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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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HNO3 dual pressure process.pmp

CORRESPONDING PROSIMPLUS HNO3 FILE

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.

PROCESS MODELING
1.1. 1.2. 1.3. 1.4. 1.5. 1.6. 1.7. Process description Process flow diagram Specifications Components Thermodynamic model Operating conditions "Hints and Tips"
Constraints and Recycles modules Information stream handler module Heat exchanger splitting Changing of the thermodynamic model

3
3 5 5 6 6 7 13
13 14 15 15

1.7.1. 1.7.2. 1.7.3. 1.7.4.

2.

RESULTS
2.1. 2.2. 2.3. 2.4. Comments on results Mass and energy balances Column C101 profiles Column C102 profiles

16
16 17 22 24

3.

REFERENCES

25

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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).

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The process diagram is provided hereafter. The liquid ammonia is vaporized by cooling water (E101), then heated (E102), filtered and sent in a mixer airammonia (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.

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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.

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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.

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1.6.

Operating conditions
Process feeds Ammonia (NH3) Air (LP AIR) 25 1 Adjusted so as to satisfy the specifications Process water (Water) 20 10 Adjusted so as to satisfy the specifications Water for steam (Water Utility S2) 20 15

Temperature (C) Pressure (bar)

10 14 Adjusted so as to satisfy the specifications

Total flow rate (t/d)

1 130

Reactor R101 Operating parameters Type of reactor Ammonia conversion rate (%) 5 O2 + 4 NH3 6 H2O + 4 NO 3 O2 + 4 NH3 6 H2O + 2N2 2 O2 + 2 NH3 3 H2O + N2O Pressure drop (bar) Output temperature Value simple 96.2 3.7 0.1 0.05 adiabatic

Heat exchangers Name Type Cooler/Heater Cooler/Heater Cooler/Heater Simple heat exchanger Cooler/Heater Simple heat exchanger Cooler/Heater Simple heat exchanger Cooler/Heater Output temperature (C) Dew temp. 80 70 125 180 290 Pressure drop (bar) 8 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 Oxidation 3 volume (m ) 1.8 1.8 1.8

E101 E102 E103a E103b E104a E104b E105a E105b E106a

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E106b E107 E108a E108b E109a E109b E112 E113 E114

Simple heat exchanger Cooler/Heater Cooler/Heater Simple heat exchanger Cooler/Heater Simple heat exchanger Cooler/Heater Simple heat exchanger Cooler/Heater

440 220 110 Dew temp. Dew temp.

0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05

1.8 1.8 -

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 Operating parameters Length of the tubes (m) Number of tubes Vapors flow Internal diameter of the tubes (mm) Cooling water temperature (C) Cooling water flow rate (t/d) Flow direction Overall heat exchange coefficient (kcal/h/m /K)
2

Value 6 840 Inside the tubes 25.4 15 9000 Counter-current 300

Moreover, one adopts: the calculation of the oxidation reaction rate by the model of Koukolik 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).

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Condenser E111 Operating parameters Length of the tubes (m) Number of tubes Vapors flow Internal diameter of the tubes (mm) Cooling water temperature (C) Cooling water flow rate (t/d) Flow direction Overall heat exchange coefficient (kcal/h/m /K)
2

Value 6 250 Inside the tubes 25.4 15 6 500 Counter-current 600

Moreover, one adopts: the calculation of the oxidation reaction rate by the model of Koukolik 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 Operating parameters Isentropic efficiency Mechanical efficiency Discharge pressure (bar) Taking into account of the chemical reaction Value 0,845 1 4.6 no

Compressor K102 Operating parameters Isentropic efficiency Mechanical efficiency Discharge pressure (bar) Taking into account of the chemical reaction Value 0,795 1 10 yes

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Moreover, one adopts: the calculation of the oxidation reaction rate by the model of Koukolik the calculation of the equilibrium constant for the N2O3 formation by the model of Miller.

Oxidation volumes Nom O101 O102 O103 O104 Oxidation volume 3 (m ) 20 25 20 20 Pressure drop (bar) 0.0125 0.0125 0.0125 0.0125 Temperature (C) Adiabatic Adiabatic Adiabatic 85

Moreover, 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 dimerisation equilibrium constant by the model of Koukolik

Column C101 Operating parameters Type of column Number of stages Weak acid feed stage Column diameter (m) Diameter of the holes (mm) Free section Pressure drop in the column (bar) Output temperature of the acid in the bottom (C) Value Plate oxido-absorption column 30 25 (stages numbered from top to bottom) 5 5 4.82 % 0,8 25

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Stage 1 (top) 2 3 4 5 6 7 8 9 10 11 12 13 14 15

Temperature C) 22 31

Oxidation 3 volume (m ) 23.2 23.2 23.2 23.2 23.2 23.2 23.2 23.2 23.2 23.2 23.2 23.2 23.2 23.2 23.2

Stage 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 (bottom)

Temperature (C) 33 35 37 38 38 39 40 40 40 40 41 42 43 44 45

Oxidation 3 volume (m ) 11.6 11.6 11.6 11.6 11.6 11.6 11.6 11.6 11.6 11.6 11.6 11.6 11.6 11.6 11.62

Moreover, one adopts: 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 oxidation reaction rate by the model of Koukolik the calculation of the dimerisation equilibrium constant by the model of Koukolik the calculation of the equilibrium of the system nitrogen oxides waternitric 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 Operating parameters Type of column Number of theoretical stages Overhead pressure (bar) Pressure drop in the column (bar) Value Absorber 5 4.2 0.2

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Pump P101 Operating parameters Exhaust pressure (bar) Volumetric efficiency Mechanical efficiency Value 11 0.65 1

Expander T101 Operating parameters Discharge pressure (bar) Isentropic efficiency Value 1 0.83

Turbine T102 Operating parameters Discharge pressure (bar) Isentropic efficiency Value 1.05 0.85

Valve V101 Operating parameters Type of valve Splitting rate for the stream AIR HP2 (%) Value Three way valve 80 This rate will be adjusted in order to reach the specifications Comments

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

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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.

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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: 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)
P

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.

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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.

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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.

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2.2.

Mass and energy balances

Streams From To Partial flows WATER NITRIC OXIDE NITROGEN DIOXIDE NITROGEN TETROXIDE NITROGEN OXYGEN NITRIC ACID AMMONIA NITROUS OXIDE Total flow Total flow Temperature Pressure Enthalpic flow Vapor fraction

Acid S1 Acid S1+S2 Acid S2 Acid S3 E111 Acids mixer C101 Dummy Acids mixer Dummy Acids mixer C102 t/d t/d t/d t/d 110.330629 719.0267179 608.696089 719.0267179 0 0 0 0 0 0.171242013 0.171242013 0.171242013 0 26.5555056 26.5555056 26.5555056 0 0 50.70934 0 0 161.039969 288.70913 91.9381166 9.89999732 -18692289.6 0 0 0 1002.750981 0 0 1748.504446 2338.240064 52.59991071 9.899997325 -143427975 0 0 0 952.0416409 0 0 1587.464477 2049.530933 45 9.899997325 -124735685 0

Acid S4 E110 P01 t/d 209.963131 0 0 0

t/d kmol/h C bar kcal/h

0 0 0 0 1002.750981 48.4400512 0 0 0 0 1748.504446 258.403182 2338.240064 517.643508 52.59991071 81.6451604 9.899997325 4.21249886 -142520016 -34196144.9 0 0

Streams From To Partial flows WATER NITRIC OXIDE NITROGEN DIOXIDE NITROGEN TETROXIDE NITROGEN OXYGEN NITRIC ACID AMMONIA NITROUS OXIDE Total flow Total flow Temperature Pressure Enthalpic flow Vapor fraction

Acid S5

AIR S1

AIR S2

AIR S3

P01 V101 E103a C102 C101 E103a C102 K102 t/d t/d t/d t/d 209.963131 9.150953613 9.150953613 4.436011318 0 0 0 0 0 0 0 22.50500389 0 0 0 4.222192633 0 0 48.4400512 0 0 258.403182 517.643508 81.9068606 10.999997 -34193628.8 0 613.4532114 186.0172684 0 0 0 808.6214333 1175.820719 215.7343361 4.599998757 359264.567 1 613.4532114 186.0172684 0 0 0 808.6214333 1175.820719 70 4.54999877 -852795.401 1 613.2970848 185.7742049 2.755109167 0 0 832.9896067 1188.483363 47.07917229 4.199998865 -300693.485 1

Condensate s E114 >>>> t/d 959.536085 0 0 0 0 0 0 0 0 959.536085 2219.26197 99.6325065 0.99999973 1220318.93 1

t/d kmol/h C bar kcal/h

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Streams From To Partial flows WATER NITRIC OXIDE NITROGEN DIOXIDE NITROGEN TETROXIDE NITROGEN OXYGEN NITRIC ACID AMMONIA NITROUS OXIDE Total flow Total flow Temperature Pressure Enthalpic flow Vapor fraction

HP AIR1 K101 V101 t/d 56.5824732 0 0 0 3793.12379 1150.18801 0 0 0 4999.89427 7270.37281 215.734336 4.59999876 2221416.32 1

HP AIR2 V101 Mixer Air+NH3 t/d 47.43151958 0 0 0 3179.670583 964.1707389 0 0 0 4191.272841 6094.552088 215.7343361 4.599998757 1862151.757 1

LP AIR >>>> K101 t/d 56.5824732 0 0 0 3793.123794 1150.188007 0 0 0 4999.894275 7270.372806 25 0.992984732 -7563428.45 1

NH3 >>>> E101 t/d 0 0 0 0

NH3 S2 E101 E102 t/d 0 0 0 0

t/d kmol/h C bar kcal/h

0 0 0 0 0 0 283.6165392 283.616539 0 0 283.6165392 283.616539 693.8895752 693.889575 10 9.36352185 13.99999622 5.99999838 -11101866.5 -7703546.38 0 1

Streams From To Partial flows WATER NITRIC OXIDE NITROGEN DIOXIDE NITROGEN TETROXIDE NITROGEN OXYGEN NITRIC ACID AMMONIA NITROUS OXIDE Total flow Total flow Temperature Pressure Enthalpic flow Vapor fraction

NH3 S3 E102 Mixer Air+NH3 t/d

Nitric Acid Production MEAS03 >>>>

PG00 Mixer Air+NH3 R101

PG01 MEAS02 E107

PG02 E107 E106a t/d 497.454159 480.713401 0 0

t/d t/d t/d 0 723.7416218 47.43151958 497.4541587 0 0 0 480.7134005 0 0.000204006 0 0 0 0 0 0 0.155163048 0.242766129 999.9960371 0 0 1724.135792 2335.689738 51.93127648 4.399998811 -143072111 0

t/d kmol/h C bar kcal/h

0 0 0 283.616539 0 283.616539 693.889575 80 5.94999839 -7280058.65 1

3179.670583 3188.301177 3188.30118 964.1707389 308.053362 308.053362 0 0 0 283.6165392 0 0 0 0.36648111 0.36648111 4474.889381 4474.88858 4474.88858 6788.441663 6961.740584 6961.74058 198.0812614 889.9999211 440 4.599998757 4.54999877 4.49999878 -5417906.89 -5417908.71 -30796025.4 1 1 1

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Streams From To Partial flows WATER NITRIC OXIDE NITROGEN DIOXIDE NITROGEN TETROXIDE NITROGEN OXYGEN NITRIC ACID AMMONIA NITROUS OXIDE Total flow Total flow Temperature Pressure Enthalpic flow Vapor fraction

PG03 E106a O101 t/d 497.454159 471.416336 14.2542765 2.8829E-05 3188.30118 303.096121 0 0 0.36648111 4474.88858 6955.28559 290 4.4499988 -38871910.2 1

PG04 PG05 PG06 O101 E108a O102 E108a O102 E105a t/d t/d t/d 497.4541587 497.4541587 497.4541587 376.4039363 368.8073881 282.2212567 159.9260257 171.5512153 304.2980458 0.001757513 0.02363313 0.0310847 3188.301177 252.435043 0 0 0.36648111 4474.88858 6889.317386 325.3800873 4.437498801 -38871910.2 1 3188.301177 248.3845261 0 0 0.36648111 4474.88858 6884.033172 220 4.387498814 -44442115.9 1

PG07 E105a OXI 03 t/d 497.454159 277.264103 311.662956 0.2665072

t/d kmol/h C bar kcal/h

3188.301177 3188.30118 202.2163753 199.573196 0 0 0 0 0.36648111 0.36648111 4474.88858 4474.88858 6823.912763 6820.36439 252.7245814 180 4.374998818 4.32499883 -44442115.9 -48230234.8 1 1

Streams From To Partial flows WATER NITRIC OXIDE NITROGEN DIOXIDE NITROGEN TETROXIDE NITROGEN OXYGEN NITRIC ACID AMMONIA NITROUS OXIDE Total flow Total flow Temperature Pressure Enthalpic flow Vapor fraction

PG08 PG09 PG10 PG11 OXI 03 E109a E110 O104 E109a E110 O104 K102 t/d t/d t/d t/d 497.454159 497.4541587 280.5665562 280.5665562 228.148186 223.6229539 222.0586562 150.6022616 387.010908 387.5943842 338.5782304 439.0036651 0.22332033 6.57795939 22.62660588 31.75847658 3188.30118 173.384348 0 0 0.36648111 4474.88858 6786.2826 198.72224 4.31249883 -48230234.8 1 3188.301177 170.9714722 0 0 0.36648111 4474.888587 6780.263058 110 4.262498848 -52799109.1 1 3188.301177 163.9877533 0 0 0.36648111 4216.48546 6230.243037 81.64516041 4.212498862 -25845022.8 1

PG13 K102 E104a t/d 285.002567 150.602262 496.534591 0.95470962

t/d kmol/h C bar kcal/h

3188.301177 3801.59826 125.8868524 311.661057 0 2.75510917 0 0 0.36648111 0.36648111 4216.48547 5049.47504 6176.495317 7380.83997 85 192.339758 4.199998865 9.9999973 -27112834.5 -21102233.3 1 1

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Streams From To Partial flows WATER NITRIC OXIDE NITROGEN DIOXIDE NITROGEN TETROXIDE NITROGEN OXYGEN NITRIC ACID AMMONIA NITROUS OXIDE Total flow Total flow Temperature Pressure Enthalpic flow Vapor fraction

PG14 E104a E111 t/d 285.002567 123.490504 525.913527 13.1436659 3801.59826 297.204935 2.75510917 0 0.36648111 5049.47505 7356.4965 125 9.94999731 -25332332.1 1

PG15 E111 C101 t/d 167.4230739 119.2119249 458.7435962 49.85086208 3801.598262 288.4858539 2.755109167 0 0.36648111 4888.435163 7023.045811 91.93811658 9.899997325 -12128773.1 1

Steam S1 E112 E113 t/d 1130 0 0 0

Steam S2 E113 V102 t/d 1130 0 0 0

Steam S3 V102 T102 t/d 959.536085 0 0 0 0 0 0 0 0 959.536085 2219.26197 393.198173 14.799996 6630218.48 1

t/d kmol/h C bar kcal/h

0 0 0 0 0 0 0 0 0 0 1130 1130 2613.519249 2613.519249 197.8505116 393.1981727 14.84999599 14.799996 2743214.284 7808092.881 1 1

Streams From To Partial flows WATER NITRIC OXIDE NITROGEN DIOXIDE NITROGEN TETROXIDE NITROGEN OXYGEN NITRIC ACID AMMONIA NITROUS OXIDE Total flow Total flow Temperature Pressure Enthalpic flow Vapor fraction

Steam S4 Steam S5 TG S1 TG S2 T102 V102 C101 E103b E114 >>>> E103b E104b t/d t/d t/d t/d 959.536085 170.4639145 7.154859967 7.154859967 0 0 2.334332508 2.334332508 0 0 3.129031469 3.323380347 0 0 0.223896879 0.029547791 0 0 3801.598262 3801.598262 0 0 111.7994054 111.7994054 0 0 0.000525795 0.000525795 0 0 0 0 0 0 0.36648111 0.36648111 959.536085 170.4639145 3926.606795 3926.606795 2219.26197 394.257276 5823.063828 5823.151838 128.789291 393.1981727 22 51.83759596 1.04999972 14.799996 9.099997541 9.049997554 1777553.49 1177874.405 -978694.335 233365.6391 1 1 1 1

TG S3 E104b E105b t/d 7.15485997 2.33433251 3.35275238 0.00017573 3801.59826 111.799405 0.00052579 0 0.36648111 3926.60679 5823.16514 155.728602 8.99999757 4463464.37 1

t/d kmol/h C bar kcal/h

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Streams From To Partial flows WATER NITRIC OXIDE NITROGEN DIOXIDE NITROGEN TETROXIDE NITROGEN OXYGEN NITRIC ACID AMMONIA NITROUS OXIDE Total flow Total flow Temperature Pressure Enthalpic flow Vapor fraction

TG S4

TG S5

TG S6

Water

E105b E106b MEAS04 >>>> E106b T101 >>>> C101 t/d t/d t/d t/d 7.15485997 7.154859967 7.154859967 367.2407048 2.33433251 2.334332508 2.334332508 0 3.35291791 3.352927815 3.352927815 0 1.0196E-05 2.89804E-07 2.89804E-07 0 3801.59826 111.799405 0.00052579 0 0.36648111 3926.60679 5823.16521 247.85697 8.94999758 8251581.95 1 3801.598262 111.7994054 0.000525795 0 0.36648111 3926.606795 5823.165218 439.3442294 8.899997595 16327464.53 1

Water Utility S2 >>>> E109b t/d 1130 0 0 0

t/d kmol/h C bar kcal/h

3801.598262 0 0 111.7994054 0 0 0.000525795 0 0 0 0 0 0.36648111 0 0 3926.606795 367.2407048 1130 5823.165218 849.3722577 2613.51925 171.0302931 20 20 0.99999973 9.999997298 14.9999959 5089518.327 -58071654.3 -27707366.3 1 0 0

Streams From To Partial flows WATER NITRIC OXIDE NITROGEN DIOXIDE NITROGEN TETROXIDE NITROGEN OXYGEN NITRIC ACID AMMONIA NITROUS OXIDE Total flow Total flow Temperature Pressure Enthalpic flow Vapor fraction

Water Utility S3 E109b E108b t/d 1130 0 0 0

Water utility S4 E108b E112 t/d 1130 0 0 0

t/d kmol/h C bar kcal/h

0 0 0 0 0 0 0 0 0 0 1130 1130 2613.51925 2613.519249 116.833991 198.0095633 14.949996 14.89999597 -23138491.9 -17568286.2 0 0.07331793

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2.3.

Column C101 profiles

Heat duty

-1.1E+07 -1.0E+07 -9.0E+06 -8.0E+06

Heat duty (kcal/h)

-7.0E+06 -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)

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Amount of NOx amount (ppmv)

90000 80000 70000 60000 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

NOx amount (ppmv)

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

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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 Stage 4 5

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 Stage 4 5

NITROGEN DIOXIDE

NITROGEN TETROXI

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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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