PROSIMPLUS HNO3 APPLICATION EXAMPLE

DUAL-PRESSURE PROCESS

EXAMPLE PURPOSE

This example corresponds to a dual-pressure nitric acid production process. It is a rather usual process of industrial
production of nitric acid. The main modules specific to the simulator ProSimPlus HNO3 are used in this simulation:
absorption column of nitrous vapors, nitrous vapors condenser, oxidation reactors, heat exchangers with oxidation
volumes, nitrous vapor compressors, etc.

The particular points which are detailed in this example are:

 Use of a constraints and recycles module to reach a set of specifications,

 Compressors – expanders coupling using information streams to model the turbo-expander and use of a
constraints and recycles module to balance the powers.
 The separation of a heat exchanger between a cooler/heater and a simple heat exchanger to avoid a
recycle stream by using an information stream.

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CORRESPONDING PROSIMPLUS HNO3 FILE PSPH_E02_EN – Dual-pressure process.pmp3

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.

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TABLE OF CONTENTS

1. MODELING OF THE PROCESS 3

1.1. Process description 3
1.2. Process flowsheet 5
1.3. Components 6
1.4. Thermodynamic models 6
1.5. Chemical reactions 7
1.6. Operating conditions 8
1.6.1. Nitric acid production process 8
1.6.2. Specifications of the nitric acid production process 15
1.6.3. Utility production 16
1.6.4. Coupling of the compressors and the expanders 18
1.7. “Tips and tricks” 21
2. RESULTS 22
2.1. Mass and energy balances 22
2.2. Process performance 25
2.3. Nitrous vapors condensers profiles 26
2.4. Columns profiles 28
2.4.1. Oxido-absorption column 28
2.4.2. Bleaching column 30
3. REFERENCES 30

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1. MODELING OF THE PROCESS

1.1. Process description

This example is extracted from [BAD96] and [CLA96], which describe summarily the process. The production of
nitric acid includes three main steps:

 Ammonia oxidation

4 +5 →4 +6

4 +3 →2 +6

2 +2 → +3

 Oxidation of the nitric oxide and condensation of the combustion water

2 + →2 ↔

| ↔ |

 Fixing of the nitrogen tetroxide

3
+ ↔2 +
2

The mathematical representations of the equilibria and kinetics of the reactions described here above is complex.
Side reactions occur, in particular the formation of nitrogen trioxide:

+ ↔

The dual-pressure process (pressure of the absorption sensibly higher than the one of the catalytic oxidation) lies
on the reaction:

3
+ ↔2 +
2

The main characteristic of this reaction is that each time two molecules of nitric acid are formed there is also
production of one molecule of nitric oxide (NO). This molecule of NO has to be oxidized in NO2, and then absorbed
and so on. These successive oxidations are mainly done in gas phase in oxido-absorption tower where the
reactions of nitric acid production and NO oxidation are performed in parallel:

2 + →2

This process is mainly characterized by the use of two different pressures for the ammonia oxidation and the
absorption of the nitrogen oxides. This ensures a high yield in nitrogen and decreases the consumption of platinum.

The process flowsheet is given in paragraph 1.2. The liquid ammonia is vaporized (E101), then after overheating
(E102), is sent in an air – ammonia mixer (AIR NH3 MIXER). The atmospheric air is compressed
(AIR COMPRESSOR), then divided in two streams: the primary air (HP AIR 2) sent to the air – ammonia mixer
(AIR NH3 MIXER) and the secondary air sent to the bleaching column (BLEACHING COLUMN). The air –
ammonia mixture is sent to the burner (BURNER).

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For the reactor modelling, three global reactions are taken onto account:

4 +5 →4 +6

4 +3 →2 +6

2 +2 → +3

The gas after combustion is composed of nitrogen oxides, nitrogen and oxygen. Its sensible heat is recovered in a
series of heat exchangers (E104, E105, E106, E107 and E108). After condensation (CONDENSER 1), a huge
quantity of weak nitric acid is formed and sent to the absorption tower (OXIDO-ABSORPTION COLUMN). The
second compressor (NOx COMPRESSOR) received the gas coming from the first condenser and from the
bleaching column. After cooling in the heat exchanger (E109), these gases enter in the sieve trays oxido-
absorption column (OXIDO-ABSORPTION COLUMN). Process water is introduced at the top of this column and
nitric acid at the whished concentration is withdrawn at its bottom. Then, this acid goes to the bleaching column
(BLEACHING COLUMN). A stripping by the secondary air (HP AIR 4) is done in this equipment. The gas leaving
the absorber C101 is sent to a serie of gas-gas heat exchangers (E103, E105, E107 and E109) and then in an
expander (EXPANDER). The gas leaves the process via a stack. The possible reactor for NOx reduction is not
modeled in this example. This aspect is detailed in the example “PSPH_E01_EN - Mono-pressure process”.

In parallel, steam is produced by energy integration. For that, the water is preheated (E106 and E108), then the
steam is produced in the boiler (BOILER) and overheated (OVERHEATER). A part of this steam is expanded
(STEAM EXPANDER) to bring the mechanical energy needed by the process. This steam is then condensed
(STEAM CONDENSER). From a practical point of view, the two compressors (AIR COMPRESSOR and
NOx COMPRESSOR) are on the same shaft than the two expanders (EXPANDER and STEAM EXPANDER).
Information streams and information stream handler modules are used to model this coupling.

The objective of this process is to produce 1 000 t/d of nitric acid (eq. 100%) at a concentration of 58% mass. At
the steam production level, this plant produces 15 bars steam by energy integration.

The oxygen amount in the tail gas is fixed at 2.5% volume (mol.). The temperature at the outlet of the burner is
fixed to 890°C. The water flow rate for absorption, the ammonia feed flow rate, the air feed flow rate and the ratio
between the primary and the secondary air are automatically adjusted to ensure this production. The amount of
steam expanded is adjusted to balance the power available at the turbines and those necessary for the
compressors.

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 Q(E1…
Q(E1…
AIR NH3 MIX… EXPANDER
NH3 1 NH3 2 NH3 3 TG 3 TG 4 TG 5
PG 00 1.2.
NH3 FEED E101 E102 E107b E105b
Q(E1… E109b
HP AIR 2 AAA
1
x(O2)
BURNER
HP AIR 1 HP AIR SPLITT… TG 2

TG 6
Dual-pressure process

AIR COMPRESS… Q(E1… E103b

Version: December 2017

AIR FEED AAA d(xO2)

T(Burn… 1 SR(HP …
LP AIR HP AIR 3 TG 1
PG 01

d(TBurn …
Water
E104 FLARE
D(Water)
WATER FEED
E103a
PG 02
D(Air)
OXIDO-ABSORPTION COL…
Process flowsheet

E106a
E105a

PG 06 PIPE 2 PG 05 PG 04 PIPE 1 PG 03 D(N… SPEC

E107a
PG 12 Constraints and Recyc…

PIPE 4 PG 11
E109a
PG 07
NOx COMPRESS… PG 13 PG 14
Q(Air compressor)
PG 15

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E108a PG 10
ACID 2
ACID 6 Q(Expand…
PIPE 3 PG 08 PG 09
CONDENSE …

d(DHN…
ACID 3 Th ACID 4
CONDENSE … ACID 1
Q(NOx compressor)
ACID MIX… Calculator Switch
d(wHN…

PUMP
BLEACHING COLU…
ACID 5

Dual-pressure HP AIR 4

process HNO3 PRODUCTI…

AAA AAA
STORAGE 1 1
Q(E1… Q(E1… Q(E104)
COMPRESSO… w(HN … D(HN…

BOILER HEAT DU… Q(COompresso …

UTILITY

STEAM 4 C ONDENSAT …
STEAM EXPAND…

STEAM CONDENS… UTILITY OUTLE…

Q(Boil… Q(Overhea…
Q(Steam expand…
STEAM 3
EXPANDE…
SPLIT RA…
Q(Expande…
SPEC DEVIATI …
WU 1
STEAM SPLITT…
WU 2 WU 3 STEAM 1 STEAM 2

WATER UTILI … Constraints and Recycle…

E108b E106b BOILER OVERHEATER
UTILITY OUTLE …
TURBO-EXPAND …
STEAM 5
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1.3. Components

Components taken into account in the simulation, their chemical formula and CAS numbers are presented in the
following table. Pure components physical properties are extracted from the ProSimPlus HNO3 specific database
(“HNO3”).

Component name Chemical formula CAS number

Water H2O 07732-18-5
Nitric oxide NO 10102-43-9
Nitrogen dioxide NO2 10102-44-0
Nitrogen tetroxide N2O4 10544-72-6
Nitrogen N2 07727-37-9
Oxygen O2 07782-44-7
Nitric acid HNO3 07697-37-2
Ammonia NH3 07664-41-7
Nitrous oxide N2O 10024-97-2

1.4. Thermodynamic models

For the main part of the process, the “HNO3 specific” thermodynamic model is selected. This model takes into
account the non-ideality of the liquid phase through correlations based on experimental data of partial pressures of
water and nitric acid over aqueous solutions of nitric acid. The perfect gas model is used for the gas phase. A
correlation based on experimental data is used to take into account the excess enthalpies of the water – nitric acid
binary.

For the bleaching column the “Engels (strong acids)” thermodynamic model is used. This model well represents the
NOx solubility and the complexity of the H2O – HNO3 equilibria. The “H*=DH0f, ideal gas, 25°C, 1 atm” enthalpy
basis is selected instead of the default one of this model, to ensure the coherence with the “HNO3 specific” model.

For the cooling water circuit, the “Specific thermodynamic model for water” is used [HAA84].

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1.5. Chemical reactions

NO oxidation, NO2 dimerization and nitric acid oxido-absorption reactions are pre-coded. Thus, they don’t have to
be described by the user for modules specific to ProSimPlus HNO3. The reactions to be described are the ones for
the combustion of the ammonia:

4 +5 →4 +6

4 +3 →2 +6

2 +2 → +3

These different reactions are defined as:

 Reaction type: Controlled

 Kinetic model: Instantaneous

The instantaneous kinetic model is chosen because conversion ratios are specified for each reaction in the
reactors “BURNER” (§ 1.6.1).

The NO2 dimerization equilibrium in gas phase is taken into account in the bleaching column. Indeed this column is
modelled by a non-specific module of ProSimPlus HNO3 (§ 1.6.1).

2 ↔

The equilibrium constant used is the one proposed by [KOU68]:

6891.64
( ) = −21.24366 +

The partial orders are 2 for the NO2 and 1 for the N2O4.

The heats of reaction of these different reactions are computed from the standard enthalpies of formation at 25°C.

Two reaction sets have to be created:

 One with only the ammonia combustion reactions,

 One with only the NO2 dimerization reaction.

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1.6. Operating conditions

1.6.1. Nitric acid production process

 Process feeds

Feed NH3 FEED AIR FEED WATER FEED

Molar fraction
Nitrogen 0 0.776 0
Oxygen 0 0.206 0
Ammonia 1 0,000 0
Water 0 0.018 1
Total flow rate (t/d) 280 5000 365
Temperature (°C) 10 25 20
Pressure (bar) 14 1 10

 “BURNER” ammonia combustion burner

Operating parameters Value

Reactor type Simple
Reaction set Ammonia combustion
Ammonia conversion ratio (%)
4 +5 →4 +6 96.2
4 +3 →2 +6 03.7
2 +2 → +3 00.1
Thermal behavior Adiabatic
Pressure drop (bar) 0.05

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 Oxidation reactors

These modules model the oxidation of the NO and the dimerization of the NO2 in the gas volumes of pipes.

PIPE 1 PIPE 2 PIPE 3 PIPE 4

Reactor type Simplified plug flow
3
Oxidation volume (m ) 20 25 20 20
Calculation of the exchanged heat duty Adiabatic T = 85°C
Oxidation efficiency 1
Reactions
Calculation of the oxidation reaction
Koukolik
rate constant
Calculation of the dimerization
Koukolik
equilibrium constant
Pressure drop (bar) 0.0125

 Cooler/Heater modules

Name Outlet temperature (°C) Pressure drop (bar) Oxidation volume (m3)
E101 Dew temperature 8,00 0,0
E102 080 0.05 0,0
E103a 070 0.05 0,0
E104 440 0.05 0,0
E105a 290 0.05 1.8
E106a 220 0.05 1.8
E107a 180 0.05 1.8
E108a 110 0.05 1.8
E109a 125 0.05 1.8

The following parameters are used for the heat exchangers in which the chemical reactions are taken into account
(the ones with an oxidation volume different from 0):

o Hydrodynamic model: Plug flow

o Oxidation efficiency: 1
o Calculation of the oxidation rate constant: Koukolik
o Calculation of the dimerization equilibrium constant: Koukolik
o Take into account of a maximum temperature for the oxidation: Yes

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 Simple heat exchangers

Name Heat duty (kW) Pressure drop (bar) Oxidation volume (m3)
E103b 0 0.05 0
E105b 0 0.05 0
E107b 0 0.05 0
E109b 0 0.05 0

The heat duties are sent by information streams from the corresponding cooler/heater modules (E103a, E105a,
E107a and E109a).

 Nitrous vapors condensers

CONDENSER 1 CONDENSER 2
Tubes length (m) 6
Number of tubes 840 250
Circulation of the vapors Inside the tubes
Inner diameter of the tubes (mm) 25.4
Equivalent diameter (mm) 0
Cooling water
Temperature (°C) 20 15
Flow rate (kg/h) 375 000 271 000
Flow direction Counter-current
Heat transfer coefficients (kcal/h/m2/K)
Oxido-absorption 300 600
Oxidation 0
Pressure drop (bar) 0.05
Reactions
Calculation of the oxidation rate constant Koukolik
Calculation of the dimerization equilibrium constant Koukolik
Calculation of the absorption constant of N2O4 in water Miller (bubble caps)
Number of intermediate points for print 10

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 Compressors

AIR COMPRESSOR NOx COMPRESSOR

Discharge pressure (bar) 4.6 10
Efficiency
Isentropic 0.845 0.795
Mechanical 1
Reactions
Taken into account No Yes
Dimerization equilibrium constant - Koukolik
Equilibrium of N2O3 formation - Miller

 “EXPANDER” tail gas expander

Operating parameters Value

Type Expander
Discharge pressure (bar) 1
Isentropic efficiency (-) 0.83
Mechanical efficiency (-) 1
Electrical efficiency (-) 1

 “PUMP” centrifugal pump

Operating parameters Value

Type centrifugal pump
Discharge pressure (bar) 11
Volumetric efficiency (-) 0.65
Mechanical efficiency (-) 1
Electrical efficiency (-) 1

 “HP AIR SPLITTER” splitter

Operating parameters Value

Type Three way valve
Splitting ratio of the stream HP AIR 2 (primary air) 0.80
Automatically calculated stream HP AIR 3 (secondary air)
Outlet pressure Equal to the feed pressure

 Mixers

The default parameters are used for the two mixers “AIR NH3 MIXER” and “ACID MIXER3.

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 “OXIDO-ABSORPTION COLUMN”

Operating parameters Value

Type Plate oxido-absorption column
Number of plates 30
Column diameter (m) 5
Holes diameter (mm) 5
Fraction free area (%) 4.82
Column temperature profile Calculated from the temperatures
Outlet acid stream temperature (°C) 25
Weak acid intermediate feed “ACID 6” Tray 25
NOx in the liquid phase
NO oxidized (%) 0
NOx solubility in the liquid phase Taken into account
Henry constant Calculated from the internal model
Total pressure drop (bar) 0.8
Correlations
Calculation of the oxidation rate constant Koukolik
Calculation of the dimerization equilibrium constant Koukolik
Equilibrium of the NOx – water – nitric acid system Zhidkov
Print profiles Complete

The column stages are numbered from top to bottom (plate 1: top plate; plate 30: bottom plate).

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The following table presents the parameters of the plates.

Oxidation Oxidation Hydrodynamic Absorption Liquid Temperature

Plate
efficiency volume (m3) model efficiency height (m) (°C)
1 1 23.2 Plug flow reactor Atroschenko 3 0.1 22
2 1 23.2 Plug flow reactor Atroschenko 3 0.1 -
3 1 23.2 Plug flow reactor Atroschenko 3 0.1 -
4 1 23.2 Plug flow reactor Atroschenko 3 0.1 -
5 1 23.2 Plug flow reactor Atroschenko 3 0.1 -
6 1 23.2 Plug flow reactor Atroschenko 3 0.1 -
7 1 23.2 Plug flow reactor Atroschenko 3 0.1 -
8 1 23.2 Plug flow reactor Atroschenko 3 0.1 -
9 1 23.2 Plug flow reactor Atroschenko 3 0.1 -
10 1 23.2 Plug flow reactor Atroschenko 3 0.1 -
11 1 23.2 Plug flow reactor Atroschenko 3 0.1 -
12 1 23.2 Plug flow reactor Atroschenko 3 0.1 -
13 1 23.2 Plug flow reactor Atroschenko 3 0.1 -
14 1 23.2 Plug flow reactor Atroschenko 3 0.1 -
15 1 23.2 Plug flow reactor Atroschenko 3 0.1 31
16 1 11.6 Plug flow reactor Atroschenko 3 0.1 33
17 1 11.6 Plug flow reactor Atroschenko 3 0.1 35
18 1 11.6 Plug flow reactor Atroschenko 3 0.1 37
19 1 11.6 Plug flow reactor Atroschenko 3 0.1 38
20 1 11.6 Plug flow reactor Atroschenko 3 0.1 38
21 1 11.6 Plug flow reactor Atroschenko 3 0.1 39
22 1 11.6 Plug flow reactor Atroschenko 3 0.1 40
23 1 11.6 Plug flow reactor Atroschenko 3 0.1 40
24 1 11.6 Plug flow reactor Atroschenko 3 0.1 40
25 1 11.6 Plug flow reactor Atroschenko 3 0.1 40
26 1 11.6 Plug flow reactor Atroschenko 3 0.1 41
27 1 11.6 Plug flow reactor Atroschenko 3 0.1 42
28 1 11.6 Plug flow reactor Atroschenko 3 0.1 43
29 1 11.6 Plug flow reactor Atroschenko 3 0.1 44
30 1 11.6 Plug flow reactor Atroschenko 3 0.1 45

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 Calculator switch

This module is used to change the thermodynamic model from the “HNO3 specific” one used in the previous
modules to the “Engels (strong acids)” used in the bleaching column. The calculation of the liquid enthalpies being
not the same between these two models, the use of a “Calculator switch” module is necessary in order to not
distort the enthalpy balance on the bleaching column. In the case of the switch from the “HNO3 specific” model to
the “Engels (strong acids)” model, and inversely, the “Calculator switch” module is necessary only on liquid streams
(except if they leave the process).

Operating parameters Value

Thermodynamic model Engels
Outlet physical state Calculated

 “BLEACHING COLUMN”

Operating parameters Value

Column type Absorber
Thermodynamic model Engels
Number of theoretical stages 5
Overhead pressure (bar) 4.2
Pressure drop (bar) 0.2
Stage efficiency 1 for each stage
Reactive column NO2/N2O4 equilibrium in gas phase
Print profiles Complete

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1.6.2. Specifications of the nitric acid production process

 Specifications

Specifications Value
Outlet temperature of the ammonia combustion burner (°C) 890
Oxygen amount in the tail gas (% molar) 2.5
Concentration of the produced nitric acid (% mass) 58
Mass flow rate (eq. 100%) of the produced nitric acid (t/j) 1 000

 Acting variables

Acting variables
Ammonia feed flow rate
Air feed flow rate
Water feed flow rate of the oxido-absorption column
Splitting ratio between the primary air and the secondary air

 “Constraints and Recycles”

Operating parameters Value

Broyden with Jacobian matrix by finite
Numerical method
differences
Step size of the recycle streams variables proportional to The variable
Step size of the adjusted variables proportional to The variable
“PG 15”
Tear streams
(top stream of the bleaching column)
Other parameters Default values

ProSimPlus HNO3 determines automatically the calculation sequence and the tear streams. The tear
stream selected by default (“PG 12” outlet stream of the NOx compressor) needs an initialization to reach
the convergence of the simulation. To avoid this, another stream, “PG 15”, is selected directly in the
module “Constraints and Recycles”. Thus, this choice avoids the need to specify an initialization of the
tear stream.

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1.6.3. Utility production

 Process feed

Feed WATER UTILITY

Molar fraction
Water 1
Total flow rate (t/d) 1 130
Temperature (°C) 20
Pressure (bar) 15

 “STEAM EXPANDER”

Operating parameters Value

Type Expander
Discharge pressure (bar) 1.05
Isentropic efficiency (-) 0.85
Mechanical efficiency (-) 1
Electrical efficiency (-) 1

 “STEAM SPLITTER” splitter

Operating parameters Value

Type Stream splitter
Splitting ratio of the stream STEAM 3 (steam expanded) 0.90
Automatically calculated stream “STEAM 5” (steam not expanded)
Outlet pressure Equal to the feed pressure

 Cooler/Heater modules

Name Outlet temperature (°C) Pressure drop (bar) Oxidation volume (m3)
BOILER Dew temperature 0.05 0
STEAM CONDENSER Bubble temperature 0.05 0

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 Simple heat exchangers

Name Heat duty (kW) Pressure drop(bar) Oxidation volume (m3)

E106b 0 0.5 0
E108b 0 0.05 0
OVERHEATER 0 0.05 0

The heat duties of the simple heat exchangers E106b and E108b are transmitted by information streams from the
corresponding cooler/heater modules (E106a and E108a).

The heat duty of the simple heat exchanger “OVERHEATER” is the sum of the heat duties calculated by the
cooler/heater modules “E104” and “BOILER”. The information is transmitted by information stream and the sum is
computed by an “Information stream handler” module (§ 1.7). The parameters of these different items are the
following:

o Information stream from the cooler/heater “E104” to the information stream handler “BOILER HEAT DUTY”

Parameters Value
Information type to be emitted Heat necessary to reach the specified temperature
Information type to be received Input information stream value (In)

o Information stream from the cooler/heater “BOILER” to the information stream handler “BOILER HEAT
DUTY”

Parameters Value
Information type to be emitted Heat necessary to reach the specified temperature
Information type to be received Value of the additive factor (B)

o Information stream from the information stream handler “BOILER HEAT DUTY” to the simple heat
exchanger “OVERHEATER”

Parameters Value
Information type to be emitted Output information stream value (Out)
Information type to be received Heat duty

o Information stream handler “BOILER HEAT DUTY”

Parameters Value
A 1
B 0
C 0
Power 1 (Integer value)

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1.6.4. Coupling of the compressors and the expanders

In this process, the compressors “AIR COMPRESSOR” and “NOx COMPRESSOR” and the expanders
“EXPANDER” and “STEAM EXPANDER” compose a turbo-expander. The objective is to adjust the steam flow rate
expanded by action on the splitting ratio of the “STEAM SPLITTER” in order to balance the power consumption of
the compressors (“AIR COMPRESSOR” and “NOx COMPRESSOR”) and the power available at the expanders
(“EXPANDER” and “STEAM EXPANDER”). For that, several information stream handlers (§ 1.7) as well as a
constraints and recycles module are used. Several information streams link these different items.

 Sum of the power of the compressors “AIR COMPRESSOR” and “NOx COMPRESSOR”
o Information stream from the compressor “NOx COMPRESSOR” to the information stream handler
“COMPRESSORS”

Parameters Value
Information type to be emitted Mechanical power
Information type to be received Input information stream value (In)

o Information stream from the compressor “AIR COMPRESSOR” to the information stream handler
“COMPRESSORS”

Parameters Value
Information type to be emitted Mechanical power
Information type to be received Value of the additive factor (B)

o Information stream handler “COMPRESSORS”

Parameters Value
A 1
B 0
C 0
Power 1 (Integer value)

 Sum of the power of the expanders “EXPANDER” and “STEAM EXPANDER”

o Information stream from the expander “EXPANDER” to the information stream handler
“EXPANDERS”

Parameters Value
Information type to be emitted Mechanical power
Information type to be received Input information stream value (In)

o Information stream from the expander “STEAM EXPANDER” to the information stream handler
“EXPANDERS”

Parameters Value
Information type to be emitted Mechanical power
Information type to be received Value of the additive factor (B)

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o Information stream handler “EXPANDERS”

Parameters Value
A 1
B 0
C 0
Power 1 (Integer value)

 Calculation of the deviation between the power needed for the compressors and the power available at the
turbines and action on the splitting ratio of the “STEAM SPLITTER” splitter
o Information stream from the information stream handler “COMPRESSORS” to the information
stream handler “TURBO-EXPANDER”

Parameters Value
Information type to be emitted Output information stream value (Out)
Information type to be received Input information stream value (In)

o Information stream from the information stream handler “EXPANDERS” to the information stream
handler “TURBO-EXPANDER”

Parameters Value
Information type to be emitted Mechanical power
Information type to be received Value of the additive factor (B)

The two values are summed although we wish to compute the deviation between the power needed for
the compressors and the power available at the turbines. In fact, the power needed for a compressor are
negative values, whereas the power available for a turbine are positive values.

o Information stream handler “TURBO-EXPANDER”

Parameters Value
A 1
B 0
C 0
Power 1 (Integer value)

o Information stream from the information stream handler “TURBO-EXPANDER” to the “Constraints
and Recycles 1” constraints and recycles module

Parameters Value
Information type to be emitted Output information stream value (Out)
Information type to be received Automatic

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o The default values are kept for the module “Constraints and Recycles 1”

o Information stream from the module “Constraints and Recycles 1” to the splitter “STEAM
SPLITTER”

Parameters Value
Information type to be emitted Automatic
Information type to be received Distribution ratios of output streams

Regarding the information type to be received, well select the stream for which the splitting ratio is
specified and not the stream automatically calculated. The choice is done from the bottom red framed of
the following figure.

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1.7. “Tips and tricks”

To minimize the risk of errors and to correct more easily those eventually committed, it’s advisable to proceed in
four steps to build this example:

1. Simulation of the nitric acid production part without the specifications, the utility production and the coupling
between the compressors and the turbines.
2. Add of the specifications to the previous simulation.
3. Add of the utility production part to the previous simulation.
4. Add of the coupling between the compressors and the turbines to the previous simulation.

In this simulation example, most of the heat exchangers are simulated by decoupling the hot stream and the cold
stream. This way of modeling a two-stream heat exchanger avoids a recycle stream that would penalize the
calculations by decoupling the heat exchanger into two parts.

Several “Information stream handler” modules are used. In ProSimPlus HNO3 this module performs simple
operation on information streams: add a constant (B), subtract a constant (C), multiply its contents (A and P = 1),
divide its contents (A and P = -1) or raised its contents to an entire or real power (P). The result of this operation is
available in the outlet information stream of the “Information stream handler” module:

= ∗( ) + −

In this formula, A, B, C, and P are constants specified by the user. By putting several information streams in an
"Information stream handler" module and playing on their position in the module parameter zone, it’s possible to
use their information to specify the values of the constants A, B, C and P. Thus, operations between several
information streams can be performed. Using several modules of this type, it’s possible to perform more complex
operations. For more complex operation on information streams it’s advised to use a “Windows Script” module.

It’s possible in ProSimPlus HNO3 to use several constraints and recycles modules in one simulation. In this
example for a better readability of the simulation, two constraints and recycles modules are used:

 One for the process itself: “Constraints and Recycles”

 The other for the steam production “Constraints and Recycles 1”

Using several constraints and recycles modules has an effect on the calculation sequence of the module (the list of
the calculations automatically determined by ProSimPlus HNO3) and on the convergence of each cycle. But this
has no effect on the results obtained at convergence.

This possibility could be used in some case for ease of the convergence of complex flowsheet, or, like here, to not
unnecessarily complicate the representation of the process.

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2. RESULTS

2.1. Mass and energy balances

This document presents only the most relevant stream results. In ProSimPlus HNO3, mass and energy balances
are provided for all streams. Results are also available at the unit operation level (“Report” tab in the configuration
window).

Streams ACID 1 ACID 2 ACID 5 CONDENSA... HNO3 PROD... HP AIR 4 LP AIR

From CONDENSE... OXIDO-ABS... CONDENSE... STEAM CO... w (HNO3) E103a WATER
AIR FEED
UTI...
Total flow t/d 161.3 1596.2 258.96 965.58 1724.1 814.68 4999.7
Total flow Nm3/h 6457.1 46030 11629 50055 52352 26552 1.6295E005
Mass fractions
WATER 0.68103 0.38143 0.81268 1 0.41976 0.011317 0.011317
NITRIC OXIDE 0 0 0 0 0 0 0
NITROGEN DIOXIDE 0 0.00014369 0 0 0 0 0
NITROGEN TETROXIDE 0 0.022554 0 0 0 0 0
NITROGEN 0 0 0 0 9.197E-005 0.75864 0.75864
OXYGEN 0 0 0 0 0.00014285 0.23004 0.23004
NITRIC ACID 0.31897 0.59587 0.18732 0 0.58 0 0
AMMONIA 0 0 0 0 0 0 0
NITROUS OXIDE 0 0 0 0 0 0 0
Mole fractions
WATER 0.88191 0.6857 0.93818 1 0.71666 0.018 0.018
NITRIC OXIDE 0 0 0 0 0 0 0
NITROGEN DIOXIDE 0 0.00010115 0 0 0 0 0
NITROGEN TETROXIDE 0 0.0079388 0 0 0 0 0
NITROGEN 0 0 0 0 0.00010098 0.776 0.776
OXYGEN 0 0 0 0 0.00013731 0.206 0.206
NITRIC ACID 0.11809 0.30626 0.061824 0 0.28311 0 0
AMMONIA 0 0 0 0 0 0 0
NITROUS OXIDE 0 0 0 0 0 0 0
Physical state Liquid Liquid Liquid Liquid Liquid Vapor Vapor
Temperature °C 92.009 45 81.628 99.632 51.109 70 25
Pressure bar 9.9 9.9 4.2125 1 4.4 4.55 1
Enthalpic flow kW -21663 -1.4501E005 -39835 -23803 -1.6633E005 -998.56 -8790
Vapor molar fraction 0 0 0 0 0 1 1

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Streams NH3 1 PG 01 PG 09 PG 10 PG 13 PG 14 STEAM 2

From NH3 FEED T(Burner) E108a CONDENSE... E109a CONDENSE... OVERHEAT...
WATER UTI...
Total flow t/d 283.6 4468.6 4468.6 4209.6 5057.7 4896.4 1130
Total flow Nm3/h 15552 1.5583E005 1.5177E005 1.3942E005 1.6503E005 1.5755E005 58579
Mass fractions
WATER 0 0.1113 0.1113 0.066506 0.056185 0.034099 1
NITRIC OXIDE 0 0.10757 0.050098 0.052814 0.02445 0.024414 0
NITROGEN DIOXIDE 0 0 0.086644 0.08031 0.10571 0.095129 0
NITROGEN TETROXIDE 0 0 0.0014708 0.0053727 0.0026833 0.010449 0
NITROGEN 0 0.71243 0.71243 0.75625 0.75161 0.77637 0
OXYGEN 0 0.068624 0.03798 0.038659 0.05878 0.058934 0
NITRIC ACID 0 0 0 0 0.00051388 0.00053081 0
AMMONIA 1 0 0 0 0 0 0
NITROUS OXIDE 0 8.2007E-005 8.2007E-005 8.7052E-005 7.2455E-005 7.4842E-005 0
Mole fractions
WATER 0 0.16545 0.16988 0.1041 0.089267 0.054937 1
NITRIC OXIDE 0 0.096005 0.045909 0.049634 0.023323 0.023616 0
NITROGEN DIOXIDE 0 0 0.051787 0.049226 0.065765 0.060016 0
NITROGEN TETROXIDE 0 0 0.00043955 0.0016466 0.00083472 0.003296 0
NITROGEN 0 0.68106 0.6993 0.76127 0.76795 0.80439 0
OXYGEN 0 0.057432 0.032637 0.034068 0.052578 0.053456 0
NITRIC ACID 0 0 0 0 0.00023342 0.0002445 0
AMMONIA 1 0 0 0 0 0 0
NITROUS OXIDE 0 4.9899E-005 5.1234E-005 5.5775E-005 4.7119E-005 4.9355E-005 0
Physical state Liquid Vapor Vapor Vapor Vapor Vapor Vapor
Temperature °C 10 890 110 81.628 125 92.009 391.36
Pressure bar 14 4.55 4.2625 4.2125 9.95 9.9 14.8
Enthalpic flow kW -12902 -6352.1 -61350 -29945 -29222 -13940 9022.6
Vapor molar fraction 0 1 1 1 1 1 1

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Streams STEAM 5 TG 6 Water WU 1

From STEAM SPLI... x(O2) WATER FEED WATER UTI...
Total flow t/d 164.42 3926.4 367.26 1130
Total flow Nm3/h 8523.5 1.3051E005 19039 58579
Mass fractions
WATER 1 0.0018222 1 1
NITRIC OXIDE 0 0.00059144 0 0
NITROGEN DIOXIDE 0 0.00084391 0 0
NITROGEN TETROXIDE 0 2.7866E-009 0 0
NITROGEN 0 0.96818 0 0
OXYGEN 0 0.028473 0 0
NITRIC ACID 0 1.3384E-007 0 0
AMMONIA 0 0 0 0
NITROUS OXIDE 0 9.3332E-005 0 0
Mole fractions
WATER 1 0.0028418 1 1
NITRIC OXIDE 0 0.00055379 0 0
NITROGEN DIOXIDE 0 0.00051539 0 0
NITROGEN TETROXIDE 0 8.5091E-010 0 0
NITROGEN 0 0.97103 0 0
OXYGEN 0 0.025 0 0
NITRIC ACID 0 5.9677E-008 0 0
AMMONIA 0 0 0 0
NITROUS OXIDE 0 5.9579E-005 0 0
Physical state Vapor Vapor Liquid Liquid
Temperature °C 391.36 171.47 20 20
Pressure bar 14.8 1.0132 10 15
Enthalpic flow kW 1312.8 5934.9 -67495 -32202
Vapor molar fraction 1 1 0 0

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2.2. Process performance

The production of 1 000 t/d of nitric acid eq. 100% at a concentration of 58% mass with this process while having a
temperature of 890°C at the outlet of the ammonia burner and 2.5% molar of oxygen in the tail gas needs:

 284 t/d of ammonia

 5 000 t/d of air with 84% for the primary air (NH3 combustion) and the remainder (16%) for the secondary
air (bleaching of the produced nitric acid)
 367 t/d of process water for the oxido-absorption

The NOx amount at the outlet of the oxido-absorption column is 1 070 ppmv eq. NO.

The balance between the consumption of compressors and the power available at the turbines needs to expand
86% of the 15 bar steam produced (966 t/d).

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2.3. Nitrous vapors condensers profiles

The following curve shows that 15% of the length of the “CONDENSER 1” are not used for the oxido-absorption.

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The following curve shows that 33% of the length of the “CONDENSER 2” are not used for the oxido-absorption.

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2.4. Columns profiles

2.4.1. Oxido-absorption column

The column stages are numbered from top to bottom (plate 1: top plate; plate 30: bottom plate).

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2.4.2. Bleaching column

The column stages are numbered from top to bottom (plate 1: top plate; plate 5: bottom plate).

3. REFERENCES
[BAD96] BADOUAL C., “Acide nitrique”, Techniques de l'Ingénieur, J6085 (1996)

[CLA96] CLARKE S.I., MAZZAFRA W.J., “Nitric Acid”, Kirk-Othmer Encyclopedia of Chemical Technology,
4th edition, 17, 80-107 (1996)

[HAA84] HAAR L., GALLAGHER J.S., KELL J. H., “NBS/NRC Steam Tables”, Hemisphere Publishing
Corporation (1984)

[JOU81] JOULIA X., “Contribution au développement d'un programme général de simulation. Application à
l'analyse du fonctionnement d'un atelier de production d'acide nitrique”, Thèse INPT (1981)

[KOU68] KOUKOLIK M., MAREK J., “Mathematical Model of HNO3 Oxidation-Absorption Equipment”, Proc.
Fourth European Symp. on Chem. Reaction Eng. (suppl. Chem. Eng. Sci.), 347-359 (1968)

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