Rigorous Modelling of NO Absorption in Tray and Packed Columns
Rigorous Modelling of NO Absorption in Tray and Packed Columns
Rigorous Modelling of NO Absorption in Tray and Packed Columns
www.elsevier.com/locate/ces
Received 15 November 2004; received in revised form 19 April 2005; accepted 19 April 2005
Available online 23 June 2005
Abstract
The absorption of NOx into pure water or nitric acid is usually a kinetically controlled operation in which complex reactions in both
gas and liquid phases are combined with multicomponent mass transfer. To be able to describe this process adequately, a rigorous general
rate-based model for the reactive absorption in tray and packed columns has been developed based on earlier works (see, e.g. [Kenig et
al., 2001. Chemical Engineering Science 56, 343–350; Kenig et al., 2003. Chemical Engineering and Technology 6, 631–646]). Heat and
multicomponent mass transfer in the film phases, chemical reactions and thermodynamic non-idealities are taken into account. Furthermore,
the influence of column internals and hydraulics is considered via relevant correlations. For tray columns, a special consideration of the
empty sections above the gas–liquid layer on a tray is included. The model is implemented into the simulation environment Aspen Custom
ModelerTM and validated by comparison with experimental data for a pilot scale packed column and an industrial sieve tray column
equipped with cooling coils. The simulation results obtained for both column types agree well with the experimental measurements. In
addition, the influence of cooling on the process behaviour is studied.
䉷 2005 Elsevier Ltd. All rights reserved.
Keywords: NOx absorption; Rate-based model; Cooling; Absorption; Simulation; Modelling; Transport processes
0009-2509/$ - see front matter 䉷 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.ces.2005.04.060
B. Hüpen, E.Y. Kenig / Chemical Engineering Science 60 (2005) 6462 – 6471 6463
transfer can be properly taken into account (Kenig et al., counter-currently to the gas and form nitric acid which is
2001). drawn off at the bottom of the first column. These columns
Absorption of NOx is one of the most complex gas–liquid can be either of a packed or of a tray type. Tray columns
reaction operations. This is the reason why various simpli- are often additionally equipped with cooling coils on trays
fications reducing the accuracy and predictivity of the rate- in order to achieve higher absorption rates via cooling.
based approach have been made, e.g. consideration of mass The reaction network of the NOx system is extremely
transport of the key components NO2 and N2 O4 only (Emig complicated. Altogether, there are more than 40 reactions
et al., 1979; Greve and Bode, 1994; Wiegand et al., 1990), known. For the simulation of the process, a relevant set of re-
assumption of equal component diffusivities (Emig et al., actions was taken from Suchak et al. (1991). It contains five
1979; Ramanand and Phaneswara Rao, 1996; Suchak et al., gas-phase and four liquid-phase reactions presented below:
1991), application of enhancement factors (de Paiva and
Kachan, 2004), or neglecting the reactions in the gas film • gas-phase reactions
(Patwardhan et al., 2002; Suchak et al., 1991).
The present work is free of such simplifications. We de- 2NO + O2 → 2NO2 , (R1)
veloped a general rate-based model which is valid for both
2NO2 ↔ N2 O4 , (R2)
packed and tray columns and applicable for a broad spec-
trum of NOx absorption operations. The model is an exten- NO + NO2 ↔ N2 O3 , (R3)
sion of previous models (see Kenig et al., 1997, 2001, 2003;
Schneider et al., 1999) developed for the description of reac- NO + NO2 + H2 O ↔ 2HNO2 , (R4)
tive absorption in packed columns. The model involves the
film model equations combined with relevant reaction and 3NO2 + H2 O ↔ 2HNO3 + NO; (R5)
diffusion kinetics for all reactions and components, in both
the gas and liquid phases, and it is extended to include an • liquid-phase reactions
additional element—the so-called gas area—which consid- 2NO2 + H2 O → HNO2 + HNO3 , (R6)
ers the influence of the gas-phase reactions on the compo-
sition in the empty section above the gas–liquid layer on a N2 O3 + H2 O → 2HNO2 , (R7)
tray. Further, the model includes the description of cooling
effects through cooling coils installed in tray columns. N2 O4 + H2 O → HNO2 + HNO3 , (R8)
The model is realised with the help of the simulation en-
vironment Aspen Custom ModellerTM and successfully val- 3HNO2 → HNO3 + H2 O + 2NO. (R9)
idated with NOx absorption experimental data for columns
of both packed and tray type. For the process performance, the oxidation of nitrogen
monoxide to nitrogen dioxide (R1) is especially significant,
because of the low solubility of nitrogen monoxide in water.
2. Process description Compared to nitrogen monoxide, the solubility of nitrogen
dioxide is one order of magnitude higher. Reaction (R1)
A typical simplified flow diagram of NOx absorption is a kinetically controlled reaction and it is assumed to be
process is shown in Fig. 1, with three columns connected irreversible for temperatures below 350 ◦ C. In reactions
counter-currently. The inlet of the raw gas consisting of (R2)–(R5), nitrogen dioxides instantaneously react to in-
nitrogen oxides and air is at the bottom of the first col- termediate products (e.g. N2 O3 or HNO2 ) whose solubility
umn. The solvent is fed at the top of the third column. increases with increasing molecular weight.
The nitrogen oxides are absorbed by the solvent flowing The liquid-phase reactions are kinetically controlled and
assumed to be irreversible at nitric acid concentrations below
35 wt% (Joshi et al., 1985). Via reactions (R6)–(R8) the
dissolved nitrogen oxides are transformed into nitric and
nitrous acids. NO produced in reaction (R9) is desorbed due
to its low solubility.
The instantaneous gas-phase reactions (R2)–(R5) are
taken into consideration by means of the mass action law
G p,r
G p (yp P )
Kr = G e,r . (1)
e (ye P )
Table 1
Chemical equilibrium and forward reaction rate constants of reactions (R1)–(R9)
ln k1 = 1468 −2 s−1 )
R1 T − 10.9043 (kPa Miller (1987)
R2 ln K2 = T − 25.865 (kPa−1 )
6893 Miller (1987)
ln K3 = 4869 −1
R3 T − 21.61 (kPa ) Hisatsune (1961)
R4 ln K4 = T2051.17 − 8.7385 (kPa−1 ) Joshi et al. (1985)
R5 ln K5 = T − 10.763 (kPa−1 )
2003.8 Joshi et al. (1985)
R6 log kc6 = 4.67209 (m2 mol−1 s−1 ) Lee and Schwartz (1981)
R7 log kc7 = 4.23044 (s−1 ) Corriveau (1971)
log kc8 = − 4139 −1
R8 T + 16.3415 (s ) Wendel and Pigford (1958)
R9 log kc9 = − 6200 + 20.1979 (atm 2 m 9 kmol−3 s−1 ) Wendel and Pigford (1958)
T
expressions:
rrG = kr,for
G
(yeG P )e,r for (R1), (2)
e
e,r
rrL = kr,for
L
(xeL L
e) for (R6).(R9). (3)
e
Similar equations can be applied for the gas bulk phase 3.3. Interface
j Gb
0=− (y G) + nGbi a A
int col
− RiG Acol Gb ; The thermodynamic equilibrium at the gas–liquid inter-
jz i face is usually calculated as follows:
i = 1, . . . , n, (7)
yiint = Ki xiint ; i = 1, . . . , n, (18)
j
0 = − (H Gb GGb ) + q Gb a int Acol + QGb
loss , (8)
jz where the distribution coefficient Ki comprises fugacities in
both phases and activity coefficients in the liquid phase. To
n
determine Ki of very diluted systems, the Henry law for the
yiGb = 1. (9) dissolved components and the Raoult law for the solvent are
i=1 used.
Gas and liquid phases are connected by the following
3.2. Equations for the film region boundary conditions:
Gf
In the liquid film region, mass transfer and chemical re- ni |Gf =Gf = nLb
i |Lf =0 ; i = 1, . . . , n, (19)
action occur simultaneously. Therefore, a differential com-
ponent balance has to be considered q Gf |Gf =Gf = q Lf |Lf =0 . (20)
Lf
jni Lf
0= − Ri ; i = 1, . . . , n. (10) 3.4. Gas area equations
jLf
For the description of tray columns, some additional con-
In dilute systems, the diffusional interactions can usually
sideration is necessary to describe the gas area (cf. Fig.
be neglected, and the Maxwell–Stefan equations, generally
2). Whereas the gas–liquid layer is still described by Eqs.
applied for the description of mutlicomponent diffusion, are
(4)–(20), the gas area is covered in a different way.
replaced by the effective diffusivity description (Taylor and
The change of the gas composition in the gas area is
Krishna, 1993)
considered through the following differential equation:
Lf
Lf Lf jx i Lf Lf j Ga
ni = −ct Dieff + x i nt ; i = 1, . . . , n. (11) 0=− (y G) − RiG Acol Ga ; i = 1, . . . , n. (21)
jLf jz i
The differential energy balance of the liquid film is as fol- Further, the summation condition for the molar fractions has
lows: to be fulfilled
n
jq Lf
0= . (12) yiGa = 1. (22)
jLf
i=1
The heat flux in the liquid film consists of a conductive and The energy balance of the gas area is
a convective term
j
n
jT Lf Lf Lf 0=− (H Ga GGa ). (23)
q Lf
= − Lf
+ (ni Hi ); i = 1, . . . , n. (13) jz
jLf
i=1
Eqs. (21)–(23) are used in combination with the equations
Similar equations for the mass and heat transport are valid for the gas–liquid layer.
in the gas film:
3.5. Model parameters
Gf
jni Gf
0 = Gf − Ri ; i = 1, . . . , n, (14)
j For the determination of the mass transfer coefficients,
specific gas–liquid interfacial area and volumetric hold-up,
Gf
Gf Gf jyi Gf Gf empirical correlations are used, which govern the influence
ni = −ct Dieff Gf
+ y i nt ; i = 1, . . . , n, (15) of column internals and hydraulics. These correlations have
j
to be incorporated into the whole system of model equations.
jq Gf The relevant correlations are taken from Billet and Schultes
0= , (16) (1999) for packed columns and from Zuiderweg (1982) for
jGf
sieve tray columns. For the description of the hydraulics in
n
jT Gf Gf Gf sieve tray columns, we included the equations for the spray
q Gf = −Gf + (ni Hi ). (17) and emulsion flow regime. The decision, which equation
jGf
i=1 should be used, is taken automatically during the simulation
6466 B. Hüpen, E.Y. Kenig / Chemical Engineering Science 60 (2005) 6462 – 6471
Table 2
Physical property models according to Aspen Properties Manual (2001)
Table 3
NRTL-parameters bij and bj i
1 2 bij bj i 1 2 bij bj i
of the absorption process. It can be changed for each tray essary for the calculation of the physical properties. These
within the same column and depends on the following ratio: models are listed in Table 2.
The activity coefficients are calculated by the NRTL-
uL L 0.5 model for multicomponent mixtures. The NRTL-parameters
. (24)
uG G aij , aj i , dij , eij , ej i , fij and fj i for each binary pair are set
In addition, pressure drop along the column is allowed for to the default value zero, whereas cij to the default value 0.3.
via the relevant pressure drop correlations (see Zuiderweg, The estimated NRTL-parameters bij and bj i are collected
1982; Billet and Schultes, 1999). in Table 3.
Fig. 6. Axial profile of the liquid temperature of column 2 and measured Fig. 7. Axial profile of the total NOx concentration in the gas phase and
values. the nitric acid concentration in the liquid phase and measured values.
Table 4 Fig. 7 shows the calculated axial profiles of the total NOx
Design parameters of the industrial sieve tray column concentration in the gas phase and the nitric acid concen-
tration in the liquid phase. The inlet and outlet values deter-
Column diameter 3.8 m
Number of trays 20 mined with a measurement error of 15% are given, too. The
Plate spacing 0.9 m agreement between the experimental and simulated values
Weir height 0.25 m of the total NOx has a maximum deviation of 8.5%. The
Weir length 3.015 m deviation of the simulated HNO3 concentration from the ex-
Flow path 2.3 m
perimental value is in a range of 10%. Thus, the agreement
Number of holes 54,000
Hole diameter 2.2 mm is good, as all deviations lie within the measurement error.
Distance of holes (pitch) 13 mm The simulated outlet temperature of the cooling water is
Hole diameter 2.2 mm 24.8 ◦ C. This value agrees very well with the measured value
of 24.9 ◦ C, the deviation being less than 1%.
From the results of both pilot plant and industrial applica-
stream. These two opposite effects result in an extremum of tions, it can be concluded that the suggested model demon-
the axial temperature profile. strates a good accuracy for the highly complex NOx absorp-
For both columns, the calculated liquid temperature at the tion processes studied.
bottom differs from the measured value by more than 5%.
The absolute deviation is 4.5 ◦ C for column 1 and 3.8 ◦ C
for column 2. These deviations should be attributed to heat 5. Sensitivity analysis
losses through the column wall. Suchak et al. (1991) men-
tioned that their columns were not isolated, however they 5.1. Internals-related parameters
did not quantify this phenomenon, and thus, it could not be
properly estimated in the calculations. The validated model has been used to carry out compre-
hensive sensitivity studies for the packed columns in order
4.3. Validation for a tray column to investigate the influence of model parameters on the sim-
ulation results. The values of the internals-related parame-
The experimental data for an industrial scale one- ters, such as the mass transfer coefficients k L and k G , the
pass sieve tray column is provided by the Phosphoric gas–liquid interfacial a int area and the liquid hold-up L ,
Fertilisers Industry (Greece) in the context of the Euro- have been increased by 10%. The influence of these param-
pean research project OPT-ABSO (G1RD-CT-2001-00649, eters is quantified by the change of the total absorption rate
http://www.opt-abso.org). The design details of the tray col- of NO, NO2 , N2 O4 and total NOx .
umn are given in Table 4. Each tray has a height of 0.9 m. In The results presented in Fig. 8 show a substantial influence
the column, a gas stream containing 0.77 mol% of nitrogen of the interfacial area a int on the absorption rate of NO2 . An
oxides is treated by an aqueous solution with 0.68 mol% increase of a int by 10% leads to a 7.2% higher absorption
of nitric acid. To cool down the gas and liquid within the rate. The influence of a int on the absorption rate of the other
column, it is equipped with cooling coils on 7 trays in the components and the influence of the other model parameters
lower part. The coils are fed with 152 m3 /h water, with an k L , k G and L is less significant. Changes by 10% lead to
average temperature of 23.6 ◦ C. deviations less than 3%.
B. Hüpen, E.Y. Kenig / Chemical Engineering Science 60 (2005) 6462 – 6471 6469
Fig. 10. Effect of cooling on the absorption rate of NOx for an increased
Fig. 8. Influence of a 10% increase of the model parameters L , k L , k G NOx inlet gas stream concentration.
and a int on the absorption rate of NO, NO2 , N2 O4 and total NOx .
equipped with cooling coils. Good agreement between ex- density, kg/m3
perimental and simulated data is obtained for both processes. volumetric hold-up, m3 /m3
This should be regarded as a success, since such processes
are usually difficult to describe adequately due to their ex- Subscripts
tremely high complexity. Thus, the suggested model can be
judged as accurate enough for the description of the NOx
absorption processes in tray columns and as both accurate c concentration-based
and predictive for the NOx absorption in packed columns. e reactant
A comprehensive parameter sensitivity study reveals that for forward reaction
the reaction rate constants of the oxidation reaction (R1) i component index
and the gas–liquid interfacial area have the most significant p product
influence on the process performance. Further, the investi- r reaction index
gation of the effect of column cooling on the process be- t total
haviour shows that there is a clear dependency between the
cooling duty and the NOx absorption rate. Superscripts
The application of the suggested model enables an ac-
curate design and operation of NOx absorption processes
and can be used for other relevant gas–liquid reaction b bulk
systems. f film
G gas phase
Ga gas area
int interface
Notation L liquid phase
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