Zdravko Kravanja, Miloš Bogataj (Editors), Proceedings of the 26th European Symposium on

Computer Aided Process Engineering – ESCAPE 26

June 12th -15th, 2016, Portorož, Slovenia © 2016 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/B978-0-444-63428-3.50251-4

Equation-based Rigorous Modelling of the NOx

Absorption Process: Model Development and
Process Optimization
Inês L.S.B. Vilarinhoa,b*, Nuno M.C. Oliveiraa, Belmiro P.M. Duartea,c, Susana
E.F.M. Pereirab
a
CIEPQPF, Department of Chemical Engineering, University of Coimbra, Rua Sílvio
Lima, Coimbra 3030-790, Portugal, inessvilarinho@gmail.com
b
Companhia União Fabril – Químicos Industriais, CUF-QI, Quinta da Indústria – Rua
do Amoníaco Português, 10, Beduído, Estarreja 3860-680, Portugal
c
Department of Chemical and Biological Engineering, Polytechnic Institute of Coimbra,
Rua Pedro Nunes, Coimbra 3030-190, Portugal

Abstract
This paper addresses the nitrogen oxides absorption process in nitric acid plants. A
mechanistic model is developed for this gas-liquid reactive absorption system, able to
predict the unit behaviour and support its optimization during regular and transient
operating regimes. A rigorous rate-based model was adopted, and a new modelling
strategy is proposed to assure the compatibility of mass transfer limitations and
equilibrium kinetics. The model has the form of a DAE system, and is solved with an
algebraic solver combined with an integration algorithm. This study was focused on the
analysis of the unit steady state. The acid strength through the whole column was
analysed and a good agreement with industrial data is observed.
Keywords: NOx abatement, Reactive absorption, Rate-based model, Process modelling

1. Introduction
Many nitric acid plants operating currently on Europe (such as the one in CUF-QI)
include advanced technology for the abatement of atmospheric emissions of nitrogen
oxides (NOx). Very often, these systems are based on the selective catalytic reduction
technology, including a reactor where nitrogen oxides, NO and NO2, are converted into
nitrogen (N2) and water (H2O), with the aid of a catalyst in the presence of a reducing
agent. However, this technology presents some limitations especially during the plant’s
start-up and shutdown. In transient regimes, total ammonia conversion through the
reactor cannot be achieved and severe safety issues arise due to the possible formation
of ammonium nitrite and nitrate, potentially explosive byproducts. Hence, during such
periods, the abatement system cannot be used, thus increasing NOx emissions that turn
the tail gas visible with a reddish-brown colour. Strictly speaking, these emissions do
not violate present environmental regulations that allow for higher emissions during
short periods. However, they have a visual impact and may lead to formal complaints by
the surrounding populations. Moreover, stricter regulations can be expected in the near
future, also covering these start-up and shutdown periods. A possible approach for the
development of more effective solutions considers the reconfiguration of the operating
1480 I.L.S.B. Vilarinho et al.

procedures during these transient phases, targeting a more complete absorption of the
key nitro compounds.
The absorption of nitrogen oxides in water has been widely studied over the past 100
years. Despite being a very common process in the chemical industry the
comprehension of its fundamental mechanisms is still challenging, mainly due to the
complexity of the interfacial phenomena and the equilibria that constrain the relations
between species. Joshi et al. (1985) presented a review on the absorption of the NOx,
gases listing the most relevant aspects of this system. Various mathematical models
have been proposed for the steady state simulation of packed columns, e.g. Suchak et al.
(1991), and plate columns, e.g. Pradhan et al. (1997). In 2005, the rate-based approach
was considered the most appropriate methodology to describe this operation by Hupen
et al. (2005). Later, an attempt was made by Loutet et al. (2011) to simulate the
absorption process in Aspen Plus; however their model is only valid for HNO3
concentrations lower than 15% wt. Given the stricter trend of the environmental
regulations, various aspects related to the operation of the NOx columns are expected to
be modified in the near future. A modelling tool that can be used to predict the impact
of changes a priori and optimize the operation is viewed as an asset that can minimize
problems and help troubleshooting. Hence, the main aim of this work is to build a
detailed model that simultaneously assures robustness and accuracy in this task.

2. Rigorous rate-based model

The NOx absorption in water involves several chemical reactions, occurring either in the
gas or liquid phase. An illustration of this mechanism is presented in Figure 1. The
formation of the NOx products is a consequence of the reactions that occur in the gas
phase; these products are subsequently absorbed and react with water to form nitric and
nitrous acid, releasing NO back into the gas phase. The film theory was used to model
the transfer of NOx species across the interface, at pre-specified temperatures, due to the
existing cooling system. In this absorption process, the gas and liquid phases can reach
a heterogeneous equilibrium, which can be described by the global reaction:
k3
3NO2 (g)+H2 O(l) ↔ 2HNO3 (l)+NO (g). This equilibrium determines the maximum nitric
concentration that can be obtained for a given composition of nitrous gases, Hoftyzer et
al. (1972). The limiting partial pressures behave like back pressures that will limit the
absorption of the NOx gases, and no absorption takes place when 𝑃𝑃Nlim2O4
= 𝑃𝑃Ni 2 O 4 .

Figure 1 – Mechanism of NOx absorption into water (adapted from Suchak et al. (1991))
Equation-based Rigorous Modelling of the NOx Absorption Process: Model
Development and Process Optimization 1481

Stage Diagram

Gas area - space between trays

Forth area - gas/liquid mixture
Material balances
1. Gas phase

2. Liquid phase

Gas phase mass transfer volumetric rates

Liquid phase mass transfer volumetric rates
1. Without reaction
2. With reaction
Thermodynamic equilibria
1. Henry’s law (interface)
2. Vapour pressures (interface)
3. Gas phase equilibria
Figure 2 – Rigorous equation-based approach – model for the nth stage
The model developed is based on sieve tray balances, and its general structure is
presented in Figure 2. Two distinct zones are considered: i. Gas area; ii. Froth area. The
gas area corresponds to the free space between consecutive trays, where the oxidation
reaction occurs; this is modelled as a piston flow reactor. This model shares various
conceptualization aspects with other models found in the literature. However several
novelties were also introduced to increase the accuracy in representing the underlying
phenomena, yet preserving the numerical tractability:
1. Contrary to other models found in the literature (e.g. Carberry (1959)), the
lim
ratio 𝑃𝑃NO /(𝑃𝑃Nlim
2O4
)3/2 included in the equilibrium constant k3 in the form of
lim lim 3
𝑃𝑃NO /(𝑃𝑃NO 2 ) , is calculated from thermodynamic data presented in Forsythe et
al. (1942) and vapor pressure correlations are used to assure its consistency at
equilibrium conditions. As a result, this kinetic rate is more accurate in extreme
concentrations of interest, such as in the vicinity of zero and azeotropic nitric
acid concentration, and allows a coherent modelling of the equilibrium state.
2. The model was firstly validated for stage equilibrium conditions at different
nitric acid concentrations (Figure 3), employing data of Hoftyzer et al. (1972).
This validation guarantees that the model is capable of capturing the main
features of the process in equilibrium conditions as well as the consistency of
the correlations used to estimate the water and nitric acid vapour pressures.
1482 I.L.S.B. Vilarinho et al.

Figure 3 – Equilibrium state at 30ºC – Comparison of data presented in Hoftyzer et at. (1972),
solid line, and calculated ones, points in graph
The changes presented above allow the development of a more robust and realistic
model, since several phenomena involved in the process, namely kinetic and
thermodynamic equilibria, are considered. The overall column model is constructed by
connecting successive trays, and imposing additional equality equations relating the
flows and concentrations of the input and output streams. Trays of four different
topologies are used: i. General trays; ii. Top tray, where the water stream enters; iii.
Bottom tray, where gas stream is fed; and iv. Lateral feed tray, where a stream of
recycled acid enters. All of them share the same model structure, although minor
modifications are required in the calculation algorithm. Further, in the gas area the
oxidation reaction will occur changing the partial pressures throughout this space. The
model has the form of an index-2 DAE system, and each stage model includes several
ODE’s and AE’s generating in a total of 637 algebraic equations per stage, for the
steady state simulation.

3. Simulation results
This mathematical model was implemented and solved in an algebraic modelling
language (GAMS), taking advantage of the robust nonlinear optimization solvers
available. The steady state simulation of unit was performed in order to: i. find the
concentrations profile along the column, which might reveal possible inefficiency
issues, and ii. validate the model with industrial data gathered in similar conditions. Due
to the model’s complexity, and the fact that the model variables change over several
orders of magnitude inside the column, special care was placed in the initialization
procedure. Firstly each tray is initialized individually, considering its evolution from an
initial state. Next, the connections between trays were activated, adding incrementally
each tray to a block of trays already converged. During this process, it was found that
the limiting partial pressures have a strong impact in the model’s convergence. To
handle this issue, successive solutions were found assuming that 𝑃𝑃jlim = γ𝑃𝑃jlim , where
γ ∈ [0,1]. Initially, γ = 0 is considered, and this value is increased till 1, by reusing the
last consistent solution, until the complete model is converged. An optimization
environment was used to solve the problem due to: i. The need of robustly and
efficiently initialize the model in a large range of operating conditions; ii. The use of
this model in a later stage of the project where process optimization and optimal control
problems will be addressed.
Equation-based Rigorous Modelling of the NOx Absorption Process: Model
Development and Process Optimization 1483

Figure 4 – Comparison between total acid concentration (TAC) of the industrial plant data and the
model’s predictions, and representation of total NO and NO2 pressure (TNP) along the column.
Figure 4 presents a comparison between industrial plant data and the model’s prediction
for the content of the liquid stream in nitric and nitrous acids combined. The first tray in
Figure 4 corresponds to the bottom tray, and the last to the top tray, where pure water is
fed. The industrial data used corresponds to measurements gathered by the plant
monitoring system of CUF-QI during the current year. In this validation test the gas
flowrate and composition are unknown, and nominal data from the process flow
diagram was used to circumvent this problem; this assumption may explain some of the
differences between data and model predictions, especially in the first trays. Despite the
differences observed, a reasonably good agreement can be noticed. A similar behaviour
is observed for the NO and NO2 pressures along the column, (see the behaviour of TNP
– Model), and the profile denotes a similar trend with the acid concentration in the
liquid phase. A slight unexpected increase in the acid concentration is noticed near the
lateral feed tray. This stream may cause a profile discontinuity, due to its relatively high
acid concentrations. Near this stage, the absorption of the nitrous gases can be reduced
or even desorption can occur, as shown in Figure 4. Nevertheless, this increase is also
observed for some operation regimes, and the model seems able to capture the most
relevant features of the unit. The increase in the acid concentration suggest that for
those operating conditions the lateral feed tray is not on the ideal position, and that the
unit can eventually be further optimized.
4. Conclusions
A new rigorous rate-based mathematical model was proposed to describe the absorption
of nitrogen oxides in water. The modifications assure the compatibility between the
mass transfer limitations and the equilibrium kinetics. The model was implemented in
the GAMS algebraic environment; due to its complexity a specialized initialization
scheme was developed. Next, a comparison between industrial data from CUF-QI and
the predictions was performed. Despite the differences observed the trends of the nitric
and nitrous acid concentrations are in reasonably good agreement with the industrial
data collected.
1484 I.L.S.B. Vilarinho et al.

In future work a parameter’s sensitivity study will be done to improve the consistency
of the model. Several scenarios will be tested in order to be able to predict a wide range
of operating conditions. After this, the model will be used to describe the dynamic state
of the whole column including the start-up and shutdown procedures. An optimization
will be also done to develop new or to improve existing technologies considering
economic and environmental aspects.

Acknowledgments
Financial support by Fundação para a Ciência e Tecnologia (FCT) for the Ph.D. Grant
SFRH/BDE/51755/2011 and by CUF - Químicos Industriais S.A. is gratefully acknowledged.

Nomenclature
a - interfacial area Greek symbols
Cj - concentration of component j α − stoichiometric constant
dz – differential height φ − enhancement factor
G – mol flowrate of inert (N2) Superscript
Hj - Henry’s coefficient of component j b - bulk
kg, kL - physical gas/liquid-side mass transfer i – interface
coefficient of component j, respectively lim – limiting
N – total number of nodes n – nth tray
L - liquid flowrate of component Subscript
Pj - partial pressure G – Gas
rx - reaction rate of reaction x j – components
RG,j, RL,j - rate of phase mass transfer l – lateral
S – cross section area of the column L – Liquid
V – Volume T – Total
xj – molar fraction in the bulk liquid phase t - nodes
Yj - molar fraction in the gas phase

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