

Operating parameters Value

Type of reactor simple

Ammonia conversion rate (%) 5 O2 + 4 NH3 6 H2O + 4 NO 96.2

3 O2 + 4 NH3 6 H2O + 2N2 3.7

2 O2 + 2 NH3 3 H2O + N2O 0.1

Pressure drop (bar) 0.05

Output temperature adiabatic

Output Pressure drop Oxidation

E101 Cooler/Heater Dew temp. 8 -

E102 Cooler/Heater 80 0.05 -

E103a Cooler/Heater 70 0.05 -

E103b Simple heat exchanger - 0.05 -

E104a Cooler/Heater 125 0.05 1.8

E104b Simple heat exchanger - 0.05 -

E105a Cooler/Heater 180 0.05 1.8

E105b Simple heat exchanger - 0.05 -

E106a Cooler/Heater 290 0.05 1.8

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E106b Simple heat exchanger - 0.05 -

E107 Cooler/Heater 440 0.05 -

E108a Cooler/Heater 220 0.05 1.8