Nitric Acid Package Report 07

Aspen Inorganics
Cambridge, MA USA
• • • • • • • • • •
Report
NITRIC ACID PACKAGE
February 2004
This report contains proprietary information of

Aspen Technology, Inc.
Modeling Nitric Acid
• • • • • • • • • • •
Table of Contents
1. Overview ...................................................................................................................................1
2. Background ..............................................................................................................................2
3. Components and Physical Property Models ..........................................................................4

3.1. Components .....................................................................................................................4
3.2. Pure Component Properties .............................................................................................5
3.3. Mixture Properties – General Discussion ........................................................................5
3.4. Mixture Properties - Gas Mixing Section........................................................................5
3.5. Mixture Properties - Ammonia Oxidation Section..........................................................6
3.6. Mixture Properties - Nitric Oxide Oxidation and Absorption Sections ..........................6
3.7. Physical Properties – Summary .....................................................................................12
4. Chemical Reaction and Mass-Transfer Models - Overview ..............................................12
5. Reactor Models.......................................................................................................................14
5.1. Modeling Approach .......................................................................................................14
5.2. Oxidation of Nitric Oxide..............................................................................................14
5.3. Nitrogen Dioxide Dimerization .....................................................................................15
5.4. Nitric Acid Formation and Condensation......................................................................16
5.5. Nitric Acid Reactor Kinetic Model ...............................................................................17
5.6. Example Reactive Heat Exchanger Models ..................................................................17
6. Absorber Models ....................................................................................................................18
6.1. Miller Nitric Acid Absorber Model ...............................................................................19
6.2. Nitric Acid Absorber Model ..........................................................................................20
6.3. Example Absorber Model .............................................................................................20
7. Applications ............................................................................................................................20
7.1. Cooler-Condenser ..........................................................................................................21
7.2. Absorber ........................................................................................................................22
8. Summary .................................................................................................................................25
9. References ...............................................................................................................................26
Aspen Inorganics
Proprietary Information of AspenTech
Unauthorized duplication or distribution strictly prohibited without prior written permission i
• • • • • • • • • • •
List of Tables
Table 1. Components in the Aspen Plus Model ............................................................................. 4
Table 2. Real Variables Used in RPLUG User Models NCKIN1 and NCKIN2 ......................... 17
Table 3. Summary of Data in Heat Exchanger Examples ............................................................ 18
Table 4. Real Variables in Radfrac User Model NOABS ............................................................ 20
List of Figures
Figure 1. Heat of Mixing of Nitric Acid – Water Mixtures at 25C .............................................. 7

Figure 2. Heat Capacity of Nitric Acid – Water Mixtures at 25C ................................................ 7
Figure 3. Density of Nitric Acid – Water Mixtures at 20 ............................................................. 8
Figure 4. Nitric Acid – Water Txy Diagram – Mole Fraction ....................................................... 9
Figure 5. Nitric Acid – Water Txy Diagram – Weight Percent ..................................................... 9
Figure 6. Viscosity of Aqueous Nitric Acid Mixtures .................................................................. 10
Figure 7. Thermal Conductivity of Aqueous Nitric Acid Mixtures at Constant Composition .... 10
Figure 8. Thermal Conductivity of Aqueous Nitric Acid Mixtures at Constant Temperature .... 11
Figure 9. Calculated Profiles in the Cooler Condenser ................................................................ 21
Figure 10. Absorber Acid-Strength Study – NOx in Tail Gas ..................................................... 22
Figure 11. Absorber Acid-Strength Study – Acid Strength ......................................................... 23
Figure 12. Absorber Acid-Strength Study – Temperature Profile ............................................... 24
Aspen Inorganics
Unauthorized duplication or distribution strictly prohibited without prior written permission ii
• • • • • • • • • • •
1. Overview
The manufacture of nitric acid is complicated due to the simultaneous physical and chemical
processes that occur in the process. The AspenTech Nitric Acid Package provides the necessary
building blocks that will enable reliable and accurate simulations of nitric acid plants.
The Nitric Acid Package contains the following building blocks:
 Accurate thermodynamic and transport-property correlations

 Special models for reaction kinetics and mass transfer
 Example Aspen Plus models for key equipment, such as the cooler-condenser and
absorber
The accurate thermodynamic and transport-property correlations are contained within the Aspen
Plus models. The special models for reaction kinetics and mass transfer have been made into
user models:
 NCKIN1 – Vapor phase reaction kinetics without condensation. Used in reactive heat
exchangers.
 NCKIN2 – Vapor phase reaction kinetics with condensation. Used in reactive heat
exchangers like the cooler-condenser.
 NOABS – Model for kinetics and mass transfer in the absorber.
These user models have been combined into a dll named NITRIC so that they can be used in
Aspen Plus simulations without the need for a Fortran compiler.
The four example Aspen Plus models included in this package demonstrate how the process
equipment is modeled:
 Exchangers.bkp – Demonstrates the simulation of heat exchangers where the process

fluid reacts according to kinetics described by NCKIN1 or NCKIN2.
 Absorber-1.bkp – Simulates absorption in trayed columns where reaction kinetics and
mass transfer rates are described by NOABS.
 Cooler-Condenser.bkp – Simulation and analysis of the cooler-condenser where the
process fluid reacts according to kinetics described by NCKIN2.
 Absorber-2.bkp – Simulation and analysis of a particular absorber where reaction kinetics
and mass transfer rates are described by NOABS.
Aspen Inorganics
Unauthorized duplication or distribution strictly prohibited without prior written permission 1
• • • • • • • • • • •
2. Background
Nitric acid is mainly used for the production of fertilizers and explosives (Kent, 1983). In 1976,
about 75% of nitric acid manufactured went into the manufacture of fertilizers, while about 15%
was used in the manufacture of explosives. The remaining 10% went into the manufacture of
miscellaneous products; these include the pickling of stainless steel in steel refining and in the
manufacture of dyes, plastics and synthetic fibers.
The manufacture of nitric acid is complicated due to the simultaneous physical and chemical
processes that occur in the process. The AspenTech Nitric Acid Package provides the necessary
building blocks that will produce reliable and accurate simulations of nitric acid plants.
Today, nitric acid is produced on an industrial scale from ammonia. Anhydrous ammonia is
oxidized with air to nitric oxide over a platinum-rhodium catalyst in accordance with the
following overall equation:
2NH 3  2.5O 2  2NO  3H 2 O  108.36 kcal (25  C) (1)
The reaction is highly exothermic and extremely rapid at the operating temperature of about
900C. In about 1 millisecond, 95 percent or more of the ammonia is converted to nitric oxide.
In fact, the reaction shown above accelerates most rapidly with temperature, while side reactions
such as:
2NH 3  1.5O 2  2N 2  3H 2 O  151 .56 kcal (25  C) (2)
and:
2NH 3  3NO  2.5N 2  3H 2 O  216.36 kcal (25  C) (3)
accelerate less and thus become relatively slower.
In practice, a nitric oxide yield of 96 percent can be expected. The nitric oxide obtained in the
oxidation reactor, together with excess oxygen and the remaining nitrogen and water vapor, is
cooled to recover the heat, and undergoes vapor phase reactions with the remaining oxygen in
accordance with the equations:
2NO  O 2  2NO 2  27.021 kcal (25  C) (4)
2 NO 2  N 2 O4  14.01 kcal (25  C ) (5)
Aspen Inorganics
• • • • • • • • • • •
The NO2/N2O4 is absorbed in water at as low a temperature as is economically feasible to form

nitric acid plus nitric oxide, which is then reoxidized and reabsorbed:
2 NO 2  H 2 O(l )  2 HNO3 (l )  NO  5 .81 kcal (25  C ) (6)
Both cooled exit gas and dilute nitric acid pass on to the absorber. The absorber-reactor is
typically a sieve-plate or bubble-cap unit with cooling coils on each of the 20 to 50 trays. Gas
enters at the bottom, dilute nitric acid enters part way up the column, with cold process water
entering at the top.
The acid leaving the bottom of the column contains some nitrogen oxides. This is bleached by
passing through a column countercurrent to air bled off from the air compressor.
There are several processes for treating the nitrogen oxides leaving the top of the column in order
to meet the air pollution regulations. One of the methods is to reheat the vent gas and react with
natural gas or feed ammonia. The combustion reaction between natural gas or ammonia and
nitrogen oxides increases the gas temperature and this increases the power recovered in the
expander.
Simulation of nitric acid processes is complicated due to the simultaneous physical and chemical
equilibrium, and the reaction-kinetics and mass-transfer limitations that occur in many parts of
the process. The purpose of this simulation package is to provide the building blocks that will
produce reliable and accurate simulations of nitric acid plants. The key building blocks are the
kinetic models for the reactors in the heat-exchange sections of the plant and the mass-transfer
and kinetic models for the absorber section of the plant.
Aspen Inorganics
• • • • • • • • • • •
3. Components and Physical Property Models
3.1. Components
The components included in the model are summarized in Table 1.
Table 1. Components in the Aspen Plus Model

Name Alias Formula Molecular Weight
Ammonia H3N NH3 17.0310
Nitrogen N2 N2 28.0130
Oxygen O2 O2 31.9990
Nitric-oxide NO NO 30.0060
Nitrogen-dioxide NO2 NO2 46.0055
Nitrogen-tetraoxide N2O4 N2O4 92.0110
Water H2O H2O 18.0150
Nitric-acid HNO3 HNO3 63.0129
Hydronium ion H3O+ H3O 19.02267
Nitrate ion NO3- NO3 62.00549
All of the above components are listed in the PURE11 data bank in Aspen Plus. In addition to
the PURE11 data bank, the databanks AQUEOUS, PURE93, PURE856 and ASPENPCD are
also included. The pure property data for the components in Table 1 are retrieved from these
data banks.
In order to describe the parts of the plants where aqueous electrolytes occur, the ionic
components, H3O+ and NO3-, are also included in the components form. The “apparent
approach” (Electrolytes Manual, 1988) has been adopted for the simulation and hence the ionic
species are not included in the stream report. The flows and concentrations of these ionic
components may be viewed in the stream report through the use of stream properties such as
FTRUE and XTRUE.
Some data for water and nitric acid were taken from the NBS Tables (1982).
Aspen Inorganics
• • • • • • • • • • •
Nitrogen, oxygen, nitric oxide, nitrogen dioxide, nitrogen tetraoxide and nitrous acid are treated
as Henry components. The Henry's law constants for nitrogen and oxygen in water solvent are
available in Aspen Plus. The others were obtained from the literature (Schwartz and White,
1981) as follows:
Solvent: Water
Henry's Law Constant: NO 5.43*107 m3-Pa/kmol (25°C)
NO2 8.47*106 m3-Pa/kmol (25°C)
4 3
N2O4 7.25*10 m -Pa/kmol (25°C)
3.2. Pure Component Properties

The pure component property data include molecular weight, normal boiling point, acentric
factor, critical properties, etc., and correlation parameters such as those for vapor pressure and
ideal heat capacity correlations. The required properties for all pure components are retrieved
mainly from the PURE11 data bank in Aspen Plus.
Updated pure-component property parameters were provided for nitric acid to improve the
description of properties such as density, vapor pressure and thermodynamic reference properties
(e.g., enthalpy and Gibbs free energy of formation).
3.3. Mixture Properties – General Discussion

The main mixture property option used in the simulation is the ELECNRTL, which provides an
accurate description of the aqueous nitric acid system. Nitric acid is a strong acid and thus it will
be largely ionized in aqueous solutions. However, much of the plant operates at high
temperature where liquid phases will not be present. For these sections we have chosen to use
the NRTL-RK option. The NRTL-RK option has exactly the same description of the vapor phase
(i.e., the Redlich-Kwong equation of state) as the ELECNRTL option and the two activity
coefficient models become identical in the absence of ionic species, hence there will not be any
artificial discontinuities introduced by the thermodynamic option. For pure water streams we use
the STEAMNBS, which calls on the NBS/NRC equation of state for the properties steam and
liquid water.
3.4. Mixture Properties - Gas Mixing Section

The gas mixing section contains air, water, ammonia, and water/ammonia mixtures. For cooling
water and steam, we recommend the use of STEAMNBS, which calls on the NBS/NRC model
for the properties of water and steam. For air compression and the ammonia-water system,
NRTL-RK is used.
Aspen Inorganics
• • • • • • • • • • •
3.5. Mixture Properties - Ammonia Oxidation Section

The ammonia oxidation is a high-temperature vapor-phase reaction under pressure. The property
set used in the simulation is NRTL-RK.
3.6. Mixture Properties - Nitric Oxide Oxidation and Absorption Sections

The properties for cooling water and steam in heat exchangers are represented by STEAMNBS
model. The properties of oxygen-nitrogen mixtures are simulated by NRTL-RK.
A consistent property option set ELECNRTL and Henry's law constants are used for the streams
after heat train. These particularly include the cooler-condenser and the absorber. When the
stream remains vapor phase, the Redlich-Kwong equation of state is called for calculating all
vapor phase properties. When the gas is cooled, condensation of liquid and ionization of the
nitric acid occurs. Important properties for simulation of the vapor-liquid mixtures include vapor-
liquid equilibrium, heat of mixing and liquid heat capacity. AspenTech has established a
proprietary mixture property data package for aqueous mixtures containing nitric acid. This data
package represents an updated version of the EHNO3 data package available in the Aspen Plus
system insert library. As part of the data package, the following electrolyte chemistry has been
incorporated to accurately model the electrolytes in the aqueous phase:
H 2 O  HNO3  H 3 O   NO3 (7)
The data package was developed using the Data Regression System (DRS) in Aspen Plus. The
Electrolyte NRTL activity coefficient model (Chen et al., 1982; Chen and Evans, 1986) was used
to represent the liquid phase nonideality and the excess thermodynamic properties like the heat of
mixing and the liquid heat capacity. The Clarke density model (Aspen Technology, Inc., 1988) is
used to correlate the density data. Data used to develop the data package included isothermal
vapor-liquid equilibrium data (Wilson and Miles, 1940; Vandoni and Landy, 1952; Yakimov and
Mishin, 1964; Haase et al., 1965; Perry and Chilton, 1973; Lemire et al., 1985), isobaric vapor-
liquid equilibrium data (Potier, 1958; Boublik and Kuchynka, 1960; Prosek, 1965), heat of
mixing data (Wagman et al., 1982 and Perry and Chilton, 1973), heat capacity data (Perry and
Chilton, 1973; Kirk-Othmer, 1983), and density data (Kirk-Othmer, 1983). The interaction
parameters for the various electrolyte-molecule pairs have been optimized to provide an over
good fit of the various kinds of data.
The data package gives an excellent representation of heat of mixing data. Figure 1 shows the
comparison between the heat of mixing data from Perry and Chilton (1973) and the model
prediction at 25C (298.15K).
Aspen Inorganics
• • • • • • • • • • •
Figure 1. Heat of Mixing of Nitric Acid – Water Mixtures at 25C
Nitric Acid-Water Excess Enthalpy at 25°C
0
0 20 40 60 80 100
-10
Hmix (Cal/gm)
-20
-30
-40
-50
-60
Weight% Nitric Acid
In addition to the heat of mixing, it is also important for the model to accurately predict the heat
capacity of liquid mixtures. Figure 2 presents a comparison between model predictions of heat
capacity and the data presented in Kirk-Othmer (1983).
Figure 2. Heat Capacity of Nitric Acid – Water Mixtures at 20C
Heat Capacity of Nitric Acid-Water at 20°C
1.2
1
Heat Capacity (cal/gm.K)
0.8
0.6
0.4
0.2
0
0 20 40 60 80 100
Weight% Nitric Acid
Aspen Inorganics
• • • • • • • • • • •
The model satisfactorily represents the density data. Figure 3 shows match between the density
data of Kirk-Othmer (1983) and the model predictions at 20C.
Figure 3. Density of Nitric Acid – Water Mixtures at 20
Density of Nitric Acid-Water Mixtures at 25°C
1.6
1.5
1.4
Density (g/cc)
1.3
1.2
1.1
1
0 20 40 60 80 100
Weight% HNO3
The vapor-liquid equilibrium data in the literature for the nitric acid water system are abundant,
but were found to be rather scattered. It is believed that the data package represents a best
possible model for the many literature data that are not consistent. Figure 4 presents a
representative comparison between model and data for the Txy diagram at 1 atmosphere.
Aspen Inorganics
• • • • • • • • • • •
Figure 4. Nitric Acid – Water Txy Diagram – Mole Fraction
Txy Diagram of Nitric Acid - Water at 760 Torr
120
115
110
Temperature (°C)
105
100
95 Full line is calculated dew point
Dashed line is calculated bubble point
90
Points are experimental data
85
80
0 0.2 0.4 0.6 0.8 1
Liquid or Vapor Mole Fraction of HNO3
Industrial practice uses weight-based concentration units, and hence the Txy diagram of Figure 4
is presented in weight-based units in Figure 5.
Figure 5. Nitric Acid – Water Txy Diagram – Weight Percent
Txy Diagram of Nitric Acid - Water at 760 Torr
120
Temperature (°C)
110
100
Full line is calculated dew point

90
Dashed line is calculated bubble point
Points are experimental data
80
0 20 40 60 80 100
Liquid or Vapor Weight% of HNO3
Aspen Inorganics
• • • • • • • • • • •
The vapor-liquid equilibria for NO, NO2, O2, N2 and N2O4 in the aqueous phase are modeled
using Henry's law. The Henry's law constants for NO, O2, and N2 are available in the Aspen Plus
Binary Data Bank. The Henry’s constant for NO was adjusted based upon the value reported by
Schwartz and White (1981). The Henry's law constants for NO2 and N2O4 at 25C are 8.47*106
and 7.25*104 m3-Pa/kmol (Schwartz and White, 1981). It was assumed that Henry's law
constants for NO2 and N2O4 have the same temperature dependency as that for SO2 in water.
The chemistry model for nitric acid ionization (Eqn. (7)) enables correlation of the transport
properties of aqueous nitric acid mixtures. Figure 6 presents comparisons between the
correlation developed in this package and the data of Razuvaev and Maksimova (1977). The
correlation is able to capture the maximum in the viscosity that occurs at about the azeotropic
concentration. The model accuracy is good, except at the lowest temperature of 288.15 K.
Figure 6. Viscosity of Aqueous Nitric Acid Mixtures
Viscosity of Nitric Acid
0.0025 288.15 K
323.15 K
0.0020 343.15 K
363.15 K
Viscosity (Pa.s)
0.0015
0.0010
0.0005
0.0000
0.0 0.2 0.4 0.6 0.8 1.0
Weight Fraction HNO3
Figure 7 and Figure 8 present two views of thermal conductivity of nitric acid mixtures; the
experimental data have been taken from Vargaftik (1972).
Figure 7. Thermal Conductivity of Aqueous Nitric Acid Mixtures at Constant Composition
Aspen Inorganics
• • • • • • • • • • •
Thermal Conductivity of Nitric Acid
Thermal Conductivity 0.7

0.6 Pure Water
0.5 25 Wt% HNO3
(W/m.K)
0.4 50 Wt% HNO3

0.3 75 Wt% HNO3
0.2 96 Wt% HNO3
0.1
0.0
250 300 350 400
Temperature (K)
Figure 8. Thermal Conductivity of Aqueous Nitric Acid Mixtures at Constant

Temperature
Thermal Conductivity of Nitric Acid
0.7
Thermal Conductivity (W/m.K)
273.15 K
0.6
373.15 K
0.5
0.4
0.3
0.2
0.1
0.0
0.0 0.2 0.4 0.6 0.8 1.0
Weight Fraction HNO3
The thermal-conductivity model broadly captures the trends of the data, but clearly does not
represent to data accurately. We will review models for the thermal conductivity of electrolytes
in the future.
Aspen Inorganics
• • • • • • • • • • •
3.7. Physical Properties – Summary

The main areas where complex physical properties are encountered are the sections of the plant
where electrolytes occur (i.e., the cooler condenser and the absorber). Significant attention has
been devoted to the properties of the electrolytic nitric acid-water system and hence accurate
results will be obtained. The steam system has been modeled with the STEAMNBS model and
hence accurate results will also be obtained for the steam system. The remainder of the plant is
mainly vapor-phase where the departures from ideal behavior will be minor and thus accurate
results are expected. We are thus confident that physical properties used for this simulation are
accurate. The physical properties developed as part of this simulation project include vapor-
liquid equilibrium, thermodynamic properties, density and transport properties (viscosity and
thermal conductivity).
4. Chemical Reaction and Mass-Transfer Models - Overview

The complex nitric acid reaction network has received extensive literature attention (Denbigh
and Prince, 1947; Treacy and Daniels, 1955; Wendel and Pigford, 1958; Carberry, 1959; Dekker
et al., 1959; Greig and Hall, 1966a; Greig and Hall, 1966b; Morrison et al., 1966; Koukolik and
Marek, 1968; Holma and Sohlo, 1979; Emig et al., 1979; Komiyama and Inoue, 1980; Counce
and Perona, 1980; Lee and Schwartz, 1981; Carta and Pigford, 1983; Miller, 1987; Inoue, 1988:
Venkataraman, et al., 1990). The interfacial mass transfer limitations are less well understood.
AspenTech has implemented practical engineering models that provide accurate, yet practical,
descriptions of the heat exchangers (effectively reactors) and the absorber in nitric acid plants.
Some proposed reaction pathways may be summarized as follows:
Vapor Phase
2NO + O 2  2NO 2 (8)
NO + NO 2 N 2O 3 (9)
NO + NO 2  H 2O 2HNO 2 (10)
2NO 2 N 2O 4 (11)
Liquid Phase
N 2O 4 + H 2O HNO 3 + HNO 2 (12)
3HNO 2 HNO 3 + 2NO + H 2O (13)
N 2O 3 + H 2O 2HO 2 (14)
Interfacial Transfer
Aspen Inorganics
• • • • • • • • • • •
N 2O 4 (g) N 2O 4 (l) (15)
N 2O 3 (g) N 2O 3 (l) (16)
NO 2 (g) NO 2 (l) (17)
The primary route towards nitric acid formation involves the oxidation of nitrous oxide
(Equation 8), followed by the gas phase dimerization of nitrogen dioxide (Equation 11). Nitrogen
tetraoxide then enters the liquid phase by absorption (Equation 15) and reacts with water to form
nitric and nitrous acids (Equation 12). Nitrous acid degradation (Equation 13) results in
additional nitric acid formation.
Nitrogen dioxide and nitric oxide also react in the gas phase, forming nitrogen trioxide (Equation
9). Nitrogen trioxide enters the liquid phase (Equation 16) where it reacts with water to form
nitrous acid (Equation 14), which goes on to degrade and form nitric acid (Equation 13).
Complete conversion of the nitric oxide gas to nitric acid is hindered by the back-formation of
NO (reverse reaction of Equation 8 and Equation 13) and by mass-transfer limitations. The off-
gas still contains some NO, and is sent to the tail gas treatment system where nitrogen oxides are
decomposed to nitrogen.
Since the oxidation reaction of the nitrogen oxides proceed more slowly at elevated temperatures,
it is necessary to keep the trays within the absorption column at a temperature of about 40C or
lower by circulating cooling water through coils on the trays.
The AspenTech nitric acid package is broadly divided into two sections: (1) the reactor section
where nitric oxide is oxidized to form NO2, N2O4 and HNO3, including condensation to form
dilute acid; and (2) the absorber section, where the same set of reactions occur, but the mass
transfer limitations of absorption in the liquid phase must also be considered.
Aspen Inorganics
• • • • • • • • • • •
5. Reactor Models
5.1. Modeling Approach

The reactor models provide a good description of plant behavior with only three vapor-phase
reactions:
2NO + O 2 2NO 2 (18)
2NO 2 N 2O 4 (19)
3NO 2 + H 2O 2HNO 3 + NO (20)
It has been found that HNO2 and N2O3 are unstable reaction intermediates (Matasa and Tonca,
1973) and hence they are not included in the model. The condensation of nitric acid and water,
and the subsequent formation of ionic species are assumed to occur rapidly.
5.2. Oxidation of Nitric Oxide

Nitric oxide undergoes a slow homogeneous reaction with oxygen to yield nitrogen dioxide by
Equation 18.
The equilibrium constant for the reaction strongly favors the production of NO2 at low
temperatures, so that below 150C almost all nitric oxide combines with any oxygen that is
present if sufficient residence time is allowed. This reaction is favored at lower temperatures and
higher pressures. The change in the partial pressure of nitrogen dioxide by Reaction 18 can be
expressed as:
dPNO2
 k1PNO
2
PO2 (21)
dt
The kinetics for this reaction is not well defined. The commonly accepted third-order rate
expression is valid if NO3 is the only reaction intermediate. However, many researchers have
revealed departures from the traditional third-order behavior. Treacy and Daniels (1955) obtained
data that indicated that the apparent order of NO is about 2.3 at low O2 and NO2 concentration
and tends toward the traditional 2.0 at high O2 and/or NO2 concentrations.
Treacy and Daniels proposed a reaction mechanism involving intermediates NO3 and N2O5 to
account for the observed rate sensitivity to O2 and NO2. Morrison et al. (1966) also produced
data inconsistent with the traditional third-order expression, which led them to propose a
mechanism involving NO3, N2O3, and N2O5 as intermediates. Trautz (1916) and Solc (1966) also
proposed mechanisms in which inert species, such as N2, contribute to the reaction by energy
Aspen Inorganics
• • • • • • • • • • •
transfer in exchange collisions. Lastly, Gershinowitz and Eyring (1935) used the theory of
trimolecular reactions to develop a significantly different rate expression.
Unfortunately, none of these proposed mechanisms has been definitively proven superior to the
others because the available data are insufficient, somewhat inaccurate, and often inconsistent.
Also, none of the available data were obtained for the high pressures (>5 atm) or for the high O2,
NO, and NO2 concentration range encountered in the important nitric acid absorption tower.
Therefore, it is possible that additional mechanisms that are insignificant in the commonly
laboratory-studied pressure range may be very important in the operation of a high-pressure nitric
acid reaction system. For these reasons, we found it best to rely upon the traditional Bodenstein
third-order rate expression (Bodenstein, 1922):
 652.1
logk1    1.0366   (k1 : atm 2sec1 ) (22)
 T 
In terms of a molar conversion rate, the kinetics expression is:
1 dN NO 2 k
 2.0 * 1 PNO  PO 2 
2 mole
(23)
V dt RT time  volume
To correct for the fact that perfect mixing is often not achieved in industrial reactors, a correction
factor, FACTR1, has been added to the expression:
1 dN NO 2 k
 FACTR1 * 2.0 * 1 PNO  PO 2 
2 mole
(24)
V dt RT time  volume
The base value of the correction factor for the Reaction 18 is 1.0. It can be used as an adjustable
parameter to match the observed extent of oxidation.
At low temperatures, the reverse reaction of Reaction 18 becomes important. The reaction rate
for the reverse reaction can be obtained from the forward reaction rate and the chemical
equilibrium constant of the NO oxidation reaction. The chemical equilibrium constant of the
oxidation reaction has been obtained from Aspen Plus computations:
 13870.9 
lnK1    17.9956   (K1 : atm 1 ) (25)
 T 
Both the forward and reverse reaction rates have been incorporated into the reaction model.
5.3. Nitrogen Dioxide Dimerization

The dimerization of nitrogen dioxide (Equation 19) proceeds much faster than the nitric oxide
oxidation reaction and this reaction is effectively at equilibrium. Lower temperatures and
increasing pressures shift the reaction to the production of the tetraoxide. Under the process
conditions, only a small fraction nitrogen dioxide is converted to dinitrogen tetraoxide.
Aspen Inorganics
• • • • • • • • • • •
The equilibrium constant for Equation 19:
PN 2O4
K2  2 (26)
PNO 2
has been taken from the work of Bronsted (1922) and correlated to be:
 6891.6 
lnK2    21.244   (K2 : atm 1 ) (27)
 T 
In this simulation, the reaction is assumed to occur along with NO oxidation in all equipment
after the ammonia oxidation reactor. The equilibrium between NO2 and N2O4 is modeled as two
opposing reactions. A rate constant of 10 times the NO oxidation rate constant has been used
with satisfactory results. This factor 10, FACTR2, is mainly set large enough to effectively model
equilibrium, but can be considered as an adjustable parameter in controlling the reaction rate for
nitrogen dioxide dimerization.
5.4. Nitric Acid Formation and Condensation

The formation of nitric acid from water vapor and nitrogen dioxide (Equation 20) is a fast, gas-
phase reaction that is effectively at equilibrium.
The equilibrium constant of this reaction has been reported by Koukolif and Marek (1968) in the
following form:
2
PNO PHNO  3625.191 
K3  3
 exp  16.218   2.122lnT Pascal 1 (28)
P3
P
NO2 H2O
 T 
where partial pressures are in Pa and temperatures are in K.
In this work we have obtained the equilibrium constant of this reaction from Aspen Plus in the
following form:
2
PNO PHNO  4282.34 
K3  3
 exp  19.7292   atm 1 (29)
P3
P
NO 2 H2O
 T 
where partial pressures are in atm and temperature are in K.
The nitric acid formation is modeled as two opposing reactions. A rate constant of 8,000 times
the basic NO oxidation rate constant has been used with satisfactory results. This factor 8,000,
FACTR3, is mainly set large enough to effectively model equilibrium, but can be considered as
an adjustable parameter in controlling the reaction rate for nitric acid formation.
Aspen Inorganics
• • • • • • • • • • •
5.5. Nitric Acid Reactor Kinetic Model

Two user Fortran kinetic subroutines have been developed to compute the reaction rates based on
the kinetics described in Sections 4.3 and 4.4:
Subroutine Description
NCKIN1 Vapor phase reaction kinetics without condensation
NCKIN2 Vapor phase reaction kinetics with condensation
The three adjustable factors for the nitric oxide reaction, nitrogen dioxide dimerization reaction,
and nitric acid formation reaction have been incorporated as input parameters to the two user
Fortran kinetic subroutines. The adjustable factors are available through the Real variables of the
User Subroutine form in the RPLUG blocks in the Aspen Plus simulation as summarized in
Table 2.
Table 2. Real Variables Used in RPLUG User Models NCKIN1 and NCKIN2
Real Variable Description Suggested Value
1 Factor for nitric oxide oxidation 1
2 Factor for nitrogen dioxide dimerization 10
3 Factor for nitric acid formation 8,000
It is noted that both NCKIN1 and NCKIN2 use the same set of three real variables and the
default values are the same in both cases.
5.6. Example Reactive Heat Exchanger Models

Several vessels in the nitric acid plant serve as both reactors and heat exchangers or coolers.
Examples are the burner outlet gas coolers, the economizers, and the gas coolers. The reaction
gas flow pattern in each of these vessels can be treated as plug flow. Therefore, the RPLUG
model is used for all of these vessels. In the RPLUG model, the diameter and length of each tube
and the number of tubes are specified in order to compute the volume for reaction and the area
for heat transfer. Application examples are supplied as Exchangers.bkp. In this file, the tube
inside diameter, total tube length, number of tubes and the overall heat transfer coefficient U
based upon the inside diameter are entered for vessels having the reacting gas flowing inside
tubes.
The example file Exchangers.bkp demonstrates the simulation of several pieces of equipment:
the waste heat boiler (B10 bottom), two tail gas heat exchangers (B12 and B13), an economizer
(B18) and a gas cooler (B19). The user subroutine NCKIN1 has been used for all vessels except
for B19 since they are single-phase vapor. B19 uses NCKIN2 since liquid condensation occurs
during the cooling.
Aspen Inorganics
• • • • • • • • • • •
The data describing the vessels are summarized in Table 3.
Table 3. Summary of Data in Heat Exchanger Examples

Unit No. B10 B12 B13 B18 B19
Tube length, m 3.94 6.0 6.0 3.55 6.0
No. of tubes 1080 1295 1287 777 1538
Tube, O.D., m 0.03 0.0217 0.0217 0.0217 0.0217
Tube I.D., m 0.0248 0.0177 0.0177 0.0177 0.0177
U, kcal/hr-m2-C 83.1 54.7 42.2 94.8 192.0
Exchangers.bkp demonstrates the use of the kinetic models and Aspen Plus to describe the heat
exchangers and coolers in nitric acid plants where chemical reactions occur.
6. Absorber Model
Nitric acid is produced by contacting nitric oxide, nitrogen dioxide and nitrogen tetraoxide with
water. The absorption usually takes place in bubble cap or sieve tray towers, which serve as
combined mass transfer equipment and chemical reactors. Cooling coils are provided on each
tray to remove the heat evolved. The simulation of such a system is extremely challenging
because mass transfer, heat transfer, interface phase equilibria, and chemical reactions take place
simultaneously.
The simulation approach presented in this report is based on rigorous steady-state mass and
energy balances in both gas and liquid phases. The ELECNRTL model in Aspen Plus is used to
describe the liquid phase solution chemistry. In addition, a scheme of chemical reactions was
adopted to represent the complex reactions in the absorber.
Ratefrac has been used for modeling the absorber. Ratefrac is a rate-based non-equilibrium
separation process model that calculates mass and heat transfer between gas and liquid phases.
Ratefrac enables engineers to simulate tray and packed columns based on actual trays and real
packings rather than on theoretical stages. Ratefrac can also handle systems involving
simultaneous absorption and reaction, and systems with cooling coils on trays. This model has
far greater predictive capabilities than the conventional equilibrium model, particularly for
systems where the tray efficiencies are very low and difficult to predict.
In this implementation of the AspenTech nitric acid modeling package, Radfrac is used together
with the mass-transfer modeling approach suggested by Miller (1987) to produce a practical
engineering model that quantitatively and effectively models the kinetic and mass-transfer effects
in nitric acid absorbers.
Aspen Inorganics
• • • • • • • • • • •
6.1. Miller Nitric Acid Absorber Model

Miller’s approach to modeling nitric acid towers is described in his 1987 paper. Here we only
provide a brief description, particularly noting the main features of the model and areas where we
have departed from the model presented by Miller (1987).
The primary route involves NO oxidation in the gas phase to form NO2:
2NO  O 2  2NO 2 (30)
Miller provided a rate expression for the rate of Reaction 30. Miller described the effect of the
thermodynamic equilibrium of Equation 30 in a different manner than that of Equation 25.
Based upon our evaluations, we choose to retain Equation 25 for the reverse reaction of Equation
30.
The NO2 formed reaches equilibrium with N2O4 very quickly:
2NO 2  N 2O 4 (31)
We have described the equilibrium of Equation 31 through the equilibrium capability in Radfrac.
For nitric acid formation, the N2O4 first absorbs in the liquid phase as a mass-transfer limited
interfacial transfer and then quickly reacts to form nitric acid. Miller approximated this effect by
a kinetically-limited reaction for the formation of nitric acid in the vapor phase represented by
Equation 32:
3N 2 O 4  2H 2 O  4HNO 3  2 NO (32)
Miller correlated the rate of Reaction 32 as a function of the partial pressure of N2O4 and
empirical factors that depend on temperature, liquid-phase concentration of nitric acid, the type
of tray (bubble cap or sieve), and key column dimensions (diameter and bubble cap slot/sieve
hole submergence). Miller used the work of Carberry (1959) to represent the equilibrium
constant of Equation 32; Carberry proposed an effective equilibrium between N2O4 and NO in
the vapor phase, with the equilibrium constant in terms of the nitric acid strength. Miller
demonstrated that his model provided quantitative agreement with plant-scale absorption data.
Aspen Inorganics
• • • • • • • • • • •
6.2. Nitric Acid Absorber Model

Miller’s model has been implemented as a Radfrac user-kinetic model (REAC-DIST) through a
user subroutine NOABS. NOABS has one integer input variable and 4 real input variables. The
integer input variable is as follows: 1 – sieve trays and 2 – bubble-cap trays. The 4 real input
variables are summarized in Table 4.
Table 4. Real Variables in Radfrac User Model NOABS

Real Variable Description Suggested Value
1 Column diameter, m -
2 Bubble cap slot or sieve hole submergence, m -
3 Factor for Reaction (30) 1.0
4 Factor for Reaction (32) 0.05
When using NOABS to develop simulations of nitric absorbers, Variables 1 and 2 should be set
to the actual equipment values and Variables 3 and 4 should be adjusted to match the actual
column performance. It is expected that Variable 3 will be close to unity. Our experience is that
Variable 4 is close to 0.05. Both Variable 3 and Variable 4 should be fine-tuned to match
observed plant performance.
6.3. Example Absorber Model

An application example of the use of the user model NOABS to simulate a nitric acid tower is
supplied as Absorber-1.bkp. This simulation example has 13 trays and the typical feeds of pure
water at the top, dilute nitric acid on intermediate trays and a NOX feed at the bottom. Cooling
coils are provided on each of the trays to remove the heat of reaction.
The example absorber provided in Absorber-1.bkp has provided excellent agreement with plant
data. However, care must be taken to provide plant values for the vapor holdup for reactions, the
heat-transfer coefficients for the cooling coils, the column diameter and the sieve hole
submergence or the bubble-cap slot. Finally, minor adjustments may need to be made for the
factors for Reactions 30 and 32. Once these adjustments are made, the simulation is expected to
track plant performance with changes, for example, in cooling-water temperature and
demineralized water feed rate.
7. Applications
Two simulation applications are presented and discussed in this section. Cooler-Condenser.bkp
provides a simulation of a cooler-condenser, and Absorber-2.bkp describes a typical absorber.
Aspen Inorganics
• • • • • • • • • • •
7.1. Cooler-Condenser
In a typical cooler-condenser, process gas flows on the shell side and cooling water flows in the
tubes. The RPLUG model in Aspen Plus only permits reaction in the tubes and so we need to
adjust the parameters in the model. In this particular case, the reactor is modeled as a single tube
(5m in length and 2.39 m in diameter) whose volume is equal to the shell-side volume. The
reactor is assumed by RPLUG to be cooled on its surface and since there are many cooling-water
tubes, the heat-transfer area will be severely underestimated. To account for this the heat-transfer
coefficient is multiplied by a factor that is equal to the area of the tubes divided by the area of the
“single tube.” In this case, since the outer diameter of the tubes is 0.025 m, the factor is 35.6.
Assuming a real heat-transfer coefficient of 244 W/m2.K, the heat-transfer coefficient specified
to RPLUG is 8686.4 W/m2.K.
In Cooler-Condenser.bkp, RPLUG has been specified as a counter-current reactor in which the

exit temperature of the cooling water is specified. If only the inlet temperature of the cooling
water is known, a design-Spec would have to be set up that varies the exit cooling-water
temperature to attain the known inlet temperature.
Figure 9 presents the calculated temperature and heat flow profiles in the cooler condenser. The
corner in the profiles corresponds to the point at which the process gas begins to condense.
Figure 9. Calculated Profiles in the Cooler Condenser
Profiles in Cooler-Condenser
140 0.0
120
-500.0
100
Heat Flow (MJ/hr)

Temperature (°C)
-1,000.0
80
60
-1,500.0
40
-2,000.0
20
0 -2,500.0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
Fractional Length
Aspen Inorganics
• • • • • • • • • • •
7.2. Absorber
Absorber-2.bkp presents a simulation of a typical absorber column that has 34 sieve trays. The
cooling layers on each tray have been defines as well as the total cooling water flow to each
cooling layer. The cooling-water feed temperature is 30C. Process water is fed to the top tray
and NOx gas is fed to the bottom tray. The weak acid stream is usually fed to an optimum tray.
In this case the optimum tray is determined to be the one that minimizes NOx concentration in
the tail gas.
Absorber-2.bkp enables useful studies to gain insight into the operation of nitric-acid absorbers.
Here we demonstrate the effect of varying acid strength. Simulations have been made at varying
acid strengths, from 55 to 70 weight% HNO3, and at each acid strength, the optimum weak-acid
feed tray is determined. The results re presented in the following figures.
Figure 10. Absorber Acid-Strength Study – NOx in Tail Gas
NOx in Tail Gas
1000
100
NOx ppm
10
1
50 55 60 65 70 75
Acid Strength (Wt% HNO3)
Figure 10 presents of a prediction of NOx emissions in the tail gas as a function of acid strength.
We see that the NOx emissions remain small and only have a slight increase with acid strength
up to an acid strength of about 65 weight%. Beyond this acid strength, NOx emissions increase
sharply with increased acid strength.
Aspen Inorganics
• • • • • • • • • • •
Figure 11. Absorber Acid-Strength Study – Acid Strength
Acid Profile in Absorber
0.8 68.6 Wt% - Base Case

55 Wt%
Acid Strength (Wt Fraction)
0.7 60 Wt%
65 Wt%
0.6 67 Wt%
70 Wt%
0.5 Weak Acid Feed
0.4
0.3
0.2
0.1
0
0 5 10 15 20 25 30 35
Tray Number
Figure 11 presents the acid profiles in the column for each of the acid strengths studied. This
figure also indicates how the optimum feed tray for the weak acid varies with acid strength. As
the raw acid strength is lowered, it is preferable to feed the weak acid at a lower tray in the
absorber.
Figure 12 presents calculated results for the temperature profiles in the column for each of the
acid strengths studied. At low acid strengths, the cooling load at the top of the column is
relatively small and this section is maintained at approximately the temperature of the cooling
water. However, since the weak acid is fed low down in the column, the temperature is the
highest at the bottom for the lowest acid strength. The temperature profile is quite complicated
at the bottom for the 70 weight% acid case. This is because there is not a good match between
the cooling layers and the trays with the highest heat generation for this case.
These results demonstrate the insight and quantitative results the absorber model can provide.
Aspen Inorganics
• • • • • • • • • • •
Figure 12. Absorber Acid-Strength Study – Temperature Profile
Temperature Profile in Absorber
60
68.6 Wt% - Base Case
55 55 Wt%
60 Wt%
Temperature (°C)
50 65 Wt%
67 Wt%
70 Wt%
45 Weak-Acid Feed
40
35
30
0 5 10 15 20 25 30 35
Tray Number
Aspen Inorganics
• • • • • • • • • • •
8. Summary
This report has discussed the key phenomena occurring in nitric acid plants and has presented a
practical approach to developing accurate and reliable models in process simulation. The
approach is demonstrated through Aspen Plus examples. These examples can be used as
building blocks to produce high-fidelity simulations of specific nitric acid plants.
Two user Fortran subroutines (NCKIN1 and NCKIN2) have been developed to provide the
kinetics in nitric acid heat exchangers. The use of this kinetic capability is demonstrated in the
Aspen Plus application files: Exchangers.bkp and Cooler-Condenser.bkp
A scheme to simulate the mass-transfer and kinetic effects in the absorber has been implemented.
The kinetic and mass transfer correlations have been incorporated into a user subroutine
(NOABS) and a demonstration simulation using Aspen Plus and Radfrac has been presented in
the Aspen Plus application files: Absorber-1.bkp and Absorber-2.bkp.
The analysis and simulation tools presented in this report provide the building blocks to develop
accurate and robust simulations of nitric acid plants.
Aspen Inorganics
• • • • • • • • • • •
9. References
“Electrolytes Manual,” 2nd ed., Aspen Technology, Inc., (1988).
Boublik, T. and K. Kuchynka, Coll. Czech. Chem. Comm., 25, 579 (1960).
Bronsted, J. N., J. Phys. Chem., 102, 169 (1922).
Carberry, J. J., “Chemical Equilibrium and Kinetics in the Nitrogen Oxides-Water System,”
Chem. Eng. Sci., 9, 2 (1959).
Carberry, J. J., Chem. Eng. Sci., 9, 189-194 (1959).
Carta, G. and R. L. Pigford, Ind. Eng. Chem. Fundam. 22, 329-335 (1983).
Chan, H. and Fair, J. R. "Prediction of Point Efficiencies on Sieve Trays 1. Binary Systems", Ind.
Eng. Chem. (Process Design and Development), Vol. 23, 814 (1984)
Chen, C.-C. And L.B. Evans, AIChE J., 32, 444 (1986).
Chen, C.-C., H.I. Britt, J.F. Boston, and L.B. Evans, AIChE J., 25, 820 (1982).
Counce, R. M. and J. J. Perona, Ind. Eng. Chem. Process Des. Dev., 19, 426-431 (1980).
Counce, R. M., "The Scrubbing of Gaseous Nitrogen Oxides in Packed Towers," Ph.D. Thesis,
University of Tennessee (1980).
Dekker, W. A., E. Snoeck, and H. Kramers, Chem. Eng. Sci., 11, 61-71 (1959).
Denbigh, K. G. and A. J. Prince, J. Chem. Soc., 59, 790-801 (1947).
Efimov, V. T. et al., "Liquid-Vapor Equilibrium of Solutions of Nitrogen Oxides in Concentrated

Nitric Acid Under Pressure", The Soviet chemical Industry, Vol. 14, No. 7 (1982)
Emig, G., K. Wohlfahrt, and U. Hoffmann, Computers and Chem. Eng., 3, 143-150, (1979).
Gershinowitz, H. and H. Eyring, J. Amer. Chem. Soc., 57, 985 (1935).
Greig, J. D. and P. G. Hall, Trans. Faraday Soc., 62, 652-654 (1966a).
Greig, J. D. and P. G. Hall, Trans. Faraday Soc., 62, 655-661 (1966b).
Haase, R., K. H. Ducker, H. A. Kuppers, Ber. Bunsenges. Phys. Chem., 69, 97 (1965).
Holma, H. and J. Sohlo, Computers & Chem. Eng., 3, 135-141 (1979).
Aspen Inorganics
• • • • • • • • • • •
Inoue, H., J. of the Faculty of Engineering, the Univ. of Tokyo (B), 39, 361-379 (1988).
Jethani, K. R. et al., Modeling and Simulation of a Spray Column for NOx Absorption, Computers
and Chemical Engineering, Vol. 16, No. 1 (1992)
Joshi, J. B. et al., "Invited Review - Absorption of NOx Gases", Chemical Engineering

Communications, Vol. 33 (1985)
Kent, James A., “Riegel’s Handbook of Industrial Chemistry,” Eight Edition, Van Nostrand
Reinhold Company (1983).
Kirk-Othmer Encyclopedia of Chemical Technology, 3rd Ed., Vol. 15, p. 885, John Wiley &
Sons, New York (1983).
Komiyama, H. and H. Inoue, Chem. Eng. Sci., 35, 154-161 (1980).
Koukolik, M. and J. Marek, "Mathematical Model of HNO3 Oxidation-absorption Equipment,"

Proc. Fourth European Symp. On Chem. Reac. Eng., (1968).
Lee, Y.-N. and S. E. Schwartz, J. Phys. Chem., 85, 840-848 (1981).
Lemire, R. J., C. P. Brown, and A. B. Campbell, J. Chem. Eng. Data, 30, 421-424 (1985).
Matasa, C. and E. Tonca, Basic Nitrogen Compounds, Chemistry, Technology and

Applications, 3rd ed., Chemical Publishing Co., Inc., New York (1973).
Miller, D. N., "Mass Transfer in Nitric Acid Absorption," AIChE J., 33, 1351-1358, (1987).
Morrison, M. E., R. G. Rinker, and W. H. Corcoran, Ind. Eng. Chem. Fundamentals, 5, 175
(1966).
Nat. Bur. Stand. (U>S>) Circ. 510, (1957).
Perry, R. H., C. H. Chilton, and S. D. Kirkpatrick, Chemical Engineer's Handbook, 4th Ed.,
McGraw Hill, New York, (1973).
Potier, J., Alger Sciences Physiques, 4, 99 (1958).
Prosek, J., Thesis, UTZCHT-CSAV, Prague (1965).
Razuvaev, V. E., I. N. Maksimova, J. Appl. Chem. USSR, 397-401 (1977).
Renon, H., Int. J. Refrig., 9, 70-73 (1986).
Schwartz, S. E., and W. H. White, Adv. Environ. Sci. Eng., 4, 1 (1981)
Solc, M., Nature, 209, 706 (1966).
Aspen Inorganics
• • • • • • • • • • •
Trautz, M., Z. Elektrochem., 22, 104 (1916).
Treacy, J. C. and F. Daniels, J. Amer. Chem. Soc., 77, 2033 (1955).
Ullmann's Encyclopedia of Industrial Chemistry, Vol. A17, p.300 (1991).
Vandoni, M. R. and M. Landy, J. Chem. Phys., 49, 99 (1952).
Vargaftik, N. B. “Dictionary of Thermophysical Properties of Gases and Liquids,” (1972).
Venkataraman, S., W. K. Chan, and J. F. Boston, Chem. Eng. Prog., 86, (8), 45-54 (August
1990).
Wagman, D. D. et al., "The NBS Tables of Chemical Thermodynamic Properties, Journal of

Physical and Chemical Reference Data", Vol. 11 (1982).
Wagman, D. D., W. H. Evans, V. B. Parker, R. H. Schumm, I. Halow, S.M. Bailey, K.L.

Churney, and R.L. Nuttall, The Tables of Chemical Thermodynamic Properties, Selected Values
for Inorganic and C1 and C2 Organic Substances in SI Units, J. of Phys. And Chem. Ref. Data,
Vol. 11, Supplement No. 2 (1982).
Wendel, M. M. and R. L. Pigford, AIChE J., 4, 249-256 (1958).
Wilson, G. L. and F. D. Miles, Trans. Faraday Soc., 36, 225, 356 (1940).
Yakimov, M. A. and V. Ya. Mishin, Radiokhimiya, 6, 545 (1964).
Aspen Inorganics

Nitric Acid Package Report 07

Transféré par

Informations du document

Copyright

Formats disponibles

Partager ce document

Partager ou intégrer le document

Options de partage

Avez-vous trouvé ce document utile ?

Ce contenu est-il inapproprié ?

Droits d'auteur :

Formats disponibles

Nitric Acid Package Report 07

Transféré par

Droits d'auteur :

Formats disponibles

Aspen Inorganics

NITRIC ACID PACKAGE

This report contains proprietary information of

3. Components and Physical Property Models ..........................................................................4

Figure 1. Heat of Mixing of Nitric Acid – Water Mixtures at 25C .............................................. 7

The Nitric Acid Package contains the following building blocks:

 Accurate thermodynamic and transport-property correlations

 Exchangers.bkp – Demonstrates the simulation of heat exchangers where the process

2NH 3  2.5O 2  2NO  3H 2 O  108.36 kcal (25  C) (1)

2NH 3  1.5O 2  2N 2  3H 2 O  151 .56 kcal (25  C) (2)

2NH 3  3NO  2.5N 2  3H 2 O  216.36 kcal (25  C) (3)

accelerate less and thus become relatively slower.

2NO  O 2  2NO 2  27.021 kcal (25  C) (4)

2 NO 2  N 2 O4  14.01 kcal (25  C ) (5)

The NO2/N2O4 is absorbed in water at as low a temperature as is economically feasible to form

2 NO 2  H 2 O(l )  2 HNO3 (l )  NO  5 .81 kcal (25  C ) (6)

3. Components and Physical Property Models

Table 1. Components in the Aspen Plus Model

3.2. Pure Component Properties

3.3. Mixture Properties – General Discussion

3.4. Mixture Properties - Gas Mixing Section

3.5. Mixture Properties - Ammonia Oxidation Section

3.6. Mixture Properties - Nitric Oxide Oxidation and Absorption Sections

H 2 O  HNO3  H 3 O   NO3 (7)

Figure 1. Heat of Mixing of Nitric Acid – Water Mixtures at 25C

Nitric Acid-Water Excess Enthalpy at 25°C

Figure 2. Heat Capacity of Nitric Acid – Water Mixtures at 20C

Heat Capacity of Nitric Acid-Water at 20°C

Figure 3. Density of Nitric Acid – Water Mixtures at 20

Density of Nitric Acid-Water Mixtures at 25°C

Figure 4. Nitric Acid – Water Txy Diagram – Mole Fraction

Txy Diagram of Nitric Acid - Water at 760 Torr

Figure 5. Nitric Acid – Water Txy Diagram – Weight Percent

Txy Diagram of Nitric Acid - Water at 760 Torr

Full line is calculated dew point

Figure 6. Viscosity of Aqueous Nitric Acid Mixtures

Viscosity of Nitric Acid

Figure 7. Thermal Conductivity of Aqueous Nitric Acid Mixtures at Constant Composition

Thermal Conductivity of Nitric Acid

Thermal Conductivity 0.7

0.4 50 Wt% HNO3

Figure 8. Thermal Conductivity of Aqueous Nitric Acid Mixtures at Constant

Thermal Conductivity of Nitric Acid

3.7. Physical Properties – Summary

4. Chemical Reaction and Mass-Transfer Models - Overview

Some proposed reaction pathways may be summarized as follows:

2NO + O 2  2NO 2 (8)

N 2O 4 + H 2O HNO 3 + HNO 2 (12)

3HNO 2 HNO 3 + 2NO + H 2O (13)

N 2O 4 (g) N 2O 4 (l) (15)

N 2O 3 (g) N 2O 3 (l) (16)

NO 2 (g) NO 2 (l) (17)

5.1. Modeling Approach

2NO + O 2 2NO 2 (18)

3NO 2 + H 2O 2HNO 3 + NO (20)

5.2. Oxidation of Nitric Oxide

In terms of a molar conversion rate, the kinetics expression is:

5.3. Nitrogen Dioxide Dimerization

The equilibrium constant for Equation 19:

5.4. Nitric Acid Formation and Condensation

where partial pressures are in Pa and temperatures are in K.

where partial pressures are in atm and temperature are in K.

5.5. Nitric Acid Reactor Kinetic Model

5.6. Example Reactive Heat Exchanger Models